Precursor concentration monitoring

Abstract

Provided are method for monitoring precursor concentration. The method includes flowing a precursor continuously from a vapor supply source toward a deposition chamber and monitoring the precursor concentration based at least in part on the spectroscopy measurements received from one or more spectral sensors or based at least in part on measurements received from a piezoelectric sensor or optical sensor. In some cases, precursor concentrations for a blended gas mixture can be monitored based at least in part on spectroscopy measurements or other measurements. A flow rate of the precursor or blended precursors can be modified according to an updated flow condition based on the monitored precursor concentration(s).

Description

LAMRP955WO-11528-1WO PRECURSOR CONCENTRATION MONITORING INCORPORATION BY REFERENCE

[0001] A PCT Request Form is filed concurrently with this specification as part of the present application. Each application that the present application claims benefit of or priority to as identified in the concurrently filed PCT Request Form is incorporated by reference herein in their entireties and for all purposes. FIELD

[0002] The present disclosure relates to semiconductor fabrication, and more particularly to monitoring precursor gas concentrations during a semiconductor fabrication process. BACKGROUND

[0003] Many semiconductor fabrication processes include providing one or more precursors to a substrate in a process chamber to form a film on the substrate. Some precursors may be in a vapor phase form and may be mixed with carrier gas. Some precursors may be delivered in a very low concentration and the amount of precursors may not be precisely known during the deposition of a film.

[0004] The background description provided herein is for the purposes of generally presenting the context of the disclosure. Work of the presently named inventors, to the extent it is described in this background section, as well as aspects of the description that may not otherwise qualify as prior art at the time of filing, are neither expressly nor impliedly admitted as prior art against the present disclosure. SUMMARY

[0005] One aspect of the disclosure relates to a method of monitoring concentrations of two or more precursors. The method includes flowing the two or more precursors continuously from one or more vapor supply sources toward a process chamber. The method further includes monitoring the concentrations of the two or more precursors based at least in part on spectroscopy measurements received from one or more spectral sensors.

[0006] In some embodiments, each of the two or more precursors is separately flowed towards the process chamber.

[0007] In some embodiments, the two or more precursors are collectively flowed towards the process chamber.

[0008] In some embodiments, the two or more precursors flow at a vapor pressure equal to orLAMRP955WO-11528-1WO less than about 50 millitorr.

[0009] In some embodiments, the two or more precursors are mixed with carrier gas to form a gas mixture.

[0010] In some embodiments, a mixing ratio of the two or more precursors to the carrier gas is about 1:100.

[0011] In some embodiments, the concentrations of the two or more precursors are monitored by the spectroscopy measurements and pressure and / or temperature measurements.

[0012] In some embodiments, the pressure is measured for a mixture of the precursor and the carrier gas by a mass flow controller.

[0013] In some embodiments, the one or more spectral sensors comprise an infrared (IR) sensor, a visible light sensor, an ultraviolet (UV) sensor, or a combination thereof.

[0014] In some embodiments, the spectroscopy measurements generate electrical or optical signals for absorption characteristics obtained for the two or more precursors.

[0015] In some embodiments, the electrical or optical signals for the two or more precursors are compared against calibrated reference signals.

[0016] In some embodiments, monitoring the concentrations of the two or more precursors includes monitoring a concentration of a contaminant mixed with the two or more precursors.

[0017] In some embodiments, the contaminant includes water, a decomposed product, or a reaction product mixed with the two or more precursors.

[0018] In some embodiments, the contaminant is identified by comparing electrical or optical signals obtained for the two or more precursors mixed with the contaminant against electrical or optical signals calibrated for the two or more precursors.

[0019] In some embodiments, the method further includes providing the two or more precursors into the process chamber for depositing a film on a substrate.

[0020] In some embodiments, the method further includes modifying a flow condition of the two or more precursors flowing from the one or more vapor supply source based on the monitored concentrations of the two or more precursors. The flow condition of the two or more precursors is modified to an updated flow rate for the two or more precursors.

[0021] In some embodiments, the flow condition of the precursor is modified by controlling a temperature of the precursor.

[0022] In some embodiments, each of the two or more precursors includes a metal-containing precursor.

[0023] In some embodiments, each of the two or more precursors includes an organometallic precursor.LAMRP955WO-11528-1WO

[0024] In some embodiments, the concentrations of the two or more precursors are determined only using IR spectroscopy measurements.

[0025] In some embodiments, the concentration of the two or more precursors are determined only using UV spectroscopy measurements.

[0026] In some embodiments, the concentrations of the two or more precursors are monitored based on the absorption of IR radiation relative to the absorption of UV radiation, or the absorption of UV radiation relative to the absorption of IR radiation in each of the two or more precursors.

[0027] Another aspect of disclosure relates to a method of monitoring precursor concentration. The method includes flowing a precursor continuously from a vapor supply source towards a process chamber. The method further includes monitoring the precursor concentration based at least in part on spectroscopy measurements received from one or more spectral sensors. The precursor includes a metal-containing precursor for depositing a metal-containing photoresist on a substrate.

[0028] In some embodiments, the precursor flows at a vapor pressure equal to or less than about 50 millitorr.

[0029] In some embodiments, the precursor is mixed with a carrier gas at a flow rate ratio of about 1 to about 100.

[0030] In some embodiments, the precursor concentration is monitored by the spectroscopy measurements and pressure and / or temperature measurements.

[0031] In some embodiments, monitoring the precursor concentration includes monitoring the concentration of a contaminant mixed with the precursor. The contaminant comprises water, a decomposed product, or a reaction product mixed with the precursor.

[0032] In some embodiments, the method further includes modifying a flow condition of the precursor flowing from the vapor supply source based on the monitored precursor concentration. The flow condition of the precursor is modified to an updated flow rate for the precursor.

[0033] In some embodiments, the flow condition of the precursor is modified by controlling a temperature of the precursor.

[0034] In some embodiments, the precursor includes an organometallic precursor.

[0035] In some embodiments, the spectral sensor includes an IR sensor, a visible light sensor, a UV sensor, or a combination thereof.

[0036] Another aspect of the disclosure relates to a method of monitoring precursor concentrations. The method includes flowing a precursor continuously from a vapor supply source towards a deposition chamber. The method further includes monitoring the precursor concentration based at least in part on sensor measurements. The precursor includes a metal-LAMRP955WO-11528-1WO containing precursor for depositing a metal-containing photoresist.

[0037] In some embodiments, the precursor flows at a vapor pressure equal to or less than about 50 millitorr.

[0038] In some embodiments, the precursor is mixed with a carrier gas at a flow rate ratio of about 1 to about 100.

[0039] In some embodiments, the precursor concentration is monitored by an optical sensor, or a piezoelectric sensor.

[0040] In some embodiments, the piezoelectric sensor includes a surface acoustic wave sensor or an acoustic time of flight sensor.

[0041] In some embodiments, monitoring the precursor concentration includes monitoring the concentration of a contaminant mixed with the precursor. The contaminant includes water, a decomposed product, or a reaction product mixed with the precursor.

[0042] In some embodiments, the method further includes modifying a flow condition of the precursor flowing from the vapor supply source based on the monitored precursor concentration. The flow condition of the precursor is modified to an updated flow rate for the precursor.

[0043] In some embodiments, the precursor includes a metal-containing precursor.

[0044] Another aspect of disclosure relates to an apparatus for processing or depositing a metal- containing photoresist on a substrate. The apparatus includes one or more process chambers for processing or depositing a metal-containing photoresist from one or more metal-containing precursors, one or more flow rate controllers, one or more spectral sensors, and a controller having at least one processor and a memory device. At least one processor and the memory device are communicatively connected with one another. At least one processor is at least operatively connected with the one or more spectral sensors and one or more flow rate controllers, and the memory device stores computer-executable instructions for controlling the at least one processor to at least control the associated one or more spectral sensors and the one or more flow rate controllers to: cause exposure of one or more metal-containing precursors mixed with a carrier gas to radiation, cause the one or more spectral sensors to receive and generate signals for absorption characteristics of the one or more metal-containing precursors; and cause the concentrations of the one or more metal-containing precursors to be monitored.

[0045] In some embodiments, at least one processor further controls the associated one or more sensors and the one or more flow rate controllers to: cause the monitored precursor concentrations to be compared against desired precursor amounts; and, depending on the difference between the desired precursor amount and the monitored precursor concentrations, cause the flow rates of the one or more metal-containing precursors mixed with the carrier gas to be increased, decreased, orLAMRP955WO-11528-1WO maintained.

[0046] In some embodiments, the one or more sensors include an IR sensor, a visible light sensor, a UV sensor, or a combination thereof.

[0047] In some embodiments, the one or more precursors mixed with the carrier gas are flowed continuously or in a series of pulses.

[0048] In some embodiments, the apparatus further includes a mixing vessel and a showerhead. The one or more spectral sensors are located upstream of the showerhead and downstream of the mass flow controller.

[0049] In some embodiments, the apparatus further includes one or more mixing vessel inlet valves. The one or more spectral sensors are located upstream of the one or more mixing vessel inlet valves.

[0050] These and other aspects are described further below with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 illustrates a flow chart of an example method of monitoring a precursor concentration according to some embodiments.

[0052] Figure 2A illustrates a flow chart of an example method of monitoring the concentrations of two precursors according to some embodiments.

[0053] Figure 2B illustrates a flow chart of an example method of monitoring the concentrations of two precursors according to some embodiments.

[0054] Figure 3 illustrates a flow chart of an example method of monitoring the concentrations of one or more precursors according to some embodiments.

[0055] Figure 4 presents a schematic of a non-limiting precursor to provide a resist material that incorporates an EUV sensitizer.

[0056] Figures 5A-5H present schematic diagrams of illustrative deposited films, in which organic moieties can provide additional EUV reactivity. Provided are non-limiting films including (A, C, E, F) and ethynyl-derived ligand as the organic moiety, (B, D, G) an oxalyl-derived ligand as the organic moiety, or (H) a labile alkyl ligand as the organic moiety. X can be H, another alkyl group, a metal atom (e.g., a Sn atom), a labile ligand, or a leaving group (e.g., any described herein).

[0057] Figures 6A-6B present schematics of (A) a resist film formed by using a non-limiting metal-containing precursor (I-1); and (B) further non-limiting metal-containing precursors : (I-2), (I-3), (I-4), (I-5), (I-6), (I-7), (I-8), and (I-9).

[0058] Figures 7A-7B present schematics of (A) a non-limiting metal-containing precursor (I-LAMRP955WO-11528-1WO 1) reacted with a non-limiting ligand-containing precursor (II-A); and (B) another non-limiting metal-containing precursor (III-A) reacted with another non-limiting ligand-containing precursor (IV-A).

[0059] Figure 8A presents a schematic diagram of an apparatus including a spectral sensor, and a flow rate controller used for monitoring a precursor or a mixture of precursors according to some embodiments.

[0060] Figure 8B presents a schematic diagram of an apparatus including at least two spectral sensors, and a flow rate controller used for monitoring at least two precursors according to some embodiments.

[0061] Figure 9 presents a schematic illustration of an embodiment of a process station 900 for dry development according to some embodiments.

[0062] Figure 10 presents a schematic illustration of an embodiment of a multi-station processing tool 1000 according to some embodiments.

[0063] Figure 11 presents a schematic illustration of an embodiment of an inductively coupled plasma apparatus 1100 according to some embodiments.

[0064] Figure 12 presents a schematic illustration of an embodiment of a semiconductor process cluster tool architecture 1200 according to some embodiments.

[0065] Figure 13 depicts a cross-sectional schematic view of an example of a dry deposition apparatus 1300 according to some embodiments. DETAILED DESCRIPTION

[0066] In the following description, numerous specific details are set forth to provide a thorough understanding of the presented embodiments. The disclosed embodiments may be practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail to not unnecessarily obscure the disclosed embodiments. While the disclosed embodiments will be described in conjunction with the specific embodiments, it will be understood that it is not intended to limit the disclosed embodiments. Terminology and Definitions

[0067] The term “acyl,” or “alkanoyl,” as used interchangeably herein, represents groups of 1, 2, 3, 4, 5, 6, 7, 8 or more carbon atoms of a straight, branched, cyclic configuration; saturated, unsaturated and aromatic; and combinations thereof, or hydrogen, attached to the parent molecular group through a carbonyl group, as defined herein. This group is exemplified by formyl (-C(O)H), acetyl (Ac or -C(O)Me), propionyl, isobutyryl, butanoyl, and the like. In some embodiments, theLAMRP955WO-11528-1WO acyl or alkanoyl group is -C(O)-R, in which R is hydrogen, an aliphatic group, or an aromatic group, as defined herein.

[0068] By “alkanoyloxy” is meant an alkanoyl group, as defined herein, attached to the parent molecular group through an oxy group, as defined herein. This group is exemplified by acetoxy (-OAc or -OC(O)Me). In some embodiments, the alkanoyloxy group is -OC(O)-R, in which R is hydrogen, an aliphatic group, or an aromatic group, as defined herein.

[0069] By “aliphatic” is meant a hydrocarbon group having at least one carbon atom to 50 carbon atoms (C1-50), such as one to 25 carbon atoms (C1-25), or one to ten carbon atoms (C1- 10), and which includes alkanes (or alkyl), alkenes (or alkenyl), alkynes (or alkynyl), including cyclic versions thereof, and further including straight- and branched-chain arrangements, and all stereo and position isomers as well. An aliphatic group is unsubstituted or substituted, e.g., by a functional group described herein. For example, the aliphatic group can be substituted with one or more substitution groups, as described herein for alkyl.

[0070] By “aliphatic-carbonyl” is meant an aliphatic group that is or can be coupled to a compound disclosed herein, wherein the aliphatic group is or becomes coupled through a carbonyl group (-C(O)-). In some embodiments, the aliphatic-carbonyl group is -C(O)-R, in which R is an optionally substituted aliphatic group, as defined herein.

[0071] By “aliphatic-carbonyloxy” is meant an aliphatic group that is or can be coupled to a compound disclosed herein, wherein the aliphatic group is or becomes coupled through a carbonyloxy group (-OC(O)-). In some embodiments, the aliphatic-carbonyloxy group is -OC(O)- R, in which R is an optionally substituted aliphatic group, as defined herein.

[0072] By “aliphatic-oxy” is meant an aliphatic group that is or can be coupled to a compound disclosed herein, wherein the aliphatic group is or becomes coupled through an oxy group (-C(O)- ). In some embodiments, the aliphatic-oxy group is -O-R, in which R is an optionally substituted aliphatic group, as defined herein.

[0073] By “aliphatic-oxycarbonyl” is meant an aliphatic group that is or can be coupled to a compound disclosed herein, wherein the aliphatic group is or becomes coupled through an oxycarbonyl group (-C(O)O-). In some embodiments, the aliphatic-oxycarbonyl group is -C(O)O- R, in which R is an optionally substituted aliphatic group, as defined herein.

[0074] By “alkyl-aryl,” “alkenyl-aryl,” and “alkynyl-aryl” is meant an alkyl, alkenyl, or alkynyl group, respectively and as defined herein, that is or can be coupled (or attached) to the parent molecular group through an aryl group, as defined herein. The alkyl-aryl, alkenyl-aryl, and / or alkynyl-aryl group can be substituted or unsubstituted. For example, the alkyl-aryl, alkenyl-aryl, and / or alkynyl-aryl group can be substituted with one or more substitution groups, as describedLAMRP955WO-11528-1WO herein for alkyl and / or aryl. Exemplary unsubstituted alkyl-aryl groups are of from 7 to 16 carbons (C7-16alkyl-aryl), as well as those having an alkyl group with 1 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C1-6 alkyl-C4-18 aryl). Exemplary unsubstituted alkenyl-aryl groups are of from 7 to 16 carbons (C7-16alkenyl-aryl), as well as those having an alkenyl group with 2 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C2-6 alkenyl-C4-18 aryl). Exemplary unsubstituted alkynyl-aryl groups are of from 7 to 16 carbons (C7-16alkynyl-aryl), as well as those having an alkynyl group with 2 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C2-6 alkynyl-C4-18aryl). In some embodiments, the alkyl-aryl group is -L-R, in which L is an aryl group or an arylene group, as defined herein, and R is an alkyl group, as defined herein. In some embodiments, the alkenyl-aryl group is -L-R, in which L is an aryl group or an arylene group, as defined herein, and R is an alkenyl group, as defined herein. In some embodiments, the alkynyl- aryl group is -L-R, in which L is an aryl group or an arylene group, as defined herein, and R is an alkynyl group, as defined herein.

[0075] By “alkenyl” is meant an unsaturated monovalent hydrocarbon having at least two carbon atom to 50 carbon atoms (C2-50), such as two to 25 carbon atoms (C2-25), or two to ten carbon atoms (C2-10), and at least one carbon-carbon double bond, wherein the unsaturated monovalent hydrocarbon can be derived from removing one hydrogen atom from one carbon atom of a parent alkene. An alkenyl group can be branched, straight-chain, cyclic (e.g., cycloalkenyl), cis, or trans (e.g., E or Z). An exemplary alkenyl includes an optionally substituted C2-24alkyl group having one or more double bonds. The alkenyl group can be monovalent or multivalent (e.g., bivalent) by removing one or more hydrogens to form appropriate attachment to the parent molecular group or appropriate attachment between the parent molecular group and another substitution. The alkenyl group can also be substituted or unsubstituted. For example, the alkenyl group can be substituted with one or more substitution groups, as described herein for alkyl. Non-limiting alkenyl groups include allyl (All), vinyl (Vi), 1-butenyl, 2-butenyl, and the like.

[0076] By “alkoxy” is meant -OR, where R is an optionally substituted aliphatic group, as described herein. Exemplary alkoxy groups include, but are not limited to, methoxy, ethoxy, n- propoxy, isopropoxy, n-butoxy, t-butoxy, sec-butoxy, n-pentoxy, trihaloalkoxy, such as trifluoromethoxy, etc. The alkoxy group can be substituted or unsubstituted. For example, the alkoxy group can be substituted with one or more substitution groups, as described herein for alkyl. Exemplary unsubstituted alkoxy groups include C1-3, C1-6, C1-12, C1-16, C1-18, C1-20, or C1-24 alkoxy groups.

[0077] By “alkoxyalkyl” is meant an alkyl group, as defined herein, which is substituted with an alkoxy group, as defined herein. Exemplary unsubstituted alkoxyalkyl groups include between 2LAMRP955WO-11528-1WO to 12 carbons (C2-12 alkoxyalkyl), as well as those having an alkyl group with 1 to 6 carbons and an alkoxy group with 1 to 6 carbons (i.e., C1-6alkoxy-C1-6alkyl). In some embodiments, the alkoxyalkyl group is -L-O-R, in which each of L and R is, independently, an alkyl group, as defined herein.

[0078] By “alkoxycarbonyl” is meant -C(O)-OR, where R is an optionally substituted aliphatic group, as described herein. In particular embodiments, the alkoxycarbonyl group is -C(O)-OAk, in which Ak is an alkyl group, as defined herein. The alkoxycarbonyl group can be substituted or unsubstituted. For example, the alkoxycarbonyl group can be substituted with one or more substitution groups, as described herein for alkyl. Exemplary unsubstituted alkoxycarbonyl groups include C2-3, C2-6, C2-7, C2-12, C2-16, C2-18, C2-20, or C2-24alkoxycarbonyl groups.

[0079] By “alkyl” is meant a saturated monovalent hydrocarbon having at least one carbon atom to 50 carbon atoms (C1-50), such as one to 25 carbon atoms (C1-25), or one to ten carbon atoms (C1- 10), wherein the saturated monovalent hydrocarbon can be derived from removing one hydrogen atom from one carbon atom of a parent compound (e.g., alkane). An alkyl group can be branched, straight-chain, or cyclic (e.g., cycloalkyl). An exemplary alkyl includes a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (nPr), iso-propyl (iPr), n-butyl (nBu), iso-butyl (iBu), sec-butyl (sBu), tert-butyl (tBu), pentyl (Pe), n-pentyl (nPe), isopentyl (iPe), s-pentyl (sPe), neopentyl (neoPe), tert-pentyl (tPe), hexyl (Hx), heptyl (Hp), octyl (Oc), nonyl (Nn), decyl (De), dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. The alkyl group can also be substituted or unsubstituted. The alkyl group can be monovalent or multivalent (e.g., bivalent) by removing one or more hydrogens to form appropriate attachment to the parent molecular group or appropriate attachment between the parent molecular group and another substitution. For example, the alkyl group can be substituted with one, two, three or, in the case of alkyl groups of two carbons or more, four substituents independently selected from the group consisting of: (1) C1-6 alkoxy (e.g., -O-R, in which R is C1-6 alkyl); (2) C1-6alkylsulfinyl (e.g., -S(O)-R, in which R is C1-6alkyl); (3) C1-6alkylsulfonyl (e.g., -SO2-R, in which R is C1-6 alkyl); (4) amino (e.g., -NR1R2, where each of R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R1and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein); (5) aryl; (6) arylalkoxy (e.g., -O-L-R, in which L is alkyl and R is aryl); (7) aryloyl (e.g., -C(O)-R, in which R is aryl); (8) azido (e.g., -N3); (9) cyano (e.g., -CN); (10) aldehyde (e.g., -C(O)H); (11) C3-8cycloalkyl; (12) halo; (13) heterocyclyl (e.g., as defined herein, such as a 5-, 6- or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (14) heterocyclyloxy (e.g., -O-R, in which R isLAMRP955WO-11528-1WO heterocyclyl, as defined herein); (15) heterocyclyloyl (e.g., -C(O)-R, in which R is heterocyclyl, as defined herein); (16) hydroxyl (e.g., -OH); (17) N-protected amino; (18) nitro (e.g., -NO2); (19) oxo (e.g., =O); (20) C1-6 thioalkyl (e.g., -S-R, in which R is alkyl); (21) thiol (e.g., -SH); (22) -CO2R1, where R1is selected from the group consisting of (a) hydrogen, (b) C1-6alkyl, (c) C4-18 aryl, and (d) C4-18 aryl-C1-6 alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (23) -C(O)NR1R2, where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C4-18 aryl-C1-6 alkyl (e.g., -L-R, in which L is C1-6alkyl and R is C4-18aryl); (24) -SO2R1, where R1is selected from the group consisting of (a) C1-6 alkyl, (b) C4-18 aryl, and (c) C4-18 aryl-C1-6 alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18aryl); (25) -SO2NR1R2, where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C4-18 aryl-C1-6 alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); and (26) -NR1R2, where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) an N-protecting group, (c) C1-6 alkyl, (d) C2-6 alkenyl, (e) C2-6 alkynyl, (f) C4-18 aryl, (g) C4-18 aryl-C1-6 alkyl (e.g., -L-R, in which L is C1-6alkyl and R is C4-18aryl), (h) C3-8cycloalkyl, and (i) C3-8cycloalkyl-C1-6alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C3-8 cycloalkyl), wherein in one embodiment no two groups are bound to the nitrogen atom through a carbonyl group or a sulfonyl group. The alkyl group can be a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halo or alkoxy). In some embodiments, the unsubstituted alkyl group is a C1-3, C1-6, C1-12, C1-16, C1-18, C1-20, or C1-24 alkyl group.

[0080] By “alkylene,” “alkenylene,” or “alkynylene” is meant a multivalent (e.g., bivalent) form of an alkyl, alkenyl, or alkynyl group, respectively, as described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, etc. In some embodiments, the alkylene group is a C1-3, C1-6, C1-12, C1-16, C1-18, C1-20, C1-24, C2-3, C2-6, C2-12, C2-16, C2-18, C2-20, or C2-24 alkylene group. In other embodiments, the alkylene group is a C2-3, C2-6, C2-12, C2-16, C2-18, C2-20, or C2-24alkenylene or alkynylene group. The alkylene, alkenylene, or alkynylene group can be branched or unbranched. The alkylene, alkenylene, or alkynylene group can also be substituted or unsubstituted. For example, the alkylene, alkenylene, or alkynylene group can be substituted with one or more substitution groups, as described herein for alkyl.

[0081] By “alkylsulfinyl” is meant an alkyl group, as defined herein, attached to the parent molecular group through an -S(O)- group. In some embodiments, the unsubstituted alkylsulfinyl group is a C1-6or C1-12alkylsulfinyl group. In other embodiments, the alkylsulfinyl group is -S(O)- R, in which R is an alkyl group, as defined herein.LAMRP955WO-11528-1WO

[0082] By “alkylsulfinylalkyl” is meant an alkyl group, as defined herein, substituted by an alkylsulfinyl group. In some embodiments, the unsubstituted alkylsulfinylalkyl group is a C2-12or C2-24 alkylsulfinylalkyl group (e.g., C1-6 alkylsulfinyl-C1-6 alkyl or C1-12 alkylsulfinyl-C1-12 alkyl). In other embodiments, the alkylsulfinylalkyl group is -L-S(O)-R, in which each of L and R is, independently, an alkyl group, as defined herein.

[0083] By “alkylsulfonyl” is meant an alkyl group, as defined herein, attached to the parent molecular group through an -SO2- group. In some embodiments, the unsubstituted alkylsulfonyl group is a C1-6or C1-12alkylsulfonyl group. In other embodiments, the alkylsulfonyl group is -SO2- R, where R is an optionally substituted alkyl (e.g., as described herein, including optionally substituted C1-12alkyl, haloalkyl, or perfluoroalkyl).

[0084] By “alkylsulfonylalkyl” is meant an alkyl group, as defined herein, substituted by an alkylsulfonyl group. In some embodiments, the unsubstituted alkylsulfonylalkyl group is a C2-12 or C2-24 alkylsulfonylalkyl group (e.g., C1-6 alkylsulfonyl-C1-6 alkyl or C1-12 alkylsulfonyl-C1-12 alkyl). In other embodiments, the alkylsulfonylalkyl group is -L-SO2-R, in which each of L and R is, independently, an alkyl group, as defined herein.

[0085] By “alkynyl” is meant an unsaturated monovalent hydrocarbon having at least two carbon atom to 50 carbon atoms (C2-50), such as two to 25 carbon atoms (C2-25), or two to ten carbon atoms (C2-10), and at least one carbon-carbon triple bond, wherein the unsaturated monovalent hydrocarbon can be derived from removing one hydrogen atom from one carbon atom of a parent alkyne. An alkynyl group can be branched, straight-chain, or cyclic (e.g., cycloalkynyl). An exemplary alkynyl includes an optionally substituted C2-24alkyl group having one or more triple bonds. The alkynyl group can be cyclic or acyclic and is exemplified by ethynyl, 1-propynyl, and the like. The alkynyl group can be monovalent or multivalent (e.g., bivalent) by removing one or more hydrogens to form appropriate attachment to the parent molecular group or appropriate attachment between the parent molecular group and another substitution. The alkynyl group can also be substituted or unsubstituted. For example, the alkynyl group can be substituted with one or more substitution groups, as described herein for alkyl.

[0086] By “ambient temperature” is meant a temperature ranging from 16°C to 26°C, such as from 19°C to 25°C or from 20°C to 25°C.

[0087] By “amide” is mean -C(O)NR1R2or -NHCOR1, where each of R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, aromatic, as defined herein, or any combination thereof, or where R1and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein.LAMRP955WO-11528-1WO

[0088] By “amino” is meant -NR1R2, where each of R1and R2is, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, as defined herein, or any combination thereof; or where R1and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein. In particular embodiments, each of R1and R2is, independently, H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, optionally substituted silyl, or optionally substituted silyloxy. In particular embodiments, R1and R2can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl.

[0089] By “aminoalkyl” is meant an alkyl group, as defined herein, substituted by an amino group, as defined herein. In some embodiments, the aminoalkyl group is -L-NR1R2, in which L is an alkyl group, as defined herein, and each of R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, or aromatic, as defined herein, or any combination thereof; or R1and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein. In other embodiments, the aminoalkyl group is -L-C(NR1R2)(R3)-R4, in which L is a covalent bond or an alkyl group, as defined herein; each of R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, or aromatic, as defined herein, or any combination thereof; or R1and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein; and each of R3and R4is, independently, H or alkyl, as defined herein.

[0090] By “aminooxy” is meant an oxy group, as defined herein, substituted by an amino group, as defined herein. In some embodiments, the aminooxy group is -O-NR1R2, in which each of R1and R2is, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, as defined herein, or any combination thereof; or R1and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein. In particular embodiments, each of R1and R2is, independently, H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, optionally substituted silyl, or optionally substituted silyloxy.

[0091] By “aromatic” is meant a cyclic, conjugated group or moiety of, unless specified otherwise, from 5 to 15 ring atoms having a single ring (e.g., phenyl) or multiple condensed ringsLAMRP955WO-11528-1WO in which at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl); that is, at least one ring, and optionally multiple condensed rings, have a continuous, delocalized π-electron system. Typically, the number of out of plane π-electrons corresponds to the Huckel rule (4n+2). The point of attachment to the parent structure typically is through an aromatic portion of the condensed ring system. An aromatic group is unsubstituted or substituted, e.g., by a functional group described herein. For example, the aromatic group can be substituted with one or more substitution groups, as described herein for alkyl and / or aryl.

[0092] By “aromatic-carbonyl” is meant an aromatic group that is or can be coupled to a compound disclosed herein, wherein the aromatic group is or becomes coupled through a carbonyl group (-C(O)-). In some embodiments, the aromatic-carbonyl group is -C(O)-R, in which R is an optionally substituted aromatic group, as defined herein.

[0093] By “aromatic-carbonyloxy” is meant an aromatic group that is or can be coupled to a compound disclosed herein, wherein the aromatic group is or becomes coupled through a carbonyloxy group (-OC(O)-). In some embodiments, the aromatic-carbonyloxy group is -OC(O)- R, in which R is an optionally substituted aromatic group, as defined herein.

[0094] By “aromatic-oxy” is meant an aromatic group that is or can be coupled to a compound disclosed herein, wherein the aromatic group is or becomes coupled through an oxy group (-O-). In some embodiments, the aromatic-oxy group is -O-R, in which R is an optionally substituted aromatic group, as defined herein.

[0095] By “aromatic-oxycarbonyl” is meant an aromatic group that is or can be coupled to a compound disclosed herein, wherein the aromatic group is or becomes coupled through an oxycarbonyl group (-C(O)O-). In some embodiments, the aromatic-carbonyl group is -C(O)O-R, in which R is an optionally substituted aromatic group, as defined herein.

[0096] By “aryl” is meant an aromatic carbocyclic group comprising at least five carbon atoms to 15 carbon atoms (C5-15), such as five to ten carbon atoms (C5-10), having a single ring or multiple condensed rings, which condensed rings can or may not be aromatic provided that the point of attachment to a remaining position of the compounds disclosed herein is through an atom of the aromatic carbocyclic group. Aryl groups may be substituted with one or more groups other than hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Exemplary aryl groups include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term aryl also includes heteroaryl, which is defined as a group that contains an aromatic group that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term non-heteroaryl, which is also included in theLAMRP955WO-11528-1WO term aryl, defines a group that contains an aromatic group that does not contain a heteroatom. The aryl group can be substituted or unsubstituted. The aryl group can be substituted with one, two, three, four, or five substituents independently selected from the group consisting of: (1) C1-6 alkanoyl (e.g., -C(O)-R, in which R is C1-6alkyl); (2) C1-6alkyl; (3) C1-6alkoxy (e.g., -O-R, in which R is C1-6 alkyl); (4) C1-6 alkoxy-C1-6 alkyl (e.g., -L-O-R, in which each of L and R is, independently, C1-6alkyl); (5) C1-6alkylsulfinyl (e.g., -S(O)-R, in which R is C1-6alkyl); (6) C1-6alkylsulfinyl-C1-6 alkyl (e.g., -L-S(O)-R, in which each of L and R is, independently, C1-6 alkyl); (7) C1-6alkylsulfonyl (e.g., -SO2-R, in which R is C1-6alkyl); (8) C1-6alkylsulfonyl-C1-6alkyl (e.g., -L-SO2-R, in which each of L and R is, independently, C1-6 alkyl); (9) aryl; (10) amino (e.g., - NR1R2, where each of R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof; or R1and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein); (11) C1-6 aminoalkyl (e.g., -L1-NR1R2or -L2- C(NR1R2)(R3)-R4, in which L1is C1-6 alkyl; L2is a covalent bond or C1-6 alkyl; each of R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof; or R1and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein; and each of R3and R4is, independently, H or C1-6 alkyl); (12) heteroaryl; (13) C4-18 aryl-C1-6alkyl (e.g., -L-R, in which L is C1-6alkyl and R is C4-18aryl); (14) aryloyl (e.g., -C(O)-R, in which R is aryl); (15) azido (e.g., -N3); (16) cyano (e.g., -CN); (17) C1-6 azidoalkyl (e.g., -L-N3, in which L is C1-6alkyl); (18) aldehyde (e.g., -C(O)H); (19) aldehyde-C1-6alkyl (e.g., -L-C(O)H, in which L is C1-6 alkyl); (20) C3-8 cycloalkyl; (21) C3-8 cycloalkyl-C1-6 alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C3-8 cycloalkyl); (22) halo; (23) C1-6 haloalkyl (e.g., -L1-X or -L2-C(X)(R1)- R2, in which L1is C1-6 alkyl; L2is a covalent bond or C1-6 alkyl; X is fluoro, bromo, chloro, or iodo; and each of R1and R2is, independently, H or C1-6 alkyl); (24) heterocyclyl (e.g., as defined herein, such as a 5-, 6- or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (25) heterocyclyloxy (e.g., -O-R, in which R is heterocyclyl, as defined herein); (26) heterocyclyloyl (e.g., -C(O)-R, in which R is heterocyclyl, as defined herein); (27) hydroxyl (-OH); (28) C1-6 hydroxyalkyl (e.g., -L1-OH or -L2-C(OH)(R1)-R2, in which L1is C1-6 alkyl; L2is a covalent bond or alkyl; and each of R1and R2is, independently, H or C1-6alkyl, as defined herein); (29) nitro; (30) C1-6 nitroalkyl (e.g., -L1-NO or -L2-C(NO)(R1)-R2, in which L1is C1-6 alkyl; L2is a covalent bond or alkyl; and each of R1and R2is, independently, H or C1-6alkyl, as defined herein); (31) N-protected amino; (32) N-protected amino-C1-6 alkyl; (33) oxo (e.g., =O); (34) C1-6thioalkyl (e.g., -S-R, in which R is C1-6alkyl); (35) thio-C1-6alkoxy-C1-6alkyl (e.g., -L-LAMRP955WO-11528-1WO S-R, in which each of L and R is, independently, C1-6 alkyl); (36) -(CH2)rCO2R1, where r is an integer of from zero to four, and R1is selected from the group consisting of (a) hydrogen, (b) C1-6alkyl, (c) C4-18 aryl, and (d) C4-18 aryl-C1-6 alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (37) -(CH2)rCONR1R2, where r is an integer of from zero to four and where each R1and R2is independently selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C4-18aryl-C1-6alkyl (e.g., -L-R, in which L is C1-6alkyl and R is C4-18aryl); (38) -(CH2)rSO2R1, where r is an integer of from zero to four and where R1is selected from the group consisting of (a) C1-6alkyl, (b) C4-18aryl, and (c) C4-18aryl-C1-6alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (39) -(CH2)rSO2NR1R2, where r is an integer of from zero to four and where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C4-18 aryl-C1-6 alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (40) -(CH2)rNR1R2, where r is an integer of from zero to four and where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) an N-protecting group, (c) C1-6 alkyl, (d) C2-6 alkenyl, (e) C2-6 alkynyl, (f) C4-18 aryl, (g) C4-18 aryl- C1-6alkyl (e.g., -L-R, in which L is C1-6alkyl and R is C4-18aryl), (h) C3-8cycloalkyl, and (i) C3-8cycloalkyl-C1-6 alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C3-8 cycloalkyl), wherein in one embodiment no two groups are bound to the nitrogen atom through a carbonyl group or a sulfonyl group; (41) thiol (e.g., -SH); (42) perfluoroalkyl (e.g., -(CF2)nCF3, in which n is an integer from 0 to 10); (43) perfluoroalkoxy (e.g., -O-(CF2)nCF3, in which n is an integer from 0 to 10); (44) aryloxy (e.g., -O-R, in which R is aryl); (45) cycloalkoxy (e.g., -O-R, in which R is cycloalkyl); (46) cycloalkylalkoxy (e.g., -O-L-R, in which L is alkyl and R is cycloalkyl); and (47) arylalkoxy (e.g., -O-L-R, in which L is alkyl and R is aryl). In particular embodiments, an unsubstituted aryl group is a C4-18, C4-14, C4-12, C4-10, C6-18, C6-14, C6-12, or C6-10 aryl group.

[0097] By “aryl-alkyl,” “aryl-alkenyl,” and “aryl-alkynyl” is meant an aryl group, as defined herein, that is or can be coupled (or attached) to the parent molecular group through an alkyl, alkenyl, or alkynyl group, respectively, as defined herein. The aryl-alkyl, aryl-alkenyl, and / or aryl- alkynyl group can be substituted or unsubstituted. For example, the aryl-alkyl, aryl-alkenyl, and / or aryl-alkynyl group can be substituted with one or more substitution groups, as described herein for aryl and / or alkyl. Exemplary unsubstituted aryl-alkyl groups are of from 7 to 16 carbons (C7-16 aryl-alkyl), as well as those having an aryl group with 4 to 18 carbons and an alkyl group with 1 to 6 carbons (i.e., C4-18 aryl-C1-6 alkyl). Exemplary unsubstituted aryl-alkenyl groups are of from 7 to 16 carbons (C7-16aryl-alkenyl), as well as those having an aryl group with 4 to 18 carbons and an alkenyl group with 2 to 6 carbons (i.e., C4-18 aryl-C2-6 alkenyl). Exemplary unsubstituted aryl- alkynyl groups are of from 7 to 16 carbons (C7-16aryl-alkynyl), as well as those having an arylLAMRP955WO-11528-1WO group with 4 to 18 carbons and an alkynyl group with 2 to 6 carbons (i.e., C4-18 aryl-C2-6 alkynyl). In some embodiments, the aryl-alkyl group is -L-R, in which L is an alkyl group or an alkylene group, as defined herein, and R is an aryl group, as defined herein. In some embodiments, the aryl-alkenyl group is -L-R, in which L is an alkenyl group or an alkenylene group, as defined herein, and R is an aryl group, as defined herein. In some embodiments, the aryl-alkynyl group is -L-R, in which L is an alkynyl group or an alkynylene group, as defined herein, and R is an aryl group, as defined herein.

[0098] By “arylene” is meant a multivalent (e.g., bivalent) form of an aryl group, as described herein. Exemplary arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthenylene, anthrylene, or phenanthrylene. In some embodiments, the arylene group is a C4-18, C4-14, C4-12, C4-10, C6-18, C6-14, C6-12, or C6-10 arylene group. The arylene group can be branched or unbranched. The arylene group can also be substituted or unsubstituted. For example, the arylene group can be substituted with one or more substitution groups, as described herein for aryl.

[0099] By “arylalkoxy” is meant an aryl-alkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the arylalkoxy group is -O-L- R, in which L is an alkyl group, as defined herein, and R is an aryl group, as defined herein.

[0100] By “aryloxy” is meant -OR, where R is an optionally substituted aryl group, as described herein. In some embodiments, an unsubstituted aryloxy group is a C4-18or C6-18aryloxy group. In other embodiments, R is an aryl group that is optionally substituted with alkyl, alkanoyl, amino, hydroxyl, and the like.

[0101] By “aryloxycarbonyl” is meant an aryloxy group, as defined herein, that is attached to the parent molecular group through a carbonyl group. In some embodiments, an unsubstituted aryloxycarbonyl group is a C5-19 aryloxycarbonyl group. In other embodiments, the aryloxycarbonyl group is -C(O)O-R, in which R is an aryl group, as defined herein.

[0102] By “aryloyl” is meant an aryl group that is attached to the parent molecular group through a carbonyl group. In some embodiments, an unsubstituted aryloyl group is a C7-11 aryloyl or C5-19 aryloyl group. In other embodiments, the aryloyl group is -C(O)-R, in which R is an aryl group, as defined herein.

[0103] By “aryloyloxy” is meant an aryloyl group, as defined herein, that is attached to the parent molecular group through an oxy group. In some embodiments, an unsubstituted aryloyloxy group is a C5-19aryloyloxy group. In other embodiments, the aryloyloxy group is -OC(O)-R, in which R is an aryl group, as defined herein.

[0104] By “azido” is meant an -N3group.LAMRP955WO-11528-1WO

[0105] By “azidoalkyl” is meant an azido group attached to the parent molecular group through an alkyl group, as defined herein. In some embodiments, the azidoalkyl group is -L-N3, in which L is an alkyl group, as defined herein.

[0106] By “azo” is meant an -N=N- group.

[0107] By “carbamoyl” is meant an amino group attached to the parent molecular group through a carbonyl group, as defined herein. In some embodiments, the carbamoyl is -C(O)NR1R2group, where each of R1and R2is, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, as defined herein, or any combination thereof; or where R1and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein.

[0108] By “carbamoyloxy” is meant a carbamoyl group, as defined herein, attached to the parent molecular group through n oxy group, as defined herein. In some embodiments, the carbamoyl is -OC(O)NR1R2group, where each of R1and R2is, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, as defined herein, or any combination thereof; or where R1and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein.

[0109] By “carbonimidoyl” is meant a -C(NR)- group. In some embodiments, R is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl, optionally substituted silyloxy, as defined herein, or any combination thereof.

[0110] By “carbonyl” is meant a -C(O)- group, which can also be represented as >C=O.

[0111] By “carboxyl” is meant a -CO2H group or an anion thereof.

[0112] By “catalyst” is meant a compound, usually present in small amounts relative to reactants, capable of catalyzing a synthetic reaction, as would be readily understood by a person of ordinary skill in the art. In some embodiments, catalysts may include transition metal coordination complex.

[0113] By “cyanato” is meant a -OCN group.

[0114] By “cyano” is meant a -CN group.

[0115] By “cycloaliphatic” is meant an aliphatic group, as defined herein, that is cyclic.LAMRP955WO-11528-1WO

[0116] By “cycloalkoxy” is meant a cycloalkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the cycloalkoxy group is -O-R, in which R is a cycloalkyl group, as defined herein.

[0117] By “cycloalkylalkoxy” is meant a -O-L-R group, in which L is an alkyl group or an alkylene group, as defined herein, and R is a cycloalkyl group, as defined herein.

[0118] By “cycloalkyl” is meant a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon group of from three to eight carbons, unless otherwise specified, and is exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.heptyl], and the like. The cycloalkyl group can also be substituted or unsubstituted. For example, the cycloalkyl group can be substituted with one or more groups including those described herein for alkyl. Further, cycloalkyl may include one or more double bonds and / or triple bonds.

[0119] By “cycloheteroaliphatic” is meant a heteroaliphatic group, as defined herein, that is cyclic.

[0120] By “disilanyl” is meant a group containing an Si-Si bond. In some embodiments, the disilanyl group is a -SiRS1RS2-SiRS3RS4RS5or -SiRS1RS2-SiRS3RS4- group, in which each of RS1, RS2, RS3, RS4, and RS5is, independently, H, optionally substituted aliphatic, optionally substituted optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino.

[0121] By “disulfide” is meant -SSR, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof.

[0122] By “electron-donating group” is meant a functional group capable of donating at least a portion of its electron density into the ring to which it is directly attached, such as by resonance.

[0123] By “electron-withdrawing group” is meant a functional group capable of accepting electron density from the ring to which it is directly attached, such as by inductive electron withdrawal.

[0124] By “halo” is meant F, Cl, Br, or I.

[0125] By “haloaliphatic” is meant an aliphatic group, as defined herein, in which one or more hydrogen atoms, such as one to 10 hydrogen atoms, independently is replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo.

[0126] By “haloalkyl” is meant an alkyl group, as defined herein, where one or more hydrogen atoms, such as one to 10 hydrogen atoms, independently is replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo. In an independent embodiment, haloalkyl can be a -CX3 group, wherein each X independently can be selected from fluoro, bromo, chloro, or iodo. In someLAMRP955WO-11528-1WO embodiments, the haloalkyl group is -L-X, in which L is an alkyl group, as defined herein, and X is fluoro, bromo, chloro, or iodo. In other embodiments, the haloalkyl group is -L-C(X)(R1)-R2, in which L is a covalent bond or an alkyl group, as defined herein; X is fluoro, bromo, chloro, or iodo; and each of R1and R2is, independently, H or alkyl, as defined herein.

[0127] By “haloheteroaliphatic” is meant a heteroaliphatic, as defined herein, in which one or more hydrogen atoms, such as one to 10 hydrogen atoms, independently is replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo.

[0128] By “heteroaliphatic” is meant an aliphatic group, as defined herein, including at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms, or one to 5 heteroatoms, which can be selected from, but not limited to oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorous, and oxidized forms thereof within the group. A heteroaliphatic group is unsubstituted or substituted, e.g., by a functional group described herein. For example, the heteroaliphatic group can be substituted with one or more substitution groups, as described herein for alkyl.

[0129] By “heteroaliphatic-carbonyl” is meant a heteroaliphatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is or becomes coupled through a carbonyl group (-C(O)-). In some embodiments, the heteroaliphatic-carbonyl group is -C(O)-R, in which R is an optionally substituted heteroaliphatic group, as defined herein.

[0130] By “heteroaliphatic-carbonyloxy” is meant a heteroaliphatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is or becomes coupled through a carbonyloxy group (-OC(O)-). In some embodiments, the heteroaliphatic-carbonyloxy group is -OC(O)-R, in which R is an optionally substituted heteroaliphatic group, as defined herein.

[0131] By “heteroaliphatic-oxy” is meant a heteroaliphatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is or becomes coupled through an oxy group (-C(O)-). In some embodiments, the heteroaliphatic-oxy group is -O-R, in which R is an optionally substituted heteroaliphatic group, as defined herein.

[0132] By “heteroaliphatic-oxycarbonyl” is meant a heteroaliphatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is or becomes coupled through an oxycarbonyl group (-C(O)O-). In some embodiments, the heteroaliphatic-oxycarbonyl group is -C(O)O-R, in which R is an optionally substituted heteroaliphatic group, as defined herein.

[0133] By “heteroalkyl,” “heteroalkenyl,” and “heteroalkynyl” is meant an alkyl, alkenyl, or alkynyl group (which can be branched, straight-chain, or cyclic), respectively, as defined herein, including at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms, or one to 5LAMRP955WO-11528-1WO heteroatoms, which can be selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorous, and oxidized forms thereof within the group.

[0134] By “heteroalkylene,” “heteroalkenylene,” and “heteroalkynylene” is meant a multivalent (e.g., bivalent) form of a heteroalkyl, heteroalkenyl, or heteroalkynyl group, respectively, as described herein.

[0135] By “heteroaromatic” is meant an aromatic group, as defined herein, including at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms, or one to 5 heteroatoms, which can be selected from, but not limited to oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorous, and oxidized forms thereof within the group. A heteroaromatic group is unsubstituted or substituted, e.g., by a functional group described herein. For example, the heteroaromatic group can be substituted with one or more substitution groups, as described herein for alkyl and / or aryl.

[0136] By “heteroaromatic-carbonyl” is meant a heteroaromatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is or becomes coupled through a carbonyl group (-C(O)-). In some embodiments, the heteroaromatic-carbonyl group is -C(O)-R, in which R is an optionally substituted heteroaromatic group, as defined herein.

[0137] By “heteroaromatic-carbonyloxy” is meant a heteroaromatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is or becomes coupled through a carbonyloxy group (-OC(O)-). In some embodiments, the heteroaromatic-carbonyloxy group is -OC(O)-R, in which R is an optionally substituted heteroaromatic group, as defined herein.

[0138] By “heteroaromatic-oxy” is meant a heteroaromatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is or becomes coupled through an oxy group (-O-). In some embodiments, the heteroaromatic-oxy group is -O-R, in which R is an optionally substituted heteroaromatic group, as defined herein.

[0139] By “heteroaromatic-oxycarbonyl” is meant a heteroaromatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is or becomes coupled through an oxycarbonyl group (-C(O)O-). In some embodiments, the heteroaromatic-carbonyl group is -C(O)O-R, in which R is an optionally substituted heteroaromatic group, as defined herein.

[0140] By “heteroaryl” is meant an aryl group including at least one heteroatom to six heteroatoms, such as one to four heteroatoms, which can be selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorous, and oxidized forms thereof within the ring. Such heteroaryl groups can have a single ring or multiple condensed rings, where theLAMRP955WO-11528-1WO condensed rings may or may not be aromatic and / or contain a heteroatom, provided that the point of attachment is through an atom of the aromatic heteroaryl group. Heteroaryl groups may be substituted with one or more groups other than hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. An exemplary heteroaryl includes a subset of heterocyclyl groups, as defined herein, which are aromatic, i.e., they contain 4n+2 pi electrons within the mono- or multicyclic ring system.

[0141] By “heteroarylene” is meant a multivalent (e.g., bivalent) form of a heteroaryl group, as described herein.

[0142] By “heteroatom” is meant an atom other than carbon, such as oxygen, nitrogen, sulfur, silicon, boron, selenium, or phosphorous. In particular disclosed embodiments, such as when valency constraints do not permit, a heteroatom does not include a halogen atom.

[0143] By “heterocyclyl” is meant a 5-, 6- or 7-membered ring, unless otherwise specified, containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorous, sulfur, or halo). The 5-membered ring has zero to two double bonds and the 6- and 7-membered rings have zero to three double bonds. The term “heterocyclyl” also includes bicyclic, tricyclic and tetracyclic groups in which any of the above heterocyclic rings is fused to one, two, or three rings independently selected from the group consisting of an aryl ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring, and another monocyclic heterocyclic ring, such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl and the like. Heterocyclics include thiiranyl, thietanyl, tetrahydrothienyl, thianyl, thiepanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyridyl, homopiperidinyl, pyrazinyl, piperazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolidinyl, oxazolidonyl, isoxazolyl, isoxazolidiniyl, morpholinyl, thiomorpholinyl, thiazolyl, thiazolidinyl, isothiazolyl, isothiazolidinyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, furyl, thienyl, thiazolidinyl, isothiazolyl, isoindazoyl, triazolyl, tetrazolyl, oxadiazolyl, uricyl, thiadiazolyl, pyrimidyl, tetrahydrofuranyl, dihydrofuranyl, dihydrothienyl, dihydroindolyl, tetrahydroquinolyl, tetrahydroisoquinolyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dithiazolyl, dioxanyl, dioxinyl, dithianyl, trithianyl, oxazinyl, thiazinyl, oxothiolanyl, triazinyl, benzofuranyl, benzothienyl, and the like.

[0144] By “heterocyclyloxy” is meant a heterocyclyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the heterocyclyloxy group is -O-R, in which R is a heterocyclyl group, as defined herein.LAMRP955WO-11528-1WO

[0145] By “heterocyclyloyl” is meant a heterocyclyl group, as defined herein, attached to the parent molecular group through a carbonyl group. In some embodiments, the heterocyclyloyl group is -C(O)-R, in which R is a heterocyclyl group, as defined herein.

[0146] By “hydrazino” is meant -NR1-NR2R3, where each of R1, R2, and R3is, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, as defined herein, or any combination thereof; or where a combination of R1and R2or a combination of R2and R3, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein. In some embodiments, each of R1, R2, or R3is, independently, H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl. In particular embodiments, R2and R3can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl.

[0147] By “hydroxyl” is meant -OH.

[0148] By “hydroxyalkyl” is meant an alkyl group, as defined herein, substituted by one to three hydroxyl groups, with the proviso that no more than one hydroxyl group may be attached to a single carbon atom of the alkyl group and is exemplified by hydroxymethyl, dihydroxypropyl, and the like. In some embodiments, the hydroxyalkyl group is -L-OH, in which L is an alkyl group, as defined herein. In other embodiments, the hydroxyalkyl group is -L-C(OH)(R1)-R2, in which L is a covalent bond or an alkyl group, as defined herein, and each of R1and R2is, independently, H or alkyl, as defined herein.

[0149] By “imidoyl” is meant a moiety including a carbonimidoyl group. In some embodiments, the imidoyl group is C(NR1)R2, in which each of R1and R2is, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl, optionally substituted silyloxy, as defined herein, or any combination thereof. In other embodiments, the imidoyl group is -C(NR1)H, -C(NR1)RAk, or -C(NRN1)RAr, in which R1is hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl, or optionally substituted silyloxy; RAkis an optionally substituted alkyl or an optionally substituted aliphatic; and RAris an optionally substituted aryl or an optionally substituted aromatic.LAMRP955WO-11528-1WO

[0150] By “imino” is meant a -NR- group. In some embodiments, R is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic. In particular embodiments, R is H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0151] By “isocyanato” is meant a -NCO group.

[0152] By “isocyano” is meant a -NC group.

[0153] By “ketone” is meant -C(O)R or a compound including such a group, where R is selected from aliphatic, heteroaliphatic, aromatic, as defined herein, or any combination thereof. An example of a ketone can include R1C(O)R, in which each of R and R1is, independently, selected from aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, as defined herein, or any combination thereof.

[0154] By “nitro” is meant an -NO2 group.

[0155] By “nitroalkyl” is meant an alkyl group, as defined herein, substituted by one to three nitro groups. In some embodiments, the nitroalkyl group is -L-NO, in which L is an alkyl group, as defined herein. In other embodiments, the nitroalkyl group is -L-C(NO)(R1)-R2, in which L is a covalent bond or an alkyl group, as defined herein, and each of R1and R2is, independently, H or alkyl, as defined herein.

[0156] By “oxo” is meant an =O group.

[0157] By “oxy” is meant -O-.

[0158] By “perfluoroalkyl” is meant an alkyl group, as defined herein, having each hydrogen atom substituted with a fluorine atom. Exemplary perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, etc. In some embodiments, the perfluoroalkyl group is -(CF2)nCF3, in which n is an integer from 0 to 10.

[0159] By “perfluoroalkoxy” is meant an alkoxy group, as defined herein, having each hydrogen atom substituted with a fluorine atom. In some embodiments, the perfluoroalkoxy group is -O-R, in which R is a perfluoroalkyl group, as defined herein.

[0160] By “salt” is meant an ionic form of a compound or structure (e.g., any formulas, compounds, or compositions described herein), which includes a cation or anion compound to form an electrically neutral compound or structure. Salts are well known in the art. For example, non-toxic salts are described in Berge S. M. et al., “Pharmaceutical salts,” J. Pharm. Sci. 1977 January; 66(1):1-19; and in “Handbook of Pharmaceutical Salts: Properties, Selection, and Use,” Wiley-VCH, April 2011 (2nd rev. ed., eds. P. H. Stahl and C. G. Wermuth. The salts can be prepared in situ during the final isolation and purification of the compounds of the invention orLAMRP955WO-11528-1WO separately by reacting the free base group with a suitable organic acid (thereby producing an anionic salt) or by reacting the acid group with a suitable metal or organic salt (thereby producing a cationic salt). Representative anionic salts include acetate, adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, borate, bromide, butyrate, camphorate, camphorsulfonate, chloride, citrate, cyclopentanepropionate, digluconate, dihydrochloride, diphosphate, dodecylsulfate, edetate, ethanesulfonate, fumarate, glucoheptonate, gluconate, glutamate, glycerophosphate, hemisulfate, heptonate, hexanoate, hydrobromide, hydrochloride, hydroiodide, hydroxyethanesulfonate, hydroxynaphthoate, iodide, lactate, lactobionate, laurate, lauryl sulfate, malate, maleate, malonate, mandelate, mesylate, methanesulfonate, methylbromide, methylnitrate, methylsulfate, mucate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphate, picrate, pivalate, polygalacturonate, propionate, salicylate, stearate, subacetate, succinate, sulfate, tannate, tartrate, theophyllinate, thiocyanate, triethiodide, toluenesulfonate, undecanoate, valerate salts, and the like. Representative cationic salts include metal salts, such as alkali or alkaline earth salts, e.g., barium, calcium (e.g., calcium edetate), lithium, magnesium, potassium, sodium, and the like; other metal salts, such as aluminum, bismuth, iron, and zinc; as well as nontoxic ammonium, quaternary ammonium, and amino cations, including, but not limited to ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, pyridinium, and the like. Other cationic salts include organic salts, such as chloroprocaine, choline, dibenzylethylenediamine, diethanolamine, ethylenediamine, methylglucamine, and procaine. Yet other salts include ammonium, sulfonium, sulfoxonium, phosphonium, iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphazinium, phosphazenium, pyridinium, etc., as well as other cationic groups described herein (e.g., optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrrolium, optionally substituted furanium, optionally substituted thiophenium, optionally substituted imidazolium, optionally substituted pyrazolium, optionally substituted isothiazolium, optionally substituted triazolium, optionally substituted tetrazolium, optionally substituted furazanium, optionally substituted pyridinium, optionally substituted pyrimidinium, optionally substituted pyrazinium, optionally substituted triazinium, optionally substituted tetrazinium, optionally substituted pyridazinium, optionally substituted oxazinium, optionally substituted pyrrolidinium, optionally substituted pyrazolidinium, optionally substituted imidazolinium, optionally substituted isoxazolidinium, optionally substituted oxazolidinium, optionally substituted piperazinium, optionally substituted piperidinium, optionally substituted morpholinium, optionally substituted azepanium, optionally substitutedLAMRP955WO-11528-1WO azepinium, optionally substituted indolium, optionally substituted isoindolium, optionally substituted indolizinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinolinum, optionally substituted quinolizinium, optionally substituted dehydroquinolizinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted purinium).

[0161] By “silyl” is meant a -SiR1R2R3or -SiR1R2- group. In some embodiments, each of R1, R2, and R3is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In particular embodiments, each of R1, R2, and R3is, independently, H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, the silyl group is -Si(R)a(OR)b(NR2)c, in which each R is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; each of a, b, and c ≥ 0; and a + b + c = 3. In particular embodiments, each R is, independently, H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0162] By “silyloxy” is meant -OR, where R is an optionally substituted silyl group, as described herein. In some embodiments, the silyloxy group is -O-SiR1R2R3, in which each of R1, R2, and R3is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In particular embodiments, each of R1, R2, and R3is, independently, H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, the silyloxy group is -O-Si(R)a(OR)b(NR2)c, in which each R is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; each of a, b, and c ≥ 0; and a + b + c = 3. In particular embodiments, each R is, independently, H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl- alkyl

[0163] By “sulfinyl” is meant an -S(O)- group.

[0164] By “sulfo” is meant an -S(O)2OH group.LAMRP955WO-11528-1WO

[0165] By “sulfonyl” or “sulfonate” is meant an -S(O)2- group or a -SO2R, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof.

[0166] By “thioalkyl” is meant an alkyl group, as defined herein, attached to the parent molecular group through a sulfur atom. Exemplary unsubstituted thioalkyl groups include C1-6 thioalkyl. In some embodiments, the thioalkyl group is -S-R, in which R is an alkyl group, as defined herein.

[0167] By “thiol” is meant an -SH group.

[0168] A person of ordinary skill in the art would recognize that the definitions provided above are not intended to include impermissible substitution patterns (e.g., methyl substituted with 5 different groups, and the like). Such impermissible substitution patterns are easily recognized by a person of ordinary skill in the art. Any functional group disclosed herein and / or defined above can be substituted or unsubstituted, unless otherwise indicated therein.In the present disclosure, the terms “semiconductor wafer,” “wafer,” “substrate,” “wafer substrate,” and “partially fabricated integrated circuit” are used interchangeably. One of ordinary skill in the art would understand that the term “partially fabricated integrated circuit” can refer to a silicon wafer during any of many stages of integrated circuit fabrication. A wafer or substrate used in the semiconductor device industry typically has a diameter of 200 mm, or 300 mm, or 450 mm. The following detailed description assumes the present disclosure is implemented on a wafer. However, the present disclosure is not so limited. The work piece may be of various shapes, sizes, and materials. In addition to semiconductor wafers, other work pieces that may take advantage of the present disclosure include various articles such as printed circuit boards and the like.

[0169] In the present disclosure, the terms “precursor” and “chemical precursor” are used interchangeably. Examples of precursors can include metal-containing precursors, organometallic precursors, and metalloid-containing precursors. One of ordinary skill in the art would understand that the term “precursor” refers to a source material, in gas form, that is provided to a deposition chamber that is typically maintained at a low pressure to form a film with controlled composition. A deposition chamber may be referred to as a process chamber. For example, the precursor in the present disclosure may be capable of forming a photoresist or a metal-containing extreme ultraviolet (EUV) photoresist film configured to absorb the EUV light at approximately 10-20 nm, or 11-14 nm wavelength, for example, 13.5 nm wavelength under the conditions of EUV patterning.

[0170] In the present disclosure, the terms “depositing,” “forming,” and “filling” may be used interchangeably. Also, the terms “layer,” “film,” and “fill” may be used interchangeably. One ofLAMRP955WO-11528-1WO ordinary skill in the art would understand that “forming” a layer in any of many stages of integrated circuit fabrication can refer to “depositing” a thin layer by one of various thin film forming methods such as physical vapor deposition (PVD) including PVD co-sputtering, spin-coat deposition, chemical vapor deposition (CVD) (e.g., low pressure CVD, plasma-enhanced CVD, hot-wire CVD), atomic layer deposition (ALD) (e.g., thermal ALD and plasma-enhanced ALD), sputter deposition, e-beam deposition including e-beam co-evaporation, etc., or a combination thereof, such as ALD with a CVD component, such as a discontinuous, ALD-like process in which precursors and counter-reactants are separated in either time or space.

[0171] As used herein, the term “photoresist” and derivatives thereof refer to a light-sensitive material used in processes such as photolithography, photoetching or photoengraving to form a patterned coating on a surface. Photoresist materials change solubility with respect to a developer solution when exposed to certain wavelengths of light. Photoresist layers may be composed of positive (exposed region becomes soluble) or negative (exposed region becomes insoluble) photoresist material.

[0172] “Tin oxide” is referred to herein as including any and all stoichiometric possibilities for SnxOy, including integer values of x and y and non-integer values of x and y. For example, “tin oxide” includes compounds having the formula SnOn, where 1 < n < 2, where n can be an integer or non-integer values. “Tin oxide” can include sub-stoichiometric compounds such as SnO1.8. “Tin oxide” also includes tin dioxide (SnO2or stannic oxide) and tin monoxide (SnO or stannous oxide). “Tin oxide” also includes both natural and synthetic variations and also includes any and all crystalline and molecular structures. “Tin oxide” also includes amorphous tin oxide. Introduction and context

[0173] Semiconductor device fabrication processes include forming various thin layers on the substrate and removing portions of the various thin layers to define patterns. The various thin films may have different compositions and may include metals, metal alloys, doped or undoped oxides, doped or undoped nitrides, doped or undoped carbides, or mixtures thereof. Some thin films may be a metal-containing photoresist and may include metal atoms (e.g. silicon, indium, tin, aluminum, gallium, tellurium, cadmium, or tantalum, etc.) coordinated to various organic ligands (e.g. functional group). The metal-containing photoresist may be a metal-containing extreme ultraviolet (EUV) photoresist capable of absorbing EUV to define very fine patterns on the substrate. A metal-containing EUV photoresist film may be formed by depositing one or more metal-containing precursors on the features of a substrate or on a substrate. A metal-containing EUV photoresist film may be deposited from one or more metal-containing precursors. A metal-LAMRP955WO-11528-1WO containing EUV photoresist film may include a metal-containing photoresist film, an EUV- sensitive film, an EUV-sensitive inorganic photoresist layer, a photoresist film, a photopatternable film, a directly photopatternable EUV resist, or a photopatternable metal-organic based metal oxide film.

[0174] Many semiconductor device fabrication processes may necessitate controlling the amount of the one or more precursors flowing from a vapor supply source towards a process chamber. In some embodiments, the process chamber may include a deposition chamber. The amount of the precursors flowing into the process chamber may determine the film deposition rate, a film thickness, or a film composition, etc. The amount of the precursor may vary during transport from a vapor supply source (e.g. an ampoule or a bulk storage tank) towards the process chamber. In that case, a precursor concentration, i.e., the amount of precursor carried by a carrier gas (e.g., an inert gas), may also vary. For example, a discrepancy from the desired precursor amount may result in a film that is thicker or thinner than the design value. In another example, flowing an inconsistent amount of precursor over time may obtain films with significant thickness variations between the substrates. In another example, for a multi-component film, failure to control the amounts of the precursors during deposition may obtain a film having a non-uniform composition in the horizontal or vertical direction of the film. Though the present disclosure may refer to precursors flowing into a deposition chamber, it will be understood that the present disclosure may include other processing chambers and are not limited to only deposition chambers.

[0175] For some semiconductor fabrication processes, the amount of a precursor may be monitored based on the flow rate of the precursor. For example, a mass flow controller (MFC) may be fluidly coupled to the conduit of a deposition apparatus to control the amount of the precursor flowed through the conduit. A precursor may be mixed with a carrier gas (e.g., nitrogen, argon, helium, or mixtures thereof) and flowed toward the process chamber. The MFC may have a particular range of flow rates for measuring the flow rate of a precursor (or a precursor mixed with carrier gas).

[0176] In some semiconductor fabrication processes, a precursor concentration may not be reliably determined. In one example, the flow rate of a precursor may be set to a value that is lower than the lower flow rate limit of the given MFC. In some examples, the precursor may be mixed with other gases, precursors, or contaminants that make it difficult to reliably monitor the concentration of one or more precursors in the mixture. Precursor concentration monitoring

[0177] Figure 1 illustrates a flow chart of an example method of monitoring a precursorLAMRP955WO-11528-1WO concentration according to some embodiments. In some embodiments, a precursor may be a metal-containing precursor in vapor form (i.e. precursor gas) for depositing a metal-containing EUV photoresist film. In some embodiments, a precursor may be an organometallic precursor including at least one metal center. A precursor may be mixed with one or more carrier gases. The operations of process 100 may be performed in different orders and / or with different, fewer, or additional operations. One or more operations of the process 100 may be performed by using an apparatus shown in Figures 8-12. In some embodiments, the operations of process 100 may be implemented, at least in part, according to software stored in one or more non-transitory computer readable media.

[0178] In operation 110, a precursor may flow according to an initial flow condition. The initial flow condition may be a flow rate for a precursor carried by a carrier gas (e.g., inert gas) from a vapor supply source. The flow rate for a precursor may correspond to a precursor concentration, which may correspond to (or correlated with) a precursor amount carried by a carrier gas. In some embodiments, the precursor amount in a carrier gas may determine a deposition rate and a film thickness and may have a preset value for obtaining a certain deposition rate. The flow rate for a precursor may be set or configured to obtain a certain film deposition rate or a certain film thickness. For example, the flow rate may be set or configured such that a certain film deposition rate may be obtained during deposition. In general, the film deposition rate may increase when the flow rate for a precursor increases, and the film deposition rate may decrease when the flow rate decreases. In some embodiments, the precursor amount in the initial flow condition is not known. For example, while a total flow rate of the precursor mixed with carrier gas may be known, the relative amounts of precursor and carrier gas may not be known in the initial flow condition.

[0179] A precursor (in vapor form) may be formed from a precursor in liquid form stored in the vapor supply source by mixing with one or more carrier gases (e.g., argon, nitrogen, helium, or combinations thereof). For example, the mixing ratio of a precursor to a carrier gas may be about 1:20 to about 1:500, about 1:40 to about 1:200, about 1:80 to about 1:120, about 1:90 to about 1:110, or about 1:100. The precursor concentration mixed with carrier gas may be low. For example, the precursor may flow at a vapor pressure equal to or less than about 100 millitorr, equal to or less than about 70 millitorr, equal to or less than about 60 millitorr, equal to or less than about 50 millitorr, or equal to or less than about 40 millitorr. The method described in Figure 1 may use a spectral sensor such as an IR sensor, a visible light sensor, or a UV sensor to monitor a precursor concentration. In one embodiment, a precursor may flow in a gas conduit towards an IR sensor equipped with an IR radiation source capable of providing energy of an infrared wavelength range. In another embodiment, a precursor may flow in a gas conduit towards an ultraviolet (UV) sensorLAMRP955WO-11528-1WO equipped with an ultraviolet radiation source capable of providing energy of an ultraviolet wavelength range. In yet another embodiment, a precursor may flow in a gas conduit towards a visible light sensor equipped with a visible light radiation source capable of providing energy of a visible light wavelength range.

[0180] In one example, a vapor supply source from which a precursor flows in vapor form may be configured to be coupled to a controller that is capable of setting the flow rate of the precursor. The controller may include a mass flow controller or other control device that is capable of increasing, decreasing, or maintaining the flow rate of the precursor provided towards the deposition chamber. In some embodiments, the precursor may continuously flow from the vapor supply source towards the deposition chamber. In some embodiments, the precursor may flow in a series of sequential, non-overlapping pulses. In some embodiments, the deposition chamber may include a chamber for chemical vapor deposition (CVD) (e.g., low pressure CVD, plasma- enhanced CVD, hot-wire CVD), or atomic layer deposition (ALD) (e.g., thermal ALD and plasma- enhanced ALD).

[0181] In operation 120, the precursor concentration may be monitored. In some embodiments, the precursor concentration may be monitored based at least in part on spectroscopy measurements received from a spectral sensor. In some embodiments, the spectral sensor may include a radiation source and a sensing device. Examples of spectral sensors include but are not limited to IR sensors, UV sensors, visible light sensors, and combinations thereof.

[0182] In some embodiments, the precursor concentration may be monitored based at least in part on IR spectroscopy measurements received from an IR sensor. The IR sensor may include the IR radiation source for providing IR radiation to the precursor and at least a portion of IR radiation may be absorbed by the precursor. In one example, the precursor may absorb specific frequencies of IR radiation that are characteristics of the corresponding structure (or chemical bonding) of the precursor. The IR sensor may include the IR sensing device for receiving and / or further processing signals from the precursor irradiated by IR radiation. In some embodiments, the IR sensor may operate in part based on the operating principle of IR spectroscopy measurements. In some embodiments, the IR sensing device may operate in part based on the operating principle of IR spectroscopy measurements. For example, IR spectroscopy measurements may include Fourier Transform Infrared Spectroscopy (FTIR) including one or more IR sensors.

[0183] In other embodiments, the precursor concentration may be monitored based at least in part on ultraviolet (UV) spectroscopy measurements received from a UV sensor. In some embodiments, the UV sensor may include a UV radiation source and a UV sensing device. TheLAMRP955WO-11528-1WO UV sensor may include the UV radiation source for providing UV radiation to the precursor and at least a portion of UV radiation may be absorbed by the precursor. In one example, the precursor may absorb specific frequencies of UV radiation that are characteristics of the corresponding structure (or chemical bonding) of the precursor. In some embodiments, the UV absorption may cause a photodissociation at least in a portion of the precursor. The energy of the UV radiation to the precursor may be sufficient to break or detach one or more chemical bonds from the precursor. The photodissociation by the UV radiation may slightly modify the chemical structure of the precursor that is supplied to the chamber for processing, e.g., deposition. In one embodiment, the degree of the photodissociation may not be extensive, and may not modify or substantially modify the physical or chemical properties of the film from the precursor irradiated by the UV radiation.

[0184] Depending on, for example, the nature of chemical bonding within a precursor, each precursor may respond differently to various radiations, for example, having a different effective wavelength range. For example, a precursor sensitive to one radiation may be less sensitive to different radiation. A precursor that is more sensitive to UV radiation may be relatively less prone to react to IR radiation, and vice versa. Depending on the precursor composition or type, UV, IR, visible, both UV and IR, both visible and UV, or both IR and visible spectroscopy may be used in monitoring the precursor concentration. The precursor may belong to at least one of the following categories that are sensitive to IR radiation, UV radiation, visible radiation, or their combinations.

[0185] The UV sensor may include the UV sensing device for receiving and / or further processing signals from the precursor irradiated by UV radiation. In some embodiments, the UV sensor may operate in part based on the operating principle of UV spectroscopy measurements. In some embodiments, the UV sensing device may operate in part based on the operating principle of UV spectroscopy measurements. For example, UV spectroscopy measurements may include UV Spectroscopy having one or more UV sensors. In yet another embodiment, the precursor concentration may be monitored based at least on the combination of IR and UV spectroscopy measurements.

[0186] In some embodiments, the precursor concentration may be monitored by combining the pressure measurement for carrier gas and spectroscopy measurements for a precursor. A flow rate controller (e.g., a mass flow controller, a pressure controller, or other gas flow sensing device) is configured to measure the pressure of the total gas mixture including the carrier gas and precursor(s). The spectroscopy measurements may determine the absorption characteristics of the precursor obtained by the spectral sensor. The absorption characteristics may be obtained in the form of electrical (or optical) signals by the spectral spectroscopy measurements. For example, the electrical signals may include a voltage signal. In some embodiments, the precursorLAMRP955WO-11528-1WO concentration may be monitored by combining the pressure and / or temperature measurements for carrier gas and spectroscopy measurements for a precursor.

[0187] In some embodiments, the electrical (or optical) signals obtained for the precursor may be compared with electrical (or optical) signals calibrated for the precursor with a known concentration by the spectroscopy measurements. For example, by comparing the electrical (or optical) signals obtained from the precursor flowing towards the deposition chamber and the electrical (or optical) signals from the calibrated reference for a precursor, the precursor concentration may be monitored.

[0188] The monitored precursor concentration obtained in operation 120, when converted to the precursor amount, may be different from the desired precursor amount. The monitored precursor concentration may be equal to, higher, or lower than the desired precursor amount. Alternately, the monitored precursor concentration may be substantially similar to the desired precursor amount. Or, the desired precursor amount may not be known. Regardless of any discrepancy between the desired precursor amount and the monitored precursor concentration, the monitored precursor concentration may be used as a feedback to set an updated flow condition to control the flow rate of the precursor that is subsequently flowing towards the deposition chamber. For example, the monitored precursor concentration may be sent to a controller associated with operation 110 to compensate for the discrepancy. For example, the monitored precursor concentration may be sent to the mass flow controller controlling the flow rate of the precursor provided from a vapor supply source of operation 110.

[0189] In one example, the monitored precursor concentration may be lower than the desired precursor amount. The reduced precursor concentration may indicate that an insufficient amount of precursor is flowing into the deposition chamber, which may result in a reduced film deposition rate. The reduced amount of precursor may be compensated by increasing the flow rate of the precursor at operation 110 by a certain level. For example, the monitored precursor concentration may indicate a deficit of about 10% of the desired precursor amount and the flow rate of the precursor from a vapor supply source may be increased by about 10% to compensate for the deficit. In one example where the precursor flows continuously from a vapor supply source towards a deposition chamber, the flow rate may be increased by increasing the flow rate setting of a mass flow controller or any flow rate control device associated with providing the precursor at operation 110. The increase in the flow rate may increase the precursor amount flowing towards the deposition chamber close to the level for achieving a certain film deposition rate as designed. In some embodiments, in addition to or in combination with increasing the flow rate setting of a mass flow controller or any flow rate control device, the temperature of the precursor may be increasedLAMRP955WO-11528-1WO to provide a higher precursor concentration delivered. In another example where the precursor flows in a series of pulses, a precursor pulsing duration and / or a precursor pulsing rate may be increased to increase the amount of the precursor to achieve a certain deposition rate.

[0190] In another example, the monitored precursor concentration obtained in operation 120 may be higher than the desired precursor amount. Higher precursor concentration indicates that more precursor than required for a certain deposition rate is provided toward the deposition chamber and a thicker film than the design specification may be deposited due to the increased film deposition rate. One way to lower the precursor amount flowing toward the deposition chamber is to reduce the flow rate of the precursor. For example, the flow rate of a mass flow controller or any flow rate control device associated with providing the precursor at operation 110 may be set to a reduced value compared to the desired precursor amount by a certain value to reduce the amount of the precursor continuously flowing toward the deposition chamber. In some embodiments, in addition to or in combination with increasing the flow rate setting of a mass flow controller or any flow rate control device, the temperature of the precursor may be decreased to provide a lower precursor concentration delivered. For a precursor supplied in a series of pulses, a precursor pulsing duration and / or a precursor pulsing rate may be decreased to reduce the amount of the precursor being delivered toward the deposition chamber.

[0191] Sending the precursor concentration monitored at operation 120 to a mass flow controller or any flow control device at operation 110 may be part of a feedback process and the feedback process may not be limited to only once. The feedback process of monitoring the precursor concentration at operation 120 and sending the monitored precursor concentration back to operation 110 may be repeated multiple times prior to and / or during deposition to maintain the monitored precursor amount close to the desired precursor amount. The feedback process may be performed continuously or with certain time intervals.

[0192] In optional operation 130, the precursor may flow toward the deposition chamber. In some embodiments, the precursor may be provided to the substrate supported on the substrate holder (i.e. pedestal). The precursor may flow from the vapor supply source to the deposition chamber via the gas conduit. The spectral sensor used for monitoring the precursor concentration may be positioned between the vapor supply source and the deposition chamber. In other words, the spectral sensor may be positioned along the gas conduit to determine the precursor concentration before the precursor is delivered into the deposition chamber. In one embodiment, the spectral sensor is an IR sensor. In another embodiment, the spectral sensor is a UV sensor. In yet another embodiment, the spectral sensor is a visible light sensor.

[0193] In optional operation 140, the precursor may react with the surface of the substrate underLAMRP955WO-11528-1WO a certain temperature and pressure condition and a film with a certain composition may be deposited. In one example, a metal-containing EUV photoresist film may be formed on the substrate for subsequent operations such as EUV exposure, development, or post-exposure treatment.

[0194] Figure 2A illustrates a flow chart of example method of monitoring concentrations of two or more precursors according to some embodiments. In particular, Figure 2A illustrates a method of concurrently monitoring concentrations of two precursors. It is noted that Figure 2A is not limited to monitoring only two precursors. Instead, the method illustrated in Figure 2A may be applied to three or more precursors. Such precursors may be part of a blended mixture of precursors. The process 200 may begin at operation 210 where two or more precursors are flowed according to initial flow conditions. In some embodiments, the initial flow conditions may be a flow rate for a gas mixture including two or more precursors carried by one or more carrier gases. The two or more precursors may be flowed from one or more vapor supply sources. The flow rate for the gas mixture may correspond to (or correlate with) a mixed precursor concentration, which may correspond to a mixed precursor amount carried by a carrier gas. In some embodiments, the mixed precursor amount in the carrier gas may determine a deposition rate and a film thickness and may have a preset value for obtaining a certain deposition rate. The flow rate for the gas mixture may be set to obtain a certain film deposition rate or a certain film thickness. For example, the flow rate may be set such that a certain film deposition rate may be obtained during deposition. In general, the film deposition rate may increase when the flow rate for a precursor increases, and the film deposition rate may decrease when the flow rate decreases.

[0195] In some embodiments, the gas mixture may be formed from two or more precursors in liquid form stored in the one or more vapor supply sources by mixing with one or more carrier gases. For example, a mixing ratio of a mixed precursor to a carrier gas may be about 1:20 to about 1:500, about 1:40 to about 1:200, about 1:80 to about 1:120, about 1:90 to about 1:110, or about 1:100. The concentration of the two or more precursors in the one or more carrier gases may be low. For example, the gas mixture may flow at a vapor pressure equal to or less than about 100 millitorr, equal to or less than about 70 millitorr, equal to or less than about 60 millitorr, equal to or less than about 50 millitorr, or equal to or less than about 40 millitorr. The gas mixture including two or more precursors may flow in a gas conduit towards a spectral sensor equipped with a radiation source capable of providing energy of a certain wavelength range. In one embodiment, the gas mixture including two or more precursors may flow in a gas conduit towards an IR sensor equipped with an IR radiation source capable of providing energy of an infrared wavelength range. In another embodiment, the gas mixture including the two or more precursorsLAMRP955WO-11528-1WO may flow in a gas conduit towards a UV sensor equipped with a UV radiation source capable of providing energy of an ultraviolet wavelength range. In yet another embodiment, both IR and UV radiation source may be provided to the gas mixture to provide energies from an IR and UV radiation sources.

[0196] In some embodiments, the gas mixture may include two or more precursors having different chemical compositions from each other, where the gas mixture is provided to the deposition chamber to deposit an EUV photoresist film including two or more metals on a substrate. An ampoule or a bulk storage may be coupled to a controller that is capable of setting the flow rate of the gas mixture. The controller may be a mass flow controller or other flow control device that is capable of increasing or decreasing the flow rate of the gas mixture flowing toward the deposition chamber. In some embodiments, the two or more precursors in the gas mixture may not chemically react with each other and no reaction product from any reaction(s) between the two or more precursors may be formed. In some embodiments, each of the two or more precursors includes a metal-containing precursor. In some embodiments, each of the two or more precursors includes an organometallic precursor.

[0197] In operation 220, the two or more precursors may be monitored based at least in part on spectroscopy measurements received from one or more spectral sensors. The one or more spectral sensors may include an IR sensor, a UV sensor, a visible light sensor, or a combination thereof. In some embodiments where the IR spectroscopy is used, the IR sensor may include an IR radiation source for providing IR radiation to the two or more precursors such that at least a portion of IR radiation may be absorbed by the two or more precursors. For example, IR radiation may be radiated to the gas mixture to monitor the absorption characteristics of the gas mixture. The gas mixture may absorb specific frequencies of the IR radiation that are characteristics of the corresponding structures (or chemical bonding) of the two or more precursors. An IR sensor may include an IR sensing device for receiving and / or processing signals from the two or more precursors that are irradiated by IR radiation. In some embodiments, an IR sensor may operate at least in part based on the operating principle of IR spectroscopy measurements. In some embodiments, the IR sensing device may operate in part based on the operating principle of IR spectroscopy measurements. For example, IR spectroscopy measurements may include FTIR.

[0198] In other embodiments where UV spectroscopy is employed, two or more precursors in the gas mixture may absorb specific frequencies of the UV radiation that are characteristics of the corresponding structures (or chemical bonding) of the two or more precursors. As described, irradiation of the UV radiation to the two or more precursors may result in a photodissociation, at least in a portion of the precursors irradiated by the UV radiation; thereby, one or more chemicalLAMRP955WO-11528-1WO bonds in the precursors may be modified or broken.

[0199] In other embodiments, the two or more precursors may have absorption characteristics to radiations having different wavelengths. For example, a first precursor in the gas mixture may have one or more chemical bonds more sensitive to IR radiation, and one or more chemical bonds in a second precursor may be more sensitive to UV radiation, and the concentrations of two precursors in a mixture may be independently monitored using the IR and UV spectroscopy measurements.

[0200] In some embodiments, the concentration of the two or more precursors may be monitored by combining pressure measurements for the carrier gas and spectroscopy measurements for the gas mixture including the two or more precursors. For example, a flow rate controller (e.g., a mass flow controller, a pressure controller, or other gas flow sensing device) is configured to measure the pressure of the total gas mixture including the carrier gas and precursor(s). The spectroscopy measurements may determine the absorption characteristics of the two or more precursors obtained by the spectral sensor. The absorption characteristics of the two or more precursors may be obtained in the form of electrical (or optical) signals by the spectroscopy measurements. For example, the electrical signals may include a voltage signal. In some embodiments, the concentration of two or more precursors may be monitored by combining the pressure and / or temperature measurements for the carrier gas and spectroscopy measurements for two or more precursors.

[0201] In some embodiments, the electrical (or optical) signals obtained for the two or more precursors may be compared against the electrical (or optical) signals calibrated for the two or more precursors with known concentrations by the spectroscopy measurements. For example, by comparing the electrical (or optical) signals obtained from the two or more precursors flowing towards the deposition chamber and the electrical (or optical) signals from the calibrated reference for the two or more precursors, the concentration of the two or more precursors in the gas mixture may be monitored. The monitored mixed precursor concentration may be correlated to the monitored precursor amount.

[0202] In other embodiments, in addition or in the alternative with the IR spectroscopy measurements, the UV spectroscopy measurements may be employed in monitoring the concentration of two or more precursors in a gas mixture. Similar to IR spectroscopy, the electrical (or optical) signals obtained for the two or more precursors may be compared with the electrical (or optical) signals calibrated for the two or more precursors with known concentrations by the UV spectroscopy measurements. In yet another embodiments, in addition to or in the alternative with the IR or UV spectroscopy measurements, visible light spectroscopy may be employed inLAMRP955WO-11528-1WO monitoring the concentration of two or more precursors in a gas mixture.

[0203] The monitored concentration of the two or more precursors obtained in operation 220, when converted to the mixed precursor amount, may be different from the desired mixed precursor amount. The discrepancy between the desired mixed precursor amount and the monitored concentration of the mixed precursors, if any, may be corrected in a similar way described herein elsewhere. The monitored concentration of the mixed precursors, higher or lower than or substantially similar to the desired mixed precursor amount, may be used as a feedback for controlling the flow rate of the mixed precursors that may subsequently flow toward the deposition chamber. For example, the monitored concentration of the mixed precursors may be sent to a mass flow controller or any flow control device that is capable of controlling the flow rate of the mixed precursors provided from one or more vapor supply sources of operation 210 toward the deposition chamber.

[0204] In one example, the monitored concentration of the mixed precursors may be lower than the desired mixed precursor amount. The reduced mixed precursor concentration may indicate that an insufficient amount of precursors are flowing into the deposition chamber and the film deposition rate is lower than the design value. The reduced amount of the mixed precursor may be compensated by increasing the flow rate of the two or more precursors at operation 210 by a certain level. In one example where the two or more precursors flow continuously from the one or more vapor supply sources towards a deposition chamber, the flow rate may be increased by increasing the flow rate setting of an MFC or any flow rate control device associated with providing the two or more precursors at operation 210. The increase in the flow rate may also increase the mixed precursor amount flowing towards the deposition chamber close to the desired mixed precursor amount for achieving a certain film deposition rate as designed. In another example where the mixed precursors flow in a series of pulses, a precursor pulsing duration and / or a precursor pulsing rate may be increased to increase the amount of the mixed precursors to achieve a certain deposition rate.

[0205] In another example, the monitored mixed precursor concentration obtained in operation 220 may be higher than the desired mixed precursor amount. Higher mixed precursor concentration indicates that more precursor amount than required is provided toward the deposition chamber and a thicker film from increased deposition rate may be expected. One way to lower the mixed precursor amount flowing toward the deposition chamber is to reduce the flow rate of the two or more precursors. For example, the flow rate of a mass flow controller or any flow rate control device associated with providing a precursor at operation 210 may be set to a reduced value compared to the desired mixed precursor amount by a certain value to reduce theLAMRP955WO-11528-1WO amount of the mixed precursors continuously flowing toward the deposition chamber. For the mixed precursors supplied in a series of pulses, a precursor pulsing duration and / or a precursor pulsing rate may be decreased to reduce the amount of the mixed precursors being delivered toward the deposition chamber.

[0206] The feedback process of monitoring the mixed precursor concentration at operation 220 and sending the monitored mixed precursor concentration back to operation 210 may be repeated multiple times prior to and / or during deposition to maintain the monitored precursor amount close to the desired precursor amount. The feedback process may be performed continuously or with certain time intervals.

[0207] After passing through the one or more spectral sensors, in optional operation 230, the two or more precursors may flow into the deposition chamber. In some embodiments, the two or more precursors may be provided to the substrate supported on the substrate holder (i.e., pedestal) for depositing a film. The two or more precursors may flow from the one or more vapor supply sources to the deposition chamber via the gas conduit. The one or more spectral sensors used for monitoring the mixed precursor concentration may be positioned between the one or more vapor supply sources and the deposition chamber. In other words, the one or more spectral sensors may be positioned along the gas conduit to determine the mixed precursor concentration before the two or more precursors are delivered into the deposition chamber.

[0208] In optional operation 240, the two or more precursors may react with other reactants or the surface of the substrate under a certain temperature and pressure condition and a film with a certain composition may be deposited. In one example, a metal-containing EUV photoresist film may be formed on the substrate.

[0209] Figure 2B illustrates process 202 for monitoring the concentrations of two precursors according to some embodiments. In particular, Figure 2B illustrates separately monitoring the concentrations of two precursors. While Figure 2B illustrates embodiments for monitoring the concentrations of two precursors, it is to be understood that these embodiments are not limited to two precursors. Instead, these embodiments may be expanded to three or more precursors. For example, the operations of embodiments in Figure 2B may be modified and applied for monitoring the concentrations of three or more precursors. The process 202 may begin at operations 212 and 214 for flowing a first precursor and a second precursor individually from a first vapor supply source and a second vapor supply source, respectively, towards a deposition chamber. A carrier gas may be provided to each of the first and second vapor supply sources to separately carry the first and second precursors in the separate gas conduits. For example, a mixing ratio of each of the first and second precursors to a carrier gas may be about 1:20 to about 1:500, about 1:40 toLAMRP955WO-11528-1WO about 1:200, about 1:80 to about 1:120, about 1:90 to about 1:110, or about 1:100. The concentration of each of the first and second precursors may be low. For example, each of the first and second precursors may flow at a vapor pressure equal to or less than about 100 millitorr, equal to or less than about 70 millitorr, equal to or less than about 60 millitorr, equal to or less than about 50 millitorr, or equal to or less than about 40 millitorr. Depending on the nature of chemical bonding in a precursor and corresponding absorption characteristic to radiation irradiated to each precursor, each of the first and second precursors may flow in the separate gas conduits towards separate radiation source(s) capable of providing energy of a desired wavelength range, such as an IR, visible light, or UV wavelength range.

[0210] In operations 222 and 224, the first and second precursor concentrations may be monitored based at least in part on spectroscopy measurements received from one or more spectral sensors. In some embodiments, the first precursor concentration may be monitored by a first spectral sensor having a first radiation source and a first sensing device, and the second precursor concentration may be monitored by a second spectral sensor having a second radiation source and a second sensing device. In some embodiments, the first spectral sensor may be an IR sensor, a visible light sensor, a UV sensor, or a combination thereof. In some embodiments, the second spectral sensor may be an IR sensor, a visible light sensor, a UV sensor, or a combination thereof.

[0211] In some embodiments, radiation from the first and second spectral sensors may be separately provided to the first and second precursors, respectively. For example, the first and second precursors may absorb specific frequencies of radiation that are characteristic of the corresponding structures (or chemical bonding) of the first and second precursors. First and second sensing devices may receive and / or process signals from the first and second precursors, respectively. In some embodiments, an IR sensor may operate in part based on the operating principle of FTIR. Similarly, in other embodiments, UV radiation from the first and second UV sensors may be separately provided to the first and second precursors, respectively. For example, the first and second precursors may absorb specific frequencies of UV radiation that are characteristic of the corresponding structures (or chemical bonding) of the first and second precursors. First and second UV sensing devices may receive and / or process signals from the first and second precursors, respectively. For example, a UV sensor may operate in part based on the operating principle of UV spectroscopy.

[0212] In some embodiments, each of the first and second precursor concentrations may be monitored by combining pressure measurements and spectroscopy measurements. For example, first and second flow rate controllers (e.g., a mass flow controller, a pressure controller, or other gas flow sensing devices) are configured to measure the pressure of each of the gas mixtureLAMRP955WO-11528-1WO including the carrier gas and first precursor, and the gas mixture including the carrier gas and second precursor, respectively. The spectroscopy measurements may determine the absorption characteristics of the first and second precursors obtained by the first and second spectral sensors. The absorption characteristics may be obtained in the form of electrical (or optical) signals. For example, the electrical signals may include a voltage signal. In some embodiments, each of the first and second precursor concentrations may be monitored by combining the pressure measurements from each gas mixture including a carrier gas and a precursor, and IR spectroscopy measurements. In other embodiments, each of the first and second precursor concentrations may be monitored by combining the pressure measurements from each gas mixture including a carrier gas and a precursor, and UV spectroscopy measurements. In some embodiments, the precursor concentration may be monitored by combining the pressure and / or temperature measurements for carrier gas and spectroscopy measurements for a precursor.

[0213] The first and second precursor concentrations may be monitored in a similar way to monitoring the precursor concentration described herein elsewhere. In some embodiments, the electrical (or optical) signals obtained for the first and second precursors may be separately compared against electrical (or optical) signals calibrated for the first and second precursors with a known concentration. By comparing the electrical (or optical) signals individually obtained from the first and second precursors against the electrical (or optical) signals calibrated from the first and second precursor references, the first and second precursor concentrations may be separately monitored.

[0214] Similar to other embodiments described herein, the monitored first and second precursor concentrations may be sent to the MFCs or other flow rate control device for modifying the flow rates of the first and second precursors as necessary. For example, the monitored first precursor concentration may be sent to a first MFC or any flow rate control device associated with providing a first precursor at operation 212. Similarly, the monitored second precursor concentration may be sent to a second MFC or any flow rate control device associated with providing a second precursor at operation 214. Depending on the monitored concentrations of the first and second precursors, the flow rates of the first and second precursors may be increased, decreased, or maintained to be substantially the same. The flow rates of the first and second precursors may be modified independently from each other.

[0215] The feedback process of monitoring the first and second precursor concentrations at operations 222 and 224 and sending the monitored precursor concentrations back to operation 212 and 214 may be repeated multiple times prior to and / or during deposition to maintain the monitored precursor amounts close to the desired precursor amounts. The feedback process may beLAMRP955WO-11528-1WO performed continuously or with certain time intervals.

[0216] Operations 232 and 242 may be similar to other operations 130, 140 in Figure 1 or operations 230, 240 in Figure 2A. In optional operation 232, the first and second precursors may be separately flowed to the deposition chamber for depositing a film with a certain composition. Alternately, the first and second precursors may be mixed to form a gas mixture before flowing into the deposition chamber. In optional operation 242, the first and second precursors may react with other reactants on the surface of the substrate under a certain temperature and pressure condition and a film with a certain composition may be deposited on the substrate. For example, a metal-containing EUV photoresist film may be formed on the substrate.

[0217] Figure 3 illustrates a flow chart of an example of monitoring the concentrations of one or more precursors according to some embodiments. A process 300 begins at operation 310, where one or more precursors are flowed according to an initial flow condition. The one or more precursors may be flowed from one or more vapor supply sources towards a deposition chamber. In some embodiments, operation 310 may be performed substantially the same as the operations described in Figures 1, 2A, and / or 2B. The details of operation 310 may not be further described with respect to process 300.

[0218] In operation 320, the concentrations of one or more precursors may be monitored using a piezoelectric sensor, an optical sensor, or combination of a piezoelectric sensor and an optical sensor. In some embodiments, the optical sensor includes an IR sensor, a visible light sensor, a UV sensor, or their combinations. In some embodiments, the piezoelectric sensor may be combined with an IR sensor, a UV sensor, or their combinations in monitoring the concentrations of one or more precursors. In one example, the piezoelectric sensor for monitoring the precursor concentration may be a piezoelectric chemical sensor. The piezoelectric chemical sensor may be fluidly coupled to a suitable location of a gas conduit for receiving the precursor. In one example, the piezoelectric chemical sensor may have a structure including two opposing electrodes with a piezoelectric material between the two electrodes. A radio wave frequency may be applied to a first electrode (i.e. transmitter) on a piezoelectric material, which may be exposed to a precursor and produce a surface acoustic wave (SAW) that may indicate the characteristics of the precursor. The SAW may be captured by a second electrode to convert the SAW into a voltage signal. The voltage signal that varies with the precursor composition may be provided for monitoring the precursor concentration. In another example, the piezoelectric sensor may be a time of flight sensor. In some embodiments, a piezoelectric chemical sensor may monitor the concentration of one precursor or mixed precursors. In some embodiments, the concentration of a gas mixture including two precursors may be monitored by employing two separate piezoelectric chemicalLAMRP955WO-11528-1WO sensors.

[0219] The monitored concentrations of one or more precursors obtained in operation 320 may be used as feedback to control the flow rate of the one or more precursors. As described with respect to processes 100, 200, and 202 in Figures 1, 2A, and 2B, the monitored concentrations of one or more precursors may be sent to a controller associated with operation 310 to compensate for any discrepancy between the monitored concentrations (i.e., the monitored precursor amount) and the desired precursor amount. The controller may be a flow rate controller (e.g., a mass flow controller, a pressure controller, or other gas flow sensing device). Depending on whether the monitored concentrations are lower or higher than a desired precursor amount, the flow rates of the one or more precursors may be increased or decreased close to the desired precursor amount. The monitoring of the concentrations of the one or more precursors at operation 320 and providing the feedback to operation 310 may be performed either in a real time basis or with a certain time interval.

[0220] In optional operation 330, the one or more precursors may flow into the deposition chamber. In some embodiments, the one or more precursors may be provided to the substrate supported on the substrate holder (i.e. pedestal) in the deposition chamber. The one or more precursors may flow from the one or more vapor supply sources to the deposition chamber via the gas conduit. The piezoelectric sensor and / or optical sensor used for monitoring the precursor concentration may be positioned between the one or more vapor supply sources and the deposition chamber. In other words, the piezoelectric sensor and / or optical sensor may be positioned along the gas conduit to determine the precursor concentration before the one or more precursors are delivered into the deposition chamber.

[0221] In optional operation 340, the one or more precursors may react with other reactants or the surface of the substrate under a certain temperature and pressure condition and a film with a certain composition may be deposited. In one example, a metal-containing EUV photoresist film may be formed on the substrate. Applications

[0222] During the semiconductor device fabrication operation, one or more precursors may be carried by one or more carrier gases into a deposition chamber. Depending on the process requirements, the precursor concentration may be set to a low level. Such low levels may correspond to very low vapor pressure, such as vapor pressures equal to or less than about 100 millitorr, equal to or less than about 70 millitorr, equal to or less than about 60 millitorr, equal to or less than about 50 millitorr, or equal to or less than about 40 millitorr. A precursor concentrationLAMRP955WO-11528-1WO may also vary over time. For example, the precursor concentration may vary with time while a precursor is stored in an ampoule or a bulk precursor storage for an extended time period. As described herein, the precursor concentration may vary due to precursor decomposition. In another example, the precursor concentration may vary due to incorporation of a contaminant during transport. The varying precursor concentration with time may be responsible for a non-uniform film thickness from one substrate to another substrate, which may be critical in depositing a very thin film because even the slightest variation from the desired precursor concentration may result in a film having a thickness that is outside an acceptable range. Monitoring the precursor concentration may be advantageous in precisely maintaining the precursor amount that is delivered to the deposition chamber and may be critical to obtaining a film with a uniform thickness from one substrate to another. For example, the precursor concentration may be continuously monitored to provide a constant and accurate amount of precursor with minimal fluctuation prior to and / or during film deposition.

[0223] In some embodiments, monitoring a precursor concentration according to some embodiments may be used in monitoring a contaminant mixed with the precursor. For example, a precursor may be contaminated with water adsorbed on an inner surface of the gas conduit while the precursor flows through the gas conduit. Water mixed with the precursor may react with and / or modify the precursor composition and also modify the reaction sequence or reaction kinetics of the precursor with any reactants or the surface of the substrate prior to or during film deposition. Monitoring the precursor concentration according to some embodiments may identify the presence and the amount (i.e., concentration) of a contaminant, e.g. water, in the precursor. In some embodiments, this identification operation may be similar to comparing the peak locations of the precursor flowing in a gas conduit with the peak locations from a known reference according to IR, visible light, or UV spectroscopy measurements. The presence of peaks that are not present in the known reference may indicate that a contaminant is present with the precursor. In some embodiments, the peak information may be processed by IR, visible light, or UV spectroscopy measurements and the presence of water may be identified by comparing the electrical (or optical) signals generated from the precursor possibly mixed with water with the electrical (or optical) signals for a known reference, e.g. the precursor in use and / or water. In some embodiments, the concentration of the contaminant, e.g. water, may be monitored by comparing the electrical (or optical) signal intensities obtained for the water in the precursor with the signals calibrated for water reference. The water concentration may be monitored with time, for example, by comparing the intensity ratio of the signals from water with time and may be used as a tool for quality control. For example, a precursor may be prevented from flowing into a deposition chamber if the waterLAMRP955WO-11528-1WO concentration in the precursor exceeds above a threshold. In another example, a precursor having water, regardless of the concentration, may be prevented from being flowed into the deposition chamber.

[0224] In some embodiments, the incorporation of one or more contaminants other than water in the precursor may also be monitored. For example, a contaminant may be a decomposed product formed in a precursor. The decomposed product may be formed, for example, from the decomposition of the precursor. For example, the decomposed product may be formed in a precursor stored for an extended time period such that the stability of the precursor is not maintained anymore. Monitoring the precursor concentration according to some embodiments may identify the presence and the amount (i.e., concentration) of a contaminant in the precursor. In some embodiments, this identification operation may be similar to the operation described herein. For example, the peak locations of the precursor potentially mixed with a contaminant may be compared with the peak locations from a known reference according to at least one of IR, visible light, and UV spectroscopy measurements. The presence of peaks that are not present in the known reference may indicate that a contaminant is present in the precursor. In some embodiments, the peak information may be processed by at least one of IR, visible light, and UV spectroscopy measurements and the presence of decomposed product may be identified by comparing the electrical (or optical) signals generated from the precursor possibly mixed with decomposed product with the electrical (or optical) signals for a known reference, e.g. the precursor in use and / or decomposed product. The amount of the decomposed product may increase with time with the progress of the decomposition in the precursor. The decomposed product concentration may be monitored with time, for example, by monitoring the electrical (or optical) signals that correspond to the chemical bonding or functional group that are not included in the precursor with time and may be used as a tool for quality control.

[0225] A contaminant may also be formed from the reaction between two or more precursors. For example, two or more precursors may be mixed in an ampoule, and one or more elements of a first precursor may react with one or more elements of a second precursor to form a reaction product. The reaction product may have different structures or chemical bonding from each of the first and second precursors, and the reaction product may have a similar structure or molecules (e.g. functional groups) from one of the first and second precursors. For example, the reaction product may have a different functional group that is not present in each of the first and second precursors. The reaction between the first and second precursors may progress with time and the reaction product, depending on the concentration, may modify a film deposited from these two or more precursors. The concentration of the contaminant may be monitored by comparing theLAMRP955WO-11528-1WO electrical (or optical) signals from the two or more precursors irradiated by at least one of IR, visible light, and UV radiation with electrical (or optical) signals calibrated for the two or more reference precursors. At least one of IR, visible light, and UV spectroscopy measurements may be used to discriminate between similar but not identical molecules that may result from impurities in manufacturing or decomposition.

[0226] In some embodiments, the concentrations of two or more precursors may be monitored to deposit a thin film having compositions as designed in horizontal and vertical directions. In one example, the concentrations of two or more precursors may be monitored to maintain the precursor amounts as designed throughout the deposition to achieve a film having a precise composition ratio between precursors across the entire substrate as designed. In another example, the concentrations of two or more precursors may be monitored to form a compositionally graded thin film. The concentrations of each of two or more precursors may be monitored to vary linearly or non-linearly with time during the deposition to form a film with a graded composition along the film thickness direction (i.e. vertical direction). In one example, for a film made of first and second precursors, the concentration of the first precursor may be monitored to be a maximum at the bottom of the film and then reduced linearly or non-linearly as the film thickness increases to have a minimum concentration at the top of the film. The concentration of the second precursor may be monitored to be a minimum at the bottom of the film and may linearly or non-linearly increase as the film thickness increases to a maximum concentration at the top of the film. An EUV resist having a vertical change in EUV absorbance may be obtained from monitoring and modifying as necessary the concentration of two or more precursors during deposition . Precursors

[0227] The precursors whose concentrations can be monitored according to some embodiments are described herein. In some embodiments, one or more precursors described herein may be selected and flowed into the deposition chamber to deposit a metal-containing EUV photoresist film, which may be subsequently exposed to an EUV radiation and developed to form a pattern. Embodiment 1 Precursor Description

[0228] In some embodiments, the precursor may be organometallic precursors that comprise at least one alkyl group on each metal atom that can survive the vapor-phase deposition reaction, while other ligands or ions coordinated to the metal can be replaced by the counter-reactants. Suitable organometallic precursors include those of the formula: M1aR1bL1c (I)LAMRP955WO-11528-1WO wherein: M1 is a metal with a high EUV absorption cross-section (e.g., equal to or greater than 1x107cm2 / mol), such as Sn, Sb, In, Bi, and combinations thereof; R1 is an alkyl (or halogen-substituted alkyl) group, such as CnH2n+1, preferably wherein n ≥ 3; L1 is a ligand, ion or other moiety which is reactive with the counter reactant; a ≥ 1 ; b ≥ 1 ; and c ≥ 1.

[0229] In addition, suitable organometallic precursors that do not have an alkyl group and instead have only ligands or ions coordinated to the metal atom that can be replaced by the counter- reactants, include: M2aL2c (II) wherein: M2 is a metal with a high EUV absorption cross-section which may be the same at M1 or different; L2 is a ligand, ion or other moiety which is reactive with the counter reactant; a ≥ 1 and c ≥ 1. Counter-reactants preferably have the ability to replace the reactive moieties ligands or ions (e.g., L1 in Formula I, above) so as to link at least two metal atoms via chemical bonding.

[0230] Counter-reactants can include water, peroxides (e.g., hydrogen peroxide), di- or polyhydroxy alcohols, fluorinated di- or polyhydroxy alcohols, fluorinated glycols, and other sources of hydroxyl moieties. In various embodiments, a counter-reactant reacts with the organometallic precursor by forming oxygen bridges between neighboring metal atoms. Other potential counter-reactants include hydrogen sulfide and hydrogen disulfide, which can crosslink metal atoms via sulfur bridges and bis(trimethylsilyl)tellurium which can crosslink metal atoms via tellurium bridges. In addition, hydrogen iodide may be utilized to incorporate iodine into the film.

[0231] In various embodiments, R1 may be fluorinated, e.g., having the formula CnFxH(2n+1). In various embodiments, R has at least one beta-hydrogen or beta-fluorine. For example, R1 may be selected from the group consisting of i-propyl, n-propyl, t-butyl, i-butyl, n-butyl, sec- butyl, n- pentyl, i-pentyl, t-pentyl, sec-pentyl, and mixtures thereof.

[0232] L1 or L2 may be any moiety readily displaced by a counter-reactant to generate a corresponding M-OH moiety, such as a moiety selected from the group consisting of amines (such as dialkylamino, monalkylamino), alkoxy, carboxylates, halogens, and mixtures thereof.

[0233] Organometallic precursors may be any of a wide variety of candidate metal-organic precursors. For example, where M is tin, such precursors include t-butyl tris(dimethylamino) tin, i-butyl tris(dimethylamino) tin, n-butyl tris(dimethylamino) tin, sec-butyl tris(dimethylamino) tin, i-propyl(tris)dimethylamino tin, n-propyl tris(diethylamino) tin, and analogous alkyl(tris)(t- butoxy) tin compounds such as t-butyl tris(t-butoxy) tin. In some embodiments, the organometallic precursors are partially fluorinated. In some embodiments, less reactive / more controllable leavingLAMRP955WO-11528-1WO groups such as t-butoxy are advantageously used. Dry Deposition of Gradient Films through ALD / CVD Methods (non-plasma)

[0234] One example system to produce graded Sn-based resists with varying alkyl groups involves the use of tetrakis(dimethylamino)tin and isopropyltris(dimethylamino)tin precursors and water as a counter- reactant. The tetrakis(dimethylamino)tin is initially introduced as a minor to significant component to produce a relatively dense component of Sn that is not bonded to an alkyl group (essentially SnO2 and Sn-OH derivatives). The ratio of tetrakis(dimethylamino)tin:isopropyltris(dimethylamino)tin precursors decreases as the film grows. This produces a film with an increasing amount of Sn-R bonds in the film toward the upper surface of the film. (An example of the increase in the absorption of a film produced by this process is described below). This process may be performed either by ALD or CVD methods.

[0235] Another example may be to add different metals to the system for enhanced absorption. For example, a gradient film with bismuth and tin metal centers may be synthesized using isopropyltris(dimethylamino)tin and tris(dimethylamino)bismuth. The ratio of tris(dimethylamino)bismuth:isopropyltris(dimethylamino)tin in the precursor flow is decreased as the film is deposited. This results in the bottom of the film containing more bismuth metal centers than the top of the film. Like Sn, Bi atoms exhibit extremely high EUV cross-section, but unlike Sn, even without a bulky, EUV labile substituent, appears less prone towards condensation to an intractable, binary metal oxide. As such, a process employing tris(dimethyamino)bismuth may be substantially superior to one based on tetrakis(dimethylamino)tin in some contexts or applications, as a substantially lower negative impact on both wet (aqueous and non-aqueous) and dry (e.g., HCl or HBr-based, such as described in our US Application No. 62 / 866,942, filed June 26, 2019, incorporated by reference herein for the purpose of describing applicable dry development techniques) development strategies is anticipated.

[0236] A related approach involving an absorption gradient targets the use of somewhat tin- based resist films using two precursors – both with alkyl groups – but one containing one or more alkyl ligands than the other. For example, isopropyltris(dimethylamino)tin and diisopropyldi(dimethylamino)tin can be used. Initially, a flow of the diisopropyldi(dimethylamino)tin is introduced during the film deposition and the ratio is increased relative to the flow of isopropyltris(dimethylamino)tin as the film is deposited. This results in a film with a higher amount of Sn bonded to two alkyl groups on the surface relative to the bottom of the film.LAMRP955WO-11528-1WO

[0237] Yet another strategy involves the introduction of an alternative (or additional) co-reactant to water for the introduction of an element with a far higher EUV absorption coefficient than oxygen. One example is the incorporation of tellurium. Bis(trimethyl)tellurium offers a viable option as a gas phase co-reactant. In some embodiments, this can be combined with an alkyltin precursor such as tris(t-butoxy)isopropyltin and water. In this way thin films absorbing 80% of EUV radiation or higher can be produced with little reduction of reactive Sn-alkyl moieties near the bottom of the films. During an initial portion of the deposition, the co-reactant includes both water and bis(trimethyl)tellurium. The initial film that forms on the underlying substrate has substantial amounts of both tin and tellurium. As the deposition progresses, the ratio of bis(trimethyl)tellurium:tris(t-butoxy)isopropyltin decreases, thereby forming film that has relatively less tellurium and relatively more tin, as compared to the initial portion of the film. In various embodiments, the film may transition to a tellurium-free composition near the top surface of the film, for example to help minimize contamination and handling issues.

[0238] A similar strategy (also employing tris(t-butoxy)isopropyltin and water as the base chemistry), can be employed for the gradient introduction of iodine using low concentrations of HI (or suitable alkyl iodide) together with water to achieve gradient doping with iodine near the interface.

[0239] While this section refers to non-plasma methods for dry deposition of gradient films, it is understood that any of the strategies can be applied to plasma-based deposition methods, as well. Embodiment 2

[0240] In some embodiments, a sensitized film can be formed using any useful precursor to provide the EUV resist material and the EUV sensitizer. In some embodiments, a non-limiting precursor may incorporate an EUV sensitizer. A precursor can include an organometallic material having an alkyl group (black) and a plurality of ligands (gray). In addition, the alkyl group can incorporate an EUV sensitizer in the β-position (left in Figure 4) or in the α-position (right in Figure 4). In some embodiments, upon EUV exposure, the alkyl group can be released by way of an elimination reaction. Additional precursors for EUV sensitizers and EUV resist materials are described herein. EUV sensitizers

[0241] The EUV sensitizer can be any useful compound having enhanced photoabsorption. In some embodiments, the compound has a photoabsorption cross-section of from about 9E+04 cm2 / g to about 1.2E+05 cm2 / g (e.g., at 93.4 eV or at 92 eV, which relates to absorption of EUV light at about 13.5 nm).LAMRP955WO-11528-1WO

[0242] In one embodiment, the EUV sensitizer is provided in a gas form. In other embodiments, the compound is characterized by a density that provides a gas at standard temperature and pressure, e.g., a density of less than about 5 g / cm3or a density of from about 0.002 g / cm3to about 5 g / cm3. In particular embodiments, the EUV sensitizer has a photoabsorption cross-section of from about 9E+04 cm2 / g to about 1.2E+05 cm2 / g (e.g., at 93.4 eV) and a density of from about 0.002 g / cm3to about 5 g / cm3at standard temperature and pressure.

[0243] Non-limiting EUV sensitizers can include any compound having or being Xe or I. Any useful isotopes of Xe and I can be employed. In particular embodiments, the EUV sensitizer is133Xe,136Xe, or129Xe. In other embodiments, two or more isotopes are employed in combination. In other embodiments, the EUV sensitizer is formed by using an iodine-containing precursor, such as RISn(NR2)3, wherein RIis an optionally substituted alkyl including one or more iodo and each R is independently alkyl. In some embodiment, the iodine-containing precursor is (1-iodo iso propyl) tris (dimethyl amino) tin, (2-iodo iso propyl) tris (dimethyl amino) tin, (2-iodo iso propyl) tris (dimethyl amino) tin, (2-iodo butyl, 1-(tris (dimethyl amino) tin)), or (3-iodo butyl, 1-(tris (dimethyl amino) tin)).

[0244] In some embodiments, the EUV sensitizer is formed by using an iodine-containing precursor, such as I2, HI, an organometallic precursor comprising an iodo-substituted alkyl group, or any metal-containing precursor described herein that further includes an iodo substitution. In particular embodiments, the metal-containing precursor having iodine can include any formula described herein (e.g., formula (I), (II), (IIa), (III), (IV), (V), (VI), (VII), or (VIII), in which at least one X is I, at least one R is an iodo-substituted alkyl (e.g., α-substituted alkyl or β-substituted alkyl), and / or at least one L includes an iodo atom. In some embodiments, the iodo-substituted alkyl (e.g., for R or as employed in L) can be methyl, ethyl, n-propyl, i-propyl, t-butyl, t-pentyl, t- hexyl, cyclohexyl, i-propyl, i-butyl, sec-butyl, n-butyl, n-pentyl, or n-hexyl or derivatives thereof having one or more iodo substitutions. The iodo-substituted alkyl can be a C1-10alkyl including one, two, three, four, or more iodo substitutions. In other embodiments, L can be iodo, an iodo- substituted alkyl (e.g., any described herein), an amino (e.g., -NR1R2, in which each of R1and R2can be H or alkyl, such as any described herein, and in which at least one of R1or R2includes an iodo-substituted alkyl), alkoxy (e.g., -OR, in which R is an iodo-substituted alkyl), or any organic moiety including one or more iodo substitutions.

[0245] Yet additional metal-containing precursors including iodine can be SnI4, (CH3)3SnI, triisopropyl(methyl(iodo)ethyl)stannane, tris(dimethylamino)(methyl(iodo)ethyl)stannane, or tris(dimethylamino)(1-methyl-2-iodo-ethyl)stannane. In other embodiments, the metal-containing precursor can be Sn(NR2)4, SnR(NR2)3, SnR2(NR2)2, or SnR3(NR2), wherein each of R isLAMRP955WO-11528-1WO independently methyl, ethyl, n-propyl, or i-propyl, and at least one R is an iodo-substituted methyl, ethyl, n-propyl, or i-propyl (e.g., having one or more iodo substitutions).

[0246] The EUV sensitizer or a precursor thereof can be provided in any useful form. In one embodiment, the EUV sensitizer or its precursor is provided in gas form. In particular embodiments, the EUV sensitizer or its precursor is provided as a vapor in an inert carrier gas (e.g., a flow of iodine vapor or xenon vapor in N2). Non-limiting carrier gases include, e.g., H2, He, Ar, or N2. In other embodiments, the EUV sensitizer or its precursor itself is provided as a gas (e.g., as I2 or Xe). The EUV sensitizer or its precursor can also be provided as a plasma (e.g., an RF plasma or any other plasma condition described herein), which can be used to create a reactive species (e.g., reactive I2, reactive atomic I species, reactive Xe, or a reactive atomic Xe species). EUV resist materials

[0247] The methods herein can include any useful EUV resist material to provide a sensitized film (e.g., an imaging layer). The EUV resist material can be composed or of include a metal (e.g., tin (Sn), tellurium (Te), bismuth (Bi), antimony (Sb), or indium (In)); a metal oxide, such as tin oxide (e.g., SnO2), tellurium oxide (e.g., TeO2), bismuth oxide (e.g., Bi2O3), antimony oxide (e.g., Sb2O3), or indium oxide (e.g., In2O3); an alloy, such as tin alloys (e.g., a tin telluride alloy, an antimony telluride alloy (e.g., Sb2Te3), a bismuth telluride alloy (e.g., Bi2Te3), or a tin bismuth alloy, including an alloy having 60% tin or above); or a combination thereof. In some embodiments, the EUV resist material includes an organometal oxide (e.g., RM(MO)n, in which M is a metal and R is an organic moiety having one or more carbon atoms, such as in alkyl, alkylamino, or alkoxy).

[0248] The EUV resist material can be formed by using one or more metal-containing precursors, optionally in the presence of one or more counter-reactants. In particular embodiments, the metal-containing precursor includes one or more ligands (e.g., labile ligands) that can be removed or cleaved by EUV radiation. Furthermore, the precursor can be deposited (e.g., using any deposition process described herein) and optionally processed (e.g., baked, treated, annealed, exposed to plasma, etc.) to provide a metal oxide layer (e.g., a layer including a network of metal oxide bonds, which may include other non-metal and non-oxygen groups).

[0249] Non-limiting metal-containing precursors can include a metal halide, a capping agent, or an organometallic agent. In a precursor, the metal (or M) can be any metal with a high EUV absorption cross-section (e.g., equal to or greater than 1x107cm2 / mol).LAMRP955WO-11528-1WO

[0250] The layers herein (e.g., an imaging layer, a resist film, and / or a sensitized film) may include an element (e.g., a metal atom or a non-metal atom) having a high photoabsorption cross- section, such as equal to or greater than 1x107cm2 / mol. Such elements can be provided by depositing one or more precursor(s) to provide the layer.

[0251] The layers, either alone or together, can be considered a film. In some embodiments, the film is a radiation-sensitive film (e.g., an EUV-sensitive film). This film, in turn, can serve as an EUV resist, as further described herein. In particular embodiments, the layer or film can include one or more ligands (e.g., EUV labile ligands) that can be removed, cleaved, or cross-linked by radiation (e.g., EUV or DUV radiation).

[0252] The precursor can provide a patternable film that is sensitive to radiation (or a patterning radiation-sensitive film or a photopatternable film). Such radiation can include EUV radiation, DUV radiation, or UV radiation that is provided by irradiating through a patterned mask, thereby being a patterned radiation. The film itself can be altered by being exposed to such radiation, such that the film is radiation-sensitive or photosensitive. In particular embodiments, the precursor is an organometallic compound, which includes at least one metal center. In some embodiments, the precursor may not be chemically decomposed or damaged by the IR radiation from a IR radiation source.

[0253] The precursor can have any useful number and type of ligand(s). In some embodiments, the ligand can be characterized by its ability to react in the presence of a counter-reactant or in the presence of patterned radiation. For instance, the precursor can include a ligand that reacts with a counter-reactant, which can introduce linkages between metal centers (e.g., an -O- linkage). In another instance, the precursor can include a ligand that eliminates in the presence of patterned radiation. Such an EUV labile ligand can include branched or linear alkyl groups having a beta- hydrogen, as well as any described herein for R in formula (I) or (II). In some embodiments, the EUV labile ligand (e.g., R in formula (I) or (II)) includes iodo.

[0254] The precursor can be any useful metal-containing precursor, such as an organometallic agent, a metal halide, or a capping agent (e.g., as described herein). In a non-limiting instance, the precursor includes a structure having formula (I): MaRb(I), wherein: M is a metal or an atom having a high EUV absorption cross-section; each R is, independently, H, halo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl,LAMRP955WO-11528-1WO optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkanoyloxy, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, oxo, an anionic ligand, a neutral ligand, or a multidentate ligand; a ≥ 1; and b ≥ 1.

[0255] In another non-limiting instance, the precursor includes a structure having formula (II): MaRbLc(II), wherein: M is a metal or an atom having a high EUV absorption cross-section; each R is, independently, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted alkoxy, or L; each L is, independently, a ligand, an anionic ligand, a neutral ligand, a multidentate ligand, ion, or other moiety that is reactive with a counter-reactant, in which R and L with M, taken together, can optionally form a heterocyclyl group or in which R and L, taken together, can optionally form a heterocyclyl group; a ≥ 1; b ≥ 1; and c ≥ 1.

[0256] In some embodiments, each ligand within the precursor can be one that is reactive with a counter-reactant. In one instance, the precursor includes a structure having formula (II), in which each R is, independently, L. In another instance, the precursor includes a structure having formula (IIa): MaLc (IIa), wherein: M is a metal or an atom having a high EUV absorption cross-section; each L is, independently, a ligand, ion, or other moiety that is reactive with a counter-reactant, in which two L, taken together, can optionally form a heterocyclyl group; a ≥ 1; and c ≥ 1. In particular embodiments of formula (IIa), a is 1. In further embodiments, c is 2, 3, or 4.

[0257] For any formula herein, M can be a metal or a metalloid or an atom with a high patterning radiation-absorption cross-section (e.g., an EUV absorption cross-section that is equal to or greater than 1x107cm2 / mol). In some embodiments, M is tin (Sn), bismuth (Bi), tellurium (Te), cesium (Cs), antimony (Sb), indium (In), molybdenum (Mo), hafnium (Hf), iodine (I), zirconium (Zr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), silver (Ag), platinum (Pt), and lead (Pb). In further embodiments, M is Sn, a is 1, and c is 4 in formula (I), (II), or (IIa). In other embodiments, M is Sn, a is 1, and c is 2 in formula (I), (II), or (IIa). In particular embodiments,LAMRP955WO-11528-1WO M is Sn(II) (e.g., in formula (I), (II), or (IIa)), thereby providing a precursor that is a Sn(II)-based compound. In other embodiments, M is Sn(IV) (e.g., in formula (I), (II), or (IIa)), thereby providing a precursor that is a Sn(IV)-based compound. In particular embodiments, the precursor includes iodine (e.g., as in periodate, an iodo-substituted alkyl, or an iodo-substituted amino).

[0258] For any formula herein, each R is, independently, H, halo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy (e.g., -OR1, in which R1can be optionally substituted alkyl), optionally substituted alkanoyloxy, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, oxo, an anionic ligand (e.g., oxido, chlorido, hydrido, acetate, iminodiacetate, propanoate, butanoate, benzoate, etc.), a neutral ligand, or a multidentate ligand. In some embodiments, R is iodo or substituted with iodo.

[0259] In some embodiments, the optionally substituted amino is -NR1R2, in which each R1and R2is, independently, H or alkyl; or in which R1and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein. In other embodiments, the optionally substituted bis(trialkylsilyl)amino is -N(SiR1R2R3)2, in which each R1, R2, and R3is, independently, optionally substituted alkyl. In yet other embodiments, the optionally substituted trialkylsilyl is -SiR1R2R3, in which each R1, R2, and R3is, independently, optionally substituted alkyl. In some embodiments, R1and / or R2is iodo or substituted with iodo.

[0260] In other embodiments, the formula includes a first R (or first L) that is -NR1R2and a second R (or second L) that is -NR1R2, in which each R1and R2is, independently, H or optionally substituted alkyl; or in which R1from a first R (or first L) and R1from a second R (or second L), taken together with the nitrogen atom and the metal atom to which each are attached, form a heterocyclyl group, as defined herein. In yet other embodiments, the formula includes a first R that is -OR1and a second R that is -OR1, in which each R1is, independently, H or optionally substituted alkyl; or in which R1from a first R and R1from a second R, taken together with the oxygen atom and the metal atom to which each are attached, form a heterocyclyl group, as defined herein.

[0261] In some embodiments, at least one of R or L (e.g., in formula (I), (II), or (IIa)) is optionally substituted alkyl. Non-limiting alkyl groups include, e.g., CnH2n+1, where n is 1, 2, 3, or greater, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl. In various embodiments, R or L has at least one beta-hydrogen or beta-fluorine or beta-iodine. InLAMRP955WO-11528-1WO other embodiments, at least one of R or L is a halo-substituted alkyl (e.g., a fluoro-substituted alkyl and / or an iodo-substituted alkyl).

[0262] In some embodiments, each R or L or at least one R or L (e.g., in formula (I), (II), or (IIa)) is halo. In particular, the precursor can be a metal halide. Non-limiting metal halides include SnBr4, SnCl4, SnI4, and SbCl3.

[0263] In some embodiments, each R or L or at least one R or L (e.g., in formula (I), (II), or (IIa)) can include a nitrogen atom. In particular embodiments, one or more R or L can be optionally substituted amino, an optionally substituted monoalkylamino (e.g., -NR1H, in which R1is optionally substituted alkyl), an optionally substituted dialkylamino (e.g., -NR1R2, in which each R1and R2is, independently, optionally substituted alkyl), or optionally substituted bis(trialkylsilyl)amino. Non-limiting R and L substituents can include, e.g., -NMe2, -NHMe, - NEt2, -NHEt, -NMeEt, -N(t-Bu)-[CHCH3]2-N(t-Bu)- (tbba), -N(SiMe3)2, and -N(SiEt3)2.

[0264] In some embodiments, each R or L or at least one R or L (e.g., in formula (I), (II), or (IIa)) can include a silicon atom. In particular embodiments, one or more R or L can be optionally substituted trialkylsilyl or optionally substituted bis(trialkylsilyl)amino. Non-limiting R or L substituents can include, e.g., -SiMe3, -SiEt3, -N(SiMe3)2, and -N(SiEt3)2.

[0265] In some embodiments, each R or L or at least one R or L (e.g., in formula (I), (II), or (IIa)) can include an oxygen atom. In particular embodiments, one or more R or L can be optionally substituted alkoxy or optionally substituted alkanoyloxy. Non-limiting R or L substituents include, e.g., methoxy, ethoxy, isopropoxy (i-PrO), t-butoxy (t-BuO), acetate (-OC(O)-CH3), and -O=C(CH3)-CH=C(CH3)-O- (acac).

[0266] Any formulas herein can include one or more neutral ligands. Non-limiting neutral ligands include an optionally substituted amine (e.g., NR3or R2N-Ak-NR2, in which each R can be, independently, H, optionally substituted alkyl, optionally substituted hydrocarbyl, or optionally substituted aryl, and Ak is optionally substituted alkylene), an optionally substituted phosphine (e.g., PR3 or R2P-Ak-PR2, in which each R can be, independently, H, optionally substituted alkyl, optionally substituted hydrocarbyl, or optionally substituted aryl, and Ak is optionally substituted alkylene), an optionally substituted ether (e.g., OR2, in which each R can be, independently, H, optionally substituted alkyl, optionally substituted hydrocarbyl, or optionally substituted aryl), an optionally substituted alkyl, an optionally substituted alkene, an optionally substituted alkyne, an optionally substituted benzene, oxo, or carbon monoxide.

[0267] Any formulas herein can include one or more multidentate (e.g., bidentate) ligands. Non- limiting multidentate ligand include a diketonate (e.g., acetylacetonate (acac) or -OC(R1)-Ak-LAMRP955WO-11528-1WO (R1)CO- or -OC(R1)-C(R2)-(R1)CO-), a bidentate chelating dinitrogen (e.g., -N(R1)-Ak-N(R1)- or -N(R3)-CR4-CR2=N(R1)-), an aromatic (e.g., -Ar-), an amidinate (e.g., -N(R1)-C(R2)-N(R1)-), an aminoalkoxide (e.g., -N(R1)-Ak-O- or -N(R1)2-Ak-O-), a diazadienyl (e.g., -N(R1)-C(R2)-C(R2)- N(R1)-), a cyclopentadienyl, a pyrazolate, an optionally substituted heterocyclyl, an optionally substituted alkylene, or an optionally substituted heteroalkylene. In particular embodiments, each R1is, independently, H, optionally substituted alkyl, optionally substituted haloalkyl, or optionally substituted aryl; each R2is, independently, H or optionally substituted alkyl; R3and R4, taken together, forms an optionally substituted heterocyclyl; Ak is optionally substituted alkylene; and Ar is optionally substituted arylene.

[0268] In particular embodiments, the precursor includes tin. In some embodiments, the tin precursor includes SnR or SnR2or SnR4or R3SnSnR3, wherein each R is, independently, H, halo, optionally substituted C1-12 alkyl, optionally substituted C1-12 alkoxy, optionally substituted amino (e.g., -NR1R2), optionally substituted C2-12alkenyl, optionally substituted C2-12alkynyl, optionally substituted C3-8 cycloalkyl, optionally substituted aryl, cyclopentadienyl, optionally substituted bis(trialkylsilyl)amino (e.g., -N(SiR1R2R3)2), optionally substituted alkanoyloxy (e.g., acetate), a diketonate (e.g., -OC(R1)-Ak-(R2)CO-), or a bidentate chelating dinitrogen (e.g., -N(R1)-Ak- N(R1)-). In particular embodiments, each R1, R2, and R3is, independently, H or C1-12 alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl); and Ak is optionally substituted C1-6alkylene. In particular embodiments, each R is, independently, halo, optionally substituted C1-12 alkoxy, optionally substituted amino, optionally substituted aryl, cyclopentadienyl, or a diketonate. Non- limiting tin precursors include SnF2, SnH4, SnBr4, SnCl4, SnI4, tetramethyl tin (SnMe4), tetraethyl tin (SnEt4), trimethyl tin chloride (SnMe3Cl), dimethyl tin dichloride (SnMe2Cl2), methyl tin trichloride (SnMeCl3), tetraallyltin, tetravinyl tin, hexaphenyl ditin (IV) (Ph3Sn-SnPh3, in which Ph is phenyl), dibutyldiphenyltin (SnBu2Ph2), trimethyl(phenyl) tin (SnMe3Ph), trimethyl (phenylethynyl) tin, tricyclohexyl tin hydride, tributyl tin hydride (SnBu3H), dibutyltin diacetate (SnBu2(CH3COO)2), tin(II) acetylacetonate (Sn(acac)2), SnBu3(OEt), SnBu2(OMe)2, SnBu3(OMe), Sn(t-BuO)4, Sn(n-Bu)(t-BuO)3, tetrakis(dimethylamino)tin (Sn(NMe2)4), tetrakis(ethylmethylamino)tin (Sn(NMeEt)4), tetrakis(diethylamino)tin(IV) (Sn(NEt2)4), (dimethylamino)trimethyl tin(IV) (Sn(Me)3(NMe2), Sn(i-Pr)(NMe2)3, Sn(n-Bu)(NMe2)3, Sn(s- Bu)(NMe2)3, Sn(i-Bu)(NMe2)3, Sn(t-Bu)(NMe2)3, Sn(t-Bu)2(NMe2)2, Sn(t-Bu)(NEt2)3, Sn(tbba), Sn(II) (1,3-bis(1,1-dimethylethyl)-4,5-dimethyl-(4R,5R)-1,3,2-diazastannolidin-2-ylidene), or bis[bis(trimethylsilyl)amino] tin (Sn[N(SiMe3)2]2).

[0269] In other embodiments, the precursor includes bismuth, such as in BiR3, wherein each R is, independently, halo, optionally substituted C1-12alkyl, mono-C1-12alkylamino (e.g., -NR1H),LAMRP955WO-11528-1WO di-C1-12 alkylamino (e.g., -NR1R2), optionally substituted aryl, optionally substituted bis(trialkylsilyl)amino (e.g., -N(SiR1R2R3)2), or a diketonate (e.g., -OC(R4)-Ak-(R5)CO-). In particular embodiments, each R1, R2, and R3is, independently, C1-12 alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl); and each R4and R5is, independently, H or optionally substituted C1-12 alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl). Non-limiting bismuth precursors include BiCl3, BiMe3, BiPh3, Bi(NMe2)3, Bi[N(SiMe3)2]3, and Bi(thd)3, in which thd is 2,2,6,6- tetramethyl-3,5-heptanedionate.

[0270] In other embodiments, the precursor includes tellurium, such as TeR2 or TeR4, wherein each R is, independently, halo, optionally substituted C1-12alkyl (e.g., methyl, ethyl, isopropyl, t- butyl, and neopentyl), optionally substituted C1-12 alkoxy, optionally substituted aryl, hydroxyl, oxo, or optionally substituted trialkylsilyl. Non-limiting tellurium precursors include dimethyl tellurium (TeMe2), diethyl tellurium (TeEt2), di(n-butyl) tellurium (Te(n-Bu)2), di(isopropyl) tellurium (Te(i-Pr)2), di(t-butyl) tellurium (Te(t-Bu)2), t-butyl tellurium hydride (Te(t-Bu)(H)), Te(OEt)4, bis(trimethylsilyl)tellurium (Te(SiMe3)2), and bis(triethylsilyl) tellurium (Te(SiEt3)2).

[0271] Yet other precursors and non-limiting substituents are described herein. For instance, precursors can be any having a structure of formulas (I), (II), and (IIa), as described above; or formulas (III), (IV), (V), (VI), (VII), or (VIII), as described below. Any of the substituents M, R, X, or L, as described herein, can be employed in any of formulas (I), (II), (IIa), (III), (IV), (V), (VI), (VII), or (VIII).

[0272] A non-limiting precursor includes a metal halide having the following formula (III): MXn, (III) in which M is a metal, X is halo (e.g., fluoro, chloro, bromo, or iodo), and n is 2 to 4, depending on the selection of M. Non-limiting metals for M include Sn, Te, Bi, Sb, or In. Non-limiting metal halides include SnBr4, SnCl4, SnI4, and SbCl3.

[0273] Another non-limiting precursor includes the following formula (IV): MRn, (IV) in which M is a metal; each R is independently H, an optionally substituted alkyl, amino (e.g., -NR2, in which each R is independently alkyl), optionally substituted (trialkylsilyl)amido (e.g., -N(SiR3), in which each R is independently alkyl), or an optionally substituted trialkylsilyl (e.g., -SiR3, in which each R is independently alkyl); and n is 2 to 4, depending on the selection of M. Non-limiting metals for M include Sn, Te, Bi, Sb, or In. The alkyl group may be CnH2n+1, where n is 1, 2, 3, or greater. Non-limiting organometallic agents include Sn(Me)4, Sn(Et)4, TeRn, RTeR, RTeH, t-butyl tellurium hydride (Te(t-Bu)(H)), dimethyl tellurium (TeMe2), di(t-butyl)LAMRP955WO-11528-1WO tellurium (Te(t-Bu)2), di(isopropyl)tellurium (Te(i-Pr)2), bis(trimethylsilyl)tellurium (Te(SiMe3)2), bis(triethylsilyl) tellurium (Te(SiEt3)2), tris(bis(trimethylsilyl)amido) bismuth (Bi[N(SiMe3)2]3), Sb(NMe2)3, and the like.

[0274] A metal-containing precursor can include a capping agent having the following formula (V): MLn, (V) in which M is a metal; each L is independently an optionally substituted alkyl, amino (e.g., -NR1R2, in which each of R1and R2can be H or alkyl, such as any described herein), alkoxy (e.g., -OR, in which R is alkyl, such as any described herein), halo, or other organic substituent; and n is 2 to 4, depending on the selection of M. Non-limiting metals for M include Sn, Te, Bi, Sb, or In. Non- limiting ligands include dialkylamino (e.g., dimethylamino, methylethylamino, and diethylamino), alkoxy (e.g., t-butoxy and isopropoxy), halo (e.g., F, Cl, Br, and I), or other organic substituents (e.g., acetylacetone or N2,N3-di-tertbutyl-butane-2,3-diamino). Non-limiting capping agents include SnCl4; SnI4; Sn(NR2)4, wherein each of R is independently methyl or ethyl; or Sn(t-BuO)4. In some embodiments, multiple types of ligands are present.

[0275] A metal-containing precursor can include a hydrocarbyl-substituted capping agent having the following formula (VI): RnMXm, (VI) wherein M is a metal, R is a C2-10 alkyl or substituted alkyl having a beta-hydrogen, and X is a suitable leaving group upon reaction with a hydroxyl group of the exposed hydroxyl groups. In various embodiments, n = 1 to 3, and m = 4 – n, 3 – n, or 2 – n, so long as m > 0 (or m ≥ 1). For example, R may be t-butyl, t-pentyl, t-hexyl, cyclohexyl, isopropyl, isobutyl, sec-butyl, n-butyl, n- pentyl, n-hexyl, or derivatives thereof having a heteroatom substituent in the beta position. Suitable heteroatoms include halogen (F, Cl, Br, or I), or oxygen (-OH or -OR). X may be dialkylamino (e.g., dimethylamino, methylethylamino, or diethylamino), alkoxy (e.g., t-butoxy, isopropoxy), halo (e.g., F, Cl, Br, or I), or another organic ligand. Examples of hydrocarbyl-substituted capping agents include t-butyltris(dimethylamino)tin (Sn(t-Bu)(NMe2)3), n-butyltris(dimethylamino)tin (Sn(n-Bu)(NMe2)3), t-butyltris(diethylamino)tin (Sn(t-Bu)(NEt2)3), di(t- butyl)di(dimethylamino)tin (Sn(t-Bu)2(NMe2)2), sec-butyltris(dimethylamino)tin (Sn(s- Bu)(NMe2)3), n-pentyltris(dimethylamino)tin (Sn(n-pentyl)(NMe2)3), i-butyltris(dimethylamino) tin (Sn(i-Bu)(NMe2)3), i-propyltris(dimethylamino)tin (Sn(i-Pr)(NMe2)3), t-butyltris(t-butoxy)tin (Sn(t-Bu)(t-BuO)3), n-butyl(tris(t-butoxy)tin (Sn(n-Bu)(t-BuO)3), or isopropyltris(t-butoxy)tin (Sn(i-Pr)(t-BuO)3).LAMRP955WO-11528-1WO

[0276] In various embodiments, a metal-containing precursor includes at least one alkyl group on each metal atom that can survive the vapor-phase reaction, while other ligands or ions coordinated to the metal atom can be replaced by the counter-reactants. Accordingly, another non- limiting metal-containing precursor includes an organometallic agent having the formula (VII): MaRbLc, (VII) in which M is a metal; R is an optionally substituted alkyl; L is a ligand, ion, or other moiety which is reactive with the counter-reactant; a ≥ 1; b ≥ 1; and c ≥ 1. In particular embodiments, a = 1, and b + c = 4. In some embodiments, M is Sn, Te, Bi, Sb, or In. In particular embodiments, each L is independently amino (e.g., -NR1R2, in which each of R1and R2can be H or alkyl, such as any described herein), alkoxy (e.g., -OR, in which R is alkyl, such as any described herein), or halo (e.g., F, Cl, Br, or I). Non-limiting agents include SnMe3Cl, SnMe2Cl2, SnMeCl3, SnMe(NMe2)3, SnMe3(NMe2), and the like.

[0277] In other embodiments, the non-limiting metal-containing precursor includes an organometallic agent having the formula (VIII): MaLc, (VIII) in which M is a metal; L is a ligand, ion, or other moiety which is reactive with the counter- reactant; a ≥ 1; and c ≥ 1. In particular embodiments, c = n – 1, and n is 2, 3, or 4. In some embodiments, M is Sn, Te, Bi, Sb, or In. Counter-reactants preferably have the ability to replace the reactive moieties ligands or ions (e.g., L in formulas herein) so as to link at least two metal atoms via chemical bonding.

[0278] In any embodiment herein, R can be an optionally substituted alkyl (e.g., C1-10 alkyl). In one embodiment, alkyl is substituted with one or more halo (e.g., halo-substituted C1-10 alkyl, including one, two, three, four, or more halo, such as F, Cl, Br, or I). Non-limiting R substituents include CnH2n+1, preferably wherein n ≥ 3; and CnFxH(2n+1-x), wherein 2n+1 ≤ x ≤ 1 and n ≥ 1; and CnIxH(2n+1-x), wherein 2n+1 ≤ x ≤ 1 and n ≥ 1. In various embodiments, R has at least one beta- hydrogen or beta-fluorine or beta-iodine. For example, R may be selected from the group consisting of i-propyl, n-propyl, t-butyl, i-butyl, n-butyl, sec-butyl, n-pentyl, i-pentyl, t-pentyl, sec- pentyl, and mixtures thereof.

[0279] In any embodiment herein, L may be any moiety readily displaced by a counter-reactant to generate an M-OH moiety, such as a moiety selected from the group consisting of an amino (e.g., -NR1R2, in which each of R1and R2can be H or alkyl, such as any described herein), alkoxy (e.g., -OR, in which R is alkyl, such as any described herein), carboxylates, halo (e.g., F, Cl, Br, or I), and mixtures thereof.LAMRP955WO-11528-1WO

[0280] Yet other non-limiting organometallic agents include SnMeCl3, (N2,N3-di-t-butyl- butane-2,3-diamido) tin(II) (Sn(tbba)), bis(bis(trimethylsilyl)amido) tin(II), tetrakis(dimethylamino) tin(IV) (Sn(NMe2)4), t-butyl tris(dimethylamino) tin (Sn(t- butyl)(NMe2)3), i-butyl tris(dimethylamino) tin (Sn(i-Bu)(NMe2)3), n-butyl tris(dimethylamino) tin (Sn(n-Bu)(NMe2)3), sec-butyl tris(dimethylamino) tin (Sn(s-Bu)(NMe2)3), i- propyl(tris)dimethylamino tin (Sn(i-Pr)(NMe2)3), n-propyl tris(diethylamino) tin (Sn(n- Pr)(NEt2)3), and analogous alkyl(tris)(t-butoxy) tin compounds, such as t-butyl tris(t-butoxy) tin (Sn(t-Bu)(t-BuO)3), t-butyl tellurium hydride, di(t-butyl) tellurium, di(i-propyl)tellurium, or bis(trimethylsilyl)tellurium. In some embodiments, the organometallic agents are partially fluorinated.

[0281] In some embodiments of this disclosure, such precursors can be employed alone to form an EUV resist material or can be used in combination with one or more counter-reactants. Counter- reactants preferably have the ability to replace the reactive moieties ligands or ions (e.g., L in formulas herein) so as to link at least two metal atoms via chemical bonding. Exemplary counter- reactants include oxygen-containing counter-reactants, such as O2, O3, water, peroxides (e.g., hydrogen peroxide), oxygen plasma, water plasma, alcohols, dihydroxy alcohols, polyhydroxy alcohols, fluorinated dihydroxy alcohol, fluorinated polyhydroxy alcohols, fluorinated glycols, formic acid, and other sources of hydroxyl moieties, as well as combinations thereof. In various embodiments, a counter-reactant reacts with the organometallic precursor by forming oxygen bridges between neighboring metal atoms. Other potential counter-reactants include hydrogen sulfide and hydrogen disulfide, which can crosslink metal atoms via sulfur bridges, and bis(trimethylsilyl)tellurium, which can crosslink metal atoms via tellurium bridges. In addition, hydrogen iodide may be utilized to incorporate iodine into the film.

[0282] In some embodiments of this disclosure, furthermore, two or more different precursors can be employed within the sensitized film. For instance, two or more of any metal-containing precursors herein can be employed, in which one precursor includes an EUV sensitizer and the other does not. In one non-limiting instance, tin telluride can be formed by employing tin precursor including an NR2 ligand with RTeH, RTeD, or R2Te precursors, in which R is an alkyl, particularly t-butyl or i-propyl. In another instance, a metal telluride can be formed by using a first metal precursor including an alkoxy or a halo ligand (e.g., SbCl3) with a tellurium-containing precursor including a trialkylsilyl ligand (e.g., bis(trimethylsilyl)tellurium).

[0283] In some embodiments of this disclosure, the EUV resist material or a precursor thereof can be provided in any useful form. In one embodiment, the EUV resist material or its precursor is provided in gas form. In particular embodiments, the EUV resist material or its precursor isLAMRP955WO-11528-1WO provided as a vapor in an inert carrier gas (e.g., H2, He, Ar, or N2). In other embodiments, the EUV resist material or its precursor is provided as a gas. The EUV resist material or its precursor can also be provided as a plasma (e.g., an RF plasma or any other plasma condition described herein), which can be used to create reactive species. Embodiment 3 Metal precursors

[0284] In some embodiments, metal precursor(s) and organic precursor(s) may be deposited to form a patterning radiation-sensitive film (e.g., an EUV-sensitive film). This film, in turn, can serve as an EUV resist. In particular embodiments, the film can include one or more ligands (e.g., EUV labile ligands) that can be removed, cleaved, or cross-linked by radiation (e.g., EUV or DUV radiation), in which such ligands can be present within the metal-containing layer (e.g., as a ligand for a metal precursor) or within the organic layer (e.g., as an organic substituent).

[0285] The metal precursor can include any precursor (e.g., described herein) that provides a patternable film that is sensitive to radiation (or a patterning radiation-sensitive film or a photopatternable film). Such radiation can include EUV radiation, DUV radiation, or UV radiation that is provided by irradiating through a patterned mask, thereby being a patterning radiation. The film itself can be altered by being exposed to such radiation, such that the film is radiation-sensitive or photosensitive. In particular embodiments, the metal precursor is an organometallic compound, which includes at least one metal center. In other embodiments, the film obtained from the metal precursor is characterized by a Beer’s absorption coefficient α of more than about 6 µm-1(e.g., more than about 7 µm-1, 8 µm-1, 9 µm-1, or 10 µm-1) at the wavelength of the patterning radiation being exposed to the film.

[0286] The organic precursor, itself, can also enhance UV / DUV / EUV sensitivity of the film (e.g., by increasing UV / DUV / EUV absorptivity) or enhance contrast selectivity during development. Furthermore, an organic moiety within the organic layer can be reactive in the presence of patterning radiation, such as by undergoing removal or elimination from the metal center or by reacting or polymerizing with other moieties within the film.

[0287] The metal precursor can have any useful number and type of ligand(s). In some embodiments, at least one ligand can react with the organic precursor. In other embodiments, the ligand can be characterized by its ability to react in the presence of a counter-reactant or in the presence of patterning radiation. For instance, the metal precursor can include a ligand that reacts with a counter-reactant, which can introduce linkages between metal centers (e.g., an -O- linkage).LAMRP955WO-11528-1WO Such a ligand (e.g., dialkylamino groups or alkoxy groups) could, in some instances, also react with an organic precursor. In another instance, the metal precursor can include a ligand that eliminates in the presence of patterning radiation. Such an EUV labile ligand can include branched or linear alkyl groups having a beta-hydrogen, as well as any described herein for R in formula (I) or (II).

[0288] The metal precursor can be any useful metal-containing precursor, such as an organometallic agent, a metal halide, or a capping agent (e.g., as described herein). In a non- limiting instance, the metal precursor includes a precursor having formulas (I), (II), or (IIa), for example, described in Embodiment 2.

[0289] Any formulas herein can include one or more neutral ligands. Non-limiting neutral ligands include an optionally substituted amine (e.g., NR3 or R2N-Ak-NR2, in which each R can be, independently, H, optionally substituted alkyl, optionally substituted hydrocarbyl, or optionally substituted aryl, and Ak is optionally substituted alkylene), an optionally substituted phosphine (e.g., PR3or R2P-Ak-PR2, in which each R can be, independently, H, optionally substituted alkyl, optionally substituted hydrocarbyl, or optionally substituted aryl, and Ak is optionally substituted alkylene), an optionally substituted ether (e.g., OR2, in which each R can be, independently, H, optionally substituted alkyl, optionally substituted hydrocarbyl, or optionally substituted aryl), an optionally substituted alkyl, an optionally substituted alkene, an optionally substituted alkyne, an optionally substituted benzene, oxo, or carbon monoxide. Any formulas herein can include one or more multidentate (e.g., bidentate) ligands, tin, bismuth, or tellurium, for example, as described in Embodiment 2.

[0290] The metal precursor can also include cesium. Non-limiting cesium precursors include Cs(OR), wherein R is optionally substituted C1-12 alkyl or optionally substituted aryl. Other cesium precursors include Cs(Ot-Bu) and Cs(Oi-Pr).

[0291] The metal precursor can include antimony, such as in SbR3, wherein each R is, independently, halo, optionally substituted C1-12 alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, and neopentyl), optionally substituted C1-12alkoxy, or optionally substituted amino (e.g., -NR1R2, in which each R1and R2is, independently, H or optionally substituted C1-12 alkyl). Non-limiting antimony precursors include SbCl3, Sb(OEt)3, Sb(On-Bu)3, and Sb(NMe2)3.

[0292] Other metal precursors include indium precursors, such as in InR3, wherein each R is, independently, halo, optionally substituted C1-12 alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, and neopentyl), or a diketonate (e.g., -OC(R4)-Ak-(R5)CO-, in which each R4and R5is, independently,LAMRP955WO-11528-1WO H or C1-12 alkyl). Non-limiting indium precursors include InCp, in which Cp is cyclopentadienyl, InCl3, InMe3, In(acac)3, In(CF3COCHCOCH3)3, and In(thd)3.

[0293] Yet other metal precursors include molybdenum precursors, such as MoR4, MoR5, or MoR6, wherein each R is, independently, optionally substituted C1-12 alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, and neopentyl), optionally substituted allyl (e.g., allyl, such as C3H5, or oxide of allyl, such as C5H5O), optionally substituted alkylimido (e.g., =N-R1), acetonitrile, optionally substituted amino (e.g., -NR1R2), halo (e.g., chloro or bromo), carbonyl, a diketonate (e.g., -OC(R3)-Ak-(R3)CO-), or a bidentate chelating dinitrogen (e.g., -N(R3)-Ak-N(R3)- or - N(R4)-CR5-CR2=N(R3)-). In particular embodiments, each R1and each R2is, independently, H or optionally substituted alkyl; each R3is, independently, H, optionally substituted alkyl, optionally substituted haloalkyl, or optionally substituted aryl; and R4and R5, taken together, forms an optionally substituted heterocyclyl. Non-limiting molybdenum precursors include Mo(CO)6, bis(t-butylimido)bis(dimethylamino) molybdenum(VI) or Mo(NMe2)2(=Nt-Bu)2, molybdenum(VI) dioxide bis(2,2,6,6-tetramethyl-3,5-heptanedionate) or Mo(=O)2(thd)2, or molybdenum allyl complexes, such as Mo(η3-allyl)X(CO)2(CH3CN)2, in which allyl can be C3H5 or C5H5O and X can be Cl, Br, or alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl).

[0294] Metal precursors can also include hafnium precursors, such as HfR3 or HfR4, wherein each R is, independently, optionally substituted C1-12 alkyl, optionally substituted C1-12 alkoxy, mono-C1-12 alkylamino (e.g., -NR1H, in which R1is optionally substituted C1-12 alkyl), di-C1-12 alkylamino (e.g., -NR1R2, in which each R1and R2is, independently, optionally substituted C1-12 alkyl), optionally substituted aryl (e.g., phenyl, benzene, or cyclopentadienyl, as well as substituted forms thereof), optionally substituted allyl (e.g., allyl or allyl oxide), or diketonate (e.g., -OC(R4)- Ak-(R5)CO-, each R4and R5is, independently, H or optionally substituted C1-12alkyl). Non- limiting hafnium precursors include Hf(i-Pr)(NMe2)3; Hf(η-C6H5R1)(η-C3H5)2 in which R1is H or alkyl; HfR1(NR2R3)3in which each of R1, R2, and R3is, independently, optionally substituted C1-12 alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl); HfCp2Me2; Hf(Ot-Bu)4; Hf(OEt)4; Hf(NEt2)4; Hf(NMe2)4; Hf(NMeEt)4; and Hf(thd)4.

[0295] Yet other metal precursors and non-limiting substituents are described herein. For instance, metal precursors can be any having a structure of formulas (I), (II), and (IIa), as described above; or formulas (III), (IV), (V), (VI), (VII), or (VIII), as described below and which are also described in Embodiment 2. Any of the substituents M, R, X, or L, as described herein, can be employed in any of formulas (I), (II), (IIa), (III), (IV), (V), (VI), (VII), or (VIII).LAMRP955WO-11528-1WO

[0296] Various atoms present in the metal precursor, organic precursor, and / or counter-reactant can be provided within a gradient film. In some embodiments of the techniques discussed herein, a non-limiting strategy that can further improve the EUV sensitivity in a PR film is to create a film in which the film composition is vertically graded, resulting in depth-dependent EUV sensitivity. In a homogenous PR with a high absorption coefficient, the decreasing light intensity throughout the film depth necessitates a higher EUV dose to ensure the bottom is sufficiently exposed. By increasing the density of atoms with high EUV absorptivity at the bottom of the film relative to the top of the film (i.e., by creating a gradient with increasing EUV absorption), it becomes possible to more efficiently use available EUV photons while more uniformly distributing absorption (and the effects of secondary electrons) towards the bottom of more highly absorbing films. In one non-limiting instance, the gradient film includes Te, I, or other atoms towards the bottom of the film (e.g., closer to the substrate).

[0297] In some embodiments of this disclosure, the strategy of engineering a vertical composition gradient in a PR film is particularly applicable to dry deposition methods, such as MLD, CVD, and ALD, and can be realized by tuning the flow ratios between different reactants during deposition. The type of composition gradients that can be engineered include: the ratios between different high-absorbing metals, the percentage of metal atoms that have EUV-cleavable organic groups, the percentages of organic precursors and / or counter-reactants that contain high- absorbing elements, and combinations of the above.

[0298] In some embodiments of this disclosure, the composition gradient in the EUV PR film can also bring additional benefits. For instance, high density of high EUV-absorbing elements in the bottom part of the film can effectively generate more secondary electrons that can better expose upper portions of the film. In addition, such compositional gradients can also be directly correlated with a higher fraction of EUV-absorbing species that are not bonded to bulky, terminal substituents. For example, in the case of Sn-based resists, the incorporation of tin precursors with four leaving groups is possible, thereby promoting the formation of Sn-O-substrate bonding at the interface for improved adhesion.

[0299] In some embodiments of this disclosure, such gradient films can be formed by using any metal precursors (e.g., tin or non-tin precursors), organic precursors, counter-reactants, and / or modified precursors described herein. Yet other films, methods, precursors, and other compounds are described in U.S. Provisional Pat. Appl. No. 62 / 909,430, filed October 2, 2019, and International Appl No. PCT / US20 / 53856, filed October 1, 2020, published as International Pub. No. WO 2021 / 067632, in which each is titled SUBSTRATE SURFACE MODIFICATION WITH HIGH EUV ABSORBERS FOR HIGH PERFORMANCE EUV PHOTORESISTS; andLAMRP955WO-11528-1WO International Appl. No. PCT / US20 / 70172, filed June 24, 2020, published as International Pub. No. WO 2020 / 264557, and titled PHOTORESIST WITH MULTIPLE PATTERNING RADIATION- ABSORBING ELEMENTS AND / OR VERTICAL COMPOSITION GRADIENT, the disclosures of which at least relating to the composition, deposition, and patterning of directly photopatternable metal oxide films to form EUV resist masks are incorporated by reference herein.

[0300] Yet other exemplary EUV-sensitive materials, as well as processing methods and apparatuses, are described in U.S. Pat. No. 9,996,004 and Int. Pat. Pub. No. WO 2019 / 217749, each of which is incorporated herein by reference in its entirety.

[0301] As described herein, the films, layers, and methods herein can be employed with any useful precursor. In some instances, the metal precursor includes precursor having formulas (III)- (VIII), for example, described in Embodiment 2. Organic precursors

[0302] Suitable organic precursors can be chosen to enable self-limiting and / or complementary reactions with the metal precursor. In particular embodiments, the reaction can be self-limiting, in that once all available sites with the adsorbed metal precursor layer have reacted, the organic precursor does not continue to react with itself. In other embodiments, the reaction can be complementary, such that the organic precursor regenerates a surface that is reactive towards a subsequent exposure to the metal precursor.

[0303] The organic precursor can include one or more polymerizable moieties, depolymerizable moieties, alkyl moieties (e.g., optionally substituted alkyl), alkynyl moieties (e.g., optionally substituted alkynyl), alkenyl moieties (e.g., optionally substituted alkenyl), cycloalkenyl moieties, hydroxyalkyl moieties, hydroxyaryl moieties, acrylate moieties, vinyl ester moieties, carboxylic acid moieties (e.g., methacrylic acids), diacid moieties (e.g., HO2C-Lk-CO2H), triacid moieties (e.g., HO2C-Lk-CO2H, in which Lk is substituted with one or more carboxyl), diacyl chloride moieties (e.g., ClC(O)-Lk-C(O)Cl), dialdehyde moieties (e.g., HC(O)-Lk-C(O)H), diamino moieties (e.g., H2N-Lk-NH2), dialcohol moieties (e.g., HO-Lk-OH), trialcohol moieties (e.g., HO- Lk-OH, in which Lk is substituted with one or more hydroxyl), dithiol moieties (e.g., HS-Lk-SH), aminoalcohol moieties (e.g., HO-Lk-NH2), diisocyanate moieties (e.g., OCN-Lk-NCO), dithioisocyanate moieties (e.g., SCN-Lk-NCS), anhydride moieties, cyclic anhydride moieties, dianhydride moieties, or diene moieties (e.g., CH2=CH-Ak-CH=CH2). Examples of Lk include optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroalkylene, optionally substituted arylene, or optionally substituted (aryl)(alkyl)ene.LAMRP955WO-11528-1WO

[0304] Such organic precursors can include homofunctional compounds or heterofunctional compounds. For instance, the organic precursor can be X1-Lk-X2, in which each of X1and X2is, independently, carboxyl, hydroxyl, thiol, isocyanato, thioisocyanato, halo, -C(O)-halo, or optionally substituted amino; and Lk is optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroalkylene, optionally substituted arylene, or optionally substituted (aryl)(alkyl)ene. A homofunctional compound is one in which X1and X2are the same, and a heterofunctional compound is one in which X1and X2are different.

[0305] In other embodiments, the organic precursor is a compound having one or more substitutions selected from hydroxyl, carboxyl, amino, or oxo. Such groups can be present to promote polymerization between precursor molecules. Exemplary compounds can include phenolic compounds, acrylates (e.g., methacrylates), acids (e.g., methacrylic acids), olefins (e.g., dienes, cyclodienes, etc.), diacids (e.g., HO2C-Ak-CO2H, in which Ak is optionally alkylene, optionally heteroalkylene, or optionally arylene), dialcohols (e.g., HO-Ak-OH, in which Ak is optionally alkylene, optionally heteroalkylene, or optionally arylene), diamines (e.g., H2N-Ak- NH2, in which Ak is optionally alkylene, optionally heteroalkylene, or optionally arylene), diisocyanates (e.g., OCN-Ak-NCO, in which Ak is optionally alkylene, optionally heteroalkylene, or optionally arylene), dialdehydes (e.g., phthalaldehyde or HC(O)-Ak-C(O)H, in which Ak is optionally alkylene, optionally heteroalkylene, or optionally arylene), and vinyl esters.

[0306] For instance, the organic precursor includes one or more hydroxyl groups. In particular embodiments, the organic precursor can include a hydroxyl moiety, a hydroxyalkyl moiety, or a hydroxyaryl moiety. Yet other non-limiting organic precursors can include HO-Ak-OH, in which Ak is an optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, or optionally substituted arylene. In particular embodiments, Ak can be substituted with one or more hydroxyl, oxo, and / or carboxyl substituents. Further organic precursors include diols, triols, polyols, ynols, benzenediols, benzenetriols, and benzenetetrols, including ethylene glycol, glycerol, propylene glycol, ethynol, diacetylene glycol (2,4-hexadiyne-1,6-diol), hydroquinone (1,4-dihydroxybenzene), catechol (1,2-dihydroxybenzene), resorcinol (1,3- dihydroxybenzene), and benzene-1,3,5-triol.

[0307] In another instance, the organic precursor includes one or more carboxyl groups. In particular embodiments, the organic precursor can include a carboxyl moiety, a carboxyalkyl moiety, or a carboxyaryl moiety. Yet other non-limiting organic precursors can include HOC(O)- Ak-C(O)OH, in which Ak is an optionally substituted alkylene or optionally substituted arylene. In particular embodiments, Ak can be substituted with one or more hydroxyl, oxo, and / or carboxylLAMRP955WO-11528-1WO substituents. Further organic precursors include diacids, triacids, and enoic acids, including oxalic acid, malonic acid, succinic acid, citric acid, acetylenedicarboxylic acid, tartronic acid, phthalic acid, terephthalic acid, isophthalic acid, and trimesic acid.

[0308] Other functional groups can be provided for the organic precursor, such as amino, thiol, selenol, and tellurol. Yet other non-limiting organic precursors can include N(RN1)(RN2)-Ak- N(RN3)(RN4), HS-Ak-SH, HSe-Ak-SeH, or HTe-Ak-TeH, in which Ak is an optionally substituted alkylene or optionally substituted arylene and each of RN1, RN2, RN3, and RN4is, independently, H or optionally substituted alkyl. In particular embodiments, Ak can be substituted with one or more hydroxyl, oxo, carboxyl, amino, thiol, selenol, and / or tellurol substituents.

[0309] Use of the organic precursor(s) can result in deposition of any useful polymer (e.g., within an organic layer or within a matrix), in which the polymer can include polymerizable moieties or depolymerizable moieties. For instance, the organic precursor can provide a film having one or more polymerizable moieties, in which exposure to radiation polymerizes these moieties. Non-limiting polymerizable moieties include those than can be cross-linked after exposure to UV, DUV, and / or EUV radiation, such as alkyne moieties and alkene moieties.

[0310] Alternatively, the organic precursor can provide a film having one or more depolymerizable moieties, in which exposure to radiation depolymerizes these moieties. Non- limiting depolymerizable moieties include those than can be unzipped or photolyzed after exposure to UV, DUV, and / or EUV radiation, such as ester moieties, acrylate moieties, or carbonate moieties.

[0311] Constituents within the organic layer can be formed by using one, two, or more organic precursors. In one instance, a single organic precursor is employed, in which reactions occur between precursors of the same type within the organic layer and the organic precursor can also react with the metal precursor. In another instance, two organic precursors are employed, in which a first organic precursor reacts with the metal precursor and the second organic precursor reacts with the first organic precursor that is bound to the metal precursor.

[0312] The first organic precursor (P1) and the second organic precursor (P2) can provided in one, two, three, or more steps. The first step can include providing P1 to the metal precursor (MP) to form MP-P1. Then, P2 can be provided to react with P1, thus forming MP-P1-P2. Optionally, further steps can be conducted, such as by providing P1 in a third step to produce MP-P1-P2-P1 or by providing P2 to produce MP-P1-P2-P2. Further organic precursors can be used to build up the organic layer, in which such precursors can be provided at the same time or sequentially in cycles.LAMRP955WO-11528-1WO

[0313] Organic precursor can include polymers or can react together to provide polymers. Non- limiting polymers (e.g., polymerizable or unzippable polymers) include a poly(ester), such as polyethylene terephthalate, polyhydroxybutyrate, polyhydroxyvalerate, poly(vinyl ester), poly(vinyl acetate), or copolymers thereof; a poly(hydroxyalkanoate); a poly(lactic acid); a poly(caprolactone); a poly(imide); a poly(urea); a poly(amide); a poly(ether), such as poly(phthalaldehyde) or poly(benzyl ether); a poly(carbamate), such as poly(benzyl carbamate); a polysaccharide or a derivative thereof, such as amylose, cellulose, or carboxymethyl cellulose; a poly(alkylene succinate), such as poly(propylene succinate) or poly(butylene succinate); a poly(aspartate) or a poly(aspartic acid); or an aliphatic-aromatic resin, such as a copolymer having at least one aliphatic section and at least one aromatic section.

[0314] In one embodiment, a poly(ester) is deposited employing a diacid (e.g., an optionally substituted alkyl or an optionally substituted aryl substituted with two carboxyl groups, such as terephthalic acid) as a first organic precursor with a dialcohol (e.g., an optionally substituted alkyl or an optionally substituted aryl substituted with two hydroxyl groups, such as ethylene glycol) as a second organic precursor. In particular embodiments, the poly(ester) is a polyethylene terephthalate. In particular embodiments, the first organic precursor is a diacyl chloride. In some embodiments, the dialcohol is HO-Lk-OH, and the diacyl chloride is ClC(O)-Lk-C(O)Cl, in which each of RN1, RN2, RN3, and RN4is, independently, H or optionally substituted alkyl, and Lk is optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroalkylene, optionally substituted arylene, or optionally substituted (aryl)(alkyl)ene.

[0315] In another embodiment, a poly(ester) (e.g., a poly(vinyl ester)) is deposited employing a vinyl ester moiety. Non-limiting vinyl esters include, for instance, vinyl acetate (VAc), vinyl propionate (VPr), vinyl butyrate (VBu), vinyl pivalate (VPiv), vinyl octanoate (VOc), vinyl neodecanoate (VNDec), vinyl stearate (VSt), vinyl benzoate (VBz), vinyl chloroacetate (VClAc), vinyl trifluoroacetate (VTFAc), isopropenyl acetate (iPAc), and 1-(trifluoromethyl)vinyl acetate (CF3VAc).

[0316] In one embodiment, a poly(imide) is deposited employing a diamine as a first organic precursor with a dianhydride as a second organic precursor. In some embodiments, the diamine is N(RN1)(RN2)-Lk-N(RN3)(RN4), in which each of RN1, RN2, RN3, and RN4is, independently, H or optionally substituted alkyl, and Lk is optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroalkylene, optionally substituted arylene, or optionally substituted (aryl)(alkyl)ene.LAMRP955WO-11528-1WO

[0317] In another embodiment, a poly(urea) is deposited employing a diamine as a first organic precursor with a diisocyanate as a second organic precursor. In some embodiments, the diamine is N(RN1)(RN2)-Lk-N(RN3)(RN4), and the diisocyanate is OCN-Lk-NCO, in which each of RN1, RN2, RN3, and RN4is, independently, H or optionally substituted alkyl, and Lk is optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroalkylene, optionally substituted arylene, or optionally substituted (aryl)(alkyl)ene. In further embodiments, a third organic precursor is a diamine, which is reacted with the diisocyanate that is the second organic precursor.

[0318] In one embodiment, a poly(amide) is deposited employing a diamine as a first organic precursor with a diacyl chloride as a second organic precursor. In some embodiments, the diamine is N(RN1)(RN2)-Lk-N(RN3)(RN4), and the diacyl chloride is ClC(O)-Lk-C(O)Cl, in which each of RN1, RN2, RN3, and RN4is, independently, H or optionally substituted alkyl, and Lk is optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroalkylene, optionally substituted arylene, or optionally substituted (aryl)(alkyl)ene.

[0319] In one embodiment, a poly(alkylene terephthalate) is deposited employing a dialcohol as a first organic precursor with a diacyl chloride as a second organic precursor. In some embodiments, the dialcohol is HO-Lk-OH, and the diacyl chloride is ClC(O)-Ar-C(O)Cl, in which each of RN1, RN2, RN3, and RN4is, independently, H or optionally substituted alkyl, Ar is optionally substituted arylene, and Lk is optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroalkylene, optionally substituted arylene, or optionally substituted (aryl)(alkyl)ene.

[0320] Copolymer can be formed. In one embodiment, a poly(imide)-poly(amide) is deposited employing a dianhydride as a first organic precursor, a diamine as a second organic precursor, and a diacyl chloride as a third organic precursor, in which non-limiting dianhydrides, diamines, and diacyl chlorides are described herein. Embodiment 4

[0321] In some embodiments, an organometallic precursor and a dopant precursor to provide a doped resist film. Dopant precursors

[0322] The dopant precursor can be any having an element having high patterning radiation absorption and / or high SEY (e.g., any described herein). Such dopant precursors can be employed before, after, or during deposition with an organometallic precursor. In one embodiment, theLAMRP955WO-11528-1WO dopant precursor include Xe as a gas. In another embodiment, the dopant precursor includes a structure having formula (II): XaZb (II), wherein: each X is, independently, an element characterized by a high SEY; each Z is, independently, H, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, optionally substituted alkoxy, or a ligand (e.g., that is reactive with a counter-reactant); a ≥ 1 (e.g., a is 1, 2, or 3); and b ≥ 2 (e.g., b is 2, 3, 4, 5, 6, 7, or 8).

[0323] Dopants including Xe and a high SEY element can be employed together or sequentially. For instance, a first dopant precursor including Xe (e.g., Xe gas) can be employed with a second dopant precursor including a high SEY element (e.g., Be, B, Mg, Al, Sc, or a combination thereof).

[0324] In yet another embodiment, the dopant precursor includes a structure having formula (IIa): XZb (IIa), wherein: X is an element characterized by a high SEY; each Z is, independently, H, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, optionally substituted alkoxy, or a ligand (e.g., that is reactive with a counter-reactant); a ≥ 1 (e.g., a is 1, 2, or 3); and b ≥ 2 (e.g., b is 2, 3, 4, 5, 6, 7, or 8).

[0325] In some embodiments, X is an element characterized by a high EUV SEY (e.g., about 0.2 to 0.45) and / or an EUV absorption cross-section equal to or greater than 1x102cm2 / mol (e.g., from about 102-107cm2 / mol, 102-104cm2 / mol, or 102-106cm2 / mol). In particular embodiments, X is Be, B, Mg, Al, Sc, or a combination thereof. In some embodiments, Z is any ligand (e.g., as R or L) described herein for formulas (I), (Ia), (III), (IV), (V), (VI), (VII), or (VIII).

[0326] Non-limiting examples of Z include H, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, or optionally substituted alkoxy (e.g., -OR1, in which R1can be alkyl). In some embodiments, the optionally substituted amino is -NR1R2, in which each R1and R2is, independently, H or alkyl; or in which R1and R2, taken together with the nitrogen atom toLAMRP955WO-11528-1WO which each are attached, form a heterocyclyl group, as defined herein. In other embodiments, the optionally substituted bis(trialkylsilyl)amino is -N(SiR1R2R3)2, in which each R1, R2, and R3is, independently, alkyl. In yet other embodiments, the optionally substituted trialkylsilyl is -SiR1R2R3, in which each R1, R2, and R3is, independently, alkyl.

[0327] In some embodiments, each Z or at least one Z can include an oxygen atom. In particular embodiments, one or more Z can be optionally substituted alkoxy (e.g., in formula (II) or (IIa)). Non-limiting Z substituents include, e.g., methoxy, ethoxy, isopropoxy (i-PrO), t-butoxy (t-BuO), 1-methoxy-2-methyl-2-propanolato (mmp), 2,2,6,6-tetramethyl-3,5-heptanedionato (THD), acetylacetonate (acac), and -O-C(Za)-CZa-C(Za)-O- (β-diketonate, in which each Zacan be, independently, H, alkyl, alkenyl, alkynyl, aryl, phenyl, or halo).

[0328] In some embodiments, each Z or at least one Z can include a nitrogen atom. In particular embodiments, one or more Z can be optionally substituted amino (e.g., in formula (II) or (IIa)). Non-limiting Z substituents include, e.g., dialkylamino; dimethylamino; diethylamino; 3‐ (dimethylamino)propyl (dmp); -NR1R2-C(Za)2-C(Za)2-C(Za)2- (dialkylaminopropyl), in which each Za, R1, and R2can be, independently, H, alkyl, alkenyl, alkynyl, aryl, phenyl, or halo; -N(Za)- C(Za)-N(Za)- (amidinato), in which each Zacan be, independently, H, alkyl, alkenyl, alkynyl, aryl, phenyl, or halo, including N,N′-di-sec-butylacetamidinato [(iPrN)2CMe]; -N(Za)-C(NR1R2)-N(Za)- (guanidinato), in which each Za, R1, and R2can be, independently, H, alkyl, alkenyl, alkynyl, aryl, phenyl, or halo; or -N(Za)-C(Za)- C(Za)-C(Za)-N(Za)- (β- diketiminato), in which each Zacan be, independently, H, alkyl, alkenyl, alkynyl, aryl, phenyl, or halo.

[0329] In some embodiments, each Z or at least one Z can include an optionally substituted cyclopentadienyl (Cp) or optionally substituted aryl. Non-limiting substitutions for Cp and aryl can include alkyl, alkenyl, alkynyl, aryl, phenyl, or halo, such as an alkylated derivative (e.g., η5- C5H4Et).

[0330] Yet other examples of dopant precursors include beryllium halides, such as beryllium chloride [BeCl2] and beryllium bromide [BeBr2]; organoberyllium, including dialkyl beryllium, such as dimethyl beryllium [Be(Me)2]; bis(dialkyl)amino beryllium, such as bis(dimethylamino) beryllium [Be(NMe2)2]; and beryllium β-ketonates, such as beryllium acetylacetonate [Be(acac)2].

[0331] Other dopant precursors can include boranes and complexes thereof, such as trihydridoboron [BH3], diborane [B2H6], and complexes including amine or organoamines, such as dialkylamine (e.g., NHRN1RN2, in which each of RN1and RN2can be optionally substituted alkyl), trialkylamine (e.g., NRN1RN2RN3, in which each of RN1, RN2, and RN3can be optionally substituted alkyl), or other amines (e.g., NRN1RN2RN3, in which each of RN1, RN2, and RN3can beLAMRP955WO-11528-1WO H, optionally substituted alkyl, optionally substituted aryl, or wherein two or more of RN1, RN2, and RN3, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein), in which complexes can include borane dimethylamine complex[NMe2H · BH3], borane-ammonia complex [NH3 · BH3], or borane trimethylamine complex[NMe3 · BH3]; boron halides, such as boron chloride [BCl3], boron bromide [BBr3], and diborontetrafluoride [B2F4]; organoboranes, such as trialkylboranes and triarylboranes, including trimethylborane [BMe3], trimethylborane [BEt3], and triphenylborane [BPh3]; organoborates, such as trialkylborates, including trimethylborate [B(OMe)3], triethylborate [B(OEt)3], and triisopropylborate [B(O-iPr)3]; and tris(dialkylamino)boranes, such as tris(dimethylamino)borane [B(NMe2)3].

[0332] Yet other dopant precursors can include organomagnesium, including bisalkylmagnesium bisarylmagnesium, bis(cyclopentadienyl)magnesium [Mg(Cp)2] and substituted forms thereof, such as bis(ethylcyclopentadienyl)magnesium [Mg(η5-C5H4Et)2], bis(n- propylcyclopentadienyl)magnesium [Mg(η5-C5H4nPr)2], and bis(pentamethylcyclopentadienyl)magnesium [Mg(η5-C5Me5)2]; magnesium β-ketonates, such as bis(2,2,6,6-tetramethyl-3,5-heptanedionato)magnesium [Mg(THD)2], magnesium acetylacetonate [Mg(acac)2], and magnesium hexafluoroacetylacetonate [Mg(hfa)2]; and magnesium β- amidinates, such as bis(N,N′-di-sec-butylacetamidinato)magnesium [Mg[(iPrN)2CMe]2] and bis(N-t-butyl-N''-ethylpropanimidamidato)magnesium [Mg[(tBuN)CEt(NEt)]2].

[0333] Other dopant precursors can include aluminum halides, such as aluminum bromide [AlBr3] and aluminum chloride [AlCl3]; organoaluminum, including trialkylaluminum and triarylaluminum, such as trimethylaluminum [AlMe3] and triethylaluminum [AlEt3]; aluminum alkoxides, such as aluminum methoxide [Al(OMe)3] and aluminum i-propoxide [Al(OiPr)3]; aluminum β-ketonates, such as aluminum acetylacetonate [Al(acac)3], tris(2,2,6,6-tetramethyl-3,5- heptanedionato)aluminum [Al(THD)3], and aluminum hexafluoroacetylacetonate [Al(hfa)3]; tris(dialkylamido)aluminum, such as tris(dimethylamido)aluminum [Al(NMe2)3or Al2(NMe2)6]; alkoxy-containing aluminum precursors, such as tris(1-methoxy-2-methyl-2-propoxy)aluminum [Al(mmp)3]; and amino-containing aluminum precursors, such as [3-(dimethylamino)propyl] dimethylaluminum [AlMe2(dmp)], [3-(dimethylamino)propyl]bis(dimethylamido)aluminum [Al(NMe2)2(dmp)], and [3-(dimethylamino)propyl]bis(diisopropylamido)aluminum [Al(iPrN)2(dmp)].

[0334] Yet other dopant precursors can include organoscandium, such as bis(cyclopentadienyl)allylscandium [ScCp2(η3-C3H5)] or tris(cyclopentadienyl)scandium [ScCp3]; scandium β-ketonates, such as scandium acetylacetonate [Sc(acac)2] and tris(2,2,6,6-tetramethyl-LAMRP955WO-11528-1WO 3,5-heptanedionato)scandium [Sc(TMHD)3]; scandium β-amidinates, such as tris(N,N′-di-sec- butylacetamidinato)scandium [Sc[(iPrN)2CMe]3], tris(N-t-butyl-N''- ethylpropanimidamidato)scandium [Sc[(tBuN)CEt(NEt)]3], and tris(N,N’- diisopropylacetamidinato)scandium [Sc[(iPrN)2CH)]3]; and trialkylsilylamide-containing scandium compounds, such as tris[N,N-bis(trimethylsilyl)amide]scandium [Sc[(N(SiMe3)2]3]. Organometallic precursors

[0335] The organometallic precursor can have any useful number and type of ligand(s). A ligand can be characterized by its ability to react in the presence of a counter-reactant or in the presence of patterning radiation. For instance, the organometallic precursor can include a ligand (e.g., dialkylamino groups or alkoxy groups) that reacts with a counter-reactant, which can introduce linkages between metal centers (e.g., an -O- linkage). In another instance, the organometallic precursor can include a ligand that eliminates in the presence of patterning radiation. Such a ligand can include branched or linear alkyl groups having a beta-hydrogen.

[0336] The organometallic precursor can be any useful metal-containing precursor, such as an organometallic agent, a metal halide, or a capping agent (e.g., as described herein). In a non- limiting instance, the organometallic precursor includes a structure having formula (I): MaRbLc (I), wherein: M is a metal; each R is, independently, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted alkoxy, or L; each L is, independently, is a ligand, ion, or other moiety that is reactive with a counter- reactant, in which R and L with M, taken together, can optionally form a heterocyclyl group or in which R and L, taken together, can optionally form a heterocyclyl group; a ≥ 1; b ≥ 1; and c ≥ 1.

[0337] In some embodiments, each ligand within the organometallic precursor can be one that is reactive with a counter-reactant. In one instance, the organometallic precursor includes a structure having formula (I), in which each R is, independently, L. In another instance, the organometallic precursor includes a structure having formula (Ia): MaLc (Ia), wherein: M is a metal; each L is, independently, is a ligand, ion, or other moiety that is reactive with a counter-LAMRP955WO-11528-1WO reactant, in which two L, taken together, can optionally form a heterocyclyl group; a ≥ 1; and c ≥ 1. In particular embodiments of formula (Ia), a is 1. In further embodiments, c is 2, 3, or 4.

[0338] For any formula herein, M can be a metal with a high patterning radiation absorption cross- section (e.g., an EUV absorption cross-section that is equal to or greater than 1x107cm2 / mol). In some embodiments, M is tin (Sn), tellurium (Te), bismuth (Bi), antimony (Sb), hafnium (Hf), or zirconium (Zr). In further embodiments, M is Sn, a is 1, and c is 4 in formula (I) or (Ia). In other embodiments, M is Sn, a is 1, and c is 2 in formula (I) or (Ia). In particular embodiments, M is Sn(II) (e.g., in formula (I) or (Ia)), thereby providing an organometallic precursor that is a Sn(II)- based compound. In other embodiments, M is Sn(IV) (e.g., in formula (I) or (Ia)), thereby providing an organometallic precursor that is a Sn(IV)-based compound.

[0339] For any formula herein, each L is, independently, H, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, or optionally substituted alkoxy (e.g., -OR1, in which R1can be alkyl). In some embodiments, the optionally substituted amino is -NR1R2, in which each R1and R2is, independently, H or alkyl; or in which R1and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein. In other embodiments, the optionally substituted bis(trialkylsilyl)amino is -N(SiR1R2R3)2, in which each R1, R2, and R3is, independently, alkyl. In yet other embodiments, the optionally substituted trialkylsilyl is -SiR1R2R3, in which each R1, R2, and R3is, independently, alkyl.

[0340] In other embodiments, the formula includes a first L that is -NR1R2and a second L that is -NR1R2, in which each R1and R2is, independently, H or alkyl; or in which R1from a first L and R1from a second L, taken together with the nitrogen atom and the metal atom to which each are attached, form a heterocyclyl group, as defined herein. In yet other embodiments, the formula includes a first L that is -OR1and a second L that is -OR1, in which each R1is, independently, H or alkyl; or in which R1from a first L and R1from a second L, taken together with the oxygen atom and the metal atom to which each are attached, form a heterocyclyl group, as defined herein.

[0341] In some embodiments, at least one of L or R is optionally substituted alkyl (e.g., in formula (I) or (Ia)). Non-limiting alkyl groups include, e.g., CnH2n+1, where n is 1, 2, 3, or greater, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl. In various embodiments, L or R has at least one beta-hydrogen or beta-fluorine. In particular, the organometallic precursor can be tetramethyl tin (SnMe4), tetraethyl tin (SnEt4), t-butyl tellurium hydride (Te(t-Bu)(H)), dimethyl tellurium (TeMe2), di(t-butyl) tellurium (Te(t-Bu)2), or di(isopropyl)tellurium (Te(i- Pr)2).LAMRP955WO-11528-1WO

[0342] In some embodiments, each L or at least one L is halo (e.g., in formula (I) or (Ia)). In particular, the organometallic precursor can be a metal halide. Non-limiting metal halides include SnBr4, SnCl4, SnI4, and SbCl3.

[0343] In some embodiments, each L or at least one L can include a nitrogen atom. In particular embodiments, one or more L can be optionally substituted amino or optionally substituted bis(trialkylsilyl)amino (e.g., in formula (I) or (Ia)). Non-limiting L substituents can include, e.g., -NMe2, -NEt2, -NMeEt, -N(t-Bu)-[CHCH3]2-N(t-Bu)- (tbba), -N(SiMe3)2, and -N(SiEt3)2. Non- limiting organometallic precursors can include, e.g., Sn(NMe2)4, Sn(NEt2)4, Sn(i-Pr)(NMe2)3, Sn(n-Bu)(NMe2)3, Sn(s-Bu)(NMe2)3, Sn(i-Bu)(NMe2)3, Sn(t-Bu)(NMe2)3, Sn(t-Bu)2(NMe2)2, Sn(t-Bu)(NEt2)3, Sb(NMe2)3, Sn(tbba), Sn[N(SiMe3)2]2, or Bi[N(SiMe3)2]3.

[0344] In some embodiments, each L or at least one L can include a silicon atom. In particular embodiments, one or more L can be optionally substituted trialkylsilyl or optionally substituted bis(trialkylsilyl)amino (e.g., in formula (I) or (Ia)). Non-limiting L substituents can include, e.g., -SiMe3, -SiEt3, -N(SiMe3)2, and -N(SiEt3)2. Non-limiting organometallic precursors can include, e.g., Sn[N(SiMe3)2]2, bis(trimethylsilyl)tellurium (Te(SiMe3)2), bis(triethylsilyl) tellurium (Te(SiEt3)2), or Bi[N(SiMe3)2]3.

[0345] In some embodiments, each L or at least one L can include an oxygen atom. In particular embodiments, one or more L can be optionally substituted alkoxy (e.g., in formula (I) or (Ia)). Non-limiting L substituents include, e.g., methoxy, ethoxy, isopropoxy (i-PrO), t-butoxy (t-BuO), and -O=C(CH3)-CH=C(CH3)-O- (acac). Non-limiting organometallic precursors include, e.g., Sn(t-BuO)4, Sn(n-Bu)(t-BuO)3, or Sn(acac)2.

[0346] Yet other organometallic precursors and non-limiting substituents are described herein. For instance, organometallic precursors can be any having a structure of formulas (I) and (Ia), as described above; or formulas (III), (IV), (V), (VI), (VII), or (VIII), as described below. Any of the substituents M, R, X, or L, as described herein, can be employed in any of formulas (I), (Ia), (III), (IV), (V), (VI), (VII), or (VIII).

[0347] To provide a doped film in one non-limiting instance, a dopant precursor can be employed to react with or to replace a ligand of the organometallic precursor. Non-limiting dopant precursors are described herein.

[0348] Such precursor(s) can be further used in combination with one or more counter-reactants. Counter-reactants preferably have the ability to replace the reactive moieties, ligands, or ions (e.g., L in formulas herein) so as to link at least two metal atoms via chemical bonding. Exemplary counter-reactants include oxygen-containing counter-reactants, such as O2, O3, water, peroxides (e.g., hydrogen peroxide), oxygen plasma, water plasma, alcohols, di- or polyhydroxy alcohols,LAMRP955WO-11528-1WO fluorinated di- or polyhydroxy alcohols, fluorinated glycols, formic acid, and other sources of hydroxyl moieties, as well as combinations thereof. In various embodiments, a counter-reactant reacts with the organometallic precursor by forming oxygen bridges between neighboring metal atoms. Other potential counter-reactants include hydrogen sulfide and hydrogen disulfide, which can crosslink metal atoms via sulfur bridges and bis(trimethylsilyl)tellurium, which can crosslink metal atoms via tellurium bridges. In addition, hydrogen iodide may be utilized to incorporate iodine into the film.

[0349] In particular embodiments, the counter-reactant is a chalcogenide precursor, e.g., that includes a structure having formula: X3-Z-X4, wherein: Z is sulfur, selenium, or tellurium; and each of X3and X4is, independently, H, optionally substituted alkyl (e.g., methyl, ethyl, n- propyl, isopropyl, n-butyl, t-butyl, etc.), optionally substituted alkenyl, optionally substituted aryl, optionally substituted amino, optionally substituted alkoxy, or optionally substituted trialkylsilyl.

[0350] Using the organometallic precursors herein, a gradient film can be formed. For instance, various atoms present in the dopant precursor and / or counter-reactant can be provided within a gradient film. In some embodiments of the techniques discussed herein, a non-limiting strategy that can further improve the EUV sensitivity in a photoresist (PR) film is to create a film in which the film composition is vertically graded, resulting in depth-dependent EUV sensitivity. In a homogenous PR with a high absorption coefficient, the decreasing light intensity throughout the film depth necessitates a higher EUV dose to ensure the bottom is sufficiently exposed. By increasing the density of atoms with high EUV absorptivity at the bottom of the film relative to the top of the film (i.e., by creating a gradient with increasing EUV absorption), it becomes possible to more efficiently use available EUV photons while more uniformly distributing absorption (and the effects of secondary electrons) towards the bottom of more highly absorbing films. In one non-limiting instance, the gradient film includes Te, I, or other atoms towards the bottom of the film (e.g., closer to the substrate). Further precursors

[0351] As described herein, the films, layers, and methods herein can be employed with any useful precursor. In some instances, the organometallic precursor includes one or more precursors (III)-(VIII) described in Embodiments 2.LAMRP955WO-11528-1WO Embodiment 5 Organotin (II) compounds

[0352] The Sn(II) precursor can include any precursor (e.g., described herein) that provides a patternable film that is sensitive to radiation (or a patterning radiation-sensitive film or a photopatternable film). Such radiation can include EUV radiation or DUV radiation that is provided by irradiating through a patterned mask, thereby being a patterning radiation. The film itself can be altered by being exposed to such radiation, such that the film is radiation-sensitive.

[0353] In particular embodiments, the Sn(II) compound is an organometallic compound, which includes at least one Sn(II) center and at least one ligand that can react with the one or more co- reagent(s) and / or counter-reactant(s). If a first co-reagent includes an organic moiety, then this moiety can react with or displace the ligand from the metal center, thereby attaching that organic moiety as a bound ligand to the metal center. The organic moiety itself can be reactive in the presence of patterning radiation, such as by undergoing removal or elimination from the metal center or by reacting or polymerizing with other moieties within the film. Furthermore, if a second co-reagent includes a chalcogen, then this chalcogen can be reduced by the metal center, thereby becoming chemically reactive and allowing the chalcogen to integrated into the deposited film.

[0354] The organotin(II) compound can be any useful Sn(II)-containing precursor. In some embodiments, the organotin(II) compound includes a structure having formula (I): L1-M1-L2(I), wherein: M1 is Sn(II); and each of L1and L2is, independently, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted alkoxy, optionally substituted bis(trialkylsilyl)alkyl, optionally substituted bis(trialkylsilyl)amino, an anionic ligand, a neutral ligand, or a multidentate ligand, wherein L1and L2with M1, taken together, can optionally form a heterocyclyl group.

[0355] In some embodiments, L1is -NRN1aRN1b, and L2is -NRN2aRN2b, in which each RN1a, RN1b, RN2a, and RN2bis, independently, H or optionally substituted alkyl, or in which RN1band RN2b, taken together, is optionally substituted alkylene, optionally substituted alkenylene, optionally substituted heteroalkylene, or optionally substituted heteroalkenylene.

[0356] In other embodiments, each of L1and L2is selected from the group consisting of -Ri, - ORi, -NRiRii, -N(SiRiRiiRiii)2, and -CRiv(SiRiRiiRiii)2. In particular embodiments, L1and L2, taken together, forms a bivalent ligand that is bound to M1. In further embodiments, the bivalent ligandLAMRP955WO-11528-1WO is -NRi-Ak-NRii-, -NRi-[CRivRv]m-NRii- (e.g., -NRi-[CRivRv]2-NRii-), or -C(SiRiRiiRiii)2-Ak-C(SiRiRiiRiii)2-. In some embodiments, each of Ri, Rii, and Riiiis, independently, optionally substituted linear alkyl or optionally substituted branched alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, etc.); Ak is optionally substituted alkylene; each of Rivand Rvis, independently, H, optionally substituted linear alkyl, or optionally substituted branched alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, etc.); and m is an integer from 1 to 3.

[0357] In a non-limiting instance, the organotin(II) compound includes a structure having formula (V): MaRb (V), wherein: M is Sn(II); each R is, independently, H, halo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkanoyloxy, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, oxo, an anionic ligand, a neutral ligand, or a multidentate ligand; a ≥ 1; and b ≥ 1. In particular embodiments of formula (V), a is 1, and b is 1 or 2.

[0358] In another non-limiting instance, the organotin(II) compound includes a structure having formula (VI): MaRbLc(VI), wherein: M is Sn(II); each R is, independently, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted alkoxy, or L; each L is, independently, is a ligand, an anionic ligand, a neutral ligand, a multidentate ligand, an ion, or other moiety that is reactive with a co-reagent or a counter-reactant, in which R and L with M, taken together, can optionally form a heterocyclyl group or in which R and L, taken together, can optionally form a heterocyclyl group; a ≥ 1; b ≥ 1; and c ≥ 1. In particular embodiments of formula (VI), a is 1; b is 1 or 2; and c is 1 or 2.LAMRP955WO-11528-1WO

[0359] In some embodiments, each ligand within the organotin(II) compound can be one that is reactive with a co-reagent or a counter-reactant. In one instance, the organotin(II) compound includes a structure having formula (VI), in which each R is, independently, L. In another instance, the organotin(II) compound includes a structure having formula (VI-A): MaLc (VI-A), wherein: M is Sn(II); each L is, independently, is a ligand, an anionic ligand, a neutral ligand, a multidentate ligand, an ion, or other moiety that is reactive with the co-reagent or a counter-reactant, in which two L, taken together, can optionally form a heterocyclyl group; a ≥ 1; and c ≥ 1. In particular embodiments of formula (VI-A), a is 1, and c is 1 or 2.

[0360] For any formula herein, each R, L, L1, or L2is, independently, H, halo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy (e.g., -OR1, in which R1can be optionally substituted alkyl), optionally substituted alkanoyloxy, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, oxo, an anionic ligand (e.g., oxido, chlorido, hydrido, acetate, iminodiacetate, etc.), a neutral ligand, or a multidentate ligand.

[0361] In some embodiments, the optionally substituted amino is -NR1R2, in which each R1and R2is, independently, H or alkyl; or in which R1and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein. In other embodiments, the optionally substituted bis(trialkylsilyl)amino is -N(SiR1R2R3)2, in which each R1, R2, and R3is, independently, optionally substituted alkyl. In yet other embodiments, the optionally substituted trialkylsilyl is -SiR1R2R3, in which each R1, R2, and R3is, independently, optionally substituted alkyl.

[0362] In other embodiments, the formula includes a first R (or first L or L1) that is -NR1R2and a second R (or second L or L2) that is -NR1R2, in which each R1and R2is, independently, H or optionally substituted alkyl; or in which R1from a first R (or first L or L1) and R1from a second R (or second L or L2), taken together with the nitrogen atom and the metal atom to which each are attached, form a heterocyclyl group, as defined herein. In yet other embodiments, the formula includes a first R that is -OR1and a second R that is -OR1, in which each R1is, independently, H or optionally substituted alkyl; or in which R1from a first R and R1from a second R, taken togetherLAMRP955WO-11528-1WO with the oxygen atom and the metal atom to which each are attached, form a heterocyclyl group, as defined herein.

[0363] In some embodiments, at least one of R, L, L1, or L2(e.g., in formula (I), (V), (VI), or (VI-A)) is optionally substituted alkyl. Non-limiting alkyl groups include, e.g., CnH2n+1, where n is 1, 2, 3, or greater, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t- butyl. In various embodiments, R, L, L1, or L2has at least one beta-hydrogen or beta-fluorine.

[0364] In some embodiments, each R, L, L1, or L2or at least one R, L, L1, or L2(e.g., in formula (I), (V), (VI), or (VI-A)) can include a nitrogen atom. In particular embodiments, one or more R or L can be optionally substituted amino, an optionally substituted monoalkylamino (e.g., -NR1H, in which R1is optionally substituted alkyl), an optionally substituted dialkylamino (e.g., -NR1R2, in which each R1and R2is, independently, optionally substituted alkyl), or optionally substituted bis(trialkylsilyl)amino. Non-limiting R, L, L1, or L2substituents can include, e.g., -NMe2, -NHMe, -NEt2, -NHEt, -NMeEt, -N(t-Bu)-[CHCH3]2-N(t-Bu)- (tbba), -N(SiMe3)2, and -N(SiEt3)2.

[0365] In some embodiments, each R, L, L1, or L2or at least one R, L, L1, or L2(e.g., in formula (I), (V), (VI), or (VI-A)) can include a silicon atom. In particular embodiments, one or more R, L, L1, or L2can be optionally substituted trialkylsilyl or optionally substituted bis(trialkylsilyl)amino. Non-limiting R, L, L1, or L2substituents can include, e.g., -SiMe3, -SiEt3, -N(SiMe3)2, and -N(SiEt3)2.

[0366] In some embodiments, each R, L, L1, or L2or at least one R, L, L1, or L2(e.g., in formula (I), (V), (VI), or (VI-A)) can include an oxygen atom. In particular embodiments, one or more R, L, L1, or L2can be optionally substituted alkoxy or optionally substituted alkanoyloxy. Non- limiting R, L, L1, or L2substituents include, e.g., methoxy, ethoxy, isopropoxy (i-PrO), t-butoxy (t-BuO), acetate (-OC(O)-CH3), and -O=C(CH3)-CH=C(CH3)-O- (acac).

[0367] Any formulas herein can include one or more neutral ligands. Non-limiting neutral ligands include an optionally substituted amine, an optionally substituted ether, an optionally substituted alkyl, an optionally substituted alkene, an optionally substituted alkyne, an optionally substituted benzene, oxo, or carbon monoxide. Any formulas herein can include one or more multidentate (e.g., bidentate) ligands, or tin, as described in Embodiment 2. Co-reagents

[0368] For methods herein, one or more co-reagents may be employed to react with or to replace a ligand of the Sn(II) compound. Any useful co-reagent can be employed (e.g., a chalcogenide precursor, an organometal compound, an organotin(IV) precursor, a tantalum precursor, an alkylLAMRP955WO-11528-1WO halide, a reducing gas, and / or a counter-reactant). Such a co-reagent can be provided in any form, e.g., as a vapor phase; alone or in combination with another co-reagents; as well as optionally with an inert gas or a carrier gas (e.g., any described herein).

[0369] In one non-limiting instance, the co-reagent is a chalcogenide precursor. In particular embodiments, the chalcogenide precursor includes a structure having formula (II-A): L3-X-L4(II-A), wherein: X is sulfur, selenium, or tellurium; and each of L3and L4is, independently, H, optionally substituted alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, etc.), optionally substituted alkenyl, optionally substituted aryl, optionally substituted amino, optionally substituted alkoxy, or optionally substituted trialkylsilyl.

[0370] In another instance, the co-reagent is an alkyl halide. In particular embodiments, the alkyl halide includes a structure having formula (II-B): L3-Z (II-B), wherein: Z is halo (e.g., iodo); and each of L3and L4is, independently, optionally substituted alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, etc.), optionally substituted alkenyl, or optionally substituted haloalkyl.

[0371] In some embodiments, optionally substituted amino includes -NR1R2, in which each R1and R2is, independently, H or optionally substituted alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, etc.); or in which R1and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein. In other embodiments, optionally substituted alkoxy includes -OR1, in which R1can be optionally substituted alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, etc.). In yet other embodiments, the optionally substituted trialkylsilyl is -SiR1R2R3, in which each R1, R2, and R3is, independently, optionally substituted alkyl.

[0372] In some embodiments, the co-reagent is an organometal compound including a structure having formula (III): M2aL5b(III), wherein: M2 is a metal or an atom having a high EUV absorption cross-section; each L5is, independently, H, halo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl,LAMRP955WO-11528-1WO optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkanoyloxy, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, an anionic ligand, a neutral ligand, or a multidentate ligand; a ≥ 1; and b ≥ 1.

[0373] In particular embodiments, M2 is tin(IV) or another metal described herein (e.g., for any of formulas (V), (VI), (VI-A), (VII), (VIII), (VIII-A), (IX), (X), (XI), (XII), (XIII), or (XIV)). In some embodiments, L5is any R, L, L1, L2, L3, L4, or L6described herein for any of formulas (I), (II-A), (II-B), (III-A), (IV), (IV-A), (V), (VI), (VI-A), (VII), (VIII), (VIII-A), (IX), (X), (XI), (XII), (XIII), or (XIV).

[0374] In other embodiments, the organometal compound includes a structure having formula (III-A): M2aR1 cL6 d (III-A), wherein: M2 is a metal; each R1is, independently, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, or L6; each L6is, independently, is a ligand, ion, or other moiety that is reactive with a co- reagent and / or counter-reactant, in which R1and L6with M2, taken together, can optionally form a heterocyclyl group or in which R1and L6, taken together, can optionally form a heterocyclyl group; a ≥ 1; c ≥ 1; and d ≥ 1.

[0375] In some embodiments, each R1is L6, and / or M2 is tin(IV). In particular embodiments, each L6is, independently, H, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted (trialkylsilyl)amino, optionally substituted trialkylsilyl, or optionally substituted alkoxy. In particular embodiments, M2 is any metal described herein (e.g., for any of formulas (V), (VI), (VI-A), (VII), (VIII), (VIII-A), (IX), (X), (XI), (XII), (XIII), or (XIV)). In some embodiments, L6is any R, L, L1, L2, L3, L4, or L5described herein for any of formulas (I), (II-A), (II-B), (III), (IV), (IV-A), (V), (VI), (VI-A), (VII), (VIII), (VIII-A), (IX), (X), (XI), (XII), (XIII), or (XIV).

[0376] Yet further organometal compounds are described herein. For instance, organometal compounds can be any having a structure of formulas (VII), (VIII), (VIII-A), (IX), (X), (XI), (XII), (XIII), or (XIV), as described below.LAMRP955WO-11528-1WO

[0377] In some embodiments, the co-reagent is a tantalum precursor. In particular embodiments, the tantalum precursor includes a structure having formula (IV): TaRbLc (IV), wherein: each R is, independently, an EUV labile group, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted imino, or optionally substituted alkylene; each L is, independently, a ligand or other moiety that is reactive with a reducing gas, in which R and L with Ta, taken together, can optionally form a heterocyclyl group or in which R and L, taken together, can optionally form a heterocyclyl group; b ≥ 0; and c ≥ 1.

[0378] In some embodiments (e.g., of formula (IV)), R and L can be any R, L, L1, L2, L3, L4, L5, or L6described herein for any of formulas (I), (II-A), (II-B), (III), (III-A), (IV-A), (V), (VI), (VI- A), (VII), (VIII), (VIII-A), (IX), (X), (XI), (XII), (XIII), or (XIV). Non-limiting EUV labile groups include branched or linear alkyl groups, as well as those having a beta-hydrogen or a beta- fluorine. Non-limiting alkyl groups include, e.g., CnH2n+1, where n is 1, 2, 3, or greater, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl.

[0379] In particular embodiment (e.g., of formula (IV)), each L is, independently, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino (e.g., -NR1R2, in which each R1and R2is, independently, H or alkyl; or in which R1and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein), optionally substituted bis(trialkylsilyl)amino (e.g., -N(SiR1R2R3)2, in which each R1, R2, and R3is, independently, optionally substituted alkyl), optionally substituted trialkylsilyl (e.g., -SiR1R2R3, in which each R1, R2, and R3is, independently, optionally substituted alkyl), or a bivalent ligand (e.g., any described herein, including those for formula (IV-A)).

[0380] In other embodiments, the tantalum precursor includes a structure having formula (IV- A): R=Ta(L)b (IV-A), wherein: R is =NRior =CRiRii; each L is, independently, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, or a bivalent ligand that is bound to Ta and the bivalent ligand is -LAMRP955WO-11528-1WO NRi-Ak-NRii-; each Riand Riiis, independently, H, optionally substituted linear alkyl, optionally substituted branched alkyl, or optionally substituted cycloalkyl; Ak is optionally substituted alkylene or optionally substituted alkenylene; and b ≥ 1.

[0381] In some embodiments (e.g., of formula (IV-A)), R and L can be any R, L, L1, L2, L3, L4, L5, or L6described herein for any of formulas (I), (II-A), (II-B), (III), (III-A), (IV), (V), (VI), (VI-A), (VII), (VIII), (VIII-A), (IX), (X), (XI), (XII), (XIII), or (XIV).

[0382] In some embodiments, the co-reagent is an alkyl halide. Non-limiting alkyl halides include R-X, in which R is optionally substituted alkyl or optionally substituted haloalkyl, and X is halo.

[0383] In other embodiments, the co-reagent is a reducing gas. Non-limiting reducing gases include hydrogen (H2), ammonia (NH3), and combinations thereof. Such reducing gases can be employed with a chalcogenide precursor (e.g., any herein) or a tantalum precursor (e.g., any herein).

[0384] In yet other embodiments, the co-reagent is a counter-reactant (e.g., an oxygen- containing counter-reactant). Non-limiting counter-reactants include O2, O3, water, a peroxide, hydrogen peroxide, oxygen plasma, water plasma, an alcohol, a dihydroxy alcohol, a polyhydroxy alcohol, a fluorinated dihydroxy alcohol, a fluorinated polyhydroxy alcohol, a fluorinated glycol, formic acid, and other sources of hydroxyl moieties, as well as combinations thereof. Such counter-reactants can be employed in any process or method herein to provide a metal-oxygen bond within the film.

[0385] In various embodiments, a counter-reactant reacts with the Sn(II) compound or a metal- containing co-reagent by forming oxygen bridges between neighboring metal atoms. Other potential counter-reactants include hydrogen sulfide and hydrogen disulfide, which can crosslink metal atoms via sulfur bridges, and bis(trimethylsilyl)tellurium, which can crosslink metal atoms via tellurium bridges. In addition, hydrogen iodide may be utilized to incorporate iodine into the film.

[0386] In particular embodiments, the counter-reactant is employed with an organotin(II) compound (e.g., to provide Sn-O bonds), a chalcogenide precursor (e.g., to provide M-O bonds with M-X bonds, where X is S, Se, or Te), an organometal compound (e.g., to provide M2-O bonds, in which M2 is present in the organometal compound), an organotin(IV) precursor (e.g., to provide Sn-O bonds), a tantalum precursor (e.g., to provide Ta-O or Ta-N bonds), an alkyl halideLAMRP955WO-11528-1WO (e.g., to react with Sn(IV) present after reacting Sn(II) with the alkyl halide), and / or a reducing gas. Further metal precursors

[0387] The methods herein can include an Sn(II) compound used in combination with any useful co-reagent. In particular instances, the co-reagent can include precursors having a chalcogen (e.g., as in a chalcogenide precursor), a metal (e.g., as in an organometal compound), or tantalum (e.g., as in a tantalum precursor). In addition these, co-reagents can also include the further metal precursors described below.

[0388] The metal precursor can have any useful number and type of ligand(s). In some embodiments, the ligand can be characterized by its ability to react in the presence of a co-reagent and / or a counter-reactant or in the presence of patterning radiation. For instance, the metal precursor can include a ligand (e.g., dialkylamino groups or alkoxy groups) that reacts with a counter-reactant, which can introduce linkages between metal centers (e.g., an -O- linkage). In another instance, the metal precursor can include a ligand that eliminates in the presence of patterning radiation. Such a ligand can include branched or linear alkyl groups having a beta- hydrogen.

[0389] The metal precursor can be any useful metal-containing precursor, such as an organometallic agent, a metal halide, or a capping agent (e.g., as described herein). In a non- limiting instance, the metal precursor includes a structure having formula (VII): MaRb (VII), wherein: M is a metal or an atom having a high EUV absorption cross-section; each R is, independently, H, halo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkanoyloxy, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, oxo, an anionic ligand, a neutral ligand, or a multidentate ligand; a ≥ 1; and b ≥ 1.

[0390] In another non-limiting instance, the metal precursor includes a structure having formula (VIII):LAMRP955WO-11528-1WO MaRbLc (VIII), wherein: M is a metal or an atom having a high EUV absorption cross-section; each R is, independently, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted alkoxy, or L; each L is, independently, a ligand, an anionic ligand, a neutral ligand, a multidentate ligand, an ion, or other moiety that is reactive with a co-reagent and / or a counter-reactant, in which R and L with M, taken together, can optionally form a heterocyclyl group or in which R and L, taken together, can optionally form a heterocyclyl group; a ≥ 1; b ≥ 1; and c ≥ 1.

[0391] In some embodiments, each ligand within the metal precursor can be one that is reactive with a co-reagent and / or a counter-reactant. In one instance, the metal precursor includes a structure having formula (VIII), in which each R is, independently, L. In another instance, the metal precursor includes a structure having formula (VIII-A): MaLc (VIII-A), wherein: M is a metal or an atom having a high EUV absorption cross-section; each L is, independently, a ligand, an anionic ligand, a neutral ligand, a multidentate ligand, an ion, or other moiety that is reactive with a co-reagent and / or a counter-reactant, in which two L, taken together, can optionally form a heterocyclyl group; a ≥ 1; and c ≥ 1. In particular embodiments of formula (VIII-A), a is 1. In further embodiments, c is 2, 3, or 4.

[0392] For any formula herein, M can be a metal, a metalloid, or an atom with a high patterning radiation absorption cross-section (e.g., an EUV absorption cross-section that is equal to or greater than 1x107cm2 / mol). In some embodiments, M is tin (Sn), tellurium (Te), bismuth (Bi), antimony (Sb), tantalum (Ta), cesium (Cs), indium (In), molybdenum (Mo), hafnium (Hf), iodine (I), zirconium (Zr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), silver (Ag), platinum (Pt), and lead (Pb). In further embodiments, M is Sn, a is 1, and c is 4 in formula (VII), (VIII), or (VIII-A). In other embodiments, M is Sn, a is 1, and c is 1 or 2 in formula (VII), (VIII), or (VIII- A). In particular embodiments, M is Sn(II) (e.g., in formula (VII), (VIII), or (VIII-A)), therebyLAMRP955WO-11528-1WO providing a metal precursor that is an Sn(II)-based compound. In other embodiments, M is Sn(IV) (e.g., in formula (VII), (VIII), or (VIII-A)), thereby providing a metal precursor that is an Sn(IV)- based compound. In particular embodiments, the precursor includes iodine (e.g., as in periodate).

[0393] For any formula herein, each R or L is, independently, H, halo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy (e.g., -OR1, in which R1can be optionally substituted alkyl), optionally substituted alkanoyloxy, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, oxo, an anionic ligand (e.g., oxido, chlorido, hydrido, acetate, iminodiacetate, etc.), a neutral ligand, or a multidentate ligand.

[0394] In some embodiments, the optionally substituted amino is -NR1R2, in which each R1and R2is, independently, H or alkyl; or in which R1and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein. In other embodiments, the optionally substituted bis(trialkylsilyl)amino is -N(SiR1R2R3)2, in which each R1, R2, and R3is, independently, optionally substituted alkyl. In yet other embodiments, the optionally substituted trialkylsilyl is -SiR1R2R3, in which each R1, R2, and R3is, independently, optionally substituted alkyl.

[0395] In other embodiments, the formula includes a first R (or first L) that is -NR1R2and a second R (or second L) that is -NR1R2, in which each R1and R2is, independently, H or optionally substituted alkyl; or in which R1from a first R (or first L) and R1from a second R (or second L), taken together with the nitrogen atom and the metal atom to which each are attached, form a heterocyclyl group, as defined herein. In yet other embodiments, the formula includes a first R that is -OR1and a second R that is -OR1, in which each R1is, independently, H or optionally substituted alkyl; or in which R1from a first R and R1from a second R, taken together with the oxygen atom and the metal atom to which each are attached, form a heterocyclyl group, as defined herein.

[0396] In some embodiments, at least one of R or L (e.g., in formula (VII), (VIII), or (VIII-A)) is optionally substituted alkyl. Non-limiting alkyl groups include, e.g., CnH2n+1, where n is 1, 2, 3, or greater, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl. In various embodiments, R or L has at least one beta-hydrogen or beta-fluorine.

[0397] In some embodiments, each R or L or at least one R or L (e.g., in formula (VII), (VIII), or (VIII-A)) is halo. In particular, the metal precursor can be a metal halide. Non-limiting metal halides include SnBr4, SnCl4, SnI4, and SbCl3.LAMRP955WO-11528-1WO

[0398] In some embodiments, each R or L or at least one R or L (e.g., in formula (VII), (VIII), or (VIII-A)) can include a nitrogen atom. In particular embodiments, one or more R or L can be optionally substituted amino, an optionally substituted monoalkylamino (e.g., -NR1H, in which R1is optionally substituted alkyl), an optionally substituted dialkylamino (e.g., -NR1R2, in which each R1and R2is, independently, optionally substituted alkyl), or optionally substituted bis(trialkylsilyl)amino. Non-limiting R and L substituents can include, e.g., -NMe2, -NHMe, - NEt2, -NHEt, -NMeEt, -N(t-Bu)-[CHCH3]2-N(t-Bu)- (tbba), -N(SiMe3)2, and -N(SiEt3)2.

[0399] In some embodiments, each R or L or at least one R or L (e.g., in formula (VII), (VIII), or (VIII-A)) can include a silicon atom. In particular embodiments, one or more R or L can be optionally substituted trialkylsilyl or optionally substituted bis(trialkylsilyl)amino. Non-limiting R or L substituents can include, e.g., -SiMe3, -SiEt3, -N(SiMe3)2, and -N(SiEt3)2.

[0400] In some embodiments, each R or L or at least one R or L (e.g., in formula (VII), (VIII), or (VIII-A)) can include an oxygen atom. In particular embodiments, one or more R or L can be optionally substituted alkoxy or optionally substituted alkanoyloxy. Non-limiting R or L substituents include, e.g., methoxy, ethoxy, isopropoxy (i-PrO), t-butoxy (t-BuO), acetate (-OC(O)-CH3), and -O=C(CH3)-CH=C(CH3)-O- (acac).

[0401] Any formulas herein can include one or more neutral ligands. Non-limiting neutral ligands include an optionally substituted amine, an optionally substituted ether, an optionally substituted alkyl, an optionally substituted alkene, an optionally substituted alkyne, an optionally substituted benzene, oxo, or carbon monoxide. Any formulas herein can include one or more multidentate (e.g., bidentate) ligands, tin, bismuth, or tellurium, for example, as described in Embodiment 2. Any formulas herein can also include cesium, antimony, indium, molybdenum, hafnium, for example, as described in Embodiment 3.

[0402] Yet other metal precursors and non-limiting substituents are described herein. For instance, metal precursors can be any having a structure of formulas (VII), (VIII), or (VIII-A), as described above; or formulas (IX), (X), (XI), (XII), (XIII), or (XIV), as described below. Any of the substituents M, R, X, or L, as described herein, can be employed in any of formulas (VII), (VIII), (VIII-A), (IX), (X), (XI), (XII), (XIII), or (XIV).

[0403] Various atoms present in the Sn(II) compound, co-reagent, and / or counter-reactant can be provided within a gradient film. In some embodiments of the techniques discussed herein, a non-limiting strategy that can further improve the EUV sensitivity in a photoresist (PR) film is to create a film in which the film composition is vertically graded, resulting in depth-dependent EUVLAMRP955WO-11528-1WO sensitivity. In a homogenous PR with a high absorption coefficient, the decreasing light intensity throughout the film depth necessitates a higher EUV dose to ensure the bottom is sufficiently exposed. By increasing the density of atoms with high EUV absorptivity at the bottom of the film relative to the top of the film (i.e., by creating a gradient with increasing EUV absorption), it becomes possible to more efficiently use available EUV photons while more uniformly distributing absorption (and the effects of secondary electrons) towards the bottom of more highly absorbing films. In one non-limiting instance, the gradient film includes Te, I, or other atoms towards the bottom of the film (e.g., closer to the substrate).

[0404] As described herein, the films, layers, and methods herein can be employed with any useful precursor. In some instances, the metal precursor includes a metal halide having the following formula (IX): MXn (IX), in which M is a metal, X is halo, and n is 2 to 4, depending on the selection of M. Exemplary metals for M include Sn, Te, Bi, or Sb. Exemplary metal halides include SnBr4, SnCl4, SnI4, and SbCl3.

[0405] Another non-limiting metal-containing precursor includes a structure having formula (X): MRn (X), in which M is a metal; each R is independently H, an optionally substituted alkyl, amino (e.g., -NR2, in which each R is independently alkyl), optionally substituted bis(trialkylsilyl)amino (e.g., -N(SiR3)2, in which each R is independently alkyl), or an optionally substituted trialkylsilyl (e.g., -SiR3, in which each R is independently alkyl); and n is 2 to 4, depending on the selection of M. Exemplary metals for M include Sn, Te, Bi, or Sb. The alkyl group may be CnH2n+1, where n is 1, 2, 3, or greater. Exemplary organometallic agents include SnMe4, SnEt4, TeRn, RTeR, t-butyl tellurium hydride (Te(t-Bu)(H)), dimethyl tellurium (TeMe2), di(t-butyl) tellurium (Te(t-Bu)2), di(isopropyl)tellurium (Te(i-Pr)2), bis(trimethylsilyl)tellurium (Te(SiMe3)2), bis(triethylsilyl) tellurium (Te(SiEt3)2), tris(bis(trimethylsilyl)amido) bismuth (Bi[N(SiMe3)2]3), Sb(NMe2)3, and the like.

[0406] Another non-limiting metal-containing precursor can include a capping agent having the following formula (XI): MLn (XI), in which M is a metal; each L is independently an optionally substituted alkyl, amino (e.g., -NR1R2, in which each of R1and R2can be H or alkyl, such as any described herein), alkoxy (e.g., -OR, in which R is alkyl, such as any described herein), halo, or other organic substituent; and n is 2 to 4,LAMRP955WO-11528-1WO depending on the selection of M. Exemplary metals for M include Sn, Te, Bi, or Sb. Exemplary ligands include dialkylamino (e.g., dimethylamino, methylethylamino, and diethylamino), alkoxy (e.g., t-butoxy, and isopropoxy), halo (e.g., F, Cl, Br, and I), or other organic substituents (e.g., acetylacetone or N2,N3-di-tertbutyl-butane-2,3-diamino). Non-limiting capping agents include SnCl4; SnI4; Sn(NR2)4, wherein each of R is independently methyl or ethyl; or Sn(t-BuO)4. In some embodiments, multiple types of ligands are present.

[0407] A metal-containing precursor can include a hydrocarbyl-substituted capping agent having the following formula (XII): RnMXm(XII), wherein M is a metal, R is a C2-10 alkyl or substituted alkyl having a beta-hydrogen, and X is a suitable leaving group upon reaction with a hydroxyl group of the exposed hydroxyl groups. In various embodiments, n = 1 to 3, and m = 4 – n, 3 – n, or 2 – n, so long as m > 0 (or m ≥ 1). For example, R may be t-butyl, t-pentyl, t-hexyl, cyclohexyl, isopropyl, isobutyl, sec-butyl, n-butyl, n- pentyl, n-hexyl, or derivatives thereof having a heteroatom substituent in the beta position. Suitable heteroatoms include halogen (F, Cl, Br, or I), or oxygen (-OH or -OR). X may be dialkylamino (e.g., dimethylamino, methylethylamino, or diethylamino), alkoxy (e.g., t-butoxy, isopropoxy), halo (e.g., F, Cl, Br, or I), or another organic ligand. Examples of hydrocarbyl-substituted capping agents include t-butyltris(dimethylamino)tin (Sn(t-Bu)(NMe2)3), n-butyltris(dimethylamino)tin (Sn(n-Bu)(NMe2)3), t-butyltris (diethylamino)tin (Sn(t-Bu)(NEt2)3), di(t- butyl)di(dimethylamino)tin (Sn(t-Bu)2(NMe2)2), sec-butyltris(dimethylamino)tin (Sn(s- Bu)(NMe2)3), n-pentyltris(dimethylamino)tin (Sn(n-pentyl)(NMe2)3), i-butyltris(dimethylamino) tin (Sn(i-Bu)(NMe2)3), i-propyltris (dimethylamino)tin (Sn(i-Pr)(NMe2)3), t-butyltris(t-butoxy)tin (Sn(t-Bu)(t-BuO)3), n-butyl(tris(t-butoxy)tin (Sn(n-Bu)(t-BuO)3), or isopropyltris(t-butoxy)tin (Sn(i-Pr)(t-BuO)3).

[0408] In various embodiments, a metal-containing precursor includes at least one alkyl group on each metal atom that can survive the vapor-phase reaction, while other ligands or ions coordinated to the metal atom can be replaced by the counter-reactants. Accordingly, another non- limiting metal-containing precursor includes an organometallic agent having the formula (XIII): MaRbLc(XIII), in which M is a metal; R is an optionally substituted alkyl; L is a ligand, ion, or other moiety which is reactive with the counter-reactant; a ≥ 1; b ≥ 1; and c ≥ 1. In particular embodiments, a = 1, and b + c = 4. In some embodiments, M is Sn, Te, Bi, or Sb. In particular embodiments, each L is independently amino (e.g., -NR1R2, in which each of R1and R2can be H or alkyl, such as any described herein), alkoxy (e.g., -OR, in which R is alkyl, such as any described herein), or haloLAMRP955WO-11528-1WO (e.g., F, Cl, Br, or I). Exemplary agents include SnMe3Cl, SnMe2Cl2, SnMeCl3, SnMe(NMe2)3, SnMe2(NMe2)2, SnMe3(NMe2), and the like.

[0409] In other embodiments, the non-limiting metal-containing precursor includes an organometallic agent having the formula (XIV): MaLc(XIV), in which M is a metal; L is a ligand, ion, or other moiety which is reactive with the counter- reactant; a ≥ 1; and c ≥ 1. In particular embodiments, c = n – 1, and n is 2, 3, or 4. In some embodiments, M is Sn, Te, Bi, or Sb. Counter-reactants preferably have the ability to replace the reactive moieties ligands or ions (e.g., L in formulas herein) so as to link at least two metal atoms via chemical bonding.

[0410] In any embodiment herein, R can be an optionally substituted alkyl (e.g., C1-10 alkyl). In one embodiment, alkyl is substituted with one or more halo (e.g., halo-substituted C1-10alkyl, including one, two, three, four, or more halo, such as F, Cl, Br, or I). Exemplary R substituents include CnH2n+1, preferably wherein n ≥ 3; and CnFxH(2n+1-x), wherein 2n+1 ≤ x ≤ 1. In various embodiments, R has at least one beta-hydrogen or beta-fluorine. For example, R may be selected from the group consisting of i-propyl, n-propyl, t-butyl, i-butyl, n-butyl, sec-butyl, n-pentyl, i- pentyl, t-pentyl, sec-pentyl, and mixtures thereof.

[0411] In any embodiment herein, L may be any moiety readily displaced by a counter-reactant to generate an M-OH moiety, such as a moiety selected from the group consisting of an amino (e.g., -NR1R2, in which each of R1and R2can be H or alkyl, such as any described herein), alkoxy (e.g., -OR, in which R is alkyl, such as any described herein), carboxylates, halo (e.g., F, Cl, Br, or I), and mixtures thereof.

[0412] Exemplary organometallic agents include SnMeCl3, (N2,N3-di-t-butyl-butane-2,3- diamido) tin(II) (Sn(tbba)), bis(bis(trimethylsilyl)amido) tin(II), tetrakis(dimethylamino) tin(IV) (Sn(NMe2)4), t-butyl tris(dimethylamino) tin (Sn(t-butyl)(NMe2)3), i-butyl tris(dimethylamino) tin (Sn(i-Bu)(NMe2)3), n-butyl tris(dimethylamino) tin (Sn(n-Bu)(NMe2)3), sec-butyl tris(dimethylamino) tin (Sn(s-Bu)(NMe2)3), i-propyl(tris)dimethyl amino tin (Sn(i-Pr)(NMe2)3), n- propyl tris(diethylamino) tin (Sn(n-Pr)(NEt2)3), and analogous alkyl(tris)(t-butoxy) tin compounds, such as t-butyl tris(t-butoxy) tin (Sn(t-Bu)(t-BuO)3). In some embodiments, the organometallic agents are partially fluorinated.LAMRP955WO-11528-1WO Embodiment 6 Ta-based precursor(s)

[0413] In some embodiments, a precursor may be a tantalum-based precursor. Any useful Ta- based precursors and other metal compounds (e.g., organometal compounds) can be employed in the methods and processes herein. Non-limiting Ta-based precursors and organometal compounds are described herein.

[0414] The Ta-based precursor can include any precursor (e.g., described herein) that provides a patternable film that is sensitive to radiation (or a patterning radiation-sensitive film or a photopatternable film). Such radiation can include EUV radiation or DUV radiation that is provided by irradiating through a patterned mask, thereby being a patterning radiation. The film itself can be altered by being exposed to such radiation, such that the film is radiation-sensitive.

[0415] In particular embodiments, the Ta-based precursor is an organometallic compound, which includes at least one Ta center and at least one ligand that can react with a reducing gas or an alkyne. In some non-limiting embodiments, the Ta-based precursor also includes an organic moiety that can be reactive in the presence of patterning radiation, such as by undergoing removal or elimination from the metal center or by reacting or polymerizing with other moieties within the film.

[0416] In some embodiments, the Ta-based precursor includes a structure having formula (I): TaRbLc(I), wherein: each R is, independently, an EUV labile group, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted imino, or optionally substituted alkylene; each L is, independently, a ligand or other moiety that is reactive with a reducing gas or an alkyne; b ≥ 0; and c ≥ 0. In other embodiments, b is 1, and c is 3. In other embodiments, c ≥ 1. In yet other embodiments, b ≥ 1. In particular embodiments, L is optionally substituted amino (e.g., -NRN1RN1, in which each RN1and RN2is, independently, H or optionally substituted alkyl, such as methyl, ethyl, butyl, isopropyl, t-butyl, n-butyl, etc.). In some embodiments, R is the EUV labile group, which includes a doubly-bonded ligand (e.g., =NRior =CRiRii, in which each Riand Riiis, independently, H, optionally substituted linear alkyl, optionally substituted branched alkyl, or optionally substituted cycloalkyl, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-butyl, etc.).LAMRP955WO-11528-1WO

[0417] In other embodiments, the Ta-based precursor comprises a structure having formula (I- A): R=Ta(L)b (I-A), wherein: R is =NRior =CRiRii; each L is, independently, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, or a bivalent ligand that is bound to Ta and the bivalent ligand is - NRi-Ak-NRii-; each Riand Riiis, independently, H, optionally substituted linear alkyl, optionally substituted branched alkyl, or optionally substituted cycloalkyl; Ak is optionally substituted alkylene or optionally substituted alkenylene; and b ≥ 1.

[0418] In some embodiments, the optionally substituted amino is -NR1R2, in which each R1and R2is, independently, H or alkyl; or in which R1and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein. In other embodiments, the optionally substituted bis(trialkylsilyl)amino is -N(SiR1R2R3)2, in which each R1, R2, and R3is, independently, optionally substituted alkyl. In yet other embodiments, the optionally substituted trialkylsilyl is -SiR1R2R3, in which each R1, R2, and R3is, independently, optionally substituted alkyl. Any of the substituents R and L for formula (I) and (I-A), can be employed as R or L in any of formulas (II), (II-A), (III), (IV), (V), (VI), (VII), (VIII), or (IX), as described herein.

[0419] In some embodiments, the Ta-based precursor is R=Ta(NRN1RN2)3, in which each of RN1and RN2is, independently, optionally substituted alkyl (e.g., methyl, ethyl, butyl, isopropyl, t-butyl, n-butyl, etc.) and R is a doubly-bonded ligand (e.g., =NRior =CHRi, in which Riis optionally substituted alkyl, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-butyl, etc.). In such precursors, the doubly-bonded ligand serves as both a nitrogen source and a EUV-labile group, while the three amino-based ligands serve as reactive sites to attach to existing functional groups on the deposition substrate surface.

[0420] Non-limiting Ta-based precursors include pentakis(dimethylamino)tantalum(V) (Ta[NMe2]5), t-amylimidotris(dimethylamino)tantalum(V) (Ta(=N-CHMe2Et)(NMe2)3, (t- butylimido)tris(diethylamino)tantalum(V) (Ta(=N-t-Bu)(NEt2)3), (t-butylimido)tris(dimethyl amino)tantalum(V) (Ta(=N-t-Bu)(NEt2)3), and (t-butylimido)tris(ethylmethylamino) tantalum(V) (Ta(=N-t-Bu)(NMeEt)3).LAMRP955WO-11528-1WO Further metal precursors

[0421] The methods herein can include a Ta-based precursor used in combination with any useful metal precursor. In particular instances, the metal precursor is an Sn-based precursor, an organometal compound, or any further metal precursors described below.

[0422] The metal precursor can include any precursor (e.g., described herein) that provides a patternable film that is sensitive to radiation (or a patterning radiation-sensitive film or a photopatternable film). Such radiation can include EUV radiation, DUV radiation, or UV radiation that is provided by irradiating through a patterned mask, thereby being a patterning radiation. The film itself can be altered by being exposed to such radiation, such that the film is radiation- sensitive. In particular embodiments, the metal precursor is an organometallic compound, which includes at least one metal center.

[0423] The metal precursor can have any useful number and type of ligand(s). In some embodiments, the ligand can be characterized by its ability to react in the presence of a counter- reactant or in the presence of patterning radiation. For instance, the metal precursor can include a ligand (e.g., dialkylamino groups or alkoxy groups) that reacts with a counter-reactant, which can introduce linkages between metal centers (e.g., an -O- linkage). In another instance, the metal precursor can include a ligand that eliminates in the presence of patterning radiation. Such a ligand can include branched or linear alkyl groups having a beta-hydrogen.

[0424] The metal precursor can be any useful metal-containing precursor, such as an organometal compound, an organometallic agent, a metal halide, or a capping agent (e.g., as described herein). In a non-limiting instance, the organometal compound includes a structure having formula (II): MaRbLc(II), wherein: M is a metal or an atom having a high EUV absorption cross-section; each R is, independently, an EUV labile ligand, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted alkoxy, or L; each L is, independently, a ligand (e.g., an anionic ligand, a neutral ligand, or a multidentate ligand), an ion, or other moiety that is reactive with a counter-reactant, in which R and L with M, taken together, can optionally form a heterocyclyl group or in which R and L, taken together, can optionally form a heterocyclyl group; a ≥ 1; b ≥ 1; and c ≥ 1.LAMRP955WO-11528-1WO

[0425] In some embodiments, R is optionally substituted alkyl, and M is tin. In other embodiments, each L is, independently, H, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, or optionally substituted alkoxy. In particular embodiments, L is optionally substituted amino (e.g., -NR1R2, in which each R1and R2is, independently, optionally substituted alkyl).

[0426] In some embodiments, the organometal compound is SnRL3, in which each L is, independently, optionally substituted amino (e.g., -NR1R2, in which each R1and R2is, independently, optionally substituted alkyl, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, etc.) and R is optionally substituted alkyl (e.g., methyl, ethyl, butyl, isopropyl, tert-butyl, n-butyl, etc.)

[0427] In some embodiments, each ligand within the metal precursor can be one that is reactive with a counter-reactant. In one instance, the metal precursor includes a structure having formula (II), in which each R is, independently, L. In another instance, the metal precursor includes a structure having formula (II-A): MaLc(II-A), wherein: M is a metal or an atom having a high EUV absorption cross-section; each L is, independently, a ligand, ion, or other moiety that is reactive with a counter-reactant, in which two L, taken together, can optionally form a heterocyclyl group; a ≥ 1; and c ≥ 1. In particular embodiments of formula (II-A), a is 1. In further embodiments, c is 2, 3, or 4.

[0428] In another non-limiting instance, the metal precursor includes a structure having formula (IV): MaRb (III), wherein: M is a metal or an atom having a high EUV absorption cross-section; each R is, independently, H, halo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkanoyloxy, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, oxo, an anionic ligand, a neutral ligand, or a multidentate ligand; a ≥ 1; and b ≥ 1.LAMRP955WO-11528-1WO

[0429] For any formula herein, M can be a metal, a metalloid, or an atom with a high patterning radiation absorption cross-section (e.g., an EUV absorption cross-section that is equal to or greater than 1x107cm2 / mol). In some embodiments, M is tin (Sn), tellurium (Te), bismuth (Bi), antimony (Sb), tantalum (Ta), cesium (Cs), indium (In), molybdenum (Mo), hafnium (Hf), iodine (I), zirconium (Zr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), silver (Ag), platinum (Pt), and lead (Pb). In further embodiments, M is Sn, a is 1, and c is 4 in formula (II), (II-A), or (III). In other embodiments, M is Sn, a is 1, and c is 1 or 2 in formula (II), (II-A), or (III). In particular embodiments, M is Sn(II) (e.g., in formula (II), (II-A), or (III)), thereby providing a metal precursor that is a Sn(II)-based compound. In other embodiments, M is Sn(IV) (e.g., in formula (II), (II-A), or (III)), thereby providing a metal precursor that is a Sn(IV)-based compound. In particular embodiments, the precursor includes iodine (e.g., as in periodate).

[0430] For any formula herein, each R or L is, independently, H, halo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy (e.g., -OR1, in which R1can be optionally substituted alkyl), optionally substituted alkanoyloxy, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, oxo, an anionic ligand (e.g., oxido, chlorido, hydrido, acetate, iminodiacetate, etc.), a neutral ligand, or a multidentate ligand.

[0431] In some embodiments, the optionally substituted amino is -NR1R2, in which each R1and R2is, independently, H or alkyl; or in which R1and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein. In other embodiments, the optionally substituted bis(trialkylsilyl)amino is -N(SiR1R2R3)2, in which each R1, R2, and R3is, independently, optionally substituted alkyl. In yet other embodiments, the optionally substituted trialkylsilyl is -SiR1R2R3, in which each R1, R2, and R3is, independently, optionally substituted alkyl.

[0432] In other embodiments, the formula includes a first R (or first L) that is -NR1R2and a second R (or second L) that is -NR1R2, in which each R1and R2is, independently, H or optionally substituted alkyl; or in which R1from a first R (or first L) and R1from a second R (or second L), taken together with the nitrogen atom and the metal atom to which each are attached, form a heterocyclyl group, as defined herein. In yet other embodiments, the formula includes a first R that is -OR1and a second R that is -OR1, in which each R1is, independently, H or optionally substituted alkyl; or in which R1from a first R and R1from a second R, taken together with the oxygen atom and the metal atom to which each are attached, form a heterocyclyl group, as defined herein.LAMRP955WO-11528-1WO

[0433] In some embodiments, at least one of R or L (e.g., in formula (II), (II-A), or (III)) is optionally substituted alkyl. Non-limiting alkyl groups include, e.g., CnH2n+1, where n is 1, 2, 3, or greater, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl. In various embodiments, R or L has at least one beta-hydrogen or beta-fluorine.

[0434] In some embodiments, each R or L or at least one R or L (e.g., in formula (II), (II-A), or (III)) is halo. In particular, the metal precursor can be a metal halide. Non-limiting metal halides include SnBr4, SnCl4, SnI4, and SbCl3.

[0435] In some embodiments, each R or L or at least one R or L (e.g., in formula (II), (II-A), or (III)) can include a nitrogen atom. In particular embodiments, one or more R or L can be optionally substituted amino, an optionally substituted monoalkylamino (e.g., -NR1H, in which R1is optionally substituted alkyl), an optionally substituted dialkylamino (e.g., -NR1R2, in which each R1and R2is, independently, optionally substituted alkyl), or optionally substituted bis(trialkylsilyl)amino. Non-limiting R and L substituents can include, e.g., -NMe2, -NHMe, - NEt2, -NHEt, -NMeEt, -N(t-Bu)-[CHCH3]2-N(t-Bu)- (tbba),-N(SiMe3)2, and -N(SiEt3)2.

[0436] In some embodiments, each R or L or at least one R or L (e.g., in formula (II), (II-A), or (III)) can include a silicon atom. In particular embodiments, one or more R or L can be optionally substituted trialkylsilyl or optionally substituted bis(trialkylsilyl)amino. Non-limiting R or L substituents can include, e.g., -SiMe3, -SiEt3, -N(SiMe3)2, and -N(SiEt3)2.

[0437] In some embodiments, each R or L or at least one R or L (e.g., in formula (II), (II-A), or (III)) can include an oxygen atom. In particular embodiments, one or more R or L can be optionally substituted alkoxy or optionally substituted alkanoyloxy. Non-limiting R or L substituents include, e.g., methoxy, ethoxy, isopropoxy (i-PrO), t-butoxy (t-BuO), acetate (-OC(O)-CH3), and -O=C(CH3)-CH=C(CH3)-O- (acac).

[0438] Any formulas herein can include one or more neutral ligands. Non-limiting neutral ligands include an optionally substituted amine, an optionally substituted ether, an optionally substituted alkyl, an optionally substituted alkene, an optionally substituted alkyne, an optionally substituted benzene, oxo, or carbon monoxide. Any formulas herein can also include one or more multidentate (e.g., bidentate) ligands, tin, bismuth, tellurium, cesium, antimony, indium, molybdenum, hafnium, for example, as described in Embodiment 3.

[0439] Yet other metal precursors and non-limiting substituents are described herein. For instance, metal precursors can be any having a structure of formulas (II), (II-A), or (III), as described above; or formulas (IV), (V), (VI), (VII), (VIII), or (IX), as described below. Any ofLAMRP955WO-11528-1WO the substituents M, R, X, or L, as described herein, can be employed in any of formulas (II), (II- A), (III), (IV), (V), (VI), (VII), (VIII), or (IX).

[0440] Various atoms present in the Ta-based precursor, metal precursor, reducing gas, hydrocarbon, alkyne, and / or counter-reactant can be provided within a gradient film. In some embodiments of the techniques discussed herein, a non-limiting strategy that can further improve the EUV sensitivity in a photoresist (PR) film is to create a film in which the film composition is vertically graded, resulting in depth-dependent EUV sensitivity. In a homogenous PR with a high absorption coefficient, the decreasing light intensity throughout the film depth necessitates a higher EUV dose to ensure the bottom is sufficiently exposed. By increasing the density of atoms with high EUV absorptivity at the bottom of the film relative to the top of the film (i.e., by creating a gradient with increasing EUV absorption), it becomes possible to more efficiently use available EUV photons while more uniformly distributing absorption (and the effects of secondary electrons) towards the bottom of more highly absorbing films. In one non-limiting instance, the gradient film includes Te, I, or other atoms towards the bottom of the film (e.g., closer to the substrate).

[0441] As described herein, the films, layers, and methods herein can be employed with any useful precursor. In some instances, the metal precursor includes a metal halide having the following formula (IV): MXn (IV), in which M is a metal, X is halo, and n is 2 to 4, depending on the selection of M. Exemplary metals for M include Sn, Te, Bi, or Sb. Exemplary metal halides include SnBr4, SnCl4, SnI4, and SbCl3.

[0442] Another non-limiting metal-containing precursor includes a structure having formula (V): MRn (V), in which M is a metal; each R is independently H, an optionally substituted alkyl, amino (e.g., -NR2, in which each R is independently alkyl), optionally substituted bis(trialkylsilyl)amino (e.g., -N(SiR3)2, in which each R is independently alkyl), or an optionally substituted trialkylsilyl (e.g., -SiR3, in which each R is independently alkyl); and n is 2 to 4, depending on the selection of M. Exemplary metals for M include Sn, Te, Bi, or Sb. The alkyl group may be CnH2n+1, where n is 1, 2, 3, or greater. Exemplary organometallic agents include SnMe4, SnEt4, TeRn, RTeR, t-butyl tellurium hydride (Te(t-Bu)(H)), dimethyl tellurium (TeMe2), di(t-butyl) tellurium (Te(t-Bu)2), di(isopropyl)tellurium (Te(i-Pr)2), bis(trimethylsilyl)tellurium (Te(SiMe3)2), bis(triethylsilyl)LAMRP955WO-11528-1WO tellurium (Te(SiEt3)2), tris(bis(trimethylsilyl)amido) bismuth (Bi[N(SiMe3)2]3), Sb(NMe2)3, and the like.

[0443] Another non-limiting metal-containing precursor can include a capping agent having the following formula (VI): MLn(VI), in which M is a metal; each L is independently an optionally substituted alkyl, amino (e.g., -NR1R2, in which each of R1and R2can be H or alkyl, such as any described herein), alkoxy (e.g., -OR, in which R is alkyl, such as any described herein), halo, or other organic substituent; and n is 2 to 4, depending on the selection of M. Exemplary metals for M include Sn, Te, Bi, or Sb. Exemplary ligands include dialkylamino (e.g., dimethylamino, methylethylamino, and diethylamino), alkoxy (e.g., t-butoxy, and isopropoxy), halo (e.g., F, Cl, Br, and I), or other organic substituents (e.g., acetylacetone or N2,N3-di-tertbutyl-butane-2,3-diamino). Non-limiting capping agents include SnCl4; SnI4; Sn(NR2)4, wherein each of R is independently methyl or ethyl; or Sn(t-BuO)4. In some embodiments, multiple types of ligands are present.

[0444] A metal-containing precursor can include a hydrocarbyl-substituted capping agent having the following formula (VII): RnMXm (VII), wherein M is a metal, R is a C2-10 alkyl or substituted alkyl having a beta-hydrogen, and X is a suitable leaving group upon reaction with a hydroxyl group of the exposed hydroxyl groups. In various embodiments, n = 1 to 3, and m = 4 – n, 3 – n, or 2 – n, so long as m > 0 (or m ≥ 1). For example, R may be t-butyl, t-pentyl, t-hexyl, cyclohexyl, isopropyl, isobutyl, sec-butyl, n-butyl, n- pentyl, n-hexyl, or derivatives thereof having a heteroatom substituent in the beta position. Suitable heteroatoms include halogen (F, Cl, Br, or I), or oxygen (-OH or -OR). X may be dialkylamino (e.g., dimethylamino, methylethylamino, or diethylamino), alkoxy (e.g., t-butoxy, isopropoxy), halo (e.g., F, Cl, Br, or I), or another organic ligand. Examples of hydrocarbyl-substituted capping agents include t-butyltris(dimethylamino)tin (Sn(t-Bu)(NMe2)3), n-butyltris(dimethylamino)tin (Sn(n-Bu)(NMe2)3), t-butyltris (diethylamino)tin (Sn(t-Bu)(NEt2)3), di(t- butyl)di(dimethylamino)tin (Sn(t-Bu)2(NMe2)2), sec-butyltris(dimethylamino)tin (Sn(s- Bu)(NMe2)3), n-pentyltris(dimethylamino)tin (Sn(n-pentyl)(NMe2)3), i-butyltris(dimethylamino) tin (Sn(i-Bu)(NMe2)3), i-propyltris (dimethylamino)tin (Sn(i-Pr)(NMe2)3), t-butyltris(t-butoxy)tin (Sn(t-Bu)(t-BuO)3), n-butyl(tris(t-butoxy)tin (Sn(n-Bu)(t-BuO)3), or isopropyltris(t-butoxy)tin (Sn(i-Pr)(t-BuO)3).

[0445] In various embodiments, a metal-containing precursor includes at least one alkyl group on each metal atom that can survive the vapor-phase reaction, while other ligands or ionsLAMRP955WO-11528-1WO coordinated to the metal atom can be replaced by the counter-reactants. Accordingly, another non- limiting metal-containing precursor includes an organometallic agent having the formula (VIII): MaRbLc (VIII), in which M is a metal; R is an optionally substituted alkyl; L is a ligand, ion, or other moiety which is reactive with the counter-reactant; a ≥ 1; b ≥ 1; and c ≥ 1. In particular embodiments, a = 1, and b + c = 4. In some embodiments, M is Sn, Te, Bi, or Sb. In particular embodiments, each L is independently amino (e.g., -NR1R2, in which each of R1and R2can be H or alkyl, such as any described herein), alkoxy (e.g., -OR, in which R is alkyl, such as any described herein), or halo (e.g., F, Cl, Br, or I). Exemplary agents include SnMe3Cl, SnMe2Cl2, SnMeCl3, SnMe(NMe2)3, SnMe2(NMe2)2, SnMe3(NMe2), and the like.

[0446] In other embodiments, the non-limiting metal-containing precursor includes an organometallic agent having the formula (IX): MaLc(IX), in which M is a metal; L is a ligand, ion, or other moiety which is reactive with the counter- reactant; a ≥ 1; and c ≥ 1. In particular embodiments, c = n – 1, and n is 2, 3, or 4. In some embodiments, M is Sn, Te, Bi, or Sb. Counter-reactants preferably have the ability to replace the reactive moieties ligands or ions (e.g., L in formulas herein) so as to link at least two metal atoms via chemical bonding.

[0447] In any embodiment herein, R can be an optionally substituted alkyl (e.g., C1-10 alkyl). In one embodiment, alkyl is substituted with one or more halo (e.g., halo-substituted C1-10 alkyl, including one, two, three, four, or more halo, such as F, Cl, Br, or I). Exemplary R substituents include CnH2n+1, preferably wherein n ≥ 3; and CnFxH(2n+1-x), wherein 2n+1 ≤ x ≤ 1. In various embodiments, R has at least one beta-hydrogen or beta-fluorine. For example, R may be selected from the group consisting of i-propyl, n-propyl, t-butyl, i-butyl, n-butyl, sec-butyl, n-pentyl, i- pentyl, t-pentyl, sec-pentyl, and mixtures thereof.

[0448] In any embodiment herein, L may be any moiety readily displaced by a counter-reactant to generate an M-OH moiety, such as a moiety selected from the group consisting of an amino (e.g., -NR1R2, in which each of R1and R2can be H or alkyl, such as any described herein), alkoxy (e.g., -OR, in which R is alkyl, such as any described herein), carboxylates, halo (e.g., F, Cl, Br, or I), and mixtures thereof.

[0449] Exemplary organometallic agents include SnMeCl3, (N2,N3-di-t-butyl-butane-2,3- diamido) tin(II) (Sn(tbba)), bis(bis(trimethylsilyl)amido) tin(II), tetrakis(dimethylamino) tin(IV) (Sn(NMe2)4), t-butyl tris(dimethylamino) tin (Sn(t-butyl)(NMe2)3), i-butyl tris(dimethylamino) tin (Sn(i-Bu)(NMe2)3), n-butyl tris(dimethylamino) tin (Sn(n-Bu)(NMe2)3), sec-butylLAMRP955WO-11528-1WO tris(dimethylamino) tin (Sn(s-Bu)(NMe2)3), i-propyl(tris) dimethylamino tin (Sn(i-Pr)(NMe2)3), n- propyl tris(diethylamino) tin (Sn(n-Pr)(NEt2)3), and analogous alkyl(tris)(t-butoxy) tin compounds, such as t-butyl tris(t-butoxy) tin (Sn(t-Bu)(t-BuO)3). In some embodiments, the organometallic agents are partially fluorinated. Embodiment 7 Modified precursors

[0450] This embodiment relates to use of initial precursor(s) in the presence of organic co- reactant(s) to generate a modified precursor, which in turn is immediately deposited to form a patterning radiation-sensitive film (e.g., an EUV-sensitive film). This film, in turn, can serve as an EUV resist or a capping layer, as further described herein. In particular embodiments, the modified precursor is generated and deposited in situ, e.g., generation occurs within the chamber for deposition.

[0451] The modified precursor can be a reaction product that is formed between the initial precursor and the organic co-reactant, in which the reaction product can then be deposited to form a film. Such reactions and depositions can be conducted in vapor form. In particular embodiments, the film can include one or more ligands (e.g., labile ligands) that can be removed, cleaved, or cross-linked by radiation (e.g., EUV or DUV radiation). The concentrations of the initial precursor, organic co-reactant, and the reaction product may be monitored according to some embodiments described herein. In addition, the concentrations of any effluent or deposition products may also be monitored according to some embodiments described herein.

[0452] The initial precursor can include any precursor (e.g., described herein) that provides a patternable film that is sensitive to radiation (or a patterning radiation-sensitive film or a photopatternable film). Such radiation can include EUV radiation or DUV radiation that is provided by irradiating through a patterned mask, thereby being a patterning radiation. The film itself can be altered by being exposed to such radiation, such that the film is radiation-sensitive. In particular embodiments, the initial precursor is an organometallic compound, which includes at least one metal center and at least one ligand that can react with the organic co-reactant. In this way, the organic moiety from the co-reactant reacts with or displaces the ligand from the metal center, thereby attaching that organic moiety as a bound ligand to the metal center. The organic moiety, itself, can enhance EUV / DUV sensitivity of the film (e.g., by increasing EUV / DUV absorptivity) or enhance contrast selectivity during development (e.g., by increasing porosity of a film). Furthermore, the organic moiety can be reactive in the presence of patterning radiation,LAMRP955WO-11528-1WO such as by undergoing removal or elimination from the metal center or by reacting or polymerizing with other moieties within the film.

[0453] The initial precursor can have any useful number and type of ligand(s). As discussed herein, at least one ligand reacts with the organic co-reactant. A ligand can also be characterized by its ability to react in the presence of a counter-reactant or in the presence of patterning radiation. For instance, the initial precursor can include a ligand that reacts with a counter-reactant, which can introduce linkages between metal centers (e.g., an -O- linkage). Such a ligand (e.g., dialkylamino groups or alkoxy groups) could, in some instances, also react with an organic co- reactant. In another instance, the initial precursor can include a ligand that eliminates in the presence of patterning radiation. Such a ligand can include branched or linear alkyl groups having a beta-hydrogen.

[0454] The initial precursor can be any useful metal-containing precursor, such as an organometallic agent, a metal halide, or a capping agent (e.g., as described herein). In a non- limiting instance, the initial precursor includes a structure having formula (I): MaRbLc (I), wherein: M is a metal; each R is, independently, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted alkoxy, or L; each L is, independently, is a ligand, ion, or other moiety that is reactive with the organic co-reactant or a counter-reactant, in which R and L with M, taken together, can optionally form a heterocyclyl group or in which R and L, taken together, can optionally form a heterocyclyl group; a ≥ 1; b ≥ 1; and c ≥ 1.

[0455] In some embodiments, each ligand within the initial precursor can be one that is reactive with an organic co-reactant or a counter-reactant. In one instance, the initial precursor includes a structure having formula (I), in which each R is, independently, L. In another instance, the initial precursor includes a structure having formula (Ia): MaLc (Ia), wherein: M is a metal; each L is, independently, is a ligand, ion, or other moiety that is reactive with the organic co-reactant or a counter-reactant, in which two L, taken together, can optionally form a heterocyclyl group;LAMRP955WO-11528-1WO a ≥ 1; and c ≥ 1. In particular embodiments of formula (Ia), a is 1. In further embodiments, c is 2, 3, or 4.

[0456] For any formula herein, M can be a metal with a high patterning radiation absorption cross-section (e.g., an EUV absorption cross-section that is equal to or greater than 1x107cm2 / mol). In some embodiments, M is tin (Sn), tellurium (Te), bismuth (Bi), antimony (Sb), hafnium (Hf), or zirconium (Zr). In further embodiments, M is Sn, a is 1, and c is 4 in formula (I) or (Ia). In other embodiments, M is Sn, a is 1, and c is 2 in formula (I) or (Ia). In particular embodiments, M is Sn(II) (e.g., in formula (I) or (Ia)), thereby providing an initial precursor that is a Sn(II)-based compound. In other embodiments, M is Sn(IV) (e.g., in formula (I) or (Ia)), thereby providing an initial precursor that is a Sn(IV)-based compound.

[0457] For any formula herein, each L is, independently, H, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, or optionally substituted alkoxy (e.g., - OR1, in which R1can be alkyl). In some embodiments, the optionally substituted amino is -NR1R2, in which each R1and R2is, independently, H or alkyl; or in which R1and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein. In other embodiments, the optionally substituted bis(trialkylsilyl) amino is -N(SiR1R2R3)2, in which each R1, R2, and R3is, independently, alkyl. In yet other embodiments, the optionally substituted trialkylsilyl is -SiR1R2R3, in which each R1, R2, and R3is, independently, alkyl.

[0458] In other embodiments, the formula includes a first L that is -NR1R2and a second L that is -NR1R2, in which each R1and R2is, independently, H or alkyl; or in which R1from a first L and R1from a second L, taken together with the nitrogen atom and the metal atom to which each are attached, form a heterocyclyl group, as defined herein. In yet other embodiments, the formula includes a first L that is -OR1and a second L that is -OR1, in which each R1is, independently, H or alkyl; or in which R1from a first L and R1from a second L, taken together with the oxygen atom and the metal atom to which each are attached, form a heterocyclyl group, as defined herein.

[0459] In some embodiments, at least one of L or R is optionally substituted alkyl (e.g., in formula (I) or (Ia)). Non-limiting alkyl groups include, e.g., CnH2n+1, where n is 1, 2, 3, or greater, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl. In various embodiments, L or R has at least one beta-hydrogen or beta-fluorine. In particular, the initial precursor can be tetramethyl tin (SnMe4), tetraethyl tin (SnEt4), t-butyl tellurium hydride (Te(t- Bu)(H)), dimethyl tellurium (TeMe2), di(t-butyl) tellurium (Te(t-Bu)2), or di(isopropyl)tellurium (Te(i-Pr)2).LAMRP955WO-11528-1WO

[0460] In some embodiments, each L or at least one L is halo (e.g., in formula (I) or (Ia)). In particular, the initial precursor can be a metal halide. Non-limiting metal halides include SnBr4, SnCl4, SnI4, and SbCl3.

[0461] In some embodiments, each L or at least one L can include a nitrogen atom. In particular embodiments, one or more L can be optionally substituted amino or optionally substituted bis(trialkylsilyl)amino (e.g., in formula (I) or (Ia)). Non-limiting L substituents can include, e.g., -NMe2, -NEt2, -NMeEt, -N(t-Bu)-[CHCH3]2-N(t-Bu)- (tbba), -N(SiMe3)2, and -N(SiEt3)2. Non- limiting initial precursors can include, e.g., Sn(NMe2)4, Sn(NEt2)4, Sn(i-Pr)(NMe2)3, Sn(n- Bu)(NMe2)3, Sn(s-Bu)(NMe2)3, Sn(i-Bu)(NMe2)3, Sn(t-Bu)(NMe2)3, Sn(t-Bu)2(NMe2)2, Sn(t- Bu)(NEt2)3, Sb(NMe2)3, Sn(tbba), Sn[N(SiMe3)2]2, or Bi[N(SiMe3)2]3.

[0462] In some embodiments, each L or at least one L can include a silicon atom. In particular embodiments, one or more L can be optionally substituted trialkylsilyl or optionally substituted bis(trialkylsilyl)amino (e.g., in formula (I) or (Ia)). Non-limiting L substituents can include, e.g., -SiMe3, -SiEt3, -N(SiMe3)2, and -N(SiEt3)2. Non-limiting initial precursors can include, e.g., Sn[N(SiMe3)2]2, bis(trimethylsilyl)tellurium (Te(SiMe3)2), bis(triethylsilyl)tellurium (Te(SiEt3)2), or Bi[N(SiMe3)2]3.

[0463] In some embodiments, each L or at least one L can include an oxygen atom. In particular embodiments, one or more L can be optionally substituted alkoxy (e.g., in formula (I) or (Ia)). Non-limiting L substituents include, e.g., methoxy, ethoxy, isopropoxy (i-PrO), t-butoxy (t-BuO), and -O=C(CH3)-CH=C(CH3)-O- (acac). Non-limiting initial precursors include, e.g., Sn(t-BuO)4, Sn(n-Bu)(t-BuO)3, or Sn(acac)2.

[0464] Yet other initial precursors and non-limiting substituents are described herein. For instance, initial precursors can be any having a structure of formulas (I) and (Ia), as described above; or formulas (III), (IV), (V), (VI), (VII), or (VIII), as described below. Any of the substituents M, R, X, or L, as described herein, can be employed in any of formulas (I), (Ia), (III), (IV), (V), (VI), (VII), or (VIII).

[0465] To provide a modified precursor, an organic co-reactant is employed to react with or to replace a ligand of the initial precursor. Any useful organic co-reactant can be employed. Such an organic co-reactant can be provided in any form, e.g., as a vapor phase.

[0466] In one non-limiting instance, the organic co-reactant is a compound having formula (II): X1-Z-X2(II), wherein:LAMRP955WO-11528-1WO each of X1and X2is, independently, a leaving group (e.g., halo, H, hydroxyl, optionally substituted alkyl, optionally substituted alkoxy, etc.); and Z is carbonyl, dicarbonyl, optionally substituted alkylene, optionally substituted haloalkylene, optionally substituted alkenylene, or optionally substituted alkynylene.

[0467] In some embodiments, Z is substituted with one or more oxo (=O) groups. In some embodiment, Z is C1-3 alkylene optionally substituted with one or more oxo groups. In particular embodiments, Z is carbonyl, oxalyl, mesoxalyl, malonyl, or oxalacetyl. In other embodiments, Z includes one or more saturated bonds. In particular embodiments, Z is ethynylene. Examples of organic co-reactants include aldehyde, ketone, carboxylic acid, carbonyl halide, oxalyl halide (e.g., oxalyl chloride), acetylene, and others, as well as derivatives thereof. In other embodiments, Z is substituted with one or more halo groups.

[0468] In some embodiments, the organic co-reactant is an acetylene derivative having formula (IIa): X1-C≡C-X2(IIa), wherein: each of X1and X2is, independently, a leaving group, such as halo, H, or optionally substituted alkyl. Such an organic co-reactant can be employed to provide an ethynyl-derived moiety, such as -C≡C-X1, that can be directly bonded to the metal center M in the initial precursor.

[0469] In other embodiments, the organic co-reactant is an oxalyl derivative having formula (IIb): X1-C(O)-C(O)-X2(IIb), wherein: each of X1and X2is, independently, a leaving group, such as halo, H, hydroxyl, optionally substituted alkyl, or optionally substituted alkoxy. Such an organic co-reactant can be employed to provide an oxalyl-derived moiety, such as -C(O)-C(O)- or -OC(O)-C(O)O-, that can be directly bonded to the metal center M in the initial precursor.

[0470] In yet other embodiments, the organic co-reactant is an alkyl derivative having formula (IIc): X1-Ak-H (IIc), wherein: X1is a leaving group, such as halo, hydroxyl, optionally substituted alkyl, or optionally substituted alkoxy; and Ak is an optionally substituted alkylene or optionally substituted haloalkylene.LAMRP955WO-11528-1WO Such an organic co-reactant can be employed to provide a labile alkyl-derived moiety, such as an EUV-responsive organic moiety (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert- butyl, etc.) that can be directly bonded to the metal center M in the initial precursor.

[0471] When at least one halo is present, then the organic co-reactant can be a haloalkyl moiety or a haloalkyl derivative. In particular embodiments, the organic co-reactant is a haloalkyl derivative (e.g., in which halo is iodo), and the initial precursor is a Sn(II)-based compound. Without wishing to be limited by mechanism, the modified precursor obtained by using such compounds can involve oxidative addition of a low valent Sn(II) species or other electron rich metallic precursor across a reactive carbon-halogen bond of the added organic co-reactant (e.g., provided in vapor phase). In some instance, the reactive carbon-halogen bond is a reactive carbon- iodine bond. Non-limiting alkyl derivatives include ethyl iodide, iso-propyl iodide, t-butyl iodide, diiodomethane, etc.

[0472] In some instances, the electron rich metallic precursor is a trivalent Sb or Bi precursor. Non-limiting precursors can include SbR3or BiR3(e.g., R is any described herein, such as a for formula (I), (IV), or (VI)), to which an alkyl halide could add to form a pentavalent complex. Of note, Sb and Bi are of interest due to their high EUV absorption cross section.

[0473] Methods can also employ a chalcogenide precursor, as a counter-reactant or an organic co-reactant. In particular embodiments, the chalcogenide precursor includes a structure having formula (IId): X3-Z-X4(IId), wherein: Z is sulfur, selenium, or tellurium; and each of X3and X4is, independently, H, optionally substituted alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, etc.), optionally substituted alkenyl, optionally substituted aryl, optionally substituted amino, optionally substituted alkoxy, or optionally substituted trialkylsilyl. Such a chalcogenide precursor can be employed to provide a chalcogenide atom Z that can be directly bonded to the metal center M in the initial precursor.

[0474] In yet other embodiments, the organic co-reactant is a carbonyl derivative having formula (IIe): X1-C(O)-X2(IIe), wherein:LAMRP955WO-11528-1WO each of X1and X2is, independently, a leaving group, such as halo, H, hydroxyl, optionally substituted alkyl, optionally substituted haloalkyl, optionally substituted heteroalkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, or optionally substituted aryl. Such an organic co-reactant can be employed to provide a carbonyl- derived moiety, such as -C(O)-X1, that can be directly bonded to the metal center M in the initial precursor. Non-limiting carbonyl derivatives include an aldehyde, a ketone, a carbonyl halide, a carboxylic acid, and the like, as described herein. In some embodiments, at least one of X1and X2is H, halo, or hydroxyl. In other embodiments, both of X1and X2is selected from the group of optionally substituted alkyl, optionally substituted haloalkyl, optionally substituted heteroalkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aryl (e.g., as in a ketone).

[0475] The organic co-reactant can be employed to replace at least one ligand of the initial precursor, in which the organic co-reactant provides a bound ligand for the modified precursor. In one instance, the organic co-reactant can include a structure having formula (II), and the bound ligand can include or be any useful substituent resulting from a reaction between the initial precursor and the organic co-reactant (optionally with a counter-reactant). In particular embodiments, the bound ligand in the modified precursor has a structure of -Xa-Z-Xb-, in which Z can be optionally substituted alkylene, optionally substituted alkenylene, or optionally substituted alkynylene (e.g., ethynylene, oxalyl, mesoxalyl, malonyl, or oxalacetyl); and each of Xaand Xbis, independently, a bond (e.g., a covalent bond), oxy, imino, carbonyl, alkylene, alkyleneoxy, heteroalkylene, and the like. In other embodiments, the bound ligand in the modified precursor has a structure of -Xa-Z-Xc, in which Z can be optionally substituted alkylene, optionally substituted alkenylene, or optionally substituted alkynylene (e.g., ethynylene, oxalyl, mesoxalyl, malonyl, or oxalacetyl); Xais, independently, a bond (e.g., a covalent bond), oxy, imino, or carbonyl; and Xcis H, halo, hydroxyl, optionally substituted alkyl, or optionally substituted alkoxy.

[0476] Within the film, the bound ligand can have a structure of -Xa-Z-Xb-, in which this structure can be bound to directly or indirect to metal atoms. Also, within the film, the bound ligand can have a structure of -Xa-Z-Xc, in which Xais bound directly or indirectly to a metal atom.

[0477] In some embodiments, the organic co-reactant includes one or more bulky substituents, thereby providing a modified precursor having a bound ligand that includes a bulky substituent. In one instance, a bulky organic co-reactant might lead to increased dry development contrast in the film, due to an increased porosity difference between radiation exposed and unexposed areas. In another instance, a bulky organic co-reactant might lead to increased dry development rate due to increased porosity difference between radiation exposed and unexposed areas. In general,LAMRP955WO-11528-1WO bulkier substituents may provide films having increased porosity, and increased porosity would provide increased access to etchant or development chemistries. Porosity can be characterized in any useful manner, e.g., such as a volumetric gas adsorption.

[0478] Figures 5A-5H show non-limiting films having various organic moieties directly bonded to a metal center M that is provided by an initial precursor. The organic moiety can be provided by an organic co-reactant during deposition. In particular, the presence of the organic moiety can provide a film having enhanced EUV reactivity.

[0479] An initial precursor can include one or more reactive ligands, which can be used to react with an organic co-reactant in order to provide a modified precursor. Within the modified precursor, an organic moiety is directly attached to the metal atom M provided by the initial precursor. Non-limiting organic moieties include any provided by an organic co-reactant, such as an ethynyl-derived moiety, an oxalyl-derived moiety, a labile alkyl-derived moiety, and others described herein.

[0480] Figure 5A shows a non-limiting film including a modified precursor having formula (II- 1a). As can be seen, this modified precursor includes two different types of organic moieties (e.g., a labile isopropyl ligand and an ethynyl-derived ligand, in which X can be H, alkyl, a metal atom, an Sn atom, a leaving group, or a labile ligand) directly attached to the Sn metal atom. Such a modified precursor can be deposited by using an initial precursor (e.g., any herein) in the presence of an organic co-reactant (e.g., any herein). In one non-limiting instance, the initial precursor has a reactive ligand (e.g., -NMe2) that can be replaced with the organic co-reactant and has a labile ligand (e.g., alkyl) that is retained until exposure to a patterning radiation. Within formula (II-1a), the modified precursor has an ethynyl-derived ligand that can be provided by an organic co- reactant and has an isopropyl ligand that is retained during film deposition.

[0481] To ensure that one or more organic moieties are provided within the deposited film, reaction conditions can be optimized to promote reactions that directly attach both the counter- reactant and the organic co-reactant with the metal atom of the initial precursor. In this way, both oxygen atoms (f...

Claims

LAMRP955WO-11528-1WO CLAIMS What is claimed is:

1. A method of monitoring concentrations of two or more precursors, the method comprising: flowing the two or more precursors continuously from one or more vapor supply sources toward a process chamber; and monitoring the concentrations of the two or more precursors based at least in part on spectroscopy measurements received from one or more spectral sensors.

2. The method of claim 1, wherein each of the two or more precursors is separately flowed towards the process chamber.

3. The method of claim 1, wherein the two or more precursors are collectively flowed towards the process chamber.

4. The method of claim 1, wherein the two or more precursors flow at a vapor pressure equal to or less than about 50 millitorr.

5. The method of claim 1, wherein the two or more precursors are mixed with a carrier gas to form a gas mixture.

6. The method of claim 5, wherein a mixing ratio of the two or more precursors to the carrier gas is about 1:

100.

7. The method of claim 1, wherein the concentrations of the two or more precursors are monitored by the spectroscopy measurements and pressure and / or temperature measurements.

8. The method of claim 7, wherein the pressure is measured for the carrier gas by a mass flow controller.

9. The method of claim 1, wherein the one or more spectral sensors comprise an infrared (IR) sensor, a visible light sensor, an ultraviolet (UV) sensor, or a combination thereof.LAMRP955WO-11528-1WO 10. The method of claim 1 wherein the spectroscopy measurements generate electrical or optical signals for absorption characteristics obtained for the two or more precursors.

11. The method of claim 10, wherein the electrical or optical signals for the two or more precursors are compared against calibrated reference signals.

12. The method of claim 1, wherein monitoring the concentrations of the two or more precursors comprises monitoring a concentration of a contaminant mixed with the two or more precursors.

13. The method of claim 12, wherein the contaminant comprises water, a decomposed product, or a reaction product mixed with the two or more precursors.

14. The method of claim 12, wherein the contaminant is identified by comparing electrical or optical signals obtained for the two or more precursors mixed with the contaminant against electrical or optical signals calibrated for the two or more precursors.

15. The method of claim 1, further comprising providing the two or more precursors into the process chamber for depositing a film on a substrate.

16. The method of claim 1, further comprising modifying a flow condition of the two or more precursors flowing from the one or more vapor supply sources based on the monitored concentrations of the two or more precursors, wherein the flow condition of the two or more precursors is modified to an updated flow rate for the two or more precursors.

17. The method of claim 16, wherein the flow condition of the precursor is modified by controlling a temperature of the precursor.

18. The method of claim 1, wherein each of the two or more precursors comprises a metal- containing precursor.

19. The method of claim 1, wherein each of the two or more precursors comprises an organometallic precursor.LAMRP955WO-11528-1WO 20. The method of claim 1, wherein the concentrations of the two or more precursors are determined only using IR spectroscopy measurements.

21. The method of claim 1, wherein the concentration of the two or more precursors are determined only using UV spectroscopy measurements.

22. The method of claim 1, wherein the concentrations of the two or more precursors are monitored based on the absorption of IR radiation relative to the absorption of UV radiation, or the absorption of UV radiation relative to the absorption of IR radiation in each of the two or more precursors.

23. A method of monitoring precursor concentration, the method comprising: flowing a precursor continuously from a vapor supply source towards a process chamber; and monitoring the precursor concentration based at least in part on spectroscopy measurements received from one or more spectral sensors, wherein the precursor comprises a metal-containing precursor for depositing a metal- containing photoresist on a substrate.

24. The method of claim 23, wherein the precursor flows at a vapor pressure equal to or less than about 50 millitorr.

25. The method of claim 23, wherein the precursor is mixed with a carrier gas at a flow rate ratio of about 1 to about 100.

26. The method of claim 23, wherein the precursor concentration is monitored by the spectroscopy measurements and pressure and / or temperature measurements.

27. The method of claim 23, wherein monitoring the precursor concentration comprises monitoring the concentration of a contaminant mixed with the precursor, wherein the contaminant comprises water, a decomposed product, or a reaction product mixed with the precursor.LAMRP955WO-11528-1WO 28. The method of claim 23, further comprising modifying a flow condition of the precursor flowing from the vapor supply source based on the monitored precursor concentration, wherein the flow condition of the precursor is modified to an updated flow rate for the precursor.

29. The method of claim 28, wherein the flow condition of the precursor is modified by controlling a temperature of the precursor.

30. The method of claim 23, wherein the precursor comprises an organometallic precursor.

31. The method of claim 23, wherein the spectral sensor comprises an IR sensor, a visible light sensor, a UV sensor, or a combination thereof.

32. A method of monitoring precursor concentrations, the method comprising: flowing a precursor continuously from a vapor supply source towards a deposition chamber; and monitoring the precursor concentration based at least in part on sensor measurements, wherein the precursor comprises a metal-containing precursor for depositing a metal- containing photoresist.

33. The method of claim 32, wherein the precursor flows at a vapor pressure equal to or less than about 50 millitorr.

34. The method of claim 32, wherein the precursor is mixed with a carrier gas at a flow rate ratio of about 1 to about 100.

35. The method of claim 32, wherein the precursor concentration is monitored by an optical sensor or a piezoelectric sensor.

36. The method of claim 35, wherein the piezoelectric sensor comprises a surface acoustic wave sensor or an acoustic time of flight sensor.

37. The method of claim 32, wherein monitoring the precursor concentration comprises monitoring the concentration of a contaminant mixed with the precursor, wherein the contaminant comprises water, a decomposed product, or a reaction product mixed with theLAMRP955WO-11528-1WO precursor.

38. The method of claim 32, further comprising modifying a flow condition of the precursor flowing from the vapor supply source based on the monitored precursor concentration, wherein the flow condition of the precursor is modified to an updated flow rate for the precursor.

39. The method of claim 32, wherein the precursor comprises an organometallic precursor.

40. An apparatus for processing or depositing a metal-containing photoresist on a substrate comprising: one or more process chambers for processing or depositing a metal-containing photoresist from one or more metal-containing precursors; one or more flow rate controllers; one or more spectral sensors; and a controller having at least one processor and a memory device, wherein the at least one processor and the memory device are communicatively connected with one another, the at least one processor is at least operatively connected with the one or more spectral sensors and one or more flow rate controllers, and the memory device stores computer- executable instructions for controlling the at least one processor to at least control the associated one or more spectral sensors and the one or more flow rate controllers to: cause exposure of one or more metal-containing precursors mixed with a carrier gas to radiation; cause the one or more spectral sensors to receive and generate signals for absorption characteristics of the one or more metal-containing precursors; and cause the concentrations of the one or more metal-containing precursors to be monitored.

41. The apparatus of claim 40, wherein the at least one processor further controls the associated one or more spectral sensors and the one or more flow rate controllers to: cause the monitored precursor concentrations to be compared against desired precursor amounts; and depending on the difference between the desired precursor amount and the monitored precursor concentrations, cause the flow rates of the one or more metal-containingLAMRP955WO-11528-1WO precursors mixed with the carrier gas to be increased, decreased, or maintained.

42. The apparatus of claim 40, wherein the one or more spectral sensors include an IR sensor, a UV sensor, or a combination thereof.

43. The apparatus of claim 40, wherein the one or more metal-containing precursors mixed with the carrier gas are flowed continuously or in a series of pulses.

44. The apparatus of claim 40, further comprising: a mixing vessel; and a showerhead, wherein the one or more spectral sensors are located upstream of the showerhead and downstream of the mass flow controller.

45. The apparatus of claim 40, further comprising: one or more mixing vessel inlet valves, wherein the one or more spectral sensors are located upstream of the one or more mixing vessel inlet valves.

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