Copper, silver and gold complexes, methods for their preparation and uses thereof

Abstract

Copper, silver and gold fluorinated alkoxide complexes such as complexes having a structure represented by the general formula (I) are described:, and multimers thereof and / or crystalline forms thereof as well as uses thereof, such as in processes to prepare materials, films and / or structures comprising copper, silver or gold using, processes including atomic layer deposition and chemical vapor deposition processes.

Description

COPPER, SILVER AND GOLD COMPLEXES, METHODS FOR THEIR PREPARATION AND USES THEREOFCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] The present application claims the benefit of priority from co-pending U.S. provisional application no. 63 / 563,070 filed on March 8, 2024, the contents of which are incorporated herein by reference in their entirety.FIELD

[0002] The present application relates, for example, to copper, silver and gold complexes, methods of synthesis, and methods of use, for example for the preparation of materials, films and / or structures comprising copper, silver or gold via processes that include cyclic vapour deposition techniques, such as atomic layer deposition and chemical vapor deposition.BACKGROUND

[0003] Examples of copper(I), silver(I), and gold(I) complexes containing one fluorinated secondary or tertiary alkoxide ligand per metal centre as well as one phosphine (with alkyl, alkoxy or amino substituents on phosphorus) or isonitrile ligand per metal centre are scarce.

[0004] For example, homometaHic silver(I) complexes with one fluorinated secondary or tertiary alkoxide ligand per metal centre as well as one phosphine or isonitrile ligand per metal centre are unknown. Compounds in which Ag interacts with an | AI(O {C'fC'FsU } 41 anion via the oxygen atoms of the alkoxide ligands have been reported by Krossing et al. {(a) Krossing, I.; Wiillen. L. van, Superweak Complexes of Tetrahedral P4 Molecules with the Silver Cation of Weakly Coordinating Anions, Chem. Eur. J. 2002, 8, 700-711. (b) Raabe, I.; Antonijevic, S.; Krossing, I., Dynamics and Counterion-Dependence of the Structures of Weakly Bound Ag+- P4S3 Complexes, Chem. Eur. J. 2007, 13, 7510-7522. (c) Weis, P.; Hettich, C.; Kratzert, D.; Krossing, I., Homoleptic Silver Complexes of the Cages P4Se3 and AS4S3, Eur. J. Inorg. Chem. 2019, 1657-1668}, including [(P4)Ag{(m-O{C(CF3)3})2Al(O{C(CF3)3})2}]. However, these compounds contain aluminium in addition to copper, and are thus all heterometallic compounds.

[0005] Gold(I) isonitrile complexes of this type with one fluorinated secondary or tertiary alkoxide ligand per metal centre as well as one phosphine or isonitrile ligand per metal centre are also unknown, and the only gold(I) phosphine complex of this type is [(Cy3P)Au{OCH(CF3)2}], reported by Komiya et al. (Komiya, S.; Iwata, M.; Sone, T.; Fukuoka, A. Isolation of Highly Nucleophilic Gold(I) Alkoxides having a Tertiary Phosphine Ligand, J. Chem. Soc., Chem.Commun. 1992, 1109-1110). This publication does not include any comments about the volatility of the complex, or discussion of metal-containing fdm deposition. Additionally, the phosphine ligand in this complex has a high boiling point (greater than 350 °C), so the complex can be expected to be poorly volatile, and therefore poorly suited for use as a precursor for thin film deposition via vapour deposition methods such as CVD or ALD.

[0006] US Patent No. 5,346,730 discloses copper(I) alkoxide complexes, including (Me3P)Cu{OCMe2(CF3)}, (zBuNC)Cu{OCMe2(CF3)}, (Me3P)Cu{OC(CF3)3} and (ZBUNC)CU{OC(CF3)3} for use in a process for depositing a copper-containing layer on a substrate. However, dimeric or tetrameric copper(I) complexes with one fluorinated secondary or tertiary alkoxide ligand per metal centre as well as one phosphine or isonitrile ligand per metal centre have not been reported.

[0007] Atomic Layer Deposition (ALD) is a cyclic vapour deposition process involving self-limiting surface-based chemical reactions between two or more different chemical precursors that are sequentially delivered to a substrate surface in the vapour phase, typically separated by inert gas purge steps, where a function of these purge steps is to remove excess precursor and reaction byproducts from the reaction chamber before introduction of the next precursor. Therefore, a typical ALD process comprises one or more cycles comprising a pulse of the first precursor, followed by a purge step to remove excess precursor and reaction byproducts from the reaction chamber, followed by a pulse of a second precursor, followed by a purge step to remove excess precursor and reaction byproducts from the reaction chamber. A defining feature of ALD is self-limiting growth, wherein the film growth rate is independent of the duration of each precursor pulse, provided that each precursor pulse is above a certain minimum duration.

[0008] Chemical vapour deposition (CVD) is a vapour deposition process in which one or more precursor molecules are delivered to a substrate surface in the vapour phase, but the process does not achieve self-limiting gr owth; a common form of CVD involves thermal decomposition of a single precursor on the surface of a heated substrate, but CVD processes involving multiple precursors, with or without purge steps between each precursor pulse are also known. Physical vapour deposition (PVD) techniques include sputtering and evaporation.

[0009] Plasma-Enhanced ALD (PEALD) refers to an ALD process in which one or more of the precursors is a plasma-generated species. In contrast, thermal ALD refers to an ALD process in which none of the precursors are plasma-generated species.

[0010] The background herein is included solely to explain the context of the application. This is not to be taken as an admission that any of the material referred to was published, known, or part of the common general knowledge as of the priority date.SUMMARY

[0011] The present application includes a metal alkoxide complex of the formula (I):or a multimer thereof, whereinM is copper, silver or gold;RFis CF3, CF2CF3, CF2Me, CF2Et, CF2CF2CF3, or CF(CF3)2;R1is Ci-3alkyl, wherein one or more available hydrogen atoms is / are optionally replaced with fluorine;R2is H or Ci-3alkyl, wherein one or more available hydrogen atoms is / are optionally replaced with fluorine;(i) when M is silver or gold, L is PR3R4R5or CNR6, wherein R3, R4and R5are each independently selected from:Ci-salkyl. wherein one or more available carbon atoms are optionally replaced with a heteroatom selected from an oxygen atom and a silicon atom,C3.5cycloalkyl, 1-norbomyl, heterocycloalkyl, -O-Cnsalkyl, and -NR'R", wherein R' and R" are each independently selected from Ci- 4alkyl provided that the total number of carbon atoms is from 2-5; and R6is Ci-7hydrocarbyl; and(ii) when M is copper, L is PR3R4R5, wherein R3is selected from:Ci-salkyl, wherein one or more available carbon atoms is replaced with a heteroatom selected from an oxygen atom and a silicon atom,1-norbomyl, heterocycloalkyl,-O-Ci-salkyl, and-NR'R", wherein R' and R" are each independently selected from Ci- 4alkyl provided that the total number of carbon atoms is from 2-5; and R4and R5are each independently selected from:Ci-salkyl, wherein one or more available carbon atoms are optionally replaced with a heteroatom selected from an oxygen atom and a silicon atom,C3-5Cycloalkyl,1-norbomyl, heterocycloalkyl,-O-Ci-salkyl, and-NR'R", wherein R' and R" are each independently selected from Ci- 4alkyl provided that the total number of carbon atoms is from 2-5.

[0012] The present application also includes a crystalline form of a metal alkoxide complex of the formula (I'):or a multimer thereof, whereinM is copper, silver or gold, wherein when M is copper, the metal alkoxide complex is in the form of a multimer;RFis CF3, CF2CF3, CF2Me, CF2Et, CF2CF2CF3, or CF(CF3)2;R1is Ci-3alkyl, wherein one or more available hydrogen atoms is / are optionally replaced with fluorine;R2is H or Ci-3alkyl, wherein one or more available hydrogen atoms is / are optionally replaced with fluorine;L is PR3R4R5or CNR6, wherein R3, R4and R5are each independently selected from:Ci-salky 1, wherein one or more available carbon atoms are optionally replaced with a heteroatom selected from an oxygen atom and a silicon atom,C3-5cycloalkyl,1-norbomyl, heterocycloalkyl,-O-Ci-salkyl, and-NR'R", wherein R' and R" are each independently selected from Ci-4alkyl provided that the total number of carbon atoms is from 2-5; andR6is Ci-7hydrocarbyl.

[0013] The present application also includes uses of a metal alkoxide complex as described herein (such as a complex of the formula (I), 1(a) or (I")) or a crystalline form of a metal alkoxide complex as described herein (such as a complex of the formula (I') in the preparation of a material comprising M in the form of an elemental metal.

[0014] The present application also includes a process for preparing a material comprising M in the form of an elemental metal, the process comprising: reducing a metal alkoxide complex as described herein (such as a complex of the formula (I), 1(a) and / or (I")) or a crystalline form of a metal alkoxide complex as described herein (such as a complex of the formula (I')).

[0015] The present application also includes a process for depositing a material comprising M, the process comprising: exposing a heated substrate to a vapor obtained by heating a metal alkoxide complex as described herein (such as a complex of the formula (I), 1(a) or (I")) or a crystalline form of a metal alkoxide complex as described herein (such as a complex of the formula (I')).

[0016] The present application also includes a process for depositing a film comprising M, the process comprising a deposition cycle comprising: exposing a heated substrate to a vapor comprising a metal-containing precursor compound, the metal -containing precursor compound being a metal alkoxide complex as described herein (such as a complex of the formula (I), 1(a) or (I")) or a crystalline form of a metal alkoxide complex as described herein (such as a complex of the formula (I')); and exposing the precursor-treated substrate to a vapor comprising a co-reactant.

[0017] The present application also includes a process for preparing a metal alloy or intermetallic, a ternary or quaternary material, a doped material, or a nanolaminate, the process comprising: depositing a film comprising M by a process for depositing a film as described herein; and one or more additional film deposition processes.

[0018] The present application also includes uses of a process for depositing a material and / or film as described herein in the fabrication of an electronic device, memory or logic device, photonic device, chemical or biological sensor, catalyst or photocatalyst material, mirror, micro-electromechanical systems (MEMS) device, electrochromic device, photovoltaic device or quantum device or in the deposition of an anti-microbial film.

[0019] The present application involves (a) copper(I), silver(I) and gold(I) fluorinated alkoxide complexes, (b) a synthetic method to synthesize the gold(I) complexes, (c) and methods to deposit materials, films and structures comprising copper, silver and gold using the complexes, including vapour deposition processes (e.g. CVD and ALD) that afford films comprising elemental copper, elemental silver, and elemental gold.

[0020] For example, provided herein are metal alkoxide complexes having the general formula [{LM(OCRFR1R2)}Z] 1(a) wherein M is copper, silver or gold, L is PR3R4R5or CNR6, RFis CF3, CF2CF3, CF2Me, CF2Et, CF2CF2CF3, or CF(CF3)2, R1is an acyclic C1-C3 alkyl group with any degree of fluorination, R2is independently selected from H, or an acyclic C1-C3 alkyl group with any degree of fluorination, R3, R4and R5are independently selected from a C1-C5 alkyl group with or without a cyclic region, a 1-norbomyl group, a CFFSiMes group, an alkoxy group containing 1-5 carbon atoms with or without a cyclic region, an amino group containing 2- 5 carbon atoms with or without a cyclic region, or a CFFOMe. CFFOEt. CH2O"Pr, CFFO'Pr. CFECFEOMe or CFECFEOEt group, R6is a C1-C7 hydrocarbyl group with or without a cyclic region, and z is an integer (most commonly 1, 2 or 4). The phosphine, isonitrile and fluorinated alkoxide ligands defined in this list are selected to obtain metal complexes with appreciable volatility and thermal stability, so as to increase the suitability of the complexes for use as precursors in vapour deposition processes such as CVD and ALD.

[0021] In a preferred embodiment, R1is independently selected from CF3, CF2CF3, CF2Me, CF2Et, CF2CF2CF3, CF(CF3)2, Me, Et, "Pr, 'Pr. CH2F, CHF2, CH2CF3, or CH(CF3)2, R2is independently selected fromH, CF3, CF2CF3, CF2Me, CF2Et, CF2CF2CF3, CF(CF3)2, Me, Et, "Pr,'Pr. CH2F, CHF2, CH2CF3, or CH(CFS)2, R3, R4and R5are independently selected from the group consisting of Me, Et, "Pr, 'Pr, "Bu, Bu. 'Bu, 'Bu. CFL'Bu. CFESiMes, Cyp, 1-Norb, OMe, OEt, O"Pr, O'Pr, O"Bu, O’Bu. O'Bu, O'Bu. O(cyclopentyl), NMe2, NMeEt, NEt2, NMeEt, NMe"Pr, NMe'Pr. NEt"Pr, NEt'Pr, NMe"Bu, NMe’Bu. NMe'Bu, NMe'Bu. or 1-pyrrolidinyl, and R6is Me, Et, "Pr, 'Pr, "Bu, Bu. 'Bu, 'Bu. Cyp, Cy or 1-Norb. In another preferred embodiment, OCRFRJR2is selected from OCH(CF3)2, OCHMe(CF3), OCMe(CF3)2, OCMe2(CF3) or OC(CF3)3, and L is selected from PMe3, PEt3, PnPr3, P'Pr3, P'Bu3, P Bu3. P'Bu? PCyp3or CNR6, wherein R6is selected from Me, Et, "Pr, 'Pr, "Bu, Bu. 'Bu, 'Bu, Cyp, Cy or 1-Norb.

[0022] With respect to complexes, in an embodiment (a) when M is silver or gold, z is any integer (most commonly 2 or 4 for Ag, and 1 for Au, not including aurophilic interactions), and (b) when M is copper, z is greater than one (most commonly 2 or 4); single crystal X-ray diffraction was used to determine the value of z for complexes featuring a range of phosphine and isonitrile ligands. The complexes may be incorporated into a precursor source package comprising a precursor storage and dispensing vessel containing the metal precursor.

[0023] Copper complexes [{LCu(OCRFR1R2)}z] may be prepared via reactions of copper(I) chloride (CuCl) with one equivalent of L and one molar equivalent of M'(OCRFR1R2) (M1= Li, Na, K, Rb or Cs; x = an integer). Silver complexes [{LAg(OCRFR1R2)}z] may be prepared via reactions of silver(I) oxide (Ag2O) with 2 molar equivalents of HOCRFR1R2in an organic solvent in the absence of light, followed by the addition of 2 molar equivalents of L. Attempted syntheses of the gold complexes via reactions of [(LAuCl)J (x = an integer) with M'(OCRFRJR2) were not successful. However, the target [{LAu(OCRFRJR2)}z] complexes may be synthesized by reaction of | (L AuCIf l with M'(OCRFRJR2) (M1= Li, Na, K, Rb or Cs; x = an integer) in the presence of M"X, wherein M" is Li, Na, K, Rb, Cs, Ag or Tl, and X is a weakly -coordinating anion such as OTf, BF4, PF6, SbF6, Sb2Fn, BPh4, B(C6F5)4, or B{C6H3(CF3)2-3,5}4.

[0024] All new complexes were characterized by solution NMR spectroscopy, and in many cases by combustion elemental analysis, and single crystal X-ray diffraction. The thermal stability and volatility of most new complexes was evaluated by thermogravimetric analysis (TGA), and sublimation temperature (at 5 mTorr). Melting points were also recorded.

[0025] In one embodiment, a material comprising elemental copper, silver or gold is obtained by reacting [{LM(OCRFR1R2)}Z] {1(a), as defined above; where M is Ag and z is any integer, M is Au and z is any integer, or M is Cu and z is two or more} with a reducing agent in an organic solvent. For the purpose of this discussion, this solution deposition process is referred to asProcess A. In one refinement, the reducing agent, for example, in Process A and / or other suitable processes described herein as would be understood by a person skilled in the art is selected from the group consisting of H2, a mono-substituted hydrosilane such as PhSi H3 and "BuSi H3, a disubstituted silane such as Et2SiH2 and Ph2SiH2, a tri-substituted hydrosilane such as EtsSiH and I feSiHCl, a hydroborane such as HBpin, HBcat, (9-BBN)„, (n = 1 or 2) and HBMes2, a hydroborane-Lewis base adduct with the formula BH,(L) wherein L is selected from an amine, a thioether or a phosphine, a hydrostannane such as HSn"Bu3, a hydroalane such as (H Al'Bmh. a trialkylalane compound such as (AIMe?),, and (Al Ets)n (ft = 1 or 2), a dialkylzinc compound such as ZnMe2 and ZnEt2, hydrazine (N2H4), and a mono-substituted or di -substituted hydrazine such as PhN2H3, / BUN2H3, Ph2NNH2, PhHNNHPh, Me2NNH2, and MeHNNHMe.

[0026] In a further embodiment, a thin film comprising a metal, M, is deposited via a process involving exposure of a heated substrate to vapors of a metal complex obtained by heating [{LM(OCRFR1R2)}Z] {1(a), as defined above; where M is Ag and z is any integer, M is Au and z is any integer, or M is Cu and z is two or more}. For the purpose of this discussion, this vapour deposition process is referred to as Process B. This process may be carried out in the absence or presence of a continuous or periodic flow of hydrogen gas or a mixture of hydrogen gas in an inert gas, and in one refinement, the temperature is between 200 and 400 °C.

[0027] In another embodiment, a thin film comprising a metal, M, is deposited via a cyclic deposition process, with each cycle comprising sequentially contacting a heated substrate with vapours of a metal complex obtained by heating [{LM(OCRFR1R2)}Z] {1(a), as defined above; where M is Ag and z is any integer, M is Au and z is any integer, or M is Cu and z is two or more} (precursor-A), and contacting the substrate with a second vapour-phase precursor (precursor-B); within each cycle, the substrate may be contacted by precursor-A and precursor-B in any order, and any number of times. For the purpose of this discussion, this cyclic vapour deposition process is referred to as Process C. In one refinement, the substrate temperature is at or below 140 °C.

[0028] In another embodiment, a thin film comprising a metal, M, is deposited via a cyclic deposition process, with each cycle comprising sequentially contacting a heated substrate with vapours of a metal complex obtained by heating [{LM(OCRFR1R2)}Z] (1(a); as defined above, where z is any integer) (precursor-A), and contacting the substrate with a second vapour-phase precursor (precursor-B); within each cycle, the substrate may be contacted by precursor-A and precursor-B in any order, and any number of times. However, in this case, the deposition cycle further comprises the use of a purge gas to remove at least a portion ofexcess vapour phase precursor-A, and reaction byproducts if any, from the reaction space after contacting the substrate with vapour phase precursor-A and before contacting the surface with precursor-B, and the use of a purge gas to remove at least a portion of excess precursor- B, and reaction byproducts if any, from the reaction space after contacting the substrate with precursor-B and prior to contacting the surface with precursor-A. For the purpose of this discussion, this cyclic vapour deposition process is referred to as Process D.

[0029] Deposition process D may be an atomic layer deposition (ALD) process, or a chemical vapour deposition (CVD) process. In one refinement, the substrate is maintained at or below 140 °C, and in another refinement, the substrate is maintained at or below 100 °C. In one embodiment, deposition process D is interspersed with one or more other vapour deposition process for the purpose of fabricating a metal alloy or intermetallic, a ternary or quaternary material, or a nanolaminate. In other embodiments, deposition process D is used for device fabrication, including (a) electronic device fabrication, (b) memory or logic device fabrication, (c) photonic device fabrication, (d) chemical or biological sensor fabrication, (e) catalyst or photocatalyst material fabrication, (f) deposition of an anti-microbial film, (g) mirror fabrication, (e) MEMS device fabrication, (f) electrochromic device fabrication, (g) photovoltaic device fabrication, and (h) quantum device fabrication.

[0030] In one embodiment of deposition process D, and / or other suitable processes described herein as would be understood by a person skilled in the art precursor-B / co-reactant is selected from O2, O3, oxygen plasma, H2O, NH3, PH3, H2S, Se(SiR1R2R3)2, Te(SiR1R2R3)2, Sb(SiR1R2R3)3, Sb(SiR1R2R3)3, TiF4, TaFs. or HF (delivered from a cylinder or other container of HF, or from a liquid source of anhydrous HF vapours such as Pyridine(HF) ). wherein R1, R2and R3are independently selected from Me, Et, "Pr, 'Pr. "Bu, 'Bu. Bu. or 'Bu. This embodiment can be used to deposit a thin film comprising a group 11 metal oxide, metal nitride, metal phosphide, metal sulfide, metal selenide, metal telluride, metal antimonide, or metal fluoride.

[0031] In an another embodiment of deposition process D, and / or other suitable processes described herein as would be understood by a person skilled in the art precursor-B / co-reactant is a reducing agent, and in one refinement, this reducing agent is selected from the group consisting of (a) H2, (b) a hydrosilane or disilane comprising SiFU, Si2Hg, HsSiR1, H2SiR1R2, HSiR1R2R3, or HsSiR4, wherein R1, R2and R3are independently selected from Cl, OMe, OEt, O"Pr, O'Pr. O"Bu, O'Bu. O Bu. O'Bu. Me, Et, "Pr, 'Pr, "Bu, 'Bu, "Bu, 'Bu, "Pent, CHMe"Pr, CHMe'Pr, CHEt2, CH2'Bu, CFE'Bu. CFE'Bu. CH2SiMe3, and cyclopentyl, and R4is an arylsubstituent selected from Ph, C^FEMe. CeH4Et, CeHf'Pr. CeHfPr. CeH3Me2, CeH2Me3, C6H4(OMe), C6H3(OMe)2, C6H4(CF3), C6H4F, C6H3F2, C6H2F3, C6HF4, and C6F5, (c) a hydroborane comprising HB(OCRJR2CR3R4O), HB(OCR1R2CR3R4CR5R6O), HBcat, (9- BBN)„, (HBR72)„, B2HS, and BH3(L), wherein n is 1 or 2, the substituents R1, R2, R3, R4, R5and R6are independently selected from H, Me, Et, "Pr, Tr, "Bu, 'Bu, Bu and Bu, R7is independently selected from Me, Et, "Pr, Tr, "Bu, 'Bu, Bu. Bu, "Pent, CHMe"Pr, CHMe'Pr, CHEt2, CH2'BU, CH2U, CH2U, CH2SiMe3, cyclopentyl, CHMenPr, CHMe'Pr, CHEt2, CMe2Et, CMe2"Pr, CMe2'Pr, CMe2"Bu, CMe2'Bu, CMe2Bu, and CMe2CH2Bu, (d) a hydroborane-Lewis base adduct with the formula BH3(L), wherein L is selected from NMe3, NMe2Et, NMeEt2, NEt3, NHMe2, NHMeEt, NHEt2, SMe2, SMeEt, SEt2, PMe3, PMe2Et, PMeEt2, and PEt3, (e) a hydrostannane with the formula HSnRJR2R3, wherein R1, R2and R3are independently selected from Me, Et, "Pr, 'Pr, "Bu, 'Bu, u, Bu, "Pent, CHMe"Pr, CHMe'Pr, CHEt2, CH2'Bu, CH2Bu, CH2Bu, CH2SiMe3, and cyclopentyl, (f) a hydroalane with the formula (HAIR1R2),,. wherein n is 1 or 2, and R1and R2are independently selected from Me, Et, "Pr, 'Pr, "Bu, 'Bu, Bu, Bu, CHMe"Pr, CHMe'Pr, CHEt2, CMe2Et, CMe2"Pr, CMe2'Pr, CMe2"Bu, CMe2'Bu, CMe2Bu, and CMe2CH2Bu, (g) a trialkylalane compound with the formula (A1R1R2R3)„ wherein n is 1 or 2, and R1, R2and R3are independently selected from Me, Et, "Pr, 'Pr, "Bu, 'Bu, Bu, and Bu, (h) a dialkylzinc compound with the formula ZnR1R2wherein R1and R2are independently selected from Me, Et, "Pr, 'Pr, "Bu, 'Bu, Bu, and Bu, or (i) hydrazine (N2H4), or a mono-substituted or di-substituted hydrazine comprising Me2NNH2or BuN2H3. In one embodiment, the resulting process is an ALD process. In another embodiment, a film comprising elemental copper, elemental silver, or elemental gold is deposited. In yet another embodiment (when a hydroalane or a trialkylalane compound is used as a reducing agent), a film comprising a copper-aluminium, silveraluminium or gold-aluminium alloy or intermetallic is deposited.

[0032] In one refinement, the reducing agent for use in deposition process D and / or other suitable processes described herein as would be understood by a person skilled in the art is selected from H2, SiH4, "BuSiH3, PhSiH3, Et2SiH2, AlMe3, AlEt3, ZnMe2, ZnEt2, or a base-free hydroborane comprising HB(OCR1R2CR3R4O), HB(OCR1R2CR3R4CR5R6O), HBcat, (9-BBN)„, (HBR72)„. wherein n is 1 or 2, the substituents R1, R2, R3, R4, R5and R6are independently selected from H, Me, Et, "Pr, 'Pr, "Bu, 'Bu, Bu and Bu, and R7is independently selected from Me, Et, "Pr, 'Pr, "Bu, 'Bu, Bu, Bu, "Pent, CHMe"Pr, CHMe'Pr, CHEt2, CH2'BU, CH2BU, CH2BU, CH2SiMe3, cyclopentyl, CHMenPr, CHMe'Pr, CHEt2,CMe2Et, CMe2"Pr, CMe2'Pr, CMe2"Bu, CMe2'Bu. CMe2"Bu, and CMe2CH2Bu. In one embodiment, the resulting process is an ALD process.

[0033] In an alternative embodiment, the reducing agent used in deposition process D and / or other suitable processes described herein as would be understood by a person skilled in the art is hydrogen plasma; in one embodiment, the resulting process is a plasma-enhanced atomic layer deposition (PEALD) process; in another embodiment, a fdm comprising elemental copper, elemental silver, or elemental gold is deposited.

[0034] Other features and advantages of the present application will become apparent from the following detailed description. It should be understood, however, that the detailed description and the specific examples, while indicating embodiments of the application, are given by way of illustration only and the scope of the claims should not be limited by these embodiments but should be given the broadest interpretation consistent with the description as a whole.BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Certain embodiments of the application will now be described in greater detail with reference to the attached drawings in which:

[0036] FIG. 1 shows single crystal X-ray diffraction (SCXRD) characterization data for [(Cu{OC(CF3)3} {PMe3})2] according to an example of the present application.

[0037] FIG. 2 shows thermogravimetric analysis (TGA) characterization data for [(CU{OC(CF3)3} {PMe3})2] according to an example of the present application.

[0038] FIG. 3 shows TGA characterization data for [(Cu{OCMe(CF3)2} {PMe3})2] according to an example of the present application.

[0039] FIG. 4 shows SCXRD characterization data for [(Cu{OCH(CF3)2} {PMe3})2] according to an example of the present application.

[0040] FIG. 5 shows SCXRD characterization data for [(Cu{OC(CF3)3} {PEt3})2] according to an example of the present application.

[0041] FIG. 6 shows TGA characterization data for [(Cu{OC(CF3)3} {PEt3})2] according to an example of the present application.

[0042] FIG. 7 shows TGA characterization data for [(Cu{OC(CF3)3} {P(NMe2)Me2})2] according to an example of the present application.

[0043] FIG. 8 shows SCXRD characterization data [(Cu{OC(CF3)3} {P(CH2SiMe3)Me2})2] according to an example of the present application.

[0044] FIG. 9 shows TGA characterization data for [(Cu{OC(CF3)3} {P(CH2SiMe3)Me2})2] according to an example of the present application.

[0045] FIG. 10 shows SCXRD characterization data for [(Cu{OC(CF3)3} {CN*Bu})2] according to an example of the present application.

[0046] FIG. 11 shows TGA characterization data for [(Cu{OC(CF3)3} {CNThi}^] according to an example of the present application.

[0047] FIG. 12 shows SCXRD characterization data for [(Ag{OC(CF3)3} {PMesJ ] according to an example of the present application.

[0048] FIG. 13 shows TGA characterization data for [(Ag{OC(CF3)3} {PMe3})2] according to an example of the present application.

[0049] FIG. 14 shows SCXRD characterization data for [(Ag{OC(CF3)3} {PMe2Et})2] according to an example of the present application.

[0050] FIG. 15 shows TGA characterization data for [(Ag{OC(CF3)3} {PMe2Et})2] according to an example of the present application.

[0051] FIG. 16 shows SCXRD characterization data for [(Ag{OC(CF3)3} {PEtsJ ] according to an example of the present application.

[0052] FIG. 17 shows TGA characterization data for [(Ag{OC(CF3)3} {PEt3})2] according to an example of the present application.

[0053] FIG. 18 shows SCXRD characterization data for [(Ag{OC(CF3)3} {PMe'Pr2})2] according to an example of the present application.

[0054] FIG. 19 shows TGA characterization data for [(Ag{OC(CF3)3} {PMe'Pr2})2] according to an example of the present application.

[0055] FIG. 20 shows SCXRD characterization data for [(Ag{OC(CF3)3} {P'Pr3})2] according to an example of the present application.

[0056] FIG. 21 shows TGA characterization data for [(Ag{OC(CF3)3} {P'Pr3})2] according to an example of the present application.

[0057] FIG. 22 shows SCXRD characterization data for [(Ag{OC(CF3)3} {P'Bu'P^J ] according to an example of the present application.

[0058] FIG. 23 shows TGA characterization data for [(Ag{OC(CF3)3} {P^BuT^}^] according to an example of the present application.

[0059] FIG. 24 shows SCXRD characterization data for [Ag{OC(CF3)3}(P Bu3)] according to an example of the present application.

[0060] FIG. 25 shows TGA characterization data for [Ag{OC(CF3)3}(PzBu3)] according to an example of the present application.

[0061] FIG. 26 shows SCXRD characterization data for [(Ag{OC(CF3)3} {P(OMe)'Pr2})2] according to an example of the present application.

[0062] FIG. 27 shows TGA characterization data for [(Ag{OC(CF3)3} {P(OzBu)'Pr2})2] according to an example of the present application.

[0063] FIG. 28 shows SCXRD characterization data for [(Ag{OC(CF3)3} {P(CH2SiMe3)'Pr2}] according to an example of the present application.

[0064] FIG. 29 shows TGA characterization data for [(Ag{OC(CF3)3} {P(CH2SiMe3)'Pr2}] according to an example of the present application.

[0065] FIG. 30 shows SCXRD characterization data for [(Ag{OC(CF3)3} {P(CH2SiMe3)Me2})2] according to an example of the present application.

[0066] FIG. 31 shows TGA characterization data for [(Ag{OC(CF3)3} {P(CH2SiMe3)Me2})2] according to an example of the present application.

[0067] FIG. 32 shows SCXRD characterization data for [(Ag{OC(CF3)3} {CNMe})2] according to an example of the present application.

[0068] FIG. 33 shows SCXRD characterization data for [(Ag{OC(CF3)3} {CNThi})^ according to an example of the present application.

[0069] FIG. 34 shows SCXRD characterization data for [Au{OC(CF3)3}(PMe3)] according to an example of the present application.

[0070] FIG. 35 shows SCXRD characterization data showing aurophilic contacts for [Au{OC(CF3)3}(PMe3)] according to an example of the present application.

[0071] FIG. 36 shows TGA characterization data for [Au{OC(CF3)3}(PMe3)] according to an example of the present application.

[0072] FIG. 37 shows SCXRD characterization data for [Au{OC(CF3)3}(P'Pr3)] according to an example of the present application.

[0073] FIG. 38 shows TGA characterization data for [Au{OC(CF3)3}(P'Pr3)] according to an example of the present application.

[0074] FIG. 39 shows SCXRD characterization data for [Au{OC(CF3)3}(PzBu3)] according to an example of the present application.

[0075] FIG. 40 shows TGA characterization data for [Au{OC(CF3)3}(P Bu3)] according to an example of the present application.

[0076] FIG. 41 shows an X-ray diffractogram of the solid deposited in Example DI, showing the associated peaks for crystalline copper.

[0077] FIG. 42 shows an X-ray diffractogram of the solid deposited in Example D2, showing the associated peaks for crystalline copper.

[0078] FIG. 43 shows an X-ray diffractogram of the solid deposited in Example D3, showing the associated peaks for crystalline silver.

[0079] FIG. 44 shows an X-ray diffractogram of the solid deposited in Example D4, showing the associated peaks for crystalline silver.

[0080] FIG. 45 shows an X-ray diffractogram of the solid deposited in Example D5, showing the associated peaks for crystalline silver.

[0081] FIG. 46 shows an X-ray diffractogram of the solid deposited in Example D6, showing the associated peaks for crystalline gold.

[0082] FIG. 47 shows an X-ray diffractogram of the solid deposited in Example D7, showing the associated peaks for crystalline gold.

[0083] FIG. 48 shows an X-ray diffractogram of the film deposited in Example El, showing the associated peaks for crystalline copper.

[0084] FIG. 49 is a plot showing average film thickness (nm) as a function of [(Cu{OC(CF3)3} {PMe3})2] pulse duration (s) data from Example E2. Vertical error bars denote maximum and minimum film thickness measurements for a given experiment.

[0085] FIG. 50 is a plot showing average film thickness (nm) as a function of trimethylaluminum pulse duration (s) data from Example E2. Vertical error bars denote maximum and minimum film thickness measurements for a given experiment.

[0086] FIG. 51 shows an X-ray diffractogram of the films deposited in Example E3, showing the associated peaks for crystalline silver. The upper diffractogram is for silver deposited on SiO Si. The lower diffractogram is for silver deposited on hydrogen-terminated silicon (H-Si). Differences in the relative peak intensities for the films deposited on SiO Si and H-Si are indicative of different preferential orientations of the films relative the substrate surface.

[0087] FIG. 52 is a plot showing average growth per cycle (GPC in A) at 150 °C substrate temperature as a function of [(Ag{OC(CF3)3} { P'Pn } ] pulse duration (s) data from Example E4. Vertical error bars denote maximum and minimum growth per cycle measurements for a given experiment.

[0088] FIG. 53 is a plot showing average growth per cycle (GPC in A) at 150 °C substrate temperature as a function of HBpin pulse duration (s) data from Example E4. Vertical error bars denote maximum and minimum growth per cycle measurements for a given experiment.

[0089] FIG. 54 is a plot showing average growth per cycle (GPC in A) for deposition experiments conducted in Example E4 using (a) 9 s precursor and 0.03 s co-reactant pulses, and (b) 15 s precursor and 0.05 s co-reactant pulses across a substrate temperature window of 125 - 225 °C. Vertical error bars denote maximum and minimum growth per cycle measurements for a given experiment.

[0090] FIG. 55 is a plot showing film thickness (nm) at 150 °C substrate temperature as a function of the number of deposition cycles from Example E4. Vertical error bars denote maximum and minimum growth per cycle measurements for a given experiment.

[0091] FIG. 56 shows X-ray photoelectron spectroscopy (XPS) depth profile data for films deposited on SiO Si (upper graph) or H-Si (lower graph) at a deposition temperature of 150 °C from Example E4.

[0092] FIG. 57 shows an X-ray diffractogram of the film deposited in Example E5, showing the associated peaks for crystalline gold.

[0093] FIG. 58 shows an X-ray diffractogram of the film deposited in Example E6, showing the associated peaks for crystalline gold. The large peak at 20 = 56.8° corresponds to the underlying Si substrate.

[0094] FIGs. 59-83 show atomic force microscopy (AFM) characterization data for selected Cu, Ag and Au thin films according to examples of the present application.DETAILED DESCRIPTIONI, Definitions

[0095] Unless otherwise indicated, the definitions and embodiments described in this, and other sections are intended to be applicable to all embodiments and aspects of the present application herein described for which they are suitable as would be understood by a person skilled in the art. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting.

[0096] In understanding the scope of the present application, the term “comprising” and its derivatives, as used herein, are intended to be open ended terms that specify the presence of the stated features, elements, components, groups, integers, and / or steps, but do not exclude the presence of other unstated features, elements, components, groups, integers and / or steps. The foregoing also applies to words having similar meanings such as the terms, “including”, “having” and their derivatives. The term “consisting” and its derivatives, as used herein, are intended to be closed terms that specify the presence of the stated features, elements, components, groups, integers, and / or steps, but exclude the presence of other unstated features, elements, components, groups, integers and / or steps. The term “consisting essentially of’, as used herein, is intended to specify the presence of the stated features, elements, components, groups, integers, and / or steps as well as those that do not materially affect the basic and novel characteristic(s) of features, elements, components, groups, integers, and / or steps.

[0097] Terms of degree such as “substantially”, “about” and “approximately” as used herein mean a reasonable amount of deviation of the modified term such that the end result is not significantly changed. These terms of degree should be construed as including a deviation of at least ±5% of the modified term if this deviation would not negate the meaning of the word it modifies. In addition, all ranges given herein include the end of the ranges and also any intermediate range points, whether explicitly stated or not.

[0098] As used in this application, the singular forms “a”, “an” and “the” include plural references unless the content clearly dictates otherwise.

[0099] In embodiments comprising an “additional” or “second” component, the second component as used herein is different from the other components or first component. A “third” component is different from the other, first, and second components, and further enumerated or “additional” components are similarly different.

[0100] The term “and / or” as used herein means that the listed items are present, or used, individually or in combination. In effect, this term means that “at least one of’ or “one or more” of the listed items is used or present.

[0101] The abbreviation, “e.g.” is derived from the Latin exempli gratia and is used herein to indicate a non-limiting example. Thus, the abbreviation “e.g.” is synonymous with the term “for example.” The word “or” is intended to include “and” unless the context clearly indicates otherwise.

[0102] The skilled person would appreciate that the term “precursor” as used herein may refer to a molecule that may be used, for example, for film deposition. The term “co-reactant” may also be used to refer to a precursor, and herein, the terms precursor and co-reactant may be used interchangeably depending on the context in which they are used.

[0103] The term “complex” as used herein refers to a molecule which contains a metal bound to one or more ligands. The terms “heterometallic compound” and “heterometallic complex” as used herein refer to a molecule containing two or more different metals. The term “ligand” as used herein refers to a chemical species that is bound to a metal.

[0104] The term “multimer” as used herein refers to a molecule or complex consisting of multiple identical molecules linked together, such as multiple metal alkoxide complexes of formula (I). Similarly, the term “dimer” as used herein refers to a molecule or complex consisting of two identical molecules linked together such as two metal alkoxide complexes of formula (I) linked together. The term “dimeric” as used herein refers to a molecule that exists as a dimer. The term “tetramer” as used herein refers to a molecule or complex consisting of four identical molecules linked together such as four metal alkoxide complexes of formula (I) linked together. In contrast, the term “monomer” as used herein, for example, in reference to the metal alkoxide complexes of formula (I) would refer to a molecule consisting of the structure of formula (I).

[0105] The terms “elemental copper”, “elemental silver”, “elemental gold”, or “elemental metal” as used herein refer to copper, silver, gold, or a metal in the zero oxidation sate, respectively. The term “group 11 metal” as used herein refers to copper, silver or gold, which are in group 11 of the periodic table.

[0106] The term “alkyl” as used herein, whether it is used alone or as part of another group, means straight or branched chain, saturated alkyl groups. The number of carbon atoms that are possible in the referenced alkyl group are indicated by the numerical prefix “Cni-n2” For example, the term Ci-salkyl means an alkyl group having 1, 2 or 3 carbon atoms.

[0107] The term “cycloalkyl” as used herein, whether it is used alone or as part of another group, means a mono- or bicyclic, saturated cycloalkyl group or an alkyl group comprising at least one cyclic region. The number of carbon atoms that are possible in the referenced cycloalkyl group are indicated by the numerical prefix “Cni-n2” For example, the term C3- scycloalkyl means a cycloalkyl group having 3, 4 or 5 carbon atoms. When a cycloalkyl group contains more than one cyclic structure or rings, the cyclic structures may be fused, bridged, spiro connected or linked by a single bond. The term “fused” as used herein in reference to a first cyclic structure being “fused” with a second cyclic structure means the first cyclic structure and the second cyclic structure share at least two adjacent atoms therebetween. The term “bridged” as used herein in reference to a first cyclic structure being “bridged” with a second cyclic structure means the first cyclic structure and the second cyclic structure share at least two non-adjacent atoms therebetween. The term “spiro-connected” in reference to a first cyclic structure being “spiro connected” with a second cyclic structure means the first cyclic structure and the second cyclic structure share one atom therebetween.

[0108] The term “heterocycloalkyl” as used herein, whether it is used alone or as part of another group, refers to a non-aromatic, ring-containing group having one or more multivalent heteroatoms, independently selected from N and O, as a part of the ring structure. Heterocycloalkyl groups are either saturated or unsaturated (i.e. contain one or more double bonds) and may contain more than one ring.

[0109] The term “available”, as used herein in reference to “available hydrogen atoms” and “available carbon atoms” and the like refers to atoms that would be known to a person skilled in the art to be capable of modification and / or replacement by another atom or substituent. A person skilled in the art would also readily appreciate that this would not encompass structures that would not be suitable for use, for example, in the processes of the present application.For example, in the case of one or more available carbon atom(s) being replaced by silicon atom(s) the carbon being replaced would typically be a tertiary carbon atom.

[0110] As used herein, Me is methyl, Et is ethyl, 'Pr is isopropyl, "Pr is «-propyl, 'Bu is isobutyl, "Bu is «-butyl, T3u is sec-butyl, 'Bu is tert-butyl, "Pent is «-pentyl, Cyp is cyclopentyl, 1-Norb is 1-norbomyl, pin is pinacolate (OCMe2CMe2O), cat is ortho- catecholate (orlho-OiCiW^). HBpin is HB(OCMe2CMe2O), HBcat is HB^rt / zo-CECeFU), 9- BBN is 9-borabicyclo[3.3.1]nonane, PTFE is poly(tetrafluoroethylene) {(CF2CF2)„}. NMR is Nuclear Magnetic Resonance, EA is combustion elemental analysis, XRD is X-ray diffraction, PXRD is powder X-ray diffraction, SCXRD is single crystal X-ray diffraction, AFM is Atomic Force Microscopy, SEM is Scanning Electron Microscopy, FESEM is Field Emission Scanning Electron Microscopy, GPC is Growth rate Per Cycle (typically in units of A), and ppb is parts per billion. SiO2 / Si refers to a silicon wafer with a layer of SiCh at the surface, and hydrogen-terminated silicon, or hydrogen-terminated Si, or H-terminated silicon, or H-terminated Si, or H-Si refers to a hydrogen-terminated silicon wafer.

[0111] The terms “group” and “substituent” may be used interchangeably in this document or may optionally be omitted, for example in some instances when referring to a moiety that would be understood by a person skilled in the to be a group or substituent. For the purposes of this application, a “hydrocarbyl substituent” is defined to be a carbon-based radical which may be linear or branched, acyclic or cyclic, and may contain any number of multiple bonds between carbon atoms. In some instances, a hydrocarbyl substituent with any degree of fluorination is specified, in which case any number of H atoms in the hydrocarbyl group may be replaced by fluorine atoms. A saturated hydrocarbyl group refers to a hydrocarbyl group that does not contain any multiple bonds. An unsaturated hydrocarbyl group refers to a hydrocarbyl group that contains one or more multiple bonds.

[0112] In some embodiments, the terms “alkoxy” and “alkoxide” may be used interchangeably to refer to an OR group, substituent or ligand (i.e., the product formed via conceptual removal of a proton or a hydrogen atom from an alcohol with the formula ROH). In some embodiments, the term “amino” may be used to refer to an NRR' group, substituent or ligand (i.e., the product formed from conceptual removal of a proton or a hydrogen atom from a non-tertiary amine with the formula RR'NH), where the R and R' groups on nitrogen may be the same or different. In some embodiments, the term “isonitrile” may be used herein to refer to CNR ligands, where the R substituent is ahydrocarbyl group. In some embodiments, the term phosphine may be used to refer broadly to PR3 ligands, where the R substituents are independently selected from alkyl, alkoxy or amino groups; the term “phosphine” as used herein therefore may encompass phosphinite, phosphonite, phosphite esters, phosphoramidite and related ligands.

[0113] The term “hydroborane” as used herein refers to a borane with at least one hydrogen substituent directly bound to boron, and may exist as a monomer or a dimer; examples include but are not limited to HB(OCMe2CMe2O), (HB'P^ and B2H6. The term “base-free hydroborane” as used herein is used to specifically refer to a hydroborane that is not a hydroborane-Lewis base adduct, and unless otherwise specified, a hydroborane refers to a base-free hydroborane. The term “hydroborane-Lewis base adduct” as used herein refers to a hydroborane that is coordinated to an external Lewis base; examples include H3B(NMe3), H3B(SMe2), and H3B(NHMe2).

[0114] The term “hydrosilane” as used herein refers to a silane with at least one hydrogen substituent directly bound to silicon, such as SiFL, FLSiPh, HsSLBu, H2SiEt2, HSiMes, HSiClMe2, FhSiCh, or FLSiCl. The term “disilane” as used herein refers to a suitable compound with a Si-Si single bond, such as Si2Hg.

[0115] The term “hydrostannane” as used herein refers to a tin compound with at least one hydrogen substituent directly bound to tin, such as HSn"Bu3.

[0116] The term “hydroalane” as used herein refers to an alane with at least one hydrogen substituent directly bound to aluminium, which may exist as a monomer or a dimer, for example ('BmAIH ?. The term “hydroalane-Lewis base adduct” as used herein refers to a hydroalane that is coordinated to an external Lewis base, such as H3Al(quinuclidine).

[0117] The term “substrate” refers to a material or materials on which a deposition process is conducted (excluding the inner surfaces of a thin fdm deposition reactor), and in one embodiment, the substrate may refer to a wafer, such as a wafer suitable for semiconductor or photonic device manufacturing. The substrate may have one or more layers of differing materials already deposited upon it from a previous manufacturing step. For example, substrates may include silicon layers (e.g., crystalline, amorphous, porous, IT- terminated silicon, etc.), silicon containing layers (e.g., SiCL, SiN, SiON, SiCOH, etc.), elemental metal containing layers (e.g., titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium,cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, aluminium etc.) or combinations thereof, or elemental semimetal or nonmetal containing layers (e.g. boron, indium, black phosphorus, antimony, bismuth, tellurium etc.). The substrate may include a polymer layer, a region with an organic monolayer on the surface, or an organic patterned photoresist fdm. The substrate may include one or more layers of oxides, such as those used as dielectric materials (e.g. materials based on TiCh. ZrCh. HfO2. TazC , SiCh, GeCh. AI2O3, rare earth oxide-based materials, ternary oxide-based materials, etc.) or nitride-based fdms (e.g. TiN, TaN, NbN or Si2N3, etc.), or other materials including carbides, silicides, germanides, sulfides, selenides, tellurides, phosphides, arsenides, antimonides, and fluorides.

[0118] One of ordinary skill in the art will recognize that the terms “film” or “layer” used herein may be used to refer to a thickness of some material distributed on a surface, and that the surface may be planar or patterned (e.g. with trenches or vias, or more complex structures), or naturally non-planar as in the case of particles, nanotubes, fibres, aerogels or cloths.II. Metal Complexes and their Preparation

[0119] The present application involves (a) copper(I), silver(I) and gold(I) fluorinated alkoxide complexes, (b) a synthetic method to synthesize the gold(I) complexes, (c) and methods to deposit materials, films and structures comprising copper, silver and gold using the new complexes, including vapour deposition processes (e.g. CVD and ALD) that afford films comprising elemental copper, elemental silver, and elemental gold.

[0120] The present application includes a metal alkoxide complex of the formula (I):or a multimer thereof, whereinM is copper, silver or gold;RFis CF3, CF2CF3, CF2Me, CF2Et, CF2CF2CF3, or CF(CF3)2;R1is Cnsalkyl, wherein one or more available hydrogen atoms is / are optionally replaced with fluorine;R2is H or Ci-3alkyl, wherein one or more available hydrogen atoms is / are optionally replaced with fluorine;(i) when M is silver or gold, L is PR3R4R5or CNR6, wherein R3, R4and R5are each independently selected from:Ci-salkyl, wherein one or more available carbon atoms are optionally replaced with a heteroatom selected from an oxygen atom and a silicon atom,C3-5cycloalkyl, 1-norbomyl, heterocycloalkyl, -O-Ci-salkyl, and-NR'R'', wherein R' and R" are each independently selected from Ci- 4alkyl provided that the total number of carbon atoms is from 2-5; and R6is Ci-7hydrocarbyl; and(ii) when M is copper, L is PR3R4R5, wherein R3is selected from:Ci-salkyl, wherein one or more available carbon atoms is replaced with a heteroatom selected from an oxygen atom and a silicon atom, 1-norbomyl, heterocycloalkyl, -O-Ci-salkyl, and-NR'R", wherein R' and R" are each independently selected from Ci- 4alkyl provided that the total number of carbon atoms is from 2-5; and R4and R5are each independently selected from:Ci-salkyl, wherein one or more available carbon atoms are optionally replaced with a heteroatom selected from an oxygen atom and a silicon atom,C3-5cycloalkyl, 1-norbomyl, heterocycloalkyl, -O-Ci-salkyl, and-NR'R", wherein R' and R" are each independently selected from Ci- 4alkyl provided that the total number of carbon atoms is from 2-5.

[0121] In an embodiment, M is silver.

[0122] In an embodiment, M is gold.

[0123] In some embodiments wherein M is silver or gold, L is PR3R4R5.

[0124] In some embodiments wherein M is silver or gold, R3, R4and R5are independently selected from a C1-C5 alkyl group with or without a cyclic region, a 1-norbomyl group, a CH2SiMe3 group, an alkoxy group containing 1-5 carbon atoms with or without a cyclic region, an amino group containing 2-5 carbon atoms with or without a cyclic region, or a CH2OMe, CH2OEt, CH2O"Pr. CH2O'Pr, CH2CH2OMe or CH2CH2OEt group. In some embodiments wherein M is silver or gold, R3, R4and R5are each independently selected from Me, Et, "Pr, 'Pr, "Bu, "Bu, 'Bu, 'Bu, CH2zBu, CH2SiMe3, Cyp, 1-Norb, OMe, OEt, O"Pr, O'Pr, O"Bu, O'Bu. O'Bu. O'Bu. O(cyclopentyl), NMe2, NMeEt, NEt2, NMeEt, NMe'Tr. NMe'Pr. NEfTr, NEt'Pr. NMe"Bu, NMe'Bu. NMe'Bu. NMe'Bu and 1-pyrrolidinyl. In some embodiments wherein M is silver or gold, R3is Ci-4alkyl, -O-Ci-4alkyl, CH2SiMe3 or NMe2and R4and R5are each independently selected from Ci-4alkyl.

[0125] In some embodiments wherein M is silver or gold, L is CNR6.

[0126] In some embodiments, R6is C1-C7 hydrocarbyl group with a cyclic region.

[0127] In an embodiment, R6is selected from Me, Et, "Pr, Tr, "Bu, "Bu, 'Bu, 'Bu, Cyp, Cy and 1-Norb. In another embodiment, R6is Me, Et, "Pr, Tr, "Bu, Bu. 'Bu, 'Bu. Cyp, Cy or 1-Norb. In another embodiment, R6is Cwalkyl.

[0128] In an embodiment, M is copper.

[0129] In some embodiments wherein M is copper, R3is CH2SiMe3, OMe or NMe2and R4and R5are each independently selected from Ci-4alkyl.

[0130] In some embodiments wherein M is silver or gold, OCRFR1R2is selected from OCH(CF3)2, OCHMe(CF3), OCMe(CF3)2, OCMe2(CF3) and OC(CF3)3, L is selected from PMe3, PEt3, PnPr3, P'Pr3, P'Bu3, P"Bu3. P'Bu? PCyp3and CNR6, wherein R6is selected from Me, Et, "Pr, Tr, "Bu, "Bu, 'Bu, "Bu, Cyp, Cy and 1-Norb.

[0131] In an embodiment, R1is an acyclic C1-C3 alkyl group with any degree of fluorination. In another embodiment, R2is independently selected from H, or an acyclic Ci- C3 alkyl group with any degree of fluorination. In an embodiment, RFis CF3, and R1and R2are each independently Ci-3alkyl, wherein one or more available hydrogen atoms is / are replaced with fluorine. In another embodiment, RF, R1and R2are all CF3.

[0132] In another embodiment, RF, R1and R2are all CF3; andM is silver and L is PMes;M is silver and L is PMe2Et;M is silver and L is PEts;M is silver and L is PMe'Pn;M is silver and L is P'Pn;M is silver and L is P'Bu'Pr?:M is silver and L is P'BuvM is silver and L is P(OMe)'Pr2;M is silver and L is P(OzBu)'Pr2;M is silver and L is P(NMe2)'Pr2;M is silver and L is P(CH2SiMe3)'Pr2;M is silver and L is P(CH2SiMe3)Me2;M is silver and L is CNMe;M is silver and L is CN'Bu;M is gold and L is PMes;M is gold and L is PTn;M is gold and L is P'Bu,;M is copper and L is P(OMe)'Pr2;M is copper and L is P(NMe2)'Pr2;M is copper and L is P(NMe2)Me2;M is copper and L is P(CH2SiMe3)'Pr2; orM is copper and L is P(CH2SiMe3)Me2.

[0133] In an embodiment, the metal alkoxide complex of the formula (I) is in the form of a monomer. For example, the complex of the formula (I) that is in the form of a monomer would be of the formula [{LM(OCRFR1R2)}Z], wherein z is 1. In another embodiment, the metal alkoxide complex of the formula (I) is in the form of a multimer. In another embodiment, the metal alkoxide complex of the formula (I) is in the form of a dimer. In another embodiment, the metal alkoxide complex of the formula (I) is in the form of a tetramer.

[0134] The present application also includes a solid form comprising a form (e.g., a monomer, dimer, tetramer or combinations thereof) of the metal alkoxide complex of theformula (I). The present application also includes a crystalline form comprising a form (e.g., a monomer, dimer or tetramer) of the metal alkoxide complex of the formula (I).

[0135] The present application also includes a crystalline form of a metal alkoxide complex of the formula (I'):or a multimer thereof, whereinM is copper, silver or gold, wherein when M is copper, the metal alkoxide complex is in the form of a multimer;RFis CF3, CF2CF3, CF2Me, CF2Et, CF2CF2CF3, or CF(CF3)2;R1is Ci-3alkyl, wherein one or more available hydrogen atoms is / are optionally replaced with fluorine;R2is H or Ci-3alkyl, wherein one or more available hydrogen atoms is / are optionally replaced with fluorine;L is PR3R4R5or CNR6, wherein R3, R4and R5are each independently selected from:Ci-salkyl, wherein one or more available carbon atoms are optionally replaced with a heteroatom selected from an oxygen atom and a silicon atom, C3.5cycloalkyl, 1-norbomyl, heterocycloalkyl, -O-Cnsalkyl, and-NR'R", wherein R' and R" are each independently selected from Ci- 4alkyl provided that the total number of carbon atoms is from 2-5; and R6is Ci-7hydrocarbyl.

[0136] In some embodiments wherein M is silver or gold, the metal alkoxide complex is in the form of a monomer. In some embodiments wherein M is copper or silver, the metalalkoxide complex is in the form of a dimer. In some embodiments wherein M is silver, the metal alkoxide complex is in the form of a tetramer.

[0137] In an embodiment, M is copper.

[0138] In an embodiment, M is silver.

[0139] In an embodiment, M is gold.

[0140] In an embodiment, L is PR3R4R5.

[0141] In an embodiment, R3, R4and R5are independently selected from a C1-C5 alkyl group with or without a cyclic region, a 1-norbomyl group, a CEESiMe? group, an alkoxy group containing 1-5 carbon atoms with or without a cyclic region, an amino group containing 2-5 carbon atoms with or without a cyclic region, or a CFEOMe. CEEOEt. CH2O"Pr, C EEO'Pr. CH2CH2OMe or CH2CH2OEt group. In some embodiments wherein M is silver or gold, R3, R4and R5are each independently selected from Me, Et, "Pr, 'Pr, "Bu, Bu. 'Bu. 'Bu. CEE'Bu. CEESiMes, Cyp, 1-Norb, OMe, OEt, O"Pr, O'Pr, O"Bu, O Bu. O'Bu, O'Bu, O(cyclopentyl), NMe2, NMeEt, NEt2, NMeEt, NMe"Pr, NMe'Pr. NEfTr, NEt'Pr. NMe"Bu, NMe'Bu. NMe'Bu, NMe'Bu and 1-pyrrolidinyl. In some embodiments wherein M is silver or gold, R3is Ci-4alkyl, -O-Ci-4alkyl, CH2SiMe3 or NMe2and R4and R5are each independently selected from Ci-4alkyl. In some embodiments wherein M is copper, R3is CH2SiMe3, OMe or NMe2and R4and R5are each independently selected from Ci-4alkyl.

[0142] In an embodiment, L is CNR6. In another embodiment, R6is C1-C7 hydrocarbyl group with a cyclic region. In an embodiment, R6is selected from Me, Et, "Pr, 'Pr, "Bu, Bu. 'Bu, 'Bu, Cyp, Cy and 1-Norb. In another embodiment, R6is Me, Et, "Pr, 'Pr, "Bu, Bu. 'Bu, 'Bu, Cyp, Cy or 1-Norb. In another embodiment, R6is Ci-4alkyl.

[0143] In an embodiment, OCRFR1R2is selected from OCH(CF3)2, OCHMe(CF3), OCMe(CF3)2, OCMe2(CF3) and OC(CF3)3, L is selected from PMe3, PEt3, PnPr3, P'Pr3, P'BU3, P"BU3, P'BU3PCyps and CNR6, wherein R6is selected from Me, Et, "Pr, 'Pr, "Bu, Bu, 'Bu, 'Bu, Cyp, Cy and 1-Norb.

[0144] In an embodiment, R1is an acyclic C1-C3 alkyl group with any degree of fluorination. In another embodiment, R2is independently selected from H, or an acyclic Ci- C3 alkyl group with any degree of fluorination. In an embodiment, RFis CF3, and R1and R2are each independently Ci-salkyl, wherein one or more available hydrogen atoms is / arereplaced with fluorine. In another embodiment, RF, R1and R2are all CF3. In another embodiment, R1is H or Me and each of R1and R2are CF3.

[0145] In an embodiment, the metal alkoxide complex is selected from:[(CU{OC(CF3)3} {P(OMe)'Pr2})2]; [(Cu{OC(CF3)3} {P(NMe2)'Pr2})2]; [(CU{OC(CF3)3} {P(NMe2)Me2})2]; [(Cu{OC(CF3)3} {P(CH2SiMe3);Pr2})2]; [(CU{OC(CF3)3} {P(CH2SiMe3)Me2} )2] ;[(Ag{OC(CF3)3} {PMe3})2];[(Ag{OC(CF3)3} {PMe2Et})2];[(Ag{OC(CF3)3} {PEt3})2];[(Ag{OC(CF3)3} {PMe r2})2];[Ag{OC(CF3)3}(PzBu3)];[(Ag{OC(CF3)3} {P(OMe)'Pr2})2];[(Ag{OC(CF3)3} {P((yBu) r2})2];[(Ag{OC(CF3)3} {P(NMe2)'Pr2})2];[(Ag{OC(CF3)3} {P(CH2SiMe3) r2}]; [(Ag{OC(CF3)3} {P(CH2SiMe3)Me2})2];[(Ag{OC(CF3)3} {CNMe})2];[(Ag{OC(CF3)3} {CNzBu})4];[Au{OC(CF3)3}(PMe3)];[Au{OC(CF3)3}(P'Pr3)]; and [AU{OC(CF3)3}(PZBU3)].

[0146] Also provided herein are metal alkoxide complexes of the present application having the general formula [{LM(OCRFR1R2)}Z] (1(a)) wherein M is copper, silver or gold, L is PR3R4R5or CNR6, RFis CF3, CF2CF3, CF2Me, CF2Et, CF2CF2CF3, or CF(CF3)2, R1is an acyclic C1-C3 alkyl group with any degree of fluorination, R2is independently selected fromH, or an acyclic C1-C3 alkyl group with any degree of fluorination, R3, R4and R5are independently selected from a C1-C5 alkyl group with or without a cyclic region, a 1-norbomyl group, a CH2SiMe3 group, an alkoxy group containing 1-5 carbon atoms with or without a cyclic region,an amino group containing 2-5 carbon atoms with or without a cyclic region, or a CH2OMe, CH2OEt, CH2O"Pr, CH2O'Pr. CH2CH2OMe or CH2CH2OEt group, R6is a C1-C7 hydrocarbyl group with or without a cyclic region, and z is an integer (most commonly 1, 2 or 4). The phosphine, isonitrile and fluorinated alkoxide ligands defined in this list are selected to obtain metal complexes with appreciable volatility and thermal stability, so as to increase their suitability for use in vapour deposition processes such as CVD and ALD. Complexes with the general formula 1(a) do not contain any additional ligands or metals that are not specified.

[0147] In a preferred embodiment, R1is independently selected from CF3, CF2CF3, CF2Me, CF2Et, CF2CF2CF3, CF(CF3)2, Me, Et, "Pr, 'Pr. CH2F, CHF2, CH2CF3, or CH(CF3)2, R2is independently selected fromH, CF3, CF2CF3, CF2Me, CF2Et, CF2CF2CF3, CF(CF3)2, Me, Et, "Pr, 'Pr, CH2F, CHF2, CH2CF3, or CH(CF3)2, R3, R4and R5are independently selected from the group consisting of Me, Et, "Pr, 'Pr, "Bu, Bu. 'Bu, 'Bu, CH2'Bu. CH2SiMe3, Cyp, 1-Norb, OMe, OEt, O"Pr, O'Pr, O"Bu, O’Bu. O'Bu, O'Bu, O(cyclopentyl), NMe2, NMeEt, NEt2, NMeEt, NMe"Pr, NMe'Pr, NEt"Pr, NEt'Pr, NMe"Bu, NMe'Bu. NMe'Bu, NMe'Bu. or 1-pyrrolidinyl, and R6is Me, Et, "Pr, 'Pr, "Bu, Bu. 'Bu, 'Bu, Cyp, Cy or 1-Norb. In another preferred embodiment, OCR’ R' R2is selected from OCH(CF3)2, OCHMe(CF3), OCMe(CF3)2, OCMe2(CF3) or OC(CF3)3, and L is selected from PMes, PEt3, PnPr3, P'Pn, P'Bus, P'Bir,. P'Bm PCyps or CNR6, where R6is selected from Me, Et, "Pr, 'Pr, "Bu, Bu. 'Bu, 'Bu, Cyp, Cy or 1-Norb.

[0148] With respect to complexes, in an embodiment, (a) when M is silver or gold, z is any integer (most commonly 1, 2 or 4), and (b) when M is copper, z is greater than one (most commonly 2 or 4), as determined by X-ray crystallography for complexes featuring a range of phosphine and isonitrile ligands. These complexes may be incorporated into a precursor source package comprising a precursor storage and dispensing vessel containing the metal precursor.

[0149] The copper complexesmay be prepared via reactions of copper(I) chloride (CuCl) with one equivalent of L and one molar equivalent of M'(OCRFR1R2) (M1= Li, Na, K, Rb or Cs; x = an integer). The silver complexes [{LAg(OCRFR1R2)}z] may be prepared via reactions of silver(I) oxide (Ag2O) with 2 molar equivalents of HOCRFR1R2in an organic solvent in the absence of light, followed by the addition of 2 molar equivalents of L. Attempted syntheses of the gold complexes via reactions integer) with M'(OCRFR1R2) were not successful. However, the target complexes may be synthesized by reaction of [(LAuCl)J withLi, Na, K, Rb or Cs; x = an integer) in the presence of M"X, whereinM" is Li, Na, K, Rb, Cs, Ag or Tl, and X is a weakly-coordinating anion such as OTf, BF4, PFg, SbFg, Sb2Fn, BPh4, B(C6Fs)4, or B{CeH3(CF3)2-3,5}4. In this reaction, (a) the solvent is an organic solvent selected from an aliphatic hydrocarbon, an aromatic solvent, a chlorinated solvent, a fluorinated solvent, or an ethereal solvent, (b) M'(OCRFR1R2) and M"X may be added to [(LAuCl)J together or separately, in any order, before or after addition of solvent, (c) to optionally achieve a high yield of [{LAu(OCRFR1R2)}z], the reactants [(LAuCl)J, M'(OCRFR1R2) and M"X are preferably added in amounts to achieve an approximate 1:1 molar ratio between Au and M', and an approximate 1 : 1 molar ratio between Au and M", (f) the reaction is preferably stirred, or otherwise agitated or mixed, (d) the reaction temperature is below 120 °C, typically room temperature, (e) the reaction time is typically less than 48 hours, or less than 24 hours, or less than 6 hours, and (g) higher yields may be obtained when the reaction is carried out in the absence of light.

[0150] Accordingly, the present application also includes a process for preparing a gold alkoxide complex of the general formula I":or a multimer thereof, the process comprising: reacting a gold(I) chloride comprising L with an alkali metal salt of the formula M'(OCRFR1R2) and an alkali metal salt of the formula M"X in an organic solvent, wherein M' is Li, Na, K, Rb or Cs, M" is Li, Na, K, Rb, Cs, Ag, Tl or combinations thereof, X is a weakly-coordinating anion and L, R1, R2and RFare as described herein.

[0151] The organic solvent can comprise any suitable organic solvent or mixtures thereof. In an embodiment, the organic solvent comprises an aliphatic hydrocarbon, an aromatic solvent, a chlorinated solvent, a fluorinated solvent, or an ethereal solvent.

[0152] In an embodiment, the gold(I) chloride, M'(OCRFR1R2) and M"X are added in amounts to achieve an about 1 : 1 molar ratio between Au and M', and an about 1 : 1 molar ratio between Au and M". In another embodiment, the process comprises mixing during the reacting.In an embodiment, the mixing comprises agitation. In another embodiment, the mixing comprises stirring. In an embodiment, the reaction temperature is below 120 °C, for example room temperature (e.g., from about 4 °C to about 40 °C or about 20 °C). In an embodiment, the reaction time is less than 48 hours, or less than 24 hours, or less than 6 hours. In an embodiment, the reaction is carried out at least substantially, optionally fully in the absence of light.

[0153] All new complexes were characterized by solution NMR spectroscopy, and in many cases by combustion elemental analysis (EA) and / or single crystal X-ray diffraction (SCXRD). The thermal stability and volatility of most new complexes was evaluated by thermogravimetric analysis (TGA), sublimation temperature (at 5 mTorr), and heating for 24h or more in a sealed flask under argon at a temperature significantly higher than the sublimation temperature. Melting points were also recorded.III. Uses of the Metal Complexes

[0154] The present application also includes uses of a metal alkoxide complex as described herein (such as a complex of the formula (I), 1(a) or (I")) or a crystalline form of a metal alkoxide complex as described herein (such as a complex of the formula (I') in the preparation of a material comprising M in the form of an elemental metal.

[0155] The present application also includes a process for preparing a material comprising M in the form of an elemental metal, the process comprising: reducing a metal alkoxide complex as described herein (such as a complex of the formula (I), 1(a) and / or (I")) or a crystalline form of a metal alkoxide complex as described herein (such as a complex of the formula (I')).

[0156] In an embodiment, the reduction comprises reacting with a reducing agent in an organic solvent. In another embodiment, the organic solvent comprises an aliphatic hydrocarbon, an aromatic solvent, a chlorinated solvent, a fluorinated solvent or an ethereal solvent. In a further embodiment, the metal is deposited on a substrate. In another embodiment, the material is in the form of a film.

[0157] The present application also includes a process for depositing a material comprising M, the process comprising: exposing a heated substrate to a vapor obtained by heating a metal alkoxide complex as described herein (such as a complex of the formula (I), 1(a) or (I")) or acrystalline form of a metal alkoxide complex as described herein (such as a complex of the formula (I')).

[0158] In an embodiment, the material is in the form of a fdm.

[0159] In an embodiment, the process comprises repeated cycles of the exposure of the heated substrate until a film of a desired thickness is reached.

[0160] The present application also includes a process for depositing a film comprising M, the process comprising a deposition cycle comprising: exposing a heated substrate to a vapor comprising a metal-containing precursor compound, the metal -containing precursor compound being a metal alkoxide complex as described herein (such as a complex of the formula (I), 1(a) or (I")) or a crystalline form of a metal alkoxide complex as described herein (such as a complex of the formula (I')); and exposing the precursor-treated substrate to a vapor comprising a co-reactant.

[0161] In an embodiment, the process further comprises repeating the deposition cycle until a film of a desired thickness is deposited.

[0162] In an embodiment, subsequent to exposing to the vapor comprising the metalcontaining precursor compound, the process further comprises: purging with a purge gas to remove at least a portion of excess metalcontaining precursor compound and / or byproducts.

[0163] In an embodiment, subsequent to exposing to the vapor comprising the coreactant, the process further comprises: purging with a purge gas to remove at least a portion of excess co-reactant and / or byproducts.

[0164] In an embodiment, the process comprises an atomic layer deposition (ALD) process. In an embodiment, the process comprises a plasma-enhanced atomic layer deposition (PEALD) process. In an embodiment, the process comprises a chemical layer deposition (CVD) process.

[0165] In an embodiment, the deposited film comprising M comprises M in the form of an oxide, nitride, phosphide, sulfide, selenide, telluride, antimonide or fluoride.

[0166] In an embodiment, the co-reactant is a reducing agent.

[0167] In an embodiment, the film comprising M is a film comprising M in the form of elemental metal.

[0168] The present application also includes a process for preparing a metal alloy or intermetallic, a ternary or quaternary material, a doped material, or a nanolaminate, the process comprising: depositing a film comprising M by a process for depositing a film as described herein; and one or more additional film deposition processes.

[0169] The present application also includes uses of a process for depositing a material and / or film as described herein in the fabrication of an electronic device, memory or logic device, photonic device, chemical or biological sensor, catalyst or photocatalyst material, mirror, micro-electromechanical systems (MEMS) device, electrochromic device, photovoltaic device or quantum device or in the deposition of an anti-microbial film.

[0170] In one embodiment, a material comprising elemental copper, silver or gold is obtained by reacting [{LM(OCRFR'R2)}Z] {1(a), as defined above; where M is Ag and z is any integer, M is Au and z is any integer, or M is Cu and z is two or more} with a reducing agent in an organic solvent. For the purpose of this discussion, this solution deposition process is referred to as Process A. In one refinement, the reducing agent in Process A is selected from the group consisting of H2, a mono-substituted hydrosilane such as PhSifh and "BuSifh. a di-substituted silane such as Et2SiH2 and Ph2SiH2, a tri-substituted hydrosilane such as EtsSiH and I feSiHCl, a hydroborane such as HBpin, HBcat, (9-BBN)„, (n = 1 or 2) and HBMes2, a hydroborane-Lewis base adduct with the formula BH3(L) wherein L is an amine, thioether or phosphine, a hydrostannane such as HSn"Bu3, a hydroalane such as (HAFBu2)2, a trialkylalane compound such as ( Al Mesfin and ( Al E ts )« (n = 1 or 2), a dialkylzinc compound such as ZnMe2 and ZnEt2, hydrazine (N2H4), and a mono-substituted or di-substituted hydrazine such as PhN2H3, 'BuN2H3. Ph2NNH2, PhHNNHPh, Me2NNH2, and MeHNNHMe.

[0171] In a further embodiment, a thin film comprising a metal, M, is deposited via a process involving exposure of a heated substrate to vapors of a metal complex obtained by heating [{LM(OCRFR1R2)}Z] {1(a), as defined above; where M is Ag and z is any integer, M is Au and z is any integer, or M is Cu and z is two or more}. For the purpose of this discussion, this vapour deposition process is referred to as Process B. This process may be carried out in the absence or presence of a continuous or periodic flow of hydrogengas or a mixture of hydrogen gas in an inert gas, and in one refinement of process B, the substrate temperature is between 200 and 400 °C.

[0172] In another embodiment, a thin fdm comprising a metal, M, is deposited via a cyclic deposition process, with each cycle comprising sequentially contacting a heated substrate with vapours of a metal complex obtained by heating [{LM(OCRFR1R2)}Z] {1(a), as defined above; where M is Ag and z is any integer, M is Au and z is any integer, or M is Cu and z is two or more} (precursor-A), and contacting the substrate with a second vapour-phase precursor (precursor-B); within each cycle, the substrate may be contacted by precursor-A and precursor-B in any order, and any number of times. For the purpose of this discussion, this cyclic vapour deposition process is referred to as Process C. In one refinement of this process, the substrate temperature is at or below 140 °C.

[0173] In another embodiment, a thin film comprising a metal, M, is deposited via a cyclic deposition process, with each cycle comprising sequentially contacting a heated substrate with vapours of a metal complex obtained by heating [{LM(OCRFR1R2)}Z] (1(a); as defined above, where z is any integer) (precursor-A), and contacting the substrate with a second vapour-phase precursor (precursor-B); within each cycle, the substrate may be contacted by precursor-A and precursor-B in any order, and any number of times. However, in this case, the deposition cycle further comprises the use of a purge gas to remove at least a portion of excess vapour phase precursor-A, and reaction byproducts if any, from the reaction space after contacting the substrate with vapour phase precursor-A and before contacting the surface with precursor-B, and the use of a purge gas to remove at least a portion of excess precursor- B, and reaction byproducts if any, from the reaction space after contacting the substrate with precursor-B and prior to contacting the surface with precursor-A. For the purpose of this discussion, this cyclic vapour deposition process is referred to as Process D.

[0174] Deposition process D may be an atomic layer deposition (ALD) process, or a chemical vapour deposition (CVD) process. In one refinement, the substrate is maintained at or below 140 °C, and in another refinement, the substrate is maintained at or below 100 °C. In one embodiment, deposition process D is interspersed with one or more other vapour deposition process for the purpose of fabricating a metal alloy or intermetallic, a ternary or quaternary material, or a nanolaminate. In other embodiments, deposition process D is used for device fabrication, including (a) electronic device fabrication, (b) memory or logic device fabrication, (c) photonic device fabrication, (d) chemical or biological sensor fabrication, (e)catalyst or photocatalyst material fabrication, (f) deposition of an anti-microbial film, (g) mirror fabrication, (e) MEMS device fabrication, (f) electrochromic device fabrication, (g) photovoltaic device fabrication, and (h) quantum device fabrication.

[0175] In one embodiment of deposition process D, precursor-B is selected from O2, O3, oxygen plasma, H2O, NH3, PH3, H2S, SeCSiR^R3^, Te(SiR1R2R3)2, Sb(SiRJR2R3)3, Sb(SiR1R2R3)3, TiF4, TaFs, or HF (delivered from a cylinder or other container of HF, or from a liquid source of anhydrous HF vapours such as Pyridine(HF ), wherein R1, R2and R3are independently selected from Me, Et, "Pr, 'Pr, "Bu, 'Bu. Bu. or 'Bu. This embodiment can be used to deposit a thin film comprising a group 11 metal oxide, metal nitride, metal phosphide, metal sulfide, metal selenide, metal telluride, metal antimonide, or metal fluoride.

[0176] In an another embodiment of deposition process D, precursor-B is a reducing agent, and in one refinement, this reducing agent is selected from the group consisting of (a) H2, (b) a hydrosilane or disilane comprising SiH4, Si2H6, HsSiR1, H2SiRJR2, HSiRJR2R3, or H3SiR4, wherein R1, R2and R3are independently selected from Cl, OMe, OEt, O"Pr, O'Pr. O"Bu, O'Bu. O Bu. O'Bu, Me, Et, "Pr, 'Pr. "Bu, 'Bu, "Bu, 'Bu, "Pent, CHMe"Pr, CHMe'Pr, CHEt2, CH2'Bu, CH2BU. CH2'BU. CH2SiMe3, and cyclopentyl, and R4is an aryl substituent selected from Ph, C6H4Me, C6H4Et, C6H4nPr, CeHfPr, C6H3Me2, C6H2Me3, C6H4(OMe), C6H3(OMe)2, CeH4(CF3), CeH4F, CeH3F2, CeH2F3, CeHF4, and GTs. (c) a hydroborane comprising HB(OCR1R2CR3R4O), HB(OCR1R2CR3R4CR5R6O), HBcat, (9-BBN)„, (HBR72)„, B2H6. and BH3(L), wherein n is 1 or 2, the substituents R1, R2, R3, R4, R5and R6are independently selected from H, Me, Et, "Pr, 'Pr, "Bu, 'Bu, "Bu and ‘Bu, R7is independently selected from Me, Et, "Pr, 'Pr, "Bu, 'Bu, "Bu, 'Bu, "Pent, CHMe"Pr, CHMe'Pr, CHEt2, CH2'Bu, CH2"Bu, CH2'Bu. CH2SiMe3, cyclopentyl, CHMenPr, CHMe'Pr, CHEt2, CMe2Et, CMe2"Pr, CMe2'Pr, CMe2"Bu, CMe2'Bu, CMe2"Bu, and CMe2CH2'Bu, (d) a hydroborane-Lewis base adduct with the formula BH3(L), wherein L is selected fromNMe3, NMe2Et, NMeEt2, NEt3, NHMe2, NHMeEt, NHEt2, SMe2, SMeEt, SEt2, PMe3, PMe2Et, PMeEt2, and PEt3, (e) a hydrostannane with the formula HSnR1R2R3, wherein R1, R2and R3are independently selected from Me, Et, "Pr, 'Pr, "Bu, 'Bu, "Bu, 'Bu, "Pent, CHMe"Pr, CHMe'Pr, CHEt2, CH2'Bu, CH2"Bu, CH2'Bu. CH2SiMe3, and cyclopentyl, (f) a hydroalane with the formula (HA1RJR2)„, wherein n is 1 or 2, and R1and R2are independently selected from Me, Et, "Pr, 'Pr, "Bu, 'Bu, "Bu, 'Bu, CHMe"Pr, CHMe'Pr, CHEE, CMe2Et, CMe2"Pr, CMe2'Pr, CMe2"Bu, CMe2'Bu, CMe2"Bu, and CMe2CH2'Bu, (g) a trialkylalane compound with the formula (AIR1R2R3)„ wherein n is 1 or 2, and R1, R2and R3are independently selected from Me, Et, "Pr, 'Pr. "Bu, 'Bu. Bu. and 'Bu. (h) a dialkylzinc compound with the formula ZnR1R2wherein R1and R2are independently selected from Me, Et, "Pr, 'Pr, "Bu, 'Bu, Bu. and 'Bu. or (i) hydrazine (N2H4), or a mono-substituted or disubstituted hydrazine comprising Me2NNH2 or 'BUN2H3. In one embodiment, the resulting process is an ALD process. In another embodiment, a fdm comprising elemental copper, elemental silver, or elemental gold is deposited. In yet another embodiment (when ahydroalane or a trialkylalane compound is used as a reducing agent), a film comprising a copperaluminium, silver-aluminium or gold-aluminium alloy or intermetallic is deposited.

[0177] In one refinement, the reducing agent for use in deposition process D is selected from H2, SiEU, "BuSiEE, PhSiFE, Et2SiH2, AlMe3, AlEt3, ZnMe2, ZnEt2, or a base-free hydroborane comprising HB(OCR1R2CR3R4O), HB(OCR1R2CR3R4CR5R6O), HBcat, (9-BBN)„, (HBR72)„, wherein n is 1 or 2, the substituents R1, R2, R3, R4, R5and R6are independently selected from H, Me, Et, "Pr, 'Pr, "Bu, 'Bu, 'Bu and ‘Bu, and R7is independently selected from Me, Et, "Pr, 'Pr, "Bu, 'Bu, Bu. ‘Bu, "Pent, CHMe"Pr, CHMe'Pr, CHEt2, CH2'Bu, CH Bu, CH2‘Bu, CH2SiMe3, cyclopentyl, CHMenPr, CHMe'Pr, CHEt2, CMe2Et, CMe2"Pr, CMe2'Pr, CMe2"Bu, CMe2'Bu, CMe2"Bu, and CMe2CH2fBu. In one embodiment, the resulting process is an ALD process.

[0178] In an alternative embodiment, the reducing agent used in deposition process D is hydrogen plasma; in one embodiment, the resulting process is a plasma-enhanced atomic layer deposition (PEALD) process; in another embodiment, a film comprising elemental copper, elemental silver, or elemental gold is deposited.IV. Additional Embodiments

[0179] The present application also includes a metal alkoxide complex of the general formula 1(a):wherein M is copper, silver or gold, L is PR3R4R5or CNR6, RFis CF3, CF2CF3, CF2Me, CF2Et, CF2CF2CF3, or CF(CF3)2, R1is an acyclic C1-C3 alkyl group with any degree of fluorination, R2is independently selected from H, or an acyclic C1-C3 alkyl group with any degree offluorination, R3, R4and R5are independently selected from a C1-C5 alkyl group with or without a cyclic region, a 1 -norbomyl group, a CFESiMes group, an alkoxy group containing 1 -5 carbon atoms with or without a cyclic region, an amino group containing 2-5 carbon atoms with or without a cyclic region, or a CFEOMe, CEEOEt. CH2O"Pr, CFEO'Pr, CH2CH2OMe or CH2CH2OEt group, R6is a C1-C7 hydrocarbyl group with or without a cyclic region, and z is an integer (most commonly 1, 2 or 4). In an embodiment, M is silver and L is PR3R4R5. In an embodiment, M is silver and L is CNR6. In an embodiment, M is gold and L is PR3R4R5. In an embodiment, M is gold and L is CNR6. In an embodiment, M is copper and z is greater than 1.

[0180] In an embodiment, R1is independently selected from CF3, CF2CF3, CF2Me, CF2Et, CF2CF2CF3, CF(CF3)2, Me, Et, "Pr, 'Pr, CH2F, CHF2, CH2CF3, or CH(CF3)2, R2is independently selected firom H, CF3, CF2CF3, CF2Me, CF2Et, CF2CF2CF3, CF(CF3)2, Me, Et, "Pr, 'Pr, CH2F, CHF2, CH2CF3, or CH(CF3)2, R3, R4and R5are independently selected from the group consisting of Me, Et, "Pr, 'Pr, "Bu, Bu. 'Bu, Tin, CFE'Bu, CFESiMes, Cyp, 1-Norb, OMe, OEt, O"Pr, O'Pr, O"Bu, O'Bu. O'Bu, O'Bu, O(cyclopentyl), NMe2, NMeEt, NEt2, NMeEt, NMe"Pr, NMe'Pr. NEt"Pr, NEt'Pr. NMe"Bu, NMe'Bu. NMe'Bu. NMe'Bu. or 1- pyrrolidinyl, and R6is Me, Et, "Pr, 'Pr, "Bu, Bu. 'Bu, 'Bu, Cyp, Cy or 1-Norb. In an embodiment, M is selected from silver or gold. In an embodiment, OCRFR1R2is selected from OCH(CF3)2, OCHMe(CF3), OCMe(CF3)2, OCMe2(CF3) or OC(CF3)3, and L is selected from PMes, PEt3, PnPr3, P'Pn, P'Bus, P'Bin. P'Bus PCyps or CNR6, where R6is selected from Me, Et, "Pr, 'Pr, "Bu, Bu. 'Bu, 'Bu, Cyp, Cy or 1-Norb.

[0181] In an embodiment, z is greater than 1. In an embodiment, OCRFR1R2is selected from OCH(CF3)2, OCHMe(CF3), OCMe(CF3)2, OCMe2(CF3) or OC(CF3)3, and L is selected from PMes, PEt3, PnPr3, P'Pn, P'Bus, P'Bus. P'Bus PCyps or CNR6, where R6is selected from Me, Et, "Pr, 'Pr, "Bu, Bu. 'Bu, 'Bu, Cyp, Cy or 1-Norb.

[0182] The present application also includes a precursor source package comprising a precursor storage and dispensing vessel holding a precursor metal complex as described herein, wherein M is selected from silver or gold.

[0183] The present application also includes a precursor source package comprising a precursor storage and dispensing vessel holding a precursor metal complex of the formula [ { LAufOCR.’ R.1R2)}Z] as described herein, wherein z is greater than 1.

[0184] The present application also includes a process for preparing a gold complex with the formula [{LAu(OCRFR1R2)}z] according to the general formula 1(a) of the metal complex as described herein, comprising reaction of [(LAuCl)J, wherein x is an integer, with M'(OCRFR1R2), wherein M' is Li, Na, K, Rb or Cs, and M"X, wherein M" is Li, Na, K, Rb, Cs, Ag or Tl, and X is a weakly-coordinating anion, such as OTf, BF4, PFe, SbFe, Sb2Fn, BPfu, B(C6FS)4, or B{CeH3(CF3)2-3,5}4, the process comprising mixing M'(OCRFRJR2) , M"X and [(LAuCl)J, in any order, before or after addition of an organic solvent, wherein the organic solvent is selected from an aliphatic hydrocarbon, an aromatic solvent, a chlorinated solvent, a fluorinated solvent, or an ethereal solvent, and [(LAuCl)J, M'(OCRFR1R2) and M"X are preferably added in amounts to achieve an approximate 1 : 1 molar ratio between Au and M', and an approximate 1 : 1 molar ratio between Au and M".

[0185] The present application also includes a process for depositing a material comprising elemental copper, silver or gold by reacting a metal complex of the formula [{LAU(OCRFR1R2)}Z] 1(a) as described herein with a reducing agent in an organic solvent, wherein the organic solvent is an aliphatic hydrocarbon, an aromatic solvent, a chlorinated solvent, a fluorinated solvent, or an ethereal solvent. In an embodiment, the reducing agent is selected from the group consisting of H2, a mono-substituted hydrosilane such as PhSi H3 and "BuSiFL, a di-substituted silane such as Et2SiH2 and Pf^SiFE, a tri-substituted hydrosilane such as EtsSiH and I feSiHCl, a hydroborane such as HBpin, HBcat, (9-BBN),,. (n = 1 or 2) and HBMes2, a hydroborane-Lewis base adduct with the formula BH3(L) wherein L is an amine, thioether or phosphine, a hydrostannane such as HSn"Bu3, a hydroalane such as (H AI'Bu2)2. a trialkylalane compound such as (AIMesJn and (AIEtA, (n = 1 or 2), a dialkylzinc compound such as ZnMe2 and ZnEt2, hydrazine (N2H4), and a mono-substituted or di-substituted hydrazine such as PhN2H3, 'BuN2H3. Ph2NNH2, PhHNNHPh, Me2NNH2, and MeHNNHMe.

[0186] The present application also includes a process for depositing a material comprising a metal, M, the process comprising exposing a heated substrate to vapors of a metal complex obtained by heating a metal complex with the formula [{LM(OCRFR1R2)}Z] according to the general formula (I) of the metal complex as described herein. In an embodiment, M is selected from silver or gold. In an embodiment, z is greater than 1. In an embodiment, the substrate is maintained between 200 and 400 °C. In an embodiment, the process is carried out in the presence of a continuous or periodic flow of hydrogen gas or a mixture of hydrogen gas in an inert gas. In an embodiment, the process comprises a pluralityof deposition cycles, each cycle comprising sequentially contacting the substrate with vapours of a metal complex [{LM(OCRFR1R2)}Z] (precursor- A), and contacting the substrate with a second vapour-phase precursor (precursor-B); wherein within each cycle, the substrate may be contacted by precursor-A and precursor-B in any order, and any number of times. In an embodiment, M is selected from silver or gold. In an embodiment, z is greater than 1. In an embodiment, the substrate is maintained at or below 140 °C. In some embodiments, the deposition cycle further comprises the use of a purge gas to remove at least a portion of excess vapour phase precursor-A, and reaction byproducts if any, from the reaction space after contacting the substrate with vapour phase precursor-A and before contacting the surface with precursor-B, and the use of a purge gas to remove at least a portion of excess precursor-B, and reaction byproducts if any, from the reaction space after contacting the substrate with precursor-B and prior to contacting the surface with precursor-A. In an embodiment, M is [{LM(OCRFR1R2)}Z] is copper. In an embodiment, M in [{LM(OCRFR1R2)}Z] is silver. In an embodiment, M in [{LM(OCRFR1R2)}Z] is gold. In an embodiment, the substrate is maintained at or below 140 °C. In an embodiment, the substrate is maintained at or below 100 °C. In an embodiment, the process is an atomic layer deposition (ALD) process. In an embodiment, the process is a chemical vapour deposition process. In an embodiment, precursor-B is selected from O2, O3, oxygen plasma, H2O, NH3, PH3, H2S, Se(SiR1R2R3)2, Te(SiR1R2R3)2, Sb(SiR1R2R3)3, Sb(SiR1R2R3)3, TiF4, TaFs, or HF (delivered from a cylinder or other container of HF, or from a liquid source of anhydrous HF vapours such as Pyridine(HF) ). wherein R1, R2and R3are independently selected from Me, Et, "Pr, 'Pr, "Bu, 'Bu, "Bu, or 'Bu. In an embodiment, the deposited film comprises a copper, silver or gold oxide, nitride, phosphide, sulfide, selenide, telluride, antimonide, or fluoride. In an embodiment, precursor-B is a reducing agent. In an embodiment, the reducing agent is selected from the group consisting of (a) H2, (b) a hydrosilane or disilane comprising SiH4, Si2He, HsSiR1, H2SiR1R2, HSiR1R2R3, or HsSiR4, wherein R1, R2and R3are independently selected from Cl, OMe, OEt, O' Pr. O'Pr, O' Bu. O'Bu. O'Bu. O'Bu. Me, Et, "Pr, 'Pr, "Bu, 'Bu, "Bu, 'Bu, "Pent, CHMe"Pr, CHMe'Pr, CHEt2, CH2'Bu, CH2Bu. CH2'Bu, CH2SiMe3, and cyclopentyl, and R4is an aryl substituent selected from Ph, CEFEMe. CEFEEt. CeH^Pr, CeHEPr, C6H3Me2, C6H2Me3, C6H4(OMe), C6H3(OMe)2, C6H4(CF3), C6H4F, C6H3F2, C6H2F3, CeHF4, and CeFs, (c) a hydroborane comprising HB(OCR1R2CR3R4O), HB(OCR1R2CR3R4CR5R6O), HBcat, (9-BBN)„, (HBR72)„, or B2H6, wherein n is 1 or 2, the substituents R1, R2, R3, R4, R5and R6are independently selected from H, Me, Et, "Pr, 'Pr,"Bu, 'Bu, "Bu and 'Bu, R7is independently selected from Me, Et, "Pr, 'Pr, "Bu, 'Bu, "Bu, 'Bu, "Pent, CHMe"Pr, CHMe'Pr. CHEt2, CH2'Bu. CH2BU. CH2'BU. CH2SiMe3, cyclopentyl, CHMenPr, CHMe'Pr, CHEt2, CMe2Et, CMe2"Pr, CMe2'Pr, CMe2"Bu, CMe2'Bu, CMef Bu. and CMe2CH2'Bu, (d) ahydroborane-Lewis base adduct with the formula BH3(L), wherein L is selected from NMe3, NMe2Et, NMeEfe, NEfe, NHMe2, NHMeEt, NHEt2, SMe2, SMeEt, SEt2, PMe3, PMe2Et, PMeEt2, and PEt3, (e) a hydrostannane with the formula HSnR1R2R3, wherein R1, R2and R3are independently selected from Me, Et, "Pr, 'Pr, "Bu, 'Bu, Bu. 'Bu, "Pent, CHMe"Pr, CHMe'Pr, CHEt2, CH2'Bu, CHfBu. CH2'Bu. CH2SiMe3, and cyclopentyl, (f) a hydroalane with the formula (HAIR1R2),,. wherein n is 1 or 2, and R1and R2are independently selected from Me, Et, "Pr, 'Pr, "Bu, 'Bu, Bu. 'Bu, CHMe"Pr, CHMe'Pr, CHEt2, CMe2Et, CMe2"Pr, CMe2'Pr, CMe2"Bu, CMe2'Bu, CMefBu. and CMe2CH2'Bu, (g) a trialkylalane compound with the formula (AIR1R2R3)„ wherein n is 1 or 2, and R1, R2and R3are independently selected from Me, Et, "Pr, 'Pr, "Bu, 'Bu, Bu. and 'Bu, (h) a dialkylzinc compound with the formula ZnR1R2wherein R1and R2are independently selected from Me, Et, "Pr, 'Pr, "Bu, 'Bu, Bu. and 'Bu, or (i) hydrazine (N2H4), or a mono-substituted or disubstituted hydrazine comprising Me2NNH2or 'BuN2H3. In an embodiment, the reducing agent is H2, SiH-i. "BuSiH3, PhSiH3, Et2SiH2, Al Me?. AlEt3, ZnMe2, ZnEt2, or a base-free hydroborane comprising HB(OCR1R2CR3R4O), HB(OCR1R2CR3R4CR5R6O), HBcat, (9-BBN)„, (HBR72)„, wherein n is 1 or 2, the substituents R1, R2, R3, R4, R5and R6are independently selected from H, Me, Et, "Pr, 'Pr, "Bu, 'Bu, Bu and 'Bu, and R7is independently selected from Me, Et, "Pr, 'Pr, "Bu, 'Bu, "Bu, 'Bu, "Pent, CHMe"Pr, CHMe'Pr, CHEt2, CH2'Bu, CHfBu. CH2'Bu. CH2SiMe3. cyclopentyl, CHMenPr, CHMe'Pr, CHEt2, CMe2Et, CMe2"Pr, CMe2'Pr, CMe2"Bu, CMe2'Bu, CMe Bu, and CMe2CH2'Bu. In an alternative embodiment, the reducing agent is hydrogen plasma. In an embodiment, precursor-A is [(Cu{OC(CF3)3} {PMe3})2] or [(Ag{OC(CF3)3} {P'Pr3})2], In an embodiment, the process is an atomic layer deposition (ALD) process. In an embodiment, the process is an atomic layer deposition (ALD) process. In an embodiment, the process is a plasma-enhanced atomic layer deposition (PEALD) process. In some embodiments, a film comprising elemental copper, elemental silver, or elemental gold is deposited. In an embodiment, the reducing agent is a hydroalane or a trialkylalane compound, and a film comprising a copper-aluminium, silver-aluminium or gold-aluminium alloy or intermetallic is deposited. In an embodiment, the process is used for electronic device fabrication. In another embodiment, the process is used for memory or logic device fabrication. In an embodiment, the process is used for photonic device fabrication. In anembodiment, the process is used for chemical or biological sensor fabrication. In an embodiment, the process is used for catalyst or photocatalyst material fabrication. In an embodiment, the process is used to deposit an anti-microbial fdm. In an embodiment, the process is used for mirror fabrication. In an embodiment, the process is used for MEMS device fabrication. In an embodiment, the process is used for electrochromic device fabrication. In an embodiment, the process is used for photovoltaic device fabrication. In an embodiment, the process is used for quantum device fabrication.

[0187] The present disclosure also includes a film deposition method in which a process for depositing a metal as described herein is interspersed with one or more other vapour deposition processes for the purpose of fabricating a metal alloy or intermetallic, a ternary or quaternary material, a doped material, or a nanolaminate.

[0188] The present application also discloses use of a deposition reactor with sources to provide vapours of each precursor (e.g. precursor-A and precursor-B) to the reaction chamber during the thin film deposition process. For a precursor that would be a gas at room temperature and atmospheric pressure, the source typically comprises a pressurized gas cylinder (containing the precursor or a mixture of the precursor and one or more compatible gas such as N2, He, Ar, or in some cases H2) that is connected to a device (e.g. a gas regulator) to control the pressure of the gas in the delivery line to the reactor, a mass flow controller to control the gas flow rate, and a valve that prevents the flow of gas into the deposition chamber of the reactor when the valve is closed, and allows passage of the gas into the deposition chamber when the valve is opened. For a solid or liquid precursor, the source typically comprises a vessel (e.g. a metal cylinder or a glass vessel) that is connected to a valve which prevents escape of the precursor vapours when the valve is closed and allows passage of the precursor vapours into the deposition chamber of the reactor when the valve is opened. Herein, this design of source vessel is referred to as a non-flow-through design. In one refinement, the source may be a vessel having an inlet and an outlet tube to allow an inert gas to flow through the vessel during each pulse of the precursor. This inert gas flow is controlled by valves (valves A and B) on the inlet and outlet tubes to / from the vessel, and a valve (valve C) on the delivery line between the connection points to the inlet and outlet tubes. When the precursor is not in use, valves A and B are closed, and valve C is open, so that inert gas can flow through the delivery line into the reaction chamber, but precursor vapours cannot exit the source. To deliver a pulse of precursor vapour into the reactor, valves A and B are opened, and valve C is closed, so that the inert gasflowing into the delivery line is required to flow through the source en route to the reaction chamber. Herein, this design of source vessel is referred to as a flow-through design.

[0189] The pressure during film deposition is set at a value suitable to the properties of the chemical precursors and film to be formed, and the type of deposition process (e.g. a process relying upon precursor thermal decomposition, versus a process relying upon surface-based reactions between two or more precursors that are delivered to the substrate surface in the vapour phase, separated by purge steps to remove excess precursor and reaction byproducts). In one refinement, the pressure is from about 106Torr to about 760 Torr. In another refinement, the pressure is from about 106Torr to about 0.1 Torr. In another refinement, the pressure is from about 0.1 mTorr to about 10 Torr. In yet another refinement, the pressure is from about 10 mTorr to about 10 Torr. In a further refinement, the pressure is from about 100 mTorr to about 2 Torr.

[0190] The deposition processes disclosed herein are typically carried out with a substrate temperature (i.e. a deposition temperature) between 20 and 500 °C, most typically between 50 and 400 °C, or between 50 and 250 °C, or between 50 and 150 °C, or between 200 and 400 °C.

[0191] The cyclic deposition processes disclosed herein typically involve between 1 and 6000 deposition cycles, or from 5 to 4000 deposition cycles, or 10 to 2000 deposition cycles.

[0192] Pulse times and purge times depend on the properties of the chemical precursors, the chemical nature of the substrate surface, the design of the deposition reactor, the geometric shape of the substrate(s), and the type of deposition experiment. In the case of a deposition experiment involving surface-based reactions between two or more precursors that are delivered to a substrate surface in the vapour phase separated by inert gas purge steps (e.g. Deposition Process D, described above), thin film growth on flat substrates enables shorter pulse and purge times, whereas film growth on 3-dimensional substrates can require much longer pulse and purge times. Therefore, in one refinement, pulse times and purge times are each independently from about 0.005 to 300 seconds. In another refinement, pulse times are from about 0.005 to 30 seconds, and purge times are from about 2 to 200 seconds.

[0193] In deposition processes where films or structures comprising elemental metal are deposited, the metal content of the film may be greater than or equal to about 90 at%, 95 at%, 98 at%, 99 at%, 99.5 at% or 99.8 at% within the bulk portion of the film.

[0194] The following non-limiting examples are illustrative of the present application:EXAMPLES

[0195] Examples have been divided into five sections. Part A (Copper Complex Synthesis and Characterization), Part B (Silver Complex Synthesis and Characterization), Part C (Gold Complex Synthesis and Characterization), Part D (Thin film deposition) and Part E Vapour Deposition Processes and Thin Film Characterization.

[0196] The following abbreviations are used in the Examples: 'Bu = / -but l; A = angstrom; AFM = atomic force microscopy; Al Me? = trimethylaluminum; d = doublet; dd = doublet of doublets; dt = doublet of triplets; dq = doublet of quartets; d7 = doublet of septets; S = chemical shift in parts per million; Et = ethyl ; HBpin = 4,4,5,5-Tetramethyl-l,3,2-dioxaborolane; Hz = hertz ; 'Pr = isopropyl; J= symbol for coupling constant; ”JX,Y = n bond coupling constant between X and Y; m = multiplet ; M = moles per litre ; Me = methyl; MHz = megahertz ; mmol = millimoles ; mL = millilitres ; nm = nanometers; NMR = nuclear magnetic resonance; OTf = trifluoromethanesulfonate anion; PhSiH? = phenylsilane; ppm = parts per million; q = quartet; s = singlet; SCXRD = single crystal X-ray diffraction; t = triplet; TGA = thermogravimetric analysis; THF = tetrahydrofiiran; pm = micrometers; and XRD = X-ray diffraction.General Details

[0197] General synthesis details: An argon-filled MBraun UNIlab™ or Innovative Technology PureLab™ HE glove box equipped with a -35 °C freezer was employed for the manipulation and storage of all air-sensitive compounds, and reactions were performed on a double manifold vacuum line using standard techniques. The vacuum was measured periodically using a Kurt J. Lesker 275i convection-enhanced Pirani gauge. Residual oxygen and moisture were removed from the argon stream by passage through an Oxisorb-W scrubber from Matheson Gas Products. Centrifugation was carried out using a Benchmark Hermle Z206A centrifuge housed within a glove box.

[0198] Hexanes, toluene, diethyl ether, tetrahydrofuran (THF), and dichloromethane were purchased from Sigma-Aldrich™, and deuterated solvents were purchased from Cambridge Isotope Laboratories. Solvents were initially dried and distilled at atmospheric pressure from sodium / benzophenone (hexanes, diethyl ether, tetrahydrofuran, CeDe), sodium (toluene), or 4 A molecular sieves (di chloromethane). All solvents (except for di chloromethane, which was stored over 4 A molecular sieves) were stored over sodium / benzophenone and introduced to reactions or solvent storage flasks via vacuum transfer with condensation at -78°C. Potassium hydride, sodium hydride, «-butyllithium (1.6 M in hexanes), / c / 7-butyllithium (1.7 M in pentane), (trimethylsilyl)methyllithium (1.0 M in pentane), methyllithium (1.6 M in Et20), lithium dimethylamide, silver tetrafluoroborate, copper(I) chloride, silver(I) oxide chlorodiisopropylphosphine, dichloroethylphosphine, tri-zc / V-butylphosphine. phosphorous trichloride, trimethylsilyl chloride, tert-butyl isonitrile, tetrahydriothiophene, methanol, tert- butanol, and phenylsilane were purchased from Sigma-Aldrich. 1,1, 1,3,3, 3-Hexafluoro-2- trifluoromethyl-2-propanol (HOC(CF3)3), 1,1,1 ,3,3,3-hexafluoro-2-methyl-2-propanol(HOC(CH3)(CF3)2), l,l,l,3,3,3-hexafluoro-2-propanol (HOCH(CF3)2), and 4, 4,5,5- tetramethyl-l,3,2-dioxaborolane (HBpin) were purchased from Oakwood Chemical. Trimethylphosphine, triethylphosphine, trimethylaluminum, triethylaluminum, and diethylzinc were purchased from Strem™ Chemicals. Hydrogen tetrachloroaurate(III) hydrate was purchased from Strem Chemicals or Ambeed. Alkali metal alkoxides were prepared via deprotonation of an alcohol with the corresponding alkali metal hydride. Phosphines which were not commercially available were prepared by reaction of a commercially available chlorophosphine with the appropriate nucleophile. Methyl isonitrile was prepared according to previously described literature procedures (Schuster, R. E.; Scott, J. E.; Casanova, J. J. Org. Synth. 1966, 46, 75). LAuCl complexes (where L = PMes, P'Prs, P'Bu?) were prepared from hydrogen tetrachloroaurate(III) hydrate through modifications to previously reported procedures that could readily be made by a person skilled in the art (Griffiths, M. B. E.; PaHister, P. J.; Mandia, D. J.; Barry, S. T. Chem. Mater. 2016, 28, 44-46).

[0199] General characterization details: NMR spectroscopy was performed on a Bruker™ AV-600 spectrometer. All ' H NMR and13C NMR spectra were referenced relative to SiMe4 through the CeDg resonance or the protio impurity in the CeDg solvent: 7.16 ppm for1H NMR and 128.06 ppm for13C NMR.19F,29Si, and31P NMR spectra were referenced by indirect referencing from a 'H NMR spectrum. Peak assignments in the spectra of all new diamagnetic compounds were made with the aid of DEPT-q, COSY, HSQC and HMBC experiments. Single-crystal X-ray crystallographic analyses were performed on crystals coated in Paratone™ oil and mounted on either a Bruker SMART APEX II diffractometer with a 3 kW sealed tube Mo generator and APEX II CCD detector, or a STOE IPDS II diffractometer with an image plate detector, or a Bruker Dual Source D8 Venture diffractometer using the IpS 3.0 Mo source at 70 W with a HELIOS Mo focusing optic (ELM33). Combustion elemental analyses were performed using a Perkin- Elmer™ Model 2400 series II analyzer. Thermogravimetric analysis was performed usinga TA Instruments™ Discovery TGA located within an argon-filled glove box. Melting point determinations were performed by packing the analyte into a thin (about 1.5 mm outer diameter) glass tube that had been flame-sealed at one end, and sealing the open face of the glass tube with Apiezon™ H-grease inside an argon-fdled glovebox. The glass tube was then removed from the glovebox and quickly flame-sealed (below the grease but sufficiently distant from the analyte) to form a sealed capillary, which was in turn used for analysis using a DigiMelt Melting Point Apparatus.

[0200] Vapour deposition experiments involving more than one precursor: Vapour deposition experiments involving more than one precursor were conducted in a home-built ALD reactor. The reactor is made up of a reaction chamber (a 6” ConFlat™ cube) housed within an oven. This reaction chamber contains a flange-mounted 2-inch heated substrate stage (Heatwave™ labs) which can be heated independently to a temperature equal to or above the temperature of the surrounding oven. The reaction chamber is connected to an Ebara™ EV- A10-2S-P dry semiconductor vacuum pump via a foreline that includes a Mass-Vac 10” body diameter multi-trap (with stainless steel gauze and activated charcoal filter elements), and several manual bellows valves. The foreline also connects to a Convection-enhanced Pirani vacuum gauge (not connected during deposition). Eight separate precursor lines are attached to the top of the reaction chamber. Two lines could be used for room temperature precursor delivery, using precursor delivery vessels of a non-flow-through design. Three lines could be used for gaseous precursor delivery. Three lines could be attached to heated bubblers of a flow- through design; the heated bubbler used in this work was housed in an oven that is connected back-to-back to the oven that contains the reaction chamber. The reactor was operated under a constant stream of argon (99.998%) which was purified by passage through an Entegris™ purifier cartridge designed to achieve O2 and H2O concentrations below 0. 1 ppb. Argon was supplied to each of the eight precursor lines via a mass flow controller and pneumatically actuated diaphragm valve, and for all deposition experiments, argon flows of 20 seem were used on each line, resulting in a reactor pressure of approximately 0.3 Torr during deposition. The copper, silver or gold precursor was contained within a precursor delivery vessel of a flow-through design, heated to between 50 and 150 °C. Co-reactants that were liquid at room temperature were contained within a precursor delivery vessel of a non-flow through design; this delivery vessel was typically maintained at room temperature (about 20 °C), except for the HBpin delivery vessel, which was cooled to 6 °C using a thermoelectric cooling plate. Precursor pulse times were between 0.02 and 20 seconds, and the purge time following eachprecursor pulse was typically 60 s or 90 s. The ALD reactor used in this work requires longer pulses than most commercial ALD reactors due to the significantly larger reaction chamber volume and the skilled person could readily adjust times accordingly.

[0201] Wafers for use in Deposition Experiments: Deposition experiments used single side polished Si(100) wafers with a layer of native oxide (about 2 nm), or freshly prepared hydrogen-terminated Si(100) substrates. Si(100) substrates with a layer of native oxide (SiC>2 / Si) were plasma cleaned (air plasma) for 10 minutes immediately prior to being loaded into the ALD reactor and placed under vacuum. Hydrogen-terminated Si(100) (H-Si) substrates were prepared using the following procedure based on previously reported literature procedures [(a) Buriak, J. M. Chem. Rev. 2002, 102, 1271-1308, (b) Jayachandran, S.; Delabie, A.; Billen, A.; Dekkers, H.; Douhard, B.; Conard, T.; Meersschaut, J.; Caymax, M.; Vandervorst, W.; Heyns, M. Appl. Surf. Sci. 2015, 324, 251-257, and (c) Sun, Q. Y.; de Smet, L.; van Lagen, B.; Wright, A.; Zuilhof, H.; Sudholter, E. J. R. Angew. Chem. Ini. Ed. 2004, 43, 1352-1355]: 1 cm x 1 cm sections of a Si(100) wafer with a <5 nm layer of native oxide were placed in a beaker containing a 3: 1 H2O2 / H2SO4 mixture at 85 °C for 10 minutes, followed by a quick rinse under a stream of ultra-pure water. The wafer was then placed in a PTFE beaker containing 2% HF(aq) for 1-2 minutes, rinsed in a stream of ultra-pure water, and dried under a rapid flow of nitrogen or argon. The wafer was then quickly (within 2 - 3 minutes) loaded into the ALD reactor and placed under vacuum.

[0202] Handling and Characterization of Thin Films from Deposition Experiments: All deposited thin films were exposed to air for minutes or hours prior to analysis. For longer term storage, films were stored in a vacuum cabinet (Scienceware F42400-4001 Vacuum Desiccator Cabinet) connected to an Edwards™ XDS Dry Scroll Vacuum Pump. Thin film X-ray diffraction (XRD) was carried out using a Bruker™ D8 Discover diffractometer equipped with a Vantec 500 area detector and a focused Cu source with Ka radiation (f = 1.5418 A) operated at 40 kV and 40 mA, or a Bruker Dual Source D8 Venture diffractometer equipped with a PHOTON CMOS (Complementary Metal Oxide Semiconductor) area detector and an Incoatec I / zS Cu source (Ka radiation; =l.54184 A) operated at 50 kV and 1.10 mA. Average film thicknesses were determined using atomic force microscopy, as detailed below. Following deposition, a portion of the deposited film was scratched away with a sharp scalpel, and the profile of the resultant step was analyzed using a Bruker Dimension FastScan™ Atomic Force Microscope. The stepprofile was then analyzed using the Bruker NanoScope Analysis software in order to determine the step height / film thickness. For all depositions, at least 3 measurements were made at varying positions along the film surface.Part A, Copper Complex Synthesis and Characterization

[0203] Copper(I) chloride (0.50 - 31 mmol) was charged to a round bottom flask and THF was added to create a suspension with approximately 0.50 mmol of solid per millilitre of solvent. This suspension was cooled to 0 °C, and one equivalent of the appropriate neutral ligand (L = PMe3, PEt3, P(OMe)'Pr2, P(NMe2)'Pr2, P(NMe2)Me2, P(CH2SiMe3)'Pr2, or CN'Bu) was added dropwise using a microsyringe. The reaction was stirred for 30 minutes at room temperature, and re-cooled to 0° C, whereupon a solution containing 1 equivalent of the appropriate alkali metal alkoxide (NaOC(CF3)3, KOC(CF3)3, NaOCMe(CF3)2, or NaOCH(CF3)2; approximately 2.0 M concentration in THF) was added dropwise. Following addition, the solution was allowed to warm to room temperature, and was stirred for 4 hours. The solution was evaporated to dryness in vacuo, and the resultant solids were redissolved in toluene. Insoluble material was removed by centrifugation, and the supernatant solution was evaporated to dryness in vacuo to yield the desired copper precursor. This precursor can be purified by sublimation in vacuo (at the temperature indicated in Table 1), or recrystallized by cooling a saturated solution in an appropriate solvent (see Table 2) to -35 °C. Synthesis details for selected complexes are provided in the Table 2, with listed yields corresponding to materials purified by recrystallization, for which elemental analysis data was obtained. The solvent used to obtain X-ray quality crystals (in all cases by cooling a concentrated solution to -35 °C) is also provided in Table 2. Thermal data (sublimation temperature at 5 mTorr, TGA data, and melting point) is provided in Table 1.Table 1. Summary of Thermal Data for Copper Precursors.Table 2. Synthesis Details for Copper Precursors.

[0204] Characterization data for selected Cu precursors (solution NMR (Nuclear Magnetic Resonance) spectroscopy, combustion elemental analysis (EA), single crystal X- ray diffraction (SCXRD), and TGA (thermogravimetric analysis):

[0205] [(Cu{OC(CF3)3}{PMe3})2]: 'H NMR (C6D6, 600 MHz, 298 K): S 0.36 ppm (d,P(CH3),2HP = 8.2 Hz).13C{JH} NMR (C6D6, 151 MHz, 298 K): S 123.38 ppm (q, CF3, C = 294.3 Hz); 83.26 ppm (m, C(CF3)3); 13.75 ppm (d, P(CH3), CP = 28.2 Hz).19F NMR (C6D6, 565 MHz, 298 K): S -75.21 ppm (5, C3).31P{1H} NMR (C6D6, 242 MHz, 298 K): - 40.36 ppm (5, P(CH3)3). EA: Anal. Calcd. for C14H18CU2F18O2P2 (%): C, 22.44; H, 2.43. Found: C, 22.54; H, 2.35. SCXRD: FIG. 1. TGA: FIG. 2.

[0206] [(Cu{OCMe(CF3)2}{PMe3})2]: 'H NMR (C6D6, 600 MHz, 298 K): S 1.59 ppm(7, 3H, OC(CTF),4JCF = 1.3 Hz); 0.66 ppm (d, 9H, P(CF3),2JHP =7.3 HZ).13C{JH} NMR (C6D6, 151 MHz, 298 K): S 126.29 ppm (q, CF3, CF = 290.9 Hz); 78.00 ppm (m, C(CF3)2(CH3)); 23.15 ppm (5, C(CH3) 14.87 ppm (d, P(CH3),2JCp = 26.1 Hz).19F NMR(C6D6, 565 MHz, 298 K): S -78.15 ppm (s, CF3).31P{JH} NMR (C6D6, 242 MHz, 298 K): - 45.76 ppm (5, F(CH3)3). EA: Anal. Calcd. for C14H24C112F12O2P2 (%): C, 26.21; H, 3.78. Found: C, 26.57; H, 3.84. SCXRD: N / A. TGA: FIG. 3.

[0207] [(Cu{OCH(CF3)2}{PMe3})2]: 'H NMR (C6D6, 600 MHz, 298 K): S 4.82 ppm (br s,1H, CH) 0.60 ppm (d, 9H, P(CF3),2. / ni> = 7.4 Hz).13C{JH} NMR (C6D6, 151 MHz, 298 K): S 124.52 ppm q, CF3, CF = 273.4 Hz); 77.49 ppm (m, C(CF3)2H); 14.80 ppm (d, P(CH3),2JCp = 26.2 Hz).19F NMR (C6D6, 565 MHz, 298 K): S -76.09 ppm (d, CF3,3JFH = 5.8 Hz).31P{1H} NMR (C6D6, 242 MHz, 298 K): -44.06 ppm (5, F(CH3)3). EA: Anal. Calcd. for C12H20CU2F12O2P2 (%): C, 23.50; H, 3.29. Found: C, 23.41; H, 3.45. SCXRD: FIG. 4. TGA: N / A.

[0208] [(Cu{OC(CF3)3}{PEt3})2]: ' H NMR (C6D6, 600 MHz, 298 K): S 1.02 ppm (dq,2H, P(C7FCH3),2JHP = 15.3 Hz,3JHH = 7.7 Hz); 0.86 ppm (dt, 3H, P(CH2CF3),3. / ni> = 17.0 Hz, 3JHH = 7.7 Hz).13C{JH} NMR (C6D6, 151 MHz, 298 K): S 123.74 ppm q, CF3, CF = 283.1 Hz); 83.59 ppm (5, C(CF3)3)*; 16.91 ppm (d, P(CH2CH3),2JCp = 22.9 Hz); 8.91 ppm (d, P(CH2CH3),2JCP = 2.9 Hz).19F NMR (C6D6, 565 MHz, 298 K): S -75.48 ppm (5, CF3).31P{1H} NMR (C6D6, 242 MHz, 298 K): -44.06 ppm (5, F(CH2CH3)3). EA: Anal. Calcd. for C20H30CU2FI8O2P2(%): C, 28.82; H, 3.64. Found: C, 29.24; H, 3.91. *Peak identified by13C{19F} NMR. SCXRD: FIG. 5. TGA: FIG. 6.

[0209] [(Cu{OC(CF3)3}{P(NMe2)‘Pr2})2]: 'H NMR (C6D6, 600 MHz, 298 K): S 2.09 ppm (d, 6H, P(N(CF3)2),3JHP = 8.8 Hz); 1.23 ppm ( 7, 2H, P(CF(CH3)2),2JHP / 3HH= 7.1 Hz); 0.68 ppm (dd, 6H, P(CH(CF3)2),3. / ni> = 18.9 Hz,3 / nn = 7.0 Hz); 0.60 ppm (dd, 6H, P(CH(CF3)2),3JHP = 14.9 Hz,3JHH = 7.1 Hz).13C{JH} NMR (C6D6, 151 MHz, 298 K): S 123.70 ppm (q, CF3, CF = 292.1 Hz); 83.61 ppm (C(CF3)3)*; 42.00 ppm (d, P(N(CH3)2),2JCP = 6.6 Hz); 26.26 ppm (d, P(CH(CH3)2,2JCP = 27.2 Hz); 18.55 ppm (d, P(CH(CH3)2),2JCP = 10.9 Hz); 18.11 ppm (5, P(CH(CH3)2)).19F NMR (C6D6, 565 MHz, 298 K): S -75.57 ppm (5, CF3).31P{1H} (C6D6, 242 MHz, 298 K): 96.07 ppm (5, F(NMe2)(;Pr)2). EA: Anal. Calcd. for C24H4OCU2FI8N202P2(%): C, 31.34; H, 4.39; N, 3.05. Found: C, 31.54; H, 4.00; N, 3.39. *Peak identified by13C{19F} NMR. SCXRD: N / A. TGA: N / A.

[0210] [(Cu{OC(CF3)3}{P(NMe2)Me2})2]: ' H NMR (C6D6, 600 MHz, 298 K): S 1.87 ppm (d, 6H, P(N(CF3)2), HP = 11.8 Hz); 0.35 ppm d, 6H, P(CF3)2,2JHP = 6.6 Hz).13C{JH} NMR (C6D6, 151 MHz, 298 K): S 123.69 ppm (q, CF3, CF = 295.5 Hz); 83.10 ppm (C(CF3)3)*; 38.87 ppm (d, P(N(CH3)2),2JCp = 7.3 Hz); 13.17 ppm (d, P(CH3)2,2JCp= 30.3 Hz).19F NMR (C6D6, 565 MHz, 298 K): S -75.58 ppm s, CF3).31P{JH} NMR (C6D6, 242 MHz, 298 K): 49.12 ppm (5, P(NMe2)(Me)2). EA: Anal. Calcd. for CI6H24CU2FI8N2O2P2(%): C, 23.80; H, 3.00; N, 3.47. Found: C, 24.10; H, 2.56; N, 3.56. *Peak identified by13C{19F} HMBC NMR. SCXRD: N / A. TGA: FIG. 7.

[0211] [(Cu{OC(CF3)3}{P(CH2SiMe3)Tr2})2]: ' H NMR (C6D6, 600 MHz, 298 K): S1.16 ppm (dl, 2H, P(CF(CH3)2),2JHP / 3HH = 7.1 Hz); 0.65 ppm « 6H, P(CH(CF3)2),3JHP = 17.1 Hz,3JHH = 7.1 Hz); 0.58 ppm (dd, 6H, P(CH(CF3)2),2JHP = 15.8 Hz,3. / nn = 7.1 Hz); 0.05 ppm (d, 2H, P(CM(CH3)3),2. / ni> = 13.3 Hz); 0.01 ppm (5, 9H, Si(CF3)3).13C{JH} NMR (C6D6, 151 MHz, 298 K): S 123.69 ppm (q, CF3, CF = 294.1 Hz); 83.55 ppm (C(CF3)3)*; 24.23 ppm (d, P(CH(CH3)2), CP = 26.8 Hz); 18.96 ppm (d, P(CH(CH3)2),2JCP = 5.1 Hz); 17.98 ppm (<7, P(CH(CH3)2, CP = 2.0 Hz); 4.99 ppm (d, P(CH2Si(CH3)3), CP = 10.0 Hz); -0.26 ppm (d, Si(CH3)3,3JCp = 4.2 Hz).19F NMR (C6D6, 565 MHz, 298 K): S - 75.53 ppm (5, CF3).29Si: 5 0.82 ppm (SzMe3)**.31P{1H} NMR (C6D6, 242 MHz, 298 K): S 19.68 ppm (5, P(CH2SiMe3)CPr)2). EA: Anal. Calcd. for C28H50Cu2Fi8O2P2Si2(%): C, 33.43; H, 5.02. Found: C, 33.23; H, 4.96. *Peak identified by13C{19F} NMR. ** Peak identified by29Si-1H HMBC NMR. SCXRD: N / A. TGA: N / A.

[0212] [(Cu{OC(CF3)3}{P(CH2SiMe3)Me2})2] : ' H NMR (C6D6, 600 MHz, 298 K): S 0.38 ppm (d, 6H, P(CF3)2),2JHP = 8.3 Hz); -0.07 ppm (d, 2H, P(CF2Si(CH3)3),2. / ni> = 13.7 Hz); - 0.10 ppm (5, 9H, P(CH2Si(CF3)3)).13C{JH} NMR (C6D6, 151 MHz, 298 K): S 123.64 ppm q, CF3, CF = 292.5 Hz); 83.52 ppm (C(CF3)3)*; 16.21 ppm (d, P(CH2Si(CH3)3),2JCp = 17. 1 Hz); 14.87 ppm (d, P(CH3)2, CP = 29.5 Hz); -0.22 ppm (d, P(CH2Si(CH3)3), CP = 3.7 Hz).19F NMR (C6D6, 565 MHz, 298 K): S -75.58 ppm (5, CF3).29Si: 5 -0.31 ppm (SzMe3)**.31P{1H} NMR (C6D6, 242 MHz, 298 K): S -33.69 ppm (5, F(CH2SiMe3)Me2). EA: Anal. Calcd. for C20H34Cu2Fi8O2P2Si2(%): C, 26.88; H, 3.84. Found: C, 26.81; H, 4.03. *Peak identified by13C{19F} NMR. ** Peak identified by29Si-JH HMBC NMR. SCXRD: FIG. 8. TGA: FIG. 9.

[0213] [(CU{OC(CF3)3}{CN'BU})2] : ' H NMR (C6D6, 600 MHz, 298 K): S 0.62 ppm(5, C(CH3)3).I3C{'H} NMR (C6D6, 151 MHz, 298 K): S 166.52 ppm (5, CuCN); 123.35 ppm (q, CF3, CF = 293.5 Hz); 83.04 ppm (s, C(CF3)3); 56.46 ppm (s, C(CH3)3); 29.14 ppm (m, C(CH3)3).19F NMR (C6D6, 565 MHz, 298 K): S -74.47 ppm (5, CF3). EA: Anal. Calcd. for Ci8Hi8Cu2Fi8N2O2(%): C, 28.32; H, 2.38; N, 3.67. Found: C, 28.62; H, 2.66; N, 3.84. SCXRD: FIG. 10. TGA: FIG. 11.

[0214] Some notes regarding the copper complexes: (a) the structurally characterized copper phosphine and isonitrile complexes are dimers in the solid state, (b) the copper complexes are sensitive to air and moisture, with noticeable decomposition occurring over the course of several minutes, (c) the purified copper complexes (solid or in solution) are not light sensitive at room temperature, (d) all compounds sublimed cleanly at 5 mTorr, with sublimation temperatures between 35 and 60 °C, (e) most of the compounds analyzed by TGA evaporated cleanly (at 760 Torr under an inert atmosphere of N2), leaving less than 3% residual mass, and (f) melting points varied from below room temperature to 135 °C.Part B, Silver Complex Synthesis and Characterization

[0215] Avoiding exposure to light for extended periods of time (for all parts of the experiment), Ag2O (0.25 - 2.8 mmol) was charged to a round bottom flask and CH2CI2 was added to create a suspension containing approximately 0.25 mmol of solid per millilitre of solvent. This suspension was cooled to 0 °C, and two equivalents of 1,1, 1,3,3, 3-hexafluoro- 2-trifluoromethyl-2-propanol (HOC(CF3)3) were added dropwise. The reaction was stirred at 0° C for 30 minutes, whereupon a dilute solution containing 2 equivalents of the appropriate neutral ligand (L = PMes, PMe2Et, PEt3, PMe'Pr2, P'Pr3, P 3u'Pr2, P'Bu,. P(OMe)'Pr2, P(O'Bu)'Pr2. P(NMe2)Tr2, P(CH2SiMe3)Tr2, P(CH2SiMe3)Me2, CNMe, or CNTlu; approximately 1.0 M concentration in CH2CI2) was added dropwise. Following addition, the solution was allowed to warm to room temperature, and was stirred for 4 hours. The solution was evaporated to dryness in vacuo, and the resultant solids were redissolved in an appropriate solvent (THF when L = P(OMe)'Pr2 or CNMe; toluene for all other complexes). Insoluble material was removed by centrifugation, and the supernatant solution was evaporated to dryness in vacuo to yield the desired silver precursor. This precursor can be purified by sublimation in vacuo (at the temperature indicated in Table 3), or recrystallized by cooling a saturated solution in an appropriate solvent (see Table 4) to -35 °C. Synthesis details for selected complexes are provided in Table 4, with listed yields corresponding to materials purified by recrystallization, for which elemental analysis data was obtained. The solvent or method used to obtain X-ray quality crystals (in all cases at - 35 °C) is also provided in Table 4. Thermal data (sublimation temperature at 5 mTorr, TGA data, and melting point) is provided in Table 3.Table 3. Summary of Thermal Data for Silver Precursors.Table 4. Synthesis Details for Silver Precursors.

[0216] Characterization data for selected Ag precursors (solution NMR (Nuclear Magnetic Resonance) spectroscopy, combustion elemental analysis (EA), single crystal X- ray diffraction (SCXRD), and TGA (thermogravimetric analysis):

[0217] [(Ag{OC(CF3)3}{PMe3})2]: ' H NMR (C6D6, 600 MHz, 298 K): S 0.39 ppm (d,P CH3)3,2JHP = 8.2 Hz).13C{JH} NMR (C6D6, 151 MHz, 298 K): S 124.04 ppm (q, C(CF3)3, CF = 295.7 Hz); 84.53 ppm (C(CF3)3)*; 14.59 ppm (d, P(CH3)3,Cp = 23.3 Hz).19F NMR (C6D6, 565 MHz, 298 K): S -75.29 ppm (5, CF3).31P{1H} NMR (C6D6, 242 MHz, 298 K): S -37.65 ppm (2 x d, F(CH3)3, pioiAg = 728.2 Hz, pioPAg = 831.1 Hz). EA: Anal. Calcd. for Ci4Hi8Ag2Fi8O2P2(%): C, 20.06; H, 2.17. Found: C, 20.41; H, 2.10. *Peak identified by13C{19F} NMR. SCXRD: FIG. 12. TGA: FIG. 13.

[0218] [(Ag{OC(CF3)3}{PMe2Et})2]: 'H NMR (C6D6, 600 MHz, 298 K): S 0.62 ppm (dq,2H, P(CF2CH3), HP / HH = 7.6 Hz); 0.50 ppm (dt, 3H, P(CH2CF3), HP = 20. 1 Hz, HH = 7.6 Hz); 0.33 ppm (d, 6H,2JHP = 8.1 Hz, P(CF3)2).13C{JH} NMR (C6D6, 151 MHz, 298 K): S 124.11 ppm (q, C(CF3)3, CF = 295.5 Hz); 84.55 ppm (C(CF3)3)*; 22.10 ppm (d, P(CH2CH3), CP = 25.2 Hz); 11.80 ppm (d, P(CH3)2, CP = 22.8 Hz); 8.57 ppm (d, P(CH2CH3),2JCP = 3.8 Hz).19F NMR (C6D6, 565 MHz, 298 K): S -75.38 ppm (5, CF3).31P{1H} NMR (C6D6, 242 MHz, 298 K): S -21.47 ppm (2 x d, F(CH3)2(CH2CH3), punAg = 707.3 Hz, noPAg = 816.4 Hz). EA: Anal. Calcd. for Ci6H22Ag2Fi8O2P2(%): C, 22.19; H, 2.57. Found: C, 22.15; H, 2.75. *Peak identified by13C{19F} NMR. SCXRD: FIG. 14. TGA: FIG. 15.

[0219] [(Ag{OC(CF3)3}{PEtj})2]: 'H NMR (C6D6, 600 MHz, 298 K): S 0.65 ppm (dq, 2H,P(CF2CH3)3.2JHP / 3HH = 7.5 Hz); 0.47 ppm (dt, 3H, P(CH2CF3)3,3JHP = 18.7 Hz,3JHH = 7.5 Hz).13C{JH} NMR (C6D6, 151 MHz, 298 K): S 124.20 ppm (q, C(CF3)3, CF = 294.1 Hz); 84.58 ppm (C(CF3)3)*; 16.85 ppm (d, P(CH2CH3)3,Cp = 23.1 Hz); 8.93 ppm (d, P(CH2CH3)3,2JCP = 3.3 Hz).19F NMR (C6D6, 565 MHz, 298 K): S -75.50 ppm (5, CF3).31P{1H} NMR (C6D6, 242 MHz, 298 K): S 12.21 ppm (2 x d, F(CH2CH3)3, pioiAg = 677.5 Hz, pioPAg = 781.5 Hz). EA: Anal. Calcd. for C20H30Ag2Fi8O2P2(%): C, 26.05; H, 3.29. Found: C, 26.22; H, 3.22. *Peak identified by13C{19F} NMR. SCXRD: FIG. 16. TGA: FIG. 17.

[0220] [(Ag{OC(CF3)3}{PMe‘Pn})2] : ' H NMR (C6D6, 600 MHz, 298 K): S 0.92 ppm (<77,2H, P(CF(CH3)2)2,2HP / HH = 7.2 Hz); 0.48 ppm « 6H, P(CH(CF3)2)2,3JHP = 18.6 Hz, HH = 7.1 Hz); 0.37 ppm (dd, 6H, P(CH(CF3)2)2,3. / ni> = 15.7 Hz,3. / nn = 7.0 Hz); 0.18 ppm (d, 3H, P(CF3)3,2JHP = 7.7 Hz).13C{JH} NMR (C6D6, 151 MHz, 298 K): S 124.25 ppm (q, C(CF3)3, CF = 291.9 Hz); 84.71 ppm (C(CF3)3)*; 23.10 ppm ( , P(CH(CH3)2)2, CP = 23.1 Hz); 19.03 ppm (d, P(CH(CH3)2)2,2CP = 7.9 Hz); 17.01 ppm (5, P(CH(CH3)2)2); 3.15 ppm (d, P(CH3), CP = 20.6 Hz).19F NMR (C6D6, 565 MHz, 298 K): S -75.63 ppm (5, CF3).31P{1H} NMR (C6D6, 242 MHz, 298 K): S 22.94 ppm (2 x d, F(Me)('Pr)2, pioiAg = 666.2 Hz, pioPAg = 766.9 Hz). EA: Anal. Calcd. for C22H34Ag2Fi8O2P2(%): C, 27.81; H, 3.61. Found: C, 28.20; H, 3.50. *Peak identified by13C{19F} NMR. SCXRD: FIG. 18. TGA: FIG. 19.

[0221] [(Ag{OC(CF3)3}{P‘Pr3})2]: ' H NMR (C6D6, 600 MHz, 298 K): S 1.17 ppm( 7, 3H, P(CF(CH3)2)3, HP / HH = 7.1 Hz); 0.53 ppm (dd, 18H, P(CH(CF3)2)3,Hp = 16.0 Hz, HH = 7.1 Hz).13C{JH} NMR (C6D6, 151 MHz, 298 K): S 124.24 ppm (q, C(CF3)3, CF = 295.2 Hz); 84.76 ppm (C(CF3)3)*; 23.10 ppm ( , P(CH(CH3)2)3, CP = 23.1 Hz); 19.03 ppm ( , P(CH(CH3)2)3,2JCp = 7.9 Hz); 17.01 ppm (s, P(CH(CH3)2)3).19F NMR (C6D6, 565 MHz, 298 K): S -75.61 ppm (5, CF3).31P{1H} NMR (C6D6, 242 MHz, 298 K): S 52.90 ppm (2 x d, F'Pr3, novAg = 648.9 Hz, pioPAg = 749.0 Hz). EA: Anal. Calcd. for Ci8H42Ag2Fi8O2P2(%): C, 31.03; H, 4.22. Found: C, 31.32; H, 4.37. *Peak identified by13C{19F} HMBC NMR. SCXRD: FIG. 20. TGA: FIG. 21.

[0222] [(Ag{OC(CF3)3}{PzBu‘Pn})2]: 'H NMR (C6D6, 600 MHz, 298 K): S 1.34 ppm(<77, 2H, P(CF(CH3)2)2,2JHP = 9.2 HZ,3 / HH = 7.2 Hz); 0.66 ppm « 6H, P(CH(CF3)2)2,3 / HP = 16.6 Hz,3JHH = 7.1 Hz); 0.62 ppm (d, 9H, P(C(CF3)3),3 / ni> = 14.2 Hz); 0.58 ppm (dd, 6H, P(CH(CF3)2)2,3JHP = 14.9 Hz,3 / nn = 7.1 Hz).13C{JH} NMR (C6D6, 151 MHz, 298 K): S 124.27 ppm (q, C(CF3)3, CF = 294.8 Hz); 84.78 ppm (C(CF3)3)*; 31.51 ppm (d, P(C(CH3)3), CP = 16.9 Hz); 29.32 ppm (d, P(C(CH3)3) ,2JCP= 7.0 Hz); 22.85 ppm (d, P(CH(CH3)2)2, CP = 16.7 Hz); 22.18 ppm (d, P(CH(CH3)2)2,2JCp = 6.8 Hz); 20.21 ppm (d, P(CH(CH3)2)2,2JCP = 3.1 Hz).19F NMR (C6D6, 565 MHz, 298 K): S -75.60 ppm (5, CF3).31P{1H} NMR (C6D6, 242 MHz, 298 K): S 65.40 ppm (br d, pAg = 688.4 Hz, F(C(CH3)3)(CH(CH3)2)2). EA: Anal. Calcd. for C28H46Ag2Fi8O2P2(%): C, 32.51; H, 4.49. Found: C, 32.21; H, 4.51. *Peak identified by13C{19F} NMR. SCXRD: FIG. 22. TGA: FIG. 23.

[0223] [Ag{OC(CF3)3}( Bu3)J: 'H NMR (C6D6, 600 MHz, 298 K): S 0.81 ppm (d,P(C(CF3)3)3,2HP= 13.5 HZ).13C{JH} NMR(C6D6, 151 MHz, 298 K): S 124.30 ppm (q, C(CF3)3, CF = 296.7 Hz); 84.63 ppm (C(CF3)3)*; 36.73 ppm (d, P(C(CH3)3), CP = 9.1 Hz); 31.74 ppm (d,2JCP = 6.5 Hz, P(C(CH3)3)).19F NMR (C6D6, 565 MHz, 298 K): S -75.54 ppm (5, CF3).31P{1H} NMR (C6D6, 242 MHz, 298 K): S 84.37 ppm (2 x d, F(C(CH3)3)3, pioiAg = 642.5 Hz, pio9Ag = 741.2 Hz). EA: Anal. Calcd. for Ci6H27AgF9OP (%): C, 35.24; H, 5.00. Found: C, 35.57; H, 5.11. *Peak identified by13C{19F} NMR. SCXRD: FIG. 24. TGA: FIG. 25.

[0224] [(Ag{OC(CF3)3}{P(OMe)‘Pn})2]: 'H NMR (C6D6, 600 MHz, 298 K): S 2.85 ppm(d, 3H, P(OC7F),3JHP = 14.7 Hz); 1.10 ppm (dl, 2H, P(CF(CH3)2)2,2JHP = 5.2 Hz, HH = 7.1 Hz); 0.56 ppm (dd, 6H, P(CH(CF3)2)2,3 / ni> = 15.3 Hz,3 / nn = 7.0 Hz); 0.46 ppm (dd, 6H, P(CH(CF3)2)2,3JHP = 20.2 Hz, HH = 7.2 Hz).13C{JH} NMR (C6D6, 151 MHz, 298 K): S 123.80 ppm (q, C(CF3)3, CF = 293.5 Hz); 84.64 ppm (C(CF3)3)*; 61.10 ppm (d, P(OCH3),2JCp = 4.2 Hz); 27.33 ppm (d, P(CH(CH3)2)2, CP = 22.3 Hz); 16.59 ppm (d, P(CH(CH3)2)2,2JCP = 11.27 Hz); 15.58 ppm (5, P(CH(CH3)2)2).19F NMR (C6D6, 565 MHz, 298 K): S -75.54 ppm (5, CF3).31P{1H} NMR (C6D6, 242 MHz, 298 K): S 159.70 ppm (2 x d, F(OMe)('Pr)2, pioiAg = 707.5 Hz, pioPAg = 803.9 Hz). EA: Anal. Calcd. for C22H34Ag2Fi8O4P2(%): C, 26.90; H, 3.50. Found: C, 26.93; H, 3.29. *Peak identified by13C{19F} NMR. SCXRD: FIG. 26. TGA: N / A.

[0225] [(Ag{OC(CF3)3}{P(O*Bu)‘Pn})2]: 'H NMR (C6D6, 600 MHz, 298 K): S 1.14 ppm(dl, 2H, P(CF(CH3)2)2,2JHP = 5.1 Hz, HH = 7.0 Hz); 0.94 ppm (y 9H, P(OC(CF3)3)); 0.61 ppm (dd, 6H, P(CH(CF3)2)2,3 / HI> = 15.5 Hz,3 / nn = 7.0 Hz); 0.54 ppm (dd, 6H, P(CH(CF3)2)2,3 / ni> = 20.4 Hz, HH = 7.0 Hz).13C{JH} NMR (C6D6, 151 MHz, 298 K): S 124.21 ppm (q, C(CF3)3, CF = 294.8 Hz); 84.68 ppm (C(CF3)3)*; 79.01 ppm (d, P(OC(CH3)3,2.FI> = 3.8 Hz); 29.67 (d, P(OC(CH3)3,2CP = 6.0 Hz); 27.78 ppm (d, P(CH(CH3)2)2, CP = 26.0 Hz); 17.83 ppm (d, PCCH OE ,2CP = 11.5 Hz); 16.38 ppm (y P(CH(CH3)2)2).19F NMR (C6D6, 565 MHz, 298 K): S -75.66 ppm (5, CF3).31P{1H} NMR (C6D6, 242 MHz, 298 K): S 122.14 ppm (br d, F(O / Bu)('Pr)2, pAg = 701.2 Hz). EA: Anal. Calcd. for C28H46Ag2Fi8O4P2(%): C, 31.53; H, 4.36. Found: C, 31.63; H, 4.31. *Peak identified by13C{19F} NMR. SCXRD: N / A. TGA: FIG. 27.

[0226] [(Ag{OC(CF3)3}{P(NMe2)‘Pr2})2]: 'H NMR (C6D6, 600 MHz, 298 K): S 2.05 ppm (d, 6H, P(N(CF3)2),2JHP = 8.9 Hz); 1.28 ppm (dl, 2H, P(CF(CH3)2)2, HP / HH = 7.0 Hz); 0.63 ppm (dd, 6H, P(CH(CF3)2)2, HP = 19.7 Hz, HH = 7.0 Hz); 0.58 ppm (dd, 6H, HH = 7.0 Hz, P(CH(CF3)2)2, HP = 15.2 Hz).13C{JH} NMR (C6D6, 151 MHz, 298 K): S124.02 ppm (q, C(CF3)3, CF = 295.4 Hz); 84.61 ppm (C(CF3)3)*; 42.43 ppm (d, P(N(CH3)3,2JCP = 7.7 Hz); 26.59 (d, P(CH(CH3)2)2, CP = 21.7 Hz); 18.61 ppm (d, P(CH(CH3)2)2,2JCP = 13.1 Hz); 18.10 ppm (d, P(CH(CH3)2)2,2JCp = 1.7 Hz).19F NMR (C6D6, 565 MHz, 298 K): S -75.36 ppm (5, CF3).31P{JH} NMR (C6D6, 242 MHz, 298 K): 5 105.27 ppm (br d, F(NMe2)('Pr)2, pAg= 707.2 Hz). EA: Anal. Calcd. for C24H4oAg2Fi8N202P2(%): C, 28.59; H, 4.01; N, 2.78. Found: C, 29.00; H, 4.24; N, 2.91. *Peak identified by13C{19F} HMBC NMR. SCXRD: N / A. TGA: N / A.

[0227] [(Ag{OC(CF3)3}{P(CH2SiMe3)‘Pr2}]: ' H NMR (C6D6, 600 MHz, 298 K): S 1.08 ppm (J7, 2H, P(CF(CH3)2)2,2JHP / 3HH = 7.0 Hz); 0.52 ppm (dd, 6H, P(CH(CF3)2)2,3JHP = 18.2 Hz,3JHH = 7.0 Hz); 0.63 ppm (dd, 6H, P(CH(CF3)2)2,3. / ni> = 16.6 Hz,3. / nn = 7.0 Hz); 0.03 ppm (dd, 2H, P(CF2Si(CH3)3) ,2JHP = 13.4 Hz,4. / nn = 5.3 Hz); -0.06 ppm (5, 9H, P(CH2Si(CF3)3)).13C{JH} NMR (C6D6, 151 MHz, 298 K): S 124.24 ppm (q, C(CF3)3, CF = 294.7 Hz); 84.63 ppm (C(CF3)3)*; 24.72 ppm (d, P(CH(CH3)2)2, CP = 21.9 Hz); 19.05 ppm (d, P(CH(CH3)2)2,2JCP = 6.5 Hz); 18.02 ppm (d, P(CH(CH3)2)2,2JCP = 2.7 Hz); 5.69 ppm (br s, P(CH2Si(CH3)3)); -0.48 ppm (d, P(CH2Si(CH3)3),3JCP = 4.4 Hz).19F NMR (C6D6, 565 MHz, 298 K): S -75.64 ppm (5, CF3).29Si NMR (C6D6, 119 MHz, 298 K): S 0.74 ppm (5, <S7(CH3)3)**.31P{1H} NMR (C6D6, 242 MHz, 298 K): S 25.62 ppm (2 x d, (CH2SiMe3)('Pr)2, pio7Ag= 660.5 Hz, pu^Ag = 761.9 Hz). EA: Anal. Calcd. for C28H50Ag2Fi8O2Si2P2(%): C, 30.72; H, 4.61. Found: C, 31.12; H, 4.22. *Peak identified by13C-19F HMBC NMR. **Peak identified byJH-29Si HMBC NMR. SCXRD: FIG. 28. TGA: FIG. 29.

[0228] [(Ag{OC(CF3)3}{P(CH2SiMe3)Me2})2] : ' H NMR (C6D6, 600 MHz, 298 K): S 0.36 ppm (d, 6H, P(CF3)2,2JHP = 8.2 Hz); -0.07 ppm (br <7, 2H, P(CF2Si(CH3)3), HP = 13.9 Hz); - 0.13 ppm (d, 9H, P(CH2Si(CF3)3),4. / ni> = 0.8 Hz).13C{JH} NMR (C6D6, 151 MHz, 298 K): S 124.18 ppm (q, C(CF3)3, CF = 295.2 Hz); 84.63 ppm (C(CF3)3)*; 17.13 ppm (br s, P(CH2Si(CH3)3)); 16.10 ppm (d, P(CH3)2, CP = 24.8 Hz); -0.41 ppm (d, P(CH2Si(CH3)3),Cp = 5.2 Hz).19F NMR (C6D6, 565 MHz, 298 K): S -75.58 ppm (5, CF3).29Si NMR (C6D6, 119 MHz, 298 K): S -0.48 ppm (5, S(CH3)3)**.31P{1H} NMR (C6D6, 242 MHz, 298 K): S -32.07 ppm (2 x d, F(CH2SiMe3)(Me)2, punAg = 701.4 Hz, pioPAg = 808.7 Hz). EA: Anal. Calcd. for C20H34Ag2Fi8O2Si2P2(%): C, 24.45; H, 4.50. Found: C, 24.55; H, 4.52. *Peak identified by13C{19F} NMR. **Peak identified byJH-29Si HMBC NMR. SCXRD: FIG. 30. TGA: FIG. 31.

[0229] [(Ag{OC(CF3)3}{CNMe})2]: 'H NMR (C6D6, 600 MHz, 298 K): S 1.32ppm s,N(CF3)).13C{JH} NMR (C6D6, 151 MHz, 298 K): S 137.91 ppm (5, AgCN); 123.96 ppm ( , C(CF3)3, CF = 293.9 Hz); 84.18 ppm (C(CF3)3)*; 26.09 ppm (t, N(CF3), CN = 7.9 Hz).19F NMR (C6D6, 565 MHz, 298 K): S -75.20 ppm (5, CF3). EA: Anal. Calcd. for C24Hi2Ag4F36N4O4 (%): C, 18.77; H, 0.79; N, 3.65. Found: C, 19.00; H, 0.65; N, 3.62. *Peak identified by13C{19F} NMR. SCXRD: FIG. 32. TGA: N / A.

[0230] [(Ag{OC(CF3)3}{CN'Bu})4]: 'H NMR (C6D6, 600 MHz, 298 K): S 0.57 ppm (5,C(CF3)3).13C{JH} NMR (C6D6, 151 MHz, 298 K): S 34.99 ppm (5, AgCN); 123.99 ppm (q, C(CF3)3, CF = 295.3 Hz); 84.24 ppm (s, C(CF3)3)*; 57.00 ppm (s, C(CH3)3); 28.99 ppm (s, C(CH3)3).19F NMR (C6D6, 565 MHz, 298 K): S -75.13 ppm (5, CF3). EA: Anal. Calcd. for C36H36Ag4F36N4O4 (%): C, 25.37; H, 2.13; N, 3.29. Found: C, 25.31; H, 2.08; N, 3.28. *Peak identified by13C{19F} NMR. SCXRD: FIG. 33. TGA: N / A.

[0231] Some notes regarding the silver complexes: (a) most of the structurally characterized silver phosphine complexes are dimers in the solid state: the exceptions are [(Ag{OC(CF3)3}(P Bu3)] and [(Ag{OC(CF3)3} {P(CH2SiMe3)'Pr2}], which are monomers,(b) the isonitrile complexes are dimers or tetramers in the solid state: [(Ag{OC(CF3)3} {CNMe})2] is a dimer, whereas [(Ag{OC(CF3)3} {CNThi})4] is a tetramer,(c) pure solid samples of the silver complexes are not sensitive to air and moisture at room temperature (tested over a period of several days), (d) pure solid samples of the silver complexes are not light sensitive (on a timescale of months) under ambient conditions, (e) all compounds sublimed cleanly at 5 mTorr in the dark, with sublimation temperatures between 45 and 85 °C, (f) several of the compounds analyzed by TGA (especially where L = P'Pr3or P'Bu3) evaporated cleanly (at 760 Torr under an inert atmosphere of N2) leaving less than 3% residual mass, whereas other compounds resulted in higher residual mass percentages, and (g) melting points that were obtained varied from 80 to 165 °C.Part C. Gold Complex Synthesis and Characterization

[0232] Avoiding exposure to tight for extended periods of time (for all parts of the experiment), equimolar amounts of LAuCl (L = PMe3, P'Pr3or P'Bu3). Na(OC(CF3)3and AgBF4 (0.18 - 0.62 mmol) were charged to a round bottom flask and CH2CI2 was added at - 78 °C to create a dilute solution (approximately 0.04 M concentration of each reactant). This solution was allowed to gradually warm to room temperature over the course of 30 minutes, whereupon the reaction was stirred for an additional 4 hours. The solution was evaporated todryness in vacuo, and the resultant solids were redissolved in toluene. Insoluble material was removed by centrifugation, and the supernatant solution was evaporated to dryness in vacuo to yield the desired gold precursor. This precursor can be purified by sublimation in vacuo (at the temperature indicated in Table 5), or recrystallized by cooling a saturated solution in an appropriate solvent (see Table 6) to -35 °C. Synthesis details for selected complexes are provided in Table 6, with listed yields corresponding to materials purified by recrystallization, for which elemental analysis data was obtained. The method used to obtain X-ray quality crystals (in all cases at -35 °C) is also provided in Table 6. Thermal data (sublimation temperature at 5 mTorr, TGA data, and melting point) is provided in Table 5.Table 5. Summary of Thermal Data for Gold Precursors.Table 6. Synthesis Details for Gold Precursors.

[0233] Characterization data for selected Au precursors (solution NMR (Nuclear Magnetic Resonance) spectroscopy, combustion elemental analysis (EA), single crystal X- ray diffraction (SCXRD), and TGA (thermogravimetric analysis):

[0234] [Au{OC(CF3)3}(PMe3)]: 'H NMR (C6D6, 600 MHz, 298 K): S 0.31 ppm (d,P(C7 / 3)3,2JHP = 11.5 Hz).13C{JH} NMR (C6D6, 151 MHz, 298 K): S 123.93 ppm (q, CF3, CF = 293.8 Hz); 84.39 ppm (5, C(CF3)3)*; 14.52 ppm (d, P(CH3)3, CP = 42.6 Hz).19FNMR (C6D6, 565 MHz, 298 K): S -74.78 ppm s, CF3).31P{JH} NMR (C6D6, 242 MHz, 298 K): S -18.95 ppm (5, PMe3). EA: Anal. Calcd. for C7H9A11F9OP (%): C, 16.55; H, 1.79. Found: C, 16.81; H, 1.81. *Peak identified by13C{19F} NMR. SCXRD: FIG. 34 and Showing Aurophilic Contacts: FIG. 35. TGA: FIG. 36.

[0235] [Au{OC(CF3)3}(P‘Pr3)]: ' H NMR (C6D6, 600 MHz, 298 K): S 1.30 ppm (<77, 1H,P(CF(CH3)2),2JHP = 9.4 Hz, HH = 7.2 Hz), 0.62 ppm (dd, 6H, P(CH(CF3)2),3JHP = 16. 1 Hz,3JHH = 7.2 Hz).13C{JH} NMR (C6D6, 151 MHz, 298 K): S 123.68 ppm (q, CF3, CF = 295.3 Hz); 84.51 ppm (5, C(CF3)3)*; 22.89 ppm (d, P(CH(CH3)2, CP = 33.6 Hz); 19.32 ppm (5, P(CH(CH3)2).19F NMR (C6D6, 565 MHz, 298 K): S -74.64 ppm (5, CF3).31P{1H} NMR (C6D6, 242 MHz, 298 K): S 58.52 ppm (5, F'Pr3). EA: Anal. Calcd. for CI3H2IAUF9OP (%): C, 26.36; H, 3.58. Found: C, 26.59; H, 3.97. *Peak identified by13C{19F} NMR. SCXRD: FIG. 37 (no close Au-Au distances). TGA: FIG. 38.

[0236] [AU{OC(CF3)3}(PZBU3)] : ' H NMR (C6D6, 600 MHz, 298 K): S 0.91 ppm (d,P(C(CF3)3),3JHP = 13.8 Hz).13C{JH} NMR (C6D6, 151 MHz, 298 K): S 124.09 ppm q, C(CF3)3, CF = 293.3 Hz); 84.24 ppm (s, C(CF3)3)*; 38.62 ppm (d, P(C(CH3)3)3,2JCp = 23.1 Hz); 31.60 ppm (5, P(C(CH3)3)3).19F NMR (C6D6, 565 MHz, 298 K): S -74.53 ppm (5, CF3).31P{1H} NMR (C6D6, 242 MHz, 298 K): S 84.12 ppm (5, PBu3). EA: Anal. Calcd. for CI6H27AUF9OP (%): C, 30.29; H, 4.30. Found: C, 30.28; H, 4.37. *Peak identified by13C{19F} NMR. SCXRD: FIG. 39 (no close Au-Au distances). TGA: FIG. 40.

[0237] Some notes regarding the gold complexes: (a) unlike the copper and silver analogues, the alkoxide ligands in the gold complexes did not bridge between metal centres to afford dimers or tetramers; the gold complexes are monomers, with aurophilic (Au—Au) interactions between monomers in the least sterically hindered complex, [Au{OC(CF3)3}(PMe3)], (b) pure solid samples of the gold complexes are not sensitive to air and moisture at room temperature (tested over a period of several days), (c) pure solid samples of the gold complexes are not light sensitive (on a timescale of months) under ambient conditions, (d) all compounds sublimed cleanly at 5 mTorr in the dark, with sublimation temperatures between 50 and 80 °C, (e) all three compounds left significant residual mass in the TGA experiment (at 760 Torr under an inert atmosphere of N2), (f) the P'Pr3compound melted without decomposition at 59-61 °C, whereas the PMe3compound decomposed, turningto a pink-red liquid at 108-109 °C, and (g) performing the synthesis using AgPFg instead of AgBF4 as the silver salt afforded the target compounds in comparable or higher yield.Part D. Solution Deposition Processes and Thin Film Characterization

[0238] General Procedure: The chosen metal-containing precursor was dissolved in CeDg and added to an NMR tube fitted with a J-Young valve. The desired number of equivalents of a co-reactant (e.g. Al Me?. HBpin, H2, or PhSiH?) was added to this solution at room temperature, the J-Young valve was sealed, and the reaction was monitored using solution NMR spectroscopy (at room temperature or 50 °C). For characterization of the reaction precipitate, the above procedure was repeated in toluene. The mother liquors were decanted, and the precipitate was washed with toluene and then dried in vacuo. The dry precipitate was subjected to Powder X-ray Diffraction (PXRD) phase analysis on a Bruker D8 Advance Powder diffractometer with Cu Ka radiation ( = 0.154 nm) operated at 40 kV and 40 mA. The diffraction pattern was analyzed using the DIFFRAC.EVA software program, wherein the observed diffractograms were compared to database entries to confirm their crystalline composition.Exemplary Embodiments:Example DI. [(Cu{OC(CF3)3}{PMe3})i] + Trimethylaluminum:

[0239] An equimolar amount of trimethylaluminum was added to a standing solution of [(Cu{OC(CF3)3} {PMe3})2] in toluene. The solution was shaken briefly and allowed to stand for approximately one hour. The solution was decanted, and the precipitate was washed with toluene and dried in vacuo. The precipitate was identified as copper metal by PXRD as shown in FIG. 41.Example D2. [(Cu{OC(CF3)3}{PMe3})2] + H2:

[0240] A toluene solution of [(Cu{OC(CF3)3} {PMesj ] was charged to a Schlenk tube and degassed via three freeze-pump-thaw cycles. Dihydrogen (H2) was transferred into the Schlenk tube at -196 °C, whereupon the Schlenk tube was sealed. The solution was heated to 50 °C with stirring for 5 days, leading to the formation of solid precipitate and a copper mirror along the walls of the Schlenk tube. The solution was decanted, and the precipitate was washed with toluene and dried in vacuo. The precipitate was identified as copper metal by PXRD as shown in FIG. 42.Example D3. [(Ag{OC(CF3)3}{PMe3})2] + Phenylsilane:

[0241] Five equivalents of phenylsilane were added to a solution of [(Ag{OC(CF3)3} {PMe3})2] in toluene. The solution was shaken briefly and allowed to stand forapproximately one hour. The solution was decanted, and the precipitate was washed with toluene and dried in vacuo. The precipitate was identified as silver metal by PXRD as shown in FIG. 43.Example D4. [(Ag{OC(CF3)3}{PMe3})i] + Pinacolborane:

[0242] Five equivalents of pinacolborane were added to a solution of [(Ag{OC(CF3)3} {PMe3})2] in toluene. The solution was shaken briefly and allowed to stand for approximately one hour. The solution was decanted, and the precipitate was washed with toluene and dried in vacuo. The precipitate was identified as silver metal by PXRD as shown in FIG. 44.Example D5. [(Ag{OC(CF3)3}{PMe3})2] + Hi:

[0243] A toluene solution of [(Ag{OC(CF3)3} {PMe3})2] was charged to a Schlenk tube and degassed via three freeze-pump-thaw cycles. Dihydrogen (H2) was transferred into the Schlenk tube at -196 °C, whereupon the Schlenk tube was sealed. The solution was stirred overnight, leading to the formation of solid precipitate and a silver mirror along the walls of the Schlenk tube. The solution was decanted, and the precipitate was washed with toluene and dried in vacuo. The precipitate was identified as silver metal by PXRD as shown in FIG. 45.Example D6. [Au{OC(CF3)3}(PMe3)] + Phenylsilane:

[0244] An equimolar amount of phenylsilane was added to a solution of [Au{OC(CF3)3}(PMe3)] in toluene. The solution was shaken briefly and allowed to stand for approximately one hour. The solution was decanted, and the precipitate was washed with toluene and dried in vacuo. The precipitate was identified as gold metal by PXRD as shown in FIG. 46.Example D7. [Au{OC(CF3)3}(PMe3)] + Pinacolborane:

[0245] An equimolar amount of pinacolborane was added to a solution of [Au{OC(CF3)3}(PMe3)] in toluene. The solution was shaken briefly and allowed to stand for approximately one hour. The solution was decanted, and the precipitate was washed with toluene and dried in vacuo. The precipitate was identified as gold metal by PXRD as shown in FIG. 47.Part E, Vapour Deposition Processes and Thin Film CharacterizationExample El.

[0246] Deposition of elemental copper was carried out using the precursor molecule [(Cu{OC(CF3)3} {PMe3})2] and the co-reactant trimethylaluminum. The copper precursor delivery vessel (flow-through design) was heated to 85 °C, while the trimethylaluminum delivery vessel (non-flow-through design) was at room temperature. Each deposition cycle involved a 10 s pulse of [(Cu{OC(CF3)3} {PMe3})2], followed by a 90 s inert gas purge, followed by a 0.1 spulse of trimethylaluminum, followed by a 90 s inert gas purge (the ALD reactor used in this work requires longer pulses than most commercial ALD reactors due to a significantly larger reaction chamber volume and the skilled person could readily adjust times accordingly). The substrate temperature was 120 °C, and the deposition was carried out on a SiCh / Si substrate using 2000 deposition cycles. Film thickness was determined via atomic force microscopy (AFM) analysis after scratching part of the film with a scalpel. The film was 54.7 nm thick, corresponding to a growth rate of 0.27 A / cycle. The film was shown to comprise crystalline copper by thin film X-ray diffraction, as shown in FIG. 48.Example E2.

[0247] Multiple depositions were carried out using modified versions of the method in Example El. These experiments investigated different precursor pulse durations in order to test self-limiting growth. Relevant data from these experiments are summarized in FIG. 49 and FIG. 50, where each data point represents a different deposition experiment. These experiments confirm that self-limiting film growth, which is a requirement for an ALD process, is achieved at 120 °C, with [(Cu{OC(CF3)3} {PMe3})2] pulses that are at least 7 seconds in duration, and trimethylaluminum pulses that are at least 0.05 seconds in duration.Example E3.

[0248] Deposition of elemental silver was carried out using the precursor molecule Ag jOCTCFsJri {P'Prri hl and the co-reactant pinacolborane (HBpin). The silver precursor deliver vessel (flow-through design) was heated to 115 °C, while the pinacolborane delivery vessel (non-flow-through design) was cooled to 6 °C. Each deposition cycle involved a 3 s pulse of [(Ag{OC(CF3)3} { P'Pn })2], followed by a 60 s inert gas purge, followed by a 0.03 s pulse of HBpin, followed by a 60 s inert gas purge (the ALD reactor used in this work requires longer pulses than most commercial ALD reactors due to a significantly larger reaction chamber volume and the skilled person could readily adjust times accordingly). The substrate temperature was 150 °C, and the deposition was carried out on both a hydrogen-terminated Si(100) substrate (H- Si) and a SiO2 / Si substrate using 1000 deposition cycles. Film thickness was determined via atomic force microscopy (AFM) analysis; the film was 35.5 nm thick on H-Si and 53.4 nm thick on SiO2 / Si, corresponding to a growth rate of 0.36 and 0.54 A / cycle, respectively. The films were shown to comprise crystalline silver by thin film X-ray diffraction, as shown in FIG. 51.Example E4.

[0249] Multiple depositions were carried out using modified versions of the method in Example E3. These experiments investigated different precursor pulse durations in order to test self-limiting growth. Relevant data from these experiments are summarized in FIGs. 52-56 (where each data point represents a different deposition experiment). These experiments confirm that (a) self-limiting film growth, which is a requirement for an ALD process, is achieved in the temperature window 125 - 225 °C on both SiO Si and H-Si substrates, with [(Ag{OC(CF3)3} J P Prs } 21 pulses that are at least 9 seconds in duration, and HBpin pulses that are at least 0.03 seconds in duration, and (b) the film growth rate at 150 °C is linearly dependent on the number of ALD cycles performed. X-ray photoelectron spectroscopy (XPS) depth profiting of films deposited on SiCL / Si and H-Si substrates at 150 °C was obtained.Example E5.

[0250] Chemical vapour deposition (CVD) of elemental gold was carried out using the precursor molecule [Au{OC(CF3)3}(P'Pr3)]. A round-bottom flask acted as the delivery vessel for the precursor and was attached via a distillation arm to a separate round-bottom flask containing a SiCL / Si substrate, which in turn was connected to a vacuum line via a cold trap. The delivery vessel was charged with the precursor, and the SiCL / Si substrate was heated to 300-310 °C. The entire apparatus was placed under dynamic vacuum (< 5 mTorr), and the flask containing the precursor was immersed in a 110 °C oil bath. Volatilization of the precursor occurred cleanly, and a metallic gold film was deposited on the heated SiCh / Si substrate. The specular gold-coloured film was shown to comprise crystalline gold by thin film X-ray diffraction, as shown in FIG. 57.Example E6.

[0251] Deposition of elemental gold was carried out using the precursor molecule | AujOCfCFA l (P'Pnll and the co-reactant pinacolborane (HBpin). The gold precursor delivery vessel (flow-through design) was heated to 85 °C, while the pinacolborane delivery vessel (non-flow-through design) was cooled to 6 °C. Each deposition cycle involved a 10 s pulse of [Au{OC(CF3)3}(P'Pr3)], followed by a 60 s inert gas purge, followed by a 0.03 s pulse of HBpin, followed by a 60 s inert gas purge (the ALD reactor used in this work requires longer pulses than most commercial ALD reactors due to a significantly larger reaction chamber volume and the skilled person could readily adjust times accordingly). The substrate temperature was 125 °C, and the deposition was carried out on a SiO Si substrate using 1000deposition cycles. Film thickness was determined via atomic force microscopy (AFM) analysis; the film was 15.2 nm thick, corresponding to a growth rate of 0.15 A / cycle. The films were shown to comprise crystalline gold by thin film X-ray diffraction, as shown in FIG. 58.Characterization data for selected Cu, Ag and Au thin films deposited as described in Examples E1-E6

[0252] Average film thicknesses were determined using Atomic Force Microscopy. Following deposition, a portion of the deposited film was removed with a sharp scalpel, and the film was analyzed using a Bruker Dimension FastScan Atomic Force Microscope. Measurements were obtained across a 10 pm wide portion of the substrate containing both the deposited metal film, and a region where the deposited film had been removed, thus generating a step profile of the deposited film. This step profile was then analyzed using the Bruker NanoScope Analysis software in order to determine the step height / film thickness. For all depositions, at least 3 measurements were made at varying positions along the film surface.

[0253] An overview of the experiments used to obtain films 1-25 is provided in Table 7 and Table 8. AFM micrographs are shown in FIGs. 59-83 as indicated in Table 8.Table 7.Table 8.

[0254] While the present application has been described with reference to examples, it is to be understood that the scope of the claims should not be limited by the embodiments set forth in the examples, but should be given the broadest interpretation consistent with the description as a whole.

[0255] All publications, patents and patent applications are herein incorporated by reference in their entirety to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated by reference in its entirety. Where a term in the present application is found to be defined differently in a document incorporated herein by reference, the definition provided herein is to serve as the definition for the term.

Claims

CLAIMSWhat is claimed is:

1. A metal alkoxide complex of the formula (I):5 or a multimer thereof, whereinM is copper, silver or gold;RFis CF3, CF2CF3, CF2Me, CF2Et, CF2CF2CF3, or CF(CF3)2;R1is Ci-3alkyl, wherein one or more available hydrogen atoms is / are optionally replaced with fluorine;R2is H or Ci-3alkyl, wherein one or more available hydrogen atoms is / are optionally replaced with fluorine;(i) when M is silver or gold, L is PR3R4R5or CNR6, wherein R3, R4and R5are each independently selected from:Ci-salkyl, wherein one or more available carbon atoms are optionally replaced with a heteroatom selected from an oxygen atom and a silicon atom,C3.5cycloalkyl, 1-norbomyl, heterocycloalkyl, -O-Ci-salkyl, and -NR'R", wherein R' and R" are each independently selected from Cn 4alkyl provided that the total number of carbon atoms is from 2-5; and R6is Ci-7hydrocarbyl; and(ii) when M is copper, L is PR3R4R5, wherein R3is selected from:Ci-salkyl, wherein one or more available carbon atoms is replaced with a heteroatom selected from an oxygen atom and a silicon atom, 1-norbomyl, heterocycloalkyl,-O-Ci-salkyl, and-NR'R", wherein R' and R" are each independently selected from Ci- 4alkyl provided that the total number of carbon atoms is from 2-5; and R4and R5are each independently selected from:Ci-salkyl, wherein one or more available carbon atoms are optionally replaced with a heteroatom selected from an oxygen atom and a silicon atom,C3-5cycloalkyl, 1-norbomyl, heterocycloalkyl, -O-Ci-salkyl, and-NR'R", wherein R' and R" are each independently selected from Ci- 4alkyl provided that the total number of carbon atoms is from 2-5.

2. The metal alkoxide complex of claim 1, wherein M is silver.

3. The metal alkoxide complex of claim 1, wherein M is gold.

4. The metal alkoxide complex of claim 2 or 3, wherein L is PR3R4R5.

5. The metal alkoxide complex of claim 4, wherein R3, R4and R5are each independently selected from Me, Et, ”Pr, 'Pr, "Bu, Bu. 'Bu, 'Bu. CEE'Bu. CEESiMes, Cyp, 1-Norb, OMe, OEt, O"Pr, O'Pr, O"Bu, O'Bu. O'Bu, O'Bu. O(cyclopentyl), NMe2, NMeEt, NEt2, NMeEt, NMe"Pr, NMe'Pr, NEt"Pr, NEt'Pr, NMe"Bu, NMe'Bu. NMe'Bu, NMe'Bu and 1-pyrrolidinyl.

6. The metal alkoxide complex of claim 4, wherein R3is Ci-4alkyl, -O-Ci-4alkyl, CEESiMes or NMe2 and R4and R5are each independently selected from Ci-4alkyl.

7. The metal alkoxide complex of claim 2 or 3, wherein L is CNR6.

8. The metal alkoxide complex of claim 7, wherein R6is selected from Me, Et, "Pr, 'Pr, "Bu, "Bu, 'Bu, "Bu, Cyp, Cy and 1-Norb.

9. The metal complex of claim 7, wherein R6is Ci-4alkyl.

10. The metal alkoxide complex of claim 1, wherein M is copper.

11. The metal alkoxide complex of claim 10, wherein R3is CH2SiMe3, OMe or NMe2 and R4and R5are each independently selected from Ci-4alkyl.

12. The metal alkoxide complex of claim 2 or 3, wherein OCRFR1R2is selected from OCH(CF3)2, OCHMe(CF3), OCMe(CF3)2, OCMe2(CF3) and OC(CF3)3, L is selected from PMe3, PEt3, PnPr3, P'Pr3, P'Bu3, PT3u3, P'Bu3PCyp3and CNR6, wherein R6is selected from Me, Et, "Pr, 'Pr. "Bu, T3u, 'Bu. 'Bu, Cyp, Cy and 1-Norb.

13. The metal alkoxide complex of any one of claims 1 to 11, wherein RFis CF3, and R1and R2are each independently Ci-3alkyl, wherein one or more available hydrogen atoms is / are replaced with fluorine.

14. The metal alkoxide complex of claim 13, wherein RF, R1and R2are all CF3.

15. The metal alkoxide complex of claim 1, wherein RF, R1and R2are all CF3; andM is silver and L is PMe3;M is silver and L is PMe2Et;M is silver and L is PEt3;M is silver and L is PMe'Pr2;M is silver and L is P'Pr3;M is silver and L is P'Bu'Pr?:M is silver and L is P'Bu3;M is silver and L is P(OMe)'Pr2;M is silver and L is P(O'Bu)'Pr2;M is silver and L is P(NMe2)'Pr2;M is silver and L is P(CH2SiMe3)'Pr2;M is silver and L is P(CH2SiMe3)Me2;M is silver and L is CNMe;M is silver and L is CN'Bu;M is gold and L is PMe3;M is gold and L is P'Pn;M is gold and L is P'BuvM is copper and L is P(0Me)'Pr2;M is copper and L is P(NMe2)'Pr2;M is copper and L is P(NMe2)Me2;M is copper and L is P(CH2SiMe3)'Pr2; orM is copper and L is P(CH2SiMe3)Me2.

16. A crystalline form of a metal alkoxide complex of the formula (!'):or a multimer thereof, whereinM is copper, silver or gold, wherein when M is copper, the metal alkoxide complex is in the form of a multimer;RFis CF3, CF2CF3, CF2Me, CF2Et, CF2CF2CF3, or CF(CF3)2;R1is Ci-3alkyl, wherein one or more available hydrogen atoms is / are optionally replaced with fluorine;R2is H or Ci-3alkyl, wherein one or more available hydrogen atoms is / are optionally replaced with fluorine;L is PR3R4R5or CNR6, wherein R3, R4and R5are each independently selected from:Ci-salkyl, wherein one or more available carbon atoms are optionally replaced with a heteroatom selected from an oxygen atom and a silicon atom,C3-5cycloalkyl, 1-norbomyl, heterocycloalkyl, -O-Ci-salkyl, and-NR'R", wherein R' and R" are each independently selected from Ci- 4alkyl provided that the total number of carbon atoms is from 2-5; and R6is Ci-7hydrocarbyl.

17. The crystalline form of a metal alkoxide complex of claim 16, wherein M is silver or gold and the metal alkoxide complex is in the form of a monomer.

18. The crystalline form of a metal alkoxide complex of claim 16, wherein M is copper or silver and the metal alkoxide complex is in the form of a dimer.

19. The crystalline form of a metal alkoxide complex of claim 16, wherein M is silver and the metal alkoxide complex is in the form of a tetramer.

20. The crystalline form of a metal alkoxide complex of claim 16, wherein the metal alkoxide complex is selected from:[(CU{OC(CF3)3} {P(OMe)'Pr2})2];[(Cu{OC(CF3)3}{P(NMe2)'Pr2})2];[(CU{OC(CF3)3} {P(NMe2)Me2})2];[(Cu{OC(CF3)3} {P(CH2SiMe3)'Pr2})2];[(CU{OC(CF3)3} {P(CH2SiMe3)Me2} )2] ;[(Ag{OC(CF3)3}{PMe3})2];[(Ag{OC(CF3)3} {PMe2Et})2];[(Ag{OC(CF3)3}{PEt3})2];[(Ag{OC(CF3)3} {PMe'Pr2})2];[(Ag{OC(CF3)3}{PTr3})2];[(Ag{OC(CF3)3} {PtonM;[Ag{OC(CF3)3}(PzBu3)];[(Ag{OC(CF3)3} {P(OMe) r2})2];[(Ag{OC(CF3)3} {P((yBu) r2})2];[(Ag{OC(CF3)3} {P(NMe2)Tr2})2];[(Ag{OC(CF3)3} {P(CH2SiMe3)'Pr2}];[(Ag{OC(CF3)3} {P(CH2SiMe3)Me2})2];[(Ag{OC(CF3)3}{CNMe})2];[(Ag{OC(CF3)3} {CNfBu})4];[Au{OC(CF3)3}(PMe3)]; [Au{OC(CF3)3}(P'Pr3)]; and[Au{OC(CF3)3}(P Bu3)].

21. Use of a metal alkoxide complex as defined in any one of claims 1 to 15 or a crystalline form of a metal alkoxide complex as defined in any one of claims 16 to 20 in the preparation of a material comprising M in the form of an elemental metal.

22. A process for preparing a material comprising M in the form of an elemental metal, the process comprising: reducing a metal alkoxide complex as defined in any one of claims 1 to 15 or a crystalline form of a metal alkoxide complex as defined in any one of claims 16 to 20.

23. The process of claim 22, wherein the reduction comprises reacting with a reducing agent in an organic solvent.

24. The process of claim 23, wherein the organic solvent comprises an aliphatic hydrocarbon, an aromatic solvent, a chlorinated solvent, a fluorinated solvent or an ethereal solvent.

25. The process of claim 23 or 24, wherein the metal is deposited on a substrate.

26. The process of any one of claims 22 to 25, wherein the material is in the form of a film.

27. A process for depositing a material comprising M, the process comprising: exposing a heated substrate to a vapor obtained by heating a metal alkoxide complex as defined in any one of claims 1 to 15 or a crystalline form of a metal alkoxide complex as defined in any one of claims 16 to 20.

28. The process of claim 27, wherein the material is in the form of a film.

29. The process of claim 28, wherein the process comprises repeated cycles of the exposure of the heated substrate until a film of a desired thickness is reached.

30. A process for depositing a film comprising M, the process comprising a deposition cycle comprising: exposing a heated substrate to a vapor comprising a metal-containing precursor compound, the metal-containing precursor compound being a metal alkoxide complex as defined in any one of claims 1 to 15 or a metal alkoxide complex obtained by heating a crystalline form of a metal alkoxide complex as defined in any one of claims 16 to 20; and exposing the precursor-treated substrate to a vapor comprising a co-reactant.

31. The process of claim 30, wherein the process further comprises repeating the deposition cycle until a film of a desired thickness is deposited.

32. The process of claim 30 or 31, wherein subsequent to exposing to the vapor comprising the metal-containing precursor compound, the process further comprises: purging with a purge gas to remove at least a portion of excess metal-containing precursor compound and / or byproducts.

33. The process of any one of claims 30 to 32, wherein subsequent to exposing to the vapor comprising the co-reactant, the process further comprises: purging with a purge gas to remove at least a portion of excess co-reactant and / or byproducts.

34. The process of any one of claims 30 to 33, wherein the process comprises an atomic layer deposition (ALD) process.

35. The process of claim 34, wherein the process comprises a plasma-enhanced atomic layer deposition (PEALD) process.

36. The process of any one of claims 30 to 33, wherein the process comprises a chemical layer deposition (CVD) process.

37. The process of any one of claims 30 to 36, wherein the deposited film comprising M comprises M in the form of an oxide, nitride, phosphide, sulfide, selenide, telluride, antimonide or fluoride.

38. The process of any one of claims 30 to 36, wherein the co-reactant is a reducing agent.

39. The process of any one of claims 30 to 36, wherein the film comprising M is a film comprising M in the form of elemental metal.

40. A process for preparing a metal alloy or intermetallic, a ternary or quaternary material, a doped material, or a nanolaminate, the process comprising: depositing a film comprising M by a process as defined in any one of claims 30 to39; and one or more additional film deposition processes.

41. Use of a process as defined in any one of claims 22 to 40 in the fabrication of an electronic device, memory or logic device, photonic device, chemical or biological sensor, catalyst or photocatalyst material, mirror, micro-electromechanical systems (MEMS) device, electrochromic device, photovoltaic device or quantum device or in the deposition of an anti-microbial film.

42. A process for preparing a gold alkoxide complex of the general formula I":or a multimer thereof, the process comprising: reacting a gold(I) chloride comprising L with an alkali metal salt of the formula M^OCR^R2) and an alkali metal salt of the formula M"X, wherein M' is Li, Na, K, Rb or Cs, M" is Li, Na, K, Rb, Cs, Ag, T1 or combinations thereof, X is a weakly- coordinating anion and L, R1, R2and RFare as defined in claim 1.

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