Region-selective deposition of metal films on silicon-containing surfaces using halides

Abstract

A method for selectively passivating the surface of a substrate, wherein the substrate surface comprises 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 step of exposing the surface to at least one organic halide which selectively reacts with silicon nitride to passivate the first surface, thereby leaving the second surface substantially unreacted.

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims priority to U.S. Provisional Patent Application No. 63 / 495,739, filed on April 12, 2023, the entire content of which is incorporated herein by reference.

[0002] Technical Field This application relates to selective deposition on a first surface relative to a second surface of a substrate. Further, additional processing can be used to subsequently deposit a different material than the first surface on the second surface.

Background Art

[0003] Selective deposition processes have gained significant momentum due to the limitations of modern lithography processes that enable the manufacture of advanced semiconductor devices based on ever - shrinking physical dimensions. Conventionally, patterning in the microelectronics industry has been achieved using various lithography and etching processes. However, as lithography has become exponentially more complex and expensive, using selective deposition to form self - aligned features has become much more attractive. The manufacture of self - aligned via structures benefits greatly from manufacturable selective deposition processes. Another potential use for 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 in 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 enables the deposition of sidewall spacers without the need for complex patterning steps. Selective deposition processes for metals and metal oxide films used as gate dielectrics and capacitor dielectrics would also be very useful in semiconductor device manufacturing.

[0004] Technical literature contains prior examples of selectively forming surface passivation coatings on wafers having multiple different exposed chemical surfaces. This has been done to delay or prevent film deposition by the ALD process on these passivated surfaces, but not to prevent deposition on surfaces where film deposition by the ALD deposition process is desired. Generally, the selectivity of the process is insufficient because it results in incomplete surface passivation and / or physicoadsorption of ALD precursor molecules, followed by the formation of ALD film material inside the passivation layer itself or on surfaces where deposition is undesirable. This disclosure aims to overcome the limitations of the prior art and provide an improved method for selectively depositing thin film materials using the ALD deposition process.

[0005] Liu, L.-H. et al. J.Phys.:Condens.Matter 28(2016)094014 (doi:10.1088 / 0953-8984 / 28 / 9 / 094014) teaches that silicon nitride may be passivated to some extent more selectively than silicon oxide by treating a surface with an aldehyde-containing solution. [Overview of the project]

[0006] In a first embodiment, 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 a. optionally a step of treating the surface with a hydrogen plasma, an argon plasma, or an ammonia plasma, and b. formula I:RX(I)[wherein R is a substituted or unsubstituted C1-C] 18 Linear alkyl groups, substituted or unsubstituted C3-C 18 Branched alkyl groups, substituted or unsubstituted C3-C8 cyclic alkyl groups, substituted or unsubstituted C3-C 10 Heterocyclic groups, substituted or unsubstituted C3-C 18 Alkenyl group, substituted or unsubstituted C4-C 18 Aryl group, substituted or unsubstituted C5-C 20An arylalkyl group, and a substituted or unsubstituted C3-C 10 At least one organic halide having a structure according to [selected from the group consisting of alkynyl groups, and X is a halide], which selectively reacts with silicon nitride to passivate the first surface, leaving the second surface substantially unreacted, and exposing the surface to at least one organic halide. A method is provided that includes the step of

[0007] In a further aspect of the first aspect, the method further includes a step of contacting the surface of the substrate with a wet chemical composition, a step of rinsing the surface with deionized water, and a step of drying the surface, which are performed before steps a and b, and the wet chemical composition is a composition containing 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. selected from the group consisting of at least one

[0008] In a further aspect of the first aspect, the second surface includes at least one selected from the group consisting of SiO2, metal oxide, copper, cobalt, tungsten, amorphous silicon, polycrystalline silicon, single crystal silicon, germanium, and hydrogenated amorphous germanium.

[0009] In a further aspect of the first aspect, the second surface includes SiO2. In a further aspect of the first aspect, at least one organic halide has a structure C n H 2n+1 having C1-C 18It is a linear alkyl group, and n is 1 to 18. In a further embodiment of the first aspect, at least one organic halide is selected from the group consisting of bromomethane, iodomethane, bromoethane, iodoethane, bromopropane, iodopropane, bromobutane, iodobutane, bromopentane, iodopentane, bromohexane, iodohexane, bromoheptane, iodoheptane, bromooctane, iodoheptane, bromononane, iodononane, bromodecane, iododecane, bromoundecane, iodonundecane, bromododecane, iodododecane, bromotridecane, iododotridecane, bromotetradecane, iodoheptadecane, bromopentadecane, iodopentadecane, bromohexadecane, iodoheptadecane, iodoheptadecane, bromooctadecane, and iodohtadecane. In a further embodiment of the first aspect, R is structure C n H 2n+1 C3~C 18It is a branched alkyl group, where n is 1 to 18. In a further embodiment of the first aspect, at least one organic halide is isopropyl bromide, isopropyl iodide, isobutyl bromide, isobutyl iodide, isopentyl bromide, isopentyl iodide, isohexyl bromide (1-bromo-4-methylpentane), isohexyl iodide (1-iodo-4-methylpentane), isoheptyl bromide, isoheptyl iodide, isooctyl bromide, isooctyl iodide, isononyl bromide, isononyl iodide, isodecyl bromide R is selected from the group consisting of isodecyl iodide, isoundecyl bromide, isoundecyl iodide, isododecyl bromide, isododecyl iodide, isotridecyl bromide, isotridecyl iodide, isotetradecyl bromide, isotetradecyl iodide, isopentadecyl bromide, isopentadecyl iodide, isohexadecyl bromide, isohexadecyl iodide, isoheptadecyl bromide, isoheptadecyl iodide, isooctadecyl bromide, and isooctadecyl iodide. In a further embodiment of the first aspect, R is a substituted or unsubstituted C3-C8 cyclic alkyl group. In a further embodiment of the first aspect, at least one organic halide is selected from the group consisting of cyclopropyl bromide, cyclopropyl iodide, cyclobutyl bromide, cyclobutyl iodide, cyclopentyl bromide, cyclopentyl iodide, cyclohexyl bromide, cyclohexyl iodide, cycloheptyl bromide, cycloheptyl iodide, cyclooctyl bromide, cyclooctyl iodide, 1-bromo-1-methylcyclohexane, and 1-iodo-1-methylcyclohexane. In a further embodiment of the first aspect, R is a substituted or unsubstituted C4-C 18 Contains an aryl group. In a further embodiment of the first embodiment, at least one organic halide is selected from the group consisting of bromobenzene, iodobenzene, benzyl bromide, and benzyl iodide. In a further embodiment of the first embodiment, R is unsubstituted C1-C 18 It is a linear alkyl group, or R is a substituted or unsubstituted C3-C 18It is a branched alkyl group. In a further embodiment of the first aspect, at least one organic halide is methyl bromide, methyl iodide, ethyl bromide, ethyl iodide, propyl bromide, propyl iodide, isopropyl bromide, isopropyl iodide, n-butyl bromide, n-butyl iodide, sec-butyl bromide, sec-butyl iodide, tert-butyl bromide, tert-butyl iodide, n-pentyl bromide, n-pentyl iodide, sec-pentyl bromide, sec-pentyl iodide, tert-pentyl bromide, tert-pentyl bromide N-Heptyl iodide, n-Hexyl bromide, n-Hexyl iodide, sec-Hexyl bromide, sec-Hexyl iodide, tert-Hexyl bromide, tert-Hexyl iodide, n-Heptyl bromide, n-Heptyl iodide, sec-Heptyl bromide, sec-Heptyl iodide, tert-Heptyl bromide, tert-Heptyl iodide, n-Octyl bromide, n-Octyl iodide, sec-Octyl bromide, sec-Octyl iodide, tert-Octyl bromide, tert-Octyl iodide, n-Bromononane, n-iodononane, sec-bromononane, sec-iodononane, tert-bromononane, tert-iodononane, n-bromodecane, n-iododecane, sec-bromodecane, sec-iododecane, tert-bromodecane, tert-iododecane, n-bromoundecane, n-iodonecane, sec-bromoundecane, sec-iodonecane, tert-bromoundecane, tert-iodonecane, n-bromododecane, n-iodododecane, sec-bromododecane, sec-iododecane, tert-bro Lomododecane, tert-iodododecane, n-bromotridecane, n-iodododecane, sec-bromotridecane, sec-iodododecane, tert-bromotridecane, tert-iodododecane, n-bromotetradecane, n-iodotetradecane, sec-bromotetradecane, sec-iodotetradecane, tert-bromotetradecane, tert-iodotetradecane, n-bromopentadecane, n-iodopentadecane, sec-bromopentadecane, sec-iodopentadecane, tert-bromopentadecane,Selected from the group consisting of tert-iodopentadecane, n-bromohexadecane, n-iodohexadecane, sec-bromohexadecane, sec-iodohexadecane, tert-bromohexadecane, tert-iodohexadecane, n-bromoheptadecane, n-iodoheptadecane, sec-bromoheptadecane, sec-iodoheptadecane, tert-bromoheptadecane, tert-iodoheptadecane, n-bromooctadecane, n-iodooctadecane, sec-bromooctadecane, sec-iodooctadecane, tert-bromooctadecane, tert-iodooctadecane, 1,1,3,3-tetramethylbutylbromide, 1,1,3,3-tetramethylbutyliodide, 1-methylheptylbromide, and 1-methylheptyliodide. ,

[0010] In a further embodiment of the first aspect, R is a substituted or unsubstituted C5-C 20 It is an arylalkyl group. In a further embodiment of the first embodiment, at least one organic halide is benzyl bromide or benzyl iodide. In a further embodiment of the first embodiment, step b is carried out using the vapor of at least one organic halide.

[0011] In a second embodiment, a method for selectively depositing a film on 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 a. optionally a step of treating the surface with a hydrogen plasma or an ammonia plasma, and b. formula I:RX(I)[wherein R is substituted or unsubstituted C1~C 18 Linear alkyl groups, substituted or unsubstituted branched C2-C 18 Alkyl alkyl groups, substituted or unsubstituted C3-C8 cyclic alkyl groups, substituted or unsubstituted C3-C 10 Heterocyclic groups, substituted or unsubstituted C3-C 18 Alkenyl group, substituted or unsubstituted C4-C 18 Aryl group, substituted or unsubstituted C5-C 20 Arylalkyl groups, and substituted or unsubstituted C3-C 10A method is provided which includes the steps of: a. exposing a surface to at least one organic halide having a structure selected from the group consisting of alkynyl groups, which selectively reacts with silicon nitride to passivate a first surface, thereby leaving a second surface substantially unreacted; and c. exposing the surface of a substrate to one or more deposition precursors to deposit a film on the second surface more selectively than on the first surface.

[0012] In a further embodiment of the second aspect, the following steps performed prior to steps a, b, and c are: 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 H2O2 (28% aqueous solution), NH4O4 (28-30%), and H2O, HF (0.01%-5% (aqueous solution)), peroxides, RCA cleaning chemicals SC-1 and SC-2, and mixtures of H2SO4 / H2O2. In a further embodiment of the second aspect, the second surface comprises at least one selected from the group consisting of SiO2, metal oxides, copper, cobalt, tungsten, amorphous silicon, polycrystalline silicon, single-crystal silicon, germanium, and hydride amorphous germanium. In a further embodiment of the second aspect, the second surface comprises SiO2.

[0013] In a further embodiment of the second aspect, at least one organic halide is structure C n H 2n+1 C1~C with -X 18 It is a linear alkyl group, and n is between 1 and 18.

[0014] In a further embodiment of the second aspect, at least one organic halide is selected from the group consisting of bromomethane, iodomethane, bromoethane, iodoethane, bromopropane, iodopropane, bromobutane, iodobutane, bromopentane, iodopentane, bromohexane, iodohexane, bromoheptane, iodoheptane, bromooctane, iodoheptane, bromononane, iodononane, bromodecane, iododecane, bromoundecane, iodonundecane, bromododecane, iodododecane, bromotridecane, iododotridecane, bromotetradecane, iodoheptadecane, bromopentadecane, iodopentadecane, bromohexadecane, iodoheptadecane, iodoheptadecane, bromooctadecane, and iodohtadecane.

[0015] In further embodiments of the first or second aspect, X is Br or I.

[0016] In a further embodiment of the second aspect, R is a substituted or unsubstituted C3-C8 cyclic alkyl group. In a further embodiment of the second aspect, at least one organic halide is selected from the group consisting of cyclopropyl bromide, cyclopropyl iodide, cyclobutyl bromide, cyclobutyl iodide, cyclopentyl bromide, cyclopentyl iodide, cyclohexyl bromide, cyclohexyl iodide, cycloheptyl bromide, cycloheptyl iodide, cyclooctyl bromide, cyclooctyl iodide, 1-bromo-1-methylcyclohexane, and 1-iodo-1-methylcyclohexane, o-methylcyclohexyl bromide, o-methylcyclohexyl iodide, m-methylcyclohexyl bromide, m-methylcyclohexyl iodide, p-methylcyclohexyl bromide, and p-methylcyclohexyl iodide. In a further embodiment of the second aspect, R is a substituted or unsubstituted C4-C 18 It is an aryl group.

[0017] In a further embodiment of the second aspect, at least one organic halide is selected from the group consisting of phenyl bromide, phenyl iodide, tolyl bromide, tolyl iodide, dimethylphenyl bromide, dimethylphenyl iodide, xyl bromide, and xyl iodide. In a further embodiment of the second aspect, R is an unsubstituted C1-C 18 Linear alkyl groups, or substituted or unsubstituted C3-C3 groups. 18It is a branched alkyl group. In a further embodiment of the second aspect, at least one organic halide is methyl bromide, methyl iodide, ethyl bromide, ethyl iodide, propyl bromide, propyl iodide, isopropyl bromide, isopropyl iodide, n-butyl bromide, n-butyl iodide, sec-butyl bromide, sec-butyl iodide, tert-butyl bromide, tert-butyl iodide, n-pentyl bromide, n-pentyl iodide, sec-pentyl bromide, sec-pentyl iodide, tert-pentyl bromide, tert-pentyl bromide N-Heptyl iodide, n-Hexyl bromide, n-Hexyl iodide, sec-Hexyl bromide, sec-Hexyl iodide, tert-Hexyl bromide, tert-Hexyl iodide, n-Heptyl bromide, n-Heptyl iodide, sec-Heptyl bromide, sec-Heptyl iodide, tert-Heptyl bromide, tert-Heptyl iodide, n-Octyl bromide, n-Octyl iodide, sec-Octyl bromide, sec-Octyl iodide, tert-Octyl bromide, tert-Octyl iodide, n-Bromononane, n-iodononane, sec-bromononane, sec-iodononane, tert-bromononane, tert-iodononane, n-bromodecane, n-iododecane, sec-bromodecane, sec-iododecane, tert-bromodecane, tert-iododecane, n-bromoundecane, n-iodonecane, sec-bromoundecane, sec-iodonecane, tert-bromoundecane, tert-iodonecane, n-bromododecane, n-iodododecane, sec-bromododecane, sec-iododecane, tert-bro Lomododecane, tert-iodododecane, n-bromotridecane, n-iodododecane, sec-bromotridecane, sec-iodododecane, tert-bromotridecane, tert-iodododecane, n-bromotetradecane, n-iodotetradecane, sec-bromotetradecane, sec-iodotetradecane, tert-bromotetradecane, tert-iodotetradecane, n-bromopentadecane, n-iodopentadecane, sec-bromopentadecane, sec-iodopentadecane, tert-bromopentadecane,Selected from the group consisting of tert-iodopentadecane, n-bromohexadecane, n-iodohexadecane, sec-bromohexadecane, sec-iodohexadecane, tert-bromohexadecane, tert-iodohexadecane, n-bromoheptadecane, n-iodoheptadecane, sec-bromoheptadecane, sec-iodoheptadecane, tert-bromoheptadecane, tert-iodoheptadecane, n-bromooctadecane, n-iodooctadecane, sec-bromooctadecane, sec-iodooctadecane, tert-bromooctadecane, tert-iodooctadecane, 1,1,3,3-tetramethylbutylbromide, 1,1,3,3-tetramethylbutyliodide, 1-methylheptylbromide, and 1-methylheptyliodide. In a further embodiment of the second aspect, R is a substituted or unsubstituted C5-C, 20 It is an arylalkyl group. In a further embodiment of the second aspect, at least one organic halide is benzyl bromide or benzyl iodide. In a further embodiment of the second aspect, step b is carried out using the vapor of at least one organic halide.

[0018] In the first or further embodiment of the second embodiment, step b is carried out using a liquid of at least one organic halide.

[0019] In a first or further embodiment of the second embodiment, the organic halide is selected from the group consisting of bromopropane, iodopropane, bromohexane, iodohexane, 1-bromo-4-methylpentane, 1-iodo-4-methylpentane, benzyl bromide, benzyl iodide, bromooctane, iodooctane, bromoundecane, and iodoundecane.

[0020] In the first or further embodiment of the second embodiment, R in formula (I) is R'-CH2, and R' is a linear C1-C 16 Alkyl group, branched C1-C 16 Alkyl groups, and C6-C 10 X is selected from the group consisting of aryl groups, and X is either Br or I.

[0021] In a further embodiment of the first aspect, d. further comprises depositing a metal film or metal nitride film on a substrate by atomic layer deposition, wherein the thickness of the metal film or metal nitride film deposited on the first surface is thinner than the thickness of the metal film or metal nitride film deposited on the second surface, the second surface contains silicon dioxide, and the deposition selectivity of the second surface relative to the first surface is greater than about 0.1. In a further embodiment of the second aspect, the film contains a metal or metal nitride.

[0022] In the first or further embodiment of the second, 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 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.

[0023] In the first or further embodiment of the second embodiment, the thickness of the metal film or metal nitride film deposited on the first surface is thinner than the thickness of the metal film or metal nitride film deposited on the second surface, the second surface contains silicon dioxide, and the deposition selectivity of the second surface relative to the first surface is greater than about 0.1.

[0024] The embodiments of this disclosure can be used individually or in combination with each other. [Brief explanation of the drawing]

[0025] The attached drawings are included to provide a further understanding of the disclosed subject matter, are incorporated herein and constitute part of this specification, illustrate embodiments of the disclosed subject matter, and, together with the detailed description, help to illustrate the principles of the disclosed subject matter. The drawings are as follows: [Figure 1]Figure 1 shows an exemplary process involving passivation and selective deposition of a silicon nitride surface, where a metal film is selectively deposited on the silicon dioxide surface while the silicon nitride surface is passivated. [Modes for carrying out the invention]

[0026] All references cited herein, including publications, patent applications, and patents, are incorporated herein by reference to the same extent as they are incorporated herein in whole, with each reference being individually and specifically indicated as being incorporated herein by reference.

[0027] In the context describing this disclosure (particularly in the context of the following claims), the use of the terms “a,” “an,” and “the,” and similar references, should be interpreted as encompassing both singular and plural forms unless otherwise indicated herein or expressly refuted by the context. The terms “comprising,” “having,” “including,” and “containing” should be interpreted as open-ended terms (i.e., “including, but not limited to”) unless otherwise indicated herein. Enumerations of value ranges herein are merely intended to serve as abbreviations for referring individually to each individual value that falls within that range, unless otherwise indicated herein, and each individual value is incorporated herein as if it were individually enumerated herein. All methods described herein may be performed in any preferred order unless otherwise indicated herein or expressly refuted by the context. Any and all examples or illustrative language provided herein (e.g., "etc.") are intended solely to better illustrate the disclosure and, unless expressly otherwise stated, do not limit the scope of the claims. No language in this specification should be construed as indicating any unclaimed element essential to the practice of the subject matter of this disclosure.

[0028] Preferred embodiments of this disclosure are described herein, including the best modes known to the inventors for carrying out the claimed subject matter. Variations of these preferred embodiments may become apparent to those skilled in the art by reading the foregoing description. The inventors anticipate that those skilled in the art will use such variations as needed, and they intend that the claimed subject matter will be practiced in ways other than those specifically described herein. Accordingly, this disclosure includes all modifications and equivalents of the subject matter enumerated in the claims appended herein, as permitted by applicable law. Furthermore, any combination of all possible variations of the above elements is encompassed by the claimed subject matter unless otherwise indicated herein or expressly rejected by the context.

[0029] There are various methods that can be used for selective deposition. Embodiments of this disclosure relate to methods that utilize surface deactivation by taking advantage of the surface chemistry of two different surfaces. Since the two different surfaces have different reactive sites, it is possible to utilize this difference to use molecules that react with one surface (deactivating that surface) but do not react with the other surface.

[0030] In one embodiment, a method for selectively passivating the surface of a substrate by a gas-phase reaction, wherein the surface of the substrate comprises at least one first surface containing silicon nitride and at least one second surface containing a material other than silicon nitride, the method comprising: 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 hydrogen plasma, argon plasma, or ammonia plasma; and e. formula I:RX(I)[wherein R is substituted or unsubstituted C1-C]. 18 Linear alkyl groups, substituted or unsubstituted C3-C 18 Branched alkyl groups, substituted or unsubstituted C3-C8 cyclic alkyl groups, substituted or unsubstituted C3-C 10 Heterocyclic groups, substituted or unsubstituted C3-C 18 Alkenyl group, substituted or unsubstituted C4-C18 Aryl group, substituted or unsubstituted C5-C 20 Arylalkyl groups, and substituted or unsubstituted C3-C 10 A method is provided which involves exposing a surface to at least one organic halide having a structure selected from the group consisting of alkynyl groups, where X is a halide, and which selectively reacts with silicon nitride to passivate a first surface, thereby leaving a second surface substantially unreacted.

[0031] In another embodiment, a method for selectively passivating the surface of a substrate by a liquid-phase reaction, wherein the surface of the substrate comprises at least one first surface containing silicon nitride and at least one second surface containing a material other than silicon nitride, the method comprising: 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 hydrogen plasma, argon plasma, or ammonia plasma; and e. formula I:RX(I)[wherein R is substituted or unsubstituted C1-C]. 18 Linear alkyl groups, substituted or unsubstituted C3-C 18 Branched alkyl groups, substituted or unsubstituted C3-C8 cyclic alkyl groups, substituted or unsubstituted C3-C 10 Heterocyclic groups, substituted or unsubstituted C3-C 18 Alkenyl group, substituted or unsubstituted C4-C 18 Aryl group, substituted or unsubstituted C5-C 20 Arylalkyl groups, and substituted or unsubstituted C3-C 10 A method is provided which involves exposing a surface to at least one organic halide having a structure selected from the group consisting of alkynyl groups, where X is a halide, and which selectively reacts with silicon nitride to passivate a first surface, thereby leaving a second surface substantially unreacted.

[0032] In another embodiment, a method for selectively depositing a film on the surface of a substrate, wherein the surface of the substrate comprises at least one first surface containing silicon nitride and at least one second surface containing a material other than silicon nitride, the method comprising: 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 hydrogen plasma or ammonia plasma; and e. formula I:RX[wherein R is substituted or unsubstituted C1-C]. 18 Linear alkyl groups, substituted or unsubstituted branched C3-C 18 Alkyl alkyl groups, substituted or unsubstituted C3-C8 cyclic alkyl groups, substituted or unsubstituted C3-C 10 Heterocyclic groups, substituted or unsubstituted C3-C 18 Alkenyl group, substituted or unsubstituted C4-C 18 Aryl group, substituted or unsubstituted C5-C 20 Arylalkyl groups, and substituted or unsubstituted C3-C 10 A method is provided which includes the steps of: f. exposing a surface to at least one organic halide having a structure selected from the group consisting of alkynyl groups, where X is a halide, and which selectively reacts with silicon nitride to passivate a first surface, thereby leaving a second surface substantially unreacted; and f. exposing the substrate to one or more deposition precursors to deposit a film on the second surface more selectively than on the first surface.

[0033] As used herein and in the appended claims, the terms “substrate” and “wafer” are interchangeable and both refer to a surface or portion of a surface on which a process is performed. Furthermore, those skilled in the art will understand that, unless the context clearly indicates otherwise, a reference to a substrate may refer to only a portion of a substrate. Moreover, a reference to depositing on a substrate may refer to both a plain substrate and a substrate on which one or more films or features have been deposited or formed.

[0034] As used herein, “substrate” refers to a substrate or a material surface formed on a substrate on which a film treatment is performed during a manufacturing process. For example, substrate surfaces on which treatment can be performed include, depending on the application, 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, as well as other materials such as metals, metal nitrides, metal alloys, and other conductive materials. 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 performing film treatment directly on the surface of the substrate itself, in this disclosure any of the disclosed film treatment steps may also be performed on an underlying layer formed on the substrate, as will be disclosed in more detail below, and the term “substrate surface” is intended to include such underlying layers as the context indicates. Therefore, for example, when a film / layer or partial film / layer is deposited on a substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate surface. What a particular substrate surface is composed of depends on the type of film to be deposited and the specific chemicals used. In one or more embodiments, the first substrate surface may contain a metal and the second substrate surface may contain a dielectric, or vice versa. In some embodiments, the substrate surface may contain specific functional groups (e.g., -OH, -NH, etc.).

[0035] Similarly, the films that can be used in the methods described herein are very diverse. In some embodiments, the film may contain a metal or a metal nitride, or be essentially composed 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 contains a dielectric. Examples include SiO2, SiN, HfO2, and the like.

[0036] In embodiments of the present disclosure, the substrate has at least two distinct surfaces, each distinct surface being characterized by a different chemical substance. For example, in one embodiment, the surface of the substrate comprises at least one first surface comprising silicon nitride and at least one second surface comprising at least a material other than silicon nitride.

[0037] The at least one second surface containing a material other than silicon nitride may be, for example, any material selected from the group consisting of SiO2, metal oxides, copper, cobalt, tungsten, amorphous silicon, polycrystalline silicon, single-crystal silicon, germanium, and hydride amorphous germanium. In some embodiments, the at least one second surface contains SiO2, which is a dielectric surface such as an SiO2 surface. In some embodiments, the SiO2-containing surface may include silicon oxide, fluorinated silica glass (FSG), carbon-doped silicon oxide (SiOC), and / or materials containing more than about 50% silicon oxide. In some embodiments, the SiO2-containing surface may include -OH groups, and may also include, for example, an alumina (Al2O3) surface having -OH surface groups.

[0038] Embodiments of this disclosure provide a method for selectively depositing a film, such as a metal film, on one surface of a substrate rather than on a second surface on the same substrate. As used herein and in the appended claims, the terms “selectively depositing a film on one surface rather than on the other” mean that one of the first or second surfaces is passivated to substantially prevent deposition on the passivated layer, and the film is deposited on the second (unpassivated) surface. The term “rather than” as used in this regard does not mean that one surface is physically located above the other, but rather indicates the relationship between the two surfaces in terms of the thermodynamic or kinetic properties of a chemical reaction. For example, selectively depositing a cobalt film on a copper surface rather than a dielectric surface means that the cobalt film is deposited on the copper surface and little 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 compared to the formation of a cobalt film on the dielectric surface.

[0039] In some situations, it may be desirable to selectively deposit material on one surface of a substrate to a second, different surface of the same substrate. For example, selective deposition may be used to form capping layers, barrier layers, etching stop layers, sacrificial layers and / or protective layers, or to seal pores in porous, low-k materials.

[0040] The method of the present disclosure includes an optional step of bringing the surface of a substrate into contact with a wet chemical composition to obtain a treated substrate. Examples of wet chemical treatments include known chemical treatments such as RCA cleaning chemicals SC-1 and SC-2, aqueous HF, peroxides, H2SO4 / H2O2, NH4OH, buffered HF solutions, and mixtures thereof.

[0041] In a preferred embodiment, the wet chemical composition comprises at least one selected from the group consisting of H2O2 (28% aqueous solution), NH4O4 (28-30%), a composition containing H2O, HF (0.01-10% (aqueous solution)), peroxides, RCA cleaning chemicals SC-1 and SC-2, and a mixture of H2SO4 / H2O2.

[0042] As is known in the art, "RCA cleaning chemicals" refer to compositions containing a mixture of ammonium hydroxide and hydrogen peroxide, and the basic cleaning procedure was developed in the 1960s by the Radio Corporation of America. The RCA Standard Cleaning 1 (SC-1) procedure uses a solution of ammonium hydroxide and hydrogen peroxide, along with water heated to approximately 70°C. The SC-1 procedure dissolves the film and removes Group I and Group II metals. Group I and Group II metals are removed by complex formation with the reagents in the SC-1 solution. The RCA Standard Cleaning 2 (SC-2) procedure utilizes a mixture of hydrogen peroxide, hydrochloric acid, and water heated to approximately 70°C. The SC-2 procedure removes metals not removed by the SC-1 procedure.

[0043] Contact with the wet chemical composition can be carried out by any method known to those skilled in the art, such as immersion or spraying. The contact step may be one separate step or two or more steps.

[0044] In some embodiments, the temperature of the wet chemical composition during the contact process may be, for example, approximately ambient temperature to about 100°C. In other embodiments, the temperature of the wet chemical composition during the contact process may be, for example, about 55°C to about 95°C. In yet another embodiment, the temperature of the wet chemical composition during the contact process may be, for example, about 60°C to about 90°C.

[0045] The embodiment also includes a step of rinsing the surface of the substrate with deionized water after the step of bringing the surface of the substrate into contact with the wet chemical composition. The rinsing step is typically performed by rinsing the surface of the substrate with deionized water by any suitable means, for example, immersion or spraying techniques.

[0046] The embodiment 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 the application of heat, isopropyl alcohol (IPA) vapor drying, or centripetal force.

[0047] Embodiments also optionally include a step of treating the surface with a hydrogen plasma, argon plasma, or ammonia plasma. Suitable processes include plasma processes (such as hydrogen plasma, NH3 / NF3 plasma, or water plasma). The optional plasma process serves to remove undesirable deposits on the surface and to activate the surface in preparation for subsequent deposition of a passivation reagent. Such plasma treatment may be performed most preferably after some deposition has been made on the surface, to non-selectively remove deposited material from a pre-passivated surface and to remove any remaining passivation reagent after a desired deposition thickness has been achieved.

[0048] The embodiment is formula I: RX(I) [In the formula, R is the substituted or unsubstituted C1-C 18 Linear alkyl groups, substituted or unsubstituted branched C3-C 18 Alkyl alkyl groups, substituted or unsubstituted C3-C8 cyclic alkyl groups, substituted or unsubstituted C3-C 10 Heterocyclic groups, substituted or unsubstituted C3-C 18 Alkenyl group, substituted or unsubstituted C4-C 18 Aryl group, substituted or unsubstituted C5-C 20 Arylalkyl groups, and substituted or unsubstituted C3-C 10 The process includes exposing a surface to a vapor or liquid containing at least one organic halide having a structure selected from the group consisting of alkynyl groups, which selectively reacts with silicon nitride to passivate a first surface, thereby leaving a second surface substantially unreacted.

[0049] In some embodiments, the organic halogen is Cn H 2n+1 C1-C, which have structures selected from the group consisting of the above. 18 It is a linear alkyl group. C1~C 18 Preferred organic halide precursors having a linear alkyl group include those selected from the group consisting of bromomethane, iodomethane, bromoethane, iodoethane, bromopropane, iodopropane, bromobutane, iodobutane, bromopentane, iodopentane, bromohexane, iodohexane, bromoheptane, iodoheptane, bromooctane, iodoheptane, bromononane, iodononane, bromodecane, iododecane, bromoundecane, iodondecane, bromododecane, iodododecane, bromotoridecane, iodoridecane, bromotetradecane, iodotetradecane, bromopentadecane, iodopentadecane, bromohexadecane, iodohexadecane, bromoheptadecane, iodoheptadecane, bromooctadecane, and iodohtadecane.

[0050] In other embodiments, R in formula I is C3~C 18 It is a branched alkyl group. Preferred organic halide precursors having a branched alkyl group include isopropyl bromide, isopropyl iodide, isobutyl bromide, isobutyl iodide, isopentyl bromide, isopentyl iodide, isohexyl bromide (1-bromo-4-methylpentane), isohexyl iodide (1-iodo-4-methylpentane), isoheptyl bromide, isoheptyl iodide, isooctyl bromide, isooctyl iodide, isononyl bromide, isononyl iodide, isodecyl bromide, isodecyl bromide, isodecyl bromide Examples include those selected from the group consisting of siliodide, isoundecylbromide, isoundecyliodide, isododecylbromide, isododecyliodide, isotridecylbromide, isotridecyliodide, isotetradecylbromide, isotetradecyliodide, isopentadecylbromide, isopentadecyliodide, isohexadecylbromide, isohexadecyliodide, isoheptadecylbromide, isoheptadecyliodide, isooctadecylbromide, and isooctadecyliodide.

[0051] In other embodiments, R in formula I is a substituted or unsubstituted C3-C8 cyclic alkyl group. In such embodiments, at least one organic halide is selected from the group consisting of cyclopropyl bromide, cyclopropyl iodide, cyclobutyl bromide, cyclobutyl iodide, cyclopentyl bromide, cyclopentyl iodide, cyclohexyl bromide, cyclohexyl iodide, cycloheptyl bromide, cycloheptyl iodide, cyclooctyl bromide, cyclooctyl iodide, 1-bromo-1-methylcyclohexane, and 1-iodo-1-methylcyclohexane.

[0052] In other embodiments, R in formula I is a substituted or unsubstituted C4-C 18 It is an aryl group. In such embodiments, the organic halide can be selected from the group consisting of phenyl bromide, phenyl iodide, tolyl bromide, tolyl iodide, dimethylphenyl bromide, dimethylphenyl iodide, xyl bromide, and xyl iodide.

[0053] In other embodiments, R in formula I is unsubstituted C1-C 18 It is a linear alkyl group, or R is a substituted or unsubstituted C3-C 18It is a branched alkyl group. In such embodiments, the organic halides include methyl bromide, methyl iodide, ethyl bromide, ethyl iodide, propyl bromide, propyl iodide, isopropyl bromide, isopropyl iodide, n-butyl bromide, n-butyl iodide, sec-butyl bromide, sec-butyl iodide, tert-butyl bromide, tert-butyl iodide, n-pentyl bromide, n-pentyl iodide, sec-pentyl bromide, sec-pentyl iodide, tert-pentyl bromide, tert-pentyl iodide, n -Hexyl bromide, n-hexyl iodide, sec-hexyl bromide, sec-hexyl iodide, tert-hexyl bromide, tert-hexyl iodide, n-heptyl bromide, n-heptyl iodide, sec-heptyl bromide, sec-heptyl iodide, tert-heptyl bromide, tert-heptyl iodide, n-octyl bromide, n-octyl iodide, sec-octyl bromide, sec-octyl iodide, tert-octyl bromide, tert-octyl iodide, n-bromononane, n-iodononane, se c-bromononane, sec-iodononane, tert-bromononane, tert-iodononane, n-bromodecane, n-iododecane, sec-bromodecane, sec-iododecane, tert-bromodecane, tert-iododecane, n-bromoundecane, n-iodonecane, sec-bromoundecane, sec-iodonecane, tert-bromoundecane, tert-iodonecane, n-bromododecane, n-iodododecane, sec-bromododecane, sec-iodonecane, tert-bromododecane, tert-yo Dododecane, n-bromotridecane, n-iodotridecane, sec-bromotridecane, sec-iodotridecane, tert-bromotridecane, tert-iodotridecane, n-bromotetradecane, n-iodotetradecane, sec-bromotetradecane, sec-iodotetradecane, tert-bromotetradecane, tert-iodotetradecane, n-bromopentadecane, n-iodopentadecane, sec-bromopentadecane, sec-iodopentadecane, tert-bromopentadecane, tert-iodopentadecane,Examples include those selected from the group consisting of n-bromohexadecane, n-iodohexadecane, sec-bromohexadecane, sec-iodohexadecane, tert-bromohexadecane, tert-iodohexadecane, n-bromoheptadecane, n-iodoheptadecane, sec-bromoheptadecane, sec-iodoheptadecane, tert-bromoheptadecane, tert-iodoheptadecane, n-bromooctadecane, n-iodooctadecane, sec-bromooctadecane, sec-iodooctadecane, tert-bromooctadecane, tert-iodooctadecane, 1,1,3,3-tetramethylbutyl bromide, 1,1,3,3-tetramethylbutyl iodide, 1-methylheptyl bromide, and 1-methylheptyl iodide.

[0054] In another embodiment, R in formula I is a substituted or unsubstituted C. 54 ~C 20 It is an arylalkyl group. In such embodiments, examples of organic halides include benzyl bromide or benzyl iodide.

[0055] As used herein, the term "alkyl" means a linear or branched saturated hydrocarbon group. In some embodiments, alkyl groups have 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 methyl (Me), ethyl (Et), propyl (e.g., n-propyl and isopropyl), butyl (e.g., n-butyl, t-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 Examples include, but are not limited to, 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.

[0056] As used throughout this specification, the term “cyclic alkyl” refers to a cyclic functional group having 3 to 10 or 4 to 10 carbon atoms. Examples of cyclic alkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

[0057] As used herein, the term "aryl" means a monocyclic, bicyclic, or polycyclic (e.g., having two, three, or four fused rings) aromatic hydrocarbon. 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, anthracenyl, phenantrenyl, indanyl, indenyl, and tetrahydronaphthyl.

[0058] As used herein, the term "arylalkyl" means an alkyl group substituted with an aryl group. In some embodiments, the alkyl group is C 1~6 It is an alkyl group.

[0059] As used throughout this specification, the term “alkenyl group” refers to a group having one or more carbon-carbon double bonds and containing 2 to 18 or 2 to 10 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl groups and allyl groups.

[0060] As used herein, the term "alkynyl" means a linear or branched alkyl group having 2 to 20 carbon atoms and one or more triple carbon-carbon 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-propylene, and 2-propylene.

[0061] As used herein, the phrase “optionally substituted” means that the substitution is optional and therefore includes both unsubstituted and substituted atoms and parts. “Substituted” atom or substructure means that any hydrogen atom on a given compound or substructure can be replaced with a group selected from the given substituents, provided that the substitution does not exceed the normal valence of the given compound or substructure and that the substitution results in a stable compound. For example, if a methyl group is optionally substituted, one, two, or three hydrogen atoms on the carbon atoms within the methyl group can be replaced with one, two, or three of the listed substituents.

[0062] As used herein, the term "phenyl" means -C6H5. The phenyl group may be unsubstituted or substituted with one, two, or three suitable substituents.

[0063] As used herein, the term “cyclic alkyl” means non-aromatic cyclic hydrocarbons containing cycloalkyl, alkenyl, and alkynyl groups having up to 20 ring-forming carbon atoms. Cycloalkyl groups have 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 cycloalkyl groups may be optionally substituted with oxo or sulfide. Cycloalkyl groups include, but are not limited to, monocyclic or polycyclic ring systems such as fused ring systems, bridging ring systems, and spiro ring systems. In some embodiments, polycyclic ring systems include 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, cycloheptatrienyl, norbornyl, norpinyl, norcarnyl, and adamantyl. Cycloalkyl groups may also have one or more aromatic rings condensed (sharing a common bond) to the cycloalkyl ring, such as benzo or thienyl derivatives of pentane, pentene, hexane, etc. (e.g., 2,3-dihydro-1H-inden-1-yl, or 1H-inden-2(3H)-on-1-yl).

[0064] As used herein, the term "halo" means a halogen group, and includes, but is not limited to, fluoro, chloro, bromo, and iodine.

[0065] As used herein, the terms “heterocyclic” or “heterocyclic ring” mean a monocyclic or bicyclic ring system of 5 to 7 members or 7 to 10 members, where each ring may be saturated or unsaturated, and the ring consists of a carbon atom and 1 to 3 heteroatoms selected from N, O, and S, where the N and S heteroatoms may be optionally oxidized, and the N heteroatom may be optionally quaternized, and includes any bicyclic group in which any of the above-defined heterocyclic rings is fused to a benzene ring. Heterocyclic rings include rings containing one oxygen or sulfur atom, 1 to 3 nitrogen atoms, or one oxygen or sulfur atom combined with one or two nitrogen atoms. Heterocyclic rings can bond to any heteroatom or carbon atom to form stable structures. Examples of heterocyclic groups include piperidinyl, piperazinyl, 2-oxopiperazinyl, 2-oxopiperidinyl, 2-oxopyrrodinyl, 2-oxoazepinyl, azepinyl, pyrrolyl, 4-piperidonyl, pyrrolidinyl, pyrazolyl, pyrazolidinyl, imidazolyl, imidazolinyl, pyridyl, imidazolidinyl, pyrazinyl, pyrimidinyl, pyridadinyl, oxazolyl, oxazolidinyl, isoxazolyl, isoxazolidinyl, morpholinyl, and cyanoacrylate. Examples include, but are not limited to, azolyl, thiazolidinyl, isothiazolyl, quinuclidinyl, isothiazolyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, thiadiazoyl, benzopyranil, benzothiazolyl, benzoxazolyl, furyl, tetrahydrofuryl, tetrahydropyranil, thienyl, benzothienyl, thiamorpholinyl, thiamorpholinyl sulfoxide, thiamorpholinyl sulfone, and oxadiazolyl.

[0066] Gas-phase reactions involve exposing a heated substrate to precursor molecules and / or co-reactants within a suitable chamber that allows for the necessary pressure control and can supply heat to the substrate and / or chamber walls. The chamber also generally needs to provide high leak-proof sealing, as well as adequate purity for the resulting reaction through the use of ultra-high purity carrier and reactive gases.

[0067] As used herein and in the appended claims, terms such as “reactive gas,” “precursor,” and “reactant” are used interchangeably to mean a gas containing species that react with the substrate surface. For example, a first “reactive gas” may simply adsorb onto the substrate surface and become available for further chemical reactions with a second reactive gas. These may be used in combination with an ultra-high purity carrier gas (as defined above) or as any desired mixture of each other (i.e., two or more types of precursors may be used together or in separate, independent processes, with the introduction order of the precursors arbitrarily set to form a desired passivation layer).

[0068] The precursor and / or co-reactants can be introduced into the reactor using a mass flow controller (which may have a heating line), a liquid injection vaporizer (which may have a heating line), or without a metering device (i.e., by introducing the vapor and / or gas directly from a container separated from the reactor using a simple valve). Any of the above can also be used in combination with each other. Any means of supplying gas and / or vapor to the reaction chamber that provides sufficient purity and reproducibility can be used.

[0069] The precursors and / or co-reactants may be introduced into the reactor independently, mixed before introduction into the reactor, mixed within the reactor, or combined with other independent steps as described above, with variations in the method of introducing the precursors between steps.

[0070] The reaction temperature range may be room temperature to 400°C. In some cases, the reaction temperature range may be room temperature to 200°C. In yet other cases, the reaction temperature range may be room temperature to 100°C. The pressure is 10 -10The pressure may be in the range of Torr ~ 3000 Torr, and may be maintained under dynamic flow conditions (i.e., a valve and butterfly valve configuration), or under static conditions (i.e., the vacuum chamber is exposed to the desired precursor and / or co-reactants, held until a predetermined total pressure is achieved, and then the chamber is isolated from both the precursor and / or co-reactant supply source and the vacuum pump). The reactor can be completely evacuated and then re-exposed to fresh precursor and / or co-reactants as many times as necessary. The precursor and / or co-reactants can be introduced using any desired mixture and / or concentration.

[0071] Surface exposure can be carried out for 0.1 to 60 minutes, preferably 1 to 5 minutes, and most preferably 1 minute. The partial pressure of the organic halide in the reaction chamber can be varied from about 1% of the saturated vapor pressure at the substrate temperature to almost 100% of the saturated vapor pressure. Most preferably, it is 20 to 50% of the saturated vapor pressure. The chamber pressure may be the same as the partial pressure of the organic halide vapor, but may be higher depending on the balance of the atmosphere including the carrier gas. Preferred carrier gases are N2, He, and Ar, but other gases such as H2, CO2, and dry O2 can also be used. The exposed vapor may be stationary (non-flowing) for all or part of the exposure period. A preferred embodiment is to flow the organic halide vapor through the exposure chamber with an optional carrier gas so that fresh vapor is exposed to the substrate surface for at least part of the exposure period.

[0072] The exposure chamber can be kept near ambient temperature or optionally heated. Heat can be supplied to the outer wall of the chamber (hot wall) 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), resistance heating of the substrate itself, heating by resistance heating elements in the platform in contact with the substrate, induction heating, or other means known in the art. The processing temperature is preferably about 20°C to about 400°C, preferably 20°C to about 200°C, and most preferably 20°C to about 100°C. The temperature can be kept constant during the exposure period or varied within a specific temperature range.

[0073] Next, unreacted vapors of at least one organic halide can optionally be removed by exhausting or purging the chamber with a suitable inert gas before removing the substrate from the chamber or before processing by chemical vapor deposition or atomic layer deposition. Optionally, the exposure chamber can also be used for subsequent processing steps to improve process efficiency, thereby allowing the process to be repeated from step c) as needed to remove the protective film and non-selective ALD deposits, and then to re-form the protective film.

[0074] The selection of at least one organic halide and exposure conditions used in this method must be optimized by standard experiments to optimize the selectivity of protection of the silicon nitride surface against potential non-selective passivation, processing time, reagent costs, etc., depending on the requirements imposed by subsequent processing steps. For example, selectivity can be adjusted / optimized by changing the properties of the R group of at least one organic halide having the structure represented by formula I. Typically, reactivity and selectivity are often inversely correlated, so experiments with the R group may be necessary to optimize the process when the two surfaces are chemically similar. For example, there is a difference in reactivity between alkyl R groups and aryl R groups. Typically, aryl groups are more reactive with surfaces having active hydrogen than alkyl groups. As a result, in some cases, alkyl groups may be required to selectively passivate SiN without passivating adjacent surfaces with less reactive active hydrogen atoms.

[0075] When the silicon nitride surface is passivated, a second surface, for example containing silicon oxide, becomes active for further selective reactions, such as the selective ALD deposition of SiCN on a 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., SiO2). x SiN x SiO x N y SiC x N y SiO x C y This includes metals, metal nitrides, and metal oxides (all of which may also contain hydrogen).

[0076] In some embodiments, a metal oxide film is selectively deposited on a second surface. In one example, the metal oxide film may function as a capping 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 one embodiment, the metal oxide film may be selected from the group consisting of HfO2, ZrO2, TiO2, Al2O3, and combinations thereof. In some examples, the metal oxide film may be deposited by ALD using alternating exposure of a metal-organic precursor and an oxidizing agent (e.g., H2O, H2O2, plasma-excited O2, or O3), as detailed in U.S. Provisional Patent Application No. 62 / 472,724, filed March 17, 2017, which is incorporated herein by reference in whole.

[0077] The selective deposition described herein may, for example, be a metal layer and a metal oxide layer, as disclosed in Hamalainen 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, Volume 17, Number 5, June 2014, both of which are incorporated herein by reference in their entirety.

[0078] In some embodiments, the metal film is selectively deposited on a second surface. In one example, the metal film may function as a capping layer on the second surface. In another example, the metal film may function as a conductive path (i.e., a line, pad, or plug) on ​​the second surface. In yet another example, the metal film can be deposited by, for example, atomic layer deposition (ALD), plasma-enhanced ALD (PEALD), chemical vapor deposition (CVD), plasma-enhanced CVD (PECVD), or pulsed CVD. According to one embodiment, the metal film may 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.

[0079] In some embodiments, a metal or metal nitride film is selectively deposited on a second surface. In one example, the metal or metal nitride film may function as a capping layer on the second surface. In another example, the metal or metal nitride film may function 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. An example is, for instance, "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.

[0080] During the selective deposition process, the aforementioned protective surface, selectively pre-deposited on the silicon nitride surface using at least one organic halide, may initiate a reaction or experience a decrease in inertness. To prevent or delay non-selective deposition on the silicon nitride surface, the reapplication of at least one organic halide can be selectively repeated, with or without the presence of an aqueous solution or plasma pretreatment step.

[0081] In some embodiments, passivation on a first surface of a substrate (such as the silicon nitride surface of the substrate) as described herein has a selectivity of at least about 90%, at least about 95%, at least about 96%, 97%, 98%, or 99% or more relative to a second surface of the substrate. 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 relative to the second surface of the substrate has a selectivity of at least about 70%, or at least about 80%, which may be sufficient selectivity for certain applications. In some embodiments, passivation on the first surface of the substrate relative to the second surface of the substrate has a selectivity of at least about 50%, which may be sufficient selectivity for certain applications.

[0082] The passivation layer can be removed using wet chemical cleaning. Examples of wet chemical cleaning include acidic, basic, and oxidizing (e.g., peroxide-containing) wet chemical compositions known in the art, for an optional step of contacting the substrate with the wet chemical composition as described above. Another method for removing the passivation layer is by the application of heat or other energy. [Examples]

[0083] Organic halides (alkyl halides or aryl halides) selectively passivate the Si3N4 surface relative to the SiO2 surface. This process is shown in Figure 1. This process allows for the selective growth of thicker metal films (or metal nitride films) on the SiO2.

[0084] A substrate 100 having a first surface 102 (Si3N4) and a second surface 104 (SiO2). The substrate is exposed to an alkyl halide or aryl halide inhibitor to form a passivation region 106, preferably a self-assembled monolayer (SAM), and selectively passivate the Si3N4 surface 102 by converting Si-NH2 groups to aliphatic or aromatic groups. Subsequently, a metal film 108 is deposited on the second surface 104.

[0085] process: (1) Wet process: Si3N4 and SiO2 substrates are immersed in an alkyl halide or aryl halide solution (5% in toluene) at 60°C for 16 hours. Si3N4 and SiO2 are rinsed with MeOH. The substrates are dried with an N2 stream. (2) Gas phase process: Si3N4 and SiO2 substrates are loaded into the reactor. Si3N4 is exposed to concentrated bromohexane vapor at 70°C for 180 minutes (reactor pressure is 8 Torr). (3) A Ru film is selectively deposited on the SiO2 surface by performing the RuP08 / (H2 or NH3)ALD process.

[0086] Embodiments:

[0087] Ru films are grown on Si3N4 and SiO2 substrates treated with alkyl halides or aryl halides (wet or vapor phase process). The thickness of the Ru film grown on the inhibitor-treated Si3N4 is thinner than the thickness of the Ru film grown on the untreated Si3N4 (Figure 1). In contrast, the thickness of the Ru film grown on all SiO2 is similar. These results demonstrate selective passivation between the first surface (Si3N4) and the second surface (SiO2). The selectivity is reported in Table 1 based on the thickness of the Ru films grown on Si3N4 and SiO2. For the purposes of this disclosure and claims, the selectivity of the second surface over the first surface is given by the following formula: Selectivity = (Thickness of film on the second surface (SiO2) - Thickness of film on the first surface (Si3N4)) / (Thickness of film on the second surface (SiO2) + Thickness of film on the first surface (Si3N4)).

[0088] The results of Ru growth on untreated substrates (Si3N4(SiN) and SiO2) and substrates treated with inhibitors are described below. In the wet process, without inhibitor treatment, the growth depth was 40.2 Å on SiN and 43.8 Å on SiO2. In the wet process, with passivation using bromopropane, the growth depth was 25.6 Å on SiN and 41.7 Å on SiO2.

[0089] In the wet process, passivation with bromohexane resulted in a depth of 25.1 Å on SiN and 42.2 Å on SiO2. In the wet process, passivation with bromoundecane resulted in a depth of 32.6 Å on SiN and 43.5 Å on SiO2. In the wet process, passivation with 1-bromo-4-methylpentane resulted in a depth of 32.6 Å on SiN and 44.8 Å on SiO2. In the wet process, passivation with benzyl bromide resulted in a depth of 32.6 Å on SiN and 44.8 Å on SiO2. In the wet process, passivation with iodohexane resulted in a depth of 31.6 Å on SiN and 43.7 Å on SiO2. In the wet process, passivation with iodooctane resulted in a depth of 28.1 Å on SiN and 43.8 Å on SiO2. The result was 28.1 Å.

[0090] In the gas-phase process, without the use of an inhibitor, the pressure was 40.3 Å on SiN and 43.8 Å on SiO2. In the gas-phase process, passivation with bromopropane resulted in pressures of 36.6 Å on SiN and 42.5 Å on SiO2. In the gas-phase process, passivation with bromohexane resulted in pressures of 32.6 Å on SiN and 44.8 Å on SiO2.

[0091] [Table 1]

[0092] While the principles of this disclosure have been described above in relation to preferred embodiments, it should be clearly understood that this description is provided for illustrative purposes only and does not limit 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 one first surface containing silicon nitride and at least one second surface containing a material other than silicon nitride, and the method is a. A step of treating the surface with hydrogen plasma, argon plasma, or ammonia plasma, which can be optionally selected. b. Formula I: R-X(I) [wherein, R is a substituted or unsubstituted C １ to C １８ linear alkyl group, substituted or unsubstituted branched C ３ to C １８ alkyl group, substituted or unsubstituted C ３ to C ８ cyclic alkyl group, substituted or unsubstituted C ３ to C １０ heterocyclic group, substituted or unsubstituted C ３ to C １８ alkenyl group, substituted or unsubstituted C ４ to C １８ aryl group, substituted or unsubstituted C ５ to C ２０ arylalkyl group, and substituted or unsubstituted C ３ to C １０ alkynyl group, and is at least one organic halide having a structure represented by [where X is a halide], and by selectively reacting with the silicon nitride to passivate the first surface, leaving the second surface substantially unreacted, exposing the surface to at least one organic halide, a method comprising.

2. The following steps are performed before steps a and b: A step of bringing the surface of the substrate into contact with a wet chemical composition, The process of rinsing the aforementioned surface with deionized water, The process further includes the step of drying the aforementioned surface, The aforementioned wet chemical composition is H ２ O ２ (28% aqueous solution), NH ４ O ４ (28-30%), and H ２ A composition containing 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 The method according to claim 1, comprising at least one selected from the group consisting of mixtures of the following.

3. The second surface is SiO ２ The method according to claim 1, comprising at least one selected from the group consisting of metal oxides, copper, cobalt, tungsten, amorphous silicon, polycrystalline silicon, single-crystal silicon, germanium, and amorphous germanium hydride.

4. The second surface is SiO ２ The method according to claim 3, including the method described in claim 3.

5. The above at least one organic halogen has structure C ｎ H ２ｎ＋１ A prominent C １ ~C １８ The method according to claim 1, wherein the linear alkyl group is 1 to 18.

6. The method according to claim 5, wherein the at least one organic halogen is selected from the group consisting of bromomethane, iodomethane, bromoethane, iodoethane, bromopropane, iodopropane, bromobutane, iodobutane, bromopentane, iodopentane, bromohexane, iodohexane, bromoheptane, iodoheptane, bromooctane, iodoheptane, bromononane, iodononane, bromodecane, iododecane, bromoundecane, iodonundecane, bromododecane, iodododecane, bromotoridecane, iodoridecane, bromotetradecane, iodotetradecane, bromopentadecane, iodopentadecane, bromohexadecane, iodohexadecane, bromoheptadecane, iodoheptadecane, bromooctadecane, and iodohtadecane.

7. R is structure C ｎ H ２ｎ＋１ A prominent C ３ ~C １８ The method according to claim 1, wherein the branched alkyl group is n from 1 to 18.

8. The above at least one organic halogen is isopropyl bromide, isopropyl iodide, isobutyl bromide, isobutyl iodide, isopentyl bromide, isopentyl iodide, isohexyl bromide (1-bromo-4-methylpentane), isohexyl iodide (1-iodo-4-methylpentane), isoheptyl bromide, isoheptyl iodide, isooctyl bromide, isooctyl iodide, isononyl bromide, isononyl iodide, isodecyl bromide, isodecyl iodide, The method according to claim 7, selected from the group consisting of isoundecylbromide, isoundecyliodide, isododecylbromide, isododecyliodide, isotridecylbromide, isotridecyliodide, isotetradecylbromide, isotetradecyliodide, isopentadecylbromide, isopentadecyliodide, isohexadecylbromide, isohexadecyliodide, isoheptadecylbromide, isoheptadecyliodide, isooctadecylbromide, and isooctadecyliodide.

9. R is a substituted or non-substituted C ３ ~C ８ The method according to claim 1, wherein the alkyl group is cyclic alkyl.

10. The method according to claim 9, wherein the at least one organic halide is selected from the group consisting of cyclopropyl bromide, cyclopropyl iodide, cyclobutyl bromide, cyclobutyl iodide, cyclopentyl bromide, cyclopentyl iodide, cyclohexyl bromide, cyclohexyl iodide, cycloheptyl bromide, cycloheptyl iodide, cyclooctyl bromide, cyclooctyl iodide, 1-bromo-1-methylcyclohexane, and 1-iodo-1-methylcyclohexane.

11. R is a substituted or non-substituted C ４ ~C １８ The method according to claim 1, comprising an aryl group.

12. The method according to claim 11, wherein the at least one organic halide is selected from the group consisting of bromobenzene, iodobenzene, benzyl bromide, and benzyl iodide.

13. R is an unsubstituted C １ ~C １８ It is a linear alkyl group, or R is a substituted or unsubstituted C. ３ ~C １８ The method according to claim 1, wherein the alkyl group is branched.

14. The above at least one organic halide is methyl bromide, methyl iodide, ethyl bromide, ethyl iodide, propyl bromide, propyl iodide, isopropyl bromide, isopropyl iodide, n-butyl bromide, n-butyl iodide, sec-butyl bromide, sec-butyl iodide, tert-butyl bromide, tert-butyl iodide, n-pentyl bromide, n-pentyl iodide, sec-pentyl bromide, sec-pentyl iodide, tert-pentyl bromide, tert-pentyl iodide, n-hexyl bromide n-hexyl iodide, sec-hexyl bromide, sec-hexyl iodide, tert-hexyl bromide, tert-hexyl iodide, n-heptyl bromide, n-heptyl iodide, sec-heptyl bromide, sec-heptyl iodide, tert-heptyl bromide, tert-heptyl iodide, n-octyl bromide, n-octyl iodide, sec-octyl bromide, sec-octyl bromide, tert-octyl iodide, n-bromononane, n-iodononane, sec-bromononane, s ec-iodononane, tert-bromononane, tert-iodononane, n-bromodecane, n-iododecane, sec-bromodecane, sec-iododecane, tert-bromodecane, tert-iododecane, n-bromoundecane, n-iodonecane, sec-bromoundecane, sec-iodonecane, tert-bromoundecane, tert-iodonecane, n-bromododecane, n-iodododecane, sec-bromododecane, sec-iodonecane, tert-bromododecane, tert-iodonecane, n-bro Motridecane, n-iodotridecane, sec-bromotridecane, sec-iodotridecane, tert-bromotridecane, tert-iodotridecane, n-bromotetradecane, n-iodotetradecane, sec-bromotetradecane, sec-iodotetradecane, tert-bromotetradecane, tert-iodotetradecane, n-bromopentadecane, n-iodopentadecane, sec-bromopentadecane, sec-iodopentadecane, tert-bromopentadecane, tert-iodopentadecane, n-bromohexadecane,n-iodohexadecane, sec-bromohexadecane, sec-iodohexadecane, tert-bromohexadecane, tert-iodohexadecane, n-bromoheptadecane, n-iodoheptadecane, sec-bromoheptadecane, sec-iodoheptadecane, tert-bromoheptadecane, tert-iodoheptadecane, n-bromooctadecane, n- The method according to claim 13, selected from the group consisting of iodooctadecane, sec-bromooctadecane, sec-iodooctadecane, tert-bromooctadecane, tert-iodooctadecane, 1,1,3,3-tetramethylbutylbromide, 1,1,3,3-tetramethylbutyliodide, 1-methylheptylbromide, and 1-methylheptyliodide.

15. R is a substituted or non-substituted C ５ ~C ２０ The method according to claim 1, wherein the alkyl group is an arylalkyl group.

16. The method according to claim 15, wherein the at least one organic halogen is benzyl bromide or benzyl iodide.

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

18. A method for selectively depositing a film on the surface of a substrate, wherein the surface of the substrate comprises at least one first surface containing silicon nitride and at least one second surface containing a material other than silicon nitride, and the method is a. Optionally, a step of treating the surface with hydrogen plasma or ammonia plasma, b. Formula I: R-X(I) [In the formula, R is a substituted or unsubstituted C] １ ~C １８ Linear alkyl groups, substituted or unsubstituted branched C ２ ~C １８ Alkyl alkyl groups, substituted or unsubstituted C ３ ~C ８ Cyclic alkyl groups, substituted or unsubstituted C ３ ~C １０ Heterocyclic groups, substituted or unsubstituted C ３ ~C １８ Alkenyl group, substituted or unsubstituted C ４ ~C １８ Aryl group, substituted or unsubstituted C ５ ~C ２０ Arylalkyl groups, and substituted or unsubstituted C ３ ~C １０ A step of exposing the surface to at least one organic halide having a structure selected from the group consisting of alkynyl groups, wherein the organic halide selectively reacts with the silicon nitride to passivate the first surface, thereby leaving the second surface substantially unreacted. c. A method comprising the step of exposing the surface of the substrate to one or more deposition precursors to deposit a film on the second surface more selectively than the first surface.

19. The following steps are performed before steps a, b, and c. A step of bringing the surface of the substrate into contact with a wet chemical composition, The process of rinsing the aforementioned surface with deionized water, The process further includes the step of drying the aforementioned surface, The aforementioned wet chemical composition is H ２ O ２ (28% aqueous solution), NH ４ O ４ (28-30%), and H ２ A composition containing 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 The method according to claim 18, comprising at least one selected from the group consisting of mixtures of the following.

20. The second surface is SiO ２ The method according to claim 18, comprising at least one selected from the group consisting of metal oxides, copper, cobalt, tungsten, amorphous silicon, polycrystalline silicon, single-crystal silicon, germanium, and amorphous germanium hydride.

21. The second surface is SiO ２ The method according to claim 20, including the method described in claim 20.

22. The above at least one organic halogen has structure C ｎ H ２ｎ＋１ -X has C １ ~C １８ The method according to claim 18, wherein the linear alkyl group is n is 1 to 18.

23. The method according to claim 22, wherein the at least one organic halogen is selected from the group consisting of bromomethane, iodomethane, bromoethane, iodoethane, bromopropane, iodopropane, bromobutane, iodobutane, bromopentane, iodopentane, bromohexane, iodohexane, bromoheptane, iodoheptane, bromooctane, iodoheptane, bromononane, iodononane, bromodecane, iododecane, bromoundecane, iodonundecane, bromododecane, iodododecane, bromotoridecane, iodoridecane, bromotetradecane, iodotetradecane, bromopentadecane, iodopentadecane, bromohexadecane, iodohexadecane, bromoheptadecane, iodoheptadecane, bromooctadecane, and iodohtadecane.

24. The method according to claim 1 or 18, wherein X is Br or I.

25. R is a substituted or non-substituted C ３ ~C ８ The method according to claim 18, wherein the alkyl group is cyclic alkyl.

26. The method according to claim 25, wherein the at least one organic halide is selected from the group consisting of cyclopropyl bromide, cyclopropyl iodide, cyclobutyl bromide, cyclobutyl iodide, cyclopentyl bromide, cyclopentyl iodide, cyclohexyl bromide, cyclohexyl iodide, cycloheptyl bromide, cycloheptyl iodide, cyclooctyl bromide, cyclooctyl iodide, 1-bromo-1-methylcyclohexane, 1-iodo-1-methylcyclohexane, o-methylcyclohexyl bromide, o-methylcyclohexyl iodide, m-methylcyclohexyl bromide, m-methylcyclohexyl iodide, p-methylcyclohexyl bromide, and p-methylcyclohexyl iodide.

27. R is a substituted or non-substituted C ４ ~C １８ The method according to claim 18, wherein the group is an aryl group.

28. The method according to claim 27, wherein the at least one organic halide is selected from the group consisting of phenyl bromide, phenyl iodide, tolyl bromide, tolyl iodide, dimethylphenyl bromide, dimethylphenyl iodide, xyl bromide, and xyl iodide.

29. R is an unsubstituted C １ ~C １８ It is a linear alkyl group, or R is a substituted or unsubstituted C. ３ ~C １８ The method according to claim 18, wherein the alkyl group is branched.

30. The above at least one organic halide is methyl bromide, methyl iodide, ethyl bromide, ethyl iodide, propyl bromide, propyl iodide, isopropyl bromide, isopropyl iodide, n-butyl bromide, n-butyl iodide, sec-butyl bromide, sec-butyl iodide, tert-butyl bromide, tert-butyl iodide, n-pentyl bromide, n-pentyl iodide, sec-pentyl bromide, sec-pentyl iodide, tert-pentyl bromide, tert-pentyl iodide, n-hexyl bromide n-hexyl iodide, sec-hexyl bromide, sec-hexyl iodide, tert-hexyl bromide, tert-hexyl iodide, n-heptyl bromide, n-heptyl iodide, sec-heptyl bromide, sec-heptyl iodide, tert-heptyl bromide, tert-heptyl iodide, n-octyl bromide, n-octyl iodide, sec-octyl bromide, sec-octyl bromide, tert-octyl iodide, n-bromononane, n-iodononane, sec-bromononane, s ec-iodononane, tert-bromononane, tert-iodononane, n-bromodecane, n-iododecane, sec-bromodecane, sec-iododecane, tert-bromodecane, tert-iododecane, n-bromoundecane, n-iodonecane, sec-bromoundecane, sec-iodonecane, tert-bromoundecane, tert-iodonecane, n-bromododecane, n-iodododecane, sec-bromododecane, sec-iodonecane, tert-bromododecane, tert-iodonecane, n-bro Motridecane, n-iodotridecane, sec-bromotridecane, sec-iodotridecane, tert-bromotridecane, tert-iodotridecane, n-bromotetradecane, n-iodotetradecane, sec-bromotetradecane, sec-iodotetradecane, tert-bromotetradecane, tert-iodotetradecane, n-bromopentadecane, n-iodopentadecane, sec-bromopentadecane, sec-iodopentadecane, tert-bromopentadecane, tert-iodopentadecane, n-bromohexadecane,n-iodohexadecane, sec-bromohexadecane, sec-iodohexadecane, tert-bromohexadecane, tert-iodohexadecane, n-bromoheptadecane, n-iodoheptadecane, sec-bromoheptadecane, sec-iodoheptadecane, tert-bromoheptadecane, tert-iodoheptadecane, n-bromooctadecane, n- The method according to claim 29, selected from the group consisting of iodooctadecane, sec-bromooctadecane, sec-iodooctadecane, tert-bromooctadecane, tert-iodooctadecane, 1,1,3,3-tetramethylbutylbromide, 1,1,3,3-tetramethylbutyliodide, 1-methylheptylbromide, and 1-methylheptyliodide.

31. R is a substituted or non-substituted C ５ ~C ２０ The method according to claim 18, wherein the alkyl group is an arylalkyl group.

32. The method according to claim 31, wherein the at least one organic halogen is benzyl bromide or benzyl iodide.

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

34. The method according to claim 1, wherein step b is carried out using the liquid of at least one organic halide.

35. The method according to claim 18, wherein step b is carried out using the liquid of at least one organic halide.

36. The method according to claim 1 or claim 18, wherein the organic halide is selected from the group consisting of bromopropane, iodopropane, bromohexane, iodohexane, 1-bromo-4-methylpentane, 1-iodo-4-methylpentane, benzyl bromide, benzyl iodide, bromooctane, iodooctane, bromoundecane, and iodoundecane.

37. In formula (I), R is R'-CH ２ where R' is selected from the group consisting of a linear C １ to C １６ alkyl group, a branched C １ to C １６ alkyl group, and a C ６ to C １０ aryl group The method according to claim 1 or 18, wherein X is Br or I.

38. d. The process further includes a step of depositing a metal film or a metal nitride film on the substrate by atomic layer deposition, The thickness of the metal film or metal nitride film deposited on the first surface is thinner than the thickness of the metal film or metal nitride film deposited on the second surface. The second surface contains silicon dioxide, and The method according to claim 1, wherein the deposition selectivity of the second surface relative to the first surface is greater than about 0.

1.

39. The method according to claim 18, wherein the film comprises a metal or a metal nitride.

40. 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 The method according to claim 38 or 39, 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.

41. The thickness of the metal film or metal nitride film deposited on the first surface is thinner than the thickness of the metal film or metal nitride film deposited on the second surface. The second surface contains silicon dioxide, and The method according to claim 39, wherein the deposition selectivity of the second surface relative to the first surface is greater than about 0.1.

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