Area selective deposition method of metal film on silicon containing surfaces and method for selectively passivating a surface of a substrate utilizing alcohols

Abstract

A method for selectively passivating the surface of a substrate, wherein the surface of the substrate includes at least one first surface comprising silicon nitride and at least one second surface comprising a material other than silicon nitride. The method includes the steps of exposing the surface to at least one alcohol, wherein the alcohol selectively reacts with the silicon nitride to passivate the first surface, thereby leaving a substantially unreacted second surface.

Description

Selective deposition of a metal film on a silicon-containing surface using an alcohol Cross-reference to related applications This application claims priority to U.S. Provisional Patent Application No. 63 / 503,418, filed May 19, 2023. This application relates to selective passivation on a first surface of a substrate relative to a second surface. Additionally, further processing can be used to deposit different materials on the second surface relative to the first surface thereafter. Selective deposition processes are gaining significant momentum, mostly due to the limitations of contemporary lithography processes in manufacturing advanced semiconductor devices while continuously shrinking physical dimensions. Traditionally, patterning in the microelectronics industry has been accomplished using various lithography and etching processes. However, as lithography becomes exponentially more complex and expensive, using selective deposition to form self-aligned features is becoming increasingly attractive. The fabrication of such self-aligned via structures clearly benefits from manufacturable selective deposition processes. Another potential application of selective deposition is gap filling. In gap filling, a dielectric "fill" film grows selectively from the bottom to the top of a trench. Selective deposition can be used for other applications such as selective sidewall deposition, where a film is selectively deposited on the exposed surfaces of a three-dimensional fin field-effect transistor (FIN-FET) structure. This would enable the deposition of sidewall spacers without the need for complex patterning steps. Selective deposition processes for metal and metal oxide films used as gate dielectrics and capacitor dielectrics will also have great utility in semiconductor device manufacturing. There are some previous examples in the technical literature regarding the selective formation of surface passivation coatings on wafers with multiple different chemical surfaces. This is done to delay or prevent film deposition on these passivated surfaces via an ALD process, but not to prevent deposition on surfaces where film deposition by an ALD deposition process is desired. Generally, due to incomplete surface passivation and / or due to physical adsorption of ALD precursor molecules and subsequent formation of the ALD film material within the passivation layer itself or on surfaces where deposition is not desired, the selectivity of the process becomes insufficient. The present invention seeks to overcome the limitations of the prior art and provide an improved method for selectively depositing thin film materials using an ALD deposition process. Liu, L.-H. et al. teach in J. Phys.: Condens. Matter 28 (2016) 094014 (doi:10.1088 / 0953-8984 / 28 / 9 / 094014) that silicon nitride can be selectively passivated to a certain extent relative to silicon oxide by treating a treated surface with an aldehyde-containing solution. In a first main aspect, there is provided a method for selectively passivating a surface of a substrate, wherein the surface of the substrate comprises at least a first surface comprising silicon nitride and at least a second surface comprising a material other than silicon nitride, the method comprising the following steps: a. Optionally, treating the surface with a hydrogen plasma, an argon plasma or an ammonia plasma; b. Exposing the surface to at least one alcohol having a structure according to formula I: R-OH (I), wherein R is selected from the group consisting of substituted or unsubstituted C 4 to C 18 linear alkyl, substituted or unsubstituted branched C 4 to C 18 alkyl, substituted or unsubstituted C 4 to C 8 cyclic alkyl, substituted or unsubstituted C 3 to C 10 heterocyclic group, substituted or unsubstituted C 4 to C 18 alkenyl, substituted or unsubstituted C 4 to C 18 aryl, substituted or unsubstituted C 5 to C 20 aralkyl and substituted or unsubstituted C 4 to C 10 alkynyl, and wherein the at least one alcohol selectively reacts with the silicon nitride to passivate the first surface, thereby leaving the second surface substantially unreacted; and c. Depositing a metal film or a metal nitride film on the substrate via atomic layer deposition. In another aspect of the first main aspect, the following steps are performed before steps a and b: contacting the surface of the substrate with a wet chemical composition; rinsing the surface with deionized water; and drying the surface; wherein the wet chemical composition comprises at least one selected from the group consisting of: comprising H 2 O 2 (28% aqueous solution), NH 4 O 4 (28 to 30 %) and H 2 O composition; HF (0.01% to 5% (aqueous solution)); peroxide; RCA cleaning chemicals SC-1 and SC-2; and H 2 SO 4 / H 2 O 2 mixture. In another aspect of the first main aspect, the second surface comprises at least one selected from the group consisting of SiO 2 , carbon-doped silicon oxide, metal oxide, copper, cobalt, tungsten, amorphous silicon, polycrystalline silicon, single-crystalline silicon, germanium, and amorphous hydrogenated germanium. In another aspect of the first main aspect, the second surface comprises SiO 2 . In another aspect of the first main aspect, the at least one alcohol has a structure C n H 2n+1 C 4 to C 18 linear alkyl, where n is 4 to 18. In another aspect of the first main aspect, the at least one alcohol is selected from the group consisting of 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 8-chloro-1-octanol, and pentadecafluoro-1-octanol linear C 8 to C 18 alcohol. In another aspect of the first main aspect, R has the formula C n H 2n+1 branched C 4 to C 18an alkyl group, where n is from 4 to 18. In another aspect of the first main aspect, the at least one alcohol is selected from the group consisting of isobutanol, isopentanol, isohexanol, isoheptanol, isooctanol, isononanol, isodecanol, isoundecanol, isododecanol, isotridecanol, isotetradecanol, isopentadecanol, isohexadecanol, isoheptadecanol, and isooctadecanol. In another aspect of the first main aspect, R is a substituted or unsubstituted C 3 to C 8 cyclic alkyl group. In another aspect of the first main aspect, the at least one alcohol is selected from the group consisting of cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, and 1-methylcyclohexanol. In another aspect of the first main aspect, R comprises a substituted or unsubstituted C 4 to C 18 aryl group. In another aspect of the first main aspect, the at least one alcohol is selected from the group consisting of phenol, p-cresol, 4-methylphenol, 4-fluorophenol, 4-n-octylphenol, 4-n-pentylphenol, and 4-hexylphenol. In another aspect of the first main aspect, R is an unsubstituted C 8 to C 18 linear alkyl group or R is a substituted or unsubstituted branched C 3 to C 18 alkyl group. In another aspect of the first main aspect, the at least one alcohol is selected from the group consisting of 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 8-chloro-1-octanol, pentadecafluoro-1-octanol, isobutanol, isopentanol, isohexanol, isoheptanol, isooctanol, isononanol, isodecanol, isoundecanol, isododecanol, isotridecanol, isotetradecanol, isopentadecanol, isohexadecanol, isoheptadecanol, and isooctadecanol. In another aspect of the first main aspect, R is a substituted or unsubstituted C 5 to C 20 aralkyl group. In another aspect of the first main aspect, the at least one alcohol is benzyl alcohol. In another aspect of the first main aspect, step b. is carried out using the vapor of the at least one alcohol. In a first main aspect, there is provided a method for selectively depositing a film on a surface of a substrate, wherein the surface of the substrate includes at least a first surface containing silicon nitride and at least a second surface containing a material other than silicon nitride, the method comprising the following steps: a. Optionally, treating the surface with a hydrogen plasma or an ammonia plasma; b. Exposing the surface to at least one alcohol having a structure according to formula I: R-OH (I), where R is selected from the group consisting of substituted or unsubstituted C 4 to C 18 linear alkyls, substituted or unsubstituted branched C 2 to C 18 alkyls, substituted or unsubstituted C 3 to C 8 cyclic alkyls, substituted or unsubstituted C 3 to C 10 heterocyclic groups, substituted or unsubstituted C 3 to C 18 alkenyls, substituted or unsubstituted C 4 to C 18 aryl groups, substituted or unsubstituted C 5 to C 20 aralkyls and substituted or unsubstituted C 3 to C 10 alkynyls, wherein the at least one alcohol selectively reacts with the silicon nitride to passivate the first surface, thereby leaving the substantially unreacted second surface; and c. Exposing the surface of the substrate to one or more deposition precursors to selectively deposit a metal film on the second surface prior to the first surface. In another aspect of the second main aspect, the following steps are performed before steps a, b, and c: contacting the surface of the substrate with a wet chemical composition; rinsing the surface with deionized water; and drying the surface; wherein the wet chemical composition includes at least one selected from the group consisting of those containing H 2 O 2(28% aqueous solution), NH 4 O 4 (28 to 30%) and H 2 O composition; HF (0.01% to 5% (aqueous solution)); peroxide; RCA cleaning chemicals SC-1 and SC-2; and H 2 SO 4 / H 2 O 2 mixture. In another aspect of this second main aspect, the second surface comprises at least one selected from the group consisting of SiO 2 , carbon-doped silicon oxide, metal oxide, copper, cobalt, ruthenium, tungsten, molybdenum, amorphous silicon, polycrystalline silicon, single-crystalline silicon, germanium, and amorphous hydrogenated germanium. In another aspect of this second main aspect, the second surface comprises SiO 2 or carbon-doped silicon oxide. In another aspect of this second main aspect, the at least one alcohol has a structure C n H 2n+1 -OH C 8 to C 18 linear alkyl, where n is 8 to 18. In another aspect of this second main aspect, the at least one alcohol is selected from the group consisting of 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 8-chloro-1-octanol, and pentadecafluoro-1-octanol. In another aspect of this second main aspect, the metal film comprises a metal or a metal nitride; and wherein the metal is selected from the group consisting of Ru, Al, Ti, Ta, Mo, Co, Rh, Ir, Fe, Ru, Os, Mo, Mn, Tc, Re, Cu, Ag, Au, Ni, Pd, Pt, and combinations thereof; or wherein the metal nitride is selected from the group consisting of tantalum nitride, titanium nitride, tungsten nitride, tungsten carbonitride, molybdenum nitride, copper silicon nitride, and combinations thereof. In another aspect of this second main aspect, R is a substituted or unsubstituted C 3 to C 8Cycloalkyl. In another aspect of the first main aspect, the at least one alcohol is selected from the group consisting of cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, 1-methylcyclohexanol, o-methylcyclohexanol, m-methylcyclohexanol, and p-methylcyclohexanol. In another aspect of the second main aspect, R is a substituted or unsubstituted C 4 to C 18 aryl. In another aspect of the second main aspect, the at least one alcohol is selected from the group consisting of phenol, cresol, xylenol, and dimethylbenzyl alcohol. In another aspect of the second main aspect, R is an unsubstituted C 4 to C 18 linear alkyl or R is a substituted or unsubstituted branched C 3 to C 18 alkyl. In another aspect of the second main aspect, the at least one alcohol is selected from the group consisting of tertiary hexanol, n-heptanol, secondary heptanol, tertiary heptanol, n-octanol, secondary octanol, tertiary octanol, n-nonanol, secondary nonanol, tertiary nonanol, n-decanol, secondary decanol, tertiary decanol, n-undecanol, secondary-undecanol, tertiary-undecanol, n-dodecanol, secondary-dodecanol, tertiary-dodecanol, n-tridecanol, secondary-tridecanol, tertiary-tridecanol, n-tetradecanol, secondary-tetradecanol, tertiary-tetradecanol, n-pentadecanol, secondary-pentadecanol, tertiary-pentadecanol, n-hexadecanol, secondary-hexadecanol, tertiary-hexadecanol, n-heptadecanol, secondary-heptadecanol, tertiary-heptadecanol, n-octadecanol, secondary-octadecanol, tertiary-octadecanol, 1,1,3,3-tetramethylbutanol, and 1-methylheptanol. In another aspect of the second main aspect, R is a substituted or unsubstituted C 5 to C 20 aralkyl. In another aspect of the second main aspect, the at least one alcohol is selected from the group consisting of phenylmethanol, 2-phenyl-1-ethanol, 3-phenyl-1-propanol, 4-phenyl-1-butanol, 5-phenyl-1-pentanol, 6-phenyl-1-hexanol, 7-phenyl-1-heptanol, 8-phenyl-1-octanol, and combinations thereof. In another aspect of the second main aspect, the at least one alcohol is benzyl alcohol. In another aspect of the second main aspect, step b is carried out using the vapor of the at least one alcohol. In another aspect of the second main aspect, step b is carried out using the liquid of the at least one alcohol. In another aspect of the second main aspect, step b is carried out using the liquid of the at least one alcohol. In another aspect of the first main aspect or the second main aspect, the alcohol is selected from the group consisting of isopropyl alcohol, 1-methylcyclohexanol, 8-chloro-1-octanol, phenol, 1-octanol, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-octanol, 1-undecanol, and 1-dodecanol. In another aspect of the first main aspect or the second main aspect, R in formula (I) is R'-CH 2 , where R' is selected from linear C 7 to C 17 alkyl, branched C 6 to C 16 alkyl, and C 6 to C 10A group consisting of aryl groups. In another aspect of the first main aspect or the second main aspect, the thickness of the metal film or metal nitride film deposited on the first surface is less than the thickness of the metal film or metal nitride film deposited on the second surface; wherein the second surface comprises silicon dioxide; and wherein the deposition selectivity of the second surface to the first surface is greater than about 0.1, more preferably greater than about 0.2, and most preferably greater than about 0.3. In another aspect of the first main aspect or the second main aspect, the metal film comprises a metal or a metal nitride. In another aspect of the first main aspect or the second main aspect, the metal is selected from the group consisting of Ru, Al, Ti, Ta, Mo, Co, Rh, Ir, Fe, Ru, Os, Mo, Mn, Tc, Re, Cu, Ag, Au, Ni, Pd, Pt and combinations thereof; or wherein the metal nitride is selected from the group consisting of tantalum nitride, titanium nitride, tungsten nitride, tungsten carbonitride, molybdenum nitride, copper silicon nitride and combinations thereof. In another aspect of the first main aspect or the second main aspect, the thickness of the metal film or metal nitride film deposited on the first surface is less than the thickness of the metal film or metal nitride film deposited on the second surface; wherein the second surface comprises silicon dioxide; and wherein the deposition selectivity of the second surface to the first surface is greater than about 0.1, more preferably greater than about 0.2, and most preferably greater than about 0.3. In another aspect of the first main aspect or the second main aspect, R comprises a structure C n F 2n+1 CH 2 -OH of fluorine-substituted C 4 to C 18 linear alkyl, where n is from 1 to 17. In another aspect of the first main aspect or the second main aspect, the at least one alcohol is selected from C 3 F 7 CH 2 -OH, C 4 F 9 CH 2 -OH, C 5 F 11 CH 2 -OH, C 6 F 13 CH 2 -OH, C 7 F 15 CH 2 -OH, C 8 F 17 CH 2 -OH and C 9 F 19 CH 2 -OH. In another aspect of the first main aspect or the second main aspect, R has the structure C n Cl 2n+1 CH 2 Chlorine-substituted C of -OH 1 to C 18 Linear alkyl, where n is 1 to 17. In another aspect of the first main aspect or the second main aspect, the at least one alcohol is selected from CCl 3 CH 2 -OH, C 2 Cl 5 CH 2 -OH, C 3 Cl 7 CH 2 -OH, C 4 Cl 9 CH 2 -OH, C 5 Cl 11 CH 2 -OH, C 6 Cl 13 CH 2 -OH, C 7 Cl 15 CH 2 -OH, C 8 Cl 17 CH 2 -OH, C 9 Cl 19 CH 2 The group consisting of -OH and 8-chloro-1-octanol. The specific examples of the present invention can be used alone or in combination with each other. All references cited herein, including published cases, patent applications, and patents, are incorporated herein by reference to the same extent as if each reference had been individually and specifically indicated to be incorporated by reference herein and set forth in full herein. In the context of describing the present invention (especially in the context of the appended claims), unless otherwise specified herein or clearly inconsistent with the context, the use of the terms "a", "the", and similar objects shall be construed to cover the singular and plural. Unless otherwise specified, the terms "comprising", "having", "including", and "containing" shall be construed as open-ended terms (i.e., meaning "including, but not limited to,"). Unless otherwise specified herein, the recitation of numerical ranges herein is only intended as a shorthand method for individually indicating each separate value falling within the range, and each separate value is incorporated into this specification as if it had been individually recited herein. Unless otherwise specified herein or clearly inconsistent with the context, all methods described herein can be performed in any suitable order. Unless otherwise expressly specified, the use of any and all examples or exemplary language (e.g., "such as") provided herein is only intended to better illustrate the present invention and does not constitute a limitation on the scope of the claims. No language in the specification should be construed as indicating that any unclaimed element is essential to the practice of the subject matter of the present invention. Preferred specific examples of the invention described herein include the best mode known to the inventors for practicing the claimed subject matter. Variations of those preferred specific examples will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations appropriately, and the inventors intend for the claimed subject matter to be practiced otherwise than as specifically described herein. Accordingly, the invention includes all modifications and equivalents of the subject matter recited in the appended claims as permitted by applicable law. In addition, unless otherwise indicated herein or clearly contradicted by context, the claimed subject matter encompasses any combination of the above-described elements in all possible variations. There are a variety of methods available for selective deposition. Specific examples of the invention relate to a method of applying surface deactivation by taking advantage of the surface chemistry of two different surfaces. Since the two different surfaces will have different reactive handles, these differences can be exploited by using molecules that react with one surface (to deactivate that surface) and do not react with the other surface. In one specific example, there is provided a method for selectively passivating the surface of a substrate by a gas-phase reaction, wherein the surface of the substrate comprises at least a first surface comprising silicon nitride and at least a second surface comprising a material other than the silicon nitride, the method comprising the steps of: a. contacting the surface of the substrate with a wet chemical composition; b. rinsing the surface with deionized water; c. drying the surface; d. optionally, treating the surface with a hydrogen plasma, an argon plasma, or an ammonia plasma; and e. exposing the surface to at least one alcohol having a structure according to Formula I: R-OH (I), wherein R is selected from the group consisting of substituted or unsubstituted C 4 to C 18 linear alkyl, substituted or unsubstituted branched C 4 to C 18 alkyl, substituted or unsubstituted C 3 to C 8 cyclic alkyl, substituted or unsubstituted C 3 to C 10 heterocyclic group, substituted or unsubstituted C 3 to C 18 alkenyl, substituted or unsubstituted C 4 to C 18A group consisting of aryl, substituted or unsubstituted C 5 to C 20 aralkyl, and substituted or unsubstituted C 3 to C 10 alkynyl, and wherein the at least one alcohol selectively reacts with the silicon nitride to passivate the first surface, thereby leaving a substantially unreacted second surface. In another embodiment, there is provided a method for selectively passivating a surface of a substrate by a liquid-phase reaction, wherein the surface of the substrate comprises at least one first surface comprising silicon nitride and at least one second surface comprising a material other than the silicon nitride, the method comprising the steps of: a. contacting the surface of the substrate with a wet chemical composition; b. rinsing the surface with deionized water; c. drying the surface; d. optionally, treating the surface with a hydrogen plasma, an argon plasma or an ammonia plasma; and e. exposing the surface to at least one alcohol having a structure according to formula I: R-OH (I), wherein R is selected from substituted or unsubstituted C 4 to C 18 linear alkyl, substituted or unsubstituted branched C 4 to C 18 alkyl, substituted or unsubstituted C 3 to C 8 cyclic alkyl, substituted or unsubstituted C 3 to C 10 heterocyclic group, substituted or unsubstituted C 3 to C 18 alkenyl, substituted or unsubstituted C 4 to C 18 aryl, substituted or unsubstituted C 5 to C 20 aralkyl, and substituted or unsubstituted C 3 to C 10a group consisting of alkynyl groups, and wherein the at least one alcohol selectively reacts with the silicon nitride to passivate the first surface, thereby leaving a substantially unreacted second surface. In another embodiment, a method for selectively depositing a film on a surface of a substrate is provided, wherein the surface of the substrate comprises at least one first surface comprising silicon nitride and at least one second surface comprising a material other than the silicon nitride, the method comprising the steps of: a. contacting the surface of the substrate with a wet chemical composition; b. rinsing the surface with deionized water; c. drying the surface; d. optionally, treating the surface with a hydrogen plasma or an ammonia plasma; e. exposing the surface to at least one alcohol having a structure according to formula I: R-OH (I), wherein R is selected from the group consisting of substituted or unsubstituted C 4 to C 18 linear alkyl, substituted or unsubstituted branched C 4 to C 18 alkyl, substituted or unsubstituted C 3 to C 8 cyclic alkyl, substituted or unsubstituted C 3 to C 10 heterocyclic group, substituted or unsubstituted C 3 to C 18 alkenyl, substituted or unsubstituted C 4 to C 18 aryl, substituted or unsubstituted C 5 to C 20 aralkyl and substituted or unsubstituted C 3 to C 10 a group consisting of alkynyl groups, and wherein the at least one alcohol selectively reacts with the silicon nitride to passivate the first surface, thereby leaving a substantially unreacted second surface; and f. exposing the substrate to one or more deposition precursors to selectively deposit a film on the second surface prior to the first surface. As used in this specification and the appended claims, the terms "substrate" and "wafer" are used interchangeably and both refer to a surface or a portion of a surface on which a process is performed. Those skilled in the art should also understand that unless the context clearly indicates otherwise, a reference to a substrate may also refer only to a portion of the substrate. In addition, a reference to depositing on a substrate may mean the bare substrate and the substrate on which one or more films or features are deposited or formed thereon. As used herein, "substrate" refers to any substrate on which film processing is performed during the manufacturing process or the surface of a material formed on a substrate. For example, substrate surfaces on which processing can be performed include materials such as silicon, silicon oxide, strained silicon, silicon-on-insulator (SOI), carbon-doped silicon oxide, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire, etc. and any other materials such as metals, metal nitrides, metal alloys, and other conductive materials, depending on the application. Substrates include, but are not limited to, semiconductor wafers. The substrate can be exposed to a pre-treatment process to polish, etch, reduce, oxidize, hydroxylate, anneal, and / or bake the surface of the substrate. In addition to performing film processing directly on the surface of the substrate itself, in the present invention, any film processing step disclosed can also be performed on an underlying layer formed on the substrate, as disclosed in more detail below, and the term "substrate surface" is intended to include such an underlying layer as referred to in the context. Thus, for example, where a film / layer or a portion of a film / layer has been deposited on a substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate surface. What the specific substrate surface contains will depend on what film is to be deposited and the specific chemicals used. In one or more specific examples, the first substrate surface will contain a metal and the second substrate surface will contain a dielectric, or vice versa. In some specific examples, the substrate surface can contain certain functionalities (e.g., -OH, -NH, etc.). Similarly, a wide variety of film types can be used in the methods described herein. In some specific examples, the film can contain a metal or a metal nitride or consist essentially of a metal or a metal nitride. Examples of metal films include, but are not limited to, ruthenium (Ru), cobalt (Co), copper (Cu), titanium (Ti), tantalum (Ta), nickel (Ni), tungsten (W), molybdenum (Mo), etc. and combinations thereof. Examples of metal nitride films include, but are not limited to, tantalum nitride (TaN), titanium nitride (TiN), tungsten nitride (WN), tungsten carbonitride (WCN), molybdenum nitride (MoN), copper silicon nitride (CuSiN), etc. and combinations thereof. In a specific example of the present invention, the substrate has at least two discrete surfaces, wherein each discrete surface is characterized by a different chemical property. For example, in one specific example, the surface of the substrate includes at least one first surface containing silicon nitride and at least one second surface containing a material other than silicon nitride. The at least one second surface comprising a material other than silicon nitride can be, for example, selected from the group consisting of SiO 2 , metal oxides, copper, cobalt, tungsten, amorphous silicon, polycrystalline silicon, single crystal silicon, germanium, and amorphous hydrogenated germanium. In some embodiments, the at least one second surface comprising SiO 2 or carbon-doped silicon oxide is a dielectric surface, such as a SiO 2 surface. In some embodiments, the surface comprising SiO 2 may comprise silicon oxides, fluorosilicate glass (FSG), carbon-doped silicon oxide (SiOC), and / or a material containing more than about 50% silicon oxide. In some embodiments, the surface comprising SiO 2 contains -OH groups and may also contain, for example, aluminum oxide (Al 2 O 3 ) surface having -OH surface groups. Embodiments of the present invention provide a method for selectively depositing a film, such as, for example, a metal film, on a first surface of a substrate prior to a second surface of the substrate. As used in this specification and the appended claims, the phrase "selectively depositing a film on one surface prior to another surface" and the like means passivating one of the first or second surfaces to substantially prevent deposition on the passivated layer and depositing a film on the second (non-passivated) surface. The phrase "prior to" used in this context does not mean the physical orientation of one surface on top of another surface, but rather refers to the relationship of the thermodynamic or kinetic properties of a chemical reaction of one surface relative to another surface. For example, selectively depositing a cobalt film on a copper surface prior to a dielectric surface means that the cobalt film is deposited on the copper surface and less or no copper film is deposited on the dielectric surface; or forming a cobalt film on the copper surface is thermodynamically or kinetically favorable relative to forming a cobalt film on the dielectric surface. In certain cases, it is desired to selectively deposit a material on one surface of the same substrate prior to a second different surface of the substrate. For example, selective deposition can be used to form a capping layer, a barrier layer, an etch stop layer, a sacrificial layer, and / or a protective layer or to seal pores in a porous low-k material. The method of the present invention includes the optional step of contacting the surface of the substrate with a wet chemical composition. Exemplary wet chemical treatments include known chemical treatments such as, for example, RCA cleaning chemicals SC-1 and SC-2, aqueous HF solutions, peroxides, H 2 SO 4 / H 2 O 2 、NH 4 OH, HF buffer solutions and mixtures thereof. In a preferred embodiment, the wet chemical composition comprises at least one selected from the group consisting of: a composition comprising H 2 O 2 (28% aqueous solution), NH 4 O 4 (28 to 30%) and H 2 O; HF (0.01% to 5% (aqueous solution)); peroxide; RCA cleaning chemicals SC-1 and SC-2; and H 2 SO 4 / H 2 O 2 mixture. As is known in the art, "RCA cleaning chemicals" refers to a composition comprising a mixture of ammonium hydroxide and hydrogen peroxide, where the basic cleaning procedure was developed by the Radio Corporation of America in the 1960s. The RCA Standard-Clean-1 (SC-1) procedure uses an ammonium hydroxide and hydrogen peroxide solution and water heated to about 70°C. The SC-1 procedure dissolves the film and removes Group I and Group II metals. The Group I and Group II metals are removed by complexing with the reagents in the SC-1 solution. The RCA Standard-Clean-2 (SC-2) procedure uses a mixture of hydrogen peroxide, hydrochloric acid, and water heated to a temperature of about 70°C. The SC-2 procedure can remove metals not removed by the SC-1 procedure. Contact with the wet chemical composition can be carried out by any method known to those skilled in the art, for example, by dipping or spraying. The contacting step can be a discrete step or more than one step. In some specific examples, during the contacting step, the temperature of the wet chemical composition can be, for example, from about ambient temperature to about 100 °C. In other specific examples, during the contacting step, the temperature of the wet chemical composition can be, for example, from about 55 °C to about 95 °C. In other specific examples, during the contacting step, the temperature of the wet chemical composition can be, for example, from about 60 °C to about 90 °C. Specific examples also include the step of rinsing the surface of the substrate with deionized water after the step of contacting the surface of the substrate with the wet chemical composition. The rinsing step is generally carried out by any suitable means, for example, rinsing the surface of the substrate with deionized water by dipping or spraying techniques. Specific examples also include the step of drying at least the surface of the substrate after the rinsing step. The drying step is generally carried out by any suitable means, for example, applying heat, drying with isopropyl alcohol (IPA) vapor or by centripetal force. Specific examples also optionally include the step of treating the surface with a hydrogen plasma, an argon plasma or an ammonia plasma. Suitable processes include plasma processes (hydrogen plasma, NH 3 / NF 3 plasma and water plasma, etc.). The optional plasma step serves to remove unwanted deposits on the surface and to activate the surface for subsequent deposition of a passivating agent. This plasma treatment can preferably be carried out after some deposition has already been carried out on the surface in order to remove non-selectively deposited material from a previously passivated surface and to remove residual passivating agents after the desired deposition thickness has been achieved. Specific examples include the step of exposing the surface to a vapor or liquid comprising at least one alcohol having a structure according to formula I: R-OH (I), wherein R is selected from substituted or unsubstituted C 1 to C 18 linear alkyl, substituted or unsubstituted branched C 3 to C 18 alkyl, substituted or unsubstituted C 3 to C 8 cyclic alkyl, substituted or unsubstituted C 3 to C 10 heterocyclic group, substituted or unsubstituted C 3 to C 18 Alkenyl, substituted or unsubstituted C 4 to C 18 Aryl, substituted or unsubstituted C 5 to C 20 Aralkyl and substituted or unsubstituted C 3 to C 10 The group consisting of alkynyl, wherein the at least one alcohol selectively reacts with the silicon nitride to passivate the first surface, thereby leaving a substantially unreacted second surface. This new series of passivating chemicals can be used to achieve selective passivation of silicon nitride (SiN) relative to silicon oxide (SiO 2 ) This new series of passivating chemicals shows better selective adsorption of silicon nitride (SiN) relative to silicon oxide (SiO 2 ) than the most advanced passivating chemicals reported. This new series of passivating chemicals shows better Ru deposition selectivity at 225 °C. This new series of passivation layers on the silicon nitride surface shows good thermal stability at temperatures up to 250 °C and even higher. This new passivation method has great potential for high-temperature ASD applications. In some embodiments, the alcohol is a C having a structure selected from the group consisting of C n H 2n+1 linear alkyl. Preferred alcohol precursors having C 4 to C 18 linear alkyl include those selected from the group consisting of 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, and 1-dodecanol. 4 to C 18 Preferred alcohol precursors having branched alkyl include those selected from the group consisting of isobutanol and tert-butanol. In other embodiments, R in formula I is C 3 to C 18 branched alkyl. Preferred alcohol precursors having branched alkyl include those selected from the group consisting of isobutanol and tert-butanol. In other specific examples, R in formula I is a substituted or unsubstituted C 3 to C 8 cyclic alkyl. In this specific example, the at least one alcohol includes those selected from the group consisting of cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, and 1-methylcyclohexanol. In other specific examples, R in formula I is a substituted or unsubstituted C 4 to C 18 aryl. In other specific examples, R in formula I is an unsubstituted C 1 to C 18 linear alkyl or R is a substituted or unsubstituted branched C 3 to C 18 alkyl. In another specific example, R in formula I is a substituted or unsubstituted C 54 to C 20 aralkyl. In this specific example, the alcohol includes benzyl alcohol. As used throughout this specification, the term "alkyl" means a straight-chain or branched saturated hydrocarbon group. In some specific examples, the alkyl has 1 to 20 carbon atoms, 2 to 20 carbon atoms, 1 to 10 carbon atoms, 2 to 10 carbon atoms, 1 to 8 carbon atoms, 2 to 8 carbon atoms, 1 to 6 carbon atoms, 2 to 6 carbon atoms, 1 to 4 carbon atoms, 2 to 4 carbon atoms, 1 to 3 carbon atoms, or 2 or 3 carbon atoms. Examples of alkyl include, but are not limited to, methyl (Me), ethyl (Et), propyl (e.g., n-propyl and isopropyl), butyl (e.g., n-butyl, tert-butyl, isobutyl), pentyl (e.g., n-pentyl, isopentyl, neopentyl), hexyl, isohexyl, heptyl, octyl, nonyl, 4,4-dimethylpentyl, 2,2,4-trimethylpentyl, decyl, undecyl, dodecyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl, 2-methyl-1-pentyl, 2,2-dimethyl-1-propyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, and 2-ethyl-1-butyl, etc. As used throughout this specification, the term "cycloalkyl" denotes a cyclic functional group having 3 to 10 or 4 to 10 carbon atoms. Exemplary cycloalkyls include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. As used herein, the term "aryl" means a monocyclic, bicyclic or polycyclic (e.g., having 2, 3 or 4 fused rings) aromatic hydrocarbon. In some embodiments, the aryl has 6 to 20 or 6 to 10 carbon atoms. Examples of aryls include, but are not limited to, phenyl, naphthyl, anthracenyl, phenanthryl, indanyl, indenyl, and tetrahydronaphthyl, etc. As used herein, the term "arylalkyl" means an alkyl substituted by an aryl. In some embodiments, the alkyl is C 1-6 alkyl. As used throughout the specification, the term "alkenyl" denotes a group having one or more carbon-carbon double bonds and having 2 to 18 or 2 to 10 carbon atoms. Exemplary alkenyls include, but are not limited to, vinyl or allyl. As used herein, the term "alkynyl" means a straight or branched alkyl having 2 to 20 carbon atoms and one or more carbon-carbon triple bonds. In some embodiments, the alkynyl has 2 to 10 carbon atoms, 2 to 8 carbon atoms, 2 to 6 carbon atoms or 2 to 4 carbon atoms. Examples of alkynyls include, but are not limited to, acetylene, 1-propyne, and 2-propyne, etc. As used herein, the phrase "optionally substituted" means that the substitution is optional and includes both unsubstituted and substituted atoms and moieties. A "substituted" atom or moiety means that any hydrogen atom on a specified compound or moiety can be replaced by a substituent designated herein, provided that the normal valency of the specified compound or moiety is not exceeded and the substitution results in a stable compound. For example, if a methyl group is optionally substituted, then 1, 2 or 3 hydrogen atoms on the carbon atom within the methyl group can be replaced by 1, 2 or 3 of the said substituents. As used herein, the term "phenyl" means -C 6 H 5 . The phenyl may be unsubstituted or substituted with one, two or three suitable substituents. As used herein, the term "cycloalkyl" means a non-aromatic cyclic hydrocarbon, including cyclized alkyl, alkenyl, and alkynyl having up to 20 ring-forming carbon atoms. The cycloalkyl has 3 to 15 ring-forming carbon atoms, 3 to 10 ring-forming carbon atoms, 3 to 8 ring-forming carbon atoms, 3 to 6 ring-forming carbon atoms, 4 to 6 ring-forming carbon atoms, 3 to 5 ring-forming carbon atoms, or 5 or 6 ring-forming carbon atoms. The ring-forming carbon atoms of the cycloalkyl may optionally be substituted with oxo or sulfido groups. The cycloalkyl includes, but is not limited to, monocyclic or polycyclic ring systems such as fused ring systems, bridged ring systems, and spiro ring systems. In some embodiments, the polycyclic ring system includes 2, 3, or 4 fused rings. Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclopentenyl, cyclohexenyl, cyclohexadienyl, cycloheptatrienyl, norbornyl, norpinyl, norcarnyl, and adamantyl, etc. The cycloalkyl may also have one or more aromatic rings fused (sharing a common bond) to the cycloalkyl ring, such as, for example, benzo- or thienyl derivatives of pentane, pentene, and hexane, etc. (e.g., 2,3-dihydro-1H-inden-1-yl or 1H-inden-2(3H)-one-1-yl). As used herein, the term "halo" means a halogen group and includes, but is not limited to, fluoro, chloro, bromo, and iodo groups. As used herein, the term "heterocyclic" or "heterocyclic ring" means a ring system of 5- to 7-membered monocyclic or 7- to 10-membered bicyclic rings, any of which rings may be saturated or unsaturated, and the ring is composed of carbon atoms and one to three heteroatoms selected from N, O, and S, and wherein the N and S heteroatoms may be oxidized as required, and the N heteroatom may be quaternized as required, and includes any bicyclic group, wherein any of the heterocyclic rings defined above is fused to a benzene ring. Heterocycles include rings containing one oxygen or sulfur, one to three nitrogen atoms, or one oxygen or sulfur in combination with one or two nitrogen atoms. The heterocyclic ring may be attached to any heteroatom or carbon atom to produce a stable structure. Examples of heterocyclic groups include, but are not limited to, hexahydropyridyl, hexahydropyrazinyl, 2-oxahexahydropyrazinyl, 2-oxahexahydropyridyl, 2-oxapyrrolidinyl, 2-oxaazepinyl, azepinyl, pyrrolyl, 4-hexahydropyridone, pyrrolidinyl, pyrazolyl, pyrazolidinyl, imidazolyl, imidazolinyl, pyridyl, imidazolidinyl, pyrazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolidinyl, isoxazolyl, isoxazolidinyl, morpholinyl, thiazolyl, thiazolidinyl, isothiazolyl, quinuclidinyl, isothiazolidinyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, thiadiazolyl, benzopyranyl, benzothiazolyl, benzoxazolyl, furyl, tetrahydrofuryl, tetrahydropyranyl, thienyl, benzothienyl, thioxanyl, thioxane sulfoxide, thioxane sulfone, and oxadiazolyl, etc. Vapor-phase or gas-phase reactions involve exposing a heated substrate to precursor molecules and / or co-reactants in a suitable chamber, which chamber must be able to provide the necessary pressure control and also supply heat to the substrate and / or chamber walls; the chamber should also provide the appropriate purity for the reaction to occur, typically through high leak integrity and the use of ultra-high purity carrier gases and reactive gases. As used in this specification and the appended claims, terms such as "reactive gas", "precursor", and "reactant" are used interchangeably and mean a gas including species that are reactive with the substrate surface. For example, a first "reactive gas" may simply adsorb onto the surface of the substrate and be used for further chemical reactions with a second reactive gas. It may be used in combination with an ultra-high purity carrier gas (as defined above) and in any desired mixture with each other (i.e., more than one type of precursor may be used together or in discrete, separate steps using any desired order of precursor introduction to form the desired passivation layer). The precursor and / or co-reactant can be introduced using a mass flow controller (possibly with a heated line), a liquid injection vaporizer (possibly with a heated line), or without a metering device (i.e., simply introducing vapor and / or gas from a container isolated from the reactor by a simple valve). Any of the foregoing can also be used in combination with each other. Any device that can supply gas and / or vapor to the reaction chamber with sufficient purity and reproducibility can be used. The precursor and / or co-reactant can be introduced into the reactor independently in multiple independent steps, mixed before introduction into the reactor, mixed in the reactor, or any combination of the foregoing, and there may be differences in how the precursor is introduced between these steps. The temperature range of the reaction can be between room temperature and 400 °C. In some cases, the temperature range of the reaction can be between room temperature and 200 °C. In still other cases, the temperature range of the reaction can be between room temperature and 100 °C. The pressure can be between 10 -10 torr and 3000 torr and can be maintained under dynamic flow conditions (i.e., with valves and butterfly valve arrangements) or can be maintained under static conditions (i.e., evacuating the chamber and exposing it to the desired precursor / or co-reactant until the desired total pressure is reached, then isolating the chamber from the precursor and / or co-reactant source and the vacuum pump). The reactor can be completely evacuated and re-exposed to fresh precursor and / or co-reactant as needed multiple times. The precursor and / or co-reactant can be introduced using any desired mixture and / or concentration. The exposure of the surface can be carried out for 0.1 to 60 minutes, preferably 1 to 5 minutes, and optimally 1 minute. The partial pressure of the alcohol in the reaction chamber can vary from about 1% of its saturated vapor pressure at the substrate temperature to almost 100% of its saturated vapor pressure. Optimally, it will be between 20% and 50% of its saturated vapor pressure. The chamber pressure can be the same as the partial pressure of the alcohol vapor, but it can also be higher, with the remainder being an atmosphere containing a carrier gas. Preferred carrier gases include N 2 、He and Ar, but other gases such as H 2 、CO 2 and dry O 2 . During all or part of the exposure period, the exposure vapor can be static (non-flowing). A preferred specific example is to flow the vapor of the alcohol together with the carrier gas as needed through the exposure chamber such that fresh vapor is exposed to the surface of the substrate during at least a portion of the exposure period. The exposure chamber can be maintained at near ambient temperature or heated as desired. Heat can be supplied to the outer wall of the chamber (hot wall) or only to the substrate (cold wall reactor). Heating of the substrate in the cold wall reactor can be achieved by applying incident radiation through the transparent window (lamp heating), by resistive heating of the substrate itself or by resistive heating elements in the platform in contact with the substrate, by induction or by other means known in the art. The temperature of the treatment is preferably from about 20 °C to about 400 °C, more preferably between 20 °C and about 200 °C, and most preferably between 20 °C and about 100 °C. The temperature can be kept constant during the exposure period or can vary within a specified temperature range. The unreacted vapors of the at least one alcohol can then be removed, if desired, by evacuating or purging the chamber with a suitable inert gas before removing the substrate from the chamber or before a chemical vapor or atomic layer deposition process. Optionally, the exposure chamber can also be used for subsequent processing steps to improve process efficiency such that the process can repeat the process from step c), if necessary, to strip the protective film and any non-selective ALD deposits and then reform a protective film. The selection of the at least one alcohol and the exposure conditions used in the method should be optimized by standard experimental methods to optimize the selectivity to protect the silicon nitride surface from potential non-selective passivation, the processing time, the reagent cost, etc., depending on the requirements of the subsequent processing steps. For example, the selectivity can be adjusted / optimized by changing the nature of the R group of the at least one alcohol having the structure shown in formula I. Generally, since reactivity and selectivity are often inversely related, if the chemical properties of the two surfaces are similar, it may be necessary to experiment with the R group to optimize the process. The reactivities are different, for example between an alkyl R group and an aryl R group; generally, an aryl is more reactive with a surface bearing active hydrogen than an alkyl. As a result, in some cases an alkyl may be required to selectively passivate the silicon nitride without simultaneously passivating adjacent surfaces that also have less reactive active hydrogen atoms. Once the silicon nitride surface is passivated, a second surface containing, for example, silicon oxide is rendered active for further selective reactions such as, for example, selective ALD deposition of SiCN on the Si-H surface. Additional materials that can be selectively deposited on the second surface include silicon films containing oxygen, nitrogen, hydrogen and carbon (i.e., SiO x 、SiN x 、SiO x N y 、SiC x N y 、SiO x C y , which may also incorporate H), metals, metal nitrides, and metal oxides. In some specific examples, a dielectric film including a metal oxide or silicon oxide is selectively deposited on the second surface. In one example, the dielectric film can be used as a covering layer on the second surface. The metal oxide film can be deposited, for example, by atomic layer deposition (ALD), plasma-enhanced ALD (PEALD), chemical vapor deposition (CVD), plasma-enhanced CVD (PECVD), or pulsed CVD. According to a specific example, the dielectric film can be selected from the group consisting of HfO 2 , ZrO 2 , TiO 2 , Ta 2 O 5 , Al 2 O 3 , SiO 2 and combinations thereof. In some examples, the metal oxide film can be deposited by ALD using alternating exposures of a volatile metal-containing precursor and an oxidizing agent (e.g., H 2 O, H 2 O 2 , plasma-excited O 2 or O 3 ), as described in detail in U.S. Provisional Patent Application Serial No. 62 / 472,724, filed on March 17, 2017, which is hereby incorporated by reference in its entirety. In other examples, the dielectric film can be deposited by ALD using alternating exposures of a volatile metal-containing precursor catalyst and trialkoxysilanol. Selective deposition according to the present invention can be, for example, metal and metal oxide layers disclosed by Hamalainen et al. in "Atomic Layer Deposition of Noble Metals and Their Oxides," Chem. Mater. 2014, 26, 786 - 801; and Johnson et al. in "A Brief review of Atomic layer Deposition: From Fundamentals to Applications", Materials Today, Volume 17, Number 5, June 2014, both of which are incorporated herein by reference in their entirety. In some specific examples, a metal film or a metal nitride is selectively deposited on the second surface. In one example, the metal film can serve as a covering, a seed, or a diffusion barrier layer on the second surface. In another example, the metal film can be used as a conductive path (i.e., a wire, a pad, or a plunger) on the second surface. In another example, the metal film can be deposited, for example, by atomic layer deposition (ALD), plasma-enhanced ALD (PEALD), chemical vapor deposition (CVD), plasma-enhanced CVD (PECVD), or pulsed CVD using volatile metal precursors. According to a specific example, the metal film can be selected from the group consisting of Ru, Al, Ti, Ta, Mo, Co, Rh, Ir, Fe, Ru, Os, Mo, Mn, Tc, Re, Cu, Ag, Au, Ni, Pd, Pt, and combinations thereof. The metal nitride can be selected from the group consisting of TiN, TiCN, TaN, TaCN, WN, MoN, WCN, and MoCN. In some examples, the metal nitride film can be deposited by ALD via alternating exposure of a volatile metal precursor and a nitrogen source. The metal precursor should have sufficient vapor pressure and be stable enough to be delivered to the reaction chamber, and can have the formula M(L 1 ) x (L 2 ) y (L 3 ) z , where L 1 , L 2 and L 3are independently selected from the group consisting of a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted imidazolyl group, an amide group, an alkoxy group, an amidino group, a linear or branched diene, a linear or branched alkyl group, a hydrogen group, carbon monoxide, a nitroso group, a halogen group (F, Cl, Br, I), and combinations thereof; x, y, and z are 0, 1, 2, 3, 4, depending on the oxidation state of the metal. Examples of the metal-containing precursor include, but are not limited to, tetra(dimethylamino)hafnium (TDMAH), tetra(diethylamino)hafnium (TDEAH), tetra(ethylmethylamino)hafnium (TEMAH), cyclopentadienyltris(dimethylamino)hafnium (CpHf(NMe 2 )) 3 ), methylcyclopentadienyltris(dimethylamino)hafnium (MeCpHf(NMe 2 )) 3 ), ethylcyclopentadienyltris(dimethylamino)hafnium (EtCpHf(NMe 2 )) 3 ), cyclopentadienyltris(dimethylamino)hafnium (CpHf(NMeEt) 3 ), methylcyclopentadienyltris(dimethylamino)hafnium (MeCpHf(NMeEt) 3 ), tetra(dimethylamino)zirconium (TDMAZ), tetra(diethylamino)zirconium (TDEAZ), tetra(ethylmethylamino)zirconium (TEMAZ), cyclopentadienyltris(dimethylamino)zirconium (CpZr(NMe 2 )) 3 ), methylcyclopentadienyltris(dimethylamino)zirconium (MeCpZr(NMe 2 )) 3 ), ethylcyclopentadienyltris(dimethylamino)zirconium (EtCpZr(NMe 2 )) 3 ), cyclopentadienyltris(dimethylamino)zirconium (CpZr(NMeEt) 3 ), methylcyclopentadienyltris(dimethylamino)zirconium (MeCpZr(NMeEt) 3 ) Third butylimido tris(diethylamino)tantalum (TBTDET), third butylimido tris(dimethylamino)tantalum (TBTDMT), third butylimido tris(ethylmethylamino)tantalum (TBTEMT), ethylimido tris(diethylamino)tantalum (EITDET), ethylimido tris(dimethylamino)tantalum (EITDMT), ethylimido tris(ethylmethylamino)tantalum (EITEMT), third pentylimido tris(dimethylamino)tantalum (TAIMAT), third pentylimido tris(diethylamino)tantalum, penta(dimethylamino)tantalum, third pentyl tris(ethylmethylamino)tantalum, bis(third butylimido)bis(dimethylamino)molybdenum (BTBMM), bis(third butylimido)bis(diethylamino)molybdenum, bis(third butylimido)bis(ethylmethylamino)molybdenum, Mo(CO) 6 CpMo(CO) 2 (NO), MeCpMo(CO) 2 (NO), EtCpMo(CO) 2 (NO), Cp 2 MoH 2 (MeCp) 2 MoH 2 Bis(third butylimido)bis(dimethylamino)tungsten (BTBMW), bis(third butylimido)bis(diethylamino)tungsten, bis(third butylimido)bis(ethylmethylamino)tungsten, W(CO) 6 CpW(CO) 2 (NO), MeCpW(CO) 2 (NO), EtCpW(CO) 2 (NO), Cp 2 WH 2 (MeCp) 2 WH 2 Hexacarbonyl third butylacetylene dicobalt (CCTBA), CpCo(CO) 2, (dimethylbutadiene)(CO) 3 Cobalt, allyl cobalt tricarbonyl, Ru(EtCp) 2 , Ru(EtCp)(2,4 - dimethylpentadienyl), bis((2,4 - dimethylpentadienyl)ruthenium, (cyclohexadiene)(CO) 3 Ruthenium, (dimethylbutadiene)(CO) 3 Ruthenium, (diazabutadiene) 2 Ruthenium, [Ru 2 (CO) 6 (3,5 - t - Bu2pz) 2 and Ru 3 (CO) 12 . In some specific examples, a metal or metal nitride film is selectively deposited on the second surface. In one example, the metal or metal nitride film can be used as a covering layer on the second surface. In another example, the metal or metal nitride film can be used as a diffusion barrier layer. The metal or metal nitride film can be deposited, for example, by atomic layer deposition (ALD), plasma enhanced ALD (PEALD), chemical vapor deposition (CVD), plasma enhanced CVD (PECVD) or pulsed CVD. Examples can be seen, for example, in “IBM Research Report, “Atomic Layer Deposition of Metal and Metal Nitride Thin Films: Current Research Efforts and Applications for Semiconductor Device Processing,” RC22737 (W0303 - 012), March 5, 2003. During the selective deposition process, the aforementioned protective surface that was previously selectively deposited with at least one alcohol on the silicon nitride surface may start to react or otherwise become less inert. The optional re - application of the at least one alcohol can be repeated as needed, with or without any aqueous or plasma pretreatment steps, to prevent or delay non - selective deposition on the silicon nitride surface. In some specific examples of passivation on the first surface of the substrate described herein, such a silicon nitride surface of the substrate has a selectivity of at least about 90%, at least about 95%, at least about 96%, 97%, 98% or 99% or higher with respect to the second surface of the substrate. In some specific examples, passivation occurs only on the first surface and not on the second surface. In some specific examples, the passivation on the first surface of the substrate has a selectivity of at least about 70% or at least about 80% with respect to the second surface of the substrate, which may be sufficient selectivity for some specific applications. In some specific examples, the passivation on the first surface of the substrate has a selectivity of at least about 50% with respect to the second surface of the substrate, which may be sufficient selectivity for some specific applications. Wet chemical cleaners can be used to remove the passivation layer. Exemplary wet chemical cleaners include acidic, basic, and oxidizing (e.g., peroxide-containing) wet chemical compositions known in the art and described above in the optional step of contacting the substrate with a wet chemical composition. Another method of removing the passivation layer is via the application of heat or other energy. Examples Demonstrative specific examples show that alcohols (alkyl alcohols or aryl alcohols) selectively passivate the silicon nitride surface with respect to the silicon oxide surface. This process is depicted in FIG. 1. This process results in the selective growth of a thicker metal film (or metal nitride film) on SiO 2 or carbon-doped silicon oxide. Substrate 100 includes a first surface 102 (silicon nitride) and a second surface 104 (silicon oxide). The substrate is exposed to an alkyl alcohol or aryl alcohol inhibitor to form a passivated region 106, preferably a self-assembled monolayer (SAM), to selectively passivate the silicon nitride surface 102 by converting the Si-NH 2 groups to aliphatic or aromatic groups. Thereafter, a metal film 108 is deposited on the second surface 104. Metal on dielectric (MoD) The substrate contains two different surfaces, silicon oxide and silicon nitride. The substrate is exposed to an inhibitor to selectively passivate the silicon nitride surface by adding aliphatic or aromatic groups on the silicon nitride surface. Specific example: (1) Wet process: The silicon nitride substrate is pre-cleaned with 1% HF at room temperature for 5 minutes. The Si is rinsed with DI water 3 N 4 by N 2The stream dries the silicon nitride substrate. The silicon nitride substrate is immersed in an inhibitor solution (5% toluene solution) at 60 °C for 18 hours. The silicon nitride substrate is rinsed with MeOH. By N 2 The stream dries the silicon nitride substrate. (2) Vapor process: The silicon nitride substrate is pre-cleaned with 1% HF at room temperature for 5 minutes. The Si is rinsed with DI water 3 N 4 . The silicon nitride substrate is loaded into the reactor. Ar plasma (150 W) bombards the silicon nitride substrate at 150 °C for 5 minutes. The silicon nitride substrate is exposed to concentrated inhibitor vapor at 70 °C for 18 hours. By performing [Ru 2 (CO) 6 (3,5-t-Bu 2 pz) 2 / H 2 ALD process, selectively deposit ruthenium film on the silica surface. Specific examples: After the substrate is treated with inhibitors (1-octanol, 2-octanol, 8-chloro-1-octanol, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-octanol, phenol, 1-methylcyclohexanol), ruthenium film selectively grows on silicon nitride (Si 3 N 4 ) and silica (SiO 2 ) substrates. For the purposes of the present invention and the claims, the selectivity of the second surface to the first surface is calculated by the following equation: Selectivity = (film thickness on the second surface (SiO 2 ) - film thickness on the first surface (Si 3 N 4 )) / (film thickness on the second surface (SiO 2 ) + film thickness on the first surface (Si 3 N 4 ). The thickness of the ruthenium film grown on inhibitor-treated silicon nitride is thinner than that on fresh silicon nitride. Conversely, the thickness of the ruthenium film grown on all silicon oxides is similar. These results show the effect of selective passivation (silicon nitride relative to silicon oxide). This selectivity is calculated by the following formula: (ruthenium on silicon oxide (Å) – ruthenium on silicon nitride (Å)) / (ruthenium on silicon oxide (Å) + ruthenium on silicon nitride (Å)). Table 1 Figure 2 illustrates deposition data related to metal film deposition after passivation with different inhibitors. Figure 3 illustrates selectivity data related to metal film deposition after passivation with different types of alcohol inhibitors. Figure 4 illustrates data on the selective deposition of ruthenium using 1-octanol by a vapor phase process. The successful selective deposition of ruthenium films (preferably greater than about 0.1, more preferably greater than about 0.2, most preferably greater than about 0.3) was achieved using the following various primary alcohols: 1-octanol, 8-chloro-1-octanol, and 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-octanol (C 7 F 15 CH 2 -OH). The successful selective deposition of ruthenium films was achieved using secondary alcohols such as 2-octanol. The successful selective deposition of ruthenium films was achieved using tertiary alcohol: 1-methylcyclohexanol. The successful selective deposition of ruthenium films was achieved using aryl alcohols such as phenol. Linear primary alkyl alcohols having more than 8 carbon atoms demonstrated better selectivity than secondary and tertiary alcohols, meaning that linear primary alkyl alcohols may be more suitable for protecting silicon nitride. Importantly, the aryl alcohol achieved better selectivity. Although the principles of the present invention have been described above in connection with preferred specific examples, it should be clearly understood that this description is by way of example only and should not be regarded as limiting the scope of the claimed subject matter. 100: Substrate 102: First surface 104: Second surface 106: Passivated region 108: Metal film The accompanying drawings, which are included to provide a further understanding of the disclosed subject matter and are incorporated into and form a part of this specification, illustrate specific examples of the disclosed subject matter and, together with the description, serve to explain the principles of the disclosed subject matter. In the drawings: Figure 1 illustrates a process for passivating a silicon nitride surface and depositing a film on a silicon dioxide surface; Figure 2 illustrates deposition data related to metal film deposition after passivation with different inhibitors; FIG. 3 illustrates selective data related to metal film deposition after passivation with different types of alcohol inhibitors; and FIG. 4 illustrates data for the selective deposition of ruthenium using 1-octanol by a vapor phase process. 100: Substrate 102: First surface 104: Second surface 106: Passivated region 108: Metal film

Claims

1. A method for selectively passivating the surface of a substrate, wherein the surface of the substrate comprises at least one first surface comprising silicon nitride and at least one second surface comprising a material other than silicon nitride, the method comprising the steps of: a., if necessary, treating the surface with a plasma, wherein the plasma is a hydrogen plasma, an argon plasma, or an ammonia plasma; b. exposing the surface to at least one alcohol having a structure according to Formula I: R-OH(I), The R group is selected from the group consisting of substituted or unsubstituted C4 to C18 linear alkyl groups, substituted or unsubstituted branched C4 to C18 alkyl groups, substituted or unsubstituted C4 to C8 cyclic alkyl groups, substituted or unsubstituted C3 to C10 heterocyclic groups, substituted or unsubstituted C4 to C18 alkenyl groups, substituted or unsubstituted C4 to C18 aryl groups, substituted or unsubstituted C5 to C20 aralkyl groups, and substituted or unsubstituted C4 to C10 alkynyl groups, and wherein the at least one alcohol selectively reacts with the silicon nitride to passivate the first surface, thereby leaving a substantially unreacted second surface; and c. depositing a metal film or a metal nitride film on the substrate via atomic layer deposition.

2. The method of claim 1, further comprising the following steps performed prior to steps a and b: contacting the surface of the substrate with a wet chemical composition; rinsing the surface with deionized water; and drying the surface; wherein the wet chemical composition comprises at least one selected from the group consisting of: a composition containing HF; and a composition containing peroxide.

3. The method of claim 2, wherein the wet chemical composition comprises: a composition comprising H2O2, NH4O4 and H2O; an aqueous solution of 0.01 vol% to 5 vol% HF; RCA cleaning chemicals SC-1 and SC-2; or a mixture of H2SO4 / H2O2.

4. The method of claim 1, wherein the second surface comprises at least one selected from the group consisting of SiO2, carbon-doped silicon oxide, metal oxide, copper, cobalt, tungsten, amorphous silicon, polycrystalline silicon, monocrystalline silicon, germanium, and amorphous germanium hydride.

5. The method of claim 4, wherein the second surface comprises SiO2.

6. The method of claim 1, wherein the at least one alcohol is a C4 to C18 linear alkyl group having the structure CnH2n+1, wherein n is 4 to 18.

7. The method of claim 6, wherein the at least one alcohol is a linear C8 to C18 alcohol selected from the group consisting of 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tetanetanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-heptadecanol, 1-octadecanol, 8-chloro-1-octanol and pentafluoro-1-octanol.

8. The method of claim 1, wherein the R group has a branch of C4 to C18 alkyl of the formula CnH2n+1, wherein the n group is 4 to 18.

9. The method of claim 8, wherein the at least one alcohol is selected from the group consisting of isobutanol, isopentanol, isohexanol, isohepanol, isooctanol, isononanol, isodecanol, isoundecanol, isoundecanol, isodedecanol, isotetradecanol, isopentadecanol, isohexadecanol, isohexadecanol, isohexadecanol, isohexadecanol, and isohexadecanol.

10. The method of claim 1, wherein R is a substituted or unsubstituted C3 to C8 cyclic alkyl group.

11. The method of claim 10, wherein the at least one alcohol is selected from the group consisting of cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol and 1-methylcyclohexanol.

12. The method of claim 1, wherein R comprises substituted or unsubstituted C4 to C18 aryl groups.

13. The method of claim 12, wherein the at least one alcohol is selected from the group consisting of phenol, p-cresol, 4-methylphenol, 4-fluorophenol, 4-octylphenol, 4-pentylphenol, and 4-hexylphenol.

14. The method of claim 1, wherein R is an unsubstituted C8 to C18 linear alkyl group or R is a substituted or unsubstituted branched C3 to C18 alkyl group.

15. The method of claim 14, wherein the at least one alcohol is selected from the group consisting of 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 8-chloro-1-octanol, pentafluoro-1-octanol, isobutanol, isoamyl alcohol, isohexanol, isohexanol, isooctanol, isononanol, isodecanol, isoundecanol, isoundecanol, isotridecanol, isotetradecanol, isopentadecanol, isohexadecanol, isohexadecanol, and isohexadecanol.

16. The method of claim 1, wherein R is a substituted or unsubstituted C5 to C20 aralkyl group.

17. The method of claim 16, wherein the at least one alcohol is benzyl alcohol.

18. The method of claim 1, wherein step b. is carried out using the vapor of the at least one alcohol.

19. A method for selectively depositing a film on the surface of a substrate, wherein the surface of the substrate comprises at least a first surface comprising silicon nitride and at least a second surface comprising a material other than silicon nitride, the method comprising the steps of: a., if necessary, treating the surface with a plasma, wherein the plasma is a hydrogen plasma or an ammonia plasma; b. exposing the surface to at least one alcohol having a structure according to Formula I: R-OH(I), The R group is selected from the group consisting of substituted or unsubstituted C4 to C18 linear alkyl groups, substituted or unsubstituted branched C4 to C18 alkyl groups, substituted or unsubstituted C3 to C8 cyclic alkyl groups, substituted or unsubstituted C3 to C10 heterocyclic groups, substituted or unsubstituted C3 to C18 alkenyl groups, substituted or unsubstituted C4 to C18 aryl groups, substituted or unsubstituted C5 to C20 aralkyl groups, and substituted or unsubstituted C3 to C10 alkynyl groups, wherein the at least one alcohol selectively reacts with the silicon nitride to passivate the first surface, thereby leaving a substantially unreacted second surface; and c. exposing the surface of the substrate to one or more deposition precursors to selectively deposit a metal film on the second surface prior to the first surface.

20. The method of claim 19, further comprising the following steps performed prior to steps a, b, and c: contacting the surface of the substrate with a wet chemical composition; rinsing the surface with deionized water; and drying the surface; wherein the wet chemical composition comprises at least one selected from the group consisting of: a composition containing HF; and a composition containing peroxide.

21. The method of claim 20, wherein the wet chemical composition comprises: a composition comprising H2O2, NH4O4 and H2O; an aqueous solution of 0.01 vol% to 5 vol% HF; RCA cleaning chemicals SC-1 and SC-2; or a mixture of H2SO4 / H2O2.

22. The method of claim 19, wherein the second surface comprises at least one selected from the group consisting of SiO2, carbon-doped silicon oxide, metal oxide, copper, cobalt, ruthenium, tungsten, molybdenum, amorphous silicon, polycrystalline silicon, monocrystalline silicon, germanium, and amorphous germanium hydride.

23. The method of claim 22, wherein the second surface comprises SiO2.

24. The method of claim 19, wherein the at least one alcohol is a C8 to C18 linear alkyl group having the structure CnH2n+1-OH, wherein n is 8 to 18.

25. The method of claim 24, wherein the at least one alcohol is selected from the group consisting of 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tetanetanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-heptadecanol, 1-octadecanol, 8-chloro-1-octanol and pentafluoro-1-octanol.

26. The method of claim 19, wherein the metal film comprises a metal or a metal nitride; and wherein the metal is selected from the group consisting of Ru, Al, Ti, Ta, Mo, Co, Rh, Ir, Fe, Ru, Os, Mo, Mn, Tc, Re, Cu, Ag, Au, Ni, Pd, Pt and combinations thereof; or wherein the metal nitride is selected from the group consisting of tantalum nitride, titanium nitride, tungsten nitride, tungsten carbonitride, molybdenum nitride, copper silicon nitride and combinations thereof.

27. The method of claim 19, wherein R is a substituted or unsubstituted C3 to C8 cyclic alkyl group.

28. The method of claim 27, wherein the at least one alcohol is selected from the group consisting of cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, 1-methylcyclohexanol, o-methylcyclohexanol, m-methylcyclohexanol and p-methylcyclohexanol.

29. The method of claim 19, wherein R is a substituted or unsubstituted C4 to C18 aryl group.

30. The method of claim 29, wherein the at least one alcohol is selected from the group consisting of phenol, toluene, dimethylphenol and xylene alcohol.

31. The method of claim 19, wherein R is an unsubstituted C4 to C18 linear alkyl group or a substituted or unsubstituted branched C3 to C18 alkyl group.

32. The method of claim 31, wherein the at least one alcohol is selected from the group consisting of trihexanol, n-heptanol, diheptanol, diheptanol, n-octanol, dioctanol, dioctanol, n-nonanol, dinonanol, dinonanol, n-decanol, didecanol, didecanol, n-undecanol, diundecanol, n-dodecanol, diundecanol, diundecanol, n-trigecanol, diundecanol, diundecanol, n-trigecanol, diundecanol, n-tetradecanol, diundecanol, diundecanol, n-tetradecanol, diundecanol, n-pentadecanol, diundecanol, diundecanol, n-hexadecanol, diundecanol, diundecanol, n-heptadecanol, diundecanol, n-heptadecanol, diundecanol, diundecanol, n-heptadecanol, diundecanol, diundecanol, 1,1,3,3-tetramethylbutanol and 1-methylheptanol.

33. The method of claim 19, wherein R is a substituted or unsubstituted C5 to C20 aralkyl group.

34. The method of claim 33, wherein the at least one alcohol is benzyl alcohol.

35. The method of claim 19, wherein step b. is carried out using the vapor of the at least one alcohol.

36. The method of claim 1, wherein step b. is carried out using a liquid of the at least one alcohol.

37. The method of claim 19, wherein step b. is carried out using a liquid of the at least one alcohol.

38. The method of claim 1, wherein the alcohol is selected from the group consisting of isopropanol, 1-methylcyclohexanol, 8-chloro-1-octanol, phenol, 1-octanol, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecano-1-octanol, 1-undecaneol and 1-dodecaneol.

39. The method of claim 1, wherein R in formula (I) is R'-CH2, wherein R' is selected from the group consisting of linear C7 to C17 alkyl, branched C6 to C16 alkyl and C6 to C10 aryl.

40. The method of claim 19, wherein the alcohol is selected from the group consisting of isopropanol, 1-methylcyclohexanol, 8-chloro-1-octanol, phenol, 1-octanol, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecano-1-octanol, 1-undecaneol and 1-dodecaneol.

41. The method of claim 19, wherein R in formula (I) is R'-CH2, wherein R' is selected from the group consisting of linear C7 to C17 alkyl, branched C6 to C16 alkyl and C6 to C10 aryl.

42. The method of claim 1, further comprising the following: the thickness of the metal film or metal nitride film deposited on the first surface is less than the thickness of the metal film or metal nitride film deposited on the second surface; wherein the second surface comprises silicon dioxide; and wherein the deposition selectivity of the second surface to the first surface is greater than about 0.

1.

43. The method of claim 19, wherein the metal film comprises a metal or a metal nitride.

44. The method of claim 42 or 43, wherein the metal system is selected from the group consisting of Ru, Al, Ti, Ta, Mo, Co, Rh, Ir, Fe, Ru, Os, Mo, Mn, Tc, Re, Cu, Ag, Au, Ni, Pd, Pt and combinations thereof; or wherein the metal nitride system is selected from the group consisting of tantalum nitride, titanium nitride, tungsten nitride, tungsten carbonitride, molybdenum nitride, copper silicon nitride and combinations thereof.

45. The method of claim 43, wherein the thickness of the metal film or metal nitride film deposited on the first surface is less than the thickness of the metal film or metal nitride film deposited on the second surface; wherein the second surface comprises silicon dioxide; and wherein the deposition selectivity of the second surface to the first surface is greater than about 0.

1.

46. ​​The method of claim 1, wherein R comprises a fluorinated C4 to C18 linear alkyl group having the structure CnF2n+1CH2-OH, wherein n is 1 to 17.

47. The method of claim 46, wherein the at least one alcohol system is selected from the group consisting of C3F7CH2-OH, C4F9CH2-OH, C5F11CH2-OH, C6F13CH2-OH, C7F15CH2-OH, C8F17CH2-OH and C9F19CH2-OH.

48. The method of claim 19, wherein R comprises a fluorinated C4 to C18 linear alkyl group having the structure CnF2n+1CH2-OH, wherein n is 1 to 17.

49. The method of claim 48, wherein the at least one alcohol system is selected from the group consisting of C3F7CH2-OH, C4F9CH2-OH, C5F11CH2-OH, C6F13CH2-OH, C7F15CH2-OH, C8F17CH2-OH and C9F19CH2-OH.

50. The method of claim 1, wherein R is a chlorinated C1 to C18 linear alkyl group having the structure CnCl2n+1CH2-OH, wherein n is 1 to 17.

51. The method of claim 50, wherein the at least one alcohol is selected from the group consisting of CCl3CH2-OH, C2Cl5CH2-OH, C3Cl7CH2-OH, C4Cl9CH2-OH, C5Cl11CH2-OH, C6Cl13CH2-OH, C7Cl15CH2-OH, C8Cl17CH2-OH, C9Cl19CH2-OH and 8-chloro-1-octanol.

52. The method of claim 19, wherein R is a chlorinated C1 to C18 linear alkyl group having the structure CnCl2n+1CH2-OH, wherein n is 1 to 17.

53. The method of claim 52, wherein the at least one alcohol is selected from the group consisting of CCl3CH2-OH, C2Cl5CH2-OH, C3Cl7CH2-OH, C4Cl9CH2-OH, C5Cl11CH2-OH, C6Cl13CH2-OH, C7Cl15CH2-OH, C8Cl17CH2-OH, C9Cl19CH2-OH and 8-chloro-1-octanol.

54. The method of claim 1, wherein the at least one alcohol is selected from the group consisting of phenylmethanol, 2-phenyl-1-ethanol, 3-phenyl-1-propanol, 4-phenyl-1-butanol, 5-phenyl-1-pentanol, 6-phenyl-1-hexanol, 7-phenyl-1-heptanol, 8-phenyl-1-octanol, and combinations thereof.

55. The method of claim 19, wherein the at least one alcohol is selected from the group consisting of phenylmethanol, 2-phenyl-1-ethanol, 3-phenyl-1-propanol, 4-phenyl-1-butanol, 5-phenyl-1-pentanol, 6-phenyl-1-hexanol, 7-phenyl-1-heptanol, 8-phenyl-1-octanol, and combinations thereof.

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