Plasma enhanced low temperature atomic layer deposition of metals

Abstract

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

Description

Incorporated by Reference

[0001] The PCT application form is filed concurrently with this specification as a part of this application. Each application identified in the concurrently filed PCT application form to which this application claims the benefit or priority is incorporated herein by reference in its entirety and for all purposes. Prior Art

[0002] Many semiconductor device manufacturing processes involve depositing metals, such as molybdenum or copper, to form ultra-thin conductive films. Plasma-enhanced atomic layer deposition (ALD) can be used to deposit metal-containing films. Film morphology is a factor to consider when designing processes for making such ultra-thin conductive films, as rough morphology can lead to increased film resistivity and can be associated with voids in the conductive fill metal and pinch-off of the fill metal in features.

[0003] The background description provided here is for the purpose of generally presenting the context of the present disclosure. The work of the presently designated inventors is neither explicitly nor implicitly admitted to be prior art against the present disclosure to the extent that it is described in this background section and to aspects of the specification that could not be determined as prior art at the time of filing the application. Summary of the invention

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

[0005] Accordingly, in a first aspect, the present invention encompasses a method for plasma enhanced atomic layer deposition of a thin metal film on a substrate surface. In some embodiments, the method includes providing a substrate in a deposition chamber, wherein the substrate is 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 plasma directly generated by a hydrogen-containing gas source or a remotely generated plasma.

[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 remotely generated from a source of hydrogen-containing gas are performed in time-separated 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 remotely generated from a hydrogen-containing gas source converts the adsorbed metal precursor to elemental metal.

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

[0012] In some embodiments, the hydrogen-containing gas source further comprises from about 0.01% to about 1% of an 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, monodeuterated ammonia, dideuterated ammonia, trideuterated ammonia, hydrazine, alcohols, aldehydes, or combinations thereof.

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

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

[0018] In some embodiments, the method further includes pre-treating the surface of the substrate with a plasma remotely generated from a hydrogen-containing gas source prior to exposing the surface of the substrate to the gas-phase molybdenum precursor.

[0019] In some embodiments, the vapor phase molybdenum precursor has the structure of formula (I): Mo(LR 1 )6, 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; and wherein two R 1The substituents can be taken together to form an optionally substituted cyclic group.

[0020] In some embodiments, the vapor phase molybdenum precursor has the structure of formula (II): Mo(LR 1 )2(Y)4, wherein each L is independently O, S or NR 2 ; R 1 and R 2 is 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 wherein R 1 The substituents can be taken together to form an optionally substituted cyclic group; and each Y is independently chloro, fluoro, bromo or iodo.

[0021] In some embodiments, the gas phase molybdenum precursor is Mo q X n Y m , wherein X is oxygen, Y is 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 gas phase molybdenum precursor is molybdenum pentachloride (MoCl5), molybdenum (V) chloride (Mo2Cl 10 ), molybdenum(VI)dichloride (MoO2Cl2), molybdenum oxychloride (MoOCl4) or any combination thereof.

[0023] In some embodiments, exposing the surface of the substrate to a vapor phase molybdenum precursor and exposing the substrate to a plasma remotely generated from a hydrogen-containing gas source are performed in time-separated 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, a plasma remotely generated 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 from about 0.01% to about 1% of an oxygen-containing gas.

[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, alcohols, aldehydes, or combinations thereof.

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

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

[0032] In some embodiments, the method further includes pre-treating the surface of the substrate with a plasma remotely generated from a source of hydrogen-containing gas 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 following structure: Cu(LR 3 ) n , Cu2(B)2, or Cu4(N(R 4 )2)4, wherein each L is independently O, NR 4 or P(R 5 )3; B is a bidentate ligand; 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; wherein when n is 4, two R 3 The substituents can be taken together to form an optionally substituted cyclic group; and wherein the copper is optionally coordinated to a compound containing an optionally substituted alkenyl, optionally substituted alkynyl, carbonyl, aryl, or heteroaryl group.

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

[0035] In some embodiments, the cuprous precursor is an acetylacetonate, ketoiminate, diiminate, cyclopentadienyl, amidinate, guanidinate, or amidinate compound.

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

[0037] In some embodiments, the copper precursor is an acetylacetonate, ketimide, or 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, alcohols, aldehydes, or combinations thereof.

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

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

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

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

[0045] In a fourth aspect, the present invention encompasses an apparatus for depositing a thin metal film on a substrate, the apparatus comprising: at least one reaction chamber comprising a susceptor for holding a substrate; at least one inlet port for delivering a vapor-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 operations in the apparatus, the controller comprising machine-readable instructions for (a) maintaining a substrate temperature at about 300° C. or less; (b) introducing a metal precursor in a vapor phase into the at least one reaction chamber; and (c) introducing a plasma from the direct plasma generator or the remote plasma generator to form a thin metal film over the substrate, the plasma being generated by a hydrogen-containing gas and about 0.01% to about 1% oxygen-containing gas.

[0046] These and other aspects are further described below with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 A process flow diagram is provided to illustrate the operation of a thin metal film deposition method according to certain disclosed embodiments.

[0048] Figure 2 Schematic diagram of various cuprous precursors for use in a thin metal film deposition method according to certain disclosed embodiments.

[0049] Figure 3 is a diagram of various copper precursors used in a thin metal film deposition method according to certain disclosed embodiments.

[0050] Figure 4 Schematic representation of various ligands for a molybdenum precursor useful in a thin metal film deposition method according to certain disclosed embodiments.

[0051] Figure 5 Schematic representation of various ligands for a molybdenum precursor useful in a thin metal film deposition method according to certain disclosed embodiments.

[0052] Figure 6 Schematic diagram of various molybdenum precursors used in a thin metal film deposition method according to certain disclosed embodiments.

[0053] Figure 7 An example of an apparatus having a remote plasma source that may be used to perform the methods described herein according to certain disclosed embodiments is shown.

[0054] Figure 8 is a schematic diagram of an exemplary plasma processing apparatus for performing methods according to certain disclosed embodiments.

[0055] Fig. 9A Graph comparison of copper thickness deposited in a remotely generated plasma hydrogen-containing gas source with and without added oxygen according to certain disclosed embodiments.

[0056] Fig. 9B Graph of copper thickness deposited for various oxygen flow rates into a remotely generated plasma hydrogen-containing gas source in accordance with certain disclosed embodiments.

[0057] Fig. 9C is a graph of the resistivity of deposited copper when various oxygen flow rates are fed into a remotely generated plasma hydrogen-containing gas source according to certain disclosed embodiments.

[0058] Fig.10 Scanning electron microscope images of copper deposited according to the method are shown, depicting the change in morphology at different oxygen flow rates (when added to hydrogen in a plasma generated by a remote plasma source), according to certain disclosed embodiments.

[0059] Fig.11A is a scanning transmission electron microscope (STEM) image of copper deposited onto features on a substrate surface when using a remotely generated plasma of a hydrogen-containing gas source without added oxygen according to certain disclosed embodiments.

[0060] Fig. 11Bis a scanning transmission electron microscope (STEM) image of copper deposited onto features on a substrate surface having less roughness when using a remotely generated plasma containing 20 seem of a hydrogen-containing gas source with added oxygen according to certain disclosed embodiments.

[0061] Fig.12 Graph comparison of Mo thickness deposited at substrate temperatures above and below 300° C. using MoCl 5 as a Mo precursor according to certain disclosed embodiments. DETAILED DESCRIPTION definition

[0062] As used herein, "heterolate complex" refers to a compound that contains at least two ligands that are different and attached to a metal center.

[0063] As used herein, "homolite complex" refers to a compound comprising ligands that are all identical and attached to a metal center.

[0064] Unless otherwise indicated, the term "about" as used herein refers to a difference of ±10% from any stated value. When used, the term modifies any stated value, range of values, or endpoints of one or more ranges.

[0065] As used herein, the terms "top", "bottom", "lower", "above", and "below" are used to provide relative relationships between multiple structures. The use of these terms does not indicate or require that a particular structure must be located at a particular position in the device.

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

[0067] The terms "acyl" or "alkanoyl" used interchangeably herein refer to a group of 1, 2, 3, 4, 5, 6, 7, 8 or more carbon atoms or hydrogen in straight chain, branched, cyclic configuration, saturated, unsaturated and aromatic and combinations thereof, attached to the parent molecular group through a carbonyl group as defined herein. Examples of such groups are formyl (-C(O)H), acetyl (Ac or -C(O)Me), propionyl, isobutyryl, butyryl, and the like. In some embodiments, the acyl or alkanoyl group is -C(O)-R, wherein R is hydrogen, an aliphatic group or an aromatic group, as defined herein.

[0068] "Alkanoyloxy" refers to an alkanoyl group, as defined herein, attached to a parent molecular group through an oxy group, as defined herein. Such a group is exemplified by acetoxy (-OAc or -OC(O)Me). In some embodiments, alkanoyloxy is -OC(O)-R, wherein R is hydrogen, an aliphatic group, or an aromatic group, as defined herein.

[0069] "Aliphatic" refers to a group having at least one carbon atom and up 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 hydrocarbon groups including alkanes (or alkyls), alkenes (or alkenyls), alkynes (or alkynyls), including cyclic forms thereof, and also including straight chain and branched arrangements, as well as all stereo and positional isomers. Aliphatic groups are unsubstituted or substituted, for example, with functional groups as described herein. For example, aliphatic groups may be substituted with one or more substituents, as described herein for alkyl groups.

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

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

[0072] "Aliphatic-oxy" refers to an aliphatic group that is or can be coupled to a compound disclosed herein, wherein the aliphatic group is or becomes coupled via an oxy group. In some embodiments, aliphatic-oxy ​​is -OR, wherein R is an optionally substituted aliphatic group as defined herein.

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

[0074] "Alkyl-aryl", "alkenyl-aryl" and "alkynyl-aryl" mean an alkyl, alkenyl or alkynyl, respectively, as defined herein, coupled (or linked) or capable of being coupled (or linked) to a parent molecular group through an aryl, as defined herein. Alkyl-aryl, alkenyl-aryl and / or alkynyl-aryl groups can be substituted or unsubstituted. For example, alkyl-aryl, alkenyl-aryl and / or alkynyl-aryl groups can be substituted with one or more substituents, as described herein for alkyl and / or aryl groups. Exemplary unsubstituted alkyl-aryl groups have 7 to 16 carbon (C 2+) atoms. 7-16 alkyl-aryl), and those having an alkyl group containing 1 to 6 carbons and an aryl group containing 4 to 18 carbons (i.e., C 1-6 Alkyl-C 4-18 Exemplary unsubstituted alkenyl-aryl groups have 7 to 16 carbon atoms (C 7-16 alkenyl-aryl), and those having an alkenyl group containing 2 to 6 carbons and an aryl group containing 4 to 18 carbons (i.e., C 2-6 Alkenyl-C 4-18 Exemplary unsubstituted alkynyl-aryl groups have 7 to 16 carbon (C 7-16 alkynyl-aryl), and those having an alkynyl group containing 2 to 6 carbons and an aryl group containing 4 to 18 carbons (i.e., C 2-6 Alkynyl-C 4-18 In some embodiments, alkyl-aryl is -LR, wherein L is aryl or arylene as defined herein, and R is alkyl as defined herein. In some embodiments, alkenyl-aryl is -LR, wherein L is aryl or arylene as defined herein, and R is alkenyl as defined herein. In some embodiments, alkynyl-aryl is -LR, wherein L is aryl or arylene as defined herein, and R is alkynyl as defined herein.

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

[0076] "Alkoxy" refers to -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, tert-butoxy, sec-butoxy, n-pentoxy, trihaloalkoxy such as trifluoromethoxy, and the like. Alkoxy groups can be substituted or unsubstituted. For example, alkoxy groups can be substituted with one or more substituents, as described herein for alkyl groups. Exemplary unsubstituted alkoxy groups include C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 or C 1-24 Alkoxy.

[0077] "Alkoxyalkyl" refers to an alkyl group, as defined herein, substituted with an alkoxy group, as defined herein. Exemplary unsubstituted alkoxyalkyl groups contain 2 to 12 carbon (C 2-12 alkoxyalkyl), and those having an alkyl group containing 1 to 6 carbons and an alkoxy group containing 1 to 6 carbons (i.e., C 1-6 Alkoxy-C 1-6 In some embodiments, the alkoxyalkyl is -LOR, wherein L and R are each independently alkyl as defined herein.

[0078] "Alkoxycarbonyl" refers to -C(O)-OR, where R is an optionally substituted aliphatic group as described herein. In specific embodiments, the alkoxycarbonyl group is -C(O)-OAk, where Ak is an alkyl group as defined herein. The alkoxycarbonyl group may be substituted or unsubstituted. For example, the alkoxycarbonyl group may 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 , C 2-12 , C 2-16 , C 2-18 , C 2-20 or C 2-24 Alkoxycarbonyl.

[0079] "Alkyl" refers to a group having at least one carbon atom and up to 50 carbon atoms (C1-50 ), for example, 1 to 25 carbon atoms (C 1-25 ) or 1 to 10 carbon atoms (C 1-10 ), wherein the saturated monovalent hydrocarbon can be obtained by removing a hydrogen atom from a carbon atom of a parent compound (e.g., an alkane). The alkyl group can be branched, straight or cyclic (e.g., a cycloalkyl group). Exemplary alkyl groups include branched or unbranched saturated hydrocarbon groups of 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (iPr), n-butyl (nBu), isobutyl (iBu), sec-butyl (sBu), tert-butyl (tBu), pentyl (Pe), n-pentyl (nPe), isopentyl (iPe), sec-pentyl (sPe), neopentyl (neoPe), tert-pentyl (tPe), hexyl (Hx), heptyl (Hp), octyl (Oc), nonyl (Nn), decyl (De), dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. The alkyl group can also be substituted or unsubstituted. The alkyl group may be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form an appropriate linkage to the parent molecular group or between the parent molecular group and another substituent. For example, the alkyl group may be substituted with one, two, three, or in the case of an alkyl group of two or more carbons, four substituents independently selected from the group consisting of: (1) C 1-6 Alkoxy (e.g., -OR, where R is C 1-6 Alkyl); (2) C 1-6 Alkylsulfinyl (e.g., C 1-6 , wherein R is a C1-6 alkyl group); (3) C 1-6 Alkylsulfonyl (e.g., -SO2-R, where R is C 1-6 (4) amino (e.g., -NR 1 R 2 , where R 1 and R 2 are each independently selected from hydrogen, an aliphatic, a heteroaliphatic, a halogenated aliphatic, a halogenated heteroaliphatic, an aromatic group, or any combination thereof as defined herein, or R 1 and R 2 (e.g., -C(O)-R, wherein R is aryl); (8) azido (e.g., -N3); (9) cyano (e.g., -CN); (10) aldehyde (e.g., -C(O)H); (11) C(O)-R; (12) C(O)-R; (13) C(O)-R; (14) C(O)-R; (15) C(O)-R; (16) C(O)-R; (17) C(O)-R; (18) C(O)-R; (19) C(O)-R; (20) C(O)-R; (21) C(O)-R; (22) C(O)-R; (23) C(O)-R; (24) C(O)-R; (25) C(O)-R; (26) C(O)-R; (27) C(O) 3-8Cycloalkyl; (12) halo; (13) heterocyclyl (e.g., as defined herein, such as a 5-, 6-, or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (14) heterocyclyloxy (e.g., -OR, wherein R is heterocyclyl, as defined herein); (15) heterocyclylacyl (e.g., -C(O)-R, wherein R is heterocyclyl, as defined herein); (16) hydroxy (e.g., -OH); (17) N-protected amino; (18) nitro (e.g., -NO2); (19) oxo (e.g., =O); (20) C 1-6 Thioalkyl (e.g., -SR, where R is alkyl); (21) thiol (e.g., -SH); (22) -CO2R 1 , where R 1 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., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (23)-C(O)NR 1 R 2 , where R 1 and R 2 are each 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., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (24)-SO2R 1 , where R 1 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., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (25)-SO2NR 1 R 2 , where R 1 and R 2 are each 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., -LR, where L is C1-6 Alkyl and R is C 4-18 aryl); and (26)-NR 1 R 2 , where R 1 and R 2 are each independently selected from the group consisting of: (a) hydrogen, (b) an N-protecting group, (c) a 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., -LR, 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., -LR, where L is C 1-6 Alkyl and R is C 3-8 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.

[0080] "Alkylene", "alkenylene" or "alkynylene" refers to a polyvalent (e.g., divalent) form of an alkyl, alkenyl or alkynyl group, respectively, as described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, and the like. In some embodiments, alkylene 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 In other embodiments, the alkylene group is C 2-3 , C 2-6 , C 2-12 , C2-16 , C 2-18 , C 2-20 or C 2-24 The alkylene, alkenylene or alkynylene groups may be branched or unbranched. The alkylene, alkenylene or alkynylene groups may also be substituted or unsubstituted. For example, the alkylene, alkenylene or alkynylene groups may be substituted with one or more substituents, as described herein for alkyl groups.

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

[0082] "Alkylsulfinylalkyl" refers to an alkyl group, as defined herein, substituted with an alkylsulfinyl group. In some embodiments, unsubstituted alkylsulfinylalkyl is C 2-12 or C 2-24 Alkylsulfinylalkyl (e.g., C 1-6 Alkylsulfinyl-C 1-6 Alkyl or C 1-12 Alkylsulfinyl-C 1-12 In other embodiments, alkylsulfinylalkyl is -LS(O)-R, wherein L and R are each independently alkyl as defined herein.

[0083] "Alkylsulfonyl" refers to an alkyl group, as defined herein, attached to the parent molecular group through a -SO2- group. In some embodiments, unsubstituted alkylsulfonyl is C 1-6 or C 1-12 In other embodiments, alkylsulfonyl is -SO2-R, wherein R is optionally substituted alkyl (e.g., as described herein, comprising optionally substituted C 1-12 alkyl, haloalkyl or perfluoroalkyl).

[0084] "Alkylsulfonylalkyl" refers to an alkyl group, as defined herein, substituted with an alkylsulfonyl group. In some embodiments, unsubstituted alkylsulfonylalkyl is C 2-12 or C 2-24 Alkylsulfonylalkyl (e.g., C 1-6 Alkylsulfonyl-C 1-6 Alkyl or C 1-12 Alkylsulfonyl-C 1-12 In other embodiments, alkylsulfonylalkyl is -L-SO2-R, wherein L and R are each independently alkyl as defined herein.

[0085] "Alkynyl" refers to a group having at least 2 carbon atoms and up 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 an unsaturated monovalent hydrocarbon having at least one carbon-carbon triple bond, wherein the unsaturated monovalent hydrocarbon can be obtained by removing a hydrogen atom from a carbon atom of a parent alkyne. The alkynyl group can be branched, straight chain or cyclic (e.g., cycloalkynyl). Exemplary alkynyl groups include optionally substituted C 2-24 Alkyl. Alkyl groups can be cyclic or acyclic, and are exemplified by ethynyl, 1-propynyl, and the like. Alkyl groups can be monovalent or polyvalent (e.g., 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. Alkyl groups can also be substituted or unsubstituted. For example, alkynyl groups can be substituted with one or more substituents, as described herein for alkyl.

[0086] By "ambient temperature" is meant 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" refers to -C(O)NR 1 R 2 or-NHCOR 1 , where R 1 and R 2 are each independently selected from hydrogen, an aliphatic, a heteroaliphatic, an aromatic group as defined herein, or any combination thereof, or wherein R 1 and R 2 Together with the respective nitrogen atom to which they are attached they may form a heterocyclyl group as defined herein.

[0088] "Amino" refers to -NR 1 R 2 , where R 1 and R 2 are each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl or optionally substituted siloxy as defined herein, or any combination thereof; or wherein R 1 and R 2 Together with the nitrogen atom to which they are attached, they may form a heterocyclic group as defined herein. 1 and R 2Each 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 siloxy. In specific embodiments, R 1 and R 2 Together with the respective nitrogen atom to which they are attached, they may form an optionally substituted heterocyclic group.

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

[0090] "Aminooxy" refers to an oxy group, as defined herein, substituted with an amino group, as defined herein. In some embodiments, aminooxy is -O-NR 1 R 2 , where R 1 and R 2 R is each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl or optionally substituted siloxy as defined herein, or any combination thereof; or R 1 and R 2 Together with the nitrogen atom to which they are attached, they may form a heterocyclic group as defined herein. 1 and R 2Each 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 siloxy.

[0091] Unless otherwise indicated, "aromatic group" refers to a cyclic conjugated group or moiety having 5 to 15 ring atoms of a single ring (e.g., phenyl) or multiple fused rings in which at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl); that is, 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 Huckel rule (4n+2). The point of connection to the parent structure is typically through the aromatic portion of the fused ring system. Aromatic groups are unsubstituted or substituted, for example, with functional groups as described herein. For example, aromatic groups may be substituted with one or more substituents, as described herein for alkyl and / or aryl groups.

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

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

[0094] "Aromatic-oxy" refers to an aromatic group that is or can be coupled to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through an oxy group (-O-). In some embodiments, aromatic-oxy ​​is -OR, wherein R is an optionally substituted aromatic group as defined herein.

[0095] "Aromatic-oxycarbonyl" refers to an aromatic group that is or can be coupled to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through an oxycarbonyl (-C(O)O-). In some embodiments, the aromatic-carbonyl is -C(O)OR, wherein R is an optionally substituted aromatic group as defined herein.

[0096] "Aryl" refers to a group comprising at least 5 carbon atoms and up to 15 carbon atoms (C 5-15), such as 5 to 10 carbon atoms (C 5-10 ), an aromatic carbocyclic group having a single ring or multiple fused rings, which may or may not be aromatic, provided that the point of attachment to the remainder of the compounds disclosed herein is through an atom of the aromatic carbocyclic group. The aryl group may be substituted with one or more groups other than hydrogen, such as aliphatic groups, heteroaliphatic groups, aromatic groups, 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 groups, which are defined as groups containing aromatic groups having at least one heteroatom bound to the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term non-heteroaryl is also included in the term aryl, which defines groups containing aromatic groups without heteroatoms. The aryl group may be substituted or unsubstituted. The aryl group may be substituted with one, two, three, four, or five 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., -OR, where R is C 1-6 Alkyl); (4) C 1-6 Alkoxy-C 1-6 Alkyl (e.g., -LOR, wherein L and R are each 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., -LS(O)-R, wherein L and R are each 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 L and R are each independently C 1-6 alkyl); (9) aryl; (10) amino (e.g., -NR 1 R 2 , where R 1 and R 2 are each independently selected from hydrogen, an aliphatic, a heteroaliphatic, a halogenated aliphatic, a halogenated heteroaliphatic, an aromatic group, or any combination thereof as defined herein; or R 1 and R 2Together with the nitrogen atom to which they are attached, they may form a heterocyclic 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 , where L 1 It is C 1-6 Alkyl; L 2 Is a covalent bond or C 1-6 Alkyl; R 1 and R 2 are each independently selected from hydrogen, an aliphatic, a heteroaliphatic, a halogenated aliphatic, a halogenated heteroaliphatic, an aromatic group, or any combination thereof as defined herein; or R 1 and R 2 Together with the nitrogen atom to which they are attached, they may form a heterocyclic group as defined herein; and 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., -LR, where L is C 1-6 Alkyl and R is C 4-18 aryl); (14) aroyl (e.g., C(O)-R, wherein R is aryl); (15) azido (e.g., -N3); (16) cyano (e.g., -CN); (17) C 1-6 Azidoalkyl (e.g., -L-N3, where L is C 1-6 alkyl); (18) aldehydes (e.g., -C(O)H); (19) aldehydes-C 1-6 Alkyl (e.g., -LC(O)H, where L is C 1-6 Alkyl); (20)C 3-8 Cycloalkyl; (21)C 3-8 Cycloalkyl-C 1-6 Alkyl (e.g., -LR, where 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 , where L 1 It is C 1-6 Alkyl; L 2 Is a covalent bond or C1-6 alkyl; X is fluorine, bromine, chlorine or iodine; and R 1 and R 2 Each independently is H or C 1-6 alkyl); (24) heterocyclyl (e.g., as defined herein, such as a 5-, 6-, or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (25) heterocyclyloxy (e.g., -OR, wherein R is a heterocyclyl, as defined herein); (26) heterocyclylacyl (e.g., -C(O)-R, wherein R is a 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 , where L 1 It is C 1-6 Alkyl; L 2 is a covalent bond or an alkyl group; and R 1 and R 2 Each independently is H or C 1-6 alkyl, as defined herein); (29) nitro; (30) C 1-6 Nitroalkyl (e.g., -L 1 -NO or -L 2 -C(NO)(R 1 )-R 2 , where L 1 It is C 1-6 Alkyl; L 2 is a covalent bond or an alkyl group; and R 1 and R 2 Each independently is H or C 1-6 alkyl, as defined herein); (31) N-protected amino; (32) N-protected amino-C 1-6 Alkyl; (33) Oxo (eg, =O); (34) C 1-6 Thioalkyl (e.g., -SR, where R is C 1-6 (35) thio-C 1-6 Alkoxy-C 1-6 Alkyl (e.g., -LSR, wherein L and R are each independently C 1-6 Alkyl); (36)-(CH2) r CO2R 1 , where r is an integer from 0 to 4, and R 1 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 1-6Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (37)-(CH2) r CONR 1 R 2 , wherein r is an integer from 0 to 4 and wherein R 1 and R 2 are each independently selected from: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (38)-(CH2) r S02R 1 , where r is an integer from 0 to 4, and where R 1 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., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (39)-(CH2) r SO2NR 1 R 2 , where r is an integer from 0 to 4, and where R 1 and R 2 are each 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., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (40)-(CH2) r NR 1 R 2 , where r is an integer from 0 to 4, and where R 1 and R 2 are each independently selected from the group consisting of: (a) hydrogen, (b) an N-protecting group, (c) a 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 1-6Alkyl (e.g., -LR, 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., -LR, where L is C 1-6 Alkyl and R is C 3-8 (41) thiols (e.g., -SH); (42) perfluoroalkyls (e.g., -(CF2) n CF3, wherein n is an integer from 0 to 10); (43) perfluoroalkoxy (e.g., -O-(CF2) n CF3, wherein n is an integer from 0 to 10); (44) aryloxy (e.g., -OR, wherein R is aryl); (45) cycloalkoxy (e.g., -OR, wherein R is cycloalkyl); (46) cycloalkylalkoxy (e.g., -OLR, wherein L is alkyl and R is cycloalkyl); and (47) arylalkoxy (e.g., -OLR, wherein L is alkyl and R is aryl). In specific embodiments, the unsubstituted aryl 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.

[0097] "Aryl-alkyl", "aryl-alkenyl" and "aryl-alkynyl" refer to an aryl group, as defined herein, coupled (or linked) to a parent molecular group through an alkyl, alkenyl or alkynyl group, respectively, as defined herein. Aryl-alkyl, aryl-alkenyl and / or aryl-alkynyl groups can be substituted or unsubstituted. For example, aryl-alkyl, aryl-alkenyl and / or aryl-alkynyl groups can be substituted with one or more substituents, as described herein for aryl and / or alkyl groups. Exemplary unsubstituted aryl-alkyl groups have 7 to 16 carbon atoms (C 7-16 aryl-alkyl), and those having an aryl group of 4 to 18 carbons and an alkyl group of 1 to 6 carbons (i.e., C 4-18 Aryl-C 1-6 Exemplary unsubstituted aryl-alkenyl groups have 7 to 16 carbon (C 7-16 aryl-alkenyl), and those having an aryl group containing 4 to 18 carbons and an alkenyl group containing 2 to 6 carbons (i.e., C 4-18 Aryl-C 2-6 Exemplary unsubstituted aryl-alkynyl groups have 7 to 16 carbon (C 7-16aryl-alkynyl), and those having an aryl group containing 4 to 18 carbons and an alkynyl group containing 2 to 6 carbons (i.e., C 4-18 Aryl-C 2-6 In some embodiments, the aryl-alkyl group is -LR, wherein L is alkyl or alkylene as defined herein, and R is aryl as defined herein. In some embodiments, the aryl-alkenyl group is -LR, wherein L is alkenyl or alkenylene as defined herein, and R is aryl as defined herein. In some embodiments, the aryl-alkynyl group is -LR, wherein L is alkynyl or alkynylene as defined herein, and R is aryl as defined herein.

[0098] "Arylene" refers to a polyvalent (e.g., divalent) form of an aryl group as described herein. Exemplary arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthene, anthracene, or phenanthrenyl. 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. Arylene can be branched or unbranched. Arylene can also be substituted or unsubstituted. For example, arylene can be substituted with one or more substituents, as described herein for aryl.

[0099] "Arylalkoxy" refers to an aryl-alkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, arylalkoxy is -OLR, wherein L is alkyl, as defined herein, and R is aryl, as defined herein.

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

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

[0102] "Aroyl" refers to an aryl group attached to the parent molecular group through a carbonyl group. In some embodiments, unsubstituted aroyl is C 7-11 Aroyl or C5-19 In other embodiments, aroyl is -C(O)-R, wherein R is aryl as defined herein.

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

[0104] "Atomic layer deposition" (ALD) means a vapor deposition process in which a deposition cycle (preferably a plurality of consecutive deposition cycles) is performed in a process chamber (i.e., a deposition chamber). Typically during each cycle, a precursor is chemically adsorbed to a deposition surface (i.e., a substrate assembly surface or a previously deposited underlying surface, such as material from a previous ALD cycle) to form a monolayer or sub-monolayer that is not susceptible to reaction with additional precursors (i.e., a self-limiting reaction). Thereafter, if desired, a reactant (i.e., another precursor or a reactive gas) may be introduced into the process chamber for conversion of the chemically adsorbed precursor into the desired material on the deposition surface. Typically, the reactant is capable of reacting with the already chemically adsorbed precursor. Further, after the chemically adsorbed precursor is converted, a sweep step may also be utilized during each cycle to remove excess precursor from the process chamber and / or to remove excess reactant and / or reaction byproducts from the process chamber.

[0105] "Azide" refers to a -N3 group.

[0106] "Azidoalkyl" refers to an azido group attached to the parent molecular group through an alkyl group, as defined herein. In some embodiments, azidoalkyl is -L-N3, wherein L is an alkyl group as defined herein.

[0107] "Azo" refers to the group -N=N-.

[0108] "Bidentate ligand" means a ligand having two atoms coordinated to a central atom in the complex, ie, an alkyl diamine.

[0109] "Carbamoyl" refers to an amino group attached to the parent molecular group through a carbonyl group, as defined herein. In some embodiments, carbamoyl is -C(O)NR 1 R 2 Group, where R 1 and R 2 are each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl or optionally substituted siloxy as defined herein, or any combination thereof; or wherein R 1 and R 2Together with the respective nitrogen atom to which it is attached, they may form a heterocyclyl group as defined herein.

[0110] "Carbamoyloxy" refers to a carbamoyl group, as defined herein, appended to the parent molecular group through n oxy groups, as defined herein. In some embodiments, the carbamoyl group is -OC(O)NR 1 R 2 Group, where R 1 and R 2 are each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl or optionally substituted siloxy as defined herein, or any combination thereof; or wherein R 1 and R 2 Together with the respective nitrogen atom to which it is attached, they may form a heterocyclyl group as defined herein.

[0111] "Carboimidoyl" refers to a -C(NR)- group. In some embodiments, R is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl or optionally substituted aryl-alkyl, optionally substituted siloxy, or any combination thereof.

[0112] "Carbonyl" refers to a -C(O)- group, which may also be represented as >C=O.

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

[0114] "Catalyst" refers to a compound capable of catalyzing a synthesis reaction, typically present in a small amount relative to the reactants, as readily understood by one of ordinary skill in the art. In some embodiments, the catalyst may include a transition metal coordination complex.

[0115] "Cyanato" refers to an -OCN group.

[0116] "Cyano" refers to a -CN group.

[0117] "Cycloaliphatic" means a cyclic aliphatic radical as defined herein.

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

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

[0120] Unless otherwise indicated, "cycloalkyl" refers to a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon radical of 3 to 8 carbons, and is exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.heptyl], and the like. Cycloalkyls may also be substituted or unsubstituted. For example, cycloalkyls may be substituted with one or more groups, including those described herein for alkyls. In addition, cycloalkyls may include one or more double bonds and / or triple bonds.

[0121] "Cycloheteroaliphatic" refers to a heteroaliphatic group as defined herein that is cyclic.

[0122] "Deposition" or "vapor deposition" means a process of forming a metal layer 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 to and / or in contact with one or more surfaces of a substrate (i.e., a semiconductor substrate or semiconductor component) placed in a deposition chamber. The substrate is usually heated. These metal-containing compounds form a non-volatile, thin, uniform metal-containing layer on the surface of the substrate. One operation of the method is one cycle, and the process can be repeated as many cycles as required to obtain the desired metal thickness.

[0123] "Disilyl" refers to a group containing a Si-Si bond. In some embodiments, the disilyl group is -SiR S1 R S2 -SiR S3 R S4 R S5 Or-SiR S1 R S2 -SiR S3 R S4 - group, where R S1 , R S2 , R S3 , R S4 and R S5 Each is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino.

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

[0125] An "electron donating group" refers to a functional group that is capable of donating at least a portion of its electron density to the ring to which it is directly attached, such as by resonance.

[0126] "Electron withdrawing group" refers to a functional group capable of accepting electron density from the ring to which it is directly attached, such as by inductive electron withdrawal.

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

[0128] “Chalcogen element” refers to O, S, Se or Te.

[0129] "Haloaliphatic" means an aliphatic group as defined herein wherein one or more hydrogen atoms (eg, 1 to 10 hydrogen atoms) are independently replaced by a halogen atom (eg, fluorine, bromine, chlorine, or iodine).

[0130] "Haloalkyl" refers to an alkyl group as defined herein, wherein one or more hydrogen atoms, e.g., 1 to 10 hydrogen atoms, are independently replaced by halogen atoms, e.g., fluorine, bromine, chlorine, or iodine. In independent embodiments, haloalkyl can be a -CX3 group, wherein each X can be independently selected from fluorine, bromine, chlorine, or iodine. In some embodiments, haloalkyl is -LX, wherein L is an alkyl group as defined herein, and X is fluorine, bromine, chlorine, or iodine. In other embodiments, haloalkyl is -LC(X)(R 1 )-R 2 , wherein L is a covalent bond or an alkyl group as defined herein; X is fluorine, bromine, chlorine or iodine; and R 1 and R 2 Each is independently H or alkyl as defined herein.

[0131] "Haloheteroaliphatic" refers to a heteroaliphatic group as defined herein wherein one or more hydrogen atoms, eg, 1 to 10 hydrogen atoms, are independently replaced by a halogen atom (eg, fluorine, bromine, chlorine, or iodine).

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

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

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

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

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

[0137] "Heteroalkyl", "heteroalkenyl" and "heteroalkynyl" refer to an alkyl, alkenyl or alkynyl group (which may be branched, straight chain or cyclic) as defined herein, respectively, which contains at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms or one to 5 heteroatoms, which heteroatoms may be selected from but are not limited to oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus and oxidized forms thereof.

[0138] "Heteroalkylene," "heteroalkenylene," and "heteroalkynylene" refer to polyvalent (eg, divalent) forms of heteroalkyl, heteroalkenyl, or heteroalkynyl groups, respectively, as described herein.

[0139] "Heteroaromatic" refers to an aromatic group as defined herein, which contains at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms or one to 5 heteroatoms within the group, the heteroatoms being selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof. Heteroaromatic groups are unsubstituted or substituted, for example, with functional groups as described herein. For example, heteroaromatic groups may be substituted with one or more substituents, such as described herein for alkyl and / or aryl groups.

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

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

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

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

[0144] "Heteroaryl" refers to an aryl group containing at least one heteroatom to six heteroatoms (e.g., one to four heteroatoms) in the ring, wherein the heteroatoms are selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof. Such heteroaryl groups may have a monocyclic or multiple condensed rings, wherein the condensed rings may or may not be aromatic and / or contain heteroatoms, provided that the point of attachment is through an atom of an aromatic heteroaryl group. Heteroaryl groups may be substituted by one or more groups that are not hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Exemplary heteroaryl groups include a subset of heterocyclic groups as defined herein, which are aromatic, i.e., they contain 4n+2 π electrons in a monocyclic or polycyclic ring system.

[0145] "Heteroarylene" refers to a polyvalent (eg, divalent) form of a heteroaryl group as described herein.

[0146] "Heteroatom" refers to an atom other than carbon, such as oxygen, nitrogen, sulfur, silicon, boron, selenium, or phosphorus. In particular disclosed embodiments, heteroatoms do not include halogen atoms, such as when valence restrictions do not permit.

[0147] Unless otherwise indicated, "heterocyclyl" refers to a 5, 6 or 7-membered ring containing one, two, three or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur or halide). 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, wherein any of the above heterocyclic rings is fused with one, two or three rings independently selected from the group consisting of an aryl ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring and another monocyclic heterocyclic ring, such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuranyl, benzothienyl, etc. The heterocyclic group includes thiirane, thietanyl, tetrahydrothienyl, thianyl, thiepanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyridinyl, homopiperidinyl, pyrazinyl, piperazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolidinyl, oxazolidinone, isoxazolyl, isoxazolidiniyl, morpholinyl, thiomorpholinyl, thiazolyl, thiazolidinyl, isoxazolidinyl, thiazolyl, isothiazolidinyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, furanyl, thienyl, thiazolidinyl, isothiazolyl, isoindazolyl, triazolyl, tetrazolyl, oxadiazolyl, uricyl, thiadiazolyl, pyrimidyl, tetrahydrofuranyl, dihydrofuranyl, dihydrothienyl, dihydroindolyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dithiazolyl, dioxanyl, dioxinyl, dithianyl, trithianyl, oxazinyl, thiazinyl, oxathiolanyl, triazinyl, benzofuranyl, benzothienyl and the like.

[0148] "Heterocyclyloxy" refers to a heterocyclyl, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, heterocyclyloxy is -OR, wherein R is heterocyclyl, as defined herein.

[0149] "Heterocycloacyl" means a heterocyclyl, as defined herein, attached to the parent molecular moiety through a carbonyl group. In some embodiments, heterocycloacyl is -C(O)-R, wherein R is a heterocyclyl, as defined herein.

[0150] "Hydrazino" refers to -NR 1 -NR 2 R3 , where R 1 , R 2 and R 3 are each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl or optionally substituted siloxy as defined herein, or any combination thereof; or wherein R 1 and R 2 A combination of or 2 and R 3 The combination of together with the nitrogen atom to which they are attached may form a heterocyclic group as defined herein. 1 , R 2 or R 3 Each is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl or optionally substituted aryl-alkyl. In specific embodiments, R 2 and R 3 Together with the respective nitrogen atom to which they are attached, they may form an optionally substituted heterocyclic group.

[0151] "Hydroxyl" refers to -OH.

[0152] "Hydroxyalkyl" refers to an alkyl group as defined herein substituted with 1 to 3 hydroxy groups, provided that no more than one hydroxy group may be attached to a single carbon atom of the alkyl group, and is exemplified by hydroxymethyl, dihydroxypropyl, and the like. In some embodiments, hydroxyalkyl is -L-OH, wherein L is an alkyl group as defined herein. In other embodiments, hydroxyalkyl is -LC(OH)(R 1 )-R 2 , wherein L is a covalent bond or an alkyl group as defined herein, and R 1 and R 2 Each is independently H or alkyl as defined herein.

[0153] "Imino" refers to a moiety comprising a carbon imino group. In some embodiments, the imino group is C(NR 1 )R 2 , where R 1 and R 2 Each 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 siloxy, or any combination thereof. In other embodiments, the imino group is -C(NR 1 )H、-C(NR 1)R Ak or -C(NR N1 )R Ar , where R 1 R is hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl or optionally substituted aryl-alkyl, or optionally substituted siloxy; R Ak is optionally substituted alkyl or optionally substituted aliphatic; and R Ar is an optionally substituted aryl group or an optionally substituted aromatic group.

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

[0155] "Isocyanato" refers to a -NCO group.

[0156] "Isocyano" refers to a -NC group.

[0157] "Ketone" refers to -C(O)R or a compound containing this group, wherein R is selected from aliphatic, heteroaliphatic, aromatic or any combination thereof as defined herein. Examples of ketones may include R 1 C(O)R, where R and R 1 Each is independently selected from aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof as defined herein.

[0158] As used herein, "platinum metal" or "metallic platinum" refers to a material that is substantially composed of molybdenum (Mo) in a zero oxidation state. Other elements (e.g., C, N, or O) may be present in small amounts in the platinum metal (e.g., a total content of less than about 15 atomic % or less than about 10%, wherein hydrogen is not included in this calculation). As used herein, "high-purity platinum metal" refers to platinum metal that includes less than about 5% of other elements, such as less than about 1% of other elements, wherein hydrogen is not included in this calculation. In some embodiments, the platinum metal deposited by the method provided herein includes at least a portion, i.e., at least about 90%, such as at least about 95% or at least about 99% pure platinum, wherein % refers to weight percentage.

[0159] "Nitro" refers to a -NO2 group.

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

[0161] "Oxo" refers to a =0 group.

[0162] "Oxy" refers to -O-.

[0163] "Perfluoroalkyl" refers to an alkyl group as defined herein in which each hydrogen atom is replaced by a fluorine atom. Exemplary perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, and the like. In some embodiments, the perfluoroalkyl group is -(CF2) n CF3, wherein n is an integer from 0 to 10.

[0164] "Perfluoroalkoxy" refers to an alkoxy group as defined herein wherein each hydrogen atom is replaced by a fluorine atom. In some embodiments, the perfluoroalkoxy group is -OR, wherein R is a perfluoroalkyl group as defined herein.

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

[0166] "Salt" refers to an ionic form of a compound or structure (e.g., any formula, compound, or composition as described herein) that contains a cationic or anionic compound to form an electrically neutral compound or structure. Salts can be prepared in situ during the final isolation and purification of the compounds of the invention, or separately by reacting a free base group with a suitable organic acid (thereby producing an anionic salt) or by reacting an acid group with a suitable metal or organic salt (thereby producing a cationic salt). Representative anionic salts include acetate, adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, borate, bromide, butyrate, camphorate, camphorsulfonate, chloride, citrate, cyclopentanepropionate, digluconate, dihydrochloride, diphosphate, dodecyl sulfate, ethylenediaminetetraacetate, ethanesulfonate, fumarate, glucoheptonate, gluconate, glutamate, glycerophosphate, hemisulfate, heptanoate, hexanoate, hydrobromide, hydrochloride, hydroiodide, isethionate, hydroxynaphthoate, iodide, lactate, lactobionate, laurate, lauryl sulfate, malate, malate, The invention also includes but is not limited to iodine, 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, triethyl iodide, toluenesulfonate, undecanoate, valerate, and the like. Representative cationic salts include metal salts, such as alkali metal or alkaline earth metal salts, for example, barium, calcium (e.g., calcium edetate), lithium, magnesium, potassium, sodium, etc.; other metal salts, such as aluminum, bismuth, iron and zinc; and non-toxic ammonium, quaternary ammonium and amino cations, including but not limited to 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.Other salts include ammonium, sulfonium, sulfoxonium, phosphonium, iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphazinium, phosphazenium, pyridinium, and the like, as well as other cationic groups described herein (e.g., optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrrolium, optionally substituted furanium, optionally substituted thiophenium, optionally substituted imidazolium, optionally substituted pyrazolium, optionally substituted isothiazolium, optionally substituted triazolium, optionally substituted tetrazolium, optionally substituted furazanium, optionally substituted pyridinium, optionally substituted pyrimidinium, optionally substituted pyrazinium, optionally substituted triazinium, optionally substituted tetrazinium, optionally substituted pyridazinium, optionally substituted oxazinium, optionally substituted 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 azepi nium), optionally substituted indolium, optionally substituted isoindolinium, optionally substituted indolizinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinolinium, optionally substituted quinolizinium, optionally substituted dehydroquinolinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted purinium).

[0167] "Monodeuterated ammonia" means NH2D.

[0168] "Dideuterated ammonia" means NHD2.

[0169] "Trideuterated ammonia" means ND3.

[0170] In the present invention, the terms "semiconductor wafer", "wafer", "substrate", "wafer substrate" and "partially manufactured integrated circuit" are used interchangeably. It should be understood by those of ordinary skill in the art that the term "partially manufactured integrated circuit" can refer to a silicon wafer during any of many stages of integrated circuit manufacturing. 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 invention is implemented on a wafer. However, the present invention is not limited to this. Workpieces can have a variety of shapes, sizes and materials. In addition to semiconductor wafers, other workpieces that can utilize the present invention include a variety of articles, such as printed circuit boards and the like. As used herein, the term "semiconductor substrate" or "substrate" refers to a substrate at any stage of semiconductor device manufacturing, which contains semiconductor material located at any position within its structure. It should be understood that the semiconductor material in the semiconductor substrate does not need to be exposed. An example of a semiconductor substrate is a semiconductor wafer having multiple layers of other materials (e.g., dielectrics) covering the semiconductor material. The following detailed description assumes that the disclosed implementation is implemented on a semiconductor wafer (e.g., on a 200 mm, 300 mm or 450 mm semiconductor wafer). However, the disclosed implementations are not limited thereto. Semiconductor wafers may be of various shapes, sizes, and materials. In addition to semiconductor wafers, other types of workpieces that may utilize the disclosed implementations include various articles, such as printed circuit boards, and the like.

[0171] "Silyl" refers to -SiR 1 R 2 R 3 Or-SiR 1 R 2 - group. In some embodiments, R 1 , R 2 and R 3 Each is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In specific embodiments, R 1 , R 2 and R 3 Each 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, silyl is -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; a, b, and c are each ≥ 0; and a+b+c=3. In specific embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0172] "Silyloxy" refers to -OR, where R is an optionally substituted silyl group as described herein. In some embodiments, silyloxy is -O-SiR 1 R 2 R 3 , where R 1 , R 2 and R 3 Each is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In specific embodiments, R 1 , R 2 and R 3 Each 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, silyloxy 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; a, b, and c are each ≥ 0; and a+b+c=3. In specific 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 functionality or reactivity. Examples of substituents include alkyl, alkenyl, alkynyl, cycloalkyl (non-aromatic ring), Si(alkyl)3, Si(alkoxy)3, alkoxy, amino, alkylamino, alkenylamino, amide, amidine, guanidine, hydroxy, thioether, alkylcarbonyl, alkylcaronyloxy, alkoxycarbonyloxy, carbonate, alkoxycarbonyl, aminocarbonyl, alkylthiocarbonyl, phosphate, and thiocarbonyl. The substituents may themselves be substituted. For example, an amino substituent may itself be monosubstituted or independently disubstituted with additional substituents as defined above, such as alkyl, alkenyl, alkynyl, and cycloalkyl (non-aromatic ring).

[0174] "Sulfinyl" refers to a -S(O)- group.

[0175] "Sulfo" refers to a -S(O)2OH group.

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

[0177] "Time-separated pulses" means that a certain amount of gas flow is delivered over a period of time.

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

[0179] "Thiol" refers to a -SH group.

[0180] "Unsubstituted" means that any open valence of an atom is occupied by hydrogen. Additionally, if the occupant of an open valence position on an atom is not specified, it is hydrogen.

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

[0182] One of ordinary skill in the art will recognize that the definitions provided above are not intended to encompass impermissible substitution patterns (e.g., a methyl group substituted with 5 different groups, etc.). Such impermissible substitution patterns are readily recognized by one of ordinary skill in the art. Any functional group disclosed herein and / or defined above may be substituted or unsubstituted, unless otherwise specified therein.

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

[0184] In semiconductor device manufacturing, deposition and etching techniques are used to form patterns of materials, such as to form metal lines embedded in dielectric layers. Some patterning schemes utilize conformal deposition of materials, where the deposited layer can follow the contours of protruding and / or recessed features on the substrate surface. Atomic layer deposition (ALD) is a method of forming conformal films on a substrate that utilizes the adsorption of one or more reactants (precursors) to the substrate surface, followed by chemical conversion of the adsorbed layer to the desired material. Because ALD utilizes sequential reactions that occur on the substrate surface, are separated in time, and may be limited by the amount of adsorbed reactants, the method can provide thin conformal layers with excellent step coverage.

[0185] ALD can use plasma to promote the reaction of deposition precursors to form the desired film. The method using plasma is called plasma enhanced ALD (PEALD). The method without plasma is called thermal ALD.

[0186] ALD can be used to deposit silicon-containing films such as silicon oxide, silicon nitride, and silicon carbide. The method is also suitable for depositing other materials such as metals.

[0187] In semiconductor manufacturing, features such as lines and vias can be filled with conductive materials such as tungsten (W), copper (Cu), and cobalt (Co). As semiconductor device dimensions shrink to the 10nm node and below, the contact resistance of the lines and vias in the metal interconnects increases rapidly. This is due to the reduction in current carrying cross-sections, increased electron scattering, and the challenges of filling narrow features with current copper or tungsten process solutions in narrow features.

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

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

[0190] The temperature reduction conditions of the molybdenum deposition method according to certain disclosed embodiments are suitable for back-end process applications. In addition, the use of remote plasma according to certain disclosed embodiments and in some cases avoids low-K material damage that may occur when using a direct plasma source.

[0191] Copper deposition can be accomplished by electroplating. However, electroplating has disadvantages due to the need for a surface conductive layer to provide the electric field for depositing copper. Specifically, in a device structure with a 50nm opening to be filled, the conductive liner layer required to distribute the electric field may occupy up to 30nm, which severely limits the fill width of low-resistivity copper metal. When the line width is reduced to below 10nm-20nm, copper scaling is limited by a sharp increase in resistivity. Morphology is another factor that must be considered in the copper deposition process. Rough, discontinuous and island-like morphologies may result in copper films being deposited by atomic layer deposition when the film approaches the limit of a few atomic monolayers. Thin copper films deposited according to certain disclosed embodiments produce smoother morphologies or lower resistivity or both smoother morphologies and lower resistivity.

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

[0193] The substrate may be a silicon wafer, for example, a 200 mm wafer, a 300 mm wafer, or a 450 mm wafer, comprising a wafer having one or more layers of material, such as dielectric, conductor, or semiconductor material deposited thereon. In various embodiments, the substrate is patterned. The patterned substrate may have "features", such as pillars, poles, grooves, through holes, or contact holes, which may be characterized by one or more narrow and / or concave openings, constrictions within the features, and high aspect ratios. The features may be formed in one or more of the above layers. An example of a feature is a pillar or pole in a semiconductor substrate or a layer on a substrate. Another example is a groove in a substrate or layer.

[0194] In some embodiments, the feature (e.g., a column) may have a depth-to-width 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 feature may also have a dimension near the opening, for example, an opening diameter or line width between about 10nm and 500nm (e.g., between about 25nm and about 300nm). The disclosed method may be performed on a substrate having a feature with an opening less than about 150nm. A through hole, a groove, or other concave feature may be referred to as an unfilled feature or feature. According to various embodiments, the feature profile may gradually narrow at the feature opening and / or include an overhang. The concave profile is a profile that narrows from the bottom, closed end, or interior of the feature to the feature opening. The concave profile may be generated by asymmetric etching dynamics during patterning and / or by an overhang caused by non-conformal film step coverage in a previous film deposition (diffusion barrier deposition). In various examples, the opening of the feature at the top of the feature may have a width less than the width of the bottom of the feature.

[0195] The features can be trenches or vias formed in a dielectric layer. Examples of dielectric materials include oxides, such as silicon oxide (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-κ dielectrics, such as carbon-doped SiO2. Metals can be deposited in features to form electrical contacts to underlying layers. 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 (CoSi x ), platinum silicide (PtSi x ), Ruthenium silicide (RuSi x ) and nickel platinum silicide (NiPty Si x ). 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 a sidewall surface and a bottom surface. In some embodiments, the sidewall surface can be the same material as the bottom surface. For example, in some embodiments, the sidewall surface and the bottom surface are titanium nitride (TiN). In some embodiments, the sidewall surface can be a different material from the material of the bottom surface. For example, the bottom surface can be a metal silicide and the sidewall surface can be a silicon oxide, such as SiO2.

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

[0198] Atomic layer deposition (ALD) is a technique for depositing thin layers of material using a continuous self-limiting reaction. The ALD process utilizes a surface-mediated deposition reaction to deposit films in a layer-by-layer manner in a cycle. As an example, an ALD cycle may include the following operations: (i) delivering / adsorbing a precursor, (ii) clearing the precursor from the chamber, (iii) delivering a second reactant and optionally igniting a plasma, and (iv) clearing byproducts from the chamber. The reaction between the second reactant and the adsorbed precursor that results in the formation of a film on the surface of the substrate affects the composition and properties of the film, such as non-uniformity, stress, wet etch rate, dry etch rate, electrical characteristics (e.g., breakdown voltage and leakage current), etc. In ALD deposition of metal films, the reaction involves the reaction of oxygen plasma with carbon and nitrogen to form gaseous species; oxidizing the metal to a metal oxide; removing trace carbon, nitrogen, and hydrogen impurities; and improving film adhesion and densification.

[0199] Unlike chemical vapor deposition (CVD) technology, the ALD process utilizes surface-mediated deposition reactions to deposit films in a layer-by-layer manner. In one example of an ALD process, a substrate surface including a large number of surface active sites is exposed to a gas phase distribution of a first precursor, such as a metal-containing precursor, which is provided in a certain dose to a chamber containing a substrate. The molecules of the 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 adsorption layer may include the compound and a derivative of the compound. For example, the adsorption layer of the metal-containing precursor may include a metal-containing precursor and a derivative of the metal-containing precursor. After the first precursor is dosed, the chamber is then evacuated to remove most or all of the first precursor remaining in the gas phase, so that most or only the adsorbed substances remain. In some implementations, the chamber may not be completely evacuated. For example, the reactor may be evacuated so that the partial pressure of the first precursor in the gas phase is low enough to slow down the reaction. A second reactant (e.g., an oxygen-containing gas) is introduced into the chamber so that a portion 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 temporarily applying the activation source. The chamber may then be evacuated again to remove unbound second reactant molecules. As described above, in some embodiments, the chamber may not be completely evacuated. Additional ALD cycles may be used to build up film thickness.

[0200] In some implementations, the ALD method includes plasma activation. As described herein, the ALD method and apparatus described herein may be a conformal film deposition (CFD) method, as summarized in U.S. Patent Application No. 13 / 084,399, filed on April 11, 2011, entitled “PLASMAACTIVATED CONFORMAL FILM DEPOSITION” (now U.S. Patent No. 8,728,956) and U.S. Patent Application No. 13 / 084,305, filed on April 11, 2011, entitled “SILICON NITRIDE FILMS AND METHODS,” the entire contents of which are incorporated herein by reference.

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

[0202] Metals can be deposited by plasma enhanced atomic layer deposition (PEALD) method. PEALD is a surface-mediated deposition technique in which precursors and reactants (reducing gases in the form of plasma) are introduced into a deposition chamber in sequence. 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 will depend on the geometry and size of the chamber. The amount of hydrogen may range from about 100% (when pure hydrogen is used) to 5% (when mixed with an inert gas) of hydrogen. For PEALD, the temperature of the substrate and the pressure of the chamber may 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 may be pressurized to less than about 10 Torr. In some embodiments, the chamber pressure may be in the range of about 0.1 Torr to about 9.9 Torr. In some embodiments, the duration of exposure is about 5 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 can be a molybdenum precursor, a copper precursor, a tungsten precursor, a cobalt precursor, or a ruthenium precursor, among others. Exemplary metal precursors are discussed in the following paragraphs. Copper Precursor

[0204] A variety of copper precursors can be used to deposit copper metal, where copper can be in the +1 or +2 oxidation state. The precursor can be a cuprous (copper (I)) compound, such as acetylacetonate, ketoiminate, diiminate, cyclopentadienyl compound, amidinate, guanidinate, or amide; or a copper (copper (II)) compound, such as acetylacetonate, ketoiminate, or aminoalkoxide, such as Figure 2 and Figure 3 In some embodiments, the precursor is a coordination complex in which the copper is coordinated to a multiple bond, such as a double or triple bond; or to the oxygen of, for example, a carbonyl group.

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

[0206] In general, the molybdenum-containing precursor can include molybdenum in a wide range of oxidation states from 0 to +6. In some embodiments, the molybdenum compound has molybdenum in low 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 silicon-containing reactants can assist in halogen removal; however, halogen-free molybdenum-containing precursors can also be used. Suitable molybdenum-containing precursors include halides and oxyhalides of molybdenum, such as fluorides, chlorides, bromides, oxyfluorides, oxychlorides, and oxybromides, wherein the molybdenum can be in any oxidation state from +2 to +6.

[0207] The molybdenum chloride precursor is of the formula MoCl x , wherein x is 2, 3, 4, 5 or 6, and includes a molybdenum dichloride precursor (MoCl2), molybdenum trichloride (MoCl3), molybdenum tetrachloride (MoCl4), molybdenum pentachloride (MoCl5) and molybdenum hexachloride (MoCl6). In some embodiments, MoCl5 or MoCl6 is used. Although the description mainly relates to MoCl x Precursors are generally used, but in other embodiments, other molybdenum halide precursors may be used. The molybdenum halide precursor is of the formula MoX z, wherein 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 fluoride (MoF6). In some embodiments, MoX6 without fluorine is used. z Precursors are used to prevent fluorine etching or incorporation. In some embodiments, bromine-free and / or iodine-free MoX z Precursors to prevent etching or incorporation of bromine or iodine.

[0208] The molybdenum oxyhalide precursor is of the formula MoO y X z , wherein X is a halogen (fluorine (F), chlorine (Cl), bromine (Br) or iodine (I)) and y and z are numbers greater than 0, such that MoO y X z Examples of molybdenum oxyhalides include molybdenum dioxide dichloride (MoO2Cl2), molybdenum oxytetrachloride (MoOCl4), molybdenum oxytetrafluoride (MoOF4), molybdenum dioxide dibromide (MoO2Br2), and molybdenum iodide MoO2I and Mo4O 11 I.

[0209] To maintain suitable volatility, precursors are selected in many of the embodiments discussed herein to have a molecular weight of less than about 450 g / mol (eg, less than about 400 g / mol).

[0210] In some embodiments, the molybdenum-containing precursor has MoX n Y m wherein X is a chalcogen element (e.g., oxygen or sulfur), Y is a halogen (e.g., 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. An example of a carbonyl-containing precursor is Mo(CO)6.

[0212] In some embodiments, the process includes using molybdenum chloride (MoCl x ) precursor to deposit a thin protective Mo layer. This can then be accomplished using molybdenum oxyhalide (MoO y X z ) precursor for Mo deposition to fill the features. The protective Mo layer can be made using MoO y X zThe precursor performs Mo filling without oxidizing the underlying surface. This is useful for oxygen sensitive surfaces such as silicon (Si), silicon germanium (SiGe), titanium (Ti), titanium nitride (TiN) and titanium silicide (TiSi2). Cleaning and etching processes are also provided, using MoCl prior to deposition. x Precursors to remove oxides from the underlying surface. Using MoCl x Subsequent deposition of the precursor may produce a liner layer and / or fill features. The protective Mo layer protects the bottom surface of the feature. In some embodiments, it is selectively deposited on the bottom surface with little or no deposition on the feature sidewalls. In some embodiments, it is non-selectively deposited on the bottom and sidewall surfaces. Heteroliganded Molybdenum Compounds Containing Halide

[0213] In one aspect, a heterocoordinated molybdenum compound containing a halide is used as a precursor for deposition of a molybdenum-containing film, for example, as a precursor for deposition of a molybdenum metal. In one embodiment, the precursor is a compound comprising molybdenum, at least one halide that forms a bond with the molybdenum, and at least one organic ligand having any one of the elements N, O, and S, wherein an atom of any one of these elements forms a bond with the molybdenum. Examples of suitable organic ligands that provide nitrogen or oxygen bonds include amidinates, amidates, iminopyrrolidinates, diazadienes, beta-imino amides, alpha-iminoalkoxides, beta-amino alkoxides, beta-diketiminates, beta-ketoiminates, beta-diketonates, amines, and pyrazolates. Examples of suitable organic ligands that provide sulfur bonding include thioethers, thiolates, dithiolenes, dithiolates, and α-imidothioenes. 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. These organic ligands can be neutral or anionic (e.g., monoanionic or dianionic), and platinum can be in various oxidation states, such as +1, +2, +3, +4, +5, and +6.

[0214] Suitable exemplary N and / or O-containing organic ligands 1-17 have structures such as Figure 4 As shown, the structures of suitable exemplary S-containing organic ligands 18-25 are as shown Figure 5 As shown, 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, tert-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 with branched alkyl substituents (e.g., isopropyl and isobutyl) are preferred because such ligands provide more volatile platinum 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 ethylenediamine), and higher dentate amines (e.g., substituted or unsubstituted diethylenetriamine). Examples of monodentate amines are Figure 4 The amine 1 shown, wherein 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, the at least one organic ligand is an amide, such as a monoanionic amide 16, wherein at least one R is alkyl or fluoroalkyl, and each R is independently selected from H, alkyl and fluoroalkyl. In some embodiments, the at least one organic ligand is an imide, such as a dianionic imide 17, wherein R is alkyl or fluoroalkyl. Although imide-containing precursors can generally be used to deposit various molybdenum-containing films (including molybdenum metal), in some embodiments they are more preferably used to deposit molybdenum nitrides and molybdenum carbonitrides because they form strong molybdenum-nitrogen bonds and can serve as a nitrogen source for the resulting film. In some embodiments, at least one organic ligand in the precursor is an amidinate. Examples of amidinates are Figure 4 The amidine salt 2 shown in , wherein each R is independently selected from H, alkyl and fluoroalkyl. The amidine salt 2 is a monoanionic ligand that can form two molybdenum-nitrogen bonds, thereby acting as a bidentate ligand.

[0216] In some embodiments, at least one organic ligand in the precursor is amidate. Examples of etomidate are Figure 4 Etomidate 3 is shown in , wherein each R is independently selected from H, alkyl and fluoroalkyl. Etomidate 3 is a monoanionic ligand that can form one molybdenum-nitrogen bond and one molybdenum-oxygen bond, thereby acting 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-diaza 1,3-butadiene (DAD) 5, 6 and 7, wherein each R is independently selected from H, alkyl and fluoroalkyl. The property of this ligand is that it can exist in neutral form 5, monoanion free radical form 6 and dianion form 7. Due to the redox activity of the monoanion (free radical) form 6, it can be relatively easily removed during deposition, making the complex of DAD6 particularly suitable for depositing platinum metal and high-purity platinum metal. DAD ligands 5, 6 and 7 can be used as bidentate ligands, each forming two platinum-nitrogen bonds. In some embodiments, the platinum precursor includes DAD ligands 5, 6 or 7 as organic ligands, wherein each R is independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

[0218] In some embodiments, the at least one organic precursor is an iminopyrrolidine salt (e.g., iminopyrrolidine salt 4, wherein each R is independently selected from H, alkyl and fluoroalkyl), β-iminoamide (e.g., β-iminoamide 8, wherein each R is independently selected from H, alkyl and fluoroalkyl), α-iminoalkoxide (e.g., α-iminoalkoxide 9, wherein each R is independently selected from H, alkyl and fluoroalkyl), β-diketimine salt (e.g., β-diketimine salt 10, wherein each R is independently selected from alkyl, fluoroalkyl), β-ketoimine salt (e.g., , β-ketoimine salt 11, wherein each R is independently selected from H, alkyl and fluoroalkyl), β-diketonate 12 (e.g., β-diketonate 12, wherein each R is independently selected from H, alkyl and fluoroalkyl), pyrazole salt (e.g., pyrazole salt 13, wherein each R is independently selected from H, alkyl and fluoroalkyl), β-aminoalkoxide (e.g., β-aminoalkoxide 14, wherein each R is independently selected from H, alkyl and fluoroalkyl) or guanidine salt 15 (guadinidate, e.g., guanidine salt 15, wherein each R is independently selected from H, alkyl and fluoroalkyl). These are all monoanionic ligands that can be bound to platinum in a bidentate manner.

[0219] In some embodiments, the 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" as used broadly herein includes monodentate and multidentate (e.g., bidentate or tridentate) thioethers, as well as ligands containing thioether and thiolate (or other) moieties. An example of a monodentate thioether is a dialkyl sulfide RS, wherein each R is an alkyl group, such as dimethyl sulfide, diethyl sulfide, diisobutyl sulfide, and the like. An example of a multidentate thioether ligand that also includes a thiolate moiety is (SCHCHSCHCHS) 2- Examples of monodentate sulfides are Figure 5 The thioether 18 is shown, 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 tert-butyl. In some embodiments, the at least one organic ligand is a thiolate, such as a monoanionic thiolate 19, wherein R is alkyl or fluoroalkyl. For example, R can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl. In some embodiments, the thiolate is a dithiolate, such as a dianionic α-dithiolate 24 (wherein each R is independently selected from H, alkyl and fluoroalkyl) or a dianionic β-dithiolate 25 (wherein each R is independently selected from H, alkyl and fluoroalkyl). The dithiolate is capable of forming two platinum-sulfur bonds with platinum.

[0220] In some embodiments, at least one organic ligand in the precursor is a dithiol. Examples of dithiols are structures 20, 21 and 22, wherein each R is independently selected from H, alkyl and fluoroalkyl. This ligand (similar to DAD) can exist in neutral form 20, monoanionic radical form 21 and dianionic form 22. Due to the redox activity of the monoanionic radical form 21, it can be relatively easily removed during the deposition and reduction of the platinum precursor, making the complex of dithiol 21 particularly suitable for depositing platinum metal and high-purity platinum metal. The dithiol ligands 20, 21 and 22 can act as bidentate ligands, each capable of forming two platinum-sulfur bonds. In some embodiments, the platinum precursor includes dithiol ligands 20, 21 and / or 22 as organic ligands, wherein each R is independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.

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

[0222] In some embodiments, the precursor is a precursor having the chemical formula Mo(X) m (L) nThe compound of , wherein m is selected from 1-4, n is selected from 1-3, each X is independently selected from the halide of F, Cl, Br and I, and each L is an organic ligand as described above, for example, a ligand independently selected from amidine salts, etomidates, iminopyrrolidine salts, diazines, β-iminoamides, α-iminoalkoxides, β-aminoalkoxides, β-diketimine salts, β-ketoimmine salts, β-diketonates, amines and pyrazole salts, thioethers, thiolates, dithiols, dithiolates and α-iminothiols. In some embodiments, each R in the nominated ligand is independently selected from H, alkyl and fluoroalkyl.

[0223] In some embodiments, L is a bidentate ligand. Figure 6 Examples of suitable molybdenum-containing precursors using bidentate ligands and having the chemical formula Mo(L)Cl4 are shown in . These molybdenum-containing precursors are Mo(V) compounds and include amidine salt molybdenum complex 27, DAD complex 28, β-diketimine salt complex 29, pyrazole salt complex 30, etomidate complex 31, β-iminoamide complex 32, β-ketoimine salt complex 33, β-aminoalkoxide complex 34, iminopyrrolidine salt complex 35, α-iminoalkoxide complex 36 and β-diketimine salt complex 37.

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

[0225] Heterocoordinated platinum compounds containing platinum-halide bonds and organic ligands as described herein can advantageously provide high purity platinum metal in CVD-type and ALD-type deposition methods provided herein. In addition, the use of these compounds may be associated with reduced etching of substrate materials (compared to conventional homocoordinated platinum halides). These advantages are described for illustrative purposes, rather than limiting the use of these compounds to platinum metal deposition, or to deposition on etching-sensitive substrates.

[0226] In some embodiments, when depositing on fluorine-sensitive materials (e.g., silicon-containing materials), non-fluorine-containing precursors are selected, such as including any of Cl, Br, and I as the halide in the complex. In addition, compounds with fluorinated alkyl substituents can be avoided in these embodiments. Sulfur-containing molybdenum compounds

[0227] In one aspect, sulfur-containing molybdenum compounds are used as molybdenum-containing precursors for deposition of molybdenum-containing films, such as molybdenum metal and molybdenum silicide deposition. In some embodiments, the molybdenum compound includes molybdenum and at least one sulfur-containing ligand that provides a molybdenum-sulfur bond. Molybdenum precursors based on sulfur-containing ligands can be used to deposit molybdenum-containing films that are substantially free of impurities, because sulfur impurities are easier to remove than 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, the molybdenum forms bonds only with sulfur atoms.

[0229] Examples of suitable sulfur-containing ligands that provide sulfur bonds include thioethers, thiolates, dithioles, dithiolates, thiocarbamates, and α-imidothioles. These ligands include one or more substituents independently selected from the group consisting of H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy substituents. These organic ligands can be neutral or anionic (e.g., monoanionic or dianionic), and the platinum 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 Figure 5 Ligands 18-25 are shown, wherein the R substituents are as described above. Examples of suitable molybdenum precursors include molybdenum thiolates Mo(SR)4, wherein R is an alkyl group, such as methyl, ethyl, propyl, butyl. In a specific example, the precursor is tetrakis(tert-butylthiolate) molybdenum(IV): Mo(SR)4, wherein R is tert-butyl. Another example of a suitable molybdenum precursor is molybdenum thiocarbamate, such as tetrakis(diethyldithiocarbamate) molybdenum(IV): Wherein each R is independently selected from alkyl (e.g., ethyl, methyl, propyl, butyl) and fluoroalkyl (e.g., CF3). In a specific example, the precursor is tetrakis(diethyldithiocarbamate) molybdenum(IV).

[0231] In some embodiments, provided are dithiol complexes of molybdenum, wherein the dithiol can be in a neutral form 20, an anion-radical form 21, and a dianion form 22, wherein each R is independently H, alkyl, or fluoroalkyl.

[0232] The disulfide complexes are redox active and can coordinate molybdenum in various oxidation states. The redox reactions of disulfide ligands 20, 21, and 22 are shown in reaction equation 1:

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

[0234] In some embodiments, these ligands can provide nitrogen bonding in addition to sulfur bonding.An example of such a ligand is α-iminothiolene 23, which can be a redox-active radical anionic ligand that behaves similarly to thioene.

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

[0236] In some embodiments, the precursor is a MoLn compound, wherein 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 by reacting 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 a starting material. Mo(III) or Mo(IV) precursors can be prepared by using the corresponding halide or MoX3(L)3 or MoX4(L)2 as a starting material, wherein 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, the Mo(IV) thiolate complex is prepared by reacting molybdenum tetrachloride with lithium thiolate. For example, MoCl4 can be reacted with t-BuSLi in a solvent of 1,2-dimethoxyethane to form a Mo(t-BuS)4 compound.

[0238] α-Iminothioene ligands can be prepared from the corresponding α-iminoketones by thionation with a suitable reagent (e.g., Lawesson's reagent). Subsequently, the radical anion form of the α-iminothioene can be prepared by treatment with an alkali metal (e.g., lithium). The resulting ligands and ligand salts can be reacted with a molybdenum halide to form a molybdenum compound containing α-iminothioene.

[0239] Platinum complexes can also be prepared by using compounds in which the oxidation state of platinum is 0 (e.g., molybdenum hexacarbonyl). The starting material can be treated with a neutral ligand (e.g., a thioether or a dialkyl sulfide) to initiate 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-dithiolene (dithiete) to initiate an oxidative addition reaction and form the sulfur-containing complex described herein.

[0240] These reactions can be carried out in various aprotic solvents.For example, the reaction can be carried out in ether solvents (for example, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, methyl-tert-butyl ether, 1,2-dimethoxyethane), in hydrocarbon solvents (for example, toluene, benzene, heptane, hexane, pentane), or in halogenated hydrocarbon solvents (for example, chlorobenzene, dichlorobenzene, fluorobenzene, difluorobenzene, dichloromethane, chloroform, etc.).Depending on the boiling point of the solvent and the solubility of the product, these reactions can be carried out in a wide temperature range.In some embodiments, starting material, reaction intermediate and desired product are unstable for water vapor and oxygen. Therefore, the reaction treatment should be carried out under anhydrous and air-free conditions and using a protective inert gas (eg, nitrogen or argon). Contains 1,4-diazobutadiene (DAD) precursor

[0241] On the other hand, a molybdenum-containing precursor containing DAD is provided. DAD can be bonded to platinum in neutral form 5, radical-anion form 6 and dianion form 7. In some embodiments, a homogeneous DAD complex having a chemical formula of Mo(DAD)m is provided, wherein m is from 1 to 3, and each DAD is independently selected from neutral DAD 5, radical-anion DAD 6 and dianion DAD 7. The oxidation state of the molybdenum in these complexes can be from 0 to +6. Non-limiting examples of suitable homogeneous DAD complexes include tri(DAD)Mo(III) precursor Mo(6)3, bis(DAD)Mo(IV) precursor Mo(7)2, bis(DAD)Mo(III) precursor Mo(6)(7) and bis(DAD)Mo(II) precursor Mo(6)2.

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

[0243] In some embodiments, a heteroleptic DAD-containing molybdenum compound is provided. In some implementations, the precursor includes molybdenum, at least one DAD ligand bonded to the molybdenum, and at least one second ligand, wherein the DAD can be a neutral DAD 6, a radical anion DAD 7, or a dianion DAD 8, and the second ligand is independently selected from anionic ligands and neutral ligands. In some embodiments, the precursor does not contain a CO ligand as the only second ligand. In some embodiments, the precursor is Mo(DAD) m (L) n (X) p , wherein L is a neutral Lewis base ligand, and each L is independently selected from CO, amine, phosphine, thioether, nitrile and isonitrile, and X is an anionic ligand, and each X is independently selected from halide, alkyl, allyl and cyclopentadienyl, and m is 1-3, n is 0-4, and p is 0-4. Nitrile is a RCN compound, wherein R is an alkyl. Isonitrile is a RNC compound, wherein R is an alkyl. Other suitable anionic ligands include alkoxides, amides, imides, and any other anionic ligands comprising donor atoms 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] Heterolate DAD-containing precursors can be prepared by a one pot or multi-step sequential salt metathesis reaction. Platinum halide starting materials, such as Mo(V), Mo(IV) or Mo(III) halides, can be treated with anionic forms of DAD ligands or other anionic ligands. Neutral Lewis base ligands can be exchanged using thermal treatment or photoexcitation.

[0246] Heteroleptic DAD-containing precursors can also be prepared using a 0-valent molybdenum starting material (eg, molybdenum hexacarbonyl) that can undergo an oxidative addition reaction with a redox-active ligand (eg, a DAD ligand).

[0247] In some embodiments, the precursor containing the radical anion DAD ligand 8 is particularly suitable for the deposition of platinum metal and high-purity platinum metal. In the radical anion form 7, the DAD ligand couples with the empty d orbital electrons of platinum and is considered to be an electron source for reducing the platinum ion to a zero-valent metal state. After the ligand-to-metal electron transfer, the volatile neutral DAD ligand 6 can be removed from the platinum metal growth surface. Since the DAD ligand can be removed from the growth surface without loss, the incorporation of impurity elements (e.g., C and N) can be reduced when using the DAD precursor compared to other metal organic precursors. Therefore, the platinum precursor containing the radical anion DAD ligand can be used to deposit high-purity platinum metal at low temperatures. Molybdenum disulfide precursor

[0248] In another aspect, the precursor used to deposit the molybdenum-containing film is a di-molybdenum compound containing a molybdenum-molybdenum bond (e.g., multiple molybdenum-molybdenum bonds, such as double bonds; or any multiple bonds with a bond order of 2 to 5). Such precursors are particularly suitable for the deposition of molybdenum metal and high purity molybdenum metal because it is easier to reduce such compounds to metallic molybdenum than many mononuclear molybdenum compounds.

[0249] In some embodiments, provided is a precursor for depositing a molybdenum-containing film, wherein the precursor is Mo2L n, wherein each L is independently selected from etomidate, amidine salt and guanidine salt ligand, n is 2-5, and the precursor includes multiple platinum-platinum bonds. In some embodiments, each L is independently selected from amidine salt ligand 2, etomidate ligand 3 and guanidine salt ligand 15, wherein each R in the amidine salt, etomidate and guanidine salt 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 amidine salt, and the precursor has the chemical formula Mo2(L)3 or Mo2(L)4. In some embodiments, each L is amidine salt, and the precursor has the chemical formula Mo2(L)3 or Mo2(L)4. In some embodiments, each L is guanidine salt, and the precursor has the chemical formula Mo2(L)3 or Mo2(L)4. In some embodiments, each L is guanidine salt, and the precursor has the chemical formula Mo2(L)3 or Mo2(L)4. In these complexes, molybdenum has low oxidation states 2+ (in Mo2(L)3) and 3+ (in Mo2(L)4), making these complexes particularly suitable for easy reduction to molybdenum metal.

[0250] Structure 38 shows an exemplary structure of an etomidate paddlewheel di-Mo(II) precursor having quadruple Mo-Mo bonds: In some embodiments, R and R' are each independently selected from alkyl groups, such as methyl, ethyl, isopropyl and tert-butyl. In some embodiments, one, two, three or four etomidate ligands in 38 may be substituted with amidine or guanidinium ligands.

[0251] The dimolybdenum precursors described herein can be synthesized using dimolybdenum tetraacetate as a starting material and treated with a ligand salt such as lithium etomidate. Cobalt Precursor

[0252] Cobalt metal can be deposited using various cobalt precursors, where the cobalt can be in the oxidation state of +1, +2 or +3. Examples of cobalt precursors include cobalt acetate, cobalt acetylacetonate (e.g., bis(acetylacetonate)cobalt(III)), cobalt amidinates (e.g., bis(N-tert-butyl-N'-ethylpropionamidino)cobalt(II)), cobaltocene, and carbonyl-containing cobalt precursors (e.g., tricarbonylnitrosylcobalt, and dicarbonylcyclopentadienylcobalt). An example of a halogen-containing cobalt precursor is CoCl2(TMEDA), where TMEDA is N,N,N',N'-tetramethylethylenediamine. Ruthenium precursor

[0253] Ruthenium metal can be deposited, for example, by using an evaporable ruthenium precursor such as bis(ethylcyclopentadienyl)ruthenium(II), bis(pentamethylcyclopentadienyl)ruthenium, ruthenocene, and cyclopentadienyl-propylcyclopentadienylruthenium(II). Tungsten precursor

[0254] Tungsten can be deposited using a variety of volatile precursors. In some embodiments, a halogen-containing tungsten precursor such as WHal is used. x , wherein Hal is a halogen (e.g., F, Cl, Br and / or I), and x is from 2 to 6. In some embodiments, tungsten chloride is used. Tungsten chloride includes tungsten pentachloride (WCl5), tungsten hexachloride (WCl6), tungsten tetrachloride (WCl4), tungsten dichloride (WCl2) and mixtures thereof. In other examples, tungsten fluoride, such as tungsten hexafluoride, can be used. Additional Precursors

[0255] 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-butylimino)bis(diethylamino)niobium, (tert-butylimino)bis(dimethylamino)niobium, and (tert-butylimino)bis(ethylmethylamino)niobium; tantalum-containing precursors such as tert-butyliminotris(dimethylamino)tantalum and tantalum pentachloride; iron-containing precursors such as tert-butoxyiron(III) dimer, ferrocene, and pentacarbonyliron; nickel-containing precursors such as allyl(cyclopentadienyl)nickel(II) and bis(acetylacetonate)nickel(II); zinc-containing precursors such as zinc acetate and diethylzinc; and chromium-containing precursors such as carbonyl chromium and bis(cyclopentadienyl)chromium(II).

[0256] return Figure 1 Prior to operation 102, the substrate may optionally be pretreated with a plasma containing 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 the conditions used to contact the reactants with the substrate.

[0257] In operation 104, after the metal precursor is introduced, the deposition chamber is optionally purged. The purge or carrier gas is selected to be non-reactive with the process gas (reactant) and volatile byproducts. Gases such as helium, argon, nitrogen and combinations thereof can be used. In some embodiments, the purge may include flowing a total of 1-20 slm or 1-40 slm of an inert gas (e.g., argon or helium). Depending on the geometry and pressure of the chamber, the purge is performed at a high flow rate. In some embodiments, the purge gas may also include hydrogen. The purge pressure may be selected to maintain an isobaric process flow, such as dosing / sweeping / plasma / sweeping all at the same pressure. In one embodiment, the pressure may be from about 1 to about 1.5 Torr, but may extend to about 10 Torr or higher. The purge time is from about 1 second to about 20 seconds. The wafer temperature remains constant during operation.

[0258] In operation 106, the surface of the substrate is exposed to a plasma of a hydrogen-containing gas source (reactant). Pretreatment step 102 may have similar conditions to operation 106, but is typically longer. Alternatively, it may differ from operation 106, depending on the incoming substrate and the material to be removed therefrom in step 102.

[0259] The direct plasma conditions sometimes employed in PEALD can result in directionality in deposition, since the energy to fragment the precursor molecules can be low frequency, which produces a large amount of ion bombardment at the surface. Directed deposition can also result in the deposition of films with poor step coverage. A direct plasma (or directly generated plasma) is a plasma that (with appropriate concentrations of electrons, neutral species, free radicals, and positive ions) exists in close proximity to the substrate surface (sometimes separated from it only by a plasma sheath) during deposition. Ions play an important role in direct plasma processes. Figure 8 An apparatus for direct plasma processing is described. In some embodiments, the plasma is remotely generated. A remote plasma (or remotely generated plasma) is a plasma generated at a distance from the substrate. The primary reactant species may be remotely generated plasma radicals. Figure 7 An apparatus for direct plasma processing is described. In certain circumstances, using a remote plasma instead of a direct plasma may have certain advantages.

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

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

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

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

[0264] In operation 110, if the desired thickness is achieved, the process may be terminated. The desired thickness may be in the range of less than about 1 nm to about 50 nm, depending on the application. If the desired thickness has not been achieved, process operations 102-108 are repeated for a number of cycles sufficient to achieve the desired metal thickness. Device with remote plasma generator

[0265] One aspect of the present invention is an apparatus configured to implement the methods described herein. Suitable apparatus include hardware for performing process operations and a system controller having instructions for controlling process operations according to the present invention. In some embodiments, the apparatus for performing the aforementioned process operations may include a remote plasma source. A remote plasma source may be preferred over a direct plasma source in some cases because it may provide milder reaction conditions than a direct plasma.

[0266] Figure 7A schematic diagram of a remote plasma device according to certain embodiments is shown. The device 200 includes a reaction chamber 210 having a showerhead 220. Inside the reaction chamber 210, a substrate 230 is retained on a platform or pedestal 235. In some embodiments, the pedestal 235 may be equipped with a heating / cooling element. A controller 240 may be connected to components of the device 200 to control the operation of the device 200. For example, the controller 240 may include instructions for controlling process conditions for the operation of the device 200, such as temperature process conditions and / or pressure process conditions. In some embodiments, the controller 240 may include instructions for controlling the flow rates of precursor gases, co-reactant gases, source gases, and carrier gases. The controller 240 may include instructions for changing the flow rates of reactant gases, source gases, and / or carrier gases over time. The controller 240 may include instructions for changing the flow rate of co-reactant gases over time. Additionally or alternatively, the controller 240 may include instructions for changing the flow rate of precursor gases over time.

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

[0268] One or more free radical species may be generated in the remote plasma source 260 and configured to enter the reaction chamber 210 via the gas inlet 265. Any type of plasma source may be used for the remote plasma source 260 to generate free 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 a capacitively coupled plasma may be a radio frequency (RF) plasma. High frequency plasmas may be configured to operate at 13.56 MHz or higher. Another example of such an RF remote plasma source 260 may be a remote plasma source that can operate at 440 kHz and may be provided as a subunit bolted to a larger device for parallel processing of one or more substrates. In some embodiments, a microwave plasma may be used as the remote plasma source 260. The microwave plasma may be configured to operate at a frequency of 2.45 GHz. The gas provided to the remote plasma source may include hydrogen, nitrogen, oxygen, carbon, or other gases as mentioned elsewhere herein. In certain embodiments, hydrogen is provided in a carrier gas (e.g., helium). As an example, hydrogen may be provided in a helium carrier gas at a concentration of about 1-10% hydrogen.

[0269] The precursor may be provided in a container 250 and may be supplied to the showerhead 220 via a first gas inlet 255. The showerhead 220 distributes the precursor into the reaction chamber 210 and toward the substrate 230. The substrate 230 may be located below the showerhead 220. It should be understood that the showerhead 220 may have any suitable shape and may have any number and arrangement of ports for distributing gas to the substrate 230. The precursor may be supplied to the showerhead 220 and ultimately to the substrate 230 at a controlled flow rate.

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

[0271] In some embodiments, a co-reactant is introduced during the deposition reaction that is not a primary metal-containing precursor or hydrogen radical. In some embodiments, the apparatus is configured to introduce the co-reactant through the second gas inlet 265, in which case the co-reactant is at least partially converted to plasma. In some implementations, the apparatus is configured to introduce the co-reactant through the showerhead 220 via the first gas inlet 255. Examples of co-reactants include oxygen, nitrogen, ammonia, carbon dioxide, carbon monoxide, etc. The flow rate of the co-reactant can be varied over time to produce a composition gradient in the gradient film.

[0272] The controller 240 may contain instructions for controlling the process conditions of the operation of the apparatus 200. The controller 240 will typically include one or more memory devices and one or more processors. The processor may include a central processing unit (CPU) or computer, analog and / or digital input / output connections, a stepper motor controller board, etc. Instructions for implementing appropriate control operations are executed on the processor. These instructions may be stored on a memory device associated with the controller 240 or it may be provided via a network.

[0273] In certain embodiments, the controller 240 controls all or most of the activities of the semiconductor processing equipment 200 described herein. For example, the controller 240 may control all or most of the activities of the semiconductor processing equipment 200 associated with depositing a graded silicon carbide film and optionally other operations in a manufacturing process (including a graded silicon carbide film). The controller 240 may execute system control software, including instruction sets 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 on a memory device associated with the controller 340 may be used in some embodiments. In order to provide relatively mild reaction conditions at the environment adjacent to the substrate 230, parameters such as RF power level, gas flow rate to the remote plasma region and the timing of plasma ignition may be adjusted and maintained by the controller 240. In addition, adjusting the substrate position may further reduce the presence of high-energy radical species in the environment adjacent to the substrate 230. In a multi-station reactor, the controller 240 may include different or identical instructions for different device stations, thereby allowing the device stations to operate independently or synchronously.

[0274] In some embodiments, controller 240 may include instructions to perform operations such as flowing a metal-containing precursor through first gas inlet 255 into reaction chamber 210, providing one or more radical species of a source gas in a relatively low energy state from remote plasma source 260, flowing a co-reactant gas through second gas inlet 265 into reaction chamber 210, varying the flow rate of the co-reactant gas over time, and flowing the one or more radical species through second gas inlet 265 into reaction chamber 210 to react with the metal-containing precursor to form a metal film on substrate 230. In some implementations, controller 240 may 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 may include a display screen, a graphical software display of apparatus and / or process conditions, and a user input device (e.g., a pointing device, keyboard, touch screen, microphone, etc.).

[0276] The computer program code for controlling the above operations may be written in a conventional computer readable programming language such as assembly language, C, C++, Pascal, Fortran or others. The compiled object code or script is implemented by the processor to perform the tasks identified in the program.

[0277] Signals for monitoring the process may be provided through analog and / or digital input connections of the system controller.Signals for controlling the process may be output through 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 case, the plasma power can be monitored by one or more voltage and current sensors (e.g., VI probes). In another case, the plasma density and / or the concentration of the process gas can be measured by one or more optical emission spectrometer sensors (OES). In some embodiments, one or more plasma parameters can be adjusted programmatically based on the measurement results from such in-situ plasma monitors. For example, an OES sensor can be used in a feedback loop to provide programmatic control of the plasma power. It should be understood that in some embodiments, other monitors can be used to monitor plasma and other processing characteristics. Such monitors may include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure sensors.

[0279] In general, the methods described herein can be performed on a system comprising semiconductor processing equipment, such as one or more processing tools, one or more chambers, one or more platforms for processing, and / or specific processing components (wafer pedestals, gas flow systems, etc.). These systems can be integrated with electronic devices for controlling their operation before, during, and after the processing of semiconductor wafers or substrates. In general, electronic devices are referred to as "controllers", which can control various components or subcomponents of one or more systems. Depending on the processing requirements and / or system type, the controller can be programmed to control any process disclosed herein, including the delivery of process gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, position and operation settings, wafer transfer in and out tools and other transfer tools and / or load locks connected or docked to a specific system.

[0280] Broadly speaking, a controller can be defined as an electronic device having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operations, enable cleaning operations, enable endpoint measurements, etc. The integrated circuit 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 or microcontrollers that execute program instructions (e.g., software). The program instructions may be instructions sent to the controller in the form of various individual settings (or program files) that define operating parameters for performing a particular process on or for a semiconductor wafer or system. In some embodiments, the operating parameters may be part of a recipe defined by a process engineer to complete one or more processing steps during the manufacture of one or more layers, materials (e.g., silicon, carbide), surfaces, circuits, and / or dies of a wafer.

[0281] In some implementations, the controller may be part of or coupled to a computer that is integrated with the system, coupled to the system, otherwise networked to the system, or a combination thereof. For example, the controller may be in the "cloud" or all or part of a wafer fab host system that may allow remote access to wafer processing. The computer may enable remote access to the system to monitor the current progress of a manufacturing operation, check the history of past manufacturing operations, check trends or performance criteria for multiple manufacturing operations, change parameters of a current process, set processing steps to follow the current process, or start a new process. In some examples, a remote computer (e.g., a server) may provide a process recipe to the system via a network (which may include a local network or the Internet). The remote computer may include a user interface that enables input or programming of parameters and / or settings, which are then sent from the remote computer to the system. In some examples, the controller receives instructions in the form of data that specify parameters for each processing step to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process to be performed and the type of tool that the controller is configured to interface with or control. Thus, as described above, the controller may be distributed, for example, by including one or more discrete controllers networked together and working toward a common purpose, such as the processes and controls described herein. An example of a distributed controller for such a purpose is one or more integrated circuits on a chamber that communicate with one or more integrated circuits remotely (e.g., at a platform level or as part of a remote computer), which combine to control the process on the chamber.

[0282] In addition to the metal deposition described herein, example systems may include plasma etching chambers or modules, deposition chambers or modules, spin rinse chambers or modules, metal plating chambers or modules, cleaning chambers or modules, chamfer edge etching chambers or modules, physical vapor deposition (PVD) chambers or modules, chemical vapor deposition (CVD) chambers or modules, atomic layer deposition (ALD) chambers or modules, atomic layer etching (ALE) chambers or modules, ion implantation chambers or modules, track chambers or modules, and any other semiconductor processing system that may be associated with or used in the manufacture and / or preparation of semiconductor wafers.

[0283] As described above, depending on one or more processing steps to be performed by the tool, the controller can communicate with one or more other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout the factory, a host computer, another controller, or tools used in material transport to transport wafer containers to and from tool locations and / or load ports in a semiconductor manufacturing facility. Device with direct plasma generator

[0284] Figure 8 Schematic diagram of an exemplary plasma processing apparatus for depositing a metal film using thermal ALD according to some implementations. The plasma apparatus or processing station 300 includes a plasma processing chamber 302 for maintaining a low pressure environment. Multiple plasma apparatuses or processing stations 300 may be included in a common low pressure process tool environment. In some implementations, one or more hardware parameters of the plasma apparatus or processing station 300 (including those discussed in detail below) may be adjusted in a programmatic manner by one or more system controllers 350. The plasma apparatus or processing station 300 may be configured to perform thermal ALD and PEALD, thermal CVD and PEALD, thermal ALD and PECVD, or thermal CVD and PECVD. In some implementations, the plasma apparatus or processing station 300 may be configured to perform one or more PEALD cycles and one or more thermal ALD cycles to deposit a metal film on a substrate 312.

[0285] The plasma device or processing station 300 is in fluid communication with a reactant delivery system 301 to deliver process gases to a distribution showerhead 306. The reactant delivery system 301 includes a mixing vessel 304 for mixing and / or conditioning process gases, such as a vapor phase silicon-containing precursor, for delivery to the showerhead 306. In some implementations, the reactant delivery system 301 includes a mixing vessel 304 for mixing and / or conditioning oxygen-containing reactants (e.g., oxygen) for delivery to the showerhead 306. In some implementations, the reactant delivery system 301 includes a mixing vessel 304 for mixing and / or conditioning hydrogen and oxygen-containing reactants (e.g., oxygen) for delivery to the showerhead 306. One or more mixing vessel inlet valves 320 can control the introduction of process gases into the mixing vessel 304. A plasma containing an oxygen-containing reactant can also be delivered to the showerhead 306 or can be generated in the plasma device or processing station 300. A showerhead 306 may be fluidly coupled to the plasma processing chamber 302 for delivering silicon-containing precursors and reactants into the plasma processing chamber 302 .

[0286] As an example, Figure 8 The implementation includes a vaporization point 303 for vaporizing liquid reactants to be supplied to the mixing container 304. In some implementations, the vaporization point 303 can be a heated vaporizer. In some implementations, the delivery pipeline downstream of the vaporization point 303 can be heat traced. In some examples, the mixing container 304 can also be heat traced. In a non-limiting example, the pipeline downstream of the vaporization point 303 has an elevated temperature curve extending from about 100°C to about 150°C at the mixing container 304. In some implementations, a liquid precursor or liquid reactant can be vaporized at a liquid injector. For example, a liquid injector can inject a pulse of a liquid reactant into a carrier gas flow upstream of the mixing container 304. In one implementation, 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 atomize the liquid into dispersed droplets, which are then vaporized in a heated delivery pipe. Smaller droplets can vaporize faster than larger droplets, thereby reducing the delay between liquid injection and complete vaporization. Faster vaporization can reduce the length of piping downstream of the vaporization point 303. In one case, the liquid injector can be mounted directly to the mixing vessel 304. In another case, the liquid injector can be mounted directly to the spray head 306.

[0287] In some embodiments, a liquid flow controller (LFC) upstream of the vaporization point 303 may be provided to control the mass flow of the liquid to be vaporized and delivered to the plasma device or processing station 300. For example, the LFC may include a thermal mass flow meter (MFM) located downstream of the LFC. The plunger valve of the LFC may then be adjusted in response to a feedback control signal provided by a proportional integral differential (PID) controller electrically connected to the MFM. However, it may take one second or longer to stabilize the flow of liquid using feedback control. This may extend the time to inject the liquid reactant. Therefore, in some implementations, the LFC may be dynamically switched between a feedback control mode and a direct control mode. In some implementations, this may be performed by closing the sensing tube and PID controller of the LFC.

[0288] The showerhead 306 distributes process gases to the substrate 312. Figure 8 In the illustrated implementation, substrate 312 is positioned below showerhead 306 and is shown resting on substrate support 308, wherein substrate support 308 is configured to support substrate 312. Substrate support 308 may include a chuck, fork, or lift pins (not shown) to hold and transfer substrate 312 during and between deposition operations. The chuck may be an electrostatic chuck, a mechanical chuck, or a variety of other types of chucks useful in industry and / or research. Showerhead 306 may have any suitable shape and may have any suitable number and arrangement of ports for distributing process gases to substrate 312.

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

[0290] In another case, adjusting the height of the substrate support 308 may allow the plasma density to be varied during a plasma activation cycle included in the process. At the end of a process phase, the substrate support 308 may be lowered during another substrate transfer phase to allow the substrate 312 to be removed from the substrate support 308 .

[0291] In some implementations, the substrate support 308 can be configured to be heated to an elevated temperature by a heater 310. In some implementations, during film deposition as described in the disclosed implementations, the substrate support 308 can be heated to a temperature less than about 700° C., such as about between about 500° C. and about 750° C. or about 500° C. and about 650° C. Further, in some implementations, pressure control of the apparatus or processing station 300 can be provided by a butterfly valve 318. Figure 8In the embodiments shown in the embodiments, 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 changing the flow rate of one or more gases introduced into the plasma processing chamber 302. In some embodiments, the pressure of the plasma processing chamber 302 can be controlled to be equal to or greater than about 7 Torr, equal to or greater than about 10 Torr, or equal to or greater than about 12 Torr during the deposition of the silicon oxide film described in the disclosed embodiments.

[0292] In some implementations, the position of the showerhead 306 can be adjusted relative to the substrate support 308 to change the volume between the substrate 312 and the showerhead 306. Further, it should be understood that the vertical position of the substrate support 308 and / or the showerhead 306 can be changed by any suitable mechanism within the scope of the present invention. In some implementations, the substrate support 308 can include a rotation axis for rotating the orientation of the substrate 312. It should be understood that in some implementations, one or more of these exemplary adjustments can be performed in a programmatic manner by one or more suitable system controllers 350.

[0293] In some implementations where plasma may be used as discussed above, the showerhead 306 and the substrate support 308 are in electrical communication with a radio frequency (RF) power supply 314 and a matching network 316 to power the plasma in the plasma processing chamber 302. In some implementations, the plasma energy may be controlled by controlling one or more of the processing station pressure, gas concentration, RF source power, RF source frequency, and plasma power pulse timing. For example, the RF power supply 314 and the matching network 316 may be operated at any suitable power to form a plasma having a desired radical species composition. In some implementations, the RF power supply 314 and the matching network 316 may be operated to apply plasma power to the plasma processing chamber 302 to ignite a plasma generated by hydrogen and oxygen-containing reactants in the plasma processing chamber 302. Exemplary plasma powers applied by the RF power supply 314 may be equal to or less than about 300 W, equal to or less than about 200 W, or between about 10 W and about 200 W. Likewise, the RF power supply 314 may provide RF power at any suitable frequency. In some implementations, the RF power supply 314 may be configured to control high-frequency and low-frequency RF power sources independently of each other. Exemplary low-frequency RF frequencies may include, but are not limited to, frequencies between 0 kHz and 500 kHz. Exemplary high-frequency RF frequencies may include, but are not limited to, frequencies between 1.8 MHz and 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 should be understood that any suitable parameter may be modulated discretely or continuously to provide plasma energy for surface reactions.

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

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

[0296] In certain implementations, the controller 350 has instructions to perform the operations described herein.

[0297] The apparatus / processes described herein can be used in conjunction with photolithographic patterning tools or processes, e.g., for preparing or manufacturing semiconductor devices, displays, LEDs, photovoltaic panels, etc. Typically, though not necessarily, these tools / processes will be used or operated together in a common manufacturing facility. Photolithographic patterning of films typically includes some or all of the following operations, each of which enables multiple available tools: (1) coating a workpiece, i.e., substrate, with photoresist using a spin coating or spray coating tool; (2) curing the photoresist using a hot plate or oven or UV curing tool; (3) exposing the photoresist to visible light or UV light or X-rays using a tool such as a wafer stepper; (4) developing the resist so as to selectively remove the resist and thereby pattern it using a tool such as a wet cleaning station; (5) transferring the resist pattern to an underlying film or workpiece by using a dry or plasma assisted etching tool; and (6) removing the resist using a tool such as a radio frequency or microwave plasma resist stripper. Example 1 Copper Deposition

[0298] Used to obtain Fig. 9A , 9B The general conditions of the atomic layer deposition method for the results in , 9C, 10, 11A and 11B include the use of copper aminoalkoxide as a copper precursor, 9 slm (standard liters per minute) of helium and 3 lm (liters per minute) of hydrogen, a pressure below 10 Torr, and a remote ICP plasma source (which is a 13.57 MHz RF generator).

[0299] Fig. 9A An embodiment of the method is shown in which the copper metal thickness can be adjusted when oxygen is added to the hydrogen source in the remote plasma generator. Without the addition of oxygen, thicker copper layers are deposited as the number of atomic layer deposition cycles increases. When oxygen is added at a flow rate of 20 sccm, the deposited thickness is approximately halved after about 225 cycles.

[0300] Fig. 9B Graphical results of deposited copper thickness as oxygen flow rate was varied in an embodiment of the method are provided, wherein copper metal thickness was adjusted when oxygen was added to a hydrogen source in a remote plasma generator. As shown, trace amounts of oxygen significantly reduced copper thickness.

[0301] Fig. 9C A graph is provided of the change in copper resistivity when the oxygen flow rate added to the hydrogen source in the remote plasma generator is varied. As shown, trace amounts of oxygen dramatically reduce resistivity.

[0302] In one embodiment, the addition of oxygen to the hydrogen source in the remote plasma generator causes a change in the morphology of the deposited copper. Fig.10 As shown in Figure 1, the film deposited in the absence of trace oxygen exhibits a rough, discontinuous, and island-like morphology. After the introduction of 20 sccm of oxygen, the film morphology changes significantly from islands to interconnected channels. Above 150 sccm of oxygen, the morphology changes to islands again.

[0303] Fig.11A Copper deposition using a remotely generated plasma of a hydrogen source without added oxygen is shown. The deposited copper has a rough appearance. Fig. 11B Copper deposition using a remotely generated hydrogen source plasma is shown when 20 seem of oxygen is added to the hydrogen source in the remote plasma generator. At only 0.16% oxygen content in the plasma gas flow, the deposited layer has improved morphology and less roughness. Example 2 Molybdenum deposition

[0304] like Fig.12 As shown, after 500 cycles of this method using a MoCl5 precursor and pre-treatment with a remotely generated plasma of hydrogen under process conditions similar to Example 1, a higher molybdenum metal thickness was achieved on the wafer using the deposition method when the wafer temperature was 270°C (corresponding to a susceptor temperature of 325°C) compared to when the wafer temperature was 310°C (corresponding to a susceptor temperature of 380°C).

[0305] Reference is made in detail to the specific embodiments of the present disclosure herein. Examples of specific embodiments are depicted in the accompanying drawings. Although the present disclosure will be described in conjunction with these specific embodiments, it should be understood that it is not intended to limit the present disclosure to such specific embodiments. On the contrary, it is intended to cover substitutions, modifications, and equivalents that may be included in the spirit and scope of the present disclosure. In the following description, numerous specific details are set forth to provide a thorough understanding of the present disclosure. The present disclosure may be implemented without some or all of these specific details. In other respects, in order not to cause unnecessary confusion to the present disclosure, well-known process operations are not described in detail.

[0306] Although the foregoing embodiments have been described in detail for the purpose of clear understanding, it is apparent that certain changes and modifications may be made 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 no longer described in detail so as not to unnecessarily obscure the disclosed embodiments. In addition, although the disclosed embodiments are described in conjunction with specific embodiments, it should be understood that the specific embodiments are not intended to limit the disclosed embodiments. It should be noted that there are many alternative ways of implementing the processes, systems and devices of the present embodiments. Therefore, the present embodiments should be considered illustrative rather than restrictive, and the embodiments are not limited to the details given herein.

Claims

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

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

3. The method of 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 of claim 1, further comprising pre-treating the surface of the substrate with the plasma remotely generated by the hydrogen-containing gas source prior to exposing the surface of the substrate to the vapor-phase metal precursor.

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

6. The method according to claim 5, wherein the gas phase molybdenum precursor comprises a structure of formula (I): Mo(LR 1 )6(I) wherein each L is independently O, S or NR 2 ;and R 1 and R 2 is 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 of the R 1 The substituents can be taken together to form an optionally substituted cyclic group.

7. The method according to claim 5, wherein the gas phase molybdenum precursor comprises a structure of formula (II): Mo(LR 1 )2(Y)4(II) wherein each L is independently O, S or NR 2 ; R 1 and R 2 is 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 Where R 1 The substituents can be taken together to form an optionally substituted cyclic group; and Each Y is independently chloro, fluoro, bromo or iodo.

8. The method according to claim 5, wherein the gas phase molybdenum precursor comprises MoCl5, Mo2Cl 10 , MoO2Cl2, MoOCl4 or any combination thereof.

9. The method of claim 5, wherein exposing the surface of the substrate to the vapor phase molybdenum precursor and exposing the substrate to the plasma remotely generated by the hydrogen-containing gas source are performed in time-separated pulses.

10. An apparatus for depositing a thin metal film on a substrate, the apparatus comprising: at least one reaction chamber comprising a susceptor for holding the substrate; at least one inlet port for delivering a vapor-phase metal precursor to the reaction chamber; a direct plasma generator or a remote plasma generator for providing plasma to the reaction chamber; as well as A controller for controlling operations in the apparatus, the controller comprising machine-readable instructions for: (a) subjecting the substrate to a temperature of about 300° C. or less; (b) introducing a metal precursor in a gas phase into the at least one reaction chamber; as well as (c) introducing plasma from the direct plasma generator or the remote plasma generator to form the thin metal film over the substrate, the plasma being generated from a hydrogen-containing gas and about 0.01% to about 1% of an oxygen-containing gas.

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