Plasma-Enhanced Low-Temperature Atomic Layer Deposition of Metals

Abstract

A low-temperature plasma enhanced atomic layer deposition process is provided that includes coating a metal thin layer by contacting a substrate surface with a metal precursor and a plasma of a hydrogen-containing gas source generated directly or remotely at a temperature below 300 °C.

Description

Incorporation by Reference

[0001] As part of this application, a PCT application form is filed simultaneously with this specification. Each application specified in the simultaneously filed PCT application form and for which this application claims benefit or priority is hereby incorporated by reference in its entirety for all purposes into this specification. Background

[0002] Many semiconductor device fabrication processes involve depositing a metal such as molybdenum or copper to form an ultrathin conductive film. Plasma enhanced atomic layer deposition (ALD) can be utilized to deposit metal-containing films. The morphology of the film is a consideration in designing such processes for preparing ultrathin conductive films, as a rough morphology can lead to an increase in film resistivity and may be related to voids in the conductive fill metal and pinch-off of the fill metal in features.

[0003] The background description provided herein is for the purpose of generally presenting the content of the present disclosure. Research by the presently named inventors within the scope described in this background art section, as well as aspects of the description that cannot be separately regarded as prior art as of the filing date of the application, are not admitted as prior art against the present disclosure, whether expressly or impliedly.

SUMMARY OF THE INVENTION

[0004] A low-temperature plasma enhanced atomic layer deposition process is provided that includes coating a thin metal layer by contacting a substrate surface with a metal precursor and a plasma of a directly or remotely generated hydrogen-containing gas source at a temperature of 300° C. or less.

[0005] Accordingly, in a first aspect, the present invention encompasses a method for plasma enhanced atomic layer deposition of a thin metal film onto a surface of a substrate. In some embodiments, the method includes providing a substrate in a deposition chamber, the substrate being at a temperature of about 300° C. or less, exposing the surface of the substrate to a vapor-phase metal precursor, and exposing the substrate to a directly generated plasma or a plasma remotely generated from a hydrogen-containing gas source.

[0006] In some embodiments, the metal is vanadium, niobium, tantalum, chromium, cobalt, tungsten, iron, ruthenium, nickel, zinc, copper, or molybdenum.

[0007] In some embodiments, the vapor-phase metal precursor is a vanadium-containing precursor, a niobium-containing precursor, a tantalum-containing precursor, a chromium-containing precursor, a cobalt-containing precursor, a tungsten-containing precursor, an iron-containing precursor, a ruthenium-containing precursor, a nickel-containing precursor, a zinc-containing precursor, a copper-containing precursor, or a molybdenum-containing precursor.

[0008] In some embodiments, exposing the surface of the substrate to the vapor-phase metal precursor and exposing the substrate to a plasma generated remotely from a hydrogen-containing gas source are performed in temporally separate pulses.

[0009] In some embodiments, the vapor-phase metal precursor adsorbs onto the surface of the substrate to form an adsorbed metal precursor.

[0010] In some embodiments, a plasma generated remotely from a hydrogen-containing gas source converts the adsorbed metal precursor to elemental metal.

[0011] In some embodiments, the method also includes pretreating the surface of the substrate with a plasma generated remotely from a hydrogen-containing gas source before exposing the surface of the substrate to the vapor-phase metal precursor.

[0012] In some embodiments, the hydrogen-containing gas source further includes from about 0.01% to about 1% oxygen-containing gas.

[0013] In some embodiments, the plasma is an inductively coupled plasma or a capacitively coupled plasma.

[0014] In some embodiments, the oxygen-containing gas is oxygen, oxygen and argon, oxygen and helium, ozone, or a combination thereof.

[0015] In some embodiments, the hydrogen-containing gas source is a gas such as hydrogen, deuterium, hydrogen and argon, hydrogen and helium, hydrogen and nitrogen, ammonia, mono-deuterated ammonia, di-deuterated ammonia, tri-deuterated ammonia, hydrazine, alcohol, aldehyde, or a combination thereof.

[0016] In some embodiments, the oxygen-containing gas is supplied at a flow rate of about 1 to about 150 sccm.

[0017] In a second aspect, the present disclosure is a method for plasma-enhanced atomic layer deposition of molybdenum onto a substrate, the method comprising providing a substrate in a deposition chamber, the substrate being at a temperature of about 300 °C or less, exposing the surface of the substrate to a vapor-phase molybdenum precursor, and exposing the substrate to a directly generated plasma or a plasma remotely generated from a hydrogen-containing gas source.

[0018] In some embodiments, the method also includes pretreating the surface of the substrate with a plasma remotely generated from a hydrogen-containing gas source before exposing the surface of the substrate to the vapor-phase molybdenum precursor.

[0019] In some embodiments, the vapor-phase molybdenum precursor has the structure of formula (I): Mo(L-R 1 )6, where each L is independently O, S, or NR 2 , and R 1 and R 2 are independently hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted heteroaromatic, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted aromatic, optionally substituted aryl, or optionally substituted arylalkylene, and two R 1 substituents may together form an optionally substituted cyclic group.

[0020] In some embodiments, the vapor-phase molybdenum precursor has the structure of formula (II): Mo(L-R 1) It has the structure of 2(Y)4, and each L is independently O, S, or NR 2 wherein, R 1 and R 2 are independently hydrogen, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted heteroaliphatic, optionally substituted heteroalkyl, optionally substituted heteroaromatic, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted aromatic, optionally substituted aryl, or optionally substituted arylalkylene, and the R 1 substituents can together form an optionally substituted cyclic group, and each Y is independently chlorine, fluorine, bromine, or iodine.

[0021] In some embodiments, the vapor-phase molybdenum precursor is Mo q X n Y m wherein X is oxygen, Y is a halogen, n is 0, 1, or 2, q is 1 or 2, and m is 2, 3, 4, 5, or 6.

[0022] In some embodiments, the vapor-phase molybdenum precursor is molybdenum pentachloride (MoCl5), molybdenum(V) chloride (Mo2Cl 10 ), molybdenum(VI) dioxide dichloride (MoO2Cl2), molybdenum oxytetrachloride (MoOCl4), or any combination thereof.

[0023] In some embodiments, exposing the surface of the substrate to the vapor-phase molybdenum precursor and exposing the substrate to a plasma remotely generated from a hydrogen-containing gas source are performed in temporally separate pulses.

[0024] In some embodiments, the vapor-phase molybdenum precursor adsorbs onto the surface of the substrate to form an adsorbed molybdenum precursor.

[0025] In some embodiments, the plasma generated remotely from a hydrogen-containing gas source converts the adsorbed molybdenum precursor to elemental molybdenum.

[0026] In some embodiments, the hydrogen-containing gas source also includes an oxygen-containing gas in an amount of from about 0.01% to about 1%.

[0027] In some embodiments, the plasma is an inductively coupled plasma or a capacitively coupled plasma.

[0028] In some embodiments, the oxygen-containing gas is oxygen, oxygen and argon, oxygen and helium, ozone, or a combination thereof.

[0029] In some embodiments, the hydrogen-containing gas source is a gas such as hydrogen, deuterium, hydrogen and argon, hydrogen and helium, hydrogen and nitrogen, ammonia, monodeuterated ammonia, dideuterated ammonia, trideuterated ammonia, hydrazine, alcohol, aldehyde, or a combination thereof.

[0030] In some embodiments, the oxygen-containing gas is supplied at a flow rate of from about 1 to about 150 sccm.

[0031] In a third aspect, the present disclosure is a method for controlling the morphology of copper deposited on a substrate by plasma-enhanced atomic layer deposition, the method including providing a substrate in a deposition chamber, the substrate being at a temperature of about 300 °C or less, exposing the surface of the substrate to a vapor-phase copper precursor, and exposing the substrate to a plasma generated remotely from a gas source, the gas source including a hydrogen-containing gas and an oxygen-containing gas in an amount of from about 0.01% to about 1%.

[0032] In some embodiments, the method also includes pretreating the surface of the substrate with a plasma generated remotely from a hydrogen-containing gas source prior to exposing the surface of the substrate to the vapor-phase copper precursor.

[0033] In some embodiments, the vapor-phase copper precursor has the formula: Cu(L-R 3 ) n, Cu2(B)2, or Cu4(N(R 4 ))2)4, where each L is independently O, NR 4 , or P(R 5 )3, B is a bidentate ligand, and R 3 , R 4 , and R 5 are each independently hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted heteroaromatic, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted aromatic, optionally substituted aryl, trimethylsilyl, or optionally substituted arylalkylene, n is an integer of 2 or 4, and when n is 4, two R 3 substituents can together form an optionally substituted cyclic group, and the copper is optionally coordinated to an optionally substituted alkenyl, optionally substituted alkynyl, carbonyl, aryl, or heteroaryl-containing compound.

[0034] In some embodiments, the vapor phase copper precursor is a first copper precursor.

[0035] In some embodiments, the first copper precursor is acetylacetonate, ketoimine, diimine, cyclopentadienyl, amidinate, guanidinate, or an amide compound.

[0036] In some embodiments, the vapor phase copper precursor is a second copper precursor.

[0037] In some embodiments, the second copper precursor is acetylacetonate, ketoimine, or an aminoalkoxide compound.

[0038] In some embodiments, the plasma is an inductively coupled plasma or a capacitively coupled plasma.

[0039] In some embodiments, the oxygen-containing gas is oxygen, oxygen and argon, oxygen and helium, ozone, or a combination thereof.

[0040] In some embodiments, the hydrogen-containing gas source is a gas such as hydrogen, deuterium, hydrogen and argon, hydrogen and helium, hydrogen and nitrogen, ammonia, monodeuterated ammonia, dideuterated ammonia, trideuterated ammonia, hydrazine, alcohol, aldehyde, or a combination thereof.

[0041] In some embodiments, exposing the surface of the substrate to the vapor-phase copper precursor and exposing the substrate to the plasma generated remotely from the hydrogen-containing gas source are performed in temporally separate pulses.

[0042] In some embodiments, the vapor-phase copper precursor adsorbs on the surface of the substrate to form an adsorbed copper precursor.

[0043] In some embodiments, the plasma generated remotely from the hydrogen-containing gas source converts the adsorbed copper precursor to elemental copper.

[0044] In some embodiments, the oxygen-containing gas is supplied at a flow rate of about 1 to about 150 sccm.

[0045] In a fourth aspect, the present disclosure is an apparatus for depositing a metal thin film on a substrate, including at least one reaction chamber including a pedestal for holding the substrate, at least one inlet port for supplying a gas-phase metal precursor to the reaction chamber, a direct plasma generator or a remote plasma generator for providing plasma to the reaction chamber, and a controller for controlling the operation in the apparatus, the controller including machine-readable instructions for (a) setting the substrate temperature to 300 °C or less, (b) introducing the metal precursor into the at least one reaction chamber in the gas phase, and (c) introducing plasma from the direct plasma generator or the remote plasma generator to form a metal thin film on the substrate, the plasma being generated from a hydrogen-containing gas and an oxygen-containing gas of about 0.01% to about 1%.

[0046] These and other aspects will be further described below with reference to the drawings.

Brief Description of the Drawings

[0047]

Figure 1

[0048]

Figure 2

[0049]

Figure 3

[0050]

Figure 4

[0051]

Figure 5

[0052]

Figure 6

[0053]

Figure 7

[0054]

Figure 8

[0055]

Figure 9A

[0056]

Figure 9B

[0057]

Figure 9C

[0058]

Figure 10

[0059]

Figure 11A

[0060]

Figure 11B

[0061]

Figure 12

[0062] Definitions As used herein, the term "heteroleptic complex" refers to a compound that contains at least two different ligands bonded to a metal center.

[0063] As used herein, the term "homoleptic complex" refers to a compound that contains all identical ligands bonded to a metal center.

[0064] As used herein, the term "about", unless otherwise specified, means ±10% of the recited value. As used herein, this term modifies the recited value, the range of values, or the endpoints of one or more ranges.

[0065] As used herein, the terms "upper", "bottom", "upper side", "lower side", "above", and "below" are used to provide a relative relationship between structures. The use of these terms does not imply or require that a particular structure must be located in a particular location within the device.

[0066] As used herein, the phrase "at least one of A, B, and C" should be interpreted in the sense of a logical (A or B or C) using non-exclusive logical OR, and should not be interpreted in the sense of "at least one of A, at least one of B, and at least one of C".

[0067] When the terms "acyl" or "alkanoyl" are used interchangeably herein, they represent a group of 1, 2, 3, 4, 5, 6, 7, 8 or more carbon atoms of linear, branched, cyclic configuration, saturated, unsaturated, and aromatic, and combinations thereof, or hydrogen, bonded to a parent molecular group via a carbonyl group as defined herein. This group is exemplified by formyl (-C(O)H), acetyl (Ac or -C(O)Me), propionyl, isobutyryl, butanoyl, etc. In some embodiments, the acyl group or alkanoyl group is -C(O)-R, where R is hydrogen, an aliphatic group, or an aromatic group as defined herein.

[0068] "Alkanoyloxy" means an alkanoyl group as defined herein bonded to a parent molecular group via an oxy group as defined herein. This group is exemplified by acetoxy (-OAc or -OC(O)Me). In some embodiments, the alkanoyloxy group is -OC(O)-R, where R is hydrogen, an aliphatic group, or an aromatic group as defined herein.

[0069] "Aliphatic" means a hydrocarbon group having at least 1 carbon atom to 50 carbon atoms (C 1-50 ), e.g., 1 to 25 carbon atoms (C 1-25 ), or 1 to 10 carbon atoms (C 1-10 ), which includes alkanes (or alkyls), alkenes (or alkenyls), alkynes (or alkynyls), including their cyclic versions, and further includes straight-chain and branched-chain arrangements, as well as all stereoisomers and positional isomers. The aliphatic group is unsubstituted or substituted, for example, by a functional group as described herein. For example, the aliphatic group can be substituted with one or more substituents as described herein for alkyl.

[0070] "Aliphatic-carbonyl" means an aliphatic group that is coupled to, or can be coupled to, a compound disclosed herein, and the aliphatic group is coupled or is to be coupled via a carbonyl group (-C(O)-). In some embodiments, the aliphatic-carbonyl group is -C(O)-R, where R is an optionally substituted aliphatic group as defined herein.

[0071] "Aliphatic-carbonyloxy" means an aliphatic group that is coupled to, or can be coupled to, a compound disclosed herein, and the aliphatic group is coupled or is to be coupled via a carbonyloxy group (-OC(O)-). In some embodiments, the aliphatic-carbonyloxy group is -OC(O)-R, where R is an optionally substituted aliphatic group as defined herein.

[0072] "Aliphatic-oxy" means an aliphatic group that is coupled to, or can be coupled to, a compound disclosed herein, and the aliphatic group is coupled or is to be coupled via an oxy group. In some embodiments, the aliphatic-oxy group is -O-R, where R is an optionally substituted aliphatic group as defined herein.

[0073] "Aliphatic-oxycarbonyl" means an aliphatic group that is coupled to, or can be coupled to, a compound disclosed herein, and the aliphatic group is coupled or is to be coupled via an oxycarbonyl group (-C(O)O-). In some embodiments, the aliphatic-oxycarbonyl group is -C(O)O-R, where R is an optionally substituted aliphatic group as defined herein.

[0074] "Alkyl-aryl", "alkenyl-aryl", and "alkynyl-aryl" mean an alkyl group, an alkenyl group, or an alkynyl group, respectively, as defined herein, which is coupled (or bonded) to a parent molecular group via an aryl group as defined herein or can be coupled (or bonded). An alkyl-aryl group, an alkenyl-aryl group, and / or an alkynyl-aryl group can be substituted or unsubstituted. For example, an alkyl-aryl group, an alkenyl-aryl group, and / or an alkynyl-aryl group can be substituted with one or more substituents described herein for alkyl and / or aryl. Exemplary unsubstituted alkyl-aryl groups are those having 7 to 16 carbons (C 7-16 alkyl-aryl), as well as those having an alkyl group with 1 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C 1-6 alkyl-C 4-18 aryl). Exemplary unsubstituted alkenyl-aryl groups are those having 7 to 16 carbons (C 7-16 alkenyl-aryl), as well as those having an alkenyl group with 2 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C 2-6 alkenyl-C 4-18 aryl). Exemplary unsubstituted alkynyl-aryl groups are those having 7 to 16 carbons (C 7-16 alkynyl-aryl), as well as those having an alkynyl group with 2 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C 2-6 alkynyl-C 4-18Those having (aryl). In some embodiments, the alkyl-aryl group is -L-R, where L is an aryl group or an arylene group as defined herein, and R is an alkyl group as defined herein. In some embodiments, the alkenyl-aryl group is -L-R, where L is an aryl group or an arylene group as defined herein, and R is an alkenyl group as defined herein. In some embodiments, the alkynyl-aryl group is -L-R, where L is an aryl group or an arylene group as defined herein, and R is an alkynyl group as defined herein.

[0075] "Alkenyl" means an unsaturated monovalent hydrocarbon having at least 2 to 50 carbon atoms (C 2-50 ), for example 2 to 25 carbon atoms (C 2-25 ), or 2 to 10 carbon atoms (C 2-10 ), and at least one carbon-carbon double bond, and the unsaturated monovalent hydrocarbon can be obtained by removing one hydrogen atom from one carbon atom of the parent alkene. The alkenyl group can be branched, straight-chain, cyclic (e.g., cycloalkenyl), cis, or trans (e.g., E or Z). Exemplary alkenyls include optionally substituted C 2-24 alkyl groups having one or more double bonds. The alkenyl group can become monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form a suitable bond to the parent molecular group or a suitable bond between the parent molecular group and another substituent. The alkenyl group can also be substituted or unsubstituted. For example, the alkenyl group can be substituted with one or more of the substituents described herein for alkyl. Non-limiting alkenyl groups include allyl (All), vinyl (VI), 1-butenyl, 2-butenyl, etc.

[0076] "Alkoxy" means -OR, where R is an optionally substituted aliphatic group as described herein. Exemplary alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, t-butoxy, sec-butoxy, n-pentoxy, trihaloalkoxy such as trifluoromethoxy, and the like. The alkoxy group can be substituted or unsubstituted. For example, the alkoxy group can be substituted with one or more substituents as described herein for alkyl. Exemplary unsubstituted alkoxy groups include C 1-3 C 1-6 C 1-12 C 1-16 C 1-18 C 1-20 C 1-24 alkoxy groups.

[0077] "Alkoxyalkyl" means an alkyl group as defined herein substituted with an alkoxy group as defined herein. Exemplary unsubstituted alkoxyalkyl groups include 2 to 12 carbon atoms (C 2-12 alkoxyalkyl), as well as those having an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms (i.e., C 1-6 alkoxy-C 1-6 alkyl). In some embodiments, the alkoxyalkyl group is -L-O-R, where each of L and R is independently an alkyl group as defined herein.

[0078] "Alkoxycarbonyl" means -C(O)-OR, where R is an optionally substituted aliphatic group as described herein. In certain embodiments, the alkoxycarbonyl group is -C(O)-OAk, where Ak is an alkyl group as defined herein. The alkoxycarbonyl group can be substituted or unsubstituted. For example, the alkoxycarbonyl group can be substituted with one or more substituents as described herein for alkyl. Exemplary unsubstituted alkoxycarbonyl groups include C 2-3 C 2-6 C 2-7 C2-12 , C 2-16 , C 2-18 , C 2-20 , or C 2-24 An alkoxycarbonyl group may be mentioned.

[0079] "Alkyl" means a saturated monovalent hydrocarbon having at least 1 carbon atom to 50 carbon atoms (C 1-50 ), for example 1 to 25 carbon atoms (C 1-25 ), or 1 to 10 carbon atoms (C 1-10 ), and the saturated monovalent hydrocarbon can be obtained by removing one hydrogen atom from one carbon atom of the parent compound (for example, an alkane). The alkyl group can be branched, straight-chain, or cyclic (for example, cycloalkyl). Exemplary alkyls include methyl (Me), ethyl (Et), n-propyl (nPr), iso-propyl (iPr), n-butyl (nBu), iso-butyl (iBu), sec-butyl (sBu), tert-butyl (tBu), pentyl (Pe), n-pentyl (nPe), isopentyl (iPe), s-pentyl (sPe), neopentyl (neoPe), tert-pentyl (tPe), hexyl (Hx), heptyl (Hp), octyl (Oc), nonyl (Nn), decyl (De), dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc., and branched or unbranched saturated hydrocarbon groups having 1 to 24 carbon atoms. The alkyl group can also be substituted or unsubstituted. The alkyl group can become monovalent or polyvalent (for example, divalent) by removing one or more hydrogens to form an appropriate bond to the parent molecular group or an appropriate bond between the parent molecular group and another substituent. For example, the alkyl group can be substituted with 4 substituents in the case of an alkyl group of 1, 2, 3, or 2 or more carbons independently selected from the group consisting of: (1) C 1-6 alkoxy (for example, -O-R, where R is C 1-6 alkyl), (2) C 1-6 alkylsulfinyl (for example, -S(O)-R, where R is C 1-6 alkyl), (3) C 1-6 alkylsulfonyl (for example, -SO2-R, where R is C1-6 is alkyl), (4) amino (e.g., -NR 1 R 2 and R 1 and R 2 each independently is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof as defined herein, or R 1 and R 2 together with the nitrogen atom to which each is attached may form a heterocyclyl group as defined herein), (5) aryl, (6) arylalkoxy (e.g., -O-L-R, L is alkyl and R is aryl), (7) aroyl (e.g., -C(O)-R, R is aryl), (8) azide (e.g., -N3), (9) cyano (e.g., -CN), (10) aldehyde (e.g., -C(O)H), (11)C 3-8 cycloalkyl, (12) halo, (13) heterocyclyl (e.g., a 5-, 6-, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms as defined herein), (14) heterocyclyloxy (e.g., -O-R, R is heterocyclyl as defined herein), (15) heterocyclylcarbonyl (e.g., -C(O)-R, R is heterocyclyl as defined herein), (16) hydroxyl (e.g., -OH), (17) N-protected amino, (18) nitro (e.g., -NO2), (19) oxo (e.g., =O), (20)C 1-6 thioalkoxy (e.g., -S-R, R is alkyl), (21) thiol (e.g., -SH), (22) -CO2R 1 where R 1 is selected from the group consisting of (a) hydrogen, (b) C 1-6 alkyl, (c) C 4-18 aryl, and (d) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, L is C 1-6 alkyl and R is C 4-18 aryl), (23) -C(O)NR 1 R 2 and R 1 and R 2Each of which is independently selected from the group consisting of (a) hydrogen, (b) C 1-6 alkyl, (c) C 4-18 aryl, and (d) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl), and (24) -SO2R 1 , where R 1 is selected from the group consisting of (a) C 1-6 alkyl, (b) C 4-18 aryl, and (c) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl), and (25) -SO2NR 1 R 2 , where R 1 and R 2 each are independently selected from the group consisting of (a) hydrogen, (b) C 1-6 alkyl, (c) C 4-18 aryl, and (d) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl), and (26) -NR 1 R 2 , where R 1 and R 2 each are independently selected from the group consisting of (a) hydrogen, (b) N-protecting group, (c) C 1-6 alkyl, (d) C 2-6 alkenyl, (e) C 2-6 alkynyl, (f) C 4-18 aryl, (g) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl), (h) C 3-8 cycloalkyl, and (i) C 3-8 cycloalkyl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6is alkyl, and R is C 3-8 (which is cycloalkyl). In one embodiment, there are also no two groups that are bonded to the nitrogen atom via a carbonyl group or a sulfonyl group. The alkyl group can be a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halo or alkoxy). In some embodiments, the unsubstituted alkyl group is C 1-3 C 1-6 C 1-12 C 1-16 C 1-18 C 1-20 or C 1-24 alkyl group.

[0080] "Alkylene", "alkenylene", or "alkynylene" each mean a polyvalent (e.g., divalent) form of the alkyl group, alkenyl group, or alkynyl group described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, etc. In some embodiments, the alkylene group is C 1-3 C 1-6 C 1-12 C 1-16 C 1-18 C 1-20 C 1-24 C 2-3 C 2-6 C 2-12 C 2-16 C 2-18 C 2-20 or C 2-24 alkylene group. In other embodiments, the alkylene group is C 2-3 C 2-6 C 2-12 C 2-16 C 2-18 C 2-20 or C 2-24It is an alkylene group, an alkenylene group, or an alkynylene group. The alkylene group, alkenylene group, or alkynylene group can be branched or unbranched. The alkylene group, alkenylene group, or alkynylene group can also be substituted or unsubstituted. For example, the alkylene group, alkenylene group, or alkynylene group can be substituted with one or more substituents described herein for alkyl.

[0081] "Alkylsulfinyl" means an alkyl group as defined herein bonded to a parent molecular group via an -S(O)- group. In some embodiments, an unsubstituted alkylsulfinyl group is C 1-6 or C 1-12 alkylsulfinyl group. In other embodiments, the alkylsulfinyl group is -S(O)-R, where R is an alkyl group as defined herein.

[0082] "Alkylsulfinylalkyl" means an alkyl group as defined herein substituted by an alkylsulfinyl group. In some embodiments, an unsubstituted alkylsulfinylalkyl group is C 2-12 or C 2-24 alkylsulfinylalkyl group (e.g., C 1-6 alkylsulfinyl-C 1-6 alkyl or C 1-12 alkylsulfinyl-C 1-12 alkyl). In other embodiments, the alkylsulfinylalkyl group is -L-S(O)-R, where each of L and R is independently an alkyl group as defined herein.

[0083] "Alkylsulfonyl" means an alkyl group as defined herein bonded to a parent molecular group via an -SO2- group. In some embodiments, an unsubstituted alkylsulfonyl group is C 1-6 or C 1-12 alkylsulfonyl group. In other embodiments, the alkylsulfonyl group is -SO2-R, where R is optionally substituted alkyl (e.g., optionally substituted C as described herein1-12 (including alkyl, haloalkyl, or perfluoroalkyl).

[0084] "Alkylsulfonylalkyl" means an alkyl group as defined herein substituted by an alkylsulfonyl group. In some embodiments, an unsubstituted alkylsulfonylalkyl group is C 2-12 or C 2-24 an alkylsulfonylalkyl group (e.g., C 1-6 alkylsulfonyl-C 1-6 alkyl or C 1-12 alkylsulfonyl-C 1-12 alkyl). In other embodiments, the alkylsulfonylalkyl group is -L-SO2-R, where each of L and R is independently an alkyl group as defined herein.

[0085] "Alkynyl" means an unsaturated monovalent hydrocarbon having at least 2 to 50 carbon atoms (C 2-50 ), e.g., 2 to 25 carbon atoms (C 2-25 ), or 2 to 10 carbon atoms (C 2-10 ), and at least one carbon-carbon triple bond, and the unsaturated monovalent hydrocarbon can be obtained by removing one hydrogen atom from one carbon atom of the parent alkyne. The alkynyl group can be branched, straight-chain, or cyclic (e.g., cycloalkynyl). Exemplary alkynyls include optionally substituted C 2-24 alkyl groups having one or more triple bonds. The alkynyl group can be cyclic or acyclic and is exemplified by ethynyl, 1-propynyl, etc. The alkynyl group can become monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form a suitable bond to the parent molecular group or a suitable bond between the parent molecular group and another substituent. The alkynyl group can also be substituted or unsubstituted. For example, the alkynyl group can be substituted with one or more of the substituents described herein for alkyl.

[0086] "Surrounding temperature" means a temperature in the range of 16°C to 26°C, for example, 19°C to 25°C or 20°C to 25°C.

[0087] "Amide" means -C(O)NR 1 R 2 or -NHCOR 1 and each of R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, aromatic, or any combination thereof as defined herein, or R 1 and R 2 may together with the nitrogen atom to which each is attached form a heterocyclyl group as defined herein.

[0088] "Amino" means -NR 1 R 2 and each of R 1 and R 2 is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, or any combination thereof, or R 1 and R 2 may together with the nitrogen atom to which each is attached form a heterocyclyl group as defined herein. In certain embodiments, each of R 1 and R 2 is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, optionally substituted silyl, or optionally substituted silyloxy. In certain embodiments, R 1 and R 2 may together with the nitrogen atom to which each is attached form an optionally substituted heterocyclyl.

[0089] "Aminoalkyl" means an alkyl group as defined herein substituted by an amino group as defined herein. In some embodiments, the aminoalkyl group is -L-NR 1 R 2 wherein L is an alkyl group as defined herein, and each of R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, or aromatic as defined herein, or any combination thereof, or R 1 and R 2 may together with the nitrogen atom to which each is attached form a heterocyclyl group as defined herein. In other embodiments, the aminoalkyl group is -L-C(NR 1 R 2 )(R 3 )-R 4 wherein L is a covalent bond or an alkyl group as defined herein, and each of R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, or aromatic as defined herein, or any combination thereof, or R 1 and R 2 may together with the nitrogen atom to which each is attached form a heterocyclyl group as defined herein, and each of R 3 and R 4 is independently H or alkyl as defined herein.

[0090] "Aminooxy" means an oxy group as defined herein substituted by an amino group as defined herein. In some embodiments, the aminooxy group is -O-NR 1 R 2 wherein R 1 and R 2Each of which is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, as defined herein, or any combination thereof, or R 1 and R 2 can together with the nitrogen atom to which each is attached form a heterocyclyl group as defined herein. In certain embodiments, each of R 1 and R 2 is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, optionally substituted silyl, or optionally substituted silyloxy.

[0091] "Aromatic", unless otherwise specified, means a cyclic conjugated group or a moiety of 5 to 15 ring atoms having a single ring (e.g., phenyl) or multiple fused rings in which at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl), i.e., at least one ring, and optionally multiple fused rings, have a continuous delocalized π - electron system. Typically, the number of out - of - plane π - electrons corresponds to the Hückel rule (4n + 2). The point of attachment to the parent structure typically occurs through the aromatic portion of the fused - ring system. Aromatic groups are unsubstituted or substituted, for example, by functional groups as described herein. For example, an aromatic group can be substituted with one or more substituents as described herein for alkyl and / or aryl.

[0092] "Aryl-carbonyl" means an aromatic group that can be coupled to or can couple with the compounds disclosed herein, and the aromatic group is coupled or is to be coupled via a carbonyl group (-C(O)-). In some embodiments, the aryl-carbonyl group is -C(O)-R, where R is an optionally substituted aromatic group as defined herein.

[0093] "Aryl-carbonyloxy" means an aromatic group that can be coupled to or can couple with the compounds disclosed herein, and the aromatic group is coupled or is to be coupled via a carbonyloxy group (-OC(O)-). In some embodiments, the aryl-carbonyloxy group is -OC(O)-R, where R is an optionally substituted aromatic group as defined herein.

[0094] "Aryl-oxy" means an aromatic group that can be coupled to or can couple with the compounds disclosed herein, and the aromatic group is coupled or is to be coupled via an oxy group (-O-). In some embodiments, the aryl-oxy group is -O-R, where R is an optionally substituted aromatic group as defined herein.

[0095] "Aryl-oxycarbonyl" means an aromatic group that can be coupled to or can couple with the compounds disclosed herein, and the aromatic group is coupled or is to be coupled via an oxycarbonyl group (-C(O)O-). In some embodiments, the aryl-carbonyl group is -C(O)O-R, where R is an optionally substituted aromatic group as defined herein.

[0096] "Aryl" means having a single ring or a plurality of fused rings, with at least 5 to 15 carbon atoms (C 5-15 ), for example 5 to 10 carbon atoms (C 5-10means an aromatic carbocyclic group containing ), and the fused ring may or may not be aromatic when the bonding point to the remaining positions of the compounds disclosed herein is through an atom of the aromatic carbocyclic group. The aryl group may be optionally substituted with one or more groups other than hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Exemplary aryl groups include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term aryl also includes heteroaryl, which is defined as a group containing an aromatic group having 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. Similarly, the term non-heteroaryl, which is also included in the term aryl, defines a group containing an aromatic group that does not contain a heteroatom. The aryl group may be substituted or unsubstituted. The aryl group can be substituted with 1, 2, 3, 4, or 5 substituents independently selected from the group consisting of: (1) C 1-6 alkanoyl (e.g., -C(O)-R, where R is C 1-6 alkyl), (2) C 1-6 alkyl, (3) C 1-6 alkoxy (e.g., -O-R, where R is C 1-6 alkyl), (4) C 1-6 alkoxy-C 1-6 alkyl (e.g., -L-O-R, where each of L and R is independently C 1-6 alkyl), (5) C 1-6 alkylsulfinyl (e.g., -S(O)-R, where R is C 1-6 alkyl), (6) C 1-6 alkylsulfinyl-C 1-6 alkyl (e.g., -L-S(O)-R, where each of L and R is independently C 1-6 alkyl), (7) C 1-6 alkylsulfonyl (e.g., -SO2-R, where R is C 1-6 alkyl), (8) C 1-6 alkylsulfonyl-C 1-6 alkyl (e.g., -L-SO2-R, where each of L and R is independently C1-6 is alkyl), (9) aryl, (10) amino (e.g., -NR 1 R 2 , R 1 and R 2 each independently is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof as defined herein, or R 1 and R 2 together with the nitrogen atom to which each is attached may form a heterocyclyl group as defined herein), (11) C 1-6 aminoalkyl (e.g., -L 1 -NR 1 R 2 or -L 2 -C(NR 1 R 2 )(R 3 )-R 4 , L 1 is C 1-6 alkyl, L2 is a covalent bond or C 1-6 alkyl, and each of R 1 and R 2 each independently is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof as defined herein, or R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl group as defined herein, and each of R 3 and R 4 each independently is H or C 1-6 alkyl), (12) heteroaryl, (13) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, L is C 1-6 alkyl, and R is C 4-18 aryl), (14) aroyl (e.g., -C(O)-R, R is aryl), (15) azide (e.g., -N3), (16) cyano (e.g., -CN), (17) C 1-6 azidoalkyl (e.g., -L-N3, L is C 1-6alkyl), (18) aldehyde (e.g., -C(O)H), (19) aldehyde-C 1-6 alkyl (e.g., -L-C(O)H, L is C 1-6 alkyl), (20) C 3-8 cycloalkyl, (21) C 3-8 cycloalkyl-C 1-6 alkyl (e.g., -L-R, L is C 1-6 alkyl and R is C 3-8 cycloalkyl), (22) halo, (23) C 1-6 haloalkyl (e.g., -L 1 -X or -L 2 -C(X)(R 1 )-R 2 , L 1 is C 1-6 alkyl, L 2 is a covalent bond or C 1-6 alkyl, X is fluoro, bromo, chloro, or iodo, and each of R 1 and R 2 is independently H or C 1-6 alkyl), (24) heterocyclyl (e.g., a 5-, 6-, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms as defined herein), (25) heterocyclyloxy (e.g., -O-R, R is heterocyclyl as defined herein), (26) heterocyclyloyl (e.g., -C(O)-R, R is heterocyclyl as defined herein), (27) hydroxyl (-OH), (28) C 1-6 hydroxyalkyl (e.g., -L 1 -OH or -L 2 -C(OH)(R 1 )-R 2 , L 1 is C 1-6 alkyl, L 2 is a covalent bond or alkyl, and each of R 1 and R 2 is independently H or C 1-6 alkyl as defined herein), (29) nitro, (30) C 1-6 nitroalkyl (e.g., -L1 -NO or -L 2 -C(NO)(R 1 )-R 2 、L 1 is C 1-6 alkyl, L 2 is a covalent bond or alkyl, R 1 and R 2 each is independently H or C as defined herein 1-6 alkyl), (31) N - protected amino, (32) N - protected amino - C 1-6 alkyl, (33) oxo (e.g., =O), (34) C 1-6 thioalkyl (e.g., -S - R, R is C 1-6 alkyl), (35) thio - C 1-6 alkoxy - C 1-6 alkyl (e.g., -L - S - R, each of L and R is independently C 1-6 alkyl), (36) -(CH2) r CO2R 1 , r is an integer from 0 to 4, R 1 is selected from the group consisting of (a) hydrogen, (b) C 1-6 alkyl, (c) C 4-18 aryl, and (d) C 4-18 aryl - C 1-6 alkyl (e.g., -L - R, L is C 1-6 alkyl, R is C 4-18 aryl), (37) -(CH2) r CONR 1 R 2 , r is an integer from 0 to 4, each R 1 and R 2 is independently selected from the group consisting of (a) hydrogen, (b) C 1-6 alkyl, (c) C 4-18 aryl, and (d) C 4-18 aryl - C 1-6 alkyl (e.g., -L - R, L is C 1-6 alkyl, R is C 4-18 aryl), (38) -(CH2) r SO2R 1 , r is an integer from 0 to 4, R1 is selected from the group consisting of (a) C 1-6 alkyl, (b) C 4-18 aryl, and (c) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl), (39)-(CH2) r SO2NR 1 R 2 , r is an integer from 0 to 4, and each of R 1 and R 2 is independently selected from the group consisting of (a) hydrogen, (b) C 1-6 alkyl, (c) C 4-18 aryl, and (d) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl), (40)-(CH2) r NR 1 R 2 , r is an integer from 0 to 4, and each of R 1 and R 2 is independently selected from the group consisting of (a) hydrogen, (b) an N-protecting group, (c) C 1-6 alkyl, (d) C 2-6 alkenyl, (e) C 2-6 alkynyl, (f) C 4-18 aryl, (g) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl), (h) C 3-8 cycloalkyl, and (i) C 3-8 cycloalkyl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 3-8 cycloalkyl), and in one embodiment, there are no two groups bonded to the nitrogen atom via a carbonyl group or a sulfonyl group, (41) thiol (e.g., -SH), (42) perfluoroalkyl (e.g., -(CF2)n CF3, where n is an integer from 0 to 10), (43) perfluoroalkoxy (e.g., -O-(CF2) n CF3, where n is an integer from 0 to 10), (44) aryloxy (e.g., -O-R, where R is aryl), (45) cycloalkoxy (e.g., -O-R, where R is cycloalkyl), (46) cycloalkylalkoxy (e.g., -O-L-R, where L is alkyl and R is cycloalkyl), and (47) arylalkoxy (e.g., -O-L-R, where L is alkyl and R is aryl). In certain embodiments, the unsubstituted aryl group is C 4-18 C 4-14 C 4-12 C 4-10 C 6-18 C 6-14 C 6-12 or C 6-10 aryl group.

[0097] "Aryl-alkyl", "aryl-alkenyl", and "aryl-alkynyl" each mean an aryl group as defined herein that is coupled (or bonded) to or can be coupled (or bonded) to a parent molecular group via an alkyl group, alkenyl group, or alkynyl group as defined herein. An aryl-alkyl group, aryl-alkenyl group, and / or aryl-alkynyl group can be substituted or unsubstituted. For example, an aryl-alkyl group, aryl-alkenyl group, and / or aryl-alkynyl group can be substituted with one or more substituents as described herein for aryl and / or alkyl. Exemplary unsubstituted aryl-alkyl groups are those having 7 to 16 carbons (C 7-16 aryl-alkyl), as well as those having an aryl group having 4 to 18 carbons and an alkyl group having 1 to 6 carbons (i.e., C 4-18 aryl-C 1-6 alkyl). Exemplary unsubstituted aryl-alkenyl groups are those having 7 to 16 carbons (C 7-16Those of (aryl - alkenyl), as well as an aryl group having 4 to 18 carbons and an alkenyl group having 2 to 6 carbons (i.e., C 4-18 aryl - C 2-6 alkenyl). Exemplary unsubstituted aryl - alkynyl groups are those of 7 to 16 carbons (C 7-16 aryl - alkynyl), as well as an aryl group having 4 to 18 carbons and an alkynyl group having 2 to 6 carbons (i.e., C 4-18 aryl - C 2-6 alkynyl). In some embodiments, the aryl - alkyl group is -L-R, where L is an alkyl group or an alkylene group as defined herein, and R is an aryl group as defined herein. In some embodiments, the aryl - alkenyl group is -L-R, where L is an alkenyl group or an alkenylene group as defined herein, and R is an aryl group as defined herein. In some embodiments, the aryl - alkynyl group is -L-R, where L is an alkynyl group or an alkynylene group as defined herein, and R is an aryl group as defined herein.

[0098] "Arylene" means a polyvalent (e.g., divalent) form of the aryl group described herein. Exemplary arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthylenylene, anthrylene, or phenanthrylene. In some embodiments, the arylene group is C 4-18 C 4-14 C 4-12 C 4-10 C 6-18 C 6-14 C 6-12 or C 6-10 arylene group. The arylene group can be branched or unbranched. The arylene group can also be substituted or unsubstituted. For example, the arylene group can be substituted with one or more substituents described herein for aryl.

[0099] "Aryloxy" means an aryl-alkyl group as defined herein, bonded to the parent molecular group through an oxygen atom. In some embodiments, the aryloxy group is -O-L-R, where L is an alkyl group as defined herein and R is an aryl group as defined herein.

[0100] "Aryloxy" means -OR, where R is an optionally substituted aryl group as described herein. In some embodiments, the unsubstituted aryloxy group is C 4-18 or C 6-18 aryloxy group. In other embodiments, R is an aryl group optionally substituted with alkyl, alkanoyl, amino, hydroxyl, etc.

[0101] "Aryloxycarbonyl" means an aryloxy group as defined herein, bonded to the parent molecular group through a carbonyl group. In some embodiments, the unsubstituted aryloxycarbonyl group is C 5-19 aryloxycarbonyl group. In other embodiments, the aryloxycarbonyl group is -C(O)O-R, where R is an aryl group as defined herein.

[0102] "Aroyl" means an aryl group bonded to the parent molecular group through a carbonyl group. In some embodiments, the unsubstituted aroyl group is C 7-11 aroyl or C 5-19 aroyl group. In other embodiments, the aroyl group is -C(O)-R, where R is an aryl group as defined herein.

[0103] "Aroyloxy" means an aroyl group as defined herein, bonded to the parent molecular group through an oxy group. In some embodiments, the unsubstituted aroyloxy group is C 5-19 aroyloxy group. In other embodiments, the aroyloxy group is -OC(O)-R, where R is an aryl group as defined herein.

[0104] "Atomic layer deposition" (ALD) means a vapor deposition process in which deposition cycles, preferably a plurality of consecutive deposition cycles, are carried out in a process chamber (i.e., a deposition chamber). Typically, during each cycle, the precursor chemisorbs onto the deposition surface (i.e., the substrate assembly surface or the previously deposited underlying surface such as the material from a previous ALD cycle) to form a monolayer or sub-monolayer that does not readily react with additional precursors (i.e., a self-limiting reaction). Thereafter, if desired, a reactant (i.e., another precursor or reaction gas) can be introduced into the process chamber for use in converting the chemisorbed precursor into the desired material on the deposition surface. Typically, this reactant is capable of reacting with the chemisorbed precursor. Further, a purge step can be utilized during each cycle to remove excess precursor from the process chamber after conversion of the chemisorbed precursor and / or to remove excess reactant and / or reaction by-products from the process chamber.

[0105] "Azide" means an -N3 group.

[0106] "Azidoalkyl" means an azide group bonded to a parent molecular group via an alkyl group as defined herein. In some embodiments, the azidoalkyl group is -L-N3, where L is an alkyl group as defined herein.

[0107] "Azo" means an -N=N- group.

[0108] "Bidentate ligand" means a ligand having two atoms that coordinate to a central atom in a complex, i.e., an alkyldiamine.

[0109] "Carbamoyl" means an amino group bonded to a parent molecular group via a carbonyl group as defined herein. In some embodiments, carbamoyl is a -C(O)NR 1 R 2 group, where R 1 and R 2Each of which is independently selected from hydrogen as defined herein, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, or any combination thereof, or R 1 and R 2 may together with the nitrogen atom to which each is attached form a heterocyclyl group as defined herein.

[0110] "Carbamoyloxy" means a carbamoyl group as defined herein attached to a parent molecular group via an n-oxy group as defined herein. In some embodiments, the carbamoyl is -OC(O)NR 1 R 2 group, and each of R 1 and R 2 is independently selected from hydrogen as defined herein, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, or any combination thereof, or R 1 and R 2 may together with the nitrogen atom to which each is attached form a heterocyclyl group as defined herein.

[0111] "Carboximidoyl" means a -C(NR)- group. In some embodiments, R is selected from hydrogen as defined herein, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl, optionally substituted silyloxy, or any combination thereof.

[0112] "Carbonyl" means a -C(O)- group and can also be represented as >C=O.

[0113] "Carboxyl" means a -CO2H group or its anion.

[0114] "Catalyst" means a compound that can catalyze a synthesis reaction and is usually present in a small amount relative to the reactants, as readily understood by those skilled in the art. In some embodiments, the catalyst may include a transition metal coordination complex.

[0115] "Cyanato" means an -OCN group.

[0116] "Cyano" means a -CN group.

[0117] "Alicyclic" means a cyclic aliphatic group as defined herein.

[0118] "Cycloalkoxy" means a cycloalkyl group as defined herein bonded to a parent molecular group through an oxygen atom. In some embodiments, the cycloalkoxy group is -O-R, where R is a cycloalkyl group as defined herein.

[0119] "Cycloalkylalkoxy" means an -O-L-R group, where L is an alkyl group or an alkylene group as defined herein and R is a cycloalkyl group as defined herein.

[0120] "Cycloalkyl" means, unless otherwise specified, a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon group having 3 to 8 carbons, exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1]heptyl, etc. The cycloalkyl group can be substituted or unsubstituted. For example, the cycloalkyl group can be substituted with one or more groups including those described herein for alkyl. Further, cycloalkyl can include one or more double bonds and / or triple bonds.

[0121] "Cycloheteroaliphatic" means a cyclic heteroaliphatic group as defined herein.

[0122] "Deposition" or "vapor deposition" means a process in which a metal layer is formed on one or more surfaces of a substrate from a vaporized precursor composition containing one or more metal-containing compounds. The metal-containing compounds are vaporized and directed and / or contacted to one or more surfaces of a substrate (i.e., a semiconductor substrate or semiconductor assembly) placed in a deposition chamber. Typically, the substrate is heated. These metal-containing compounds form a thin, uniform, non-volatile metal-containing layer on the surface of the substrate. One operation of this method is one cycle, and the process can be repeated for the number of cycles necessary to obtain the desired metal thickness.

[0123] "Disilanyl" means a group containing an Si-Si bond. In some embodiments, the disilanyl group is a -SiR S1 R S2 -SiR S3 R S4 R S5 or -SiR S1 R S2 -SiR S3 R S4 - group, where each of R S1 R S2 R S3 R S4 and R S5 is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino.

[0124] "Disulfide" means -SSR, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof as defined herein.

[0125] The term "electron-donating group" means a functional group capable of donating at least a part of its electron density to the ring directly bonded thereto by resonance or the like.

[0126] The term "electron-withdrawing group" means a functional group capable of receiving electron density from the ring directly bonded thereto by inductive electron withdrawal or the like.

[0127] "Halo" means F, Cl, Br, or I.

[0128] "Chalcogen" means O, S, Se, or Te.

[0129] "Haloaliphatic" means an aliphatic group as defined herein, and one or more hydrogen atoms such as 1 to 10 hydrogen atoms are independently replaced by halogen atoms such as fluoro, bromo, chloro, or iodo.

[0130] "Haloalkyl" means an alkyl group as defined herein, and one or more hydrogen atoms such as 1 to 10 hydrogen atoms are independently replaced by halogen atoms such as fluoro, bromo, chloro, or iodo. In an independent embodiment, the haloalkyl can be a -CX3 group, and each X can be independently selected from fluoro, bromo, chloro, or iodo. In some embodiments, the haloalkyl group is -L-X, where L is an alkyl group as defined herein and X is fluoro, bromo, chloro, or iodo. In other embodiments, the haloalkyl group is -L-C(X)(R 1 )-R 2 where L is a covalent bond or an alkyl group as defined herein, X is fluoro, bromo, chloro, or iodo, and each of R 1 and R 2 is independently H or alkyl as defined herein.

[0131] "Haloheteroaliphatic" means heteroaliphatic as defined herein, and one or more hydrogen atoms, such as 1 to 10 hydrogen atoms, are independently replaced by halogen atoms such as fluoro, bromo, chloro, or iodo.

[0132] "Heteroaliphatic" means an aliphatic group as defined herein, containing at least 1 heteroatom to 20 heteroatoms, such as 1 to 15 heteroatoms, or 1 to 5 heteroatoms, which can be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and their oxidized forms within the group. The heteroaliphatic group is unsubstituted or substituted, for example, by functional groups described herein. For example, the heteroaliphatic group can be substituted by one or more substituents described herein for alkyl.

[0133] "Heteroaliphatic-carbonyl" means a heteroaliphatic group that is coupled or can be coupled to a compound disclosed herein, and the heteroaliphatic group is coupled or is to be coupled via a carbonyl group (-C(O)-). In some embodiments, the heteroaliphatic-carbonyl group is -C(O)-R, where R is an optionally substituted heteroaliphatic group as defined herein.

[0134] "Heteroaliphatic-carbonyloxy" means a heteroaliphatic group that is coupled or can be coupled to a compound disclosed herein, and the heteroaliphatic group is coupled or is to be coupled via a carbonyloxy group (-OC(O)-). In some embodiments, the heteroaliphatic-carbonyloxy group is -OC(O)-R, where R is an optionally substituted heteroaliphatic group as defined herein.

[0135] "Heteroaliphatic-oxy" means a heteroaliphatic group that is coupled to or can be coupled to a compound disclosed herein, and the heteroaliphatic group is coupled or is to be coupled via an oxy group (-C(O)-). In some embodiments, the heteroaliphatic-oxy group is -O-R, where R is an optionally substituted heteroaliphatic group as defined herein.

[0136] "Heteroaliphatic-oxycarbonyl" means a heteroaliphatic group that is coupled to or can be coupled to a compound disclosed herein, and the heteroaliphatic group is coupled or is to be coupled via an oxycarbonyl group (-C(O)O-). In some embodiments, the heteroaliphatic-oxycarbonyl group is -C(O)O-R, where R is an optionally substituted heteroaliphatic group as defined herein.

[0137] "Heteroalkyl", "heteroalkenyl", and "heteroalkynyl" each mean an alkyl group, an alkenyl group, or an alkynyl group (which may be branched, straight-chain, or cyclic) as defined herein, containing from at least 1 to 20 heteroatoms, such as from 1 to 15 heteroatoms, or from 1 to 5 heteroatoms, which can be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and their oxidized forms within the group.

[0138] "Heteroalkylene", "heteroalkenylene", and "heteroalkynylene" each mean the polyvalent (e.g., divalent) form of a heteroalkyl group, a heteroalkenyl group, or a heteroalkynyl group as described herein.

[0139] "Heteroaromatic" means an aromatic group as defined herein, containing from at least 1 to 20 heteroatoms, such as from 1 to 15 heteroatoms, or from 1 to 5 heteroatoms, which can be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and their oxidized forms within the group. The heteroaromatic group is unsubstituted or substituted, for example, by a functional group as described herein. For example, the heteroaromatic group can be substituted with one or more substituents as described herein for alkyl and / or aryl.

[0140] "Heteroaromatic-carbonyl" means a heteroaromatic group that is coupled or can be coupled to a compound disclosed herein, and the heteroaromatic group is coupled or becomes coupled via a carbonyl group (-C(O)-). In some embodiments, the heteroaromatic-carbonyl group is -C(O)-R, where R is an optionally substituted heteroaromatic group as defined herein.

[0141] "Heteroaromatic-carbonyloxy" means a heteroaromatic group that is coupled or can be coupled to a compound disclosed herein, and the heteroaromatic group is coupled or becomes coupled via a carbonyloxy group (-OC(O)-). In some embodiments, the heteroaromatic-carbonyloxy group is -OC(O)-R, where R is an optionally substituted heteroaromatic group as defined herein.

[0142] "Heteroaromatic-oxy" means a heteroaromatic group that is coupled or can be coupled to a compound disclosed herein, and the heteroaromatic group is coupled or becomes coupled via an oxy group (-O-). In some embodiments, the heteroaromatic-oxy group is -O-R, where R is an optionally substituted heteroaromatic group as defined herein.

[0143] "Heteroaromatic-oxycarbonyl" means a heteroaromatic group that is coupled to or can be coupled to a compound disclosed herein, and the heteroaromatic group is coupled or is to be coupled via an oxycarbonyl group (-C(O)O-). In some embodiments, the heteroaromatic-carbonyl group is -C(O)O-R, where R is an optionally substituted heteroaromatic group as defined herein.

[0144] "Heteroaryl" means an aryl group containing at least 1 to 6 heteroatoms, such as 1 to 4 heteroatoms, which can be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and their oxidized forms within the ring. Such heteroaryl groups can have a monocyclic or multiple fused rings, and the fused rings may or may not be aromatic when the point of attachment is through an atom of the aromatic heteroaryl group and / or may contain heteroatoms. The heteroaryl group may be substituted with one or more groups other than hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Exemplary heteroaryls include a subset of the heterocyclyl groups defined herein that are aromatic, i.e., contain 4n + 2 π electrons within a monocyclic or polycyclic ring system.

[0145] "Heteroarylene" means a polyvalent (e.g., divalent) form of the heteroaryl group described herein.

[0146] "Heteroatom" means an atom other than carbon, such as oxygen, nitrogen, sulfur, silicon, boron, selenium, or phosphorus. In certain disclosed embodiments, such as when valence constraints do not permit, the heteroatom does not include a halogen atom.

[0147] "Heterocyclyl", unless otherwise specified, means a 5-, 6-, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms (independently selected from the group consisting of, for example, nitrogen, oxygen, phosphorus, sulfur, or halogen). The 5-membered ring has 0 to 2 double bonds, and the 6-membered and 7-membered rings have 0 to 3 double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic, and tetracyclic groups, and any of the above heterocycles is condensed to one, two, or three rings independently selected from the group consisting of an aryl ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring, and another monocyclic heterocycle such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl. Heterocycles include thianyl, thietanyl, tetrahydrothienyl, thianyl, thiepanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyridyl, homopiperidinyl, pyrazinyl, piperazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolidinyl, oxazolidonyl, isoxazolyl, isoxazolidinyl, morpholinyl, thiomorpholinyl, thiazolyl, thiazolidinyl, isothiazolyl, isothiazolidinyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, furyl, thienyl, thiazolidinyl, isothiazolyl, isoindazolyl, triazolyl, tetrazolyl, oxadiazolyl, uracil, thiadiazolyl, pyrimidyl, tetrahydrofuranyl, dihydrofuranyl, dihydrothienyl, dihydroindolyl, tetrahydroquinolyl, tetrahydroisoquinolyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dithiazolyl, dioxanyl, dioxinyl, dithianyl, trithianyl, oxazinyl, thiazinyl, oxothiolanyl, triazinyl, benzofuryl, benzothienyl, and the like.

[0148] "Heterocyclyloxy" means a heterocyclyl group as defined herein, bonded to a parent molecular group through an oxygen atom. In some embodiments, the heterocyclyloxy group is -O-R, where R is a heterocyclyl group as defined herein.

[0149] "Heterocyclylcarbonyl" means a heterocyclyl group as defined herein, bonded to a parent molecular group through a carbonyl group. In some embodiments, the heterocyclylcarbonyl group is -C(O)-R, where R is a heterocyclyl group as defined herein.

[0150] "Hydrazino" means -NR 1 -NR 2 R 3 wherein each of R 1 and R 2 and R 3 is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, or any combination thereof, or the combination of R 1 and R 2 or the combination of R 2 and R 3 may together with the nitrogen atom to which each is attached form a heterocyclyl group as defined herein. In some embodiments, each of R 1 and R 2 or R 3 is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl. In certain embodiments, R 2 and R 3 may together with the nitrogen atom to which each is attached form an optionally substituted heterocyclyl.

[0151] "Hydroxyl" means -OH.

[0152] "Hydroxyalkyl" means an alkyl group as defined herein substituted by one to three hydroxyl groups, provided that one or fewer hydroxyl groups can be attached to a single carbon atom of the alkyl group, and this group is exemplified by hydroxymethyl, dihydroxypropyl, etc. In some embodiments, the hydroxyalkyl group is -L-OH, where L is an alkyl group as defined herein. In other embodiments, the hydroxyalkyl group is -L-C(OH)(R 1 )-R 2 where L is a covalent bond or an alkyl group as defined herein, and each of R 1 and R 2 is independently H or alkyl as defined herein.

[0153] "Imidoyl" means a moiety containing a carboximideoyl group. In some embodiments, the imidoyl group is C(NR 1 )R 2 where each of R 1 and R 2 is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl, optionally substituted silyloxy, or any combination thereof. In other embodiments, the imidoyl group is -C(NR 1 )H, -C(NR 1 )R Ak , or -C(NR N1 )R Ar where R 1is hydrogen, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, an optionally substituted heteroaromatic, an optionally substituted silyl, an optionally substituted alkyl, an optionally substituted aryl, an optionally substituted alkyl-aryl, or an optionally substituted aryl-alkyl, or an optionally substituted silyloxy, and R Ak is an optionally substituted alkyl or an optionally substituted aliphatic, and R Ar is an optionally substituted aryl or an optionally substituted aromatic.

[0154] "Imino" means an -NR- group. In some embodiments, R is selected from hydrogen, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, or an optionally substituted heteroaromatic. In certain embodiments, R is H, an optionally substituted alkyl, an optionally substituted alkoxy, an optionally substituted aryl, an optionally substituted aryloxy, an optionally substituted alkyl-aryl, or an optionally substituted aryl-alkyl.

[0155] "Isocyanato" means an -NCO group.

[0156] "Isocyano" means an -NC group.

[0157] "Ketone" means a compound containing -C(O)R or such a group, and R is selected from aliphatic, heteroaliphatic, aromatic, or any combination thereof as defined herein. An example of a ketone includes R 1 C(O)R, and each of R and R 1 is independently selected from aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof as defined herein.

[0158] "Molybdenum metal" or "metallic molybdenum", as used herein, refers to a material consisting essentially of molybdenum (Mo) in the zero oxidation state. Other elements (e.g., C, N, or O) may be present in the molybdenum metal in small amounts (e.g., with a total content of less than about 15 atomic percent, or less than about 10%, and hydrogen is not included in the calculation). "High-purity molybdenum metal", as used herein, refers to a molybdenum metal containing less than about 5% of other elements, e.g., less than about 1% of other elements, and hydrogen is not included in the calculation. In some embodiments, the molybdenum metal deposited by the provided method contains at least a portion that is at least about 90%, such as at least about 95%, or at least about 99% pure molybdenum, where % refers to weight percent.

[0159] "Nitro" means a -NO2 group.

[0160] "Nitroalkyl" means an alkyl group as defined herein substituted with 1 to 3 nitro groups. In some embodiments, the nitroalkyl group is -L-NO, where L is an alkyl group as defined herein. In other embodiments, the nitroalkyl group is -L-C(NO)(R 1 )-R 2 where L is a covalent bond or an alkyl group as defined herein, and each of R 1 and R 2 is independently H or alkyl as defined herein.

[0161] "Oxo" means a =O group.

[0162] "Oxy" means -O-.

[0163] "Perfluoroalkyl" means an alkyl group as defined herein having each hydrogen atom substituted with a fluorine atom. Exemplary perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, and the like. In some embodiments, the perfluoroalkyl group is -(CF2) nIt is CF3, and n is an integer from 0 to 10.

[0164] "Perfluoroalkoxy" means an alkoxy group defined herein having each hydrogen atom substituted by a fluorine atom. In some embodiments, the perfluoroalkoxy group is -O-R, where R is a perfluoroalkyl group as defined herein.

[0165] "Remotely generated plasma" means plasma formed at a location different from the deposition chamber, or outside the deposition chamber.

[0166] "Salt" means an ionic form of a compound or structure (e.g., any formula, compound, or composition described herein) that includes a cationic or anionic compound forming an electrically neutral compound or structure. Salts can be prepared separately during the final isolation and purification of the compounds of the invention in situ or by reacting the free base group with a suitable organic acid (thereby forming an anionic salt) or by reacting an acid group with a suitable metal or organic salt (thereby forming a cationic salt). Representative anionic salts include acetate, adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, borate, bromide, butyrate, camphorate, camphorsulfonate, chloride, citrate, cyclopentanepropionate, digluconate, dihydrochloride, diphosphate, dodecyl sulfate, edetate, ethanesulfonate, fumarate, glucoheptonate, gluconate, glutamate, glycerophosphate, hemisulfate, heptonate, hexanoate, hydrobromide, hydrochloride, hydroiodide, hydroxyethanesulfonate, hydroxynaphthoate, iodide, lactate, lactobionate, laurate, lauryl sulfate, malate, maleate, malonate, mandelate, mesylate, methanesulfonate, methyl bromide, methyl nitrate, methyl sulfate, mucate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphate, picrate, pivalate, polygalacturonate, propionate, salicylate, stearate, subacetate, succinate, sulfate, tannate, tartrate, theophyllinate, thiocyanate, triethiodide, toluenesulfonate, undecanoate, valerate, and the like.Representative cationic salts include metal salts, such as alkali or alkaline earth salts, such as barium, calcium (e.g., calcium edetate), lithium, magnesium, potassium, sodium, etc.; other metal salts, such as aluminum, bismuth, iron, and zinc; and, without limitation, non-toxic ammonium, quaternary ammonium, and aminocations, including ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, pyridinium, etc. Other cationic salts include organic salts such as chloroprocaine, choline, dibenzylethylenediamine, diethanolamine, ethylenediamine, methylglucamine, and procaine.Still other salts include ammonium, sulfonium, sulfoxonium, phosphonium, iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphaziniun, phosphazenium, pyridinium, and other cationic groups described herein (e.g., optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrrolium, optionally substituted furanium, optionally substituted thiophenium, optionally substituted imidazolium, optionally substituted pyrazolium, optionally substituted isothiazolium, optionally substituted triazolium, optionally substituted tetrazolium, optionally substituted furazanium, optionally substituted pyridinium, optionally substituted pyrimidinium, optionally substituted pyrazinium, optionally substituted triazinium, optionally substituted tetrazinium, optionally substituted pyridazinium, optionally substituted oxazinium, optionally substituted pyrrolidinium, optionally substituted pyrazolidinium, optionally substituted imidazolinium, optionally substituted isoxazolidinium, optionally substituted oxazolidinium, optionally substituted piperazinium, optionally substituted piperidinium, optionally substituted morpholinium, optionally substituted azepanium, optionally substituted azepinium, optionally substituted indolium, optionally substituted isoindolium, optionally substituted indolidinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinolinium, optionally substituted quinolidinium, optionally substituted dehydroquinolinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted purinium).

[0167] "Monodeuterated ammonia" means NH2D.

[0168] "Di-deuterated ammonia" means NHD2.

[0169] "Tri-deuterated ammonia" means ND3.

[0170] In the present disclosure, the terms "semiconductor wafer", "wafer", "substrate", "wafer substrate", and "partially fabricated integrated circuit" are used interchangeably. Those skilled in the art will understand that the term "partially fabricated integrated circuit" can refer to a silicon wafer at any of many stages of integrated circuit fabrication. Wafers or substrates used in the semiconductor device industry typically have a diameter of 200 mm, or 300 mm, or 450 mm. The following detailed description assumes that the present disclosure is implemented on a wafer. However, the present disclosure is not so limited. The workpiece may be of various shapes, sizes, and materials. In addition to semiconductor wafers, other workpieces on which the present disclosure can be utilized include various articles such as printed circuit boards. The term "semiconductor substrate" or "substrate" as used herein refers to a substrate at any stage of semiconductor device fabrication that includes semiconductor material anywhere within its structure. It is understood that the semiconductor material in the semiconductor substrate need not be exposed. A semiconductor wafer having multiple layers of other materials (e.g., dielectrics) covering the semiconductor material is an example of a semiconductor substrate. The following detailed description assumes that the disclosed embodiments are implemented on a semiconductor wafer such as a 200 mm, 300 mm, or 450 mm semiconductor wafer. However, the disclosed embodiments are not so limited. The workpiece may be of various shapes, sizes, and materials. In addition to semiconductor wafers, other workpieces on which the disclosed embodiments can be utilized include various articles such as printed circuit boards.

[0171] "Silyl" means -SiR 1 R 2 R 3 or -SiR 1 R 2 - group. In some embodiments, R 1, R 2 , and R 3 Each of is independently H, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, an optionally substituted heteroaromatic, or an optionally substituted amino. In certain embodiments, R 1 , R 2 , and R 3 Each of is independently H, an optionally substituted alkyl, an optionally substituted alkoxy, an optionally substituted aryl, an optionally substituted aryloxy, an optionally substituted alkyl-aryl, an optionally substituted aryl-alkyl, or an optionally substituted amino. In other embodiments, the silyl group is -Si(R) a (OR) b (NR2) c where each R is independently H, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, or an optionally substituted heteroaromatic, and each of a, b, and c is ≧0 and a + b + c = 3. In certain embodiments, each R is independently H, an optionally substituted alkyl, an optionally substituted aryl, an optionally substituted alkyl-aryl, or an optionally substituted aryl-alkyl.

[0172] "Silyloxy" means -OR, where R is an optionally substituted silyl group as described herein. In some embodiments, the silyloxy group is -O-SiR 1 R 2 R 3 where R 1 , R 2 , and R 3 Each of is independently H, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, an optionally substituted heteroaromatic, or an optionally substituted amino. In certain embodiments, R 1 , R 2 , and R 3Each of which is 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 wherein each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic, and each of a, b, and c is ≧0 and a + b + c = 3. In certain embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0173] "Substituted" means having one or more substituent moieties whose presence does not interfere with the desired function or reactivity. Examples of substituents are alkyl, alkenyl, alkynyl, cycloalkyl (non-aromatic ring), Si(alkyl)3, Si(alkoxy)3, alkoxy, amino, alkylamino, alkenylamino, amide, amidine, guanidine, hydroxyl, thioether, alkylcarbonyl, alkylcarbonyl-oxy, alkoxycarbonyl-oxy, carbonate, alkoxycarbonyl, aminocarbonyl, alkylthiocarbonyl, phosphoric acid, phosphate ester, phosphonato, cyano, halo, acylamino, imino, sulfhydryl, alkylthio, thiocarboxylate, dithiocarboxylate, sulfate, sulfato, sulfonate, sulfamoyl, sulfonamide, nitro, nitrile, azide, heterocyclyl, ether, ester, silicon-containing moiety, thioester, or combinations thereof. Substituents may themselves be substituted. For example, an amino substituent may be mono-substituted or independently di-substituted by further substituents as defined above such as alkyl, alkenyl, alkynyl, and cycloalkyl (non-aromatic ring).

[0174] "Sulfinyl" means the -S(O)- group.

[0175] "Sulfo" means the -S(O)2OH group.

[0176] "Sulfonyl" or "sulfonate" means the -S(O)2- group or -SO2R, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof as defined herein.

[0177] "Temporally separate pulses" means supplying an amount of gas flow within an amount of time.

[0178] "Thioalkyl" means an alkyl group as defined herein bonded to a parent molecular group through a sulfur atom. Exemplary unsubstituted thioalkyl groups include C 1-6 thioalkyl. In some embodiments, the thioalkyl group is -S-R, where R is an alkyl group as defined herein.

[0179] "Thiol" means the -SH group.

[0180] "Unsubstituted" means any open valence of an atom occupied by hydrogen. Also, when the occupancy of the open valence position on an atom is not specified, it is hydrogen.

[0181] "Vapor phase metal precursor" means a metal precursor that is in the gaseous state at a temperature at which it can exist in both the liquid and solid states.

[0182] One of ordinary skill in the art will recognize that the above definitions are not intended to include unacceptable substitution patterns (e.g., methyl substituted with five different groups, etc.). Such unacceptable substitution patterns will be readily recognized by one of ordinary skill in the art. Any functional group disclosed herein and / or defined above can be substituted or unsubstituted unless otherwise indicated.

[0183] Other features and advantages of the present invention will become apparent from the following description and claims. According to various embodiments, one or more of the following advantages can be achieved by the methods described herein.

[0184] In semiconductor device fabrication, deposition and etching techniques are used to form patterns of materials, such as to form metal lines embedded in a dielectric layer. Some patterning methods utilize conformal deposition of materials, and the deposited layer can follow the contours of the protrusions and / or recessed features on the surface of the substrate. Atomic layer deposition (ALD) is a method of forming a conformal film on a substrate, which uses the adsorption of one or more reactants (precursors) onto the surface of the substrate and subsequent chemical conversion of the adsorbed layer into the desired material. Since ALD uses sequential reactions that occur on the surface of the substrate, are separated in time, and can be limited by the amount of adsorbed reactant, this method can provide a thin conformal layer with excellent step coverage.

[0185] ALD can promote the reaction of deposition precursors using plasma, and as a result, form the desired film. The method using plasma is known as plasma-enhanced ALD (PEALD). The method that does not use plasma is called thermal ALD.

[0186] ALD can be used for the deposition of silicon-containing films such as silicon oxide, silicon nitride, and silicon carbide, but this method is also suitable for the deposition of other materials such as metals.

[0187] In semiconductor fabrication, features such as lines and vias can be filled with conductive materials such as tungsten (W), copper (Cu), and cobalt (Co). As semiconductor devices are scaled down to 10 nm node and below, the contact resistance of lines and vias in metal interconnects increases rapidly. This is due to the decrease in the cross-sectional area through which current flows, the increase in electron scattering, and the increase in challenges in filling narrow features with current Cu or W process schemes in narrow features.

[0188] A low temperature plasma enhanced atomic layer deposition (PEALD) process is provided that includes depositing a metal thin layer by contacting a substrate surface with a metal precursor and a plasma of a remotely generated hydrogen-containing gas source at a temperature below 300°C. In some embodiments, the metal is molybdenum.

[0189] Atomic layer deposition of molybdenum can be achieved by a thermal reaction with H2 gas to remove molybdenum precursor ligands at a temperature of 400°C or higher. However, such high temperature conditions may not be very suitable for back-end-of-line applications due to the sensitivity of previously deposited layers.

[0190] The low temperature conditions of the molybdenum deposition method according to certain disclosed embodiments are suitable for back-end-of-line applications. Further, using a remote plasma in certain situations according to certain disclosed embodiments avoids damage to low-k materials that can occur when using a direct plasma source.

[0191] Copper deposition can be achieved by electroplating. However, electroplating has drawbacks due to requirements for a surface conductive layer that provides the electric field used to deposit copper. Specifically, in a device structure with an opening of 50 nm to be filled, up to 30 nm may be occupied by a conductive liner required to disperse the electric field, severely limiting the filling width of the low resistivity copper metal. Copper scaling is limited by the fact that the resistivity increases rapidly when the line width decreases to less than 10 - 20 nm. Morphology is another factor that must be considered with respect to the copper deposition process. As the film approaches the limit of a few atomic monolayers, a rough, discontinuous, and island-like morphology may result in the deposition of a copper film by atomic layer deposition. The copper thin films deposited according to certain disclosed embodiments result in a smoother morphology or a lower resistivity, or both a smoother morphology and a lower resistivity.

[0192] Figure 1 schematically illustrates a non-limiting process for ultra-thin film metal deposition. Examples of applications include middle-of-line (MOL) or back-end-of-line (BEOL) interconnects. In one example, this method can be used for source / drain contact filling. Process 100 begins with providing a substrate that includes a surface and / or features on which the metal is to be deposited. The substrate may be provided to a semiconductor processing tool.

[0193] The substrate may be a silicon wafer, such as a 200 mm wafer, a 300 mm wafer, or a 450 mm wafer, having one or more layers of material, such as a dielectric material, a conductive material, or a semiconductive material, deposited thereon. In various embodiments, the substrate is patterned. The patterned substrate may have "features" such as pillars, poles, trenches, vias, or contact holes, which can be characterized by one or more of narrow and / or re-entrant openings, constrictions within the features, and high aspect ratios. The features may be formed in one or more of the aforementioned layers. An example of a feature is a pillar or pole in a semiconductor substrate or a layer on the substrate. Another example is a trench in the substrate or layer.

[0194] In some embodiments, features such as pillars can have an aspect ratio of at least about 1:1, at least about 2:1, at least about 4:1, at least about 6:1, at least about 10:1, or more. The features may also have dimensions near the opening, e.g., an opening diameter or line width of about 10 nm to 500 nm, e.g., about 25 nm to about 300 nm. The disclosed methods can be implemented on substrates with features having openings less than about 150 nm. Vias, trenches, or other recessed features may be referred to as unfilled features or features. According to various embodiments, the feature profile may gradually narrow and / or include an overhang at the feature opening. A reentrant profile is a profile that narrows from the bottom, closed end, or interior of the feature to the feature opening. A reentrant profile can be generated by overhangs due to non-conformal film step coverage in previous film depositions, such as asymmetric etching kinetics during patterning and / or deposition of a diffusion barrier. In various examples, the feature may have a smaller width at the opening of the upper part of the feature than at the width of the bottom of the feature.

[0195] The feature may be a trench or via formed in a dielectric layer. Examples of dielectric materials include oxides such as silicon dioxide (SiO2) and aluminum oxide (Al2O3), nitrides such as silicon nitride (SiN), carbides such as nitrogen-doped silicon carbide (NDC) and oxygen-doped silicon carbide (ODC), and low-k dielectrics such as carbon-doped SiO2. It is possible to deposit a metal on the feature and make electrical contact with the underlying layer. Examples of underlying layers include metals, metal silicides, and semiconductors. Examples of metals include Co, Ru, copper (Cu), W, Mo, nickel (Ni), iridium (Ir), rhodium (Rh), tantalum (Ta), and titanium (Ti). Examples of metal silicides include TiSi x , nickel silicide (NiSi x ), molybdenum silicide (MoSi x ), cobalt silicide (CoSix ) Platinum silicide (PtSi x ) Ruthenium silicide (RuSi x ) and nickel platinum silicide (NiPt y Si x ) may be mentioned. Examples of semiconductors include silicon (Si), silicon germanium (SiGe), and gallium arsenide (GaAs) with or without semiconductor dopants such as carbon (C), arsenic (As), boron (B), phosphorus (P), tin (Sn), and antimony (Sb).

[0196] Features generally have side wall surfaces and bottom surfaces. In some embodiments, the side wall surface may be of the same material as the bottom surface. For example, in some embodiments, the side wall surface and the bottom surface are titanium nitride (TiN). In some embodiments, the side wall surface may be of a material different from that of the bottom surface. For example, the bottom surface may be a metal silicide, and the side wall surface may be silicon oxide such as SiO2.

[0197] The substrate provided in the chamber may have a liner layer deposited on the features on the substrate. The exposed surface of the substrate may include the liner material. Before metal deposition, the liner layer may line the unfilled features and form the side wall surface and / or the bottom surface. In some embodiments, the liner layer lines the entire feature and forms the side wall surface and the bottom surface. In some other embodiments, the liner layer lines only a part of the feature. For example, a TiN layer lines the side wall and the bottom surface is not lined. Examples of materials for the liner layer include metal nitrides (e.g., TiN or tantalum nitride (TaN) barrier layer) and metals (e.g., Ti adhesion layer).

[0198] Atomic layer deposition (ALD) is a technique for depositing thin layers of materials using sequential self-limiting reactions. The ALD process uses surface-mediated deposition reactions to deposit films layer by layer in cycles. As an example, an ALD cycle can include the following operations: (i) supply / adsorption of a precursor, (ii) purge of the precursor from the chamber, (iii) supply of a second reactant and optionally ignition of a plasma, and (iv) purge of by-products from the chamber. The reaction between the adsorbed precursor and the second reactant to form a film on the surface of the substrate affects the composition and properties of the film, such as non-uniformity, stress, wet etching rate, dry etching rate, electrical properties (e.g., breakdown voltage and leakage current), etc. In the ALD deposition of metal films, this reaction involves reacting an oxygen plasma with carbon and nitrogen to form gaseous species, oxidizing the metal to a metal oxide, eliminating trace impurities of carbon, nitrogen, and hydrogen, and enhancing the bonding and densification of the film.

[0199] Unlike chemical vapor deposition (CVD) techniques, the ALD process deposits a film layer by layer using surface-mediated deposition reactions. In one example of an ALD process, a substrate surface containing a collection of surface active sites is exposed to the gas-phase distribution of a first precursor, such as a metal-containing precursor, in a dosage provided to a chamber containing the substrate. The molecules of this first precursor are adsorbed onto the substrate surface. It should be understood that when a compound is adsorbed onto the substrate surface as described herein, the adsorbed layer may include the compound as well as derivatives of the compound. For example, the adsorbed layer of a metal-containing precursor can include the metal-containing precursor as well as derivatives of the metal-containing precursor. After the dosing of the first precursor, the chamber is evacuated to remove most or all of the first precursor remaining in the gas phase, thereby leaving mostly or only the adsorbed species. In some embodiments, the chamber may not be completely evacuated. For example, it is possible to evacuate the reactor such that the partial pressure of the first precursor in the gas phase is low enough to moderate the reaction. A second reactant, such as an oxygen-containing gas, is introduced into the chamber, whereby some of these molecules react with the first precursor adsorbed on the surface. In some processes, the second precursor reacts immediately with the adsorbed first precursor. In other embodiments, the second reactant reacts only after an activation source has been temporarily applied. The chamber can then be evacuated again to remove unreacted second reactant molecules. As described above, in some embodiments, the chamber may not need to be completely evacuated. Additional ALD cycles can be used to build up the film thickness.

[0200] In some embodiments, the ALD process includes plasma activation. As described herein, the ALD processes and apparatuses described herein may be conformal film deposition (CFD) processes, which are generally described in U.S. Patent Application No. 13 / 084,399, entitled "PLASMA ACTIVATED CONFORMAL FILM DEPOSITION," filed Apr. 11, 2011 (currently U.S. Patent No. 8,728,956), and U.S. Patent Application No. 13 / 084,305, entitled "SILICON NITRIDE FILMS AND METHODS," filed Apr. 11, 2011, the disclosures of which are incorporated herein by reference in their entirety.

[0201] When a substrate is provided, in process 100, a metal is deposited on the features and / or the substrate surface. Metals that can be deposited include vanadium, niobium, tantalum, chromium, cobalt, tungsten, iron, ruthenium, nickel, zinc, copper, or molybdenum. The metal can include less than about 5% of other elements, such as less than about 1% of other elements, with hydrogen not included in the calculation. In some embodiments, the metal deposited by the provided method includes at least a portion that is at least about 90%, such as at least about 95%, or at least about 99% pure metal, where % refers to weight percent.

[0202] The metal may be deposited by plasma enhanced atomic layer deposition (PEALD). PEALD is a surface-mediated deposition technique in which precursor and reactant doses (a reducing gas in plasma form) are sequentially introduced into the deposition chamber. In some embodiments, the gas is pure hydrogen, hydrogen mixed with inert argon or helium. In some embodiments, a small amount of oxygen may also be added. The total flow rate depends on the geometry and size of the chamber. The amount of hydrogen can range from about 100% when pure hydrogen is used to about 5% hydrogen when mixed with an inert gas. In the case of PEALD, the temperature of the substrate and the pressure of the chamber can be controlled. In some embodiments, the substrate may be heated to a temperature of about 300 °C or less, for example, about 300 °C to about 50 °C. In some embodiments, the chamber can be pressurized to less than about 10 Torr. In some embodiments, the chamber pressure may range from about 0.1 to about 9.9 Torr. In some embodiments, the duration of exposure is from about 5 seconds or 10 seconds to about 2 minutes.

[0203] In operation 102, the substrate surface is exposed to a metal precursor. In some embodiments, the metal precursor may be, inter alia, a molybdenum precursor, a copper precursor, a tungsten precursor, a cobalt precursor, or a ruthenium precursor. Exemplary metal precursors are described in the following paragraphs.

[0204] Copper precursor Copper metal can be deposited using various copper precursors, and copper can be in the +1 or +2 oxidation state. The precursor may be a cuprous (copper(I)) compound such as acetylacetonate, ketoimine, diimine, cyclopentadienyl compound, amidinate, guanidinate, or amide, or a cupric (copper(II)) compound such as acetylacetonate, ketominate, or aminoalkoxide, as shown in FIGS. 2 and 3. In some embodiments, the precursor is a coordination complex and copper coordinates to a multiple bond such as a double or triple bond or to the oxygen of a carbonyl group.

[0205] Examples of copper precursors include Cu(acac)2 (acac = acetylacetonate), Cu(thd)2 (thd = tetrahydrodionato), hexafluoroacetylacetonate - copper - trimethylsilane, CpCu(CNMe), CpCu(CNCMe3), CpCuCO, CPCuPR3 (R = Me, Et, or Ph), and cyclopentadienyl (Cp) compounds such as CpCu(CSiMe3)2, MeCu(PPh3)3, CuMe, CuCCH (ethynyl copper), CuCMe3 (methylacetylide copper), (H2C = CMeCC)Cu (3 - methyl - 3 - buten - 1 - ynyl copper), CuCCPh, C6H5Cu (phenyl copper), (Me)3CCCCu (3,3 - dimethyl - 1 - butynyl) copper, Me3SiCCCH2Cu, and other alkyl or aryl compounds, as well as CuCN, n (OAc = acetate), Cu2Cl2(butadiene), C7H7CuO (2 - methoxyphenyl copper), (MeCN)4CuX (X is a halide, alkyl, amine, or phenyl group), Me3SiOCu(PMe3)3, Cu(C4H4S), and other compounds such as Cu carbene compounds derived from imidazolium.

[0206] Molybdenum - containing precursors Generally, molybdenum - containing precursors can include molybdenum in a wide range of oxidation states from 0 to +6. In some embodiments, the molybdenum compound has molybdenum in lower oxidation states of +3, +4, and +5. The provided method is particularly useful for depositing molybdenum - containing materials from halogen - containing molybdenum - containing compounds because the silicon - containing reactant can assist in the removal of halogens, but halogen - free molybdenum - containing precursors can also be used. Suitable molybdenum - containing precursors include molybdenum halides and oxyhalides of molybdenum, such as fluorides, chlorides, bromides, oxyfluorides, oxychlorides, and oxybromides, where molybdenum can be in any oxidation state from +2 to +6.

[0207] Molybdenum chloride precursors have the formula MoCl xrepresented by, where x is 2, 3, 4, 5, or 6, and includes molybdenum dichloride (MoCl2), molybdenum trichloride (MoCl3), molybdenum tetrachloride (MoCl4), molybdenum pentachloride (MoCl5), and molybdenum hexachloride (MoCl6). In some embodiments, MoCl5 or MoCl6 is used. The description mainly refers to MoCl x precursor, but in other embodiments, other molybdenum halide precursors may be used. The molybdenum halide precursor is of the formula MoX z represented by, where X is a halogen (fluorine (F), chlorine (Cl), bromine (Br), or iodine (I)), and z is 2, 3, 4, 5, or 6. MoX z Examples of precursors include molybdenum hexafluoride (MoF6). In some embodiments, a non-fluorine-containing MoX z precursor is used to prevent fluorine etching or incorporation. In some embodiments, a non-bromine-containing and / or non-iodine-containing MoX z precursor is used to prevent etching or bromine or iodine incorporation.

[0208] The molybdenum oxyhalide precursor is of the formula MoO y X z represented by, where X is a halogen (fluorine (F), chlorine (Cl), bromine (Br), or iodine (I)), and y and z are numbers greater than 0, whereby MoO y X z forms a stable compound. Examples of molybdenum oxyhalides include molybdenum dioxide dichloride (MoO2Cl2), molybdenum oxychloride (MoOCl4), molybdenum oxyfluoride (MoOF4), molybdenum dioxide dibromide (MoO2Br2), and molybdenum oxyiodide MoO2I, and Mo4O 11 I.

[0209] In some embodiments described herein, the precursor has a molecular weight of less than about 450 g / mol, for example less than about 400 g / mol.

[0210] In some embodiments, the molybdenum-containing precursor has the formula MoX n Y m wherein X is a chalcogen (e.g., oxygen or sulfur), Y is a halogen (fluorine, chlorine, bromine, or iodine), n is 0, 1, or 2, and m is 2, 3, 4, 5, or 6. Examples of halogen-containing molybdenum-containing precursors include, but are not limited to, MoCl5, Mo2Cl 10 , MoO2Cl2, and MoOCl4. Another example of a halogen-containing molybdenum-containing precursor is MoF6.

[0211] In some embodiments, the molybdenum-containing precursor includes a carbonyl ligand. One example of a carbonyl-containing precursor is Mo(CO)6.

[0212] In some embodiments, the process includes depositing a thin protective Mo layer using a molybdenum chloride (MoCl x ) precursor. Mo deposition may then be performed to fill features using a molybdenum oxyhalide (MoO y X z ) precursor. The protective Mo layer allows Mo to be filled using the MoO y X z precursor without oxidizing the underlying surface. This can be useful for oxygen-sensitive surfaces such as silicon (Si), silicon germanium (SiGe), titanium (Ti), titanium nitride (TiN), and titanium silicide (TiSi2). A cleaning and etching process is also provided in which the MoCl x precursor is used to remove oxides from the underlying surface prior to deposition. Subsequent deposition using the MoCl x precursor can result in the formation of a liner layer and / or filling of features. The protective Mo layer protects the bottom surface of the feature. In some embodiments, the protective Mo layer is selectively deposited on the bottom surface with little or no deposition on the feature sidewalls. In some embodiments, the protective Mo layer is non-selectively deposited on the bottom and sidewall surfaces.

[0213] Halide-containing heteroleptic molybdenum compound In one aspect, the halide-containing heteroleptic molybdenum compound is used as a precursor for the deposition of a molybdenum-containing film, such as the deposition of molybdenum metal. In one embodiment, the precursor is a compound comprising molybdenum, at least one halide that forms a bond with molybdenum, and at least one organic ligand having any of the N, O, and S elements, and atoms of any of these elements form a bond with molybdenum. Examples of suitable organic ligands that provide a nitrogen bond or an oxygen bond include amidinate, amidate, iminopyrrolidinate, diazadiene, beta-iminoamide, alpha-iminoalkoxide, beta-aminoalkoxide, beta-diketiminate, beta-ketoiminate, beta-diketonate, amine, and pyrazolate. Examples of suitable organic ligands that provide a sulfur bond include thioether, thiolate, dithiolene, dithiolate, and alpha-iminothiolene. These ligands can be substituted or unsubstituted. In some embodiments, these ligands include one or more substituents independently selected from the group consisting of H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy substituents. The organic ligand can be neutral or anionic (e.g., monoanionic or dianionic), and molybdenum can be in various oxidation states such as +1, +2, +3, +4, +5, and +6.

[0214] The structures of exemplary suitable N and / or O-containing organic ligands 1 to 17 are shown in FIG. 4, and the structures of exemplary suitable S-containing organic ligands 18 to 25 are shown in FIG. 5. Each R is independently selected from H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy. In some embodiments, each R is independently selected from H, alkyl, and fluoroalkyl. In some embodiments, each R is independently selected from H, methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, and cyclobutylethyl. In some embodiments, each R is an independently selected alkyl. In some embodiments, ligands having branched alkyl substituents such as isopropyl and isobutyl are preferred because such ligands provide more volatile molybdenum precursors.

[0215] In some embodiments, at least one organic ligand in the precursor is an amine. Suitable amines include monodentate amines (e.g., monoalkylamines, dialkylamines), bidentate amines (e.g., unsubstituted or N-alkyl-substituted ethylenediamines), and higher-order amines (e.g., substituted or unsubstituted diethylenetriamine). An example of a monodentate amine is Amine 1 shown in FIG. 4, where at least one R is alkyl or fluoroalkyl, and each R is independently selected from the group consisting of H, alkyl, and fluoroalkyl. In some embodiments, at least one R is alkyl, and each R is independently selected from H and alkyl. In some embodiments, at least one organic ligand is an amide such as monoanionic amide 16, where at least one R is alkyl or fluoroalkyl, and each R is independently selected from the group consisting of H, alkyl, and fluoroalkyl. In some embodiments, at least one organic ligand is an imide such as dianionic imide 17, where R is alkyl or fluoroalkyl. In general, imide-containing precursors can be used for the deposition of various molybdenum-containing films (including molybdenum metal), but in some embodiments, imide-containing precursors are more preferred for the deposition of molybdenum nitride and molybdenum carbonitride because they can form strong molybdenum-nitrogen bonds and serve as a nitrogen source for the resulting film. In some embodiments, at least one organic ligand in the precursor is an amidinate. An example of an amidinate is Amidinate 2 shown in FIG. 4, where each R is independently selected from the group consisting of H, alkyl, and fluoroalkyl. Amidinate 2 is a monoanionic ligand that can form two molybdenum-nitrogen bonds and serves as a bidentate ligand.

[0216] In some embodiments, at least one organic ligand in the precursor is an amidate. An example of an amidate is amidate 3 shown in FIG. 4, where each R is independently selected from H, alkyl, and fluoroalkyl. Amidate 3 is a monoanionic ligand that can form one molybdenum-nitrogen bond and one molybdenum-oxygen bond and serves as a bidentate ligand.

[0217] In some embodiments, at least one organic ligand in the precursor is a diazadiene. Examples of diazadienes are 1,4-diazabuta-1,3-dienes (DAD) 5, 6, and 7, where each R is independently selected from H, alkyl, and fluoroalkyl. An interesting property of this ligand is that it can exist in the neutral form 5, the monoanionic radical form 6, and the dianionic form 7. Due to the redox activity of the monoanionic (radical) form 6, this ligand can be relatively easily removed during deposition and forms complexes of DAD 6 that are particularly useful for the deposition of molybdenum metal and high-purity molybdenum metal. The DAD ligands 5, 6, and 7 can each serve as a bidentate ligand that forms two molybdenum-nitrogen bonds. In some embodiments, the molybdenum precursor contains a DAD ligand 5, 6, or 7 as an organic ligand, and each R is independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and t-butyl.

[0218] In some embodiments, at least one organic precursor is an iminopyrrolidinate (such as iminopyrrolidinate 4, where each R is independently selected from H, alkyl, and fluoroalkyl), a beta-iminoamide (such as beta-iminoamide 8, where each R is independently selected from H, alkyl, and fluoroalkyl), an alpha-iminoalkoxide (such as alpha-iminoalkoxide 9, where each R is independently selected from H, alkyl, and fluoroalkyl), a beta-diketonimate (such as beta-diketonimate 10, where each R is independently selected from H, alkyl, and fluoroalkyl), a beta-ketoiminato (such as beta-ketoiminato 11, where each R is independently selected from H, alkyl, and fluoroalkyl), a beta-diketonate 12 (such as beta-diketonate 12, where each R is independently selected from H, alkyl, and fluoroalkyl), a pyrazolate (such as pyrazolate 13, where each R is independently selected from H, alkyl, and fluoroalkyl), a beta-aminoalkoxide (such as beta-aminoalkoxide 14, where each R is independently selected from H, alkyl, and fluoroalkyl), or a guanidinidate 15 (such as guanidinidate 15, where each R is independently selected from H, alkyl, and fluoroalkyl). These are monoanionic ligands capable of binding to molybdenum in a bidentate manner.

[0219] In some embodiments, at least one organic precursor is a sulfur-containing ligand capable of forming a molybdenum-sulfur bond. In some embodiments, at least one organic ligand in the precursor is a thioether. The term "thioether" is used herein broadly to include both monodentate thioethers and polydentate (e.g., bidentate or tridentate) thioethers, as well as ligands containing both a thioether moiety and a thiolate (or other) moiety. An example of a monodentate thioether is a dialkyl sulfide R2S, where each R is an alkyl such as dimethyl sulfide, diethyl sulfide, diisobutyl sulfide. An example of a polydentate thioether ligand containing a thiolate moiety is (SCH2CH2SCH2CH2S) 2-An example of a monodentate thioether is thioether 18 shown in FIG. 5, where each R is independently selected from the group consisting of alkyl and fluoroalkyl. In some embodiments, each R is independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and t-butyl. In some embodiments, at least one organic ligand is a thiolate such as monoanionic thiolate 19, and R is alkyl or fluoroalkyl. For example, R can be methyl, ethyl, n-propyl, isolopropyl, n-butyl, sec-butyl, isobutyl, or t-butyl. In some embodiments, the thiolate is a dithiolate, such as dianionic alpha-dithiolate 24 (each R is independently selected from H, alkyl, and fluoroalkyl) or dianionic beta-dithiolate 25 (each R is independently selected from H, alkyl, and fluoroalkyl). The dithiolate is capable of forming two molybdenum-sulfur bonds with molybdenum.

[0220] In some embodiments, at least one organic ligand in the precursor is a dithiolene. Examples of dithiolene are structures 20, 21, and 22, where each R is independently selected from H, alkyl, and fluoroalkyl. This ligand (similar to DAD) can exist in a neutral form 20, a monoanionic radical form 21, and a dianionic form 22. Due to the redox activity of the monoanionic radical form 21, this ligand can be relatively easily removed during the deposition and reduction of the molybdenum precursor, forming complexes of dithiolene 21 that are particularly useful for the deposition of molybdenum metal and high-purity molybdenum metal. The dithiolene ligands 20, 21, and 22 can each serve as a bidentate ligand capable of forming two molybdenum-sulfur bonds. In some embodiments, the molybdenum precursor includes a dithiolene ligand 20, 21, and / or 22 as an organic ligand, and each R is independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and t-butyl.

[0221] In some embodiments, at least one organic ligand in the precursor is an alpha-iminothiolene such as structure 23, and each R is independently selected from H, alkyl, and fluoroalkyl. In some embodiments, each R substituent at the carbon atom is independently selected from H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy substituents, and the R substituent at nitrogen is independently selected from alkyl and fluoroalkyl. In some embodiments, the R substituent at nitrogen is independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and t-butyl. This ligand (similar to DAD and dithiolene) has a monoanionic radical form as shown in structure 23, is redox active, and can be easily removed during the reduction process.

[0222] In some embodiments, the precursor is a compound having the formula Mo(X) m (L) n where m is selected from 1 to 4, n is selected from 1 to 3, each X is a halide independently selected from F, Cl, Br, and I, and each L is an organic ligand as described above, for example, amidinate, amidate, iminopyrrolidinate, diazadiene, beta-iminoamide, alpha-iminoalkoxide, beta-aminoalkoxide, beta-diketiminate, beta-ketoiminate, beta-diketonate, amine, and pyrazolate, thioether, thiolate, dithiolene, dithiolate, and α-iminothiolene. In some embodiments, for the specified ligand, each R is independently selected from H, alkyl, and fluoroalkyl.

[0223] In some embodiments, L is a bidentate ligand. Examples of suitable molybdenum-containing precursors of the formula Mo(L)Cl4 that utilize bidentate ligands are shown in Figure 6. These are Mo(V) compounds and include amidinate molybdenum complex 27, DAD complex 28, beta-diketiminate complex 29, pyrazolate complex 30, amidate complex 31, beta-iminoamide complex 32, beta-ketoiminate complex 33, beta-aminoalkoxide complex 34, iminopyrrolidinate complex 35, alpha-iminoalkoxide complex 36, and beta-diketonate complex 37.

[0224] The heteroleptic complexes having molybdenum-halide bonds and organic ligands described herein can be synthesized using the reaction of a molybdenum halide starting material with a compound containing an organic ligand in neutral or anionic form. For example, a molybdenum(V) precursor can be prepared using MoCl5 as the starting material. A Mo(III) precursor can be prepared using MoX3(THF)3 as the starting material, where X is selected from chloride, bromide, and iodide, and THF is tetrahydrofuran. The starting material is treated with a ligand in neutral or anionic form (e.g., a salt such as a lithium salt or a sodium salt) to form the heteroleptic complexes described herein.

[0225] The heteroleptic molybdenum compounds containing molybdenum-halide bonds and organic ligands described herein can advantageously provide high-purity molybdenum metal in the CVD-type and ALD-type deposition methods provided herein. Further, the use of these compounds may be accompanied by a reduction in etching of the substrate material compared to conventional homoleptic molybdenum halides. These advantages are described for illustrative purposes and are not intended to limit the use of these compounds to only the deposition on substrates sensitive to the deposition or etching of molybdenum metal.

[0226] In some embodiments, when deposition is performed on a fluorine-sensitive material (e.g., a silicon-containing material), the precursor is selected to be fluorine-free and includes, for example, any of Cl, Br, and I as the halide in the complex. Further, in these embodiments, the use of compounds having fluoroalkyl substituents can be avoided.

[0227] Sulfur-containing molybdenum compound In one aspect, the sulfur-containing molybdenum compound is used as a molybdenum-containing precursor for the deposition of molybdenum-containing films, such as the deposition of molybdenum metal and molybdenum silicide. In some embodiments, the molybdenum compound includes molybdenum and at least one sulfur-containing ligand that provides a molybdenum-sulfur bond. Using a molybdenum precursor based on a sulfur-containing ligand, it is possible to deposit a substantially impurity-free molybdenum-containing film because sulfur impurities can be more easily removed compared to oxygen, carbon, and nitrogen impurities. In some embodiments, the molybdenum compound does not include a molybdenum-carbon bond and / or does not include a molybdenum-oxygen double bond.

[0228] In some embodiments, the molybdenum compound does not include a molybdenum-nitrogen double bond. In some embodiments, in the provided molybdenum precursor, molybdenum forms bonds only with sulfur atoms.

[0229] Examples of suitable sulfur-containing ligands that provide a sulfur bond include thioether, thiolate, dithiolene, dithiolate, thiocarbamate, and α-iminothiolene. The ligand can include one or more substituents independently selected from the group consisting of H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy substituents. The ligand can be neutral or anionic (e.g., monoanionic or dianionic), and molybdenum can be in various oxidation states such as 0, +1, +2, +3, +4, +5, 10, and +6.

[0230] In some embodiments, the sulfur-containing ligand is ligands 18-25 shown in FIG. 5, and the R substituents are as described above. Examples of suitable molybdenum precursors include molybdenum thiolates Mo(SR)4, where R is alkyl, such as methyl, ethyl, propyl, butyl. In one specific example, the precursor is tetrakis(tert-butylthiolato)molybdenum(IV): Mo(SR)4, where R is t-butyl. Another example of a suitable molybdenum precursor is a molybdenum thiocarbamate such as tetrakis(diethyldithiocarbamato)molybdenum(IV):

Chemical formula

[0231] In some embodiments, dithiolene complexes of molybdenum are provided, where the dithiolene may be in any of the neutral form 20, anion-radical form 21, and dianionic form 22, and each R is independently H, alkyl, or fluoroalkyl.

[0232] The dithiolene complexes are redox-active and can support molybdenum in various oxidation states. The redox reactions of the dithiolene ligands 20, 21, and 22 are shown in Equation 1:

Chemical formula

[0233] In one embodiment, the precursor is Mo(21)3, and each R in 21 is independently selected from H, alkyl, and fluoroalkyl. For example, R may be methyl, ethyl, CF3, etc. This is a homoleptic Mo(III) compound containing only molybdenum-sulfur bonds.

[0234] In some embodiments, the ligand can provide a nitrogen bond in addition to the sulfur bond. An example of such a ligand is alpha-iminothiolene 23, a redox-active radical anion ligand that can exhibit behavior similar to thiophene.

[0235] In some embodiments, the precursor is the Mo(III) compound Mo(23)3, and each R in the 10 compound 23 is independently selected from H, alkyl, and fluoroalkyl.

[0236] In some embodiments, the precursor is MoL n is a compound, n is from 2 to 6, and L is a sulfur-containing ligand, such as any of the sulfur-containing ligands described herein. In some embodiments, each L is the same sulfur-containing ligand. In other embodiments, the precursor may include different sulfur-containing ligands L. Examples of precursors include Mo(19)2, Mo(19)3, Mo(19)4, Mo(19)5, Mo(19)6, Mo(19)2(18)2, Mo(19)3(18), Mo(19)4(18)2, Mo(21)3, Mo(20)(21)2, Mo(22)3, Mo(21)(22)2, Mo(20)(22)2, Mo(23)3, Mo(24)3, Mo(25)3. The sulfur-containing molybdenum compounds described herein can be synthesized using the reaction of a molybdenum halide starting material with a compound containing an organic sulfur-containing ligand in neutral or anionic form. For example, a molybdenum(V) precursor can be prepared using MoCl5 as the starting material. Mo(III) or Mo(IV) precursors can be prepared using the corresponding halide or MoX3(L)3 or MoX4(L)2 as the starting material, where X is selected from chloride, bromide, and iodide, and L is a neutral Lewis base such as tetrahydrofuran or diethyl ether. The starting material can be treated with the desired sulfur-containing ligand in neutral or anionic form (e.g., a salt such as a lithium salt or a sodium salt) to form the sulfur-containing complex described herein.

[0237] In one example, a Mo(IV) thiolate complex is prepared by reacting molybdenum tetrachloride with lithium thiolate. For example, MoCl4 can be reacted with t-BuSLi in a 1,2-dimethoxytane solvent to form the Mo(t-BuS)4 compound.

[0238] The α-imino thiole ligand can be prepared from the corresponding α-imino ketone by thionation using a suitable reagent such as Lawesson's reagent. The radical anionic form of the α-imino thiole can subsequently be prepared by treatment with an alkali metal such as lithium. The resulting ligand and ligand salt can be reacted with molybdenum halide to form an α-imino thiole-containing molybdenum compound.

[0239] The molybdenum complex can also be prepared using a compound in which molybdenum is in the zero oxidation state, such as molybdenum hexacarbonyl. The starting material can be treated with a neutral ligand such as a thioether (dialkyl sulfide) to induce a redox-neutral ligand exchange. The zero-valent starting material can also be treated with a ligand precursor such as bis(diethylthiocarbamoyl) disulfide or bis(trifluoromethyl)-1,2-dithiete to induce oxidative addition and form the sulfur-containing complexes described herein.

[0240] The reaction can be carried out in various aprotic solvents. For example, the reaction can be carried out in an ether solvent such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, methyl-tert-butyl ether, 1,2-dimethoxyethane, in a hydrocarbon solvent such as toluene, benzene, heptane, hexane, pentane, or in a halocarbon solvent such as chlorobenzene, dichlorobenzene, fluorobenzene, difluorobenzene, dichloromethane, chloroform. The reaction can be carried out over a wide temperature range depending on the boiling point of the solvent and the solubility of the product. In some embodiments, the starting materials, reaction intermediates, and desired products are unstable to moisture and oxygen. Therefore, the reaction process is

Chemical formula

[0241] 1,4-diazabutadiene (DAD)-containing precursor In another aspect, a DAD-containing molybdenum-containing precursor is provided. DAD can bind to molybdenum in its neutral form 5, its radical-anionic form 6, and its dianionic form 7. In some embodiments, a homoleptic DAD complex of the formula Mo(DAD)m is provided, where m is from 1 to 3, and each DAD is independently selected from neutral DAD 5, radical-anionic DAD 6, and dianionic DAD 7. The oxidation state of molybdenum in these complexes can range from 0 to +6. Non-limiting examples of suitable homoleptic DAD complexes include the tris-DAD Mo(III) precursor Mo(6)3, the bis-DAD Mo(IV) precursor Mo(7)2, the bis-DAD Mo(III) precursor Mo(6)(7), and the bis-DAD Mo(II) precursor Mo(6)2.

[0242] In some embodiments, the homoleptic DAD complex is prepared using a reaction between molybdenum halide and a source of DAD ligand of the required electronic configuration. For example, the tris-DAD Mo(III) precursor Mo(6)3 can be synthesized by reacting MoCl3 with 3 equivalents of the radical anion form of the DAD ligand, which can be prepared from the neutral form of the DAD ligand by treatment with an alkali metal such as lithium in a solvent such as THF, as shown in Equation 2.

[0243] In some embodiments, a heteroleptic DAD-containing molybdenum compound is provided. In some embodiments, the precursor comprises molybdenum, at least one DAD ligand bonded to the molybdenum, and at least one second ligand, where DAD may be neutral DAD6, radical anionic DAD7, or dianionic DAD8, and the second ligand is independently selected from anionic ligands and neutral ligands. In some embodiments, the precursor does not include a CO ligand as the only second ligand. In some embodiments, the precursor is Mo(DAD) m (L) n (X) p where L is a neutral Lewis base ligand, each L is independently selected from CO, amine, phosphine, thioether, nitrile, and isonitrile, X is an anionic ligand, each X is independently selected from halide, alkyl, allyl, and cyclopentadienyl, m is from 1 to 3, n is from 0 to 4, and p is from 0 to 4. Nitrile is an RCN compound where R is alkyl. Isonitrile is an RNC compound where R is alkyl. Other suitable anionic ligands include alkoxides, amides, imides, and any other anionic ligand containing a donor atom selected from C, N, O, B, S, Si, Al, and P.

[0244] Examples of heteroleptic DAD-containing precursors include, but are not limited to, Mo(7)2(RCN)Cl, Mo(7)2(RNC)Cl, Mo(8)(CO)3, Mo(6)(13)Cl, Mo(6)(18)Cl2, Mo(6)2Cl, Mo(6)2(14), Mo(6)2(19), Mo(6)2(24).

[0245] Heteroleptic DAD-containing precursors can be prepared by a continuous salt metathesis reaction in one pot or using multiple steps. Molybdenum halide starting materials such as Mo(V), Mo(IV), or Mo(III) halides can be treated with an anionic form of the DAD ligand or other anionic ligands. Neutral Lewis base ligands can be exchanged using heat treatment or photoexcitation.

[0246] Heteroleptic DAD-containing precursors can also be prepared using zerovalent molybdenum starting materials such as molybdenum hexacarbonyl that can undergo oxidative addition with a redox-active ligand such as the DAD ligand.

[0247] In some embodiments, precursors containing the radical anionic DAD ligand 8 are particularly preferred for the deposition of molybdenum metal and high-purity molybdenum metal. In the radical anionic form 7, the DAD ligand is thought to electronically bond to the empty molybdenum d orbitals and serve as an electron source to reduce the molybdenum ion to the zerovalent metal state. After electron transfer from the ligand to the metal, the volatile neutral DAD ligand 6 can be purged from the molybdenum metal growth surface. Since the DAD ligand can be removed from the growth surface as is, the incorporation of impurity elements such as C and N is reduced when using DAD precursors compared to other organometallic precursors. Therefore, molybdenum precursors containing the radical anionic DAD ligand can be used to deposit high-purity molybdenum metal at low temperatures.

[0248] Dimolybdenum precursor In another aspect, the precursor for the deposition of a molybdenum-containing film is a dimolybdenum compound containing a molybdenum-molybdenum bond (e.g., a multiple molybdenum-molybdenum bond such as a double bond, or any multiple bond with a bond order of 2 to 5). Such precursors are particularly useful for the deposition of molybdenum metal and high-purity molybdenum metal because they are more easily reduced to such compounds to metallic molybdenum than many mononuclear molybdenum compounds.

[0249] In some embodiments, a precursor for the deposition of a molybdenum-containing film is provided, the precursor being Mo2L n wherein each L is independently selected from amidate, amidinidate, and guanidinidate ligands, n is from 2 to 5, and the precursor contains multiple molybdenum-molybdenum bonds. In some embodiments, each L is independently selected from 2 amidinidate ligands, 3 amidate ligands, and 15 guanidinidate ligands, and each R in the amidine, amidate, and guanidine is independently selected from H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy substituents. In some embodiments, each R is independently selected from H, alkyl, and fluoroalkyl. In some embodiments, each L is an amidinidate and the precursor has the formula Mo2(L)3 or Mo2(L)4. In some embodiments, each L is an amidinidate and the precursor has the formula Mo2(L)3 or Mo2(L)4. In some embodiments, each L is a guanidinidate and the precursor has the formula Mo2(L)3 or Mo2(L)4. In these complexes, molybdenum has a low oxidation state of 2+ (in Mo2(L)3) and 3+ (in Mo2(L)4), making these complexes particularly suitable for the facile reduction to molybdenum metal.

[0250] One exemplary structure of an amidate paddlewheel di-Mo(II) precursor having a molybdenum-molybdenum quadruple bond is shown by Structure 38: [Chemical formula] In some embodiments, each of R and R' is independently selected from alkyls such as methyl, ethyl, isopropyl, and t-butyl. In some embodiments, 1, 2, 3, or 4 of the amidate ligands in 38 can be replaced by amidinidate or guanidinidate ligands.

[0251] The dimolybdenum precursor described in this specification can be synthesized by using dimolybdenum tetraacetate as a starting material and treating it with a ligand salt such as lithium amido acid.

[0252] Cobalt precursor Cobalt metal can be deposited using various cobalt precursors, and cobalt may be in an oxidation state of +1, +2, or +3. Examples of cobalt precursors include cobalt acetate, cobalt acetylacetonate (e.g., cobalt(III) bis(acetylacetonate)), cobalt amidinate (e.g., bis(N-t-butyl-N'-ethylpropanimidamidato)cobalt(II)), cobaltocene, and carbonyl-containing cobalt precursors (e.g., cobalt tricarbonyl nitrosyl, and cyclopentadienylcobalt dicarbonyl). An example of a halogen-containing cobalt precursor is CoCl2(TMEDA), where TMEDA is N,N,N',N'-tetramethylethylenediamine.

[0253] Ruthenium precursor Ruthenium metal can be deposited using volatile ruthenium precursors such as bis(ethylcyclopentadienyl)ruthenium(II), bis(pentamethylcyclopentadienyl)ruthenium, ruthenocene, and cyclopentadienyl-propylcyclopentadienylruthenium(II).

[0254] Tungsten precursor Tungsten can be deposited using various volatile precursors. In some embodiments, Hal is a halogen (e.g., F, Cl, Br, and / or I), and x is 2 - 6, WHal xHalogen-containing tungsten precursors such as those described above are used. In some embodiments, tungsten chloride is used. Tungsten chlorides include tungsten pentachloride (WCl5), tungsten hexachloride (WCl6), tungsten tetrachloride (WCl4), tungsten dichloride (WCl2), and mixtures thereof. In other examples, tungsten fluoride such as tungsten hexafluoride may be used.

[0255] Additional Precursors In some embodiments, other useful precursors include vanadium-containing precursors such as tetrakis(dimethylamino)vanadium, tris(dimethylamino)cyclopentadienylvanadium, tetrakis(ethylmethylamino)vanadium; niobium-containing precursors such as (tert-butylimido)bis(diethylamino)niobium, (tert-butylimido)bis(dimethylamino)niobium, and (tert-butylimido)bis(ethylmethylamino)niobium; tantalum-containing precursors such as tert-butylimidotris(dimethylamide)tantalum and tantalum pentachloride; iron-containing precursors such as iron(III) tert-butoxide dimer, ferrocene, and iron pentacarbonyl; nickel-containing precursors such as allyl(cyclopentadienyl)nickel(II) and nickel(II) bis(acetylacetonate); zinc-containing precursors such as zinc acetate and diethylzinc; and chromium-containing precursors such as chromium carbonyl and bis(cyclopentadienyl)chromium(II).

[0256] Returning to FIG. 1, prior to operation 102, the substrate may optionally be pretreated with a plasma of a hydrogen-containing gas source. The pretreatment may also optionally include an oxygen-containing gas source. Typically, the process conditions for the pretreatment are similar to those utilized to bring the reactants into contact with the substrate.

[0257] In operation 104, the deposition chamber is optionally purged after the introduction of the metal precursor. The purge gas or carrier gas is selected to not react with the process gas (reactant) and volatile by-products. Gases such as helium, argon, nitrogen, and combinations thereof can be used. In some embodiments, the purge may consist of flowing an inert gas such as argon or helium at a total of 1 to 20 slm or 1 to 40 slm. The purge is performed at a high flow rate depending on the geometry and pressure of the chamber. In some embodiments, the purge gas may contain hydrogen. The purge pressure may be selected to maintain an isobaric process flow, for example, maintaining all of dose / purge / plasma / purge at one pressure. In one embodiment, the pressure is about 1 to about 1.5 Torr, but may be extended up to about 10 Torr or more. The purge time is about 1 second to about 20 seconds. During operation, the wafer temperature is kept constant.

[0258] In operation 106, the surface of the substrate is exposed to the plasma of a hydrogen-containing gas source (reactant). The pretreatment step 102 may have conditions similar to operation 106, but is typically much longer. Alternatively, the pretreatment step 102 may be different from operation 106 depending on the incoming substrate and what is being cleaned from the substrate in step 102.

[0259] The direct plasma conditions sometimes used in PEALD are frequencies with low energy to decompose precursor molecules and may generate a large amount of ion bombardment on the surface, which may lead to directionality in deposition. Directional deposition can also lead to the deposition of films with poor step coverage. Direct plasma (or directly generated plasma) is a plasma in which plasma (electrons, neutral species, radicals, and appropriate concentrations of positive ions) exists very close to the substrate surface during deposition and is sometimes separated from the substrate surface only by a plasma sheath. Ions can play an important role in direct plasma processes. The apparatus for direct plasma treatment is described in FIG. 8 below. In some embodiments, the plasma is generated remotely. Remote plasma (or remotely generated plasma) is one in which the plasma is generated at a location remote from the substrate. The main reactive species may be radicals for remotely generated plasma. The apparatus for direct plasma treatment is described in FIG. 7 below. Depending on the situation, specific advantages may be obtained by using remote plasma instead of direct plasma.

[0260] In some embodiments, a plasma of reactive species is formed. Plasma species may include electrons, positive ions, neutral species, radicals, and other plasma species. In some embodiments, the plasma may be a hydrogen-based plasma as a hydrogen-containing source including hydrogen atoms, hydrogen radicals, hydrogen reactive species, hydrogen plasma, or combinations thereof. The plasma may be an oxygen-based plasma as an oxygen-containing source including oxygen atoms, oxygen radicals, oxygen reactive species, oxygen plasma, or combinations thereof. In some embodiments, the plasma may also include noble gas species such as argon, neon, krypton, xenon, or helium species. In some cases, the plasma may include other species such as nitrogen atoms, nitrogen radicals, nitrogen plasma, or combinations thereof.

[0261] In some embodiments, the substrate is contacted with a reactant comprising hydrogen, oxygen, and helium plasma. The plasma can be formed in or upstream of the reaction chamber by flowing hydrogen, oxygen, and helium, for example, through a remote plasma generator, thereby generating plasma species that are introduced downstream of the reaction chamber. Alternatively, hydrogen and helium plasma can be supplied to the reaction chamber separately from oxygen and helium plasma. In some embodiments, hydrogen gas is supplied in a volume of about 500 to about 5000 sccm (standard cubic centimeters per minute per one-station chamber). In some embodiments of the plasma pretreatment, oxygen gas is supplied in a volume of about 1 to about 150 sccm. In some embodiments, oxygen gas is supplied in a volume of about 15 to about 100 sccm. In some embodiments of the plasma pretreatment, helium gas is supplied in a volume of about 1000 to about 10,000 sccm. In some embodiments, helium may be omitted. In some embodiments, another inert gas may be used instead of or in addition to helium.

[0262] One cycle of process 100 may be operations 102 and 106, or optionally may further include one or both of purge operations 104 and 108.

[0263] In operation 108, the deposition chamber may optionally be purged again.

[0264] In operation 110, when the desired thickness is achieved, the process can be terminated. The desired thickness can range from less than about 1 nm to about 50 nm, depending on the application. If the desired thickness has not yet been achieved, process operations 102 - 108 are repeated for a number of cycles sufficient to achieve the desired metal thickness.

[0265] Apparatus having a remote plasma generator One aspect of the present disclosure is an apparatus configured to perform the methods described herein. Suitable apparatus includes hardware for performing process operations and a system controller having instructions for controlling the process operations in accordance with the present disclosure. In some embodiments, the apparatus for performing the foregoing process operations can include a remote plasma source. The remote plasma source can provide milder reaction conditions compared to direct plasmas and may be preferred over direct plasma sources in certain situations.

[0266] FIG. 7 shows a schematic diagram of a remote plasma apparatus according to a particular embodiment. Device 200 includes a reaction chamber 210 having a showerhead assembly 220. Within reaction chamber 210, a substrate 230 is placed on a stage or pedestal 235. In some embodiments, a heating / cooling element can be attached to pedestal 235. A controller 240 is connected to the components of device 200 and can control the operation of device 200. For example, controller 240 can include instructions for controlling process conditions for the operation of device 200, such as temperature process conditions and / or pressure process conditions. In some embodiments, controller 240 can include instructions for controlling the flow rates of precursor gas, co-reactant gas, source gas, and carrier gas. Controller 240 can include instructions for varying the flow rate of the co-reactant gas over time. Additionally, or alternatively, controller 240 may include instructions for varying the flow rate of the precursor gas over time.

[0267] During operation, gas or a gas mixture is introduced into reaction chamber 210 via one or more gas inlets coupled to reaction chamber 210. In some embodiments, more than two gas inlets are coupled to reaction chamber 210. A first gas inlet 255 is coupled to reaction chamber 210 and connected to vessel 250, and a second gas inlet 265 is coupled to reaction chamber 210 and connected to remote plasma source 260. In embodiments including a remote plasma configuration, the supply lines for the precursor and the radical species generated by the remote plasma source are separated. Thus, the precursor and the radical species do not substantially interact before reaching substrate 230.

[0268] One or more radical species can be generated at remote plasma source 260 and configured to enter reaction chamber 210 via gas inlet 265. Any type of plasma source may be used at remote plasma source 260 to generate the radical species. This includes, but is not limited to, capacitively coupled plasma, inductively coupled plasma, microwave plasma, DC plasma, and laser-generated plasma. An example of capacitively coupled plasma can be radio frequency (RF) plasma. The RF plasma can be configured to operate at 13.56 MHz or higher. Another example of such an RF remote plasma source 260 can be operable at 440 kHz and provided as a sub-unit bolted to a large-scale apparatus for processing one or more substrates in parallel. In some embodiments, microwave plasma can be used as remote plasma source 260. The microwave plasma can be configured to operate at a frequency of 2.45 GHz. The gas provided to the remote plasma source may include hydrogen, nitrogen, oxygen, and other gases described elsewhere in this specification. In certain embodiments, hydrogen is provided with a carrier such as helium. As an example, hydrogen gas may be provided to a helium carrier at a hydrogen concentration of about 1 - 10%.

[0269] The precursor can be provided to a container 250 and supplied to a showerhead 220 via a first gas inlet 255. The showerhead 220 distributes the precursor from within the reaction chamber 210 towards the substrate 230. The substrate 230 can be positioned below the showerhead 220. It will be understood that the showerhead 220 can have any suitable shape and can have any number and arrangement of ports for distributing gas to the substrate 230. The precursor can be supplied to the showerhead 220 at a controlled flow rate and ultimately to the substrate 230.

[0270] One or more radical species formed by a remote plasma source 260 can be transported in the gas phase towards the substrate 230. One or more radical species can flow into the reaction chamber 210 through a second gas inlet 265. It will be understood that the second gas inlet 265 need not be lateral to the surface of the substrate 230. In certain embodiments, the second gas inlet 265 can be directly above the substrate 230 or in other locations. The distance between the remote plasma source 260 and the reaction chamber 210 is configured to provide mild reaction conditions such that the ionized species generated by the remote plasma source 260 are substantially neutralized, while at least some of the radical species in a substantially low energy state remain in the environment adjacent to the substrate 230. Such radical species in a low energy state do not recombine to form stable compounds. The distance between the remote plasma source 260 and the reaction chamber 210 can be a function of the aggressiveness of the plasma (e.g., partially determined by the RF power level of the source), the density of the gas in the plasma (e.g., when the concentration of hydrogen atoms is high, a significant proportion of them may recombine to form H2 before reaching the reaction chamber 210), and other factors. In some embodiments, the distance between the remote plasma source 260 and the reaction chamber 210 can be about 1 cm to 30 cm, such as about 5 cm or about 15 cm.

[0271] In some embodiments, a co-reactant other than the main metal-containing precursor or hydrogen radical is introduced during the deposition reaction. In some embodiments, the apparatus is configured to introduce the co-reactant through a second gas inlet 265, in which case the co-reactant is at least partially converted to plasma. In some embodiments, the apparatus is configured to introduce the co-reactant through the showerhead 220 via a first gas inlet 255. Examples of co-reactants include oxygen, nitrogen, ammonia, carbon dioxide, carbon monoxide, and the like. The flow rate of the co-reactant can vary over time and can result in a composition gradient in the inclined film.

[0272] The controller 240 can include instructions for controlling process conditions for the operation of the device 200. The controller 240 typically includes one or more memory devices and one or more processors. The processor can include a CPU or computer, analog and / or digital input / output connections, a stepping motor controller board, and the like. Instructions for implementing appropriate control operations are executed on the processor. These instructions may be stored in a memory device associated with the controller 240 or may be provided via a network.

[0273] In certain embodiments, controller 240 controls all or most of the activities of semiconductor processing device 200 described herein. For example, controller 240 can control all or most of the activities of semiconductor processing device 200 related to the deposition of the inclined silicon carbide film, and optionally, other operations in the fabrication flow including the inclined silicon carbide film. Controller 240 can execute system control software including a set of instructions for controlling timing, gas composition, gas flow rate, chamber pressure, chamber temperature, RF power level, substrate position, and / or other parameters. Other computer programs, scripts, or routines stored in a memory device associated with controller 340 may be used in some embodiments. Parameters such as RF power level, gas flow rate to the remote plasma region, and timing of plasma ignition can be adjusted and maintained by controller 240 to provide relatively mild reaction conditions in the environment adjacent to substrate 230. Additionally, by adjusting the substrate position, the presence of high-energy radical species in the environment adjacent to substrate 230 can be further reduced. In a multi-station reactor, controller 240 includes different or identical instructions for different device stations, thereby enabling the device stations to operate independently or synchronously.

[0274] In some embodiments, controller 240 may include instructions for performing operations such as flowing a metal-containing precursor into reaction chamber 210 through first gas inlet 255, providing one or more radical species of a source gas in a substantially low-energy state from remote plasma source 260, flowing a co-reactant gas into reaction chamber 210 through second gas inlet 265, varying the flow rate of the co-reactant gas over time, flowing one or more radical species into reaction chamber 210 through second gas inlet 265 to react with the metal-containing precursor, and forming a metal thin film on substrate 230. In some embodiments, controller 240 can include instructions for varying the flow rate of the metal-containing precursor over time.

[0275] In some embodiments, the apparatus may include a user interface associated with the controller 240. The user interface can include a display screen, a graphical software display of the apparatus and / or process conditions, and user input devices such as a pointing device, keyboard, touch screen, microphone, and the like.

[0276] The computer program code for controlling the above operations can be written in any conventional computer-readable programming language (e.g., assembly language, C, C++, Pascal, Fortran, etc.). The compiled object code or script is executed by a processor to perform the tasks identified by the program.

[0277] Signals for monitoring the process may be provided by analog and / or digital input connections of the system controller. Signals for controlling the process are output on the analog and digital output connections of the processing system.

[0278] In some embodiments, the plasma can be monitored in-situ by one or more plasma monitors. In one scenario, the plasma power can be monitored by one or more voltage and current sensors (e.g., VI probes). In another scenario, the plasma density and / or process gas concentration may be measured by one or more optical emission spectrometers (OES). In some embodiments, one or more plasma parameters can be programmatically adjusted based on measurements from such in-situ plasma monitors. For example, an OES sensor can be used in a feedback loop to provide program control of the plasma power. It will be understood that in some embodiments, other monitors can be used to monitor the plasma and other process characteristics. Such monitors can include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure transducers.

[0279] Generally, the methods described herein can be implemented on a system, such a system including semiconductor processing equipment such as one or more processing tools, one or more chambers, one or more processing platforms, and / or certain processing components (wafer pedestals, gas flow systems, etc.). These systems may be integrated with electronics for controlling system operation before, during, and after processing of a semiconductor wafer or substrate. Generally, the electronics are referred to as a controller and may control various components or sub-parts of one or more systems. The controller may be programmed to control any of the processes disclosed herein, depending on the processing requirements and / or the type of system. Such processes include supply of processing gases, temperature setting (e.g., heating and / or cooling), pressure setting, vacuum setting, power setting, radio frequency (RF) generator setting, RF matching circuit setting, frequency setting, flow rate setting, fluid supply setting, position and motion setting, loading and unloading of wafers to and from tools and other transfer tools connected or interfaced to a particular system, and / or loading and unloading of wafers to and from a load lock.

[0280] Broadly speaking, a controller may be defined as an electronic device having various integrated circuits, logic, memory, and / or software that receives commands, issues commands, controls operations, enables cleaning operations, enables endpoint measurements, etc. The integrated circuits may include a chip in the form of firmware that stores program instructions, a digital signal processor (DSP), a chip defined as an application specific integrated circuit (ASIC), and / or one or more microprocessors, i.e., a microcontroller that executes program instructions (e.g., software). The program instructions are instructions communicated to the controller in the form of various individual settings (or program files) that may define the operating parameters for performing a particular process on or for a semiconductor wafer or for a system. The operating parameters may, in some embodiments, be part of a recipe defined by a process engineer to implement one or more processing steps in the fabrication of one or more layers, materials (e.g., silicon carbide), surfaces, circuits, and / or wafer dies.

[0281] In some embodiments, the controller may be part of a computer that is integrated or coupled with the system or otherwise network-connected to the system, or may be coupled to such a computer, or may be a combination thereof. For example, the controller may be within the "cloud" or may be all or part of a fab host computer system. This enables remote access to wafer processing. The computer enables remote access to the system, monitors the current progress of the fabrication operation, considers the history of past fabrication operations, considers trends or performance criteria from multiple fabrication operations, changes the parameters of the current process, sets the process steps following the current process, or may initiate a new process. In some examples, a remote computer (e.g., a server) can provide a process recipe to the system through a network. Such a network 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, and such parameters and / or settings are then communicated from the remote computer to the system. In some examples, the controller receives instructions in the form of data. Such data specifies the parameters for each process step to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process being performed and the type of tool that the controller is configured to interact with or control. Thus, as described above, the controller may be distributed, for example, by comprising one or more individual controllers that are network-connected to each other and cooperate towards a common purpose (such as the processes and controls described herein). Examples of distributed controllers for such purposes include one or more integrated circuits on a chamber that communicate with one or more integrated circuits that are remotely located (e.g., at the platform level or as part of a remote computer) and combined to control the process in the chamber.

[0282] In addition to the metal deposition described herein, exemplary systems can include a plasma etching chamber or module, a deposition chamber or module, a spin rinse chamber or module, a metal plating chamber or module, a cleaning chamber or module, a bevel edge etching chamber or module, a physical vapor deposition (PVD) chamber or module, a chemical vapor deposition (CVD) chamber or module, an atomic layer deposition (ALD) chamber or module, an atomic layer etching (ALE) chamber or module, an ion implantation chamber or module, a tracking chamber or module, and any other semiconductor processing system that may be associated with or used in the fabrication and / or manufacture of semiconductor wafers.

[0283] As described above, depending on one or more process steps performed by a tool, the controller may communicate with one or more other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, proximate tools, tools located throughout the factory, the main computer, another controller, or a tool used for material transport to load and unload a wafer container to and from a tool location and / or load port within a semiconductor manufacturing facility.

[0284] Apparatus having a direct plasma generator FIG. 8 is a schematic diagram of an exemplary plasma processing apparatus for depositing a metal film using thermal ALD according to some embodiments. The plasma apparatus or process station 300 includes a plasma processing chamber 302 for maintaining a low pressure environment. A plurality of plasma apparatuses or process stations 300 may be included in a common low pressure process tool environment. In some embodiments, one or more hardware parameters of the plasma apparatus or process station 300 (including those described in detail below) can be programmatically adjusted by one or more system controllers 350. The plasma apparatus or process station 300 can be configured to perform thermal ALD and PEALD, thermal CVD and PEALD, thermal ALD and PECVD, or thermal CVD and PECVD. In some embodiments, the plasma apparatus or process station 300 can be configured to perform one or more PEALD cycles and one or more thermal ALD cycles to deposit a metal film on the substrate 312.

[0285] The apparatus or process station 300 is in fluid communication with a reactant supply system 301 for supplying process gas to a distribution showerhead 306. The reactant supply system 301 includes a mixing vessel 304 for blending and / or conditioning process gas such as a silicon-containing precursor in the gas phase supplied to the showerhead 306. In some embodiments, the reactant supply system 301 includes a mixing vessel 304 for blending and / or conditioning an oxygen-containing reactant (e.g., oxygen) supplied to the showerhead 306. In some embodiments, the reactant supply system 301 includes a mixing vessel 304 for blending and / or conditioning a hydrogen and oxygen-containing reactant (e.g., oxygen) supplied to the showerhead 306. One or more mixing vessel inlet valves 320 can control the introduction of process gas into the mixing vessel 304. A plasma of the oxygen-containing reactant may also be supplied to the showerhead 306 or generated at the plasma apparatus or process station 300. The showerhead 306 is fluidly coupled to a plasma processing chamber 302 and can supply a silicon-containing precursor and reactant to the plasma processing chamber 302.

[0286] As an example, the embodiment of FIG. 8 includes a vaporization point 303 for vaporizing the liquid reactant supplied to the mixing vessel 304. In some embodiments, the vaporization point 303 can be a heated vaporizer. In some embodiments, the supply piping downstream of the vaporization point 303 can be heat traced. In some examples, the mixing vessel 304 can also be heat traced. In one non-limiting example, the piping downstream of the vaporization point 303 has a rising temperature profile ranging from about 100° C. to about 150° C. in the mixing vessel 304. In some embodiments, the liquid precursor or liquid reactant may be vaporized by a liquid injector. For example, the liquid injector can inject pulses of the liquid reactant into the carrier gas stream upstream of the mixing vessel 304. In one embodiment, the liquid injector can vaporize the reactant by flashing the liquid from a higher pressure to a lower pressure. In another example, the liquid injector can spray the liquid into dispersed microdroplets and then vaporize them in a heated supply pipe. Smaller droplets can vaporize faster than larger droplets, reducing the delay between liquid injection and complete vaporization. Faster vaporization can reduce the length of the piping downstream from the vaporization point 303. In one scenario, the liquid injector can be mounted directly to the mixing vessel 304. In another scenario, the liquid injector can be mounted directly to the showerhead 306.

[0287] In some embodiments, a liquid flow controller (LFC) can be provided upstream of the vaporization point 303 to control the mass flow rate of the liquid that is vaporized and supplied to the plasma device or process station 300. For example, the LFC can include a thermal mass flow meter (MFM) located downstream of the LFC. Next, the plunger valve of the LFC can be adjusted in response to a feedback control signal provided by a proportional-integral-derivative (PID) controller in electrical communication with the MFM. However, it can take more than one second to stabilize the liquid flow using feedback control. This can potentially extend the time for administering the liquid reactant. Thus, in some embodiments, the LFC can be dynamically switched between a feedback control mode and a direct control mode. In some embodiments, this can be accomplished by disabling the sense tubes of the LFC and the PID controller.

[0288] The showerhead 306 distributes the process gas toward the substrate 312. In the embodiment shown in FIG. 8, the substrate 312 is located below the showerhead 306 and is shown at rest on a substrate support 308, which is configured to support the substrate 312. The substrate support 308 can include a chuck, fork, or lift pins (not shown) for holding and transferring the substrate 312 during and between deposition operations. The chuck can be an electrostatic chuck, a mechanical chuck, or any of the various other types of chucks available for use in industry and / or research. The showerhead 306 can have any suitable shape and can have any suitable number and arrangement of ports for distributing the process gas to the substrate 312.

[0289] In some embodiments, the substrate support 308 can be raised or lowered to expose the substrate 312 to the volume between the substrate 312 and the showerhead 306. It will be appreciated that in some embodiments, the height of the substrate support can be programmatically adjusted by a suitable system controller 350.

[0290] In another scenario, by adjusting the height of the substrate support 308, it is possible to vary the plasma density during the plasma activation cycle included in the process. At the end of the process stage, the substrate support 308 can be lowered during the transfer stage of another substrate, enabling the removal of the substrate 312 from the substrate support 308.

[0291] In some embodiments, the substrate support 308 may be configured to be heated to a high temperature via the heater 310. In some embodiments, the substrate support 308 may be heated to a temperature of less than about 700 °C, such as from about 500 °C to about 750 °C, or from about 500 °C to about 650 °C, during the deposition of the film as described in the disclosed embodiments. Further, in some embodiments, pressure control for the apparatus or process station 300 can be provided by the butterfly valve 318. As shown in the embodiment of FIG. 8, the butterfly valve 318 throttles the vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, the pressure control of the plasma processing chamber 302 can also be adjusted by varying the flow rate of one or more gases introduced into the plasma processing chamber 302. In some embodiments, the pressure within the plasma processing chamber 302 may be controlled to be about 7 Torr or more, about 10 Torr or more, or about 12 Torr or more during the deposition of the silicon oxide film as described in the disclosed embodiments.

[0292] In some embodiments, the position of the showerhead 306 can be adjusted relative to the substrate support 308 to vary the volume between the substrate 312 and the showerhead 306. Further, it will be understood that the vertical positions of the substrate support 308 and / or the showerhead 306 may be varied by any suitable mechanism within the scope of the present disclosure. In some embodiments, the substrate support 308 may include a rotation axis for rotating the orientation of the substrate 312. It will be understood that one or more of these exemplary adjustments can be implemented programmatically by one or more suitable system controllers 350.

[0293] In some embodiments where the plasma can be used as described above, the showerhead 306 and the substrate support 308 are in electrical communication with a radio frequency (RF) power source 314 and a matching network 316 to supply power to the plasma processing chamber 302. In some embodiments, the plasma energy can be controlled by controlling one or more of the process station pressure, gas concentration, RF source power, RF source frequency, and plasma power pulse timing. For example, the RF power source 314 and the matching network 316 can operate at any suitable power to form a plasma having a desired composition of radical species. In some embodiments, the RF power source 314 and the matching network 316 can operate to apply plasma power to the plasma processing chamber 302 and ignite the plasma generated from hydrogen and oxygen-containing reactants within the plasma processing chamber 302. Exemplary plasma power applied by the RF power source 314 can be about 300 W or less, about 200 W or less, or about 10 W to about 200 W. Similarly, the RF power source 314 can provide RF power at any suitable frequency. In some embodiments, the RF power source 314 can be configured to control high-frequency and low-frequency RF power sources independently of each other. Exemplary low-frequency RF frequencies can include, but are not limited to, frequencies from 0 kHz to 500 kHz. Exemplary high-frequency RF frequencies can include, but are not limited to, frequencies from 1.8 MHz to 2.45 GHz, or at least about 13.56 MHz, or at least about 27 MHz, or at least about 40 MHz, or at least about 60 MHz. It will be appreciated that any suitable parameters can be adjusted discretely or continuously to provide plasma energy for surface reactions.

[0294] In some embodiments, the plasma can be monitored in-situ by one or more plasma monitors. In one scenario, the plasma power can be monitored by one or more voltage and current sensors (e.g., VI probes). In another scenario, the plasma density and / or the process gas concentration may be measured by one or more optical emission spectroscopy sensors (OES). In some embodiments, one or more plasma parameters can be programmatically adjusted based on measurements from such in-situ plasma monitors. For example, the OES sensor can be used in a feedback loop to provide programmatic control of the plasma power. It will be appreciated that in some embodiments, other monitors can be used to monitor the plasma and other process characteristics. Such monitors can include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure transducers.

[0295] In some embodiments, the instructions for the controller 350 may be provided via input / output control (IOC) sequence instructions. In one example, the instructions for setting conditions for a process step may be included in the corresponding recipe step of a process recipe. In some cases, the process recipe steps may be arranged in order such that all instructions for a process step are executed simultaneously with that process step. In some embodiments, the instructions for setting one or more reactor parameters may be included in the recipe steps. For example, the first recipe step may include instructions for setting the flow rate of an inert gas and / or a precursor gas (e.g., a silicon-containing precursor), instructions for setting the flow rate of a carrier gas (such as argon), and a time delay instruction for the first recipe step. The second subsequent recipe step may include instructions for adjusting or stopping the flow rate of the inert gas and / or the precursor gas, instructions for adjusting the flow rate of the carrier gas or a purge gas, and a time delay instruction for the second recipe step. The third recipe step may include instructions for adjusting the flow rate of an oxygen-containing reactant gas such as oxygen, instructions for adjusting the flow rate of hydrogen gas, instructions for adjusting the flow rate of the carrier gas or a purge gas, and a time delay instruction for the third recipe step. The fourth subsequent recipe step may include instructions for adjusting or stopping the flow rate of the inert gas and / or the reactant gas, instructions for adjusting the flow rate of the carrier gas or a purge gas, and a time delay instruction for the fourth recipe step. The fourth recipe may, in some embodiments, include instructions for igniting a plasma of an oxygen-containing reactant. It will be understood that these recipe steps may be further subdivided and / or repeated in any suitable manner within the scope of the disclosed embodiments.

[0296] In certain embodiments, the controller 350 has instructions for performing the operations described in this disclosure.

[0297] The described apparatus / process may be used in conjunction with lithography patterning tools or processes, for example, for the fabrication or manufacture of semiconductor devices, displays, LEDs, solar panels, etc. Typically, although not necessarily, such tools / processes are used or implemented together in a common fabrication facility. Lithographic patterning of a film typically includes some or all of the following operations, each enabled using a number of tools available: (1) an operation of applying a photoresist to a workpiece (i.e., a substrate) using a spin-on tool or a spray-on tool, (2) an operation of curing the photoresist using a hot plate or a furnace or a UV curing tool, (3) an operation of exposing the photoresist with visible light or UV light or X-ray light using a tool such as a wafer stepper, (4) an operation of developing the resist to selectively remove the resist, thereby patterning the resist, using a tool such as a wet bench, (5) an operation of transferring the resist pattern to the underlying film or workpiece by using a dry etching tool or a plasma-assisted etching tool, and (6) an operation of removing the resist by using a tool such as an RF or microwave plasma resist stripper.

[0298] Example 1 Copper deposition General conditions for the atomic layer deposition method utilized to obtain the results of FIGS. 9A, 9B, 9C, 10, 11A, and 11B include copper aminoalkoxide as a copper precursor, 9 slm (standard liter per minute) of helium gas and 3 lm (liter per minute) of hydrogen gas, a pressure of less than 10 Torr, and the use of a remote ICP plasma source that is a 13.57 MHz RF generator.

[0299] Figure 9A shows an embodiment of a method capable of adjusting the thickness of copper metal when oxygen gas is added to a hydrogen gas source in a remote plasma generator. When oxygen is not added, as the number of atomic layer deposition cycles increases, a thicker copper layer is deposited. When oxygen gas with a flow rate of 20 sccm is added, the thickness of the deposit becomes approximately half after about 225 cycles.

[0300] Figure 9B shows the graph results of the thickness of deposited copper as the oxygen gas flow rate changes. In one embodiment of this method, the thickness of copper metal is adjusted when oxygen gas is added to the hydrogen gas source in a remote plasma generator. As shown, the thickness of copper is significantly reduced by a small amount of oxygen.

[0301] Figure 9C shows a graph of the change in copper resistivity when the flow rate of oxygen added to the hydrogen gas source in a remote plasma generator changes. As shown, the resistivity is dramatically reduced by a small amount of oxygen.

[0302] In one embodiment, when oxygen gas is added to the hydrogen gas source in a remote plasma generator, the morphology of the deposited copper changes. As shown in Figure 10, the film deposited in the absence of a small amount of oxygen gas is rough, discontinuous, and shows an island-like morphology. When 20 sccm of oxygen gas is introduced, the morphology of the film changes dramatically from island-like to interconnected channels. When the oxygen gas exceeds 150 sccm, the morphology becomes island-like again.

[0303] Figure 11A shows the deposition of copper using the plasma of a remotely generated hydrogen gas source without adding oxygen gas. The deposited copper has a rough appearance. Figure 11B shows the deposition of copper using the plasma of a remotely generated hydrogen gas source when 20 sccm of oxygen gas is added to the hydrogen gas source in a remote plasma generator. When the amount of oxygen in the plasma gas stream is only 0.16%, the morphology of the deposited layer is improved and the roughness is reduced.

[0304] Example 2 Deposition of Molybdenum As shown in FIG. 12, after performing the method 500 cycles under the same process conditions as in Example 1 using a MoCl5 precursor and pretreatment with remotely generated hydrogen plasma, when the deposition method is used at a wafer temperature of 270° C. (corresponding to a pedestal temperature of 325° C.) rather than at a wafer temperature of 310° C. (corresponding to a pedestal temperature of 380° C.), the thickness of the molybdenum metal on the wafer becomes thicker.

[0305] In this specification, reference is made in detail to specific embodiments of the present disclosure. Examples of specific embodiments are shown in the accompanying drawings. Although the present disclosure is described in conjunction with these specific embodiments, it will be understood that the present disclosure is not intended to be limited to such specific embodiments. On the contrary, it is intended to cover alternatives, modifications, and equivalents that may be included within the spirit and scope of the present 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 process operations are not described in detail so as not to unnecessarily obscure the present disclosure.

[0306] The foregoing embodiments have been described in some detail for purposes of clarity of understanding, but it will be apparent that certain changes and modifications may be practiced within the scope of the appended claims. The embodiments disclosed herein may be practiced without some or all of these specific details. In other instances, well-known process operations are not described in detail so as not to unnecessarily obscure the disclosed embodiments. Further, although the disclosed embodiments are described in conjunction with specific embodiments, it will be understood that the specific embodiments are not intended to limit the disclosed embodiments. It should be noted that there are many other ways to implement the processes, systems, and apparatuses of the present embodiments. Therefore, the present embodiments should be regarded as illustrative rather than restrictive, and those embodiments should not be limited to the details described herein.

Claims

1. A method for plasma-enhanced atomic layer deposition of a metal onto a substrate, comprising: providing the substrate in a deposition chamber, the substrate being at a temperature of about 300 °C or less; exposing a surface of the substrate to a vapor-phase metal precursor; exposing the substrate to a plasma generated directly or remotely from a hydrogen-containing gas source. A method as claimed in claim 1.

2. The method according to claim 1, wherein the metal comprises vanadium, niobium, tantalum, chromium, cobalt, tungsten, iron, ruthenium, nickel, zinc, copper, or molybdenum.

3. The method according to claim 1, wherein the vapor-phase metal precursor comprises a vanadium-containing precursor, a niobium-containing precursor, a tantalum-containing precursor, a chromium-containing precursor, a cobalt-containing precursor, a tungsten-containing precursor, an iron-containing precursor, a ruthenium-containing precursor, a nickel-containing precursor, a zinc-containing precursor, a copper-containing precursor, or a molybdenum-containing precursor.

4. The method according to claim 1, further comprising pretreating the surface of the substrate with the plasma remotely generated from the hydrogen-containing gas source before exposing the surface of the substrate to the vapor-phase metal precursor.

5. A method for plasma-enhanced atomic layer deposition of molybdenum onto a substrate, comprising: providing the substrate in a deposition chamber, the substrate being at a temperature of about 300 °C or less; exposing a surface of the substrate to a vapor-phase molybdenum precursor; exposing the substrate to a plasma generated directly or remotely from a hydrogen-containing gas source. A method as claimed in claim 5.

6. The method according to claim 5, wherein the vapor-phase molybdenum precursor has the structure of formula (I): Mo(L-R 1 ) 6 (I) wherein Each L is independently O, S, or NR 2 and R 1 and R 2 are, independently, hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted heteroaromatic, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted aromatic, optionally substituted aryl, or optionally substituted arylalkylene, the two R1 substituents may together form an optionally substituted cyclic group. A method as claimed in claim 6.

7. The method according to claim 5, wherein the vapor-phase molybdenum precursor has the structure of formula (II): Mo(L-R 1 ) 2 (Y) 4 (II) wherein Each L is independently O, S, or NR 2 and R 1 and R 2 are each, independently, hydrogen, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted heteroaliphatic, optionally substituted heteroalkyl, optionally substituted heteroaromatic, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted aromatic, optionally substituted aryl, or optionally substituted arylalkylene, R 1 The substituents can together form an optionally substituted cyclic group, each Y is independently chlorine, fluorine, bromine, or iodine. A method as claimed in claim 7.

8. The method according to claim 5, wherein The gas-phase molybdenum precursor is MoCl 5 , Mo 2 Cl 10 , MoO 2 Cl 2 , MoOCl 4 , or any combination thereof, method.

9. The method according to claim 5, wherein exposing the surface of the substrate to the vapor-phase molybdenum precursor and exposing the substrate to the plasma remotely generated from the hydrogen-containing gas source are carried out in temporally separate pulses.

10. An apparatus for depositing a metal thin film onto a substrate, comprising: At least one reaction chamber including a pedestal for holding the substrate, At least one inlet port for supplying a gas-phase metal precursor to the reaction chamber, A direct plasma generator or a remote plasma generator for providing plasma to the reaction chamber, A controller for controlling the operation in the apparatus, (a) bringing the substrate to a temperature of about 300 °C or less, (b) introducing the metal precursor into the at least one reaction chamber in the gas phase, (c) introducing plasma from the direct plasma generator or the remote plasma generator to form the metal thin film on the substrate, and a controller including machine-readable instructions therefor, wherein the plasma is generated from a hydrogen-containing gas and an oxygen-containing gas of about 0.01% to about 1%, apparatus

Images