Positive tone dry development on metal oxide photoresist

Abstract

A positive tone dry development process is performed on a radiation-sensitive film such as a metal oxide photoresist film. A photoresist material is deposited on a substrate having a metal, an oxygen, and at least one unsaturated carbon bond. The photoresist material is exposed to patterning radiation to provide a photopatterned metal oxide photoresist film having an exposed region and an unexposed region. The exposed region may include one or more carbon-based polymers composed of cross-linked organic moieties. The photopatterned metal oxide photoresist film undergoes a bake that includes exposure to a gaseous environment including an oxygen-containing species. After bake, the photopatterned metal oxide photoresist film is dry developed by selectively removing the exposed region relative to the unexposed region.

Description

Atorney Docket No.: LAM1P118WO-12279-1WO POSITIVE TONE DRY DEVELOPMENT ON METAL OXIDE PHOTORESISTINCORPORATION BY REFERENCE

[0000] 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

[0001] The present disclosure relates to photoresist processing in semiconductor fabrication, and more particularly to positive tone development of radiation-sensitive films or photoresists.BACKGROUND

[0002] The fabrication of semiconductor devices, such as integrated circuits, is a multi-step process involving photolithography. In general, the process includes the deposition of material on a wafer, and patterning the material through lithographic techniques to form structural features (e.g., transistors and circuitry) of the semiconductor device. The steps of atypical photolithography process know n in the art include: preparing the substrate; applying a photoresist, such as by spin coating; exposing the photoresist to light in a desired pattern, causing the exposed areas of the photoresist to become more or less soluble in a developer solution; developing by applying a developer solution to remove either the exposed or the unexposed areas of the photoresist; and subsequent processing to create features on the areas of the substrate from w hich the photoresist has been removed, such as by etching or material deposition.

[0003] The background description provided herein is for the purpose of generally presenting the context of the present technology. 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 technology.SUMMARY

[0004] A method of processing a substrate is disclosed herein. The method includes providing the substrate in a processing chamber, w here the substrate includes a photopattemed metal oxide resist film having an exposed region and an unexposed regions, where the exposed region of the photopattemed metal oxide resist film includes one or more carbon-based polymers. The method further includes dry developing the photopattemed metal oxide resist film by selectively removingAtorney Docket No.: LAM1P118WO-12279-1WO the exposed region relative to the unexposed region of the photopattemed metal oxide resist film to form a resist mask.

[0005] In some implementations, the method further includes baking the photopattemed metal oxide resist film by exposure to a gaseous environment comprising at least one oxygen-containing species. In some implementations, baking the photopattemed metal oxide resist film reduces a carbon content in the unexposed region by a greater percentage than a carbon content in the exposed region. In some implementations, baking the photopattemed metal oxide resist film densifies the unexposed region relative to the exposed region. In some implementations, baking the photopattemed metal oxide resist film substantially removes organic ligands from the unexposed region and substantially preserves the carbon-based polymers in the exposed region. In some implementations, the method further includes depositing a photoresist material on the substrate, where the photoresist material includes a metal and oxygen, where the photoresist material further includes at least one unsaturated carbon bond. In some implementations, depositing the photoresist material includes depositing a metal-containing precursor on a surface of the substrate, where the metal-containing precursor comprises a metal (M) selected from the group consisting of lead, germanium, tin, and hafnium. In some implementations, the metalcontaining precursor has the formula M(R1)r, where at least one R1is an unsaturated substituent, where the metal-containing precursor forms a primary metal oxide network film having one or more unsaturated substituents after depositing the photoresist material. In some implementations, the one or more unsaturated substituents in the pri mary metal oxide network film form a secondary hydrocarbon cross-linked network upon exposure to radiation. In some implementations, at least one other R1is a saturated substituent. In some implementations, the photoresist material includes a vinyl group (-CH=CH2) or other unsaturated substituent. In some implementations, the other unsaturated substituent includes an aliphatic chain, cyclic, aryl, or heteroaryl group. In some implementations, the photoresist material further includes at least one saturated substituent, in addition to the vinyl group or other unsaturated substituent.

[0006] Also provided herein is a method of performing a positive tone dry development. The method includes depositing a photoresist material on a surface of a substrate, where the photoresist material includes a metal and oxygen, where the photoresist material further includes an unsaturated carbon bond. The method further includes exposing the photoresist material to radiation to form a photopattemed metal oxide resist film, thereby providing an exposed region and an unexposed region of the photopattemed metal oxide resist film. The method further includes baking the photopattemed metal oxide resist film by exposure to a gaseous environment including at least one oxygen-containing species, and dry developing the photopattemed metalAtorney Docket No.: LAM1P118WO-12279-1WO oxide resist film by selectively removing the exposed region relative to the unexposed region of the photopattemed metal oxide resist film to form a resist mask.

[0007] In some implementations, exposing the photoresist material to radiation photoinduces polymerization to form cross-linked organic moieties in the exposed region of the photopatterned metal oxide resist film. In some implementations, baking the photopattemed metal oxide resist film substantially removes organic ligands from the unexposed region and substantially preserves the cross-linked organic moieties in the exposed region. In some implementations, the photoresist material includes one or more saturated substituents and one or more unsaturated substituents having the unsaturated carbon bond. In some implementations, dry developing the photopattemed metal oxide resist film includes exposure to a dry development chemistry that selectively breaks metal-carbon bonds relative to metal-oxygen bonds. In some implementations, the photoresist material includes a vinyl group (-CH^CFb) or other unsaturated substituent. In some implementations, the other unsaturated substituent includes an aliphatic chain, cyclic, aryl, or heteroaryl group. In some implementations, the photoresist material further includes at least one saturated substituent, in addition to the vinyl group or other unsaturated substituent.BRIEF DESCRIPTION OF DRAWINGS

[0008] Figure 1 presents a flow diagram of an example patterning process flow involving a metal-containing photoresist film according to some implementations.

[0009] Figure 2 presents schematic illustrations of various stages for making a negative tone resist film according to some implementations.

[0010] Figure 3 presents schematic illustrations of various stages for making a positive tone resist film according to some implementations.

[0011] Figure 4 presents a flow diagram of an example method of performing positive tone dry development according to some implementations.

[0012] Figure 5 presents a reaction scheme illustrating initiation, polymerization, and termination of a tin-oxo network having unsaturated substituents upon exposure to patterning radiation according to some implementations.

[0013] Figure 6 presents a reaction scheme illustrating initiation, polymerization, and termination of a tin-oxo network having unsaturated substituents and at least one saturated substituent upon exposure to patterning radiation according to some implementations.

[0014] Figure 7 depicts a schematic illustration of an example process station that is suitable for maintaining a low-pressure environment that is suitable for performing the methods in accordance with certain disclosed embodiments.Atorney Docket No.: LAM1P118WO-12279-1WO

[0015] Figure 8 depicts a schematic illustration of an example multi-station processing tool suitable for implementation of various operations in accordance with certain disclosed embodiments.

[0016] Figure 9 shows a cross-sectional schematic view of an example plasma apparatus for implementing certain implementations and operations described herein.

[0017] Figure 10 depicts a semiconductor process cluster tool architecture with vacuum-integrated deposition and patterning modules that interface with a vacuum transfer module, suitable for implementations of processes described herein.

[0018] Figure 11 depicts a cross-sectional schematic view of an example dry’ deposition apparatus according to some implementations.DETAILED DESCRIPTION

[0019] 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 ty pically 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.

[0020] This disclosure relates generally to the field of semiconductor processing. In particular aspects, the disclosure is directed to processes and apparatuses for processing of photoresists (e.g., EUV-sensitive metal and / or metal oxide-containing photoresists), and for performing reactive chemical treatments of photoresists. While discussion below may be focused on photoresist patterning and lithographic processes, it will be apparent that the techniques and apparatuses discussed herein are not limited solely to photoresist manufacturing and lithographic processes.

[0021] Reference is made herein in detail to specific embodiments of the disclosure. Examples of the specific embodiments are illustrated in the accompanying drawings. While the disclosure will be described in conjunction with these specific embodiments, it will be understood that it is not intended to limit the disclosure to such specific embodiments. On the contrary, it is intended to cover alternatives, modifications, and equivalents as may be included within the spirit and scope of the disclosure. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present disclosure. The present disclosure may be practiced without some or all of these specific details. In other instances, well known processAtorney Docket No.: LAM1P118WO-12279-1WO operations have not been described in detail so as to not unnecessarily obscure the present disclosure.Definitions

[0022] By ‘‘aliphatic” is meant a hydrocarbon moiety 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 (Ci- 10), and which includes saturated groups such as alkanes (or alkyl) and unsaturated groups such as alkenes (or alkenyl), alkynes (or alkynyl), and also includes cyclic versions thereof, and further including straight- and branched-chain arrangements, and all stereo and position isomers as well. Such a hydrocarbon can be unsubstituted or substituted with one or more groups, such as halogens or groups described herein for an alkyl group.

[0023] By “alkenyl” is meant an optionally substituted C2-24 alkyl group having one or more double bonds. The alkenyl group can be cyclic (e.g., C3-24 cycloalkenyl) or acyclic. 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 unsubstituted alkenyl groups include C2-8 alkenyl, C2-6 alkenyl, C2-5 alkenyl, C2-4 alkenyl, or C2-3 alkenyl. Exemplary, non-limiting alkenyl groups include vinyl or ethenyl (-CH=CH2), 1 -propenyl (-CH=CHCH3), allyl or 2-propenyl (-CH2-CH=CH2), 1-butenyl (-CH=CHCH2CH3), 2-butenyl (-CH2CHCHCH3), 3-butenyl (e g. -CH2CH2CH=CH2). 2-butenylidene (e.g., =CH-CH=CHCH3), and the like.

[0024] By “alkenylene” is meant a multivalent (e.g., bivalent) form of an alkenyl group, which is an optionally substituted C2-24 alky l group having one or more double bonds. The alkenylene group can be cyclic (e.g.. C3-24 cycloalkenyl) or acyclic. The alkenylene group can be substituted or unsubstituted. For example, the alkenylene group can be substituted with one or more substitution groups, as described herein for alkyl. Exemplary, non-limiting alkenylene groups include -CH=CH- or -CH=CHCH2-.

[0025] By “alkoxy” is meant -OR, where R is an optionally substituted alkyl group, as described herein. Exemplary alkoxy groups include methoxy, ethoxy, butoxy, 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, Ci-16, Ci-18, C1-20, or C1-24 alkoxy groups.

[0026] By “alkyl” and the prefix “alk” is meant a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (n-Pr or nPr), isopropyl (i-Pr or iPr), cyclopropyl, n-butyl (n-Bu or nBu), isobutyl (i-Bu or iBu), s-butyl (s-Bu or sBu), t-butyl (t-Bu or tBu), cyclobutyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl,Atorney Docket No.: LAM1P118WO-12279-1WO decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. The alkyl group can be cyclic (e.g., C3-24 cycloalkyl) or acyclic. The alkyl group can be branched or unbranched. The alkyd group can also be substituted or unsubstituted. For example, the alkyl group can include haloalkyl, in which the alky 1 group is substituted by one or more halo groups, as described herein. In another 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-Ak, wherein Ak is optionally substituted C1-6 alkyl); (2) amino (e.g., -NRN1RN2, where each of RN1and RN2is, independently, H or optionally substituted alkyl, or RN1and RN2. taken together with the nitrogen atom to which each are attached, form a heterocyclyl group); (3) aryl; (4) arylalkoxy (e.g., -O-Lk-Ar, wherein Lk is a bivalent form of optionally substituted alky l and Ar is optionally substituted ary l); (5) aryloyl (e.g., -C(O)-Ar, wherein Ar is optionally substituted aryl); (6) cyano (e.g., -CN); (7) carboxyaldehyde (e.g., -C(O)H); (8) carboxyl (e.g., -CO2H); (9) C3-8 cycloalkyl (e.g., a monovalent saturated or unsaturated non-aromatic cyclic C3-8 hydrocarbon group); (10) halo (e.g.. F, Cl, Br, or I); (11) heterocyclyl (e.g., a 3-, 4-, 5-, 6- or 7-membered ring, unless otherwise specified, containing one, two, three, or four non-carbon heteroatoms, such as nitrogen, oxygen, phosphorous, sulfur, or halo); (12) heterocyclyloxy (e.g., -O-Het, wherein Het is heterocyclyl, as described herein); (13) heterocyclyloyl (e.g.. -C(O)-Het. wherein Het is heterocyclyl. as described herein); (14) hydroxyl (e.g., -OH); (15) N-protected amino; (16) nitro (e.g., -NO2); (17) oxo (e.g., =0); (18) -CO2RA, where RAis selected from the group consisting of (a) C1-6 alkyl, (b) C4-18 aryl, and (c) (C4-18 aryl) C1-6 alky l (e.g., -Lk-Ar, wherein Lk is a bivalent form of optionally substituted alkyl group and Ar is optionally substituted aryl); (19) -C(0)NRBRc, where each of RBand Rcis, 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., -Lk-Ar, wherein Lk is a bivalent form of optionally substituted alkyl group and Ar is optionally substituted ary l); and (20) -NRGRH, where each of RGand RHis, independently, selected from the group consisting of (a) hydrogen, (b) an N-protecting group, (c) C1-6 alkyl, (d) C2-6 alkenyl (e.g., optionally substituted alkyd having one or more double bonds), (e) C2-6 alkynyl (e.g., optionally substituted alkyl having one or more triple bonds), (f) C4-18 aryl, (g) (C4-18 aryl) C1-6 alkyl (e.g., Lk-Ar, wherein Lk is a bivalent form of optionally substituted alkyd group and Ar is optionally substituted ary 1), (h) C3-8 cycloalkyl, and (i) (C3-8 cycloalkyd) C1-6 alkyl (e.g., -Lk-Cy, wherein Lk is a bivalent form of optionally substituted alkyd group and Cy is optionally substituted cycloalkyl, as described herein), wherein in one embodiment no two groups are bound to the nitrogen atom through a carbonyl group, dire alkyl group can be a primary, secondary, or tertiary alkyd group substituted with one or more substituents (e.g., one or more halo or alkoxy). In someAtorney Docket No.: LAM1P118WO-12279-1WO embodiments, the unsubstituted alkyl group is aCi-2, C1-3, C1-6, C1-12, C1-16, Ci-is, C1-20, C1-24.C2-3, C2-6, C2-12, C2-16, C2-18, C2-20, or C2-24 alkyl group.

[0027] By “alkydene” is meant a multivalent (e.g., bivalent) form of an alkyl group, as described herein. Exemplary alky dene groups include methylene, ethylene, propylene, butylene, etc. In some embodiments, the alkylene group is a C1-3, C1-6, C1-12, C1-16. Ci-18, C1-20, C1-24, C2-3, C2-6, C2-12, C2-16, C2-18, C2-20, or C2-24 alkylene group. The alkylene group can be branched or unbranched. The alkylene group can also be substituted or unsubstituted. For example, the alkylene group can be substituted with one or more substitution groups, as described herein for alkyl.

[0028] By “alkylcarbonyl” is meant an alkyl group as previously defined appended to the parent molecular moiety through a carbonyl group. Exemplary, non-limiting alkylcarbonyl groups include methylcarbonyl, ethylcarbonyl, and isopropylcarbonyl among others.

[0029] By “alkyny 1” is meant an optionally substituted C2-24 alkyl group having one or more triple bonds. The alky nyl group can be cy clic or acyclic and is exemplified by ethynyl. 1-propy nyl, and the like. 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. Nonlimiting unsubstituted alkynyl groups include C2-8 alky nyl, C2-6 alkynyl, C2-5 alkynyl, C2-4 alkynyl, or C2-3 alkynyl. Exemplary', non-limiting alkynyl groups include ethynyl (-C=CH), 1-propynyl (-OCCH3), 2-propynyl or propargyl (-CH2OCH), 1-butynyl (-OCCH2CH3), 2-butynyl (-CH2OCCH3), 3-butynyl (-CH2CH2OCH), and the like.

[0030] By “alkynylene” is meant a multivalent (e.g., bivalent) form of an alkynyl group, which is an optionally substituted C2-24 alkyl group having one or more triple bonds. The alkynylene group can be cyclic or acyclic. The alkynylene group can be substituted or unsubstituted. For example, the alkynylene group can be substituted with one or more substitution groups, as described herein for alkyl. Exemplary, non-limiting alkynylene groups include -C=C-or -C =CCH2-

[0031] By “amido” is meant -N(RN1)C(O)-, where RN1is H, optionally substituted alkyl, or optionally substituted aryl.

[0032] By “amino” is meant -NRN1RN2, where each of RN1and RN2is, independently, H, optionally substituted alkyl, or optionally substituted aryl, or RN1and RN2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein.

[0033] By “aminoalkyl” is meant an alkyl group, as defined herein, substituted by an amino group, as defined herein.

[0034] By “aminoaryl” is meant an ary l group, as defined herein, substituted by an amino group, as defined herein.Atorney Docket No.: LAM1P118WO-12279-1WO

[0035] By “aryl” is meant a group that contains any carbon-based aromatic group including, but not limited to, phenyl, benzyl, anthracenyl, anthryl, benzocyclobutenyl, benzocyclooctenyl, biphenylyl, chrysenyl, dihydroindenyl, fluoranthenyl, indacenyl, indenyl, naphthyl, phenanthryl, phenoxybenzyl, picenyl, pyrenyl, terphenyl, and the like, including fused benzo-C4-s cycloalkyl radicals (e.g.. as defined herein) such as. for instance, indanyl, tetrahydronaphthyl, fluorenyl, 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 the 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, such as any described herein for alkyl.

[0036] By “azido” is meant -Ns.

[0037] By “branched alkenyl” is meant an isomer of a straight chain alkenyl compound: one having alky l groups bonded to the main carbon chain.

[0038] By “cyano” is meant -CN.

[0039] By “carbonyl” is meant a -C(O)- group, which can also be represented as >C=O.

[0040] By “cycloalkyl” is meant a monovalent saturated or unsaturated non-aromatic or aromatic cyclic hydrocarbon group of from three to eight carbons, unless otherwise specified, and is exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclopentadienyl, 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.

[0041] By “deposition” or “vapor deposition” is meant a process in which a metal layer is formed on one or more surfaces of a substrate from vaporized precursor composition(s) including one or more metal containing compounds. The metal-containing compounds are vaporized and directed to and / or contacted with one or more surfaces of a substrate (i.e. , semiconductor substrate or semiconductor assembly) placed in a deposition chamber. Typically, the substrate is heated. These metal containing compounds form a non-volatile, thin, uniform metal -containing layer on the surface(s) of the substrate. One operation of the method is one cycle, and the process can be repeated for as many cycles necessary to obtain the desired metal thickness.

[0042] By “dicarbonyl” is meant any moiety or compound including two carbonyl groups, as defined herein. Non-limiting dicarbonyl moieties include 1 ,2-dicarbonyl (e.g., Rcl-C(O)-C(O)RC2, in which each of RC1and RC2is, independently, optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or a leaving group): 1,3-dicarbonyl (e g., Rcl-C(O)-Atorney Docket No.: LAM1P118WO-12279-1WO C(RlaR2a)-C(O)RC2, in which each of RC1and RC2is, independently, optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or a leaving group and in which each of Rlaand R2ais, independently, H or an optional substituent provided for alkyl, as defined herein); and 1,4-dicarbonyl (e.g., Rcl-C(O)-C(RlaR2a)-C(R3aR4a)-C(O)RC2, in which each of RC1and RC2is, independently, optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or a leaving group and in which each of Rla, R2a, R3a, and R4ais, independently, H or an optional substituent provided for alkyl, as defined herein).

[0043] By “halo” is meant F, Cl, Br, or I.

[0044] By “halo containing substituent” is meant a group that contains a halo, such as a haloaliphatic or haloalkyl group.

[0045] By “haloaliphatic” is meant an aliphatic group, as defined herein, substituted with one or more halo.

[0046] By “haloalkenyl” is meant an alkenyl group, as defined herein, substituted with one or more halo.

[0047] By “haloalkynyl” is meant an alkynyl group, as defined herein, substituted with one or more halo.

[0048] By “haloalkyl” is meant an alkyl group, as defined herein, substituted with one or more halogen. Non-limiting unsubstituted haloalkyl groups include C1-2 haloalkyl, C1-3 haloalkyl. C1-4 haloalkyl, C1-5 haloalkyl, C1-6 haloalkyl, C2-3 haloalkyl, C2-4 haloalkyl, C2-5 haloalkyl, C2-6 haloalkyl, or C3-6 haloalkyl. Other non-limiting haloalkyl groups include -CXyHs-y, wherein y is 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I); -CXzFb-zCXyHs-y, wherein z is 0, 1, or 2, wherein y is 0, 1, 2, or 3, and wherein each X is, independently, halo (F, Cl. Br, or I), in which at least one of z or y is not 0; -CFbCXyFb-y, wherein y is 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I); -CXziH2-ziCXZ2H2-z2CXyH3-y, wherein each of zl and z2 is, independently, 0, 1, or 2, wherein y is 0, 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I), in which at least one of zl, z2, or y is not 0; and -CXzHi-z[CXyiH3-yi][CXy2H3-y2], wherein z is 0 or 1. wherein each of y 1 and y2 is, independently, 0, 1. 2, or 3, and wherein each X is, independently, halo (F, CL Br, or I), in which at least one of z, yl, or y2 is not 0.

[0049] By “haloalkylene” is meant an alky lene group, as defined herein, substituted with one or more halo.

[0050] By “heterocyclyl” is meant a 3-, 4-, 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, selenium, or halo). The 3-membered ring has zero to one double bonds, the 4- and 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”Atorney Docket No.: LAM1P118WO-12279-1WO also includes bicyclic, tricyclic and tetracyclic groups in which any of the above heterocyclic rings is fused to one, tw o. 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 acridinyl, adenyl, alloxazinyl, azaadamantanyl, azabenzimidazolyl, azabicyclononyl, azacycloheptyl, azacyclooctyl, azacyclononyl, azahypoxanthinyl, azaindazolyl, azaindolyl, azecinyl, azepanyl, azepinyl, azetidinyl, azetyl, aziridinyl, azirinyl, azocanyl, azocinyl, azonanyl, benzimidazolyl, benzisothiazolyl, benzisoxazolyl, benzodiazepinyl, benzodiazocinyl. benzodihydrofuryl, benzodioxepinyl, benzodioxinyl, benzodi oxanyl, benzodioxocinyl, benzodioxolyl, benzodithiepinyl, benzodithiinyl, benzodioxocinyl, benzofuranyl, benzophenazinyl, benzopyranonyl, benzopyranyl, benzopyrenyl, benzopyronyl, benzoquinolinyl, benzoquinolizinyl, benzothiadiazepinyl, benzothiadiazolyl, benzothiazepinyl, benzothiazocinyl, benzothiazolyl, benzothienyl. benzothiophenyl. benzothiazinonyl, benzothiazinyl. benzothiopyranyl, benzothiopyronyl, benzotriazepinyl, benzotriazinonyl, benzotriazinyl, benzotriazolyl, benzoxathiinyl, benzotrioxepinyl, benzoxadiazepinyl, benzoxathiazepinyl, benzoxathiepinyl, benzoxathiocinyl, benzoxazepinyl, benzoxazinyl, benzoxazocinyl, benzoxazolinonyl, benzoxazolinyl, benzoxazolyl, benzylsultamyl, benzylsultimyl, bipyrazinyl. bipyridinyl, carbazolyl (e.g., 4H-carbazolyl), carbolinyl (e.g., 0-carbolinyl), chromanonyl, chromanyl, chromenyl, cinnolinyl, coumarinyl, cytdinyl, cytosinyl, decahydroisoquinolinyl, decahydroquinolinyl, di azabi cyclooct}' I. diazetyl, diaziridinethionyl, diaziridinonyl, diaziridinyl, diazirinyl, dibenzisoquinolinyl, dibenzoacridinyl, dibenzocarbazolyl, dibenzofuranyl, dibenzophenazinyl, di benzopyranonyl. dibenzopyronyl (xanthonyl), dibenzoquinoxalinyl, dibenzothiazepinyl, dibenzothiepinyl, dibenzothiophenyl, dibenzoxepinyl, dihydroazepinyl, dihydroazetyl, dihydrofuranyl, dihydrofuryl, dihydroisoquinolinyl, dihydropyranyl, dihydropyridinyl, dihydroypyridyl, dihydroquinolinyl, dihydrothienyl, dihydroindolyl, dioxanyl, dioxazinyl, dioxindolyl, dioxiranyl, dioxenyl, dioxinyl. dioxobenzofuranyl, dioxolyl, dioxotetrahydrofuranyl, dioxothiomorpholinyl, dithianyl, dithiazolyl, dithienyl, dithiinyl, furanyl, furazanyl, furoyl, furyl, guaninyl, homopiperazinyl, homopiperidinyl, hypoxanthinyl, hydantoinyl, imidazolidinyl, imidazolinyl, imidazolyl, indazolyl (e.g., IH-indazolyl), indolenyl, indolinyl, indolizinyl. indolyl (e.g., IH-indolyl or 3H-indolyl), isatinyl, isatyl, isobenzofuranyl, isochromanyl, isochromenyl, isoindazoyl, isoindolinyl, isoindolyl, isopyrazolonyl, isopyrazolyl, isoxazolidiniyl, isoxazolyl, isoquinolinyl, isoquinolinyl, isothiazolidinyl, isothiazolyl, morpholinyl, naphthindazolyl, naphthindolyl, naphthiridinyl, naphthopyranyl, naphthothiazolyl, naphthothioxolyl, naphthotriazolyl, naphthoxindolyl, naphthyridinyl, octahydroisoquinolinyl,Atorney Docket No.: LAM1P118WO-12279-1WO oxabicycloheptyl, oxauracil, oxadiazolyl, oxazinyl, oxaziridinyl, oxazolidinyl, oxazolidonyl, oxazolinyl, oxazolonyl, oxazolyl, oxepanyl, oxetanonyl, oxetanyl, oxetyl, oxtenayl, oxindolyl, oxiranyl, oxobenzoisothiazolyl, oxochromenyl, oxoisoquinolinyl, oxoquinolinyl, oxothiolanyl, phenanthridinyl, phenanthrolinyl, phenazinyl. phenothiazinyl, phenothienyl (benzothiofuranyl), phenoxathiinyl, phenoxazinyl, phthalazinyl, phthalazonyl. phthalidyl, phthalimidinyl. piperazinyl, piperidinyl, piperidonyl (e.g., 4-piperidonyl), pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolopyrimidinyl, pyrazolyl, pyridazinyl, pyridinyl, pyridopyrazinyl, pyridopyrimidinyl, pyridyl, pyrimidinyl, pyrimidyl, pyronyl, pyrrolidinyl, pyrrolidonyl (e.g., 2-pyrrolidonyl). pyrrolinyl. pyrrolizidinyl, pyrrolyl (e.g., 2H-pyrrolyl), pyrylium, quinazohnyl, quinohnyl, quinohzinyl (e.g., 4H-quinolizinyl), quinoxalinyl, quinuclidinyl, selenazinyl, selenazolyl, selenophenyl, succinimidyl, sulfolanyl, tetrahydrofuranyl, tetrahydrofuryl, tetrahydroisoquinolinyl, tetrahydroisoquinolyl, tetrahydropyridinyl, tetrahydropyridyl (piperidyl), tetrahydropyranyl, tetrahydropyronyl, tetrahydroquinolinyl, tetrahydroquinolyl, tetrahydrothienyl, tetrahydrothiophenyl, tetrazinyl, tetrazolyl, thiadiazinyl (e.g., 6H-l,2,5-thiadiazinyl or 2H,6H-l,5,2-dithiazinyl), thiadiazolyl, thianthrenyl, thianyl, thianaphthenyl, thiazepinyl, thiazinyl, thiazolidinedionyl, thiazolidinyl, thiazolyl, thienyl, thiepanyl, thiepinyl, thietanyl, thietyl, thiiranyl, thiocanyl, thiochromanonyl, thiochromanyl, thiochromenyl, thiodiazinyl, thiodiazolyl, thioindoxyl, thiomorpholinyl, thiophenyl, thiopyranyl, thiopyronyl, thiotriazolyl, thiourazolyl, thioxanyl, thioxolyl, thymidinyl, thyminyl, triazinyl, triazolyl, trithianyl, urazinyl, urazolyl, uretidinyl, uretinyl, uricyl, uridinyl, xanthenyl, xanthinyl, xanthionyl, and the like, as well as modified forms thereof (e.g., including one or more oxo and / or amino) and salts thereof. The heterocyclyl group can be substituted or unsubstituted. For example, the heterocyclyl group can be substituted with one or more substitution groups, as described herein for aryl.

[0051] By “hydroxyl” is meant -OH.

[0052] By “imino” is meant -NR-, in which R can be H or optionally substituted alky l.

[0053] By “isocyanato” is meant -NCO.

[0054] By “isothiocyanate” is meant -N=C=S.

[0055] By “oxo” is meant an =0 group.

[0056] By “oxy” is meant -O-.

[0057] By “silyl” is meant a -Si R1R2R3or -SiR'R2- 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,Atorney Docket No.: LAM1P118WO-12279-1WO optionally substituted ary I oxy. 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.

[0058] By “silyloxy’' is meant -OR, where R is an optionally substituted silyl group, as described herein. In some embodiments, the silyloxy group is -O-SiR'R2R 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 alkyd, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0059] Use of the above terms is meant to encompass substituted and unsubstituted moieties. Substitution may be by one or more groups such as alcohols, ethers, esters, amides, sulfones, sulfides, hydroxyl, nitro, cyano, carboxy, amines, heteroatoms, lower alkyl, lower alkoxy, lower alkoxycarbonyl, alkoxyalkoxy, acyloxy, halogens, trifluoromethoxy, trifluoromethyl, alkyl, aralkyl, alkenyl, alkynyl, aryl, cyano, carboxy, carboalkoxy, carboxyalkyl, cycloalkyl, cycloalkylalkyl, heterocyclyl, alky dheterocyclyl, heterocyclylalkyl, oxo, arylsulfonyl and aralkyaminocarbonyl, or any of the substituents of the preceding paragraphs or any of those substituents either directly attached or by suitable linkers. The linkers are typically short chains of 1-3 atoms containing any combination of -C-, -C(O)-, -NH-, -S-, -S(O)-, -O-, -C(O)- or -S(O)O-. Rings may be substituted multiple times.

[0060] The term “lower” modifying “alkyl”, “alkenyl”, “alkynyl”, “alkoxy” or “alkoxycarbonyl” refers to a Ci-Ce unit for a particular functionality. For example, “lower alkyl” means Ci-Ce alkyd.

[0061] By “substituted” is meant having one or more substituent moieties whose presence does not interfere with the desired function or reactivity. Examples of substituents alkyl, alkenyl,Atorney Docket No.: LAM1P118WO-12279-1WO alkynyl, cycloalkyl (non-aromatic ring), Si(alkyl)3, Si(alkoxy)3, alkoxy, amino, alkylamino, alkenylamino, amide, amidine, guanidine, hydroxyl, thioether, alkydcarbonyl, alkylcaronyloxy, alkoxycarbonyloxy, carbonate, alkoxycarbonyl, aminocarbonyl, alkylthiocarbonyl, phosphate, phosphate ester, phosphonato, cyano, halo, acylamino, imino, sulfhydryl, alkylthio, thiocarboxylate, dithiocarboxylate, sulfate, sulfato, sulfonate, sulfamoyl, sulfonamide, nitro, nitrile, azido, heterocyclyl, ether, ester, silicon-containing moieties, thioester or a combination thereof. The substituents may themselves be substituted. For instance, an amino substituent may itself be mono or independently disubstituted by further substituents defined above, such as alkyl, alkenyl, alkynyl, and cycloalkyl (non-aromatic ring).

[0062] By ‘'thiocyanate” is meant -SCN.

[0063] By “unsubstituted” is meant any open valence of an atom being occupied by hydrogen. Also, if an occupant of an open valence position on an atom is not specified, then it is hydrogen.

[0064] As used herein, the term “about” is understood to account for minor increases and / or decreases beyond a recited value, which changes do not significantly impact the desired function of the parameter beyond the recited value(s). In some cases, “about” encompasses + / -10% of any recited value. As used herein, this term modifies any recited value, range of values, or endpoints of one or more ranges.

[0065] As used herein, the terms “top.” “bottom,” “upper,” “lower.” “above.” and “below” are used to provide a relative relationship between structures. The use of these terms does not indicate or require that a particular structure must be located at a particular location in the apparatus.

[0066] The implementations disclosed below describe deposition of a material on a substrate such as a wafer, substrate, or other work piece. The work piece may be of various shapes, sizes, and materials. In this application, 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 thereon. A wafer or substrate used in the semiconductor device industry typically has a diameter of 200 mm, or 300 mm, or 450 mm. Unless otherwise stated, the processing details recited herein (e g., flow rates, power levels, etc.) are relevant for processing 300 mm diameter substrates, or for treating chambers that are configured to process 300 mm diameter substrates and can be scaled as appropriate for substrates or chambers of other sizes. In addition to semiconductor wafers, other work pieces that may be used implementations disclosed herein include various articles such as printed circuit boards and the like. The processes and apparatuses can be used in the fabrication of semiconductor devices, displays, LEDs, photovoltaic panels and the like.Atorney Docket No.: LAM1P118WO-12279-1WO

[0067] "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 SnOi.s. “Tin oxide” also includes tin dioxide (SnCh or 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.

[0068] By “unsaturated” is meant a moiety that contains double or triple carbon-carbon bonds. “Unsaturated” is also meant to include any moiety that has double or triple bond between a carbon and a heteroatom, such as carbonyl groups. “Unsaturated” is also meant to include any moiety with a carbon ring structure.

[0069] By “unsaturated substituent” is meant a double or triple bond containing aliphatic chain, cyclic, aryl or heteroaryl group.Introduction

[0070] Patterning of thin films in semiconductor processing is often an important step in the fabrication of semiconductors. Patterning involves lithography. In conventional photolithography, such as 193 nm photolithography, patterns are printed by emitting photons from a photon source onto a mask and printing the pattern onto a photosensitive photoresist, thereby causing a chemical reaction in the photoresist that, after development, removes certain portions of the photoresist to form the pattern.

[0071] Directly photopattemable resists maybe composed of or contain metals and / or metal oxides mixed within organic components. The metals / metal oxides are highly promising in that they can enhance photon absorption, generate secondary electrons, and / or show increased etch selectivity to an underlying film stack and device layers. Up to date, these resists have been developed using a wet (solvent) approach, which requires the wafer to move to the track, where it is exposed to developing solvent, dried, and then baked. This wet development step does not only limit productivity but can also lead to line collapse due to surface tension effects during the evaporation of solvent between fine features.

[0072] Generally, resists can be employed as a positive tone resist or as a negative tone resist by controlling the chemistry of the resist and / or the solubility or reactivity' of the developer. It would be beneficial to have a resist that can serve as either a negative tone resist or a positive tone resist.Positive Tone Dry Development

[0073] The present disclosure relates to positive tone dry7development of metal oxide photoresist. An organometal oxide photoresist material is deposited on a substrate, where the organometal oxide photoresist material includes one or more unsaturated carbon bonds. TheAtorney Docket No.: LAM1P118WO-12279-1WO organometal oxide photoresist material may be deposited using metal-containing precursors having at least one unsaturated substituent. In some embodiments, the organometal oxide photoresist material may be a blended photoresist material having at least one unsaturated substituent and at least one saturated substituent. The organometal oxide photoresist material is exposed to patterning radiation to form a photopattemed metal oxide resist film having an exposed region and an unexposed region, where the patterning radiation photoinduces polymerization to form cross-linked organic moieties in the exposed region. The photopattemed metal oxide resist film undergoes a bake process that exposes the photopattemed metal oxide resist film to an environment including at least one oxygen-containing species. The bake process may cleave metal-carbon bonds in the unexposed region and preserve metal-carbon bonds in the exposed region having the cross-linked organic moieties. After the bake process, a positive tone dry development is performed that selectively removes the exposed region relative to the unexposed region of the photopattemed metal oxide resist film to form a patterned resist mask.

[0074] Figure 1 presents a flow diagram of an example patterning process flow involving a metal -containing photoresist according to some implementations. The operations of a process flow 100 may be performed in different orders and / or with different, fewer, or additional operations. In some implementations, the operations of the process flow 100 may be implemented, at least in part, according to software stored in one or more non-transitory computer readable media.

[0075] The process flow 100 for patterning a metal-containing photoresist is performed on a substrate such as a semiconductor substrate. In some embodiments, the substrate is or includes a partially fabricated semiconductor device film stack. At block 104 of the process flow 100, an underlayer may be deposited on the substrate. In some embodiments, the underlayer may be deposited over a hard mask such as an ashable hard mark (AHM). The underlayer is configured to increase adhesion between the subsequently-formed photoresist and the substrate. The underlayer is also configured to reduce radiation dose for effective patterning exposure of the photoresist. The underlayer may include a vapor-deposited film of hydronated carbon doped with a non-carbon heteroatom such as oxygen (O), silicon (Si), nitrogen (N), tungsten (W), boron (B), iodine (I), chlorine (Cl), or a combination thereof. For example, an underlayer comprising a hydronated carbon film doped with iodine may improve generation of secondary electrons in the photoresist upon exposure to patterning radiation. The underlayer may have a thickness equal to or less than about 25 nm, such as a thickness between about 2 nm and about 20 nm. In some implementations, the underlayer may be deposited using a vapor deposition technique such as PECVD or ALD.

[0076] At block 106, a photoresist (PR) is deposited over the substrate. In some embodiments,Atorney Docket No.: LAM1P118WO-12279-1WO the photoresist may be deposited on the underlayer. Deposition of the photoresist may be a dry deposition process such as a vapor deposition process or a wet process such as a spin-on deposition process. In some implementations, the photoresist includes an organometallic material or organometal oxide material. The photoresist can include a metal that can have a high patterning radiation absorption. In some implementations, the metal is selected from a group consisting of 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), germanium (Ge), and lead (Pb). For example, the metal includes tin. As such, the photoresist may include organotin oxide in some implementations.

[0077] In some embodiments, a metal-containing precursor and an optional ligand-containing precursor can be provided in the optional presence of a counter-reactant to deposit the photoresist. A metal-containing precursor can be used alone or, alternatively, with additional precursors, such as a ligand-containing precursor to further modify the functional groups attached to M in the metalcontaining precursor. The ligand-containing precursor can react with the metal-containing precursor to install additional L and / or R groups on M. By combining such metal- and ligandcontaining precursors, further metal-containing precursors can be provided. In this way, the final combination of cleavable groups (R) and / or ligands (L) can be modified, either in situ (within the chamber) or prior to delivery to the chamber for deposition. Ligand-containing precursors can include an organolithium compound (e.g., LiL), an organosodium compound (e.g., NaL), an organomagnesium compound (e.g., MgL2), a Grignard reagent (e.g., MgLX, in which X is halo), an organozinc compound (e.g., ZnL2), an organosilicon compound (e.g., SiL4), or an organoaluminum compound (e.g., AlLs). In particular embodiments, such reagents are not employed within a deposition chamber but employed to synthesize the precursor prior to delivery to the deposition chamber.

[0078] Useful ligands in the ligand-containing precursor can include any described herein, including an organic moiety (e.g., optionally substituted alkyl, optionally substituted amino, optionally substituted alkoxy, optionally substituted bis(trialkylsilyl)amino (e.g., -N(SiMe3)2), optionally substituted trialkylsilyl, or others). Other ligand-containing precursors can include an aliphatic halide (e.g., RX, in which X is halo and R is an optionally substituted alkyl) or a haloaliphatic halide (e.g., RX, in which X is halo and R is an optionally substituted haloalkyl). Non-limiting R groups include an optionally substituted C1-2 haloalkyl. such as -CXzHs-z or -CFLCXzFL-z, in which z is 1, 2, or 3; and an optionally substituted Ci-4 alkyl, such as -CnFbn+i, in which n is 1 or 2; or such as -CnFhn-i or -CnFbn-s, in which n is 2, 3, or 4.

[0079] The photoresist film can be deposited in any useful manner. Exemplary7deposition techniques include chemical vapor deposition (CVD). plasma enhanced CVD (PECVD), lowAtorney Docket No.: LAM1P118WO-12279-1WO pressure CVD (LPCVD), atomic layer deposition (ALD) (e.g., thermal ALD and plasma-enhanced ALD (PEALD)), molecular layer deposition (MLD), spin-coat deposition, physical vapor deposition (PVD) including PVD co-sputtering, sputter deposition, electron-beam (e-beam) deposition including e-beam co-evaporation, etc., or a combination thereof. Other deposition processes and conditions are described herein.

[0080] The metal- and / or ligand-containing precursors can be optionally deposited in the presence of one or more counter-reactants. Counter-reactants preferably have the abi 1 i ty 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 counterreactants, such as O2, O3, water, peroxides (e.g., hydrogen peroxide), oxygen plasma, water plasma, alcohols, di- or polyhydroxy alcohols, acetamides, 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 metal- and / or ligand-containing 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. Yet other counter-reactants can include any chalcogenide-containing precursors or chalcogenide-containing compounds described herein.

[0081] The photoresist film can have any useful structure. In one embodiment, the film has a thickness of from about 0.5 nm to about 100 nm (e.g., about 5 nm to 100 nm, as well as other thickness described herein). The film can include an optional underlayer or an optional surface activation step prior to deposition of the metal-containing precursor.

[0082] The film can have a vertical gradient that is characterized by a vertical change in EUV absorbance. In some instances, an increase in EUV absorbance along a depth (e.g., going from a top surface of the film towards the substrate) can correspond with an increase in metal content or halogen content along that same depth through the film layer. Non-limiting gradients include a linear gradient, an exponential gradient, a sigmoidal gradient, and the like. In particular embodiments, gradient density films of EUV-responsive moieties can yield more homogeneous film properties of EUV exposed areas at all depths in the film, which might improve development processes, improve EUV sensitivity, and / or improve patterning quality (e.g.. having improved line-width-roughness (LWR) and / or hne-edge-roughness (LER)).

[0083] The film can be a radiation-sensitive film that can include metal constituents and organic substituents, each of which may include UV-, DUV-, or EUV-sensitive moieties. Non-limiting examples of these include, e.g., a metal or a metalloid or an atom with a high EUV absorptionAtorney Docket No.: LAM1P118WO-12279-1WO cross-section, such as equal to or greater than IxlO7cm2 / mol. In some embodiments, the constituent includes a metal-containing precursor, a ligand-containing precursor, or a reaction product thereof.

[0084] The film can be homogenous. In particular embodiments, the homogenized matrix can be an alloy film. Co-deposition can occur in any useful methodology that uses co-flow of both the metal- and ligand-containing precursors (e.g., CVD).

[0085] The film can be used as a photoresist. In particular non-limiting embodiments, the film can include moieties that promote radiation absorption after radiation exposure (e.g., exposure to UV, DUV, and / or EUV radiation). After deposition, the film can be patterned by radiation exposure and then developed, thereby providing a negative tone or positive tone resist. Such methods can include any useful lithography processes, deposition processes, EUV / DUV exposure processes, development processes, and post-application processes, as described herein. In particular embodiments, the film exhibits minimal film shrinkage after EUV / DUV exposure, development, and / or post-application processes.

[0086] Though not shown in the process flow 100, an optional cleaning process is performed to clean a backside and bevel edge of the substrate. This can be performed after deposition of the photoresist and prior to patterning radiation exposure. The backside and bevel edge clean may remove unintended deposits of the metal-containing photoresist from the backside and bevel edge of the substrate. The backside and bevel edge clean may be accomplished using wet cleaning techniques or dry cleaning techniques, or in combination with one another.

[0087] Though not show n in the process flow' 100, an optional post- application bake (PAB) may be performed after deposition of the photoresist and prior to patterning radiation exposure. The PAB treatment may involve a combination of thermal treatment, chemical exposure, and moisture to increase the patterning radiation sensitivity of the photoresist, which can reduce the radiation dose to develop a pattern.

[0088] At block 108 of the process flow 100, the photoresist is exposed to patterning radiation. This forms a photopattemed resist film such as a photopattemed metal oxide resist film. Various radiation sources may be employed, including EUV (generally about 13.5 nm), DUV (deep-UV, generally in the 248 nm or 193 nm range with excimer laser sources), X-ray (including EUV at the lower energy range of the X-ray range), UV (generally in the 100 nm to 400 nm range), and e-beam (including a wide energy’ range). Exposure to patterning radiation forms a photo pattern in the photoresist to define exposed areas and unexposed areas. Generally speaking, patterning radiation exposure causes a change in the chemical composition and cross-linking in the photoresist, creating a contrast in etch selectivity that can be exploited for subsequent development. The photoresist may be photo patterned by exposing a region to patterning radiation,Atorney Docket No.: LAM1P118WO-12279-1WO typically under relatively high vacuum. Exposed areas of the photoresist are created through photo patterning that have altered physical or chemical properties relative to unexposed areas. The difference in properties between exposed and unexposed areas may be exploited in subsequent processing.

[0089] In some embodiments, the photoresist is exposed to EUV radiation to form a photopattemed resist film having exposed and unexposed areas. Generally, the EUV exposure causes a change in the chemical composition of the film, creating a contrast in etch selectivity that can be used to remove a portion of the film. Such a contrast can provide a positive tone resist or a negative tone resist, as described herein. In some embodiments. EUV exposure may occur at doses ranging from about 10 mJ / cm2to about 100 mJ / cm2

[0090] At block 110 of the process flow 100, the photopattemed resist film is exposed to a postexposure bake (PEB). The PEB treatment may further increase contrast in etch selectivity of the photopattemed resist film after photo patterning. During PEB, the photopattemed resist film is thermally treated in the presence of various chemical species such as an oxygen-containing species and / or nitrogen-containing species. The PEB treatment temperature may be controlled to further increase etch contrast in the photopattemed resist film, where the PEB treatment temperature may be between about 100°C and about 300°C, such as between about 170°C and about 290°C. The bake ambient may be controlled to further increase etch contrast in the photopattemed resist film, where the bake ambient may control pressure as well as introduction of reactive gases such as air, H2O, H2O2, CO2, CO, O2, 03, CH4, CH3OH, N2, H2, NH3, N2O, NO, alcohol, acetyl acetone, formic acid, Ar, He, or their mixtures. In some embodiments, the PEB treatment can be designed to drive evaporation of organic fragments that are generated during EUV exposure, oxidize the metal hydride species into metal hydroxide, and / or facilitate cross-linking between neighboring -OH groups and form a cross-linked metal oxide network.

[0091] At block 112 of the process flow 100, the photopattemed resist film is developed to form a resist mask. In various embodiments, the exposed regions are removed (positive tone) or the unexposed regions are removed (negative tone). Negative tone development may involve selective removal of unexposed regions of the photopattemed resist film relative to exposed regions of the photopattemed resist film. Positive tone development may involve selective removal of exposed regions of the photopattemed resist film relative to unexposed regions of the photopattemed resist film. Development may be performed using wet or dry processes. A wet development process exposes the photopattemed resist film to a solvent for selective removal of portions of the photopattemed resist film. A dry development process exposes the photopattemed resist film to an etch gas for selective removal of portions of the photopattemed resist film. In some embodiments, the etch gas can include a halide such as a hydrogen halide. Accordingly,Atorney Docket No.: LAM1P118WO-12279-1WO development chemistries may include but are not limited to a halide-containing gas includes a hydrogen halide (e.g., HBr, HC1, etc ), hydrogen and halogen gas (e.g., H2 and Ch, H2 and Bn, etc.), boron trichloride, an organic halide, an acyl halide, a carbonyl halide, and a thionyl halide, or mixtures thereof. An organic halide can include but is not limited to CxHyFz, CxHyClz, CxHyBrz, and CxHylz, where x, y. and z are values equal to or greater than 0. An acyl halide can include but is not limited to CH3COF, CH3COCL CFFCOBr, and CH3COI. A carbonyl halide can include but is not limited to COF2, COCI2, COBn, and COI2. A thionyl halide can include but is not limited to SOF2, SOCI2, SOBr2, and SOI2. In some embodiments, the etch gas may be flowed with or without inert / carrier gas such as He, Ne, Ar. Xe, and N2. In some embodiments, the dry¬ development can involve a thermal process, a plasma process, or a combination of a thermal process and a plasma process. Parameters such as chamber pressure, gas flow rates, substrate temperature, and duration of exposure may be tuned. In some embodiments, a chamber pressure may be between about 100 and about 760 Torr. In some embodiments, a substrate temperature may be between about -60°C and about 300°C. In some embodiments where plasma is applied, the RF levels may be tuned at RF power levels equal to or less than about 1000 W. Selection of the development method along with optimization of the development parameters may influence development selectivity-, roughness, descumming, and other characteristics of development.

[0092] At block 114 of the process flow 100, pattern transfer is performed using the resist mask. During pattern transfer, one or more substrate layers are etched using the resist mask for pattern transfer. Such substrate layers are underlying the resist mask and may be removable by lithographic etching. Pattern transfer etching may etch materials to a desired depth to form a plurality of patterned features. In some embodiments, the one or more substrate layers include the hard mask and the underlayer. Any defects, roughness, or variations in CD in the resist mask are replicated in the material(s) being patterned during pattern transfer etching.

[0093] Figure 2 presents schematic illustrations of various stages for making a negative tone resist film according to some implementations. In the example method 200, a substrate 210 is provided. At a deposition step 201, a photoresist material 212 is deposited on a top surface of the substrate 210. The photoresist material 212 may include a metal -containing photoresist material. In some implementations, the photoresist material 212 includes a metal oxide or organometal oxide. The photoresist material 212 may be dry or wet deposited on the substrate layer and / or underlayer. The photoresist material 212 may be deposited on the substrate by any suitable technique, including wet (e.g., spin-on) or dry (e.g., CVD) deposition techniques.

[0094] In some embodiments, the photoresist material 212 may be EUV-sensitive and may comprise materials, which, upon exposure to EUV, undergo changes, such as the loss of bulkyAtorney Docket No.: LAM1P118WO-12279-1WO pendant substituents bonded to metal atoms in low density M-OH rich materials, allowing their crosslinking to denser M-O-M bonded metal oxide materials. Through EUV patterning, areas of the film are created that have altered physical or chemical properties relative to unexposed areas. These properties may be exploited in subsequent processing, such as to remove either unexposed or exposed areas, or to selectively deposit materials on either the exposed or unexposed areas. In some implementations, the unexposed film has a more hydrophobic surface than the exposed film under the conditions at which such subsequent processing is performed. For example, the removal of material may be performed by leveraging differences in chemical composition, density, and cross-linking of the film.

[0095] In some embodiments, the photoresist material 212 includes organometallic materials, for example organotin materials comprising tin oxide, or other metal oxide materials / moieties. The organometallic compounds may be made in a vapor phase reaction of an organometallic precursor with a counter reactant. In various implementations, the organometallic compounds are formed through mixing specific combinations of organometallic precursors having bulky alkyl groups or fluoroalkyl groups with counter-reactants and polymerizing the mixture in the vapor phase to produce a low-density, EUV-sensitive material that deposits onto the substrate. In some implementations, organometallic precursors comprise 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. Organometallic precursors include those of the formula:MaRbLc(Formula 1)wherein: M is an element with a high patterning radiation-absorption cross-section; R is alkyd, such as CnFbn+i, preferably wherein n = 1-6; L is a ligand, ion or other moiety which is reactive with the counter-reactant; a > 1; b > 1; and c > 1.

[0096] In various implementations, M has an atomic absorption cross section equal to or greater than 1x107cm2 / mol. M may be, for example, selected from the group consisting of tin, hafnium, tellurium, bismuth, indium, antimony, iodine, germanium, and combinations thereof. In some implementations. M is selected from the group consisting of tin, lead, germanium, and hafnium. In some implementations, M is tin. R may be fluorinated, e.g., having the formula CnFxH(2n+i). In various implementations, R has at least one beta-hydrogen or beta-fluorine. For example, R may be selected from the group consisting of methyl, ethyl, i-propyl, n-propyl, t-butyl, i-butyl, n-butyl, sec- butyl, n-pentyl, i-pentyl, t-pentyl, sec-pentyl, and mixtures thereof. L may be any moiety' readily displaced by a counter-reactant to generate an M-OH moiety, such as a moiety selectedAtorney Docket No.: LAM1P118WO-12279-1WO from the group consisting of amines (such as dialkylamino, monoalkylamino), alkoxy, carboxylates, halogens, and mixtures thereof.

[0097] 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(dimethylamino) tin, ethyl tris(dimethylamino) tin and analogous alkyl(tris)(t-butoxy) tin compounds such as t-butyl tris(t-butoxy) tin. In some implementations, the organometallic precursors are partially fluorinated.

[0098] Counter-reactants have the ability to replace the reactive moieties, ligands or ions (e.g., L in Formula 1, above) so as to link at least two metal atoms via chemical bonding. Counterreactants 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 implementations, a counter-reactant reacts with the organometallic precursor by forming oxygen bridges between neighboring metal atoms.

[0099] The photoresist material 212 can include metal constituents and organic substituents, each of which may include UV-, DUV-, or EUV-sensitive moieties. At an exposure step 202, the photoresist material 212 is exposed to patterning radiation 215 to provide a photopattemed resist film having unexposed regions 213a and exposed regions 213b. The exposure step 202 can involve use of a mask 214 having transparent regions and opaque regions, in which the beams of the patterning radiation 215 are transmitted through the transparent regions and into the photoresist material 212. For example, EUV exposure can include, e.g., an exposure having a wavelength in the range of about 10 nm to about 20 nm in a vacuum ambient (e.g., about 13.5 nm in a vacuum ambient). Without being limited by any theory, organic ligands in the photoresist material 212 may be removed, cleaved, or cross-linked by the patterning radiation 215 during the exposure step 202.

[0100] At a bake step 203, the photopatterned resist film having unexposed regions 213a and exposed regions 213b is treated prior to development. The bake step 203 can remove residual moisture and promote chemical condensation within the photopattemed resist film. The bake step 203 can harden the photopattemed resist film to further cross-link the unexposed regions 213a and / or exposed regions 213b. During the bake step 203, a thermal treatment is performed that modifies the material properties of the photopattemed resist film having unexposed regions 213a and exposed regions 213b. In some embodiments, the thermal treatment is typically performed at high temperatures using an oxygen-containing gas ambient such as air, water, oxygen, ozone, hydrogen peroxide, carbon monoxide, or carbon dioxide. High temperatures associated with the thermal treatment may be greater than about 100°C, such as temperatures between about 120°CAtorney Docket No.: LAM1P118WO-12279-1WO and about 290°C. The bake step 203 may further increase chemical contrast between the unexposed regions 213a and the exposed regions 213b. Without being limited by any theory, the thermal treatment in the bake step 203 may further promote ligand cleavage and cross-linking to form more M-O-M bonds.

[0101] At a negative tone development step 204, the unexposed regions 213a are selectively removed and the exposed regions 213b are preserved to create a patterned resist mask. The development step 204 may involve dry processes and / or wet processes.

[0102] Metal oxide or organometal oxide photoresists are attractive candidates for advanced photolithography. Metal oxide or organometal oxide photoresists can operate with higher resolution, high etch selectivity, and lower dose. In addition, metal oxide or organometal oxide photoresists enable photon absorption enhancement and secondary electron generation.

[0103] Metal oxide or organometal oxide photoresists often undergo negative tone development (as shown in the method 200 of Figure 2) instead of positive tone development. Negative tone development of metal oxide or organometal oxide photoresists typically involve wet processes. However, wet processing generally involves moisture and / or oxygen, which more easily leads to scum formation. Wet development is limited by solubility and cluster size, whereas dry development is not limited by solubility' and cluster size. Wet development is more prone to pattern collapse and delamination issues that dry development avoids. Accordingly, after patterning radiation exposure, the negative tone resist may have increased defectivity due to interface failure and / or line collapse caused by surface tension. However, dry processing can provide more tunability and add further critical dimension (CD) control and scum removal. In addition, all-dry processing operations can be more readily integrated within an interconnected vacuum processing chamber or tool. More recently, negative tone development of metal oxide or organometal oxide photoresists have applied dry processes. Such dry processes for negative tone dry development involve exposure to an etch gas to selectively remove portions of the photopatterned resist film. In some implementations, the dry process is a thermal process or plasma process. In some implementations, the dry process is a combination of a thermal process and plasma process. Parameters such as chamber pressure, RF power, gas flow rates, substrate temperature, and duration of exposure may be tuned to optimize negative tone dry development.

[0104] Dry development of metal oxide or organometal oxide photoresists has been limited to negative tone dry development. Dry’ development in the negative tone can have limitations associated with pattern swelling and distortion. When exposed regions of a photoresist are exposed to a developer, the exposed regions that define the resist mask can swell, leading to potential distortion in the final pattern. Negative tone resists can also suffer a drawback of low resolution due to light scattering or proximity effects during exposure. Variations in exposure dose canAtorney Docket No.: LAM1P118WO-12279-1WO significantly impact the quality of negative tone development patterns due to the non-hnear nature of cross-linking reactions. Additionally, negative tone resists may have increased line edge roughness compared to positive tone resists. Negative tone resists may be limited in terms of technological applications, whereas positive tone resists may enable more technological applications. Due to defect concerns associated with negative tone resists, positive tone resists can be applied to technological applications that require large, exposed areas. Whereas negative tone resists may achieve a ratio of exposed area: unexposed area on the order of up to about 50:50, positive tone resists may achieve a ratio of exposed area: unexposed area on the order of up to about 80:20 or even about 90:10. By way of an example, such technological applications for positive tone resists may include contact holes. Negative tone resists may be more limited in its technological applications, such as limited to line space applications.

[0105] Figure 3 presents schematic illustrations of various stages for making a positive tone resist film according to some implementations. In the example method 300, a substrate 310 is provided. At a deposition step 301, a photoresist material 312 is deposited on a top surface of the substrate 310. The photoresist material 312 may include a metal -containing photoresist material. In some implementations, the photoresist material 312 includes a metal oxide or organometal oxide. The photoresist material 312 may be dry or wet deposited on the substrate layer and / or underlayer. The photoresist material 312 may be deposited on the substrate by any suitable technique, including wet (e.g., spin-on) or dry (e.g., CVD) deposition techniques.

[0106] The photoresist material 312 can have any useful structure. In some embodiments, the photoresist material 312 has a thickness of from about 0.5 nm to about 100 nm (e.g., about 5 nm to 100 nm, as well as other thickness described herein). The photoresist material 312 can be deposited on an optional underlayer or an optional surface activation step can occur prior to deposition of the photoresist material 312.

[0107] In some embodiments, the photoresist material 312 include organometallic materials, for example organotin materials comprising tin oxide, or other metal oxide materials / moieties. The organometallic compounds may be made in a vapor phase reaction of metal-containing precursor with a counter reactant. In some embodiments, the metal-containing precursors include haloaliphatic or unsaturated substituents, or other reactive moieties. In some embodiments, the metal-containing precursors include a Ci-4 haloaliphatic or Ci-6 aliphatic group or vinyl group (-CH=CH2) or other unsaturated substituents. In one example, the aliphatic group is a C1-2 alkyl or vinyl group or other unsaturated substituents, which can be dry deposited. In the present disclosure, the metal-containing precursor comprises at least a vinyl group or other unsaturated substituent. Thus, the photoresist material 312 may include an unsaturated carbon bond. In one example, the unsaturated carbon bond can include a carbon-carbon double bond or carbon-carbonAtorney Docket No.: LAM1P118WO-12279-1WO triple bond. In some examples, the unsaturated carbon bond can include a double bond or triple bond between a carbon atom and a heteroatom, such as an alkylcarbonyl. In some examples, the unsaturated carbon bond can include carbon ring structures such as a cyclopropyl, cyclobutyl, and cyclopentyl. In some implementations, the metal-containing precursors may include R groups that contain the unsaturated carbon bond, such as carbon-carbon double or triple bonds, carbonyls, or small carbon rings. In some implementations, the one or more counter-reactants that are used in combination with the metal-containing precursors may be incorporated in the photoresist material 312 so that the counter-reactant that remains in the photoresist material 312 includes the unsaturated carbon bond, such as carbon-carbon double or triple bonds, carbonyls, or small carbon rings.

[0108] The metal-containing precursor can have any useful number R groups, that generally remain in the deposited fdm, and / or removable ligands (L) that generally get removed during deposition. For depositing positive tone resists, the metal-containing precursor contains one or more substituents that are capable of being cross-linked rather than cleaved. In some instances, the metal -containing 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). The metal-containing precursor can be, e.g., an organometallic agent, a metal halide, or a capping agent (e.g., as described herein). In some embodiments, the metal is characterized by a high patterning radiation absorption cross-section (e.g., an EUV absorption cross-section that is equal to or greater than 1x107cm2 / mol).

[0109] In some embodiments, the metal -containing precursor has at least one optionally substituted alkyd group, optionally substituted alkenyl, or optionally substituted alkynyl. Nonlimiting groups include -CnH2n+i, in which n is 1 or 2; -Cntbn-i, in which n is 2, 3, or 4; or -CnH2n-3, in which n is 2, 3, or 4. Yet other non-limiting groups include methyl (-CH3), ethyl (-CH2CH3), vinyl or ethenyl (-CH=CH2), 1 -propenyl (-CH=CHCH3), allyl or 2-propenyl (-CH2-CH=CH2), 1-butenyl (-CH=CHCH2CH3), 2-butenyl (-CH2CH=CHCH3), 3-butenyl (e g. -CH2CH2CH=CH2), ethynyl (-C=CH), 1-propynyl (-C=CCH3). 2-propynyl or propargyl (-CH2C=CH), 1-butynyl (-C=CCH2CH3), 2-butynyl (-CH2C=CCH3), 3-butynyl (-CH2CH2C=CH), 2-methyl-l -propenyl (CH=C(CH3)2, isopropenyl (C(CH3)=CH2, 1-methylallyl (CH(CH3)CH=CH2and the like. These groups may be advantageous in forming positive tone resists.

[0110] In some embodiments, each ligand within the metal-containing precursor can be one that is reactive with a counter-reactant and / or a ligand-containing precursor.[OlH] For any formula herein, the metal 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 IxlO7cm2 / mol). In some embodiments, M is lead (Pb), germanium (Ge), tin (Sn), tellurium (Te),Atorney Docket No.: LAM1P118WO-12279-1WO bismuth (Bi), antimony (Sb), hafnium (Hf), or zirconium (Zr). In further embodiments, M is Sn, a is 1, and b + c is 4. In other embodiments, M is Sn, a is 1, and b + c is 2. In yet other embodiments, M is Sn, a is 1 , and c is 2. In particular embodiments, M is Sn(II), thereby providing a metal-containing precursor that is a Sn(II)-based compound. In other embodiments, M is Sn(IV), thereby providing a metal-containing precursor that is a Sn(IV)-based compound.

[0112] For any formula herein, each L is, independently, H, halo, azido, cyano, alkylcarbonyl, isothiocyanate, thiocyanato, 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 or haloalkyl). In some embodiments, the optionally substituted amino is -NR'R2. 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 -SiR^R3, in which each R1, R2, and R3is, independently, alkyd. Each L in the metal-containing precursor may be removed during the deposition process and do not remain in the deposited photoresist.

[0113] In some 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, alkyd or haloalkyl; 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.

[0114] There are several types of alkynyl tin precursors for use in positive tone dry' resist. These precursors can react in different ways depending on where the carbon-carbon triple bond is located. If the carbon-carbon triple bond is not bound directly to the tin center, for example in a formula R1CCCH2SnLs where R1is a C1-C2 linear or branched alkane such as methyl or ethyl; and L is an amino (dimethylamino, diethylamino, ethylmethylamino, methylpropylamino, aminiocyclopentane, aminocyclohexane) or alkoxy group (methoxy, ethoxy, n-propoxy, isopropoxy, t-butoxy, sec-butoxy, or n-butoxy). In this type of precursor, the unsaturated triple bond will be incorporated into the film and is expected to crosslink with other unsaturated groups.

[0115] Alkyne compounds which have a carbon-carbon triple bond directly bonded to the tin atom will hydrolyze in the presence of water similar to, although much slower than, amino andAtorney Docket No.: LAM1P118WO-12279-1WO alkoxy groups. Therefore, compounds such as (R1C=C)sSnR2and (R'C=C)4Sn where R1is a simple alkane such as methyl or ethyl, and R2is a C1-C2 hydrocarbon are another method of introducing alkyl and groups into a tin-oxo compounds. In compound (R1C=C)sSnR2the tin center has three alky nes with the carbon-carbon triple bond bonded to the tin center. These precursors will react in a mechanism similar to the previously described amino or alkoxy tin compounds although the alkyne precursors may be more stable thermally or hydrolytically than the alkoxy or amino compounds. Due to the slow hydrolysis of the alkyne compounds it may be possible to use tetra-alkynes such as those shown for (R1C=C)4Sn. Using (R1C=C)4Sn it may be possible by controlling the water to precursor ratio to deposit films which contain a tin oxo network while still maintaining some amount of alkyne groups in the film which can crosslink.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. 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 metal-containing precursors can include, e g., Sn(, Sn(CH=CH2)(NMe2)3, Sn(CH=CHCH3)(NMe2)3, Sn(CH2-CH=CH2)(NMe2)3, Sn(C=CH)(NMe2)3. Sn(C=CCH3)(NMe2) , Sn(CH2C=CH)(NMe2)3, Sn(NMe2)2, Sn(NEt2)2, or Sn[N(SiMe3)2]2.

[0116] In some embodiments, the metal-containing precursor is RSn(NMe2)3, RSn(NMe2)2(NEt2), RSn(NEt2)3, or RSn[N(SiMe3)2]3, in which R is C2-4 haloalkenyl, C2-4 haloalkynyl, , C2-4 alkenyl, or C2-4 alkynyl. In other embodiments, the metal-containing precursor is R2Sn(NMe2)2, R2Sn(NMe2)(NEt2), R2Sn(NEt2)2, or R2Sn[N(SiMe3)2]2, in which each R is, independently, C2-4 haloalkenyl, C2-4 haloalkynyl, , C2-4 alkenyl, or C2-4 alkynyl.

[0117] In other embodiments, the metal-containing precursor is RSnLs. in which R is, C2-4 haloalkenyl, C2-4 haloalkynyl, , C2-4 alkenyl, or C2-4 alkynyl; and in which each E is, independently, selected from the group of -NMe2, -NEt2, -NMeEt, -N(t-Bu)-[CHCH3]2-N(t-Bu)- (tbba), -N(SiMes)2, and -N(SiEts)2.

[0118] In other embodiments, the metal-containing precursor is RSnLs. in which R is Ci- C3 aliphatic (wherein the C1-C3 aliphatic may be optionally substituted with a ketone, an alkoxy group, an epoxy group) or a -C(O)Ci-Cs alkyl group; and in which each L is, independently, selected from the group of optionally substituted alkoxy, -NMe2, -NEt2, -NMeEt, -N(t-Bu)-[CHCH3]2-N(t-Bu)- (tbba). -N(SiMe3)2, and -N(SiEt3)2. Ethers, ketones or epoxide-containing R groups on the metal-containing precursors may be advantageous to assist in crosslinking.

[0119] 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. Non-limiting L substituents include, e.g., methoxy, ethoxy, isopropoxy (i-PrO), t-butoxy (t-BuO), and -O=C(CH3)-Atorney Docket No.: LAM1P118WO-12279-1WO CH=C(CH?)-O- (acac). Non-limiting metal -containing precursors include, e.g., Sn(t-BuO)2, , Sn(CH=CH2)(t-BuO)3, Sn(CH=CHCH3)(t-BuO)3, Sn(CH2-CH=CH2)(t-BuO)3, Sn(C=CH)(t-BUO)3, Sn(C =CCH3)(t-BuO)3. Sn(CH2C=CH)(t-BuO)3, or Sn(acac)2.

[0120] In some embodiments, the metal -containing precursor is RSn(t-BuO)3, in which R is, C2-4 haloalkenyl, C2-4 haloalkynyl, . C2-4 alkenyl, or C2-4 alkynyl. In other embodiments, the metalcontaining precursor is R2Sn(t-BuO)2, in which each R is, independently, , C2-4 haloalkenyl, C2-4 haloalkynyl, , C2-4 alkenyl, or C2-4 alkynyl. In yet other embodiments, the metal-containing precursor is RSnL3, in which R is, C2-4 haloalkenyl, C2-4 haloalky nyl, , C2-4 alkenyl, or C2-4 alky nyl; and in which each L is, independently, selected from the group of methoxy, ethoxy, i-PrO. and t-BuO.

[0121] 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, 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 metal- and / or ligand-containing 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.

[0122] In some embodiments, R groups or ligands from the metal -containing precursor may be incorporated in the photoresist material 312 so that an R group or ligand from the metal -containing precursor includes the unsaturated carbon bond. In some embodiments, a counter-reactant reacts with the metal -containing precursor so that the counter-reactant that remains in the photoresist material 312 includes the unsaturated carbon bond. In one example, the counter-reactant includes methacrylic acid. In a subsequent exposure step, cross-linking can take place between unsaturated carbon bonds in the counter-reactant, between unsaturated carbon bonds in the metal-containing precursor, and / or between unsaturated carbon bonds in the metal-containing precursor and the counter-reactant.

[0123] The photoresist material 312 can include metal constituents and organic substituents, each of which may include UV-, DUV-, or EUV-sensitive moieties. At an exposure step 302, the photoresist material 312 is exposed to patterning radiation 315 to provide a photopattemed resist film having unexposed regions 313a and exposed regions 313b. The exposure step 302 can involveAtorney Docket No.: LAM1P118WO-12279-1WO use of a mask 314 having transparent regions and opaque regions, in which the beams of the patterning radiation 315 are transmitted through the transparent regions and into the photoresist material 312. For example, EUV exposure can include, e.g., an exposure having a wavelength in the range of about 10 nm to about 20 nm in a vacuum ambient (e.g., about 13.5 nm in a vacuum ambient). Without being limited by any theory, organic ligands in the photoresist material 312 may be removed, cleaved, or cross-linked by the patterning radiation 315 during the exposure step 302. In the present disclosure, the vinyl groups or other unsaturated substituents in the photoresist material 312 may undergo cross-linking upon exposure to the patterning radiation 315. Crosslinking that is desirable for a positive tone resist may occur between unsaturated carbon bonds in the counter-reactants, between unsaturated carbon bonds in the metal -containing precursors, and / or between unsaturated carbon bonds in the metal-containing precursor and the counterreactant. In some instances, the vinyl groups or other unsaturated substituents may be linked to form one or more rings or linked to form long stable carbon chains. As such, the patterning radiation 315 photoinduces polymerization to form cross-linked organic moieties in the exposed regions 313b of the photopattemed resist film. Carbon-based polymers in the exposed regions 313b may be relatively stable during a subsequent bake step 303. The carbon-based polymers may include one or more rings, such as rings with C-Sn-0 bonds. In some embodiments, the carbonbased polymers may include long stable carbon chains.

[0124] At a bake step 303, the photopattemed resist film having unexposed regions 313a and exposed regions 313b is treated prior to development. The bake step 303 can remove residual moisture and promote chemical condensation within the photopattemed resist film. The bake step 303 can harden the photopattemed resist film to further cross-link the unexposed regions 313a and / or exposed regions 313b. During the bake step 303, a thermal treatment is performed that modifies the material properties of the photopattemed resist film having unexposed regions 313a and exposed regions 313b. In some embodiments, the thermal treatment is ty pically performed at high temperatures using an oxy gen-containing gas ambient such as air, water, oxygen, ozone, hydrogen peroxide, carbon monoxide, or carbon dioxide. High temperatures associated with the thermal treatment may be greater than about 100°C, such as temperatures between about 120°C and about 290°C. The bake step 303 may further increase chemical contrast between the unexposed regions 313a and the exposed regions 313b. Without being limited by any theory , the thermal treatment in the bake step 303 may further promote ligand cleavage and cross-linking to form more M-O-M bonds. In the present disclosure, the thermal treatment of the photopattemed resist film exposes the photopattemed resist film to a gaseous environment comprising at least one oxy gen-containing species. The unexposed regions 313a may comprise vinyl groups or other unsaturated substituents. The exposed regions 313b may comprise cross-linked organic moieties.Atorney Docket No.: LAM1P118WO-12279-1WO In some embodiments, the cross-linked organic moieties may be linked to form one or more rings, such as rings with C-Sn-0 bonds. In some embodiments, the cross-linked organic moieties may form long stable carbon chains. Without being limited by any theoiy. the oxygen-containing species may remove organic ligands such as the vinyl groups or other unsaturated substituents from the unexposed regions 313a. The cross-linked organic moieties that form a carbon-based polymer may be preserved during exposure to the oxy gen-containing species. Accordingly, the exposed regions 313b after the bake step 303 may comprise a carbon-based polymer network (e.g., secondary hydrocarbon network) in addition to a metal oxide network (e g., primary metal oxide network), and the unexposed regions 313a after the bake step 303 may comprise a metal oxide network with little to no organic ligands.

[0125] At a positive tone development step 304, the exposed regions 313b are selectively removed and the unexposed regions 313a are preserved to create a patterned resist mask. The development step 304 may involve dry processes. In recent advances, positive tone development has been accomplished using wet processes. However, as discussed above, wet processing involves moisture and / or oxygen, which more easily leads to scum formation. Wet development is limited by solubility and cluster size, and is more prone to pattern collapse and delamination issues. Therefore, wet development of positive tone resists can suffer from defectivity due to interface failure and / or line collapse caused by surface tension. Dry development can avoid some or all of the aforementioned issues and can be more easily integrated in an all-dry processing chamber or tool. In the present disclosure, the positive tone development step 304 is a dry development step. The dry development can selectively remove the exposed regions 313b relative to the unexposed regions 313a to form the patterned resist mask. As discussed below, the dry¬ development at the positive tone development step 304 may involve multiple steps. One step in the dry development process may weaken or break metal-carbon or carbon-carbon bonds in the exposed regions 313b. Dangling bonds may form in the exposed regions 313b. Another step in the dry development process may use a dry development gas such as a halide-containing gas to react with the dangling bonds and etch material in the exposed regions 313b. These steps in the dry development process can occur sequentially or cyclically. Alternatively, these steps in the dry development process can occur simultaneously in one step.

[0126] Figure 4 presents a flow diagram of an example method of performing positive tone dry¬ development according to some implementations. The operations of a process 400 may be performed in different orders and / or with different, fewer, or additional operations. Aspects of the process 400 may be described with reference to Figures 5 and 6. One or more operations of the process 400 may be performed using an apparatus described in any one of Figures 7-11. In someAtorney Docket No.: LAM1P118WO-12279-1WO embodiments, the operations of the process 400 may be implemented, at least in part, according to softw are stored in one or more non-transitory computer readable media.

[0127] At block 402 of the process 400, a photoresist material is deposited on a surface of a substrate. The photoresist material includes a metal and oxygen, and the photoresist material further includes an unsaturated carbon bond. The photoresist material is a radiation-sensitive film. The metal and the oxygen in the photoresist material form a metal oxide network or metal-oxo network. Attached to the metal atoms are ligands such as organic ligands or R groups. The organic ligands may comprise one or more organic moieties. Generally speaking, the organic ligands are responsive to radiation, where the organic ligands can be removed, cleaved, or cross-linked by the radiation.

[0128] In some embodiments, the metal can be selected from the group consisting of lead, germanium, tin, tellurium, bismuth, antimony, hafnium, and zirconium. In some cases, the metal is tin(II). In some other cases, the metal is tin(IV).

[0129] One or more organic ligands in the photoresist material may include the unsaturated carbon bond. The unsaturated carbon bond may be formed from an unsaturated substituent in an organic ligand. The unsaturated substituent may comprise an aliphatic chain, cyclic, aryl, or heteroaryl group.

[0130] With reference to the unsaturated carbon bond, the photoresist material may include, for example, an alkenyl group such as vinyl or ethenyl (-CH=CH2), 1 -propenyl (-CH=CHCH3), allyl or 2 -propenyl (-CH2-CH=CH2), 1-butenyl (-CH=CHCH2CH3), 2-butenyl (-CH2CH=CHCH3), 3-butenyl (e.g. -CH2CH2CH=CH2), iso-propenyl (-C(CH3)=CH2), iso-butenyl (-CH=C(CH3)2), and the like. Additionally or alternatively with reference to the unsaturated carbon bond, the photoresist material may include, for example, an alkynyl group such as ethynyl (-C=CH), 1-propynyl (-C=CCH3), 2-propynyl or propargyl (-CH2C=CH), 1-butynyl (-C=CCH2CH3), 2-butynyl (-CH2OCCH3), 3-butynyl (-CH2CH2C =CH). and the like.

[0131] The photoresist material may be deposited using any suitable deposition technique. Exemplary deposition techniques include chemical vapor deposition (CVD). plasma enhanced CVD (PECVD), low pressure CVD (LPCVD), atomic layer deposition (ALD) (e.g., thermal ALD and plasma-enhanced ALD (PEALD)), molecular layer deposition (MLD), spin-coat deposition, physical vapor deposition (PVD) including PVD co-sputtering, sputter deposition, electron-beam (e-beam) deposition including e-beam co-evaporation, etc., or a combination thereof.

[0132] The photoresist material may be deposited by depositing a metal-containing precursor on a surface of the substrate. Examples of metal-containing precursors are described above. Depositing the photoresist material may involve providing a metal-containing precursor, a ligandcontaining precursor, and / or a counter-reactant in vapor form. Non-limiting counter-reactantsAtorney Docket No.: LAM1P118WO-12279-1WO include an oxygen-containing or a chalcogenide-containing precursor, as well as any described herein (e.g., an oxygen-containing counter-reactant, including oxygen (O2), ozone (Os), 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). In some embodiments, deposition of the photoresist material involves using multiple metal-containing precursors that are deposited on the surface of the substrate.

[0133] In some embodiments, the metal-containing precursor comprises a metal (M) selected from the group consisting of lead, germanium, tin, and hafnium. In some embodiments, the metalcontaining precursor has the formula M(R1)4, where at least one R1is an unsaturated substituent.

[0134] At block 404 of the process 400, the photoresist material is exposed to radiation to form a photopattemed metal oxide resist film, thereby providing an exposed region and an unexposed region of the photopattemed metal oxide resist film. Exposure to radiation causes a change in the chemical composition of the photoresist material, creating a contrast in etch selectivity that can be used to remove a portion of the photoresist material. Such a contrast between the exposed region and the unexposed region can provide a positive tone resist, as described herein. EUV, DUV, UV, and e-beam radiation methods may be used in exposing the photoresist material to patterning radiation to form the exposed region and unexposed region. By way of an example, EUV exposure can have a wavelength in the range of about 10 nm to about 20 nm in a vacuum ambient, such as a wavelength of from 10 nm to 15 nm, e.g., 13.5 nm.

[0135] In some implementations, the exposure at block 404 may be performed without any oxygen-containing species such as H2O, O2, etc. The presence of any oxygen-containing species may quench the radical(s) generated to initiate polymerization during exposure.

[0136] In some implementations, the exposure at block 404 may maintain or substantially maintain a carbon content in the exposed region rather than reducing the carbon content in the exposed region. Whereas exposure radiation may typically cleave metal-carbon bonds to reduce carbon content in conventional metal oxide photoresists, the exposure radiation in the present disclosure facilitates cross-linking between carbon atoms to form a carbon-based polymer. The carbon-based polymer may include one or more carbon rings, such as carbon rings with C-Sn-0 bonds. Alternatively, the carbon-based polymer may include a long stable carbon chain.

[0137] Exposing the photoresist material to radiation can photoinduce polymerization to form cross-linked organic moieties in the exposed region of the photopattemed metal oxide resist film. In other words, exposure provides cross-linked organic moieties by photopolymerizing ligands within the photoresist material, where such ligands may include one or more unsaturated carbon bonds. The unsaturated carbon bonds may include carbon-carbon double or triple bonds, doubleAtorney Docket No.: LAM1P118WO-12279-1WO or triple bonds with carbon and a heteroatom, or carbon ring structures. These unsaturated carbon bonds may be activated during exposure to the radiation to form a carbon-based polymer within the metal oxide or metal-oxo network.

[0138] Figure 5 presents a reaction scheme illustrating initiation, polymerization, and termination of a tin-oxo network having unsaturated substituents upon exposure to patterning radiation according to some implementations. The tin-oxo network may include alkenyl substituents such as vinyl groups. Patterning radiation exposure represented by hv can break one or more Sn-C bonds that result in the formation of a radical. That radical will initiate polymerization during radiation exposure. Put another way, the radiation exposure results in reduction of some of the adjacent double bonds appended to tin to form carbon-carbon bonds. In some embodiments, dealkylation occurs. The presence of bridging hydrocarbon groups provides a secondary hydrocarbon cross-linked network in addition to a primary7metal oxide network in an exposed region. As shown in Figure 5, termination of the chain reaction of polymerization may occur, where patterning radiation exposure represented by hv can break a Sn-C bond that results in the formation of another radical that is used to terminate the chain reaction. The tin-oxo network may include carbon-carbon bonds that form bridges between two tin centers.

[0139] Returning to Figure 4, the exposed region comprises a carbon-based polymer. Specifically, the exposed region comprises cross-linked organic moieties formed by photoinduced polymerization during exposure to patterning radiation. The exposed region may include a secondary hydrocarbon cross-linked network with a primary7metal oxide network. In contrast, the unexposed region comprises a metal oxide network without a secondary hydrocarbon cross-linked network. The unexposed region retains organic ligands having one or more unsaturated carbon bonds. Such unsaturated carbon bonds in the unexposed region are not polymerized. In some embodiments, the organic ligands are relatively^ small cleavable groups such as C1-2 aliphatic or C1-2 haloaliphatic groups.

[0140] In some embodiments, the photoresist material deposited at block 402 may be a blended or heterogeneous metal oxide photoresist material. The blended photoresist material may include at least one unsaturated substituent bonded to a metal atom and at least one saturated substituent bonded to another metal atom. By way of an example, the blended photoresist material may include at least one alkenyl group or at least one alkynyl group, and at least one alkyl group. The blended photoresist material may be formed by depositing a first metal precursor which is an organometal and a second metal precursor, where the two precursors may be co-deposited. The second metal precursor may have no direct metal-carbon bonds or is a second organometal having a weaker metal-carbon bond than the metal-carbon bond in the first metal precursor. As such, theAtorney Docket No.: LAM1P118WO-12279-1WO blended photoresist material may have a mixture of stronger metal-carbon bonds and weaker metal-carbon bonds in the metal oxide network.

[0141] The blended photoresist material at block 404 may be exposed to radiation to form a photopatterned metal oxide resist film, thereby providing an exposed region and an unexposed region of the photopattemed metal oxide resist film. The weaker metal-carbon bonds may be more easily broken during exposure to the radiation compared to stronger metal-carbon bonds in the blended photoresist material. Radicals can be more easily formed from the weaker metal-carbon bonds to initiate polymerization, which means that less energy may be required to form carbonbased polymers in the exposed region. Furthermore, the radicals that are more easily formed from the weaker metal-carbon bonds can terminate polymerization, which means that the carbon-based polymers are less likely to expand from the exposed region to the unexposed region. Thus, the blended photoresist material can advantageously reduce the radiation dose for exposure as well as limit polymerization from growing into the unexposed region that would otherwise reduce etch contrast.

[0142] Figure 6 presents a reaction scheme illustrating initiation, polymerization, and termination of a tin-oxo network having unsaturated substituents and at least one saturated substituent upon exposure to patterning radiation according to some implementations. The tinoxo network may include alkenyl substituents such as vinyl groups. The tin-oxo network may also include alkyl groups such as isopropyl groups. Patterning radiation exposure represented by hv can break w eaker Sn-C bonds in the isopropyl groups to generate a radical. That radical will initiate polymerization during radiation exposure. Put another way, the radiation exposure results in reduction of some of the adjacent double bonds appended to tin to form carbon-carbon bonds. The presence of bridging hydrocarbon groups provides a secondary hydrocarbon cross-linked network in addition to a primary metal oxide network in an exposed region. As shown in Figure 6, termination of the chain reaction of polymerization may occur, where patterning radiation represented by hr’ can break another one of the weaker Sn-C bonds in the isopropyl groups that generates another radical that is used to terminate the chain reaction. The tin-oxo network may include carbon-carbon bonds that form bridges betw een two tin centers.

[0143] The tin-oxo network may include alkenyl substituents such as vinyl groups. Patterning radiation exposure represented by hv can break one or more Sn-C bonds that result in the formation of a radical. That radical will initiate polymerization during radiation exposure. Put another way, the radiation exposure results in reduction of some of the adjacent double bonds appended to tin to form carbon-carbon bonds. In some embodiments, dealkylation occurs. The presence of bridging hydrocarbon groups provides a secondary’ hydrocarbon cross-linked network in addition to a primary metal oxide network in an exposed region. As shown in Figure 5, termination of theAtorney Docket No.: LAM1P118WO-12279-1WO chain reaction of polymerization may occur, where paterning radiation exposure represented by hv can break a Sn-C bond that results in the formation of another radical that is used to terminate the chain reaction. The tin-oxo network may include carbon-carbon bonds that form bridges between two tin centers. The presence of weaker Sn-C bonds from the isopropyl groups can reduce the radiation dose required to form a positive tone resist during the exposure step. Moreover, the presence of weaker Sn-C bonds may more easily facilitate termination of polymerization to prevent polymerization from expanding from the exposed region to the unexposed region of a photopatemed metal oxide resist film.

[0144] Returning to Figure 4, at block 406 of the process 400, the photopatemed metal oxide resist film is exposed to a gaseous environment comprising at least one oxygen-containing species. The treatment at block 406 may be a bake process or post-exposure bake (PEB) process that thermally treats the photopattemed metal oxide resist film to increase chemical contrast for development. The bake process at block 406 may exposure the photopattemed metal oxide resist film to an oxidizing atmosphere at an elevated temperature. In some implementations, the elevated temperature in the bake process may be greater than about 100°C, such as between about 150°C and about 290°C, or between about 170°C and about 250°C. In some implementations, the oxy gen-containing species may include oxygen (O2), ozone (O3), water (H2O), hydrogen peroxide (H2O2). carbon monoxide (CO), carbon dioxide (CO2), or combinations thereof.

[0145] The oxygen-rich environment at elevated temperatures may break metal-carbon bonds in the unexposed region, converting the network in the unexposed region to densified metal oxide. However, the exposed regions remain largely unchanged due to the carbon-based polymer serving a protective function during exposure to the oxygen-rich environment. Specifically, the secondary hydrocarbon cross-linked network in the exposed region is stable during exposure to the oxygenrich environment. The carbon-based polymer in the exposed region is resistant to the gaseous environment comprising the oxygen-containing species at the elevated temperature. The temperature at block 406 may be optimized to break metal-carbon bonds in the unexposed region without breaking the metal-carbon bonds in the exposed region.

[0146] The unexposed region comprises organic ligands having one or more unsaturated carbon bonds. The unsaturated carbon bonds are not polymerized and are usually small cleavable groups such as C1-2 aliphatic or C1-2 haloaliphatic groups. For example, the organic ligands may include alkenyl groups such as vinyl groups. The unsaturated substituents in the unexposed region are more sensitive to the oxygen-containing bake than the carbon-based polymer in the exposed region. The elevated temperature and the oxygen-containing species may cleave metal-carbon bonds in the unexposed region without cleaving metal-carbon bonds in the exposed region. The oxy gen-containing bake removes or substantially removes organic ligands from the unexposedAtorney Docket No.: LAM1P118WO-12279-1WO region. The oxygen-containing bake preserves or substantially preserves the cross-linked organic moieties in the exposed region.

[0147] By cleaving metal-carbon bonds in the unexposed region, the oxygen-containing bake can reduce a carbon content in the unexposed region by a greater percentage than a carbon content in the exposed region. As a result, the unexposed region comprises a densified metal oxide network with little to no organic ligands. The oxygen-containing bake may incorporate oxygen in the unexposed region to facilitate cross-linking and form additional metal-oxygen-metal (M-O-M) bonds. The oxygen-containing bake may densify the unexposed region relative to the exposed region. After the thermal treatment with an oxy gen-containing species at block 406, the exposed region retains a primary metal oxide network with a secondary hydrocarbon cross-linked network and the unexposed region is converted to a densified metal oxide network with a reduced carbon content.

[0148] At block 408 of the process 400, the photopattemed metal oxide resist film is dry- developed to selectively remove the exposed region relative to the unexposed region of the photopattemed metal oxide resist film to form a resist mask. Dry development at block 408 is a positive tone dry development. Dry developing the photopattemed metal oxide resist film includes exposure to a dry development chemistry that selectively breaks metal-carbon bonds in the exposed region relative to metal-oxygen bonds in the unexposed region.

[0149] The positive tone dry development at block 408 leverages selective polymer protection in the exposed region during the exposure step and material transformation of the unexposed region during the bake step. The exposure step creates a photo-activated carbon-based polymer to selective protect the exposed region during a subsequent bake step. The bake step breaks metal-carbon bonds to selectively remove organic ligands from the unexposed region while the exposed region remains stable. The bake step densifies the unexposed region to form densified metal oxide, which enhances etch resistance and stability during a subsequent dry development step.

[0150] The exposed region may comprise metal-carbon bonds from the secondary hydrocarbon cross-linked network. The unexposed region may7comprise metal-oxygen bonds from the densified metal oxide network. The metal-oxygen bonds may be stronger and more etch resistant than the metal-carbon bonds. In some implementations, the dry- development is a thermal dry¬ development. In some implementations, the dry development is a plasma dry development. Radicals and / or ions of an etch gas may be generated in-situ or generated in a remote plasma source. In some implementations, the dry development is a combination of a plasma dry development and a thermal dry development.Atorney Docket No.: LAM1P118WO-12279-1WO

[0151] The positive tone dry development may take place in one or more steps. A first step may weaken or break carbon-carbon bonds or metal-carbon bonds in the exposed region. This can be achieved by exposure to reactive chemistries, photons, plasma, and / or thermal energy . Upon breaking the metal-carbon bonds or carbon-carbon bonds in the exposed region, dangling bonds are formed in the exposed region. In the unexposed region, there are little to no carbon-carbon bonds and metal-carbon bonds, and the metal-oxygen bonds in the unexposed region are preserved or substantially preserved during the first step. In a second step, an etch gas or radicals / ions of the etch gas can attack the dangling bonds and etch exposed material in the exposed region. The first and second steps may take place sequentially or cyclically. Alternatively, the first and second steps may be combined into a single step.

[0152] The dry development approach of the present disclosure is free of wet chemical developers, which reduces the risk of contamination and improves compatibility with high aspect ratio structures. Positive tone dry' development with metal oxide photoresist films is advantageous for producing advanced and small features in semiconductor substrates. This can enable fine, complex patterns that are critical for next-generation semiconductor devices. In addition, the positive tone dry development expands the potential applications for metal oxide photoresists. Apparatus

[0153] An apparatus of the present disclosure is configured for positive tone dry' development. The apparatus may be additionally configured for photoresist deposition, bevel and backside cleaning, post-application baking, EUV scanning, photoresist development, post-exposure baking, photoresist reworking, chamber clean, and other operations. In some implementations, the apparatus is configured to perform all dry operations. In some implementations, the apparatus is configured to perform a combination of wet and dry operations. The apparatus may include a single wafer chamber or multiple stations in the same process chamber. With multiple stations in the same process chamber, various processing operations such as those described in the present disclosure may7be performed in different stations in the same process chamber. In one example, post-exposure bake may be performed in one station and dry' development in another station.

[0154] The apparatus configured for positive tone dry development includes a process chamber with a substrate support. The substrate support may be configured to support a semiconductor substrate. In some cases, the semiconductor substrate may have a photopattemed metal oxide resist film formed thereon. The apparatus may include a gas line coupled to the process chamber for delivery' of dry development gas(es). In some implementations, the dry development gas includes a hydrogen halide (e.g.. HBr. HC1, etc.), hydrogen and halogen gas (e.g., H2 and Ch, H2 and Bn, etc.), boron trichloride, an organic halide, an acyl halide, a carbonyl halide, and a thionylAtorney Docket No.: LAM1P118WO-12279-1WO halide, or mixtures thereof. The apparatus may include a vacuum line coupled to the process chamber. The vacuum line may be configured for pumping / purging of gas from the process chamber. The apparatus may include one or more heaters for temperature control. Such heaters may be provided in the process chamber and / or in the substrate support.

[0155] In some implementations, the process chamber is made of an inexpensive material such as plastic. In some other implementations, the process chamber is made of a metal such as anodized aluminum or a ceramic such as aluminum oxide.

[0156] In some implementations, the process chamber may be selected from a group consisting of: a dry deposition chamber, a bevel edge and / or backside clean chamber, a bake chamber, an exposure chamber, a dry development chamber, or etch chamber. In some implementations, the process chamber may be configured to perform a dry development such as a positive tone dry development, where a substrate is provided to the process chamber having a photopattemed metal oxide resist film. The photopattemed metal oxide resist film can include exposed areas having a carbon-based polymer and unexposed areas having a densified metal oxide network.

[0157] Figure 7 depicts a schematic illustration of an example process station that is suitable for performing deposition, bake, or dry development operations according to some implementations. A plurality of process stations 700 may be included in a common low-pressure process tool environment. For example, Figure 8 depicts an implementation of a multi-station processing tool 800, such as a VECTOR® processing tool available from Lam Research Corporation, Fremont, CA. In some implementations, one or more hardware parameters of the process tool 800 including those discussed in detail below may be adjusted programmatically by one or more computer controllers.

[0158] A process station may be configured as a module in a cluster tool. Figure 8 depicts a semiconductor process cluster tool architecture with vacuum-integrated deposition and patterning modules suitable for implementation of the implementations described herein. Such a cluster process tool architecture can include resist deposition, resist exposure (EUV scanner), resist treatment, resist baking, resist development and etch modules, as described above and further below with reference to Figures 9 and 10.

[0159] In some implementations, certain processing functions can be performed consecutively in the same module, for example dry' development and etch or dry deposition and post-exposure bake. And implementations of this disclosure are directed to methods and apparatus for receiving a wafer, including resist thin film layer disposed on a layer or layer stack to be etched, to a dry development / etch chamber following photopatteming in an patterning radiation scanner; dry developing photopattemed resist thin film layer; and then etching the underlying layer using the patterned resist as a mask, as described herein.Atorney Docket No.: LAM1P118WO-12279-1WO

[0160] Returning to Figure 7, process station 700 may include a single processing chamber 702 for maintaining a low-pressure environment. The processing chamber 702 fluidly communicates with reactant delivery system 701 for delivering process gases to a distribution showerhead 706. Reactant delivery' system 701 optionally includes a mixing vessel 704 for blending and / or conditioning process gases, for delivery’ to showerhead 706. One or more mixing vessel inlet valves 720 may control introduction of process gases to mixing vessel 704. Where plasma exposure is used, plasma may also be delivered to the showerhead 706 or may be generated in the processing chamber 702. The plasma may be generated in a chamber space 707 located beneath the showerhead 706.

[0161] Figure 7 includes an optional vaporization point 703 for vaporizing liquid reactant to be supplied to the mixing vessel 704. In some implementations, a liquid flow controller (LFC) upstream of vaporization point 703 may be provided for controlling a mass flow of liquid for vaporization and delivery to the processing chamber 702. For example, the LFC may include a thermal mass flow meter (MFM) located downstream of the LFC. A plunger valve of the LFC may then be adjusted responsive to feedback control signals provided by a proportional-integral-derivative (PID) controller in electrical communication with the MFM.

[0162] Showerhead 706 distributes process gases toward substrate 712, the flow of which is controlled by one or more valves (e.g., valves 705, 720) upstream from the showerhead 706. In the implementation shown in Figure 7, the substrate 712 is located beneath showerhead 706 and is shown resting on a pedestal 708. Showerhead 706 may7have any7suitable shape, and may have any suitable number and arrangement of ports for distributing process gases to substrate 712.

[0163] In some implementations, pedestal 708 may be raised or lowered to expose substrate 712 to a chamber space 707 between the substrate 712 and the showerhead 706. It will be appreciated that, in some implementations, pedestal height may be adjusted programmatically by a suitable computer controller 750. In some implementations, the showerhead 706 may have multiple plenum volumes with multiple temperature controls.

[0164] In some implementations, pedestal 708 may be temperature controlled via heater 710. In some implementations, the pedestal 708 may be heated to a temperature of greater than -20°C and up to 300°C or more, for example 80°C to 180°C, such as about 100°C to 180°C, during operations such as a bake process as described in disclosed implementations. In some implementations, the heater 710 of the pedestal 708 may include a plurality of independently controllable temperature control zones.

[0165] Further, in some implementations, pressure control for process station 700 may be provided by a butterfly valve 718. As shown in the implementation of Figure 7, butterfly valve 718 throttles a vacuum provided by a downstream vacuum pump (not shown). The butterfly valveAtorney Docket No.: LAM1P118WO-12279-1WO 718 may serve as a throttle valve for regulating pressure in the process station 700. However, in some implementations, pressure control of process station 700 may also be adjusted by varying a flow rate of one or more gases introduced to the process station 700.

[0166] In some implementations, a position of showerhead 706 may be adjusted relative to pedestal 708 to vary a volume between the substrate 712 and the showerhead 706. Further, it will be appreciated that a vertical position of pedestal 708 and / or showerhead 706 may be varied by any suitable mechanism within the scope of the present disclosure. In some implementations, pedestal 708 may include a rotational axis for rotating an orientation of substrate 712. It will be appreciated that, in some implementations, one or more of these example adjustments may be performed programmatically by one or more suitable computer controllers.

[0167] Where plasma may be used, for example in pattern transfer etch operations or plasma dry development operations, showerhead 706 and / or pedestal 708 electrically communicate with a radio frequency (RF) power supply 714 and matching network 716 for powering a plasma. Thus, one or both of the showerhead 706 and the pedestal 708 may be powered for plasma generation. In some implementations, the plasma energy may be controlled by controlling one or more of a process station pressure, a gas concentration, an RF source power, an RF source frequency, and a plasma pow er pulse timing. For example, RF power supply 714 and matching network 716 may be operated at any suitable power to form a plasma having a desired composition of radical species. Examples of suitable powers are up to about 1000 W.

[0168] In some implementations, instructions for a controller may be provided via input / output control (IOC) sequencing instructions. In one example, the instructions for setting conditions for a process phase may be included in a corresponding recipe phase of a process recipe. In some cases, process recipe phases may be sequentially arranged, so that all instructions for a process phase are executed concurrently with that process phase. In some implementations, instructions for setting one or more reactor parameters may be included in a recipe phase. For example, a recipe phase may include instructions for setting a flow rate of reactive gas(es), such as halogen gases, and time delay instructions for the recipe phase. In some implementations, the controller may include any of the features described below with respect to system controller 850 of Figure 8.

[0169] As described above, one or more process stations may be included in a multi-station processing tool. Figure 8 shows a schematic view of an implementation of a multi-station processing tool 800 with an inbound load lock 802 and an outbound load lock 804, either or both of which may include a remote plasma source. A robot 806 at atmospheric pressure is configured to move wafers from a cassette loaded through a pod 808 into inbound load lock 802 via an atmospheric port 810. A wafer is placed by the robot 806 on a pedestal 812 in the inbound loadAtorney Docket No.: LAM1P118WO-12279-1WO lock 802, the atmospheric port 810 is closed, and the load lock is pumped down. Where the inbound load lock 802 includes a remote plasma source, the wafer may be exposed to a remote plasma treatment to treat the substrate surface in the load lock prior to being introduced into a processing chamber 814. Further, the wafer also may be heated in the inbound load lock 802 as well, for example, to remove moisture and adsorbed gases. Next, a chamber transport port 816 to processing chamber 814 is opened, and another robot (not shown) places the wafer into the reactor on a pedestal of a first station shown in the reactor for processing. While the implementation depicted in Figure 8 includes load locks, it will be appreciated that, in some implementations, direct entry of a wafer into a process station may be provided.

[0170] The depicted processing chamber 814 includes four process stations, numbered from 1 to 4 in the implementation shown in Figure 8. Each station has a heated pedestal (shown at 818 for station 1), and gas line inlets. It will be appreciated that in some implementations, each process station may have different or multiple purposes. For example, in some implementations, a process station may be switchable between thermal and plasma process modes. Additionally or alternatively, in some implementations, processing chamber 814 may include one or more matched pairs of thermal and plasma process stations. While the depicted processing chamber 814 includes four stations, it will be understood that a processing chamber according to the present disclosure may have any suitable number of stations. For example, in some implementations, a processing chamber may have five or more stations, while in other implementations a processing chamber may have three or fewer stations.

[0171] Figure 8 depicts an implementation of a wafer handling system 890 for transferring wafers within processing chamber 814. In some implementations, wafer handling system 890 may¬ transfer wafers between various process stations and / or between a process station and a load lock. It will be appreciated that any suitable wafer handling system may be employed. Non-limiting examples include wafer carousels and wafer handling robots. Figure 8 also depicts an implementation of a system controller 850 employed to control process conditions and hardware states of process tool 800. System controller 850 may include one or more memory devices 856, one or more mass storage devices 854, and one or more processors 852. Processor 852 may include a CPU or computer, analog, and / or digital input / output connections, stepper motor controller boards, etc.

[0172] In some implementations, system controller 850 controls all of the activities of process tool 800. System controller 850 executes system control software 858 stored in mass storage device 854, loaded into memory device 856, and executed on processor 852. Alternatively, the control logic may be hard coded in the system controller 850. Applications Specific Integrated Circuits, Programmable Logic Devices (e.g., field-programmable gate arrays, or FPGAs) and theAtorney Docket No.: LAM1P118WO-12279-1WO like may be used for these purposes. In the following discussion, wherever “software” or “code” is used, functionally comparable hard coded logic may be used in its place. System control software 858 may include instructions for controlling the timing, mixture of gases, gas flow rates, chamber and / or station pressure, chamber and / or station temperature, wafer temperature, target power levels, RF power levels, substrate pedestal, chuck and / or susceptor position, and other parameters of a particular process performed by process tool 800. System control software 858 may be configured in any suitable way. For example, various process tool component subroutines or control objects may be written to control operation of the process tool components used to carry' out various process tool processes. System control software 858 may be coded in any suitable computer readable programming language.

[0173] In some implementations, system control software 858 may include input / output control (IOC) sequencing instructions for controlling the various parameters described above. Other computer software and / or programs stored on mass storage device 854 and / or memory device 856 associated with system controller 850 may be employed in some implementations. Examples of programs or sections of programs for this purpose include a substrate positioning program, a process gas control program, a pressure control program, a heater control program, and a plasma control program.

[0174] A substrate positioning program may include program code for process tool components that are used to load the substrate onto pedestal 818 and to control the spacing between the substrate and other parts of process tool 800.

[0175] A process gas control program may include code for controlling process gas (e.g., etch gas) composition and flow rates and optionally for flowing gas into one or more process stations prior to deposition in order to stabilize the pressure in the process station. A pressure control program may include code for controlling the pressure in the process station by regulating, for example, a throttle valve in the exhaust system of the process station, a gas flow into the process station, etc.

[0176] A heater control program may include code for controlling the current to a heating unit that is used to heat the substrate or internal chamber surfaces. Alternatively, the heater control program may control delivery of a heat transfer gas (such as helium) to the substrate or internal chamber surfaces.

[0177] A plasma control program may include code for setting RF power levels applied to the process electrodes in one or more process stations in accordance with the implementations herein.

[0178] In some implementations, there may be a user interface associated with system controller 850. The user interface may include a display screen, graphical software displays of theAtorney Docket No.: LAM1P118WO-12279-1WO apparatus and / or process conditions, and user input devices such as pointing devices, keyboards, touch screens, microphones, etc.

[0179] In some implementations, parameters adjusted by system controller 850 may relate to process conditions. Non-limiting examples include process gas composition and flow rates, temperature, pressure, plasma conditions (such as RF bias power levels), etc. These parameters may be provided to the user in the form of a recipe, which may be entered utilizing the user interface.

[0180] In some implementations, the system controller 850 may be configured with instructions to perform the following operations: provide a substrate in a processing chamber 814, where the substrate includes a photopattemed metal oxide resist film having an exposed region and an unexposed region, where the exposed region comprises one or more carbon-based polymers. In some implementations, the system controller 850 may be configured with instructions to further perform the following operations: dry develop the photopattemed metal oxide resist film by selectively removing the exposed region relative to the unexposed region of the photopattemed metal oxide resist film to form a resist mask. The unexposed region may comprise a densified metal oxide network, whereas the exposed region may comprise a secondary' hydrocarbon crosslinked network with a primary metal oxide network. In some implementations, the system controller 850 may be configured with instructions to further perform the following operations: bake the photopattemed metal oxide resist film by exposure to a gaseous environment comprising at least one oxy gen-containing species.

[0181] Signals for monitoring the process (e.g., reactive chemical treatment) may be provided by analog and / or digital input connections of system controller 850 from various process tool sensors. The signals for controlling the process may be output on the analog and digital output connections of process tool 800. Non-limiting examples of process tool sensors that may be monitored include mass flow controllers, pressure sensors (such as manometers), thermocouples, etc. Appropriately programmed feedback and control algorithms may be used with data from these sensors to maintain process conditions.

[0182] System controller 850 may provide program instructions for implementing the abovedescribed deposition processes. The program instructions may control a variety' of process parameters, such as DC power level, RF bias power level, pressure, temperature, etc. The instructions may control the parameters to operate development, clean, and / or etch processes according to various implementations described herein.

[0183] The system controller 850 will typically include one or more memory devices and one or more processors configured to execute the instructions so that the apparatus will perform a method in accordance with disclosed implementations. Machine-readable media containing instructionsAtorney Docket No.: LAM1P118WO-12279-1WO for controlling process operations in accordance with disclosed implementations may be coupled to the system controller 850.

[0184] In some implementations, the system controller 850 is part of a system, which may be part of the above-described examples. Such systems can include semiconductor processing equipment, including a processing tool or tools, chamber or chambers, a platform or platforms for processing, and / or specific processing components (a wafer pedestal, a gas flow system, etc ). These systems may be integrated with electronics for controlling their operation before, during, and after processing of a semiconductor wafer or substrate. The electronics may be referred to as the “controller,” which may control various components or subparts of the system or systems. The system controller 850, depending on the processing conditions and / or the type of system, may be programmed to control any of the processes disclosed herein, including the delivery of processing gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency¬ settings, flow rate settings, fluid delivery settings, positional and operation settings, wafer transfers into and out of a tool and other transfer tools and / or load locks connected to or interfaced with a specific system.

[0185] Broadly speaking, the system controller 850 may be defined as electronics having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operation, enable cleaning operations, enable endpoint measurements, and the like. The integrated circuits may include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and / or one or more microprocessors, or microcontrollers that execute program instructions (e.g., software). Program instructions may be instructions communicated to the system controller 850 in the form of various individual settings (or program files), defining operational parameters for carrying out a particular process on or for a semiconductor wafer or to a system. The operational parameters may, in some implementations, be part of a recipe defined by process engineers to accomplish one or more processing steps during the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or dies of a wafer.

[0186] The system controller 850, in some implementations, may be a part of or coupled to a computer that is integrated with, coupled to the system, otherwise networked to the system, or a combination thereof. For example, the system controller 850 may be in the “cloud” or all or a part of a fab host computer system, which can allow- for remote access of the wafer processing. The computer may enable remote access to the system to monitor current progress of fabrication operations, examine a history- of past fabrication operations, examine trends or performance metrics from a plurality of fabrication operations, to change parameters of current processing, toAtorney Docket No.: LAM1P118WO-12279-1WO set processing steps to follow a current processing, or to start a new process. In some examples, a remote computer (e g. a server) can provide process recipes to a system over a network, which may include a local network or the Internet. The remote computer may include a user interface that enables entry or programming of parameters and / or settings, which are then communicated to the system from the remote computer. In some examples, the system controller 850 receives instructions in the form of data, which specify parameters for each of the processing steps to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process to be performed and the type of tool that the system controller 850 is configured to interface with or control. Thus as described above, the system controller 850 may¬ be distributed, such as by including one or more discrete controllers that are networked together and working towards a common purpose, such as the processes and controls described herein. An example of a distributed controller for such purposes w ould be one or more integrated circuits on a chamber in communication with one or more integrated circuits located remotely (such as at the platform level or as part of a remote computer) that combine to control a process on the chamber.

[0187] Without limitation, example systems may include a plasma etch chamber or module, a deposition chamber or module, a spin-rinse chamber or module, a metal plating chamber or module, a clean chamber or module, a bevel edge etch chamber or module, a physical vapor deposition (PVD) chamber or module, a chemical vapor deposition (CVD) chamber or module, an ALD chamber or module, an atomic layer etch (ALE) chamber or module, an ion implantation chamber or module, a track chamber or module, an EUV lithography chamber (scanner) or module, a development chamber or module, and any other semiconductor processing systems that may be associated or used in the fabrication and / or manufacturing of semiconductor wafers.

[0188] As noted above, depending on the process step or steps to be performed by the tool, the system controller 850 might communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout a factory, a main computer, another controller, or tools used in material transport that bring containers of wafers to and from tool locations and / or load ports in a semiconductor manufacturing factory.

[0189] ICP reactors which, in certain implementations, may be suitable for etch operations suitable for implementation of some implementations, are now described. Although ICP reactors are described herein, in some implementations, it should be understood that capacitively coupled plasma reactors may also be used.

[0190] Figure 9 schematically shows a cross-sectional view of an inductively coupled plasma apparatus 900 appropriate for implementing certain implementations or aspects of implementations such as dry development, clean, and / or etch, an example of which is a Kiyo®Atorney Docket No.: LAM1P118WO-12279-1WO reactor, produced by Lam Research Corp, of Fremont, CA. In other implementations, other tools or tool types having the functionality to conduct the dry development, clean, and / or etch processes described herein may be used for implementation.

[0191] The inductively coupled plasma apparatus 900 includes an overall process chamber 924 structurally defined by chamber walls 901 and a window 911. The chamber walls 901 may be fabricated from stainless steel, aluminum, or plastic. The window 911 may be fabricated from quartz or other dielectric material. An optional internal plasma grid 950 divides the overall process chamber into an upper sub-chamber 902 and a lower sub chamber 903. In most implementations, plasma grid 950 may be removed, thereby utilizing a chamber space made of sub chambers 902 and 903. A chuck 917 is positioned within the lower sub-chamber 903 near the bottom inner surface. The chuck 917 is configured to receive and hold a semiconductor wafer 919 upon which the etching and deposition processes are performed. The chuck 917 can be an electrostatic chuck for supporting the wafer 919 when present. In some implementations, an edge ring (not shown) surrounds chuck 917, and has an upper surface that is approximately planar with a top surface of the wafer 919, when present over chuck 917. The chuck 917 also includes electrostatic electrodes for chucking and dechucking the wafer 919. A filter and DC clamp power supply (not shown) may be provided for this purpose. Other control systems for lifting the wafer 919 off the chuck 917 can also be provided. The chuck 917 can be electrically charged using an RF power supply 923. The RF power supply 923 is connected to matching circuitry 921 through a connection 927. The matching circuitry 921 is connected to the chuck 917 through a connection 925. In this manner, the RF power supply 923 is connected to the chuck 917. In various implementations, a bias power of the electrostatic chuck may be set at about 50 V or may be set at a different bias power depending on the process performed in accordance with disclosed implementations. For example, the bias power may be between about 20 Vb and about 100 V, or between about 30 V and about 150 V.

[0192] Elements for plasma generation include a coil 933 is positioned above window 911. In some implementations, a coil is not used in disclosed implementations. The coil 933 is fabricated from an electrically conductive material and includes at least one complete turn. The example of a coil 933 shown in Figure 9 includes three turns. The cross sections of coil 933 are shown with symbols, and coils having an “X” extend rotationally into the page, while coils having aextend rotationally out of the page. Elements for plasma generation also include an RF power supply 941 configured to supply RF pow er to the coil 933. In general, the RF power supply 941 is connected to matching circuitry 939 through a connection 945. The matching circuitry 939 is connected to the coil 933 through a connection 943. In this manner, the RF power supply 941 is connected to the coil 933. An optional Faraday shield 949 is positioned between the coil 933 and the windowAtorney Docket No.: LAM1P118WO-12279-1WO 911. The Faraday shield 949 may be maintained in a spaced apart relationship relative to the coil 933. In some implementations, the Faraday shield 949 is disposed immediately above the window 911. In some implementations, the Faraday shield 949 is between the window 911 and the chuck 917. In some implementations, the Faraday shield 949 is not maintained in a spaced apart relationship relative to the coil 933. For example, the Faraday shield 949 may be directly below the window 911 without a gap. The coil 933, the Faraday shield 949, and the window 911 are each configured to be substantially parallel to one another. The Faraday shield 949 may prevent metal or other species from depositing on the window 911 of the process chamber 924.

[0193] Process gases may be flowed into the process chamber through one or more main gas flow inlets 960 positioned in the upper sub-chamber 902 and / or through one or more side gas flow inlets 970. Likewise, though not explicitly shown, similar gas flow inlets may be used to supply process gases to a capacitively coupled plasma processing chamber. A vacuum pump, e.g., a one or two stage mechanical dry pump and / or turbomolecular pump 940, may be used to draw process gases out of the process chamber 924 and to maintain a pressure within the process chamber 924. For example, the vacuum pump may be used to evacuate the lower sub-chamber 903 during a purge operation. A valve-controlled conduit may be used to fluidically connect the vacuum pump to the process chamber 924 so as to selectively control application of the vacuum environment provided by the vacuum pump. This may be done employing a closed loop-controlled flow restriction device, such as a throttle valve (not shown) or a pendulum valve (not shown), during operational plasma processing. Likewise, a vacuum pump and valve controlled fluidic connection to the capacitively coupled plasma processing chamber may also be employed.

[0194] During operation of the apparatus 900. one or more process gases may be supplied through the gas flow inlets 960 and / or 970. In certain implementations, process gas may be supplied only through the main gas flow inlet 960, or only through the side gas flow inlet 970. In some cases, the gas flow inlets shown in the figure may be replaced by more complex gas flow inlets, one or more showerheads, for example. The Faraday shield 949 and / or optional grid 950 may include internal channels and holes that allow delivery of process gases to the process chamber 924. Either or both of Faraday shield 949 and optional grid 950 may serve as a showerhead for delivery of process gases. In some implementations, a liquid vaporization and delivery' system may be situated upstream of the process chamber 924, such that once a liquid reactant or precursor is vaporized, the vaporized reactant or precursor is introduced into the process chamber 924 via a gas flow inlet 960 and / or 970.

[0195] Radio frequency power is supplied from the RF power supply 941 to the coil 933 to cause an RF current to flow through the coil 933. The RF current flowing through the coil 933 generates an electromagnetic field about the coil 933. The electromagnetic field generates an inductiveAtorney Docket No.: LAM1P118WO-12279-1WO current within the upper sub-chamber 902. The physical and chemical interactions of various generated ions and radicals with the wafer 919 etch features of and selectively deposit layers on the wafer 919.

[0196] If the plasma grid 950 is used such that there is both an upper sub-chamber 902 and a lower sub-chamber 903, the inductive current acts on the gas present in the upper sub-chamber 902 to generate an electron-ion plasma in the upper sub-chamber 902. The optional internal plasma grid 950 limits the amount of hot electrons in the lower sub-chamber 903. In some implementations, the apparatus 900 is designed and operated such that the plasma present in the lower sub-chamber 903 is an ion-ion plasma.

[0197] Both the upper electron-ion plasma and the lower ion-ion plasma may contain positive and negative ions, though the ion-ion plasma will have a greater ratio of negative ions to positive ions. Volatile etching and / or deposition byproducts may be removed from the lower sub-chamber 903 through port 922. The chuck 917 disclosed herein may operate at elevated temperatures ranging between about 10°C and about 250°C. The temperature will depend on the process operation and specific recipe.

[0198] Apparatus 900 may be coupled to facilities (not shown) when installed in a clean room or a fabrication facility. Facilities include plumbing that provide processing gases, vacuum, temperature control, and environmental particle control. These facilities are coupled to apparatus 900, when installed in the target fabrication facility. Additionally, apparatus 900 may be coupled to a transfer chamber that allows robotics to transfer semiconductor wafers into and out of apparatus 900 using typical automation.

[0199] In some implementations, a system controller 930 (which may include one or more physical or logical controllers) controls some or all of the operations of a process chamber 924. The system controller 930 may include one or more memory devices and one or more processors. In some implementations, the apparatus 900 includes a switching system for controlling flow rates and durations when disclosed implementations are performed. In some implementations, the apparatus 900 may have a switching time of up to about 500 ms. or up to about 750 ms. Switching time may depend on the flow' chemistry, recipe chosen, reactor architecture, and other factors.

[0200] In some implementations, the system controller 930 is part of a system, which may be part of the above-described examples. Such systems can include semiconductor processing equipment, including a processing tool or tools, chamber or chambers, a platform or platforms for processing, and / or specific processing components (a wafer pedestal, a gas flow system, etc.). These systems may be integrated with electronics for controlling their operation before, during, and after processing of a semiconductor wafer or substrate. The electronics may be integrated into the system controller 930, which may control various components or subparts of the system orAtorney Docket No.: LAM1P118WO-12279-1WO systems. The system controller 930, depending on the processing parameters and / or the type of system, may be programmed to control any of the processes disclosed herein, including the delivery of processing gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, RF generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, positional and operation settings, wafer transfers into and out of a tool and other transfer tools and / or load locks connected to or interfaced with a specific system.

[0201] As noted above, depending on the process step or steps to be performed by the tool, the controller might communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout a factory, a main computer, another controller, or tools used in material transport that bring containers of wafers to and from tool locations and / or load ports in a semiconductor manufacturing factory.

[0202] EUVL patterning may be conducted using any suitable tool, often referred to as a scanner, for example the TWINSCAN NXE: 3400C platform, the TWTNSCAN NXE: 3600D platform, and the TWINSCAN NXE 3800E platform supplied by ASML of Veldhoven, NL. The EUVL patterning tool may be a standalone device from which the substrate is moved into and out of for deposition and etching as described herein. Or, as described below, the EUVL patterning tool may be a module on a larger multi-component tool. Figure 10 depicts a semiconductor process cluster tool architecture with vacuum-integrated deposition, EUV patterning and dry development / etch modules that interface with a vacuum transfer module, suitable for implementation of the processes described herein. While the processes may be conducted without such vacuum integrated apparatus, such apparatus may be advantageous in some implementations.

[0203] Figure 10 depicts a semiconductor process cluster tool architecture with vacuum-integrated deposition and patterning modules that interface with a vacuum transfer module, suitable for implementations of processes described herein. The arrangement of transfer modules to ■’transfer" wafers among multiple storage facilities and processing modules may be referred to as a “cluster tool architecture” system. Deposition and patterning modules are vacuum-integrated, in accordance with the requirements of a particular process. Other modules, such as for etch, may also be included on the cluster.

[0204] A vacuum transport module (VTM) 1038 interfaces with four processing modules 1020a-1020d, which may be individually optimized to perform various fabrication processes. By way of example, processing modules 1020a-1020d may be implemented to perform deposition, evaporation, ELD, dry development, clean, etch, strip, and / or other semiconductor processes. For example, module 1020a may be an ALD reactor that may be operated to perform in a non-plasma,Atorney Docket No.: LAM1P118WO-12279-1WO thermal atomic layer depositions, such as Vector tool, available from Lam Research Corporation, Fremont, CA. And module 1020b may be a PECVD tool, such as the Lam Vector®. It should be understood that the figure is not necessarily drawn to scale.

[0205] Airlocks 1042 and 1046, also known as a loadlocks or transfer modules, interface with the VTM 1038 and a patterning module 1040. For example, as noted above, a suitable patterning module may be the TWINSCAN NXE: 3300B® platform supplied by ASML of Veldhoven, NL). This tool architecture allows for work pieces, such as semiconductor substrates or wafers, to be transferred under vacuum so as not to react before exposure. Integration of the deposition modules with the lithography tool is facilitated by the fact that EUVL also requires a greatly reduced pressure given the strong optical absorption of the incident photons by ambient gases such as H2O, O2, etc.

[0206] As noted above, this integrated architecture is just one possible implementation of a tool for implementation of the described processes. The processes may also be implemented with a more conventional stand-alone EUVL scanner and a deposition reactor, such as a Lam Vector tool, either stand alone or integrated in a cluster architecture with other tools, such as etch, strip etc. (e.g., Lam Kiyo or Gamma tools), as modules, for example as described with reference to Figure 10 but without the integrated patterning module.

[0207] Airlock 1042 may be an "‘outgoing” loadlock, referring to the transfer of a substrate out from the VTM 1038 serving a deposition module 1020a to the patterning module 1040, and airlock 1046 may be an “ingoing” loadlock, referring to the transfer of a substrate from the patterning module 1040 back in to the VTM 1038. The ingoing airlock 1046 may also provide an interface to the exterior of the tool for access and egress of substrates. Each process module has a facet that interfaces the module to VTM 1038. For example, deposition process module 1020a has facet 1036. Inside each facet, sensors, for example, sensors 1-18 as shown, are used to detect the passing of wafer 1026 when moved between respective stations. Patterning module 1040 and airlocks 1042 and 1046 may be similarly equipped with additional facets and sensors, not shown.

[0208] Main VTM robot 1022 transfers wafer 1026 between modules, including airlocks 1042 and 1046. In one implementation, robot 1022 has one arm, and in another implementation, robot 1022 has two arms, where each arm has an end effector 1024 to pick wafers such as wafer 1026 for transport. Front-end robot 1044, in is used to transfer wafers 1026 from outgoing airlock 1042 into the patterning module 1040, from the patterning module 1040 into ingoing airlock 1046. Front-end robot 1044 may also transport wafers 1026 between the ingoing loadlock and the exterior of the tool for access and egress of substrates. Because ingoing airlock module 1046 has the ability to match the environment between atmospheric and vacuum, the wafer 1026 is able to move between the two pressure environments without being damaged.Atorney Docket No.: LAM1P118WO-12279-1WO

[0209] It should be noted that an EUVL tool typically operates at a higher vacuum than a deposition tool. If this is the case, it is desirable to increase the vacuum environment of the substrate during the transfer between the deposition to the EUVL tool to allow the substrate to degas prior to entry into the patterning tool. Outgoing airlock 1042 may provide this function by holding the transferred wafers at a lower pressure, no higher than the pressure in the patterning module 1040, for a period of time and exhausting any off-gassing, so that the optics of the patterning module 1040 are not contaminated by off-gassing from the substrate. A suitable pressure for the outgoing, off-gassing airlock is no more than IE-8 Torr.

[0210] In some implementations, a system controller 1050 (which may include one or more physical or logical controllers) controls some or all of the operations of the cluster tool and / or its separate modules. It should be noted that the controller can be local to the cluster architecture, or can be located external to the cluster architecture in the manufacturing floor, or in a remote location and connected to the cluster architecture via a network. The system controller 1050 may include one or more memory devices and one or more processors. The processor may include a central processing unit (CPU) or computer, analog and / or digital input / output connections, stepper motor controller boards, and other like components. Instructions for implementing appropriate control operations are executed on the processor. These instructions may be stored on the memory' devices associated with the controller or they may be provided over a network. In certain implementations, the system controller executes system control software.

[0211] The system control software may include instructions for controlling the timing of application and / or magnitude of any aspect of tool or module operation. System control software may be configured in any suitable way. For example, various process tool component subroutines or control objects may be written to control operations of the process tool components necessary to carry out various process tool processes. System control software may be coded in any suitable compute readable programming language. In some implementations, system control software includes input / output control (IOC) sequencing instructions for controlling the various parameters described above. For example, each phase of a semiconductor fabrication process may include one or more instructions for execution by the system controller. The instructions for setting process conditions for condensation, deposition, evaporation, patterning and / or etching phase may be included in a corresponding recipe phase, for example.

[0212] In various implementations, an apparatus for forming a negative pattern mask is provided. The apparatus may include a processing chamber for patterning, deposition and etch, and a controller including instructions for forming a negative pattern mask. The instructions may include code for, in the processing chamber, patterning a feature in a chemically amplified (CAR) resist on a semiconductor substrate by EUV exposure to expose a surface of the substrate,Atorney Docket No.: LAM1P118WO-12279-1WO developing the photopattemed resist, and etching the underlying layer or layer stack using the patterned resist as a mask.

[0213] It should be noted that the computer controlling the wafer movement can be local to the cluster architecture, or can be located external to the cluster architecture in the manufacturing floor, or in a remote location and connected to the cluster architecture via a network. A controller as described above with respect to any of Figures 7, 8, or 9 may be implemented with the tool in Figure 10.

[0214] Figure 11 shows an example of a deposition chamber (e.g., for vapor-based deposition of a film). As can be seen, an apparatus 1100 is depicted that has a processing chamber 1102 that includes a lid 1108. The processing chamber 1102 may include a wafer transfer passage 1104 through one of the walls of the processing chamber 1102 that is sized to allow a substrate 1122 to be passed therethrough and into the interior of the processing chamber 1102, where the substrate 1122 may be placed on a wafer support 1124. The wafer transfer passage 1104 may have a gate valve 1106 or similar door mechanism that may be operated to seal or unseal the wafer transfer passage, thereby allowing the environment within the processing chamber 1102 to be isolated from the environment on the other side of the gate valve 1106. For example, the processing chamber 1102 may be provided substrates 1122 via a wafer handling robot that is located in an adjoining transfer chamber. Such a transfer chamber may. for example, have multiple processing chambers 1102 arranged around its periphery, with each such processing chamber 1102 connected with the transfer chamber via a corresponding gate valve 1106.

[0215] The wafer support 1124 may, for example, include an electrostatic chuck (ESC) 1126, which may be used to provide a wafer support surface for supporting the substrate 1122. The ESC 1126 may include, for example, a base plate 1134 that is bonded to a top plate 1128 that is placed atop the base plate 1134. The top plate 1128 may, for example, be made of a ceramic material and may have embedded within it several other components. In the depicted example, the top plate 1128 has two separate electrical systems embedded within it. One such system is an electrostatic clamping electrode system, which may have one or more clamping electrodes 1132 that may be used to generate an electric charge within the substrate 1122 that causes the substrate 1122 to be drawn against the w afer support surface of the top plate 1128. In the implementation of Figure 11, there are two clamping electrodes 1132 that provide a bi-polar electrostatic clamping system, although some implementations may use only a single clamping electrode 1132 to provide a mono-polar electrostatic clamping system.

[0216] The other system is a thermal control system that may be used to control the temperature of the substrate 1122 during processing conditions. In Figure 11, the thermal control system is a multi-zone thermal control system featuring four annular resistance heater traces 1130a, 1130b,Atorney Docket No.: LAM1P118WO-12279-1WO 1130c, and 1130d that are concentric with one another and positioned beneath the clamping electrodes 1132. The center resistance heater traces 1130a may, in some implementations, fill a generally circular area, and each resistance heater trace 1130a / b / c / d may follow a generally serpentine or otherwise meandering path within a corresponding annular region. Each resistance heater trace 1130a / b / c / d may be individually controlled to provide a variety of radial heating profiles in the top plate 1128; such a four-zone heating system may, for example, be controlled to maintain the substrate 1122 so as to have a temperature uniformity of ±0.5°C in some cases. While the apparatus 1100 of Figure 11 features a four-zone heating system in the ESC 1126, other implementations may use single-zone or multi-zone heating systems having more or fewer than four zones.

[0217] In some implementations, of, for example, temperature control mechanisms discussed above, heat pumps may be used instead of resistance heating traces. For example, in some implementations, the resistance heater traces may be replaced by, or augmented by, Peltier junctions or other, similar devices that may be controlled to "‘pump’7heat from one side thereof to another. Such mechanisms may be used, for example, to draw heat from the top plate 1 128 (and thus the substrate 1122) and direct it into the baseplate 1134 and the heat exchange passages 1136, thereby allowing the substrate 1122 to be cooled more rapidly and more effectively, if desired.

[0218] The ESC 1126 may also include, for example, a base plate 1134 that may be used to provide structural support to the underside of the top plate 1128 and which may also act as a heat dispersion system. For example, the base plate 1134 may include one or more heat exchange passages 1136 that are arranged in a generally distributed fashion throughout the base plate 1134, e.g., the heat exchange passages 1136 may follow a serpentine, circular switchback, or spiral pattern around the center of the base plate 1134. A heat exchange medium, e.g., water or inert fluorinated liquid, may be circulated through the heat exchange passages 1136 during use. The flow rate and temperature of the heat exchange medium may be externally controlled so as to result in a particular heating or cooling behavior in the base plate 1134.

[0219] The ESC 1126 may, for example, be supported by a wafer support housing 1142 that is connected with, and supported by, a wafer support column 1144. The wafer support column 1144 may, for example, have a routing passage 1148 other pass-throughs for routing cabling, fluid flow conduits, and other equipment to the underside of the base plate 1134 and / or the top plate 1128. For example, while not shown in Figure 11, cabling for providing electrical power to the resistance heater traces 1130a / b / c / d may be routed through the routing passage 1148, as may cabling for providing electrical power to the clamping electrodes 1132. Other cables, e.g., cables for temperature sensors, may also be routed through the routing passage 1148 to locations in the interior of the wafer support 1124. In implementations with a temperature-controllable base plateAtorney Docket No.: LAM1P118WO-12279-1WO 1134, conduits for conveying heat exchange medium to and from the base plate 1134 may also be routed through the routing passage 1148. To avoid undue clutter, such cables and conduits are not depicted in Figure 11, but it is to be understood that they would, nonetheless, be present.

[0220] The apparatus 1100 of Figure 11 also includes a wafer support z-actuator 1146 that may provide movable support to the wafer support column 1144. The wafer support z-actuator 1146 may be actuated to cause the wafer support column 1144, and the wafer support 1124 supported thereby, to move up or down vertically, e.g., by up to several inches, within a reaction space 1120 of the processing chamber 1102. In doing so, a gap distance X between the substrate 1122 and the underside of the showerhead 1110 may be tuned depending on various process conditions.

[0221] The wafer support 1124 may also include, in some implementations, one or more edge rings that may be used to control and / or fine-tune various process conditions. In Figure 11, an upper edge ring 1138 is provided that lies on top of, for example, lower edge rings 1140a and 1140b, which, in turn, are supported by the wafer support housing 1142 and a third lower edge ring 1140c. The upper edge ring 1138 may, for example, be generally subjected to the same processing environment as the substrate 1122, whereas the lower edge rings 1140a / b / c may generally be shielded from the processing environment. Due to the increased exposure of the upper edge ring 1138, the upper edge ring 1138 may have a limited lifespan and may require more frequent replacement or cleaning as compared with the lower edge rings 1140a / b / c.

[0222] The apparatus 1100 may also include a system for removing process gases from the processing chamber 1102 during and after processing concludes. For example, the processing chamber 1102 may include an annular plenum 1156 that encircles the wafer support column 1144. The annular plenum 1156 may, in turn, be fluidically connected ith a vacuum foreline 1152 that may be connected with a vacuum pump, e.g., such as may be located beneath a subfloor below the apparatus 1100. A regulator valve 1154 may be provided in between the vacuum foreline 1152 and the processing chamber 1102 and actuated to control the flow' into the vacuum foreline 1152. In some implementations, a baffle 1150, e.g., an annular plate or other structure that may serve to make the flow into the annular plenum 1156 more evenly distributed about the circumference of the wafer support column 1144, may be provided to reduce the chances of flow non-uniformities developing in reactants flowed across the substrate 1122.

[0223] The showerhead 1110, as shown, is a dual-plenum showerhead 1110 and includes a first plenum 1112 that is provided process gas via a first inlet 1116 and a second plenum 1114 that is provided process gas via a second inlet 1118. Generally, two plenums can be employed to maintain separation between the precursor(s) and the counter-reactant(s) prior to release of the precursor and the counter-reactant. The showerhead 1110 may, in some implementations, have more than two plenums. In some instances, a single plenum is used to deliver the precursor(s) intoAtorney Docket No.: LAM1P118WO-12279-1WO the reaction space 1120 of the processing chamber 1102. Each plenum may have a corresponding set of gas distribution ports that fluidically connect the respective plenum with the reaction space 1120 through the faceplate of the showerhead 1110 (the faceplate being the portion of the showerhead 1110 that is interposed between the lowermost plenum and the reaction space 1120).

[0224] The first inlet 1116 and the second inlet 1118 of the showerhead 1110 may be provided processing gases via a gas supply system, which may be configured to provide one or more precursor(s) and / or counter-reactant(s), as discussed herein. The depicted apparatus 1100 is configured to provide multiple precursors and multiple counter-reactants. For example, a first valve manifold 1168a may be configured to provide precursor(s) to the first inlet 1116, while a second valve manifold 1168b may be configured to provide other precursor(s) or other counterreactants to the second inlet 1118.

[0225] A first valve manifold 1168a may be configured to provide one or more precursor(s) to the first inlet 1116, while a second valve manifold 1168b may be configured to provide other precursor(s) or other reactant to the second inlet 1118. In this example, the first valve manifold 1168a, for example, includes multiple valves A1-A5. Valve A2 may, for example, be a three-way valve that has one port fluidically connected with a first vaporizer 1172a, another port fluidically connected with a bypass line 1170a, and a third port fluidically connected with a port on another 3-way valve A3. Similarly, valve A4 may be another three-way valve that has one port fluidically connected with a second vaporizer 1172b, another port fluidically connected with the bypass line 1170a, and a third port fluidically connected with a port on another 3-way valve A5. One of the other ports on valve A5 may be fluidically connected with the first inlet 1116 while the remaining port on valve A5 may be fluidically connected with one of the remaining ports on the valve A3. The remaining port on the valve A3 may, in turn, be fluidically connected with the valve Al which may be fluidically interposed between the valve A3 and a purge gas source 1174, e.g., nitrogen, argon, or other suitably inert gas (with respect to precursor(s) and / or counter-reactant(s)). In some embodiments, only the first valve manifold is employed.

[0226] For the purposes of this disclosure, the term “fluidically connected” is used with respect to volumes, plenums, holes, etc., that may be connected with one another in order to form a fluidic connection, similar to how the term “electrically connected” is used with respect to components that are connected together to form an electric connection. The term “fluidically interposed,” if used, may be used to refer to a component, volume, plenum, or hole that is fluidically connected with at least two other components, volumes, plenums, or holes such that fluid flowing from one of those other components, volumes, plenums, or holes to the other or another of those components, volumes, plenums, or holes would first flow through the “fluidically interposed” component before reaching that other or another of those components, volumes, plenums, or holes.Atorney Docket No.: LAM1P118WO-12279-1WO For example, if a pump is fluidically interposed between a reservoir and an outlet, fluid that flowed from the reservoir to the outlet would first flow through the pump before reaching the outlet.

[0227] The first valve manifold 1168a may, for example, be controllable to cause vapors from one or both of the vaporizers 1172a and 1172b to be flowed either to the processing chamber 1102 or through the first bypass line 1170a and into the vacuum foreline 1152. The first valve manifold 1168a may also be controllable to cause a purge gas to be flowed from the purge gas source 1174 and into the first inlet 1116.

[0228] For example, to flow vapor from the first vaporizer 1172a into the reaction space 1120, the valve A2 may be actuated to cause the vapor from the first vaporizer 1172a to first flow into the first bypass line 1170a. This flow may be maintained for a period of time sufficient to allow the flow of the vapor to reach steady state flow conditions. After sufficient time has passed (or after a flow meter, if used, indicates that the flow rate is stable), valves A2, A3, and A5 may be actuated to cause the vapor flow from the first vaporizer 1172a to be directed to the first inlet. Similar operations with valves A4 and A5 may be performed to deliver vapor from the second vaporizer 1172b to the first inlet 1116. In some instances, it may be desirable to purge one of the vapors from the first plenum 1112 by actuating the valves Al, A3, and A5 so as to cause the purge gas from the purge gas source 1174 to be flowed into the first inlet 1116. In some additional implementations, it may be desirable to simultaneously flow vapor from one of the vaporizers 1172a or 1172b in tandem with flowing gas from the purge gas into the first inlet 1116. Such implementations may be used to dilute the concentration of the reactant(s) contained in such vapor(s).

[0229] It will be appreciated that the second valve manifold 1168b may be controlled in a similar manner, e.g., by controlling valves B1-B5, to provide vapors from vaporizers 1172c and 1172d to the second inlet 1118 or to the second bypass line 1170b. It will be further appreciated that different manifold arrangements may be utilized as well, including a single unitary' manifold that includes valves for controlling flow of the precursor(s). counter-reactant(s), or other reactants to the first inlet 1116 and the second inlet 1118.

[0230] As mentioned earlier, some apparatuses 1100 may feature a lesser number of vapor sources, e.g., only two vaporizers 1172, in which case the valve manifold(s) 1168 may be modified to have a lesser number of valves, e.g., only valves A1-A3.

[0231] As discussed above, apparatuses such as apparatus 1100, which may be used to provide for dry deposition of films, may be configured to maintain particular temperature profiles within the processing chamber 1102. In particular, such apparatuses 1100 may be configured to maintain the substrate 1122 at a lower temperature, e.g., at least 25°C to 50°C lower, than most of the equipment of the apparatus 1100 that comes into direct contact with the precursor(s) and / orAtorney Docket No.: LAM1P118WO-12279-1WO counter-reactant(s). Additionally, the temperature of the equipment of the apparatus 1100 that comes into direct contact with the precursor(s) and / or counter-reactant(s) may be kept to an elevated level that is sufficiently high that condensation of the vaporized reactants on the surfaces of such equipment is discouraged. At the same time, the substrate 1122 temperature may be controlled to a level that promotes condensation, or at least deposition, of the reactants on the substrate 1122.

[0232] To provide for such temperature control, various heating systems may be included in the apparatus 1100. For example, the processing chamber 1102 may have receptacles for receiving cartridge heaters 1158, e.g., for a processing chamber 1102 that has a generally cylindrical interior volume but a square or rectangular external shape, vertical holes for receiving cartridge heaters 1158 may be bored into the four comers of the chamber 1102 housing. In some implementations, the showerhead 1110 may be covered with heater blankets 1160, which may be used to apply heat across the exposed upper surface of the showerhead 1110 to keep the showerhead temperature elevated. It may also be beneficial to heat various gas lines that are used to conduct the vaporized reactants from the vaporizers 1172 to the showerhead 1110. For example, resistive heater tape may be wound around such gas lines and used to heat them to an elevated temperature. As show n in Figure 11, all of the gas lines that potentially have precursor(s) and / or counter-reactant(s) flowing through them are shown as being heated, including the bypass lines 1170. The only exceptions are the gas lines from the valve manifolds 1168 to the first inlet 1116 and the second inlet 1118, which may be quite short and may be indirectly heated by the showerhead 1110. Of course, even these gas lines may be actively heated, if desired. In some implementations, heaters may be provided proximate to the gate valve 1106 to provide heat to the gate valve as well.

[0233] The various operational systems of the apparatus 1100 may be controlled by a controller 1184, which may include one or more processors 1186 and one or more memory devices 1188 that are operatively connected with each other and that are communicatively connected with various systems and subsystems of the apparatus 1100 so as to provide for control functionality for those systems. For example, the controller 1184 may be configured to control the valves A1-A5 and B1-B5, the various heaters 1158, 1160, the vaporizers 1172, the regulator valve 1154, the gate valve 1106, the wafer support z-actuator, and so forth.

[0234] Once the film layer has been deposited on the substrate 1122, the substrate 1122 may, as noted above, be transferred to one or more subsequent processing chambers or tool for additional operations (e.g., any described herein). Further deposition apparatuses are described in International Patent Application No. PCT / US2020 / 038968, filed June 22, 2020, published as International Publication No. WO 2020 / 263750, titled “APPARATUS FOR PHOTORESIST DRY DEPOSITION.” which is herein incorporated by reference in its entirety.Attorney Docket No.: LAM1P118WO-12279-1WO Conclusion

[0235] It is understood that the examples and implementations described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art. Although various details have been omitted for clarity ’s sake, various design alternatives may be implemented. Therefore, the present examples are to be considered as illustrative and not restrictive, and the disclosure is not to be limited to the details given herein, but may be modified within the scope of the disclosure.

Claims

1. Atorney Docket No.: LAM1P118WO-12279-1WO CLAIMS1. A method of processing a substrate, comprising:providing the substrate in a processing chamber, wherein the substrate comprises a photopattemed metal oxide resist film having an exposed region and an unexposed region, wherein the exposed region of the photopattemed metal oxide resist film comprises one or more carbon-based polymers; anddry7developing the photopattemed metal oxide resist film by selectively removing the exposed region relative to the unexposed region of the photopattemed metal oxide resist film to form a resist mask.

2. The method of claim 1. further comprising:baking the photopattemed metal oxide resist film by exposure to a gaseous environment comprising at least one oxygen-containing species.

3. The method of claim 2. wherein baking the photopattemed metal oxide resist film reduces a carbon content in the unexposed region by a greater percentage than a carbon content in the exposed region.

4. The method of claim 2, wherein baking the photopattemed metal oxide resist film densifies the unexposed region relative to the exposed region.

5. The method of claim 2, wherein baking the photopattemed metal oxide resist film substantially removes organic ligands from the unexposed region and substantially preserves the carbon-based polymers in the exposed region.

6. The method of claim 1, further comprising:depositing a photoresist material on the substrate, wherein the photoresist material comprises a metal and oxygen, wherein the photoresist material further comprises at least one unsaturated carbon bond.

7. The method of claim 6. wherein depositing the photoresist material comprises depositing a metal-containing precursor on a surface of the substrate, wherein the metalcontaining precursor comprises a metal (M) selected from the group consisting of lead, germanium, tin, and hafnium.

8. The method of claim 7, wherein the metal-containing precursor has the formula M(R1)4, wherein at least one R1is an unsaturated substituent, wherein the metal-containing precursorAtorney Docket No.: LAM1P118WO-12279-1WO forms a primary metal oxide network film having one or more unsaturated substituents after depositing the photoresist material.

9. The method of claim 8, wherein the one or more unsaturated substituents in the primary metal oxide network film form a secondary hydrocarbon cross-linked network upon exposure to radiation.

10. The method of claim 8, wherein at least one other R1is a saturated substituent.

11. The method of claim 6, wherein the photoresist material comprises a vinyl group (-CH=CH2) or other unsaturated substituent.

12. The method of claim 11, wherein the other unsaturated substituent comprises an aliphatic chain, cyclic, aryl, or heteroaryl group.

13. The method of claim 11, wherein the photoresist material further comprises at least one saturated substituent, in addition to the vinyl group or other unsaturated substituent.

14. A method of performing positive tone dry7development, the method comprising:depositing a photoresist material on a surface of a substrate, wherein the photoresist material comprises a metal and oxygen, wherein the photoresist material further comprises an unsaturated carbon bond:exposing the photoresist material to radiation to form a photopattemed metal oxide resist film, thereby providing an exposed region and an unexposed region of the photopattemed metal oxide resist film;baking the photopattemed metal oxide resist film by exposure to a gaseous environment comprising at least one oxygen-containing species; anddry developing the photopattemed metal oxide resist film by selectively removing the exposed region relative to the unexposed region of the photopattemed metal oxide resist film to form a resist mask.

15. The method of claim 14, wherein exposing the photoresist material to radiation photoinduces polymerization to form cross-linked organic moieties in the exposed region of the photopattemed metal oxide resist film.

16. The method of claim 15, wherein baking the photopattemed metal oxide resist film substantially removes organic ligands from the unexposed region and substantially preserves the cross-linked organic moieties in the exposed region.Atorney Docket No.: LAM1P118WO-12279-1WO 17. The method of claim 14, wherein the photoresist material comprises one or more saturated substituents and one or more unsaturated substituents having the unsaturated carbon bond.

18. The method of claim 14, wherein dry developing the photopattemed metal oxide resist fdm comprises exposure to a dry development chemistry' that selectively breaks metal-carbon bonds relative to metal-oxygen bonds.

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