Regional selective deposition of dielectric films on silicon-containing surfaces using alcohols

Abstract

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

Description

Cross-reference to related applications

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 503,415, filed May 19, 2023, the entire contents of which are incorporated herein by reference.

[0002] Invention Field This application relates to selective deposition on a first surface of a substrate relative to a second surface. Furthermore, different materials can subsequently be deposited on the second surface relative to the first surface using further processing. Background of the Invention Selective deposition has gained significant momentum, primarily due to the limitations of contemporary photolithography processes, enabling the fabrication of advanced semiconductor devices based on ever-shrinking physical dimensions. Traditionally, patterning in the microelectronics industry has been accomplished using various photolithography and etching processes. However, as photolithography becomes exponentially more complex and expensive, the appeal of using selective deposition to form self-aligned features has become far greater. The fabrication of self-aligned via structures will significantly benefit from the manufacturability of selective deposition processes. Another potential application of selective deposition is gap filling. In gap filling, a dielectric “fill” film grows selectively from the bottom of the trench towards the top. 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-FET structure. This allows for the deposition of sidewall spacers without the need for complex patterning steps. Selective deposition processes for metal and metal oxide films used as gate and capacitor dielectrics are also very useful in semiconductor device fabrication.

[0004] Prior examples exist in the technical literature involving the selective formation of surface passivation coatings on wafers with multiple exposed surfaces of different chemicals. The aim is to delay or prevent film deposition on these passivated surfaces via an ALD process, but not to prevent deposition on the surfaces on which the ALD deposition process requires the film to be deposited. Typically, process selectivity is insufficient due to incomplete surface passivation and / or due to the physical adsorption of ALD precursor molecules and the subsequent formation of ALD film material within the passivation layer itself or on surfaces where deposition is not desired. This disclosure attempts to overcome the limitations of the prior art and provides an improved method for selectively depositing thin film materials using an ALD deposition process.

[0005] Liu, L.-H. et al., J. Phys.: Condens. Matter 28 (2016) 094014 (doi:10.1088 / 0953-8984 / 28 / 9 / 094014) teach that silicon nitride can be selectively passivated to some extent relative to silicon oxide by treating the treated surface with a solution containing aldehyde. Invention Overview In a first aspect, a method is provided for selectively passivating a substrate surface, wherein the substrate surface 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. optionally treating the surface with hydrogen plasma, argon plasma, or ammonia plasma; and b. 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 C5 to C6 groups. 18 Straight-chain alkyl, substituted or unsubstituted branched C4 to C5 18 Alkyl, substituted or unsubstituted C4 to C8 cycloalkyl, substituted or unsubstituted C3 to C8 cycloalkyl 10 Heterocyclic groups, substituted or unsubstituted C4 to C5 groups 18 Alkenyl, substituted or unsubstituted C4 to C 18 Aryl, substituted or unsubstituted C5 to C 20 Arylalkyl and substituted or unsubstituted C4 to C5 10 The alkynyl group, and wherein at least one alcohol selectively reacts with silicon nitride to passivate the first surface, thereby leaving the second surface substantially unreacted; and c. depositing a dielectric film onto the substrate by atomic layer deposition.

[0007] In a further aspect of the first principal aspect, prior to steps a and b, the following steps are performed: contacting the substrate surface 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 compositions comprising: H2O2 (28% aqueous solution), NH4O4 (28-30%) and H2O; HF (0.01%-5% aqueous solution); peroxide; RCA cleaning chemicals SC-1 and SC-2; and a mixture of H2SO4 / H2O2. In a further aspect of the first principal aspect, the second surface comprises at least one selected from SiO2, carbon-doped silicon oxide, metal oxides, copper, cobalt, tungsten, amorphous silicon, polycrystalline silicon, monocrystalline silicon, germanium, and amorphous germanium hydride. In a further aspect of the first principal aspect, the second surface comprises SiO2 or carbon-doped silicon oxide. In a further aspect of the first principal aspect, at least one alcohol is having the structure C. n H 2n+1 C5 to C 18 A straight-chain alkyl group, wherein n is 5 to 18. In a further aspect of the first main aspect, at least one alcohol is a straight-chain C8 to C18 alkyl group selected from 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tetranol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 8-chloro-1-octanol, and pentafluoro-1-octanol. 18Alcohols. In a further aspect of the first principal aspect, R is an alcohol having the formula C n H 2n+1 Branches C4 to C 18 Alkyl group, wherein n is 4 to 18. In a further aspect of the first principal aspect, at least one alcohol is selected from isobutanol, isopentanol, isohexylol, isohepaniol, isooctanol, isononanol, isodecanol, isoundecanol, isoundecanol, isotridecanol, isotetradecanol, isopentadecanol, isohexadecanol, isohexadecanol, isohexadecanol, isohexadecanol, and isohexadecanol. In a further aspect of the first principal aspect, R is a substituted or unsubstituted C3 to C8 cycloalkyl group. In a further aspect of the first principal aspect, at least one alcohol is selected from cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, and 1-methylcyclohexanol. In a further aspect of the first principal aspect, R comprises a substituted or unsubstituted C4 to C8 cycloalkyl group. 18 Aryl. In a further aspect of the first principal aspect, at least one alcohol is selected from phenol, p-cresol, 4-methylphenol, 4-ethylphenol, 4-n-propylphenyl, 4-isopropylphenyl, 4-n-butylphenyl, 4-sec-butylphenyl, 4-isobutylphenyl, 4-trifluoromethylphenol, 4-n-octylphenol, 4-n-pentylphenol, and 4-hexylphenol. In a further aspect of the first principal aspect, R is an unsubstituted C8 to C9 alcohol. 18 Straight-chain alkyl, or R is a substituted or unsubstituted branched C3 to C4 chain. 18 Alkyl group. In a further aspect of the first principal aspect, at least one alcohol is selected from 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, isohepanol, isooctanol, isononanol, isodecanol, isoundecanol, isoundecanol, isotridecanol, isotetradecanol, isopentadecanol, isohexadecanol, isohexadecanol, and isohexadecanol. In a further aspect of the first principal aspect, R is a substituted or unsubstituted C5 to C6 alcohol. 20 Arylalkyl. In a further aspect of the first principal aspect, at least one alcohol is a benzyl alcohol. In a further aspect of the first principal aspect, step b is carried out using the vapor of at least one alcohol.

[0008] In a second principal aspect, a method for selectively depositing a film on a substrate surface is provided, wherein the substrate surface 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. optionally treating the surface with hydrogen plasma or 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 substituted or unsubstituted C5 to C6 groups. 18Straight-chain alkyl, substituted or unsubstituted branched C2 to C3 18 Alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C3 to C8 cycloalkyl 10 Heterocyclic group, substituted or unsubstituted C3 to C4 18 Alkenyl, substituted or unsubstituted C4 to C 18 Aryl, substituted or unsubstituted C5 to C 20 Arylalkyl and substituted or unsubstituted C3 to C4 10 a. an alkynyl group, wherein at least one alcohol selectively reacts with silicon nitride to passivate the first surface, thereby leaving the second surface substantially unreacted; and c. exposing the substrate surface to one or more deposition precursors to selectively deposit a dielectric film on the second surface relative to the first surface.

[0009] In a further aspect of the second principal aspect, the method further includes the following steps performed prior to steps a, b, and c: contacting the substrate surface 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 compositions comprising: H₂O₂ (28% aqueous solution), NH₄O₄ (28-30%) and H₂O; HF (0.01%-5% aqueous solution); peroxide; RCA cleaning chemicals SC-1 and SC-2; and a mixture of H₂SO₄ / H₂O₂. In a further aspect of the second principal aspect, the second surface comprises at least one selected from SiO₂, carbon-doped silicon oxide, metal oxides, copper, cobalt, ruthenium, tungsten, molybdenum, amorphous silicon, polycrystalline silicon, monocrystalline silicon, germanium, and amorphous germanium hydride. In a further aspect of the second principal aspect, the second surface comprises SiO₂ or carbon-doped silicon oxide. In a further aspect of the second principal aspect, at least one alcohol is a C₂-containing alcohol. n H 2n+1 -OH C8 to C 18 A straight-chain alkyl group, wherein n is 8 to 18. In a further aspect of the second main aspect, at least one alcohol is selected from 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tetranol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 8-chloro-1-octanol, and pentafluoro-1-octanol. In a further aspect of the second main aspect, the dielectric film comprises TiO2, HfO2, ZrO2, Al2O3, Ta2O5, SiO2, or combinations thereof. In a further aspect of the second main aspect, R is a substituted or unsubstituted C3 to C8 cycloalkyl group. In a further aspect of the second main aspect, at least one alcohol is selected from cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, and 4-methylcyclohexanol. In a further aspect of the second main aspect, R is substituted or unsubstituted C4 to C4.18 Aryl. In a further aspect of the second principal aspect, at least one alcohol is selected from phenol, tolylethanol, dimethylphenol, and benzenediethanol. In a further aspect of the second principal aspect, R is an unsubstituted C5 to C6 alcohol. 18 Straight-chain alkyl, or R is a substituted or unsubstituted branched C3 to C4 chain. 18 alkyl.

[0010] In a further aspect of the second main aspect, at least one alcohol is selected from tert-hexanol, n-heptanol, sec-heptanol, tert-heptanol, n-octanol, sec-octanol, tert-octanol, n-nonanol, sec-nonanol, tert-nonanol, n-decanol, sec-decanol, tert-decanol, n-undecanol, sec-undecanol, tert-undecanol, n-dodecanol, sec-dodecanol, tert-dodecanol, n-tridecanol, sec-tridecanol, tert-tridecanol, n-tetradecanol, sec-tetradecanol, tert-tetradecanol, n-pentadecanol, sec-pentadecanol, tert-pentadecanol, n-hexadecanol, sec-hexadecanol, tert-hexadecanol, n-heptadecanol, sec-heptadecanol, tert-heptadecanol, n-heptadecanol, sec-heptadecanol, tert-heptadecanol, n-octadecanol, sec-octadecanol, tert-octadecanol, 1,1,3,3-tetramethylbutanol and 1-methylheptanol. In a further aspect of the second main aspect, R is substituted or unsubstituted C5 to C6. 20 Arylalkyl.

[0011] In a further aspect of the second main aspect, at least one alcohol is selected from 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, and 8-phenyl-1-octanol.

[0012] In a further aspect of the second principal aspect, at least one alcohol is benzyl alcohol. In a further aspect of the second principal aspect, step b is carried out using the vapor of at least one alcohol. In a further aspect of the second principal aspect, step b is carried out using a liquid of at least one alcohol. In a further aspect of the second principal aspect, step b is carried out using a liquid of at least one alcohol.

[0013] In a further aspect of the first principal aspect or the second principal aspect, the alcohol is selected from 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-undecanol, and 1-dodecanol. In a further aspect of the first principal aspect or the second principal aspect, R in formula (I) is R'-CH2, wherein R' is selected from straight-chain C7 to C6. 17 Alkyl, branched C6 to C 16 Alkyl and C6 to C 10 Aryl.

[0014] In a further aspect of the first or second principal aspect, the thickness of the dielectric film deposited on the first surface is less than the thickness of the dielectric 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 a further aspect of the first or second principal aspect, R includes a structure C. n F 2n+1 The C4 to C5 fluorine-substituted CH2-OH 18 A straight-chain alkyl group, wherein n is 1 to 17. In a further aspect of the first principal aspect or the second principal aspect, at least one alcohol is selected from C3F7CH2-OH, C4F9CH2-OH, C5F... 11 CH2-OH, C6F 13 CH2-OH, C7F 15 CH2-OH, C8F 17 CH2-OH and C9F 19 CH2-OH. In a further aspect of the first principal aspect or the second principal aspect, R is a C having the structure C n Cl 2n+1 The chlorinated C1 to C2-OH of CH2-OH 18 A straight-chain alkyl group, wherein n is 1 to 17. In a further aspect of the first principal aspect or the second principal aspect, at least one alcohol is selected from CCl3CH2-OH, C2Cl5CH2-OH, C3Cl7CH2-OH, C4Cl9CH2-OH, C5Cl... 11 CH2-OH, C6Cl 13 CH2-OH, C7Cl 15 CH2-OH, C8Cl 17 CH2-OH, C9Cl 19 CH2-OH and 8-chloro-1-octanol.

[0015] The embodiments disclosed herein can be used individually or in combination with each other. Attached Figure Description

[0016] The accompanying drawings are included to provide a further understanding of the disclosed subject matter and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the disclosed subject matter and, together with the specification, serve to explain the principles of the disclosed subject matter. In the drawings: Figure 1 A method for passivating a silicon nitride surface and depositing a film on a silicon dioxide surface is shown; Figure 2 Data on dielectric film deposition performed after passivation with different inhibitors are shown; Figure 3This demonstrates the effect of annealing before depositing the dielectric layer; Figure 4 Data on the saturation of 1-butanol and 1-octanol on silicon nitride surfaces are shown; and Figure 5 The deposition of silicon oxide on a silicon nitride surface passivated with 1-butanol and 1-octanol is shown. Invention Details All references cited in this article, including publications, patent applications and patents, are incorporated herein by reference as if each reference were individually and specifically indicated to be incorporated by reference and fully elaborated in this article.

[0018] In the context of describing the disclosed subject matter (particularly in the context of the following claims), the use of the terms “a” and “an”, as well as “the” and similar designations, should be interpreted as encompassing both singular and plural, unless otherwise stated herein or obviously contradicted by the context. Unless otherwise stated, the terms “comprising,” “having,” “including,” and “containing” should be interpreted as open-ended terms (i.e., meaning “including, but not limited to”). Unless otherwise stated herein, the descriptions of numerical ranges herein are intended only as a shorthand method for individually referring to each individual value falling within that range, and each individual value is incorporated into the specification as if it were individually described herein. Unless otherwise stated herein or obviously contradicted by the context, all methods described herein can be performed in any suitable order. The use of any and all instances or exemplary language (e.g., “such”) provided herein is intended only to better elucidate the disclosed subject matter and, unless expressly stated otherwise, does not constitute a limitation on the scope of the disclosed subject matter. No language in the specification should be construed as indicating any unclaimed element as necessary for implementing the subject matter of this disclosure.

[0019] This document describes preferred embodiments of the present disclosure, including the best modes known to the inventors for implementing the claimed subject matter. Variations of those preferred embodiments will be apparent to those skilled in the art after reading the foregoing description. The inventors anticipate that those skilled in the art will appropriately employ such variations, and the inventors intend to implement the claimed subject matter in a manner different from that specifically described herein. Therefore, this disclosure includes all modifications and equivalents of the subject matter described in the appended claims as permitted by applicable law. Furthermore, any combination of the foregoing elements in all their possible variations is included in the claimed subject matter unless otherwise stated herein or the context clearly contradicts it.

[0020] Various methods exist for selective deposition. Embodiments of this disclosure relate to a method for surface deactivation by utilizing the surface chemistry of two different surfaces. Since the two different surfaces have different reactive handles, this difference can be utilized by employing molecules that react with one surface (deactivating that surface) but not with the other.

[0021] In one embodiment, a method is provided for selectively passivating a substrate surface via a gas-phase reaction, wherein the substrate surface 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. contacting the substrate surface with a wet chemical composition; b. rinsing the surface with deionized water; c. drying the surface; d. optionally treating the surface with hydrogen plasma, argon plasma, or ammonia plasma; and e. exposing the surface to at least one alcohol having the structure according to Formula I: R-OH, wherein R is selected from substituted or unsubstituted C5 to C6 groups. 18 Straight-chain alkyl, substituted or unsubstituted branched C3 to C4 18 Alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C3 to C8 cycloalkyl 10 Heterocyclic group, substituted or unsubstituted C3 to C4 18 Alkenyl, substituted or unsubstituted C4 to C 18 Aryl, substituted or unsubstituted C5 to C 20 Arylalkyl and substituted or unsubstituted C3 to C4 10 The alcohol contains an alkynyl group, and at least one of the alcohols selectively reacts with silicon nitride to passivate the first surface, thereby leaving the second surface substantially unreacted.

[0022] In another embodiment, a method is provided for selectively passivating a substrate surface by a liquid-phase reaction, wherein the substrate surface 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. contacting the substrate surface with a wet chemical composition; b. rinsing the surface with deionized water; c. drying the surface; d. optionally treating the surface with hydrogen plasma, argon plasma, or ammonia plasma; and e. exposing the surface to at least one alcohol having the structure according to Formula I: R-OH, wherein R is selected from substituted or unsubstituted C5 to C6 groups. 18 Straight-chain alkyl, substituted or unsubstituted branched C3 to C4 18 Alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C3 to C8 10 Heterocyclic group, substituted or unsubstituted C3 to C4 18 alkenyl, substituted or unsubstituted C4 to C 18 Aryl, substituted or unsubstituted C5 to C20 Arylalkyl and substituted or unsubstituted C3 to C4 10 An alkynyl group and at least one of the alcohols selectively react with silicon nitride to passivate the first surface, thereby leaving the second surface substantially unreacted.

[0023] In another embodiment, a method for selectively depositing a film on a substrate surface is provided, wherein the substrate surface 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. contacting the substrate surface with a wet chemical composition; b. rinsing the surface with deionized water; c. drying the surface; d. optionally treating the surface with hydrogen plasma or ammonia plasma; e. exposing the surface to at least one alcohol having a structure according to Formula I: R-OH, wherein R is selected from substituted or unsubstituted C5 to C6 groups. 18 Straight-chain alkyl, substituted or unsubstituted branched C3 to C4 18 Alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C3 to C8 10 Heterocyclic group, substituted or unsubstituted C3 to C4 18 alkenyl, substituted or unsubstituted C4 to C 18 Aryl, substituted or unsubstituted C5 to C 20 Arylalkyl and substituted or unsubstituted C3 to C4 10 f. an alkynyl group, wherein at least one of the alcohols selectively reacts with silicon nitride to passivate the first surface, thereby leaving the second surface substantially unreacted; and f. exposing the substrate to one or more deposition precursors to selectively deposit a film on the second surface relative to the first surface.

[0024] As used in this specification and the appended claims, the terms "substrate" and "wafer" are used interchangeably and both refer to a surface or portion thereof on which a process is performed. Those skilled in the art will also understand that, unless the context clearly indicates otherwise, reference to a substrate may also refer only to a portion of the substrate. Furthermore, references to deposition on a substrate can refer to a bare substrate and a substrate on which one or more films or features are deposited or formed.

[0025] As used herein, “substrate” refers to any substrate on which film processing is performed during the manufacturing process, or a material surface 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, 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. Substrates may be exposed to pretreatment processes to polish, etch, reduce, oxidize, hydroxylate, anneal, and / or bake the substrate surface. In addition to film processing directly on the surface of the substrate itself, any of the disclosed film processing steps may 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 indicated by the context. Thus, for example, when a film / layer or a portion of a film / layer has already been deposited onto a substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate surface. What a given substrate surface contains depends on what film is being deposited and the specific chemistry used. In one or more embodiments, the first substrate surface comprises a metal and the second substrate surface comprises a dielectric, or vice versa. In some embodiments, the substrate surface may contain certain functional groups (e.g., -OH, -NH, etc.).

[0026] Similarly, the films that can be used in the methods described herein are quite diverse. In some embodiments, the film may comprise 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), 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), and combinations thereof. In some embodiments, the film comprises a dielectric. Examples include SiO2, carbon-doped silicon oxide, SiN, HfO2, etc.

[0027] In embodiments of this disclosure, the substrate has at least two discrete surfaces, each characterized by a different chemical property. For example, in one embodiment, the substrate surface includes at least a first surface comprising silicon nitride and at least a second surface comprising a material other than silicon nitride.

[0028] At least one second surface comprising a material other than silicon nitride can be, for example, any material selected from SiO2, carbon-doped silicon oxide, metal oxides, copper, cobalt, tungsten, amorphous silicon, polycrystalline silicon, monocrystalline silicon, germanium, and amorphous germanium hydride. In some embodiments, at least one second surface comprising SiO2 is a dielectric surface, such as a SiO2 surface. In some embodiments, the surface comprising SiO2 may comprise silicon oxide, silicon fluoride glass (FSG), carbon-doped silicon oxide (SiOC), and / or a material containing more than about 50% silicon oxide. In some embodiments, the surface comprising SiO2 comprises -OH groups and may also comprise, for example, an alumina (Al2O3) surface having -OH surface groups.

[0029] Embodiments of this disclosure provide a method for selectively depositing a film (e.g., a metal film) onto a surface of the same substrate relative to a second surface on a substrate. As used in this specification and the appended claims, the term "selectively depositing a film on a surface relative to another surface" means that one of the first or second surfaces is passivated to substantially prevent deposition on a passivation layer, and the film is deposited on the second (non-passivated) surface. The term "relative" as used in this aspect does not imply a physical orientation of one surface on top of another surface, but rather a relationship of the thermodynamic or kinetic properties of the chemical reactions of one surface relative to the other. For example, selectively depositing a cobalt film on a copper surface relative to a dielectric surface means that a cobalt film is deposited on the copper surface, while less or no cobalt film is deposited on the dielectric surface; or that the formation of a cobalt film on the copper surface is thermodynamically or kinetically advantageous relative to the formation of a cobalt film on the dielectric surface.

[0030] In some cases, it is desirable to selectively deposit material on one surface of a substrate relative to a second, different surface of the same substrate. For example, selective deposition can be used to form capping layers, barrier layers, etch-stop layers, sacrificial and / or protective layers, or to seal vias, such as in porous low-k materials.

[0031] The methods disclosed herein include the optional step of contacting a substrate surface with a wet chemical composition to obtain a treated substrate. Exemplary wet chemical treatments include known chemical treatments such as, for example, RCA cleaning chemicals SC-1 and SC-2, aqueous HF solutions, peroxides, H2SO4 / H2O2, NH4OH, buffered HF solutions, and mixtures thereof.

[0032] In a preferred embodiment, the wet chemical composition comprises at least one selected from compositions comprising: H2O2 (28% aqueous solution), NH4O4 (28-30%) and H2O; HF (0.01%-10% aqueous solution); peroxides; RCA cleaning chemicals SC-1 and SC-2; and mixtures of H2SO4 / H2O2.

[0033] As is known in the art, "RCA Cleaning Chemicals" refers to compositions comprising a mixture of ammonium hydroxide and hydrogen peroxide, wherein the basic cleaning process was developed by Radio Corporation of America in the 1960s. The RCA Standard-Clean-1 (SC-1) process uses a solution of ammonium hydroxide and hydrogen peroxide heated to approximately 70°C and water. The SC-1 process dissolves the film and removes Group I and Group II metals. Group I and Group II metals are removed by complexation with reagents in the SC-1 solution. The RCA Standard-Clean-2 (SC-2) process utilizes a mixture of hydrogen peroxide, hydrochloric acid, and water heated to approximately 70°C. The SC-2 process removes metals not removed by the SC-1 process.

[0034] Contact with the wet chemical composition can be made by any method known to those skilled in the art, such as impregnation or spraying. The contact step can be a single step or more than one step.

[0035] In some embodiments, the temperature of the wet chemical composition during the contact step can be, for example, from about ambient temperature to about 100°C. In other embodiments, the temperature of the wet chemical composition during the contact step can be, for example, from about 55°C to about 95°C. In other embodiments, the temperature of the wet chemical composition during the contact step can be, for example, from about 60°C to about 90°C.

[0036] The embodiment also includes a step of rinsing the substrate surface with deionized water after the step of contacting the substrate surface with the wet chemical composition. The rinsing step is typically performed by any suitable method, such as rinsing the substrate surface with deionized water by immersion or spraying techniques.

[0037] The implementation also includes a step of drying at least the surface of the substrate after the rinsing step. The drying step is typically carried out by any suitable means, such as applying heat, isopropanol (IPA) vapor drying, or centrifugal force.

[0038] The embodiments may also optionally include a step of treating the surface with hydrogen plasma, argon plasma, or ammonia plasma. Suitable treatments include plasma treatment (hydrogen plasma, NH3 / NF3 plasma, water plasma, etc.). The optional plasma step is used to remove unwanted deposits on the surface and activate the surface for subsequent deposition of passivating agents. This plasma treatment is most preferably performed after some deposition has been made on the surface to remove non-selectively deposited material from the previously passivated surface and to remove residual passivating agents after the desired deposition thickness has been reached.

[0039] The implementation includes the step of exposing the surface to a vapor or liquid containing at least one alcohol having a structure according to Formula I: R-OH (I), Where R is selected from substituted or unsubstituted C5 to C6. 18 Straight-chain alkyl, substituted or unsubstituted branched C3 to C4 18 Alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C3 to C8 10 Heterocyclic group, substituted or unsubstituted C3 to C4 18 alkenyl, substituted or unsubstituted C4 to C 18 Aryl, substituted or unsubstituted C5 to C 20 Arylalkyl and substituted or unsubstituted C3 to C4 10 An alkynyl group, wherein at least one alcohol selectively reacts with silicon nitride to passivate the first surface, thereby leaving the second surface substantially unreacted.

[0040] This new family of passivation chemicals can be used to achieve selective passivation of SiN relative to SiO2.

[0041] This new family of passivation chemicals shows better selective adsorption on SiN relative to SiO2 compared to reported prior art passivation chemicals.

[0042] This new family of passivation chemicals exhibits better selectivity for oxide deposition at 250°C.

[0043] This new family of passivation layers on SiN exhibits good thermal stability at temperatures up to 250°C and even higher.

[0044] This new passivation method has great potential for high-temperature ASD applications.

[0045] In some embodiments, the alcohol is selected from C n H 2n+1 The structure of C5 to C 18 Straight-chain alkyl. Having C1 to C2. 18 Preferred alcohol precursors of straight-chain alkyl groups include those selected from 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, and 1-dodecanol.

[0046] In other embodiments, R in Formula I is C3 to C 18 Branched alkyl groups. Preferred alcohol precursors having branched alkyl groups include those selected from isobutanol and tert-butanol.

[0047] In other embodiments, R in Formula I is a substituted or unsubstituted C3 to C8 cycloalkyl group. In such embodiments, at least one alcohol comprises those selected from cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, and 1-methylcyclohexanol.

[0048] In other embodiments, R in Formula I is substituted or unsubstituted C4 to C6. 18 Aryl.

[0049] In other embodiments, R in Formula I is unsubstituted C5 to C6. 18 Straight-chain alkyl, or R is a substituted or unsubstituted branched C5 to C6 chain. 18 alkyl.

[0050] In another embodiment, R in Formula I is substituted or unsubstituted C5 to C6. 20 Arylalkyl. In such embodiments, the alcohol includes benzyl alcohol.

[0051] As used throughout this specification, the term "alkyl" refers to a straight-chain or branched saturated hydrocarbon group. In some embodiments, the alkyl group 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 groups 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, 2-Ethyl-1-Butyl, etc.

[0052] As used throughout this specification, the term "cycloalkyl" refers to a cyclic functional group having 3 to 10 or 4 to 10 carbon atoms. Exemplary cycloalkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0053] As used herein, the term "aryl" refers to a monocyclic, bicyclic, or polycyclic aromatic hydrocarbon (e.g., having 2, 3, or 4 fused rings). In some embodiments, the aryl group has 6 to 20 carbon atoms or 6 to 10 carbon atoms. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, anthracene, phenanthryl, indanyl, indenyl, and tetrahydronaphthyl.

[0054] As used herein, the term "arylalkyl" refers to an alkyl group that has been substituted with an aryl group. In some embodiments, the alkyl group is C10. 1-6 alkyl.

[0055] As used throughout this specification, the term "alkenyl" means a group having one or more carbon-carbon double bonds and having 2 to 18 or 2 to 10 carbon atoms. Exemplary alkenyl groups include, but are not limited to, vinyl or allyl.

[0056] As used herein, the term "alkynyl" refers to a straight-chain or branched alkyl group having 2 to 20 carbon atoms and one or more carbon-carbon triple bonds. In some embodiments, the alkynyl group has 2 to 10 carbon atoms, 2 to 8 carbon atoms, 2 to 6 carbon atoms, or 2 to 4 carbon atoms. Examples of alkynyl groups include, but are not limited to, acetylene, 1-propene, 2-propene, etc.

[0057] As used herein, the phrase “optionally substituted” means that substitution is optional and therefore includes both unsubstituted and substituted atoms and portions. A “substituted” atom or portion indicates that any hydrogen atom on a specified compound or portion may be selectively substituted by an indicated substituent, provided that the substitution does not exceed the normal valence of the specified compound or portion and that the substitution produces a stable compound. For example, if the methyl group is optionally substituted, one, two, or three hydrogen atoms on the carbon atom within the methyl group may be substituted by one, two, or three of the stated substituents.

[0058] As used herein, the term "phenyl" refers to -C6H5. A phenyl group may be unsubstituted or substituted with one, two, or three suitable substituents.

[0059] As used herein, the term "cycloalkyl" refers to a non-aromatic cyclic hydrocarbon, including cycloalkyl, alkenyl, and alkynyl groups having up to 20 cyclic carbon atoms. Cycloalkyl groups have 3 to 15 cyclic carbon atoms, 3 to 10 cyclic carbon atoms, 3 to 8 cyclic carbon atoms, 3 to 6 cyclic carbon atoms, 4 to 6 cyclic carbon atoms, 3 to 5 cyclic carbon atoms, or 5 or 6 cyclic carbon atoms. The cyclic carbon atoms of a cycloalkyl group may optionally be substituted with oxo or sulfido. Cycloalkyl groups include, but are not limited to, monocyclic or polycyclic systems, such as fused ring systems, bridged ring systems, and spirocyclic systems. In some embodiments, polycyclic ring systems comprise 2, 3, or 4 fused rings. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclopentenyl, cyclohexenyl, cyclohexadienyl, cycloheptanetrienyl, norbornyl, norpinyl, norcarnyl, adamantyl, etc. Cycloalkyl groups may also have one or more aromatic rings fused to (sharing a common bond with) the cycloalkyl ring, such as benzo or thiophene derivatives of pentane, pentene, hexane, etc. (e.g., 2,3-dihydro-1H-inden-1-yl or 1H-inden-2(3H)-one-1-yl).

[0060] As used herein, the term "halogenated" refers to a halogen group, including but not limited to fluorine, chlorine, bromine, and iodine.

[0061] As used herein, the term "heterocycle" or "ring of heterocycles" refers to a 5- to 7-membered monocyclic or 7- to 10-membered bicyclic system, any ring of which may be saturated or unsaturated, and which consists of a carbon atom and one to three heteroatoms selected from N, O, and S, wherein the N and S heteroatoms may optionally be oxidized, and the N heteroatomium may optionally be quaternized, and includes any bicyclic system in which any heterocycle defined above is fused to a benzene ring. Heterocycles include rings containing one oxygen or sulfur atom, one to three nitrogen atoms, or a combination of one oxygen or sulfur atom and one or two nitrogen atoms. Heterocycles may be attached to any heteroatom or carbon atom, resulting in a stable structure. Examples of heterocyclic groups include, but are not limited to, piperidinyl, piperazinyl, 2-oxopirarinyl, 2-oxopirarinyl, 2-oxopirarinyl, 2-oxopirarinyl, 2-oxoazadiazinyl, azaadiazinyl, pyrroleyl, 4-piperidinoneyl, pyrroleyl, pyrazolyl, pyrazolyl, imidazolyl, imidazolinyl, pyridinyl, imidazolinyl, pyrazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolyl, isoxazolyl, isoxazolyl, morpholinyl, thiazolyl, thiazolinyl, isothiazolyl, quininecycloyl, isothiazolyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, thiadiazolyl, benzopyranyl, benzothiazolyl, benzoxazolyl, furanyl, tetrahydrofuranyl, tetrahydropyranyl, thiophenyl, benzothiaphenyl, thiomorpholinyl, thiamorpholinyl sulfoxide. Sulfoxide), thiamorpholinyl sulfone, oxadiazole, etc.

[0062] Vapor-phase or gas-phase reactions involve exposing a heated substrate to precursor molecules and / or co-reactants in a suitable chamber that must be able to provide the necessary pressure control and also provide heat to the substrate and / or chamber walls; the chamber should also provide suitable purity for the reaction to occur, typically through high leak integrity and the use of ultra-high purity carriers and reactive gases.

[0063] As used in this specification and the appended claims, the terms “reactive gas,” “precursor,” “reactant,” etc., are used interchangeably to refer to a gas comprising a substance reactive with the substrate surface. For example, a first “reactive gas” may simply be adsorbed onto the surface of the substrate and may be used for further chemical reaction with a second reactive gas. They may be used in combination with ultra-high purity carrier gases (as described above) or in any desired mixture of them (i.e., more than one type of precursor may be used together or in discrete, independent steps to form the desired passivation layer, regardless of the order in which the precursors are introduced).

[0064] Precursors and / or co-reactants can be delivered to the reactor using a mass flow controller (possibly with a heating element), a liquid injection evaporator (possibly with a heating element), or without metering (i.e., by net introduction of vapors and / or gases from a separate vessel using simple valves). Any of the above can also be used in combination. Gases and / or vapors can be supplied to the reaction chamber (providing sufficient purity and repeatability) using any method.

[0065] Precursors and / or co-reactants may be introduced into the reactor independently, mixed prior to introduction into the reactor, mixed in the reactor, or introduced in any combination of the foregoing in multiple independent steps (which may include differences in how the precursors are introduced between steps).

[0066] The reaction temperature range can be between room temperature and 400°C. In some cases, the reaction temperature range can be between room temperature and 200°C. In other cases, the reaction temperature range can be between room temperature and 100°C. The pressure range can be from 10-10 Torr to 3000 Torr and can be maintained under dynamic flow conditions (i.e., using valves and butterfly valve arrangements) or under static conditions (i.e., the emptied chamber is exposed to the desired precursors and / or co-reactants until the desired total pressure is reached, and then the chamber is isolated from the precursor and / or co-reactant source and vacuum pump). The reactor can be completely emptied and re-exposed to fresh precursors and / or co-reactants multiple times as needed. Precursors and / or co-reactants can be introduced using any desired mixture and / or concentration.

[0067] The surface exposure can last from 0.1 to 60 minutes, preferably 1 to 5 minutes, and most preferably 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. Most preferably, it is 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 can be higher as the atmosphere containing the carrier gas becomes balanced. Preferred carrier gases include N2, He, and Ar, but other gases such as H2, CO2, and dry O2 can also be used. The exposed vapor can be static (non-flowing) for the entire or partial exposure period. In a preferred embodiment, the alcohol vapor is allowed to flow through the exposure chamber along with an optional carrier gas, such that fresh vapor is exposed to the substrate surface for at least a portion of the exposure period.

[0068] The exposure chamber can be maintained at a temperature close to ambient temperature, or optionally heated. Heat can be supplied to the outer walls of the chamber (hot walls) or only to the substrate (cold wall reactor). Substrate heating in the cold wall reactor can be achieved by using incident radiation through a transparent window (lamp heating), by resistance heating of the substrate itself or from resistance heating elements in a platform in contact with the substrate, by induction, or by other means known in the art. The processing temperature is preferably between about 20°C and 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 exposure or can be varied within a specified temperature range.

[0069] Then, before removing the substrate from the chamber or before chemical vapor deposition or atomic layer deposition, unreacted vapors of at least one alcohol may optionally be removed by purging the chamber or purging it with a suitable inert gas. Optionally, the exposed chamber may also be used for subsequent processing steps to improve processing efficiency, such that the process can be repeated from step c), if necessary, to strip the protective film and any non-selective ALD deposits, and then reform the protective film.

[0070] The selection of at least one alcohol and the exposure conditions used in this method should be optimized through standard experiments to optimize the selectivity, processing time, reagent cost, etc., of the protection provided by the silicon nitride surface against potential non-selective passivation, based on the requirements imposed by subsequent processing steps. For example, selectivity can be tuned / optimized by changing the properties of the R group of at least one alcohol having the structure represented by Formula I. Typically, since reactivity and selectivity are often negatively correlated, if two surfaces are chemically similar, it may be necessary to experiment with the R group to optimize the method. For example, there is a difference in reactivity between alkyl and aryl R-groups; generally, aryl groups are more reactive with surfaces carrying active hydrogen than alkyl groups. Therefore, in some cases, alkyl groups may be needed to selectively passivate SiN without simultaneously passivating adjacent surfaces with less reactive active hydrogen atoms.

[0071] Once the silicon nitride surface is passivated, the second surface, containing, for example, silicon oxide, is active for further selective reactions. Other materials that can be selectively deposited on the second surface include silicon films containing oxygen, nitrogen, hydrogen, and carbon (i.e., SiO₂). x SiN x SiO x N y SiC x N y SiO x C yAll of these may also include H), metals, metal nitrides, and metal oxides. In some embodiments, the dielectric film (including metal oxides or silicon oxides) is selectively deposited on the second surface. In one example, a metal oxide film can be used as a capping layer on the second surface. For example, the dielectric film can be deposited by atomic layer deposition (ALD), plasma-enhanced ALD (PEALD), chemical vapor deposition (CVD), plasma-enhanced CVD (PECVD), or pulsed CVD. According to one embodiment, the dielectric film may be selected from HfO2, ZrO2, TiO2, Ta2O5, Al2O3, SiO2, and combinations thereof. In some instances, as detailed in U.S. Provisional Patent Application Serial No. 62 / 472,724, filed March 17, 2017 (the entire contents of which are incorporated herein by reference), the dielectric film, such as a metal oxide film, can be deposited by ALD utilizing alternating exposure of volatile metal-containing precursors and oxidants (e.g., H2O, H2O2, plasma-excited O2, or O3). In other instances, dielectric films (such as silicon oxide) can be deposited via alternating exposure to volatile metal-containing precursor catalysts (such as trimethylaluminum, triethylaluminum, dimethylisopropoxide aluminum, diethylisopropoxide aluminum) and trialkoxysilanols (such as tri(tert-butoxy)silanol, tri(tert-pentoxy)silanol, bis(tert-butoxy)(tert-pentoxy)silanol, bis(tert-pentoxy)(tert-butoxy)silanol).

[0072] The selective deposition according to this disclosure can be, for example, metal and metal oxide layers disclosed in Hamalarenen et al., “Atomic Layer Deposition of Noble Metals and Their Oxides”, Chem. Mater. 2014, 26, 786-801; and Johnson et al., “A Brief review of Atomic layer Deposition: From Fundamentals to Applications”, Materials Today, Vol. 17, No. 5, June 2014 (both incorporated herein by reference).

[0073] In some embodiments, a metal oxide is selectively deposited on the second surface using a metal-containing precursor. The metal-containing precursor should have sufficient vapor pressure and be sufficiently stable to be transported into the reaction chamber, and may have the formula M(L1). x (L2) y (L3) zM is a metal from group 3 to 13; L1, L2 and L3 are independently selected from substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted pyrroleyl, substituted or unsubstituted imidazolyl, amide, alkoxy, amidine, straight or branched diene, straight or branched alkyl, hydride, carbon monoxide, nitrosyl, halogen (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 metal precursors include, but are not limited to, tetra(dimethylamino)hafnium (TDMAH), tetra(diethylamino)hafnium (TDEAH), tetra(ethylmethylamino)hafnium (TEMAH), cyclopentadienyltris(dimethylamino)hafnium (CpHf(NMe2)3), methylcyclopentadienyltris(dimethylamino)hafnium (MeCpHf(NMe2)3), ethylcyclopentadienyltris(dimethylamino)zirconium (EtCpHf(NMe2)3), and cyclopentadienyltris(dimethylamino)hafnium (CpHf(NMe2)3). Et)3), Methylcyclopentadienyl tris(dimethylamino)hafnium (MeCpHf(NMeEt)3), Tetra(dimethylaminozirconium) (TDMAZ), Tetra(diethylamino)zirconium (TDEAZ), Tetra(ethylmethylamino)zirconium (TEMAZ), Cyclopentadienyl tris(dimethylamino)zirconium (CpZr(NMe2)3), Methylcyclopentadienyl tris(dimethylamino)zirconium (MeCpZr(NMe2)3), Ethylcyclopentadienyl tris(dimethylamino)zirconium (EtCpZr(NMe2)3) Cyclopentadienyltris(dimethylamino)zirconium (CpZr(NMeEt)3), methylcyclopentadienyltris(dimethylamino)zirconium (MeCpZr(NMeEt)3), tert-butyliminotris(diethylamino)tantalum (TBTDET), tert-butyliminotris(dimethylamino)tantalum (TBTDMT), tert-butyliminotris(ethylmethylamino)tantalum (TBTEMT), ethyliminotris(diethylamino)tantalum (EITDET), ethyliminotris(dimethylamino)tantalum (EITDMT), Ethyliminotris(ethylmethylamino)tantalum (EITEMT), tert-pentyliminotris(dimethylamino)tantalum (TAIMAT), tert-pentyliminotris(diethylamino)tantalum, penta(dimethylamino)tantalum, tert-pentyliminotris(ethylmethylamino)tantalum, bis(tert-butylimino)bis(dimethylamino)molybdenum (BTBMM), bis(tert-butylimino)bis(diethylamino)molybdenum, bis(tert-butylimino)bis(ethylmethylamino)molybdenum, trimethylaluminum, triethylaluminum, dimethylisopropoxide aluminum, diethylisopropoxide aluminum. In some other embodiments, silicon oxide is selectively deposited on the second surface using Si(NCO)4 via thermal atomic layer deposition.

[0074] During selective deposition, the aforementioned protective surface, previously selectively deposited on the silicon nitride surface with at least one alcohol, may begin to react or otherwise become less inert. With or without any aqueous or plasma pretreatment steps, optional reapplication of at least one alcohol may be repeated to prevent or delay non-selective deposition on the silicon nitride surface.

[0075] In some embodiments, passivation on a first surface of the substrate (such as a silicon nitride surface of the substrate) relative to a second surface of the substrate, as described herein, is at least about 90% selective, at least about 95% selective, and at least about 96%, 97%, 98%, or 99% or higher selective. In some embodiments, passivation occurs only on the first surface and not on the second surface. In some embodiments, passivation on the first surface of the substrate is at least about 70% selective or at least about 80% selective relative to the second surface of the substrate, which may be sufficiently high selective for certain applications. In some embodiments, passivation on the first surface of the substrate is at least about 50% selective relative to the second surface of the substrate, which may be sufficiently high selective for certain applications.

[0076] The passivation layer can be removed using wet chemical cleaning. Exemplary wet chemical cleaning includes acidic, basic, and oxidizing (e.g., peroxide-containing) wet chemical compositions known in the art, and as described above for the optional step of contacting the substrate with the wet chemical composition. Another method for removing the passivation layer is by applying heat or other energy.

[0077] Example Exemplary embodiments show that alcohols (alkyl alcohols or aryl alcohols) selectively passivate silicon nitride (Si3N4) surfaces relative to silicon oxide (SiO2) surfaces. This process is described in... Figure 1 This process leads to selectivity in the growth of thicker metal films (or metal nitride films) on SiO2.

[0078] The substrate 100 includes a first surface 102 (Si3N4) and a second surface 104 (SiO2). The substrate is exposed to an alkyl alcohol or aryl alcohol inhibitor to form a passivation region 106, preferably a self-assembled monolayer (SAM), to selectively passivate the Si3N4 surface 102 by converting Si-NH2 groups into aliphatic or aromatic groups. Subsequently, a dielectric film 108 is deposited on the second surface 104.

[0079] Dielectrics on Dielectrics (DoD) CVD silicon nitride (Si3N4) and thermally heated silicon oxide (SiO2) were used as growth and non-growth substrates to test the passivation capabilities of the novel chemicals. Thin organic passivation layers were formed by immersing the substrates overnight in a 10 mM toluene solution at 60 °C. Prior to immersion, the unmodified SiN and SiO2 substrates were etched for 1 minute in diluted HF at a concentration of 100:1 to remove the SiON and native oxide layers, respectively. After pre-cleaning, the SiN and SiO2 surfaces became hydrophilic, as confirmed by water contact at 27 °C and 0 °C. The low contact angles indicated the formation of NHx and OH-terminated surfaces with differential functionality. SAM solutions were prepared by dissolving the chemicals in toluene to create solutions of varying concentrations.

[0080] Four different representative passivation chemicals were selected to demonstrate passivation capabilities, and the passivation layer's ability to inhibit the adsorption and reaction of ALD precursors and reactants was tested using Cp2ZrMe(OMe) and water ALD processes. ALD deposition was performed at 250°C for high-quality metal oxide film deposition.

[0081] The passivating chemicals tested are listed below: 1-dodecanool, a representative family of molecules with an alcohol head group; 1-octanol, a representative molecule with an alcohol head group and a short chain; isopropanol, a representative molecule with an alcohol and the shortest hydrocarbon chain; and benzaldehyde, a representative molecule with an aldehyde head group.

[0082] Figure 2 The ALD nucleation inhibition capabilities of three different passivation chemicals were demonstrated. Consistent with WCA observations, dodecyl alcohol passivated SiN exhibited better ZrO2 deposition selectivity than the other two chemicals, and the loss of selectivity for benzaldehyde during ALD deposition is believed to be due to its low thermal stability at 250 °C, which leads to degradation of the passivation layer and thus reduced ALD deposition inhibition. Annealing dodecyl alcohol passivated SiN at 250 °C in a N2 environment for 1 hour showed no decrease in passivation layer quality, and WCA increased slightly after annealing due to desorption of physically adsorbed substances, resulting in better passivation layer quality. The deposition nucleation inhibition of the alcohol passivation layer showed a certain chain length dependence; shorter hydrocarbon chains did not show good selectivity in the deposited film.

[0083] Figure 2Selective growth of ZrO2 on passivated SiN and SiO2 using different chemical substances is illustrated. For the purposes of this disclosure and the claims, the selectivity of the second surface relative to the first surface is determined by the following equation: Selectivity = (film thickness on the second surface (SiO2) - film thickness on the first surface (Si3N4)) / (film thickness on the second surface (SiO2) + film thickness on the first surface (Si3N4)). Notably, successful selectivity (preferably greater than about 0.1, more preferably greater than about 0.2, most preferably greater than about 0.3) is achieved by passivation with 1-dodecanol and 1-octanol. The success rate of passivation with isopropanol and benzaldehyde is significantly lower.

[0084] Figure 3 The good thermal stability of alcohol passivated SiN after annealing at 250 °C was demonstrated.

[0085] Table 1. Selectivity of different inhibitors

[0086] As shown in Table 1, successful selective deposition of dielectric films (ZrO2, with selectivity greater than about 0.3) was achieved using various primary alcohols: 1-octanol and 1-dodecanool, while smaller alkyl alcohols such as isopropanol and existing-technology inhibitors such as benzaldehyde showed much lower selectivity, indicating the presence of C4-C... 18 Straight-chain alkyl groups, preferably C6-C 18 Straight-chain alkyl groups, with C8-C being the most preferred. 18 Straight-chain alcohols of straight-chain alkyl groups are suitable inhibitors for the selective deposition of dielectric films on silicon oxide relative to silicon nitride.

[0087] Two different representative passivation chemicals were selected to demonstrate the passivation capability of the R-OH structure, where R is a straight-chain alkyl group. The passivation layer's ability to inhibit the ALD process was tested using Si(NCO)4, triethylamine, and water. ALD deposition was performed at 100°C to achieve silicon oxide film deposition.

[0088] Passivating chemicals are present in the alcohol head group; 1-butanol is used for testing short-chain alcohols, and 1-octanol is used for testing long-chain alcohols.

[0089] Figure 4 The saturation of the two passivation chemicals is shown. Clearly, 1-octanol exhibits greater reactivity with the SiN surface compared to 1-butanol. This results in the formation of an excellent passivation layer on the SiN surface, leading to reduced SiO2 growth in subsequent steps. Applying the same inhibitory chemicals to a silicon oxide substrate does not result in passivation layer formation. This leads to immediate SiO2 growth on the silicon dioxide surface, highlighting the selectivity of the proposed inhibitor.

[0090] Figure 5 This study demonstrates the selective growth of silicon oxide on passivated SiN and SiO2 using 1-butanol and 1-octanol. The thickness of SiO2 deposited on the passivated silicon nitride substrate is less than that deposited on the passivated silicon oxide substrate. However, passivation with 1-butanol was significantly less successful. This confirms the crucial role of hydrocarbon chain length in passivation inhibitors.

[0091] While the principles of this disclosure have been described above in conjunction with preferred embodiments, it should be clearly understood that this description is by way of example only and not as a limitation on the scope of the claimed subject matter.

Claims

1. A method for selectively passivating 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. Optionally, the surface may be treated with hydrogen plasma, argon plasma, or ammonia plasma; b. Expose the surface to at least one alcohol having a structure according to Formula I: R-OH (I), Where R is selected from substituted or unsubstituted C5 to C6. 18 Straight-chain alkyl, substituted or unsubstituted branched C4 to C5 18 Alkyl, substituted or unsubstituted C4 to C8 cycloalkyl, substituted or unsubstituted C3 to C8 cycloalkyl 10 Heterocyclic groups, substituted or unsubstituted C4 to C5 groups 18 Alkenyl, substituted or unsubstituted C4 to C 18 Aryl, substituted or unsubstituted C5 to C 20 Arylalkyl and substituted or unsubstituted C4 to C5 10 Alkyne group, wherein the at least one alcohol selectively reacts with the silicon nitride to passivate the first surface, thereby rendering the second surface substantially unreacted; and c. Deposit a dielectric film onto the substrate by atomic layer deposition.

2. The method of claim 1, further comprising the following steps performed prior to steps a and b: The surface of the substrate is brought into contact with the wet chemical composition; Rinse the surface with deionized water; and Dry the surface. The wet chemical composition comprises at least one selected from the following: H2O2 (28% aqueous solution), NH4O4 (28-30%) and H2O; HF (0.01%-5% aqueous solution); peroxide; RCA cleaning chemicals SC-1 and SC-2; and mixtures of H2SO4 / H2O2.

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

4. The method of claim 3, wherein the second surface comprises SiO2 or carbon-doped silicon oxide.

5. The method of claim 1, wherein the at least one alcohol is a C-shaped alcohol having a structural value of 1. n H 2n+1 C5 to C 18 Straight-chain alkyl, wherein n is 5 to 18.

6. The method of claim 5, wherein the at least one alcohol is a straight-chain C8 to C10 group selected from 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tetranol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-heptadecanol, 1-octadecanol, 8-chloro-1-octanol, and pentafluoro-1-octanol. 18 alcohol.

7. The method of claim 1, wherein R is a class of elements having the formula C. n H 2n+1 Branches C4 to C 18 Alkyl groups, wherein n is 4 to 18.

8. The method of claim 7, wherein the at least one alcohol is selected from isobutanol, isopentanol, isohexanol, isohepanol, isooctanol, isononanol, isodecanol, isoundecanol, isoundecanol, isodedecanol, isotetradecanol, isotetradecanol, isopentadecanol, isohexadecanol, isohexadecanol, isohexadecanol, and isooctadecanol.

9. The method of claim 1, wherein R is a substituted or unsubstituted C3 to C8 cycloalkyl group.

10. The method of claim 9, wherein the at least one alcohol is selected from cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, and 1-methylcyclohexanol.

11. The method of claim 1, wherein R comprises substituted or unsubstituted C4 to C 18 Aryl.

12. The method of claim 11, wherein the at least one alcohol is selected from phenol, p-cresol, 4-methylphenol, 4-ethylphenol, 4-n-propylphenyl, 4-isopropylphenyl, 4-n-butylphenyl, 4-sec-butylphenyl, 4-isobutylphenyl, 4-trifluoromethylphenol, 4-hexylphenol, 4-n-octylphenol, and 4-n-pentylphenol.

13. The method of claim 1, wherein R is unsubstituted C8 to C8. 18 Straight-chain alkyl, or R is a substituted or unsubstituted branched C3 to C4 chain. 18 alkyl.

14. The method of claim 13, wherein the at least one alcohol is selected from 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tetranol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 8-chloro-1-octanol, pentadecano-1-octanol, isobutanol, isopentanol, isohexanol, isohepanol, isooctanol, isononanol, isodecanol, isoundecanol, isoundecanol, isotetradecanol, isopentadecanol, isohexadecanol, isohexadecanol, and isohexadecanol.

15. The method of claim 1, wherein R is a substituted or unsubstituted C5 to C6 compound. 20 Arylalkyl.

16. The method of claim 15, wherein the at least one alcohol is a benzyl alcohol.

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

18. 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. Optionally, the surface is treated with hydrogen plasma or ammonia plasma; b. Expose the surface to at least one alcohol having a structure according to Formula I: R-OH (I), Where R is selected from substituted or unsubstituted C5 to C6. 18 Straight-chain alkyl, substituted or unsubstituted branched C2 to C3 18 Alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C3 to C8 cycloalkyl 10 Heterocyclic group, substituted or unsubstituted C3 to C4 18 Alkenyl, substituted or unsubstituted C4 to C 18 Aryl, substituted or unsubstituted C5 to C 20 Arylalkyl and substituted or unsubstituted C3 to C4 10 Alkyne group, 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. Exposing the surface of the substrate to one or more deposition precursors to selectively deposit a dielectric film on the second surface relative to the first surface.

19. The method of claim 18, further comprising the following steps performed prior to steps a, b, and c: The surface of the substrate is brought into contact with the wet chemical composition; Rinse the surface with deionized water; and Dry the surface; The wet chemical composition comprises at least one selected from the following: H2O2 (28% aqueous solution), NH4O4 (28-30%) and H2O; HF (0.01%-5% aqueous solution); peroxide; RCA cleaning chemicals SC-1 and SC-2; and mixtures of H2SO4 / H2O2.

20. The method of claim 18, wherein the second surface comprises at least one selected from: SiO2, carbon-doped silicon oxide, metal oxide, copper, cobalt, ruthenium, tungsten, molybdenum, amorphous silicon, polycrystalline silicon, monocrystalline silicon, germanium, and amorphous germanium hydride.

21. The method of claim 20, wherein the second surface comprises SiO2 or carbon-doped silicon oxide.

22. The method of claim 18, wherein the at least one alcohol is a C-shaped alcohol having the structure C. n H 2n+1 -OH C8 to C 18 Straight-chain alkyl, wherein n is 8 to 18.

23. The method of claim 22, wherein the at least one alcohol is selected from 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tetanetanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 8-chloro-1-octanol, and pentafluoro-1-octanol.

24. The method of claim 18, wherein the dielectric film comprises TiO2, HfO2, ZrO2, Al2O3, Ta2O5, SiO2, or a combination thereof.

25. The method of claim 18, wherein R is a substituted or unsubstituted C3 to C8 cycloalkyl group.

26. The method of claim 25, wherein the at least one alcohol is selected from cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, 1-methylcyclohexanol, o-methylcyclohexanol, m-methylcyclohexanol and p-methylcyclohexanol.

27. The method of claim 18, wherein R is substituted or unsubstituted C4 to C4. 18 Aryl.

28. The method of claim 27, wherein the at least one alcohol is selected from phenol, toluene, dimethylphenol and benzenediethanol.

29. The method of claim 18, wherein R is unsubstituted C5 to C6. 18 Straight-chain alkyl, or R is a substituted or unsubstituted branched C5 to C6 chain. 18 alkyl.

30. The method according to claim 29, wherein the at least one alcohol is selected from tert-hexanol, n-heptanol, sec-heptanol, tert-heptanol, n-octanol, sec-octanol, tert-octanol, n-nonanol, sec-nonanol, tert-nonanol, n-decanol, sec-decanol, tert-decanol, n-undecanol, sec-undecanol, tert-undecanol, n-dodecanol, sec-dodecanol, tert-dodecanol, n-tridecanol, sec-tridecanol, tert-tridecanol, n-tetradecanol, sec-tetradecanol, tert-tetradecanol, n-pentadecanol, sec-pentadecanol, tert-pentadecanol, n-hexadecanol, sec-hexadecanol, tert-hexadecanol, n-heptadecanol, sec-heptadecanol, tert-heptadecanol, n-octadecanol, sec-octadecanol, tert-octadecanol, 1,1,3,3-tetramethylbutanol and 1-methylheptanol.

31. The method of claim 18, wherein R is substituted or unsubstituted C5 to C6. 20 Arylalkyl.

32. The method of claim 31, wherein the at least one alcohol is a benzyl alcohol.

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

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

35. The method of claim 18, wherein step b is carried out with a liquid of the at least one alcohol.

36. The method of claim 1, wherein the alcohol is selected from 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-undecanol, and 1-dodecanol.

37. The method of claim 1, wherein R in formula (I) is R'-CH2, wherein R' is selected from linear C7 to C2. 17 Alkyl, branched C6 to C 16 Alkyl and C6 to C 10 Aryl.

38. The method of claim 1, further comprising: The thickness of the dielectric film deposited on the first surface is less than the thickness of the dielectric film deposited on the second surface. The second surface comprises silicon dioxide; and The deposition selectivity of the second surface relative 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.

39. The method of claim 18, wherein the thickness of the dielectric film deposited on the first surface is less than the thickness of the metal film or metal nitride film deposited on the second surface; The second surface comprises silicon dioxide; and The deposition selectivity of the second surface relative 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.

40. The method of claim 1, wherein R comprises having a structure C n F 2n+1 The C4 to C5 fluorine-substituted CH2-OH 18 Straight-chain alkyl, wherein n is 1 to 17.

41. The method of claim 40, wherein the at least one alcohol is selected from C3F7CH2-OH, C4F9CH2-OH, C5F... 11 CH2-OH, C6F 13 CH2-OH, C7F 15 CH2-OH, C8F 17 CH2-OH and C9F 19 CH2-OH.

42. The method of claim 1, wherein R is a structure C n Cl 2n+1 The chlorinated C1 to C2-OH of CH2-OH 18 Straight-chain alkyl, wherein n is 1 to 17.

43. The method of claim 42, wherein the at least one alcohol is selected from CCl3CH2-OH, C2Cl5CH2-OH, C3Cl7CH2-OH, C4Cl9CH2-OH, C5Cl... 11 CH2-OH, C6Cl 13 CH2-OH, C7Cl 15 CH2-OH, C8Cl 17 CH2-OH, C9Cl 19 CH2-OH and 8-chloro-1-octanol.

44. The method of claim 1, wherein R is substituted or unsubstituted C5 to C6. 20 Arylalkyl.

45. The method of claim 44, wherein the at least one alcohol is selected from 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.

46. ​​The method of claim 18, wherein the dielectric film is silicon oxide deposited using a precursor comprising Si(NCO)4.

47. The method of claim 46, wherein the thickness of the dielectric film deposited on the first surface by Si(NCO)4 is less than the thickness of the silicon oxide film deposited on the second surface; The first surface comprises silicon nitride; and The second surface comprises silicon dioxide; and The at least one alcohol is 1-octanol.

48. The method of claim 47, wherein the deposition selectivity of the second surface relative to the first surface is greater than about 0.2.

Images