Spin-on Metallization

Abstract

The present invention describes the deposition of conductive metal films on surfaces comprising topography. The deposition uses metal precursors comprising neutral (uncharged) metal compounds, wherein the metal atoms are in a zero valent state and are stabilized by ligands that are stabilized by uncharged volatile species.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Application No. 62 / 653,753 filed on April 6, 2018 and U.S. Application No. 16 / 365,109 filed on March 26, 2019, the entire contents of which are incorporated herein by reference. Background Art

[0003] The present invention relates to a process technology for manufacturing semiconductor devices and related devices. In particular, the present invention relates to a technology for film deposition using a compound containing a metal element as a liquid or as a solution in a suitable solvent.

[0004] There are many conventional methods for arranging wires or through holes in semiconductor devices. One method is to perform physical vapor deposition, which involves a physical process, such as evaporating or sputtering a metal or alloy from a metal target onto the surface of a semiconductor wafer by applying heat, an ion beam or other energy source. Chemical vapor deposition, in which a metal or metal halide precursor in the gas phase is selectively decomposed or chemically reduced on the surface. A subset of chemical vapor deposition is atomic layer deposition, in which a metal precursor and a reducing agent are sequentially exposed to the surface to grow a metal film in a layer-by-layer manner. Other commonly used techniques include electroplating, in which a wafer is coated with an electrolyte and connected to a DC circuit, in which the substrate serves as a cathode. When an electric current passes through, the metal ions dissolved in the electrolyte are chemically reduced on the cathode surface. Other techniques known in the art include electroless deposition (autocatalytic deposition), in which a mixture of metal ions and a chemical reducing agent dissolved in a solvent is contacted with a substrate. A surface-catalyzed chemical reaction causes the reducing agent to react with the metal ions to form a reduced metal coating.

[0005] Examples of prior art interconnect metallization: US6048445, US5151168, US5674787.

[0006] There are many challenges with existing technologies. Specifically, many of these technologies, especially physical vapor deposition technologies, have significant challenges in completely filling high aspect ratio features (i.e., features that are much deeper than they are wide at the opening). Vapor phase processes are also generally unable to completely fill recessed features (i.e., features that have a narrow opening but expand laterally below the surface). Incomplete filling can result in spots of high resistance and cause current fluctuations and lead to localized heating or increased electromigration.

[0007] In principle, atomic layer deposition (ALD) can fill complex, high-aspect-ratio features, but in practice, it often leaves seams (where the deposits growing inward from each sidewall merge). Such seams can also cause undesirable defects in the electrical performance of the interconnect.

[0008] Electroplating requires the deposition of a seed layer, and this becomes increasingly difficult as feature sizes become smaller as technology advances.

[0009] Another challenge in the prior art is achieving acceptable electrical conductivity of the interconnect circuits.

[0010] US8232647 describes a method for dealing with the formation of so-called keyhole defects or seams in conventional metallization.

[0011] JP2012012647A2 (WO201163235) from Tokyo Electron discloses the use of spin-orbit in an inert atmosphere, wherein a solvent-borne metal complex is deposited on a surface. The patent focuses on aluminum-containing precursors, but silver, gold or copper are also disclosed. No preferred or suitable complexes for the present application are described, nor is the use of zero-valent metal complexes, their pre-condensation, the preferential use of liquid or low-melting complexes. The aluminum compounds mentioned are aluminum (III) hydrides and their amine adducts. Such compounds decompose by reductive elimination, i.e. the ligand itself acts as a reducing agent.

[0012] US6852626B1 of Applied Materials, also mentioned above, discloses the decomposition of metal complexes, particularly copper(I)hfac(TMVs), on a surface to deposit a metallic copper film. The copper metal is formed by disproportionation into Cu(II) and Cu(0).

[0013] US Pat. No. 9,653,306 B2 of JSR details the use of a zero-valent cobalt precursor and a silicon precursor (silane or halosilane) to form a self-aligned cobalt silicide film.

[0014] Maria Careri et al. studied the high performance liquid chromatography of trinuclear acetylido-carbonyl ruthenium compounds in Journal of Chromatography, 634 (1993) 143-148.

[0015] Therefore, the development of precursors is necessary and there is a need for high-purity membranes with controlled grain boundaries that maximally fill the circuit paths. Summary of the invention

[0016] Described herein is the deposition of conductive metal films on surfaces comprising topography. The present invention uses neutral (uncharged) metal compounds as precursors, wherein the metal atoms are in a zero valent state and are stabilized by ligands that are stabilized as uncharged volatile species.

[0017] In order to form a conductive path on a surface that has been patterned with depressions in a semiconductor substrate; a liquid metal precursor containing a metal compound is applied to the surface as a liquid or a solution in a suitable solvent. The pool of liquid can be spread on the surface in a known manner under inert conditions so that the depressed area is filled with the liquid by capillary action, and the excess liquid is optionally retained on the top of the surface by the surface tension of the liquid. The substrate is then heated, which causes the optional solvent and some stabilizing ligands to evaporate, thereby causing partial decomposition of the precursor to form agglomerated metal clusters or nanoparticles, which agglomerate in the depressions upon further heating, while releasing most of the stabilizing ligands and leaving conductive metal solids. In a preferred embodiment of the present invention, the metal solid partially or substantially fills the gaps or depressions originally present in the high aspect ratio or concave features of the substrate surface, thereby enabling gap filling.

[0018] The metal precursors most suitable for this method comprise neutral (uncharged) metal compounds having the metal in its zero valent state and at least one neutral stabilizing ligand (which can be released as a neutral molecule).

[0019] The neutral (uncharged) metal compound may be a liquid or solid which is soluble in a solvent selected from saturated linear, branched and cyclic hydrocarbons at ambient temperature (defined as 15°C to 25°C); or may be a solid which melts at a temperature below the decomposition temperature.

[0020] The metal precursor comprises a neutral (uncharged) metal compound or a neutral (uncharged) metal compound and a solvent.

[0021] The viscosity of the liquid metal precursor at ambient temperature is between 0.5 cP and 20 cP, preferably between 1 cP and 10 cP, and more preferably between 2 cP and 5 cP.

[0022] Examples of suitable metals include, but are not limited to, cobalt, ruthenium, iridium, rhodium, iron, osmium, nickel, platinum, palladium, copper, silver, gold, and combinations thereof.

[0023] Suitable neutral stable ligands include, but are not limited to, carbon monoxide (CO); nitric oxide (NO); dinitrogen (N2); acetylene (C2H2); ethylene (C2H4); C4-C 18 Diene or C4-C 18 Cyclodiene; C6-C 18 Triene; C8 to C 18 Tetraene; organic isocyanide RNC, where R = C1 to C 12 Straight-chain or branched hydrocarbon or halogenated hydrocarbon (halocarbyl); organic nitrile RCN, wherein R = C1 to C 12 Hydrocarbon or halogenated hydrocarbon; organic phosphine PR'3, wherein R'=H, Cl, F, Br or C1 to C12 Hydrocarbon or halogenated hydrocarbon; amine NRaRbRc, wherein Ra, Rb and Rc can be independently selected from H or C1 to C 12 A hydrocarbon group or a halogenated hydrocarbon group, wherein they can be connected to each other; an organic ether of the general formula R*OR**, wherein R* and R** can be independently selected from C1 to C 12 A hydrocarbon group or a halogenated hydrocarbon group and a terminal alkyne or an internal alkyne of the general formula R1CCR2, wherein R1 and R2 can be independently selected from H, C1 to C 12 Straight chain, branched, cyclic or aromatic halogenated hydrocarbon or hydrocarbon groups, silyl or organosilyl (eg Si(CH3)3), SiCl3), stannyl or organostannyl, and combinations thereof.

[0024] Suitable metal precursors include, but are not limited to

[0025] R 1 Co2(CO)6, where R 1 It is a straight or branched chain of C2 to C 10 Alkyne, straight or branched C1 to C 10 Alkoxyalkyne, straight or branched C1 to C 10 Organic aminoalkynes, such as (tert-butylacetylene) dicobalt hexacarbonyl; [Co2(CO)6HC:::CC(CH3)3];

[0026] R 1 CoFe(CO)7, where R 1 It is a straight or branched chain of C2 to C 10 Alkyne, straight or branched C1 to C 10 Alkoxyalkyne, straight or branched C1 to C 10 Organic aminoalkynes;

[0027] R 2 CCo3(CO)9, where R 2 selected from hydrogen, linear or branched C1 to C 10 Alkyl, linear or branched C1 to C 10 Alkoxy, Cl, Br, COOH, COOMe, COOEt;

[0028] R 2 CCo2Mn(CO) 10 , where R 2 selected from hydrogen, linear or branched C1 to C 10 Alkyl, linear or branched C1 to C 10 Alkoxy, Cl, Br, COOH, COOMe, COOEt;

[0029] R 3Co4(CO) 12 , where R 3 Selected from linear or branched C1 to C 10 alkenylene; and

[0030] R 4 Ru3(CO) 11 , where R 4 Selected from disubstituted alkynes (R # CCR ## ), where R # and R ## Can be independently selected from C1 to C 12 Straight chain, branched, cyclic or aromatic halogenated hydrocarbon or hydrocarbon group, silyl or organosilyl (e.g. Si(CH3)3), SiCl3), stannyl or organostannyl, and combinations thereof. Suitable examples of metal precursors include, but are not limited to, tert-butylacetylene dicobalt hexacarbonyl [Co2(CO)6HC:::CC(CH3)3], (1-decyne) dodecacarbonyl tetracobalt (Co4(CO) 12 (C8H 17 C:::CH)), (1,6-heptadiyne) tetracobalt dodecacarbonyl, (2,2,6-trimethyl-3-heptyne) dicobalt hexacarbonyl, (2,2-dimethyl-3-octyne) dicobalt hexacarbonyl (CCTNBA), (2,2-dimethyl-3-decyne) dicobalt hexacarbonyl, (2,2-dimethyl-3-heptyne) dicobalt hexacarbonyl, (tert-butylmethylacetylene) dicobalt hexacarbonyl (CCTMA), triruthenium dodecacarbonyl, (ethylbenzene) ( 1,3-butadiene)ruthenium, (isopropyl-4-methyl-benzene)(1,3-butadiene)ruthenium, 1,3,5-cycloheptatriene dicarbonylruthenium, 1,3-cyclohexadiene tricarbonylruthenium, 2,3-dimethyl-1,3-butadiene tricarbonylruthenium, 2,4-hexadiene tricarbonylruthenium, 1,3-pentadiene tricarbonylruthenium, (benzene)(1,3-butadiene)ruthenium, (benzene)(2,3-dimethyl-1,3-butadiene)ruthenium, Co2Ru(CO) 11 、HCoRu3(CO) 13 , Ru3(CO)9(PPh2(CH2)3Si(OEt)3)3, bis(phenyl)chromium, bis(cyclooctadiene)nickel, bis(tri-tert-butylphosphine)platinum, bis(tri-tert-butylphosphine)palladium and combinations thereof.

[0031] In another aspect, described herein is a method of depositing a conductive metal film on a substrate, comprising:

[0032] a. providing a substrate having a surface comprising a topography;

[0033] b. providing a metal precursor as described above;

[0034] c. and

[0035] d. Applying a metal precursor to the surface to deposit a conductive metal film onto the substrate.

[0036] The deposition method is selected from the group consisting of spray coating, roller coating, doctor blade drawdown (doctor coating), spin coating, surface convergence, supersaturated vapor condensation, inkjet printing, curtain coating, dip coating, and combinations thereof.

[0037] When the metal precursor is a liquid, it is applied to the surface in such a way that the contact angle between the metal precursor and the surface is ≤ 90°, preferably ≤ 45°, or more preferably ≤ 30°.

[0038] The method may further include applying energy to the liquid metal precursor to dissociate ligands that stabilize the metal; and the energy is selected from visible light, infrared light or ultraviolet light; heated gas flow; conduction of a resistive or liquid heated receiver; inductively heated receiver; electron beam; ion beam; remote hydrogen plasma; direct argon; helium or hydrogen plasma; vacuum; ultrasound; and combinations thereof.

[0039] The method may further include applying a post-deposition annealing treatment.

[0040] In another aspect, a system for depositing a conductive metal film onto a substrate is described, comprising:

[0041] a. A substrate having a surface comprising a topography;

[0042] b. a metal precursor as described above; and

[0043] c. A deposition tool selected from the group consisting of spray coating, roller coating, doctor blade coating, spin coating, surface collection, supersaturated vapor condensation, inkjet printing, curtain coating, dip coating, and combinations thereof.

[0044] In yet another aspect, described herein is a container containing a metal precursor as disclosed above. The container may have a dip-tube extending below the surface of the liquid metal precursor to facilitate delivery of the precursor to a deposition location.

[0045] In yet another aspect, a conductive metal film is described herein that is deposited on a surface comprising a topography by using the liquid metal precursor and method described above. The conductive metal film has a relative humidity of less than or equal to 1×10 -4 Conductivity of Ωcm. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] The present invention will be described below with reference to the accompanying drawings, in which the same numerals represent the same elements:

[0047] Figure 1 Shown are thermogravimetric analysis (TGA) data of (1-decyne)tetracobalt dodecacarbonyl measured under flowing nitrogen.

[0048] Figure 2 A typical conductive cobalt-containing film deposited on a wafer coupon in this application is shown. DETAILED DESCRIPTION

[0049] The following detailed description only provides preferred exemplary embodiments and is not intended to limit the scope, applicability or configuration of the present invention. On the contrary, the subsequent detailed description of the preferred exemplary embodiments will provide a feasible description of the preferred exemplary embodiments of the present invention for those skilled in the art. Various changes may be made to the functions and arrangements of the elements without departing from the spirit and scope of the present invention as described in the appended claims.

[0050] In the claims, letters may be used to identify claimed method steps (e.g., a, b, and c). These letters are used to aid in referring to the method steps and are not intended to indicate the order in which the claimed steps are to be performed, unless and only if that order is explicitly recited in the claims.

[0051] The present invention uses neutral (uncharged) metal compounds as precursors, where the metal atoms are in a zero-valent state and are stabilized by ligands that are stable, uncharged volatile species, to deposit conductive metal films on surfaces containing topography.

[0052] To form a conductive path on a surface patterned with depressions in a dielectric material; a liquid metal precursor containing a metal compound is applied to the surface as a liquid or a solution in a suitable solvent. A pool of liquid can be spread over the surface in a known manner under inert conditions so that the depressed areas fill with the liquid by capillary action, optionally with excess liquid retained on top of the surface by the surface tension of the liquid. The substrate is then heated, which causes the optional solvent and some of the stabilizing ligands to evaporate, resulting in partial decomposition of the precursor to form agglomerated metal clusters or nanoparticles, which upon further heating coalesce in the depressions while releasing most of the stabilizing ligands to leave a conductive metal solid.

[0053] This approach is particularly advantageous when the features have a high aspect ratio. The aspect ratio (depth-to-width ratio) of the surface features (if present) is 4:1 or greater, or 8:1 or greater, or 10:1 or greater, or 20:1 or greater, or 40:1 or greater.

[0054] The neutral (uncharged) metal compound may most advantageously be a liquid or a solid (which melts at a temperature below its decomposition temperature or has a high solubility in a suitable solvent).

[0055] The metal precursor comprises a neutral (uncharged) metal compound or a neutral (uncharged) metal compound and a solvent.

[0056] To facilitate delivery of the metal precursor into the topography on the surface, the metal precursor should be in the form of a low viscosity liquid.

[0057] If the neutral (uncharged) metal compound is a solid or viscous liquid at ambient temperature, it can be conveniently provided as a solution in a suitable solvent. The viscosity of the liquid at ambient temperature should be between 0.5 cP and 20 cP, preferably between 1 cP and 10 cP, and most preferably between 2 cP and 5 cP.

[0058] Suitable metals for the neutral (uncharged) metal precursor include all elements of the transition metal series, especially Fe, Co, Ni, Ru, Ir, Rh, Pd, Pt, Cu, Ag, Au, Os and combinations thereof.

[0059] Suitable ligands include, but are not limited to, carbon monoxide (CO), nitric oxide (NO), dinitrogen (N2), acetylene (C2H2), ethylene (C2H4), dienes, trienes, tetraenes, cyclic dienes, organic isocyanides RNC, wherein R = C1 to C 12 A straight or branched hydrocarbon or halogenated hydrocarbon; an organic nitrile RCN, wherein R = C1 to C 12 A hydrocarbon group or a halogenated hydrocarbon group; an organic phosphine PR'3, wherein R'=H, Cl, F, Br or C1 to C 12 Amine NRaRbRc, wherein Ra, Rb and Rc can be independently selected from H or C1 to C 12 A hydrocarbon group or a halogenated hydrocarbon group, wherein they can be connected to each other; an organic ether of the general formula R*OR**, wherein R* and R** can be independently selected from C1 to C 12 and a terminal alkyne or an internal alkyne of the general formula R1CCR2, wherein R1 and R2 can be independently selected from H, C1 to C 12 A linear, branched, cyclic or aromatic halogenated hydrocarbon group or hydrocarbon group, a silyl group or an organic silyl group (e.g., Si(CH3)3), SiCl3), a stannyl group or an organic stannyl group.

[0060] Examples of terminal or internal alkynes include, but are not limited to, propyne, 1-butyne, 3-methyl-1-butyne, 3,3-dimethyl-1-butyne, 1-pentyne, 1-hexyne, 1-decyne, cyclohexylacetylene, phenylacetylene, 2-butyne, 3-hexyne, 4,4-dimethyl-2-pentyne, 5,5-dimethyl-3-hexyne, 2,2,5,5-tetramethyl-3-hexyne, trimethylsilylacetylene, phenylacetylene, diphenylacetylene, trichlorosilylacetylene, trifluoromethylacetylene, cyclohexylacetylene, trimethylstannylacetylene.

[0061] Examples of organic phosphines include, but are not limited to, phosphine (PH3), phosphorus trichloride (PCl3), phosphorus trifluoride (PF3), trimethylphosphine (P(CH3)3), triethylphosphine (P(C2H5)3), tributylphosphine (P(C4H9)3), triphenylphosphine (P(C6H5)3), tri(tolyl)phosphine (P(C7H7)3), dimethylphosphine ethane ((CH3)2PCH2CH2P(CH3)2), and diphenylphosphine ethane ((C6H5)2PCH2CH2P(C6H5)2).

[0062] Examples of organic isocyanides include, but are not limited to, methyl isocyanide (CH3NC), ethyl isocyanide (C2H5NC), tert-butyl isocyanide ((CH3)3CNC), phenyl isocyanide (C6H5NC), tolyl isocyanide (C7H7NC), trifluoromethyl isocyanide (F3CNC).

[0063] Examples of amines include, but are not limited to, ammonia (NH3), trimethylamine ((CH3)3N), piperidine, ethylenediamine, pyridine.

[0064] Examples of ethers include, but are not limited to, dimethyl ether (CH3OCH3), diethyl ether (C2H5OC2H5), methyl tert-butyl ether (CH3OC(CH3)3), tetrahydrofuran, furan, ethylene glycol dimethyl ether (CH3OCH2CH2OCH3), and diethylene glycol dimethyl ether (CH3OCH2CH2OCH2CH2OCH3).

[0065] Examples of organic nitriles include, but are not limited to, acetonitrile (CH3CN), propionitrile (C2H5CN), benzonitrile (C6H5CN), and acrylonitrile (C2H3CN).

[0066] Examples of neutral (uncharged) metal precursors include, but are not limited to, R 1 Co2(CO)6, where R 1 It is a straight or branched chain of C2 to C 10 Alkyne, straight or branched C1 to C 10 Alkoxyalkyne, straight or branched C1 to C 10 Organic aminoalkyne, such as (tert-butylacetylene) dicobalt hexacarbonyl; [Co2(CO)6HC:::CC(CH3)3]; R 1 CoFe(CO)7, where R 1 It is a straight or branched chain of C2 to C 10 Alkyne, straight or branched C1 to C 10 Alkoxyalkyne, straight or branched C1 to C 10 Organic aminoalkyne; R 2 CCo3(CO)9, where R 2 selected from hydrogen, linear or branched C1 to C 10Alkyl, linear or branched C1 to C 10 Alkoxy, Cl, Br, COOH, COOMe, COOEt; R 2 CCo2Mn(CO) 10 , where R 2 selected from hydrogen, linear or branched C1 to C 10 Alkyl, linear or branched C1 to C 10 Alkoxy, Cl, Br, COOH, COOMe, COOEt; R 3 Co4(CO) 12 , where R 3 Selected from linear or branched C1 to C 10 Alkenylene; R 4 Ru3(CO) 11 , where R 4 Selected from disubstituted alkynes (R # CCR ## ), where R # and R ## Can be independently selected from C1 to C 12 A linear, branched, cyclic or aromatic halogenated hydrocarbon group or hydrocarbon group, a silyl group or an organic silyl group (e.g., Si(CH3)3), SiCl3), a stannyl group or an organic stannyl group, and combinations thereof.

[0067] Examples of neutral (uncharged) metal precursors more specifically include, but are not limited to, tert-butylacetylene dicobalt hexacarbonyl [Co2(CO)6HC:::CC(CH3)3], (1-decyne) dodecacarbonyl tetracobalt (Co4(CO) 12 (C8H 17 C:::CH)), (1,6-heptadiyne) tetracobalt dodecacarbonyl, (2,2,6-trimethyl-3-heptyne) dicobalt hexacarbonyl, (2,2-dimethyl-3-octyne) dicobalt hexacarbonyl (CCTNBA), (2,2-dimethyl-3-decyne) dicobalt hexacarbonyl, (2,2-dimethyl-3-heptyne) dicobalt hexacarbonyl, (tert-butylmethylacetylene) dicobalt hexacarbonyl (CCTMA), triruthenium dodecacarbonyl, (ethylbenzene) (1,3-butadiene)ruthenium, (isopropyl-4-methylbenzene)(1,3-butadiene)ruthenium, 1,3,5-cycloheptatriene dicarbonylruthenium, 1,3-cyclohexadiene tricarbonylruthenium, 2,3-dimethyl-1,3-butadiene tricarbonylruthenium, 2,4-hexadiene tricarbonylruthenium, 1,3-pentadiene tricarbonylruthenium, (benzene)(1,3-butadiene)ruthenium, (benzene)(2,3-dimethyl-1,3-butadiene)ruthenium, Co2Ru(CO) 11 、HCoRu3(CO) 13, Ru3(CO)9(PPh2(CH2)3Si(OEt)3)3, bis(phenyl)chromium, bis(cyclooctadiene)nickel, bis(tri-tert-butylphosphine)platinum and bis(tri-tert-butylphosphine)palladium.

[0068] Some of the above precursors can be dissolved in a suitable solvent to make them into low viscosity liquids.

[0069] Suitable solvents include, but are not limited to, saturated straight chain, branched chain, and cyclic hydrocarbons.

[0070] Suitable solvents include, but are not limited to, n-hexane, n-pentane, isomeric hexanes, octane, isooctane, decane, dodecane, heptane, cyclohexane, methylcyclohexane, ethylcyclohexane, decalin; aromatic solvents such as benzene, toluene, xylene (single isomer or isomer mixture), mesitylene, o-dichlorobenzene, nitrobenzene; nitriles such as acetonitrile, propionitrile or benzonitrile; ethers such as tetrahydrofuran, dimethoxyethane, diglyme, tetrahydropyran, methyltetrahydrofuran, butyltetrahydrofuran, p-dioxane; amines such as triethylamine, piperidine, pyridine, pyrrolidine, morpholine; amides such as N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, N-cyclohexylpyrrolidone; compounds having the formula R 4 R 5 NR 6 OR 7 NR 8 R 9 , R 4 OR 6 NR 8 R 9 、O(CH2CH2)2NR 4 , R 4 R 5 NR 6 N(CH2CH2)2O、R 4 R 5 NR 6 OR 7 N(CH2CH2)2O、O(CH2CH2)2NR 4 OR 6 Amino ethers of N(CH2CH2)2O; wherein R 4-9 are independently selected from linear or branched C1 to C 10 Alkyl, and mixtures thereof.

[0071] The pure precursor liquid or the solution of the precursor in the solvent can be applied to the substrate having topographical features by means known in the art, including spraying, roller coating, doctor blade (doctor coating), spin coating, surface convergence, supersaturated vapor condensation, inkjet printing, curtain coating, dip coating, etc.

[0072] In order to obtain high quality films, the liquid can be applied to the substrate under a controlled atmosphere with reduced oxygen or moisture content compared to ambient air. To achieve this process, the metal-containing liquid of the present invention can be contained in a sealed vessel or container, as disclosed in US2002108670A1, the contents of which are incorporated herein by reference.

[0073] The container may be connected to a deposition apparatus known in the art by using a valved closure and a sealable outlet connection. For convenience, the outlet connection may be connected to a dip tube extending below the surface of the liquid so that the liquid may be delivered to the substrate by exploiting a pressure differential.

[0074] Most preferably, the container can be constructed of high purity materials including stainless steel, glass, fused quartz, polytetrafluoroethylene, etc. The container may be sealed with one or more valves. The headspace of the container is preferably filled with a suitable gas, such as nitrogen, argon, helium or carbon monoxide. One or more valves may be connected to a dip tube extending below the surface of the liquid, and the one or more valves may be in fluid communication with the headspace gas.

[0075] Liquid applied to a surface is drawn into the fine features on the surface due to capillary action. Therefore, in order to fill fine topographical features, the contact angle between the liquid and the coated surface needs to be ≤ 90°, preferably ≤ 45°, or more preferably ≤ 30°.

[0076] Contact angle is one of the common methods to measure the wettability of a surface or material. Wetting refers to the study of how a liquid deposited on a substrate spreads or the ability of a liquid to form a boundary surface with a substrate. Wettability is determined by measuring the contact angle formed by the liquid in contact with the substrate. The greater the wetting tendency, the smaller the contact angle or surface tension. A wetting liquid is a liquid that forms a contact angle of less than 90° with a solid, while a non-wetting liquid forms a contact angle between 90° and 180 degrees with a solid.

[0077] In order to carry out this filling at a reasonable rate, the viscosity of the liquid at ambient temperature should be between 0.5 cP and 20 cP, preferably between 1 cP and 10 cP, and most preferably between 2 cP and 5 cP.

[0078] In the next step, energy is applied to the liquid precursor, resulting in the dissociation of the neutral ligands that stabilize the metal. As these ligands dissociate, the metal ions will begin to aggregate, forming small aggregates or clusters. As the optional solvent evaporates and more ligands dissociate, these aggregates continue to grow and concentrate. As these metal clusters grow, they become nano-sized particles (nanoparticles). As the solvent and unreacted zero-valent metal-organic liquid evaporate, the nanoparticles concentrate in the depressions of the morphology. Then, a conductive film is formed.

[0079] The conductivity of the conductive film at ambient temperature should be less than or equal to (≤) about 1X10 -4 Ωcm.For For thick films, this corresponds to a measured sheet resistance of less than about 100 Ω / square.

[0080] The resistivity of conductive deposits can be improved by applying energy to the deposited material. The energy is most conveniently applied by external heating using visible or infrared or ultraviolet light or a combination of these radiation sources, by convection using a heated gas stream, or by conduction from a resistively or fluid heated susceptor or from an inductively heated susceptor on which the substrate is placed.

[0081] Other energy sources can also be used for the process, including electron beam, ion beam, remote hydrogen plasma, direct argon, helium or hydrogen plasma, vacuum and ultrasound.

[0082] The conductive film may be further subjected to a post-deposition annealing treatment.

[0083] The post-deposition annealing treatment can be carried out in a reducing atmosphere (including but not limited to hydrogen, ammonia, diborane, silane) at a temperature of or higher than (≥) 300°C (e.g., 300°C to 700°C); the annealing time is or higher than (≥) 5 minutes, e.g., 5-60 minutes.

[0084] The reducing atmosphere may be a pure reducing gas or a mixture of a reducing gas and an inert gas such as nitrogen or argon. The pressure of the reducing atmosphere may be equal to or higher than (≥) 10 Torr, for example, 10 Torr to 760 Torr; and the flow rate of the reducing gas may be equal to or higher than (≥) 100 sccm, for example, 100-1000 sccm.

[0085] In another aspect, the present invention also utilizes a container or container of metal precursors, which contains at least one neutral (uncharged) metal precursor or at least one neutral (uncharged) metal precursor and a solvent.

[0086] The methods described herein can be used to deposit a conductive film on at least a portion of a substrate. Examples of suitable semiconductor substrates include, but are not limited to, silicon, SiO2, Si3N4, OSG, FSG, silicon carbide, hydrogenated silicon oxycarbon, hydrogenated silicon oxynitride, silicon oxycarbon nitride, hydrogenated silicon oxycarbon nitride, anti-reflective coatings, photoresists, germanium, germanium-containing, boron-containing, Ga / As, flexible substrates, organic polymers, porous organic and inorganic materials, metals such as copper and aluminum, metal silicides such as titanium silicide, tungsten silicide, molybdenum silicide, nickel silicide, cobalt silicide, and diffusion barriers such as, but not limited to, cobalt, TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN.

[0087] Example

[0088] Example 1

[0089] The silicon wafer had a surface layer of carbon-doped silicon oxide into which trenches 20 nm wide and 200 nm deep were etched.

[0090] The silicon wafer is placed on a platform in a sealed chamber under inert conditions of a dry, oxygen-free nitrogen environment.

[0091] Liquid tert-butylacetylene dicobalt hexacarbonyl (Co2(CO)6HC:::CC(CH3)3) was placed on a silicon wafer as a precursor.

[0092] The chamber pressure is first reduced so that any N2 trapped in the trench can be removed and the liquid can flow into the trench by capillary action.

[0093] The pressure was then increased by adding nitrogen, and then the plateau temperature was gradually increased.

[0094] As the liquid begins to decompose tert-butylacetylene vapor, CO gas will be released and the precursor molecules will begin to oligomerize. The volume of the liquid shrinks, and the liquid on the top of the groove is sucked into the groove. As the condensation continues, solid nanoparticles may form and pack tightly in the groove.

[0095] When the temperature reaches 400 °C, most of the CO and tert-butylacetylene ligands will be released into the gas phase, leaving behind mostly conductive Co metal deposits in the trenches.

[0096] At this point the deposited material may be further optionally annealed with H2 gas or by using plasma or electron beam to increase the conductivity of the metal.

[0097] Conventional processing can then be performed, such as chemical mechanical planarization (CMP) to remove the overburden (excess Co on the upper surface).

[0098] If the trench is not completely filled, the deposition process may be repeated one or more times until the trench is completely filled with conductive cobalt metal.

[0099] Example 2

[0100] The silicon wafer had a surface layer of carbon-doped silicon oxide into which trenches 20 nm wide and 200 nm deep were etched.

[0101] The silicon wafer is placed on a platform in a sealed chamber under inert conditions of a dry, oxygen-free nitrogen environment.

[0102] Liquid tert-butylacetylene dicobalt hexacarbonyl (Co2(CO)6HC:::CC(CH3)3) mixed with about 10 wt% of dry n-octane was placed on a silicon wafer as a precursor.

[0103] The chamber pressure is first reduced so that any N2 trapped in the trench can be removed and the liquid can flow into the trench by capillary action.

[0104] The pressure was then increased by adding nitrogen, and then the plateau temperature was gradually increased.

[0105] As the liquid begins to decompose tert-butylacetylene vapor, CO gas will be released and the precursor molecules will begin to oligomerize. The volume of the liquid shrinks, and the liquid on the top of the groove is sucked into the groove. As the condensation continues, solid nanoparticles may form and pack tightly in the groove.

[0106] When the temperature reaches 400 °C, most of the CO and tert-butylacetylene ligands will be released into the gas phase, leaving behind mostly conductive Co metal deposits in the trenches.

[0107] At this point the deposited material may be further optionally annealed with H2 gas or by using plasma or electron beam to increase the conductivity of the metal.

[0108] Conventional processing can then be performed, such as chemical mechanical planarization (CMP) to remove the overburden (excess Co on the upper surface).

[0109] If the trench is not completely filled, the deposition process may be repeated one or more times until the trench is completely filled with conductive cobalt metal.

[0110] Example 3

[0111] (1-Decyne) dodecacarbonyltetracobalt(Co4(CO) 12 (C8H 17 Synthesis of C:::CH))

[0112] In a nitrogen glove box, tetracobalt (500 mg, 0.87 mmol) was placed in a 25 cc Schlenk flask, and 10 ml of tetrahydrofuran was added to the flask.

[0113] After stirring, tetracobalt dodecacarbonyl dissolved to form a black solution. 1-Decyne (550 mg, 4.0 mmol) was added to the solution.

[0114] The solution was stirred at ambient temperature for 2 days. During this time, the color of the solution turned to dark red.

[0115] The volatiles were removed under vacuum to give a highly viscous black liquid.

[0116] Example 4

[0117] Thermal Decomposition of (1-Decyne) Tetracobalt Dodecacarbonyl

[0118] In a nitrogen glove box, a sample of (1-decyne) tetracobalt dodecacarbonyl was placed on a flat pan and transferred to a thermogravimetric analyzer (TGA).

[0119] Using TGA, the sample temperature was raised to 400°C at a rate of 10°C / min while monitoring the sample weight. A total of 76% of the initial weight was lost, with 24% ( Figure 1 ). In the compound (1-decyne) dodecacarbonyltetracobalt, cobalt accounts for about 33% of the mass and the ligand accounts for about 67% of the mass. Therefore, most of the cobalt originally present in the mixture remains on the surface of the disk.

[0120] Example 5

[0121] Synthesis of Ru3(CO)9(PPh2(CH2)3Si(OEt)3)3 as a precursor

[0122] Ru3(CO) from Colonial Metals inc. 12 (0.5 g, 0.78 mmol) and PPh2(CH2)3Si(OEt)3 (1 g, 2.56 mmol) from Strem Chemicals were charged into a 250 ml flask in the glove box. The flask was then moved out of the glove box and connected to a Schlenk line (under N2).

[0123] Under N2 purge and stirring, anhydrous hexane (100ml) from Sigma-Aldrich was added to the flask with a syringe. The flask was heated at 68-70°C for 2 hours under reflux. After 2 hours, the reaction was cooled to ambient temperature. All solvents were extracted under vacuum at ambient temperature. The product was washed with cold hexane 3x10ml. The final product was dried under vacuum. A reddish oil was then obtained, 0.55g, yield 85%.

[0124] Example 6

[0125] A mixture of triruthenium dodecacarbonyl and 20% dry n-octane is placed on a silicon wafer having a surface layer of carbon-doped silicon oxide in which a 20 nm wide and 200 nm deep groove is etched. The wafer is sealed in a chamber under inert conditions of a dry, oxygen-free nitrogen environment. The pressure of the chamber is reduced so that any N2 trapped in the groove can be removed, and the liquid can flow into the groove by capillary action while the solvent begins to evaporate. The pressure is then increased by adding nitrogen, and the temperature of the platform on which the wafer is located is gradually increased. As the liquid begins to decompose, decylene vapor and CO gas will be released and the precursor molecules will begin to oligomerize. The volume of the liquid shrinks, and the liquid located on the top of the groove is sucked into the groove. As the condensation continues, solid nanoparticles may form and be densely packed in the groove. When the temperature reaches 400°C, most of the CO ligands will be released into the gas phase, leaving most of the conductive ruthenium metal deposits in the groove. At this time, the deposited material can be further optionally thermally annealed with H2 or O2 or by using plasma or electron beam to improve the conductivity of the metal. Conventional processing may then be performed, such as chemical mechanical planarization (CMP) to remove the overburden (excess Ru on the upper surface). If the trench is not completely filled, the process may be repeated one or more times until the trench is completely filled with conductive ruthenium or a different metal.

[0126] Example 7

[0127] (1,6-heptadiyne) tetracobalt dodecacarbonyl in combination with about 10 wt% dry n-octane is placed on a silicon wafer having a surface layer of carbon-doped silicon oxide into which trenches 20 nm wide and 200 nm deep have been etched. The wafer is sealed in a chamber under inert conditions of a dry, oxygen-free nitrogen environment. The chamber pressure is reduced so that any N2 trapped in the trenches can be removed and the liquid can flow into the trenches by capillary action while the solvent begins to evaporate. The pressure is then increased by adding nitrogen and the temperature of the platform on which the wafer sits is gradually increased. As the liquid begins to decompose, 1,6-heptadiyne vapor and CO gas will be released and the precursor molecules will begin to oligomerize. The volume of the liquid shrinks and the liquid at the top of the trenches is drawn into the trenches. As condensation continues, solid nanoparticles may form and pack tightly in the trenches. When the temperature reaches 400°C, most of the CO and 1,6-heptadiyne ligands will be released into the gas phase, leaving behind a conductive Co metal deposit that is mostly within the trenches. At this point, the deposited material may be further optionally annealed with H2 gas or by using plasma or electron beam to improve the conductivity of the metal. Conventional treatment may then be performed, such as chemical mechanical planarization (CMP) to remove the overburden (excess Co on the upper surface). If the trench is not completely filled, the process may be repeated one or more times until the trench is completely filled with conductive cobalt metal.

[0128] Example 8

[0129] Synthesis of 2,2-Dimethyl-3-octyne (tert-butyl n-butylacetylene)

[0130] In a nitrogen glove box, tert-butyl acetylene (3,3-dimethyl-1-butyne) solution was prepared by placing tert-butyl acetylene (32.8 g, 0.4 mol) in a 1000 ml round-bottom flask with 500 ml of anhydrous THF. 2.5 M n-butyl lithium in 150 ml of hexane (0.375 mol) was added to a 500 ml addition funnel. The flask and addition funnel were taken out of the glove box and assembled in a fume hood. The tert-butyl acetylene solution was cooled to 0 ° C. Under stirring, the n-butyl lithium solution was added dropwise to the tert-butyl acetylene solution within 30 minutes. After the addition was completed, the colorless solution was allowed to warm to ambient temperature within two hours under stirring. 1-iodobutane (64.4 g, 0.35 mol) and 100 ml of anhydrous THF were added to a 500 ml addition funnel. The solution was added dropwise to the lithium tert-butyl acetylide solution within 30 minutes under stirring. The solution was stirred at ambient temperature for 3 days. Gas chromatography-mass spectrometry analysis of a small sample showed complete conversion to the product. The solution was extracted twice with 100 ml of deionized water. The water wash was extracted with 200 ml of hexane, and the extract was combined with a THF / hexane solution. The organic solution was dried over magnesium sulfate for 30 minutes. During this period, the colorless solution turned pale yellow. The combined organic solution was distilled under reduced pressure (~10 Torr) while the reboiler was maintained at 20°C, the condenser was maintained at 0°C, and the collecting flask was maintained at -78°C. After removing the solvent, another collecting flask was installed to distill the remaining volatile substances while the reboiler was maintained at 25°C, the condenser was maintained at 0°C, and the collecting flask was maintained at -78°C. The pressure during the second distillation was about 2 Torr. When all volatile substances were transferred, the collecting flask was allowed to warm to ambient temperature. The colorless liquid was analyzed using gas chromatography-mass spectrometry to confirm the presence of a high-purity product (purity>99%, 42.2g, yield 87%).

[0131] 2,2-Dimethyl-3-octyne 1 H NMR analysis gave the following chemical shifts: 2.03 (t, 2H); 1.33 (m, 4H); 1.19 (s, 9H); 0.80 (t, 3H).

[0132] Example 9

[0133] Synthesis of (2,2-dimethyl-3-octyne) dicobalt hexacarbonyl (tert-butyl-n-butylacetylene cobalt carbonyl, CCTNBA)

[0134] In a fume hood, a solution of 2,2-dimethyl-3-octyne (21.5 g, 0.15 mol) in hexane (100 ml) was added to a solution of Co2(CO)8 (47.5 g, 0.14 mol) in hexane (700 ml) over 30 minutes. Visible CO release was observed upon addition of the 2,2-dimethyl-3-octyne solution. The resulting dark brown solution turned dark reddish brown over the course of four hours of stirring at ambient temperature. The hexane was removed using vacuum distillation while maintaining the reboiler at 25°C (condenser temperature -5°C; collecting flask temperature -78°C) to produce a dark red liquid with black solids. A chromatographic column (approximately 3 inches in diameter) was filled with 8 inches of neutral activated alumina using pure hexane as the eluent. The crude material was placed on the column and eluted with hexane. The brown band moved rapidly down the column with the hexane. The dark purple material remained in the top 2-3 inches of the column. The reddish brown band was collected on a Schlenk line (about 700 mTorr) and evacuated to yield 40.0 g of a dark red liquid.

[0135] CCTNBA 1 H NMR analysis showed high purity (NMR analysis 99.6%). Chemical shift (d8-toluene): 2.66 (t, 2H), 1.60 (m, 2H), 1.29 (m, 2H), 1.17 (s, 9H), 0.86 (t, 3H).

[0136] Example 10

[0137] Formation of Cobalt-Containing Films Using CCTNBA

[0138] In a nitrogen glove box, a solution of approximately 20 wt % CCTNBA in hexane and toluene was prepared by weighing 250 mg of CCTNBA and 1 g of hexane / toluene into two 25 ml glass bottles.

[0139] Place hot SiO2 and silicon wafer samples of approximately 1" x 1" size into a nitrogen glove box. Place two samples of each type into a glass evaporating dish.

[0140] The sample was covered with a thin film of the hexane solution of CCTNBA or the toluene solution of CCTNBA by dropping the solution onto the surface of the sample.

[0141] The wetting properties of the solutions differ slightly. About 5-6 drops of a solution containing hexane are needed to cover the entire sample surface. 8-9 drops of a solution containing toluene are needed to cover the entire sample surface.

[0142] For both sets of solutions, it was possible to cover substantially the entire surface area of ​​the specimen without any solution overflowing the edges of the specimen.

[0143] The sample with about 20 wt% CCTNBA solution was left at room temperature in a glove box. During this time, the hexane solution evaporated completely. However, the toluene solution evaporated only partially.

[0144] Carefully place the glass dish containing the sample on a hot plate. Heat the hot plate to 80°C. After a few minutes, it is clear that toluene evaporates and CCTNBA is still present on the sample surface. After 5 minutes, remove the glass dish from the hot plate.

[0145] The temperature of the hot plate is raised to 370°C. When the hot plate surface stabilizes at 370°C, the glass dish containing the sample is placed back on the hot plate. A second, slightly larger evaporating dish is placed on top of the glass dish containing the sample (as a lid). After about 30 seconds, a small amount of brown vapor is observed to rise from the surface of the sample. The vapor condenses on the sides of the dish containing the sample and on part of the larger dish that serves as a lid. The sample is heated at 370°C for 15 minutes. Within a few minutes at 370°C, the surface of the sample is mostly bright silver with some dark gray areas. Terminate the hot plate heating and allow the glass dish to cool to ambient temperature. A conductive cobalt-containing film is deposited on the sample. Figure 2 An example is shown.

[0146] Samples were removed from the dishes for analysis.

[0147] X-ray fluorescence (XRF) was used to measure the film thickness. The film sheet resistance was measured using a four-point probe. The film sheet resistance was measured after film deposition. The results are shown in Table 1.

[0148] The sample was then placed in a chamber for annealing in a hydrogen atmosphere. The conditions for the post-deposition annealing treatment were: nitrogen flow rate 450 sccm, hydrogen flow rate 50 sccm, temperature 400° C., chamber pressure 50 Torr, and annealing time 30 minutes.

[0149] After annealing, the film sheet resistance was measured again using a four-point probe. The results are shown in Table 1.

[0150] The effect of annealing on the resistivity of deposited cobalt films is shown in Table 1. Annealing treatment reduces the resistivity of cobalt-containing films.

[0151] Table 1:

[0152]

[0153] The film was deposited on silicon dioxide and silicon surfaces. Most of the films so deposited contained cobalt and were conductive as measured by a four point probe measurement setup. Impurities such as carbon appear to be present in the cobalt film, which results in high sheet resistance. Annealing the cobalt film under a reducing atmosphere, such as a mixture of hydrogen and nitrogen, is a method to reduce impurity levels.

[0154] The results in Table 1 show that resistivity can be reduced in the films of the present invention. The resulting films can be used to create conductive layers or conductive features, such as conductive lines or vias, in semiconductor devices.

[0155] Although the principles of the present invention have been described above in conjunction with the preferred embodiments, it should be clearly understood that this description is intended as an example only and not a limitation of the scope of the invention.

Claims

1. A method for depositing a conductive metal film on a substrate, comprising: a. providing the substrate having a surface comprising a topography, the topography comprising a patterned depression; b. providing a liquid metal precursor comprising a neutral metal compound having a metal in a zero valent state and at least one neutral stabilizing ligand; in The metal is selected from Fe, Co, Ni, Ru, Ir, Rh, Pd, Pt, Cu, Ag, Au, Os and combinations thereof; The at least one neutral stabilizing ligand is selected from Carbon monoxide (CO); Nitrogen monoxide (NO); Dinitrogen (N2); Acetylene (C2H2); Ethylene (C2H4); C4-C 18 Diene or C4-C 18 Cyclodiene; C6-C 18 Triene; C8 to C 18 Tetraene; organic isocyanide RNC, wherein R is selected from C1 to C 12 A straight or branched hydrocarbon or halogenated hydrocarbon; an organic nitrile RCN, wherein R is selected from C1 to C 12 A hydrocarbon group or a halogenated hydrocarbon group; an organic phosphine PR'3, wherein R' is selected from H, Cl, F, Br and C1 to C 12 Amine NRaRbRc, wherein Ra, Rb and Rc may be connected to each other and are each independently selected from H or C1 to C 12 an organic ether R*OR**, wherein R* and R** may be connected to each other and are each independently selected from C1 to C 12 and a terminal alkyne or an internal alkyne of the general formula R1CCR2, wherein R1 and R2 may be independently selected from H, C1 to C 12 A linear, branched, cyclic or aromatic halogenated hydrocarbon group or hydrocarbon group, a silyl group or an organosilyl group, a stannyl group or an organostannyl group, and combinations thereof; The neutral metal compound is a liquid or solid, which is soluble at ambient temperature in a solvent selected from saturated straight-chain, branched and cyclic hydrocarbons; an aromatic solvent selected from benzene, toluene, xylene, mesitylene, o-dichlorobenzene, nitrobenzene; a nitriles selected from acetonitrile, propionitrile or benzonitrile; an ether selected from tetrahydrofuran, dimethoxyethane, diglyme, tetrahydropyran, methyltetrahydrofuran, butyltetrahydrofuran, p-dioxane; an amine selected from triethylamine, piperidine, pyridine, pyrrolidine, morpholine; an amide selected from N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, N-cyclohexylpyrrolidone; a compound having the formula R 4 R 5 NR 6 OR 7 NR 8 R 9 , R 4 OR 6 NR 8 R 9 、O(CH2CH2)2NR 4 , R 4 R 5 NR 6 N(CH2CH2)2O、R 4 R 5 NR 6 OR 7 N(CH2CH2)2O、O(CH2CH2)2NR 4 OR 6 Amino ethers of N(CH2CH2)2O; wherein R 4-9 are independently selected from linear or branched C1 to C 10 Alkyl; and combinations thereof; or a solid that melts at a temperature below its decomposition temperature; and The viscosity of the liquid metal precursor at ambient temperature is between 0.5 cP and 20 cP; and c. applying the liquid metal precursor to the surface by spraying, roller coating, doctor blade coating, spin coating, surface pooling, supersaturated vapor condensation, inkjet printing, curtain coating, dip coating or a combination thereof to deposit the conductive metal film onto the substrate. 2 . The method according to claim 1 , wherein the aspect ratio (depth-to-width ratio) of the patterned recess is 4:1 or greater.

3. The method according to claim 1, wherein the neutral metal compound is selected from a 1 Co2(CO)6, where R 1 It is a straight or branched chain of C2 to C 10 Alkyne, straight or branched C1 to C 10 Alkoxyalkyne, straight or branched C1 to C 10 Organic aminoalkynes; B R 1 CoFe(CO)7, where R 1 It is a straight or branched chain of C2 to C 10 Alkyne, straight or branched C1 to C 10 Alkoxyalkyne, straight or branched C1 to C 10 Organic aminoalkynes; C 2 CCo3(CO)9, where R 2 selected from hydrogen, linear or branched C1 to C 10 Alkyl, linear or branched C1 to C 10 Alkoxy, Cl, Br, COOH, COOMe, COOEt; dR 2 CCo2Mn(CO) 10 , where R 2 selected from hydrogen, linear or branched C1 to C 10 Alkyl, linear or branched C1 to C 10 Alkoxy, Cl, Br, COOH, COOMe, COOEt; eR 3 Co4(CO) 12 , where R 3 Selected from linear or branched C1 to C 10 alkenylene; and f 4 Ru3(CO) 11 , where R 4 is selected from disubstituted alkynes R # C≡CR ## , where R # and R ## Can be independently selected from C1 to C 12 The invention further comprises a linear, branched, cyclic or aromatic halogenated hydrocarbon group or hydrocarbon group, a silyl group or an organic silyl group, a stannyl group or an organic stannyl group, and combinations thereof.

4. The method according to claim 1, wherein the neutral metal compound is selected from tert-butylacetylene dicobalt hexacarbonyl, (1-decyne) tetracobalt dodecacarbonyl, (1,6-heptadiyne) tetracobalt dodecacarbonyl, (2,2,6-trimethyl-3-heptadiyne) dicobalt hexacarbonyl, (2,2-dimethyl-3-octyne) dicobalt hexacarbonyl, (2,2-dimethyl-3-decyne) dicobalt hexacarbonyl, (2,2-dimethyl-3-heptadiyne) dicobalt hexacarbonyl, (tert-butylmethylacetylene) dicobalt hexacarbonyl, Cobalt, dodecacarbonyl triruthenium, (ethylbenzene)(1,3-butadiene)ruthenium, (isopropyl-4-methylbenzene)(1,3-butadiene)ruthenium, 1,3,5-cycloheptatriene dicarbonylruthenium, 1,3-cyclohexadiene tricarbonylruthenium, 2,3-dimethyl-1,3-butadiene tricarbonylruthenium, 2,4-hexadiene tricarbonylruthenium, 1,3-pentadiene tricarbonylruthenium, (benzene)(1,3-butadiene)ruthenium, (benzene)(2,3-dimethyl-1,3-butadiene)ruthenium, Co2Ru(CO) 11 、HCoRu3(CO) 13 , Ru3(CO)9(PPh2(CH2)3Si(OEt)3)3, bis(phenyl)chromium, bis(cyclooctadiene)nickel, bis(tri-tert-butylphosphine)platinum, bis(tri-tert-butylphosphine)palladium and combinations thereof.

5. The process according to claim 1, wherein the solvent is selected from n-hexane, n-pentane, isohexane, octane, isooctane, decane, dodecane, heptane, cyclohexane, methylcyclohexane, ethylcyclohexane, decalin; an aromatic solvent selected from benzene, toluene, xylene as a single isomer or as a mixture of isomers, mesitylene, o-dichlorobenzene, nitrobenzene; a nitrile selected from acetonitrile, propionitrile or benzonitrile; an ether selected from tetrahydrofuran, dimethoxyethane, diglyme, tetrahydropyran, methyltetrahydrofuran, butyltetrahydrofuran, p-dioxane; an amine selected from triethylamine, piperidine, pyridine, pyrrolidine, morpholine; an amide selected from N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, N-cyclohexylpyrrolidone; a solvent having the formula R 4 R 5 NR 6 OR 7 NR 8 R 9 , R 4 OR 6 NR 8 R 9 、O(CH2CH2)2NR 4 , R 4 R 5 NR 6 N(CH2CH2)2O、R 4 R 5 NR 6 OR 7 N(CH2CH2)2O、O(CH2CH2)2NR 4 OR 6 Amino ethers of N(CH2CH2)2O; wherein R 4-9 are independently selected from linear or branched C1 to C 10 Alkyl; and combinations thereof.

6. The method according to claim 1, wherein The neutral metal compound is selected from tert-butylacetylene dicobalt hexacarbonyl, (1-decyne) tetracobalt dodecacarbonyl, (1,6-heptadiyne) tetracobalt dodecacarbonyl, (2,2,6-trimethyl-3-heptyne) dicobalt hexacarbonyl, (2,2-dimethyl-3-octyne) dicobalt hexacarbonyl and Ru3(CO)9(PPh2(CH2)3Si(OEt)3)3; and The solvent is selected from tetrahydrofuran, octane, hexane and toluene.

7. The method of claim 1, wherein the liquid metal precursor is applied to the surface at a contact angle between the liquid metal precursor and the surface of ≤ 90°.

8. The method of claim 1, wherein the liquid metal precursor has a viscosity of between 1 cP and 10 cP at ambient temperature; and is applied to the surface with a contact angle between the liquid metal precursor and the surface of less than 45°.

9. The method of claim 1 further comprises applying energy to the liquid metal precursor to dissociate the ligands that stabilize the metal; wherein the energy is selected from visible light, infrared light, or ultraviolet light; a heated gas stream; conduction from a resistive or fluid heated recipient; an inductively heated recipient; an electron beam; an ion beam; a remote hydrogen plasma; direct argon; helium or hydrogen plasma; a vacuum; ultrasound; and combinations thereof.

10. The method according to claim 1, further comprising performing a post-deposition annealing treatment under a reducing atmosphere using a reducing gas selected from hydrogen, ammonia, diborane, silane and a combination thereof, the annealing time being 5 minutes or more; wherein the reducing atmosphere optionally further comprises an inert gas of nitrogen, argon or a combination of nitrogen and argon, and the reducing atmosphere is at a temperature equal to or higher than 300° C.; and the flow rate of the reducing gas is or higher than 100 sccm.

11. A system for depositing a conductive metal film on a substrate, comprising: a. The substrate having a surface comprising a topography, the topography comprising patterned depressions; b. a liquid metal precursor comprising a neutral metal compound having a metal in a zero valent state and at least one neutral stabilizing ligand; in The metal is selected from Fe, Co, Ni, Ru, Ir, Rh, Pd, Pt, Cu, Ag, Au, Os and combinations thereof; The at least one neutral stabilizing ligand is selected from Carbon monoxide (CO); Nitrogen monoxide (NO); Dinitrogen (N2); Acetylene (C2H2); Ethylene (C2H4); C4-C 18 Diene or C4-C 18 Cyclodiene; C6-C 18 Triene; C8 to C 18 Tetraene; organic isocyanide RNC, wherein R is selected from C1 to C 12 A straight or branched hydrocarbon or halogenated hydrocarbon; an organic nitrile RCN, wherein R is selected from C1 to C 12 A hydrocarbon group or a halogenated hydrocarbon group; an organic phosphine PR'3, wherein R' is selected from H, Cl, F, Br and C1 to C 12 Amine NRaRbRc, wherein Ra, Rb and Rc may be connected to each other and are each independently selected from H or C1 to C 12 an organic ether R*OR**, wherein R* and R** may be connected to each other and are each independently selected from C1 to C 12 and a terminal alkyne or an internal alkyne of the general formula R1CCR2, wherein R1 and R2 may be independently selected from H, C1 to C 12 A linear, branched, cyclic or aromatic halogenated hydrocarbon group or hydrocarbon group, a silyl group or an organosilyl group, a stannyl group or an organostannyl group, and combinations thereof; The neutral metal compound is a liquid or solid which is soluble in a solvent selected from saturated linear, branched and cyclic hydrocarbons at ambient temperature; or a solid which melts at a temperature below its decomposition temperature; and The liquid metal precursor has a viscosity between 0.5 cP and 20 cP at ambient temperature; and c. A deposition tool selected from the group consisting of spray coating, roller coating, doctor blade coating, spin coating, surface collection, supersaturated steam condensation, inkjet printing, curtain coating, dip coating, and combinations thereof.

12. The system of claim 11, wherein the neutral metal compound is selected from a 1 Co2(CO)6, where R 1 It is a straight or branched chain of C2 to C 10 Alkyne, straight or branched C1 to C 10 Alkoxyalkyne, straight or branched C1 to C 10 Organic aminoalkynes; B R 1 CoFe(CO)7, where R 1 It is a straight or branched chain of C2 to C 10 Alkyne, straight or branched C1 to C 10 Alkoxyalkyne, straight or branched C1 to C 10 Organic aminoalkynes; C 2 CCo3(CO)9, where R 2 selected from hydrogen, linear or branched C1 to C 10 Alkyl, linear or branched C1 to C 10 Alkoxy, Cl, Br, COOH, COOMe, COOEt; dR 2 CCo2Mn(CO) 10 , where R 2 selected from hydrogen, linear or branched C1 to C 10 Alkyl, linear or branched C1 to C 10 Alkoxy, Cl, Br, COOH, COOMe, COOEt; eR 3 Co4(CO) 12 , where R 3 Selected from linear or branched C1 to C 10 alkenylene; and f 4 Ru3(CO) 11 , where R 4 is selected from disubstituted alkynes R # C≡CR ## , where R # and R ## Can be independently selected from C1 to C 12 A linear, branched, cyclic or aromatic halogenated hydrocarbon group or hydrocarbon group, a silyl group or an organic silyl group, a stannyl group or an organic stannyl group, and combinations thereof.

13. The system of claim 11, wherein the neutral metal compound is selected from the group consisting of tert-butylacetylene dicobalt hexacarbonyl, (1-decyne) tetracobalt dodecacarbonyl, (1,6-heptadiyne) tetracobalt dodecacarbonyl, (2,2,6-trimethyl-3-heptyne) dicobalt hexacarbonyl, (2,2-dimethyl-3-octyne) dicobalt hexacarbonyl, (2,2-dimethyl-3-decyne) dicobalt hexacarbonyl, (2,2-dimethyl-3-heptyne) dicobalt hexacarbonyl, (tert-butylmethylacetylene) dicobalt hexacarbonyl, Dicobalt, dodecacarbonyl triruthenium, (ethylbenzene)(1,3-butadiene)ruthenium, (isopropyl-4-methylbenzene)(1,3-butadiene)ruthenium, 1,3,5-cycloheptatriene dicarbonylruthenium, 1,3-cyclohexadiene tricarbonylruthenium, 2,3-dimethyl-1,3-butadiene tricarbonylruthenium, 2,4-hexadiene tricarbonylruthenium, 1,3-pentadiene tricarbonylruthenium, (benzene)(1,3-butadiene)ruthenium, (benzene)(2,3-dimethyl-1,3-butadiene)ruthenium, Co2Ru(CO) 11 、HCoRu3(CO) 13 , Ru3(CO)9(PPh2(CH2)3Si(OEt)3)3, bis(phenyl)chromium, bis(cyclooctadiene)nickel, bis(tri-tert-butylphosphine)platinum, bis(tri-tert-butylphosphine)palladium and combinations thereof.

14. The system according to claim 11, wherein the solvent is selected from the group consisting of n-hexane, n-pentane, isohexane, octane, isooctane, decane, dodecane, heptane, cyclohexane, methylcyclohexane, ethylcyclohexane, decalin; aromatic solvents selected from the group consisting of benzene, toluene, xylene as a single isomer or as a mixture of isomers, mesitylene, o-dichlorobenzene, nitrobenzene; nitriles selected from the group consisting of acetonitrile, propionitrile or benzonitrile; ethers selected from the group consisting of tetrahydrofuran, dimethoxyethane, diglyme, tetrahydropyran, methyltetrahydrofuran, butyltetrahydrofuran, p-dioxane; amines selected from the group consisting of triethylamine, piperidine, pyridine, pyrrolidine, morpholine; amides selected from the group consisting of N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, N-cyclohexylpyrrolidone; 4 R 5 NR 6 OR 7 NR 8 R 9 , R 4 OR 6 NR 8 R 9 、O(CH2CH2)2NR 4 , R 4 R 5 NR 6 N(CH2CH2)2O、R 4 R 5 NR 6 OR 7 N(CH2CH2)2O、O(CH2CH2)2NR 4 OR 6 Amino ethers of N(CH2CH2)2O; wherein R 4-9 are independently selected from linear or branched C1 to C 10 Alkyl; and combinations thereof.

15. The system of claim 11, wherein the viscosity of the liquid metal precursor at ambient temperature is between 1 cP and 10 cP.

16. The system of claim 11, wherein The neutral metal compound is selected from tert-butylacetylene dicobalt hexacarbonyl, (1-decyne) tetracobalt dodecacarbonyl, (1,6-heptadiyne) tetracobalt dodecacarbonyl, (2,2,6-trimethyl-3-heptyne) dicobalt hexacarbonyl, (2,2-dimethyl-3-octyne) dicobalt hexacarbonyl and Ru3(CO)9(PPh2(CH2)3Si(OEt)3)3; and The solvent is selected from tetrahydrofuran, octane, hexane and toluene.

17. A container for containing a liquid metal precursor, wherein the liquid metal precursor comprises a neutral metal compound selected from a 1 Co2(CO)6, where R 1 It is a straight or branched chain of C2 to C 10 Alkyne, straight or branched C1 to C 10 Alkoxyalkyne, straight or branched C1 to C 10 Organic aminoalkynes; B R 1 CoFe(CO)7, where R 1 It is a straight or branched chain of C2 to C 10 Alkyne, straight or branched C1 to C 10 Alkoxyalkyne, straight or branched C1 to C 10 Organic aminoalkynes; C 2 CCo3(CO)9, where R 2 selected from hydrogen, linear or branched C1 to C 10 Alkyl, linear or branched C1 to C 10 Alkoxy, Cl, Br, COOH, COOMe, COOEt; dR 2 CCo2Mn(CO) 10 , where R 2 selected from hydrogen, linear or branched C1 to C 10 Alkyl, linear or branched C1 to C 10 Alkoxy, Cl, Br, COOH, COOMe, COOEt; eR 3 Co4(CO) 12 , where R 3 Selected from linear or branched C1 to C 10 alkenylene; and f 4 Ru3(CO) 11 , where R 4 is selected from disubstituted alkynes R # C≡CR ## , where R # and R ## Can be independently selected from C1 to C 12 Straight chain, branched, cyclic or aromatic halogenated hydrocarbon or hydrocarbon groups, silyl or organosilyl, stannyl or organostannyl groups and combinations thereof; The neutral metal compound is a liquid or solid, which is soluble at ambient temperature in a solvent selected from saturated straight-chain, branched and cyclic hydrocarbons; an aromatic solvent selected from benzene, toluene, xylene, mesitylene, o-dichlorobenzene, nitrobenzene; a nitrile selected from acetonitrile, propionitrile or benzonitrile; an ether selected from tetrahydrofuran, dimethoxyethane, diethylene glycol dimethyl ether, tetrahydropyran, methyltetrahydrofuran, butyltetrahydrofuran, p-dioxane; an amine selected from triethylamine, piperidine, pyridine, pyrrolidine, morpholine; an amide selected from N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, N-cyclohexylpyrrolidone; a compound having the formula R 4 R 5 NR 6 OR 7 NR 8 R 9 , R 4 OR 6 NR 8 R 9 、O(CH2CH2)2NR 4 , R 4 R 5 NR 6 N(CH2CH2)2O、R 4 R 5 NR 6 OR 7 N(CH2CH2)2O、O(CH2CH2)2NR 4 OR 6 Amino ethers of N(CH2CH2)2O; wherein R 4-9 are independently selected from linear or branched C1 to C 10 Alkyl; and combinations thereof; or a solid that melts at a temperature below its decomposition temperature; The liquid metal precursor has a viscosity between 0.5 cP and 20 cP at ambient temperature; and The container has a dip tube extending below the surface of the liquid metal precursor.

18. The container of claim 17, wherein the neutral metal compound is selected from the group consisting of tert-butylacetylene dicobalt hexacarbonyl, (1-decyne) tetracobalt dodecacarbonyl, (1,6-heptadiyne) tetracobalt dodecacarbonyl, (2,2,6-trimethyl-3-heptadiyne) dicobalt hexacarbonyl, (2,2-dimethyl-3-octyne) dicobalt hexacarbonyl, (2,2-dimethyl-3-decyne) dicobalt hexacarbonyl, (2,2-dimethyl-3-heptadiyne) dicobalt hexacarbonyl, (tert-butylmethylacetylene) dicobalt hexacarbonyl, Cobalt, dodecacarbonyl triruthenium, (ethylbenzene)(1,3-butadiene)ruthenium, (isopropyl-4-methyl-benzene)(1,3-butadiene)ruthenium, 1,3,5-cycloheptatriene dicarbonylruthenium, 1,3-cyclohexadiene tricarbonylruthenium, 2,3-dimethyl-1,3-butadiene tricarbonylruthenium, 2,4-hexadiene tricarbonylruthenium, 1,3-pentadiene tricarbonylruthenium, (benzene)(1,3-butadiene)ruthenium, (benzene)(2,3-dimethyl-1,3-butadiene)ruthenium, Co2Ru(CO) 11 、HCoRu3(CO) 13 , Ru3(CO)9(PPh2(CH2)3Si(OEt)3)3, bis(phenyl)chromium, bis(cyclooctadiene)nickel, bis(tri-tert-butylphosphine)platinum, bis(tri-tert-butylphosphine)palladium and combinations thereof.

19. The container according to claim 17, wherein the solvent is selected from n-hexane, n-pentane, isohexane, octane, isooctane, decane, dodecane, heptane, cyclohexane, methylcyclohexane, ethylcyclohexane, decalin; an aromatic solvent selected from benzene, toluene, xylene as a single isomer or as a mixture of isomers, mesitylene, o-dichlorobenzene, nitrobenzene; nitriles selected from acetonitrile, propionitrile or benzonitrile; ethers selected from tetrahydrofuran, dimethoxyethane, diglyme, tetrahydropyran, methyltetrahydrofuran, butyltetrahydrofuran, p-dioxane; amines selected from triethylamine, piperidine, pyridine, pyrrolidine, morpholine; amides selected from N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, N-cyclohexylpyrrolidone; having the formula R 4 R 5 NR 6 OR 7 NR 8 R 9 , R 4 OR 6 NR 8 R 9 、O(CH2CH2)2NR 4 , R 4 R 5 NR 6 N(CH2CH2)2O、R 4 R 5 NR 6 OR 7 N(CH2CH2)2O、O(CH2CH2)2NR 4 OR 6 Amino ethers of N(CH2CH2)2O; wherein R 4-9 are independently selected from linear or branched C1 to C 10 Alkyl; and combinations thereof.

20. The container of claim 17, wherein the viscosity of the liquid metal precursor at ambient temperature is between 1 cP and 10 cP.

21. The container according to claim 17, wherein The neutral metal compound is selected from tert-butylacetylene dicobalt hexacarbonyl, (1-decyne) tetracobalt dodecacarbonyl, (1,6-heptadiyne) tetracobalt dodecacarbonyl, (2,2,6-trimethyl-3-heptyne) dicobalt hexacarbonyl, (2,2-dimethyl-3-octyne) dicobalt hexacarbonyl and Ru3(CO)9(PPh2(CH2)3Si(OEt)3)3; and The solvent is selected from tetrahydrofuran, octane, hexane and toluene.

22. A conductive metal film deposited on a surface comprising a topography comprising patterned depressions by using a liquid metal precursor, the liquid metal precursor comprising a neutral metal compound selected from the group consisting of tert-butylacetylene dicobalt hexacarbonyl, (1-decyne) tetracobalt dodecacarbonyl, (1,6-heptadiyne) tetracobalt dodecacarbonyl, (2,2,6-trimethyl-3-heptyne) dicobalt hexacarbonyl, (2,2-dimethyl-3-octyne) dicobalt hexacarbonyl, and Ru3(CO)9(PPh2(CH2)3Si(OEt)3)3; and A solvent selected from tetrahydrofuran, octane, hexane, toluene.

23. The conductive metal film of claim 22, which is deposited by spraying, roller coating, spin coating, inkjet printing, dip coating, and combinations thereof.

24. The conductive metal film according to claim 22, which has a value less than or equal to 1×10 -4 Conductivity of Ωcm.

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