Selective passivation of silicon nitride using passivation molecule having hydroxyl functional groups

Abstract

A method for selectively passivating a surface of a substrate, wherein the surface of the substrate includes 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 diol wherein the diol selectively reacts with the silicon nitride to passivate the first surface thereby leaving the second surface substantially unreacted.

Description

Selective Passivation of Silicon Nitride Using Passivation Molecule Having Hydroxyl Functional GroupsCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to United States Provisional Patent Application number 63 / 717,008, filed on November 6, 2024, and United States Provisional Patent Application number 63 / 654,563, filed on May 31 , 2024, the entire contents of which are incorporated by reference.FIELD

[0002] The present application relates to selective deposition on a first surface of a substrate relative to a second surface. In addition, further processing can be used to subsequently deposit a different material on the second surface relative to the first.BACKGROUND

[0003] Area Selective Deposition (ASD) is a cutting-edge technique used in thin film deposition. It enables precise control over where materials are deposited on a substrate surface, allowing for selective deposition in predefined areas while leaving others untouched. One of the key advantages of selective deposition lies in its ability to create self-aligned features with precision and efficiency. This is particularly beneficial in the fabrication of self-aligned via structures, where the selective deposition process can offer significant advantages over traditional methods. Additionally, in gap fill applications, selective deposition enables the controlled growth of dielectric films from the bottom of a trench to the top, providing a solution to the challenges associated with achieving uniform gap fill in semiconductor manufacturing. Selective deposition also holds promise for applications such as selective sidewall deposition, where films are selectively deposited on exposed surfaces of three-dimensional FIN-FET structures. By eliminating the need for complex patterning steps, selective sidewall deposition offers a streamlined approach to semiconductor device fabrication.

[0004] A promising inhibitor for ASD is crucial for achieving precise control in material deposition. Previous research has explored the selective formation of surface passivation coatings, particularly focusing on passivating silicon nitride (SiNx) oversilicon oxide (SiOx) surfaces. This endeavor aims to inhibit film deposition through atomic layer deposition (ALD) processes on SiNx-passivated surfaces while allowing deposition on SiOx surfaces, thereby enabling selective deposition of thin films. However, challenges such as incomplete passivation and undesired film formation have been encountered, highlighting the need for further refinement of passivation strategies to achieve optimal selectivity and efficacy. The present challenge calls for the acquisition of a specialized inhibitor to selectively impede the advancement of silicon nitride film growth. Concurrently, during this inhibition phase, ALD is intended to exclusively enhance the unobstructed silicon oxide surface. This requirement is crucial for achieving self-aligned patterning in logic and memory devices. In this regard, various inhibitors have been explored including self-assembled monolayers (SAMs), functionalized polymers, surface ligands, surface treatments, and templating techniques.

[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 might be selectively passivated to some extent relative to silicon oxide by treatment of a treated surface with a solution containing an aldehyde.SUMMARY

[0006] In a first main aspect of the disclosure, a method designed for the selective passivation of a substrate is provided. This substrate encompasses at least a first surface composed of silicon nitride and at least a second surface composed of a material distinct from silicon nitride. The method encompasses the following steps: a. optionally, treating the substrate with hydrogen plasma, argon plasma, or ammonia plasma; b. exposing the substrate to at least one passivation molecule having a structure according to Formula I: HO-R-OH (I), wherein R is a diradical derived from a linear or branched C4 to C20 alkyl group, a C5 to Cs cyclic alkyl group, a substituted or unsubstituted C4 to Cis alkenyl group, a substituted or unsubstituted C4 to C18 alkynyl group, a C7 to C20 arylalkyl group, a C4 to C20 alkyl group having at least one heteroatom such as oxygen or nitrogen, or a Ce to C20 aryl group by removal of two hydrogen atoms, wherein the at least one passivation molecule selectively reacts with the silicon nitride to passivate the first surface, while leaving the second surface substantially unreacted.

[0007] In a further aspect of the first main aspect, the second surface comprises at least one selected from the group consisting of silicon oxide, a metal oxide, copper, cobalt, tungsten, amorphous silicon, polysilicon, monocrystalline silicon, germanium, and amorphous hydrogenated germanium. In a further aspect of the first main aspect, the second surface comprises silicon oxide.

[0008] In a further aspect of the first main aspect, R is a C4 to C20 linear alkyl group having a structure CnHzn+i, wherein n is 4 to 20. In a further aspect of the first main aspect, the at least one passivation molecule is a linear Cs to C20 diol selected from the group consisting of 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,7-heptanediol, 1 ,8-octanediol, 1 ,9-nonanediol, 1 ,10-decanediol, 1 ,1 1 -undecanediol, 1 ,12- dodecanediol, 1 ,13-tridecanediol, 1 ,14-tetradecanediol, 1 ,15-pentadecanediol, 1 ,16- hexadecanediol, 1 ,17-heptadecanediol, 1 ,18-octadecanediol, 1 ,19-nonaecanediol, and 1 ,20-eicosanediol.

[0009] In a further aspect of the first main aspect, R is a branched Ce to C20 alkyl group having a formula CnH2n+i , wherein n is 6 to 20. In a further aspect of the first main aspect, the at least one passivation molecule is selected from the group consisting of hexane-2,5-diol, heptane-2,6-diol, octane-2, 7-diol, nonane-2,8-diol, decane-2, 9-diol, undecane-2,10-diol, dodecane-2,1 1 -diol, tridecane-2,12-diol, tetradecane-2, 13-diol, pentadecane-2, 14-diol, hexadecane-2,15-diol, heptadecane- 2,16-diol, octadecane-2,17-diol, nonadecane-2,18-diol, and eicosane-2,19-diol.

[0010] In a further aspect of the first main aspect, R is a substituted or unsubstituted C5to Cs cyclic alkyl group. In a further aspect of the first main aspect, the at least one passivation molecule is selected from the group consisting of 1 ,3-cyclopentanediol, 1 ,4-cyclohexanediol, 1 ,4-cycloheptanediol, cyclooctane-1 ,4-diol, and 1 - methylcyclohexane-1 ,4-diol, and 5-norbornene-2-exo,3-exo-dimethanol.

[0011] In a further aspect of the first main aspect, R is an unsubstituted C7 to C20 arylalkyl group. In a further aspect of the first main aspect, the at least one passivation molecule is selected from the group consisting of 1 ,2-benzenedimethanol, 1 ,3- benzenedimethanol, 1 ,4-benzenedimethanol, 3-hydroxybenzyl alcohol, 2-(4- hydroxyphenyl)ethanol, and 3-(4-hydroxyphenyl)-1 -propanol.

[0012] In a further aspect of the first main aspect, R is a substituted or unsubstituted C4 to Cis alkenyl group. In a further aspect of the first main aspect, the at least one passivation molecule is selected from the group consisting of 2-butene-1 ,4-diol, 2-pentene-1 ,5-diol, 3-hexene-1 ,6-diol, 3-heptene-1 ,7-diol, 2, 4-hexadiene-1 ,6-diol, and 3,5-octadiene-1 ,8-diol.

[0013] In a further aspect of the first main aspect, R is a substituted or unsubstituted C4 to Cis alkynyl group. In a further aspect of the first main aspect, the at least one passivation molecule is selected from the group consisting of 2-butyne-1 ,4-diol, 3- hexyne-1 ,6-diol, 2,4-hexadiyne-1 ,6-diol, and 3, 5-octadiyne-1 ,8-diol.

[0014] In a further aspect of the first main aspect, R is a substituted or unsubstituted Cs to C20 aryl group. In a further aspect of the first main aspect, the at least one passivation molecule is selected from the group consisting of 1 ,2-dihydroxybenzene, hydroquinone, 2-methylbenzene-1 ,4-diol, 2-ethylbenzene-1 ,4-diol, 2-propylbenzene- 1 ,4-diol, 2-butylbenzene-1 ,4-diol, 2-pentylbenzene-1 ,4-diol, 2-hexylbenzene-1 ,4-diol, 2-heptylbenzene-1 ,4-diol, 4-methylcatechol, 4-ethylcatechol, 4-propylbenzene-1 ,2- diol, 4-butybenzene-1 ,2-diol, 4-pentylbenzene-1 ,2-diol, 4-hexylbenzene-1 ,2-diol, 4- heptylbenzene-1 ,2-diol, 4-octylbenzene-1 ,2-diol, 5-methylbenzene-1 ,3-diol, 5- ethylbenzene-1 ,3-diol, 5-propylbenzene-1 ,3-diol, 5-butylbenzene-1 ,3-diol, 5- pentylbenzene-1 ,3-diol, 5-hexylbenzene-1 ,3-diol, 5-heptylbenzene-1 ,3-diol, and 5- octylbenzene-1 ,3-diol.

[0015] In a further aspect of the first main aspect, R is a C4 to C20 alkyl group having at least one heteroatom such as oxygen or nitrogen. In a further aspect of the first main aspect, the at least one passivation molecule is selected from the group consisting of diethylene glycol, bis(hydroxyethyl)amine, bis(3-hydroxypropyl)amine, N- methyldiethanolamine, 3, 3’-(methylamino)bis-1 -propanol, 2,2-(phenylamino)bis- ethanol, 3,3’-(phenylamino)bis-propanol, 2,2-(4-methylphenylamino)bis-ethanol, 3,3’- (3-methylphenylamino)bis-ethanol, 2,2-(4-methylphenylamino)bis-ethanol, dipropylene glycol, and pyridine-2,6-diethanol.

[0016] In a further aspect of the first main aspect, step b. is conducted with a vapor of the at least one passivation molecule.

[0017] In a second main aspect, a method of selectively depositing a dielectric film on a substrate is provided. 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, treating the substrate with hydrogen plasma or ammonia plasma; b. exposing the substrate to at least one passivation molecule having a structure according to Formula I: HO-R-OH (I), wherein R is a diradical derived from a linear or branched C4 to C20 alkyl group, a C5to Cs cyclicalkyl group, a C? to C20 arylalkyl group, a C4 to C20 alkyl group having at least one heteroatom such as oxygen or nitrogen, or a Cs to C20 aryl group by removal of two hydrogen atoms, wherein the at least one passivation molecule is a diol, and wherein the diol selectively reacts with the silicon nitride to passivate the first surface, while leaving the second surface substantially unreacted; and c. exposing the substrate to one or more deposition precursors to deposit a dielectric film on the second surface selectively over the first surface.

[0018] In a further aspect of the second main aspect, the second surface comprises at least one selected from the group consisting of silicon oxide, a metal oxide, copper, cobalt, ruthenium, tungsten, molybdenum, amorphous silicon, polysilicon, monocrystalline silicon, germanium, and amorphous hydrogenated germanium.

[0019] In a further aspect of the second main aspect, the second surface comprises silicon oxide.

[0020] In a further aspect of the second main aspect, R in the at least one passivation molecule is a Cs to C20 linear alkyl group.

[0021] In a further aspect of the second main aspect, the at least one passivation molecule is selected from the group consisting of 1 ,8-octanediol, 1 ,9-nonanediol, 1 ,10- decanediol, 1 ,1 1 -undecanediol, 1 ,12-dodecanediol, 1 ,13-tridecanediol, 1 ,14- tetradecanediol, 1 ,15-pentadecanediol, 1 ,16-hexadecanediol, 1 ,17-heptadecanediol, 1 ,18-octadecanediol, 1 ,19-nonaecanediol, and 1 ,20-eicosanediol.

[0022] In a further aspect of the second main aspect, the dielectric film comprises titanium oxide, hafnium oxide, zirconium oxide, aluminum oxide, tantalum oxide, silicon oxide, carbon doped silicon oxide, or combinations thereof.

[0023] In a further aspect of the second main aspect, R is a substituted or unsubstituted C5to Cs cyclic alkyl group.

[0024] In a further aspect of the second main aspect, the at least one passivation molecule is selected from the group consisting of 1 ,3-cyclopentanediol, 1 ,4- cyclohexanediol, 1 ,4-cycloheptanediol, cyclooctane-1 ,4-diol, and 1 - methylcyclohexane-1 ,4-diol.

[0025] In a further aspect of the second main aspect, R is a substituted or unsubstituted C7to C20 arylalkyl group.

[0026] In a further aspect of the second main aspect, the at least one passivation molecule is selected from the group consisting of 1 ,2-benzenedimethanol, 1 ,3- benzenedimethanol, 1 ,4-benzenedimethanol, 3-hydroxybenzyl alcohol, 2-(4- hydroxyphenyl)ethanol, and 3-(4-hydroxyphenyl)-1 -propanol.

[0027] In a further aspect of the second main aspect, R is a substituted or unsubstituted C& to C20 aryl group.

[0028] In a further aspect of the second main aspect, the at least one passivation molecule is selected from the group consisting of 1 ,2-dyhydroxybenzene, hydroquinone, 2-methylbenzene-1 ,4-diol, 2-ethylbenzene-1 ,4-diol, 2-propylbenzene- 1 ,4-diol, 2-butylbenzene-1 ,4-diol, 2-pentylbenzene-1 ,4-diol, 2-hexylbenzene-1 ,4-diol, 2-heptylbenzene-1 ,4-diol, 4-methylcatechol, 4-ethylcatechol, 4-propylbenzene-1 ,2- diol, 4-butybenzene-1 ,2-diol, 4-pentylbenzene-1 ,2-diol, 4-hexylbenzene-1 ,2-diol, 4- heptylbenzene-1 ,2-diol, 4-octylbenzene-1 ,2-diol, 5-methylbenzene-1 ,3-diol, 5- ethylbenzene-1 ,3-diol, 5-propylbenzene-1 ,3-diol, 5-butylbenzene-1 ,3-diol, 5- pentylbenzene-1 ,3-diol, 5-hexylbenzene-1 ,3-diol, 5-heptylbenzene-1 ,3-diol, and 5- octylbenzene-1 ,3-diol.

[0029] In a further aspect of the second main aspect, the at least one passivation molecule is selected from the group consisting of diethylene glycol, bis(hydroxyethyl)amine, bis(3-hydroxypropyl)amine, N-methyldiethanolamine, 3,3’- (methylamino)bis-l -propanol, 2,2-(phenylamino)bis-ethanol, 3,3’-(phenylamino)bis- propanol, 2,2-(4-methylphenylamino)bis-ethanol, 3,3’-(3-methylphenylamino)bis- ethanol, 2,2-(4-methylphenylamino)bis-ethanol.

[0030] In a further aspect of the second main aspect, step b. is conducted with a vapor of the at least one passivation molecule.

[0031] In a further aspect of the second main aspect, further comprising wherein a thickness of the dielectric film deposited on the first surface is less than a thickness of the dielectric film deposited on the second surface; wherein the second surface comprises silicon oxide; and wherein a 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.

[0032] In a further aspect of the second main aspect, a thickness of the dielectric film deposited on the first surface is less than a thickness of the dielectric film deposited on the second surface; wherein the second surface comprises silicon oxide; and whereina 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.

[0033] In a further aspect of the second main aspect, the dielectric film is silicon oxide, and wherein the one or more deposition precursors comprising a silicon precursor selected from the group consisting of tetraisocyanatosilane (Si(NCO)4), tetraisothiocyanatosilane (Si(NCS)4), tetrathiocyanatosilane (Si(SNC)4), and hexaisocyanatodisiloxne (NCO)3Si-O-Si(NCO)3).

[0034] In a further aspect of the second main aspect, in step c, the one or more deposition precursors comprise Si(NCO)4, and wherein the dielectric film has a refractive index ranging from about 1 .40 to about 1 .60.

[0035] In a further aspect of the second main aspect, the dielectric film comprises silicon oxide, and the one or more deposition precursors comprise Si(NCO)4, and wherein a thickness of silicon oxide film on the first surface is less than a thickness of silicon oxide film deposited on the second surface; wherein the first surface comprises silicon nitride; wherein the second surface comprises silicon oxide; and wherein the at least one passivation molecule comprises 1 ,8-octanediol.

[0036] In a further aspect of the second main aspect, the at least one passivation molecule comprises 1 ,8-octanediol, and a deposition selectivity of the second surface relative to the first surface is greater than about 0.3.

[0037] In a third main aspect, a method for selectively passivating a silicon nitride surface of a substrate is provided. The method comprising: (a) providing the substrate in a reaction vessel at temperatures ranging from about 20°C to about 300°C; (b) forming at least one passivation layer on the silicon nitride surface by exposing the substrate to at least one passivation molecule having a structure according to Formula I: HO-R-OH (I), wherein R is a diradical derived from a linear or branched C4 to C20 alkyl group, a C5 to Cs cyclic alkyl group, a substituted or unsubstituted C4 to C alkenyl group, a substituted or unsubstituted C4 to C alkynyl group, a C7to C20 arylalkyl group, a C4 to C20 alkyl group having at least one heteroatom such as oxygen or nitrogen, and a Cs to C20 aryl group by removal of two hydrogen atoms; and (c) purging the reactor with inert gas.

[0038] In a further aspect of the third main aspect, steps (b) to (c) are repeated to provide a fully covered passivation layer on the silicon nitride.

[0039] In a further aspect of the third main aspect, steps (b) to (c) are performed at one temperature to ensure all available reactive sites are consumed to provide a blocking layer and then the substrate is heated up to a higher temperature to allow further reactions to provide denser blocking layer.

[0040] In a fourth main aspect, a method for treatment of a substrate, comprising: a. providing the substrate, wherein the substrate comprises at least a first surface comprising silicon nitride and at least a second surface comprising a material other than silicon nitride; and b. thermally exposing the substrate to ammonia, hydrogen, and combination thereof at temperature ranging from 450°C to 550°C to provide more Si-NH2groups on the first surface vs the second surface.

[0041] In a further aspect of the fourth main aspect, the substrate is cleaned with a diluted hydrogen fluoride solution prior to step b.

[0042] The embodiments of the disclosure can be used alone or in combinations with each other.BRIEF DESCRIPTION OF DRAWINGS

[0043] The accompanying drawings, which are included to provide a further understanding of the disclosed subject matter and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosed subject matter and together with the description serve to explain the principles of the disclosed subject matter. In the drawings:

[0044] FIG. 1A illustrates a process of passivating a first surface and depositing a film on a second surface;

[0045] FIG. 1 B illustrates a process of passivating a silicon nitride surface and depositing a film on a silicon oxide surface;

[0046] FIG. 2 illustrates data regarding inhibitor reaction on silicon nitride surfaces;

[0047] FIG. 3 illustrates data regarding inhibitor reaction on silicon oxide surfaces;

[0048] FIG. 4 illustrates silicon oxide deposition on passivated silicon nitride surfaces with 1 ,2-ethanediol and 1 ,8-octanediol;

[0049] FIG. 5 illustrates silicon oxide deposition on passivated silicon oxide surfaces with 1 ,2-ethanediol and 1 ,8-octanediol;

[0050] FIG. 6 illustrates the growth of silicon oxide using Si(NCO)4 on passivated silicon oxide and passivated silicon nitride, respectively; and

[0051] FIG. 7 illustrates the impact of pre-treatment on selectivity of ALD silicon oxide using Si(NCO)4 on passivated silicon nitride and passivated silicon oxide using 1 ,8- octanediol. The pre-treatments are conducted as following: diluted hydrogen fluoride solution (dHF) wet clean, dHF wet clean followed by NH3thermal treatment, and dHF wet clean followed by NH3and hydrogen thermal treatment.DETAILED DESCRIPTION

[0052] All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.

[0053] The use of the terms "a" and "an" and "the" and similar referents in the context of describing the disclosure (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms “comprising,” “having,” “including,” and “containing” are to be construed as open-ended terms (i.e. , meaning “including, but not limited to,”) unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the disclosure and does not pose a limitation on the scope of the claims unless otherwise stated explicitly. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the subject matter of this disclosure.

[0054] Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. It is expected that skilled artisans may employ such variations as appropriate, and the claimed subject matter may be practiced otherwise than as specifically described herein. Accordingly, thisdisclosure includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the claimed subject matter unless otherwise indicated herein or otherwise clearly contradicted by context.

[0055] There are a variety of methods that could be used for selective depositions. Embodiments of the disclosure are directed to methods that employ surface deactivation by taking advantage of the surface chemistry of two different surfaces. Since two different surfaces will have different reactive handles, the differences can be taken advantage of by utilizing molecules that will react with one surface (to deactivate that surface) and not react with the other surface.

[0056] In one embodiment, there is provided a method for selectively passivating a surface of a substrate by vapor phase reaction, wherein the surface of the substrate comprises at least a first surface comprising silicon nitride and at least a second surface comprising a material other than the silicon nitride, the method comprising the steps of: a. treating the surface with hydrogen plasma, argon plasma, or ammonia plasma; and b. exposing the surface to at least one diol having a structure according to Formula I: HO-R-OH, wherein R is a diradical derived from a linear or branched C4 to C20 alkyl group, a C5 to Cs cyclic alkyl group, a C7 to C20 arylalkyl group, and a Ce to C20 aryl group by removal of two hydrogen. Furthermore, the diol selectively reacts with the silicon nitride to passivate the first surface, while leaving the second surface substantially unreacted.

[0057] In another embodiment, there is provided a method of selectively depositing a film on a surface of a substrate wherein the surface of the substrate comprises at least a first surface comprising silicon nitride and at least a second surface comprising a material other than the silicon nitride, the method comprising the steps of: a. treating the surface with hydrogen plasma or ammonia plasma; b. exposing the surface to at least one diol having a structure according to Formula I: HO-R-OH, wherein R is a diradical derived from a linear or branched C4 to C20 alkyl group, a C5 to Cs cyclic alkyl group, a C7 to C20 arylalkyl group, and a Ce to C20 aryl group by removal of two hydrogen atoms. Furthermore, the diol selectively reacts with the silicon nitride to passivate the first surface, while leaving the second surface substantially unreacted; and c. exposing the substrate to one or more deposition precursors to deposit a film on the second surface selectively over the first surface.

[0058] As used in this specification and the appended claims, the term “substrate” and “wafer” are used interchangeably, both referring to a surface, or portion of a surface, upon which a process acts. It will also be understood by those skilled in the art that reference to a substrate can also refer to only a portion of the substrate, unless the context clearly indicates otherwise. Additionally, reference to depositing on a substrate can mean both a bare substrate and a substrate with one or more films or features deposited or formed thereon.

[0059] A “substrate” as used herein, refers to any substrate or material surface formed on a substrate upon which film processing is performed during a fabrication process. For example, a substrate surface on which processing can be performed include materials such as silicon, silicon oxide, strained silicon, silicon on insulator (SOI), carbon doped silicon oxides, 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, without limitation, semiconductor wafers. Substrates may be exposed to a pre-treatment process to polish, etch, reduce, oxidize, hydroxylate, anneal and / or bake the substrate surface. When an etchant is employed for removal a few atomic layers from the first surface comprising silicon nitride and the second surface comprising a material other than silicon nitride, the etchant can be selected from the group consisting of fluorocarbon, NF3, HF, NF3plasma, CIF3plasma and combination thereof. In addition to film processing directly on the surface of the substrate itself, in the present disclosure, any of the film processing steps disclosed may also be performed on an underlayer formed on the substrate as disclosed in more detail below, and the term “substrate surface” is intended to include such underlayer as the context indicates. Thus, for example, where a f i I m / layer or partial film / layer has been deposited onto a substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate surface. What a given substrate surface comprises will depend on what films are to be deposited, as well as the particular chemistry used. In one or more embodiments, the first substrate surface will comprise a metal, and the second substrate surface will comprise a dielectric, or vice versa. In some embodiments, a substrate surface may comprise certain functionality (e.g., -OH, -NH, etc.).

[0060] Likewise, the films that can be used in the methods described herein are quite varied. In some embodiments, the films may comprise, or consist essentially of a metal or metal nitride. Examples of metal films include, but are not limited to, ruthenium (Ru), cobalt (Co), copper (Cu), titanium, (Ti), tantalum (Ta), nickel (Ni), tungsten (W),molybdenum (Mo), etc., and combinations thereof. Examples of metal nitride films include, but are not limited to, tantalum nitride (TaN), titanium nitride (TiN), tungsten nitride (WN), tungsten carbonitride (WCN), molybdenum nitride (MoN), copper silicon nitride (CuSiN), etc., and combinations thereof. In some embodiments, the film comprises a dielectric. Examples include, silicon oxide, silicon nitride, hafnium oxide, etc.

[0061] In embodiments of the present disclosure, the substrate has at least two discrete surfaces wherein each discrete surface is characterized by a different chemistry. For example, in an embodiment, 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.

[0062] The at least one second surface comprising a material other than silicon nitride can be, for example, any of the materials selected from the group consisting of silicon oxide, a metal oxide, copper, cobalt, tungsten, amorphous silicon, polysilicon, monocrystalline silicon, germanium, and amorphous hydrogenated germanium. In some embodiments the at least one second surface comprises silicon oxide is a dielectric surface, such as a silicon oxide surface. In some embodiments the surface comprising silicon oxide may comprise silicon oxides, fluorinated silica glass (FSG), carbon doped silicon oxide (SiOC) and / or materials containing more than about 50% silicon oxide. In some embodiments the surface comprising silicon oxide comprises - OH groups and may also comprise, for example, an alumina (AI2O3) surface with -OH surface groups.

[0063] Embodiments of the disclosure provide methods of selectively depositing a film such as, for example, a metal film, onto one surface of a substrate over a second surface on the same substrate. As used in this specification and the appended claims, the term “selectively depositing a film on one surface over another surface,” and the like, means that one of the first or second surface is passivated to substantially prevent deposition on the passivated layer and a film is deposited on the second (nonpassivated) surface. The term “over” used in this regard does not imply a physical orientation of one surface on top of another surface, rather a relationship of the thermodynamic or kinetic properties of the chemical reaction with one surface relative to the other surface. For example, selectively depositing a cobalt film onto a copper surface over a dielectric surface means that the cobalt film deposits on the copper surface and less or no cobalt film deposits on the dielectric surface; or that theformation of the cobalt film on the copper surface is thermodynamically or kinetically favorable relative to the formation of a cobalt film on the dielectric surface.

[0064] In some situations, it is desirable to selectively deposit a material on one surface of a substrate relative to a second, different surface of the same substrate. For example, selective deposition may be used to form capping layers, barrier layers, etch stop layers, sacrificial and / or protective layers or for sealing pores, such as in porous low k materials.

[0065] Embodiments also optionally include the step of treating the surface with hydrogen plasma, argon plasma, or ammonia plasma. Suitable processes include plasma processes hydrogen plasma, NH3 / NF3plasmas, CIF3plasma, and the like). The optional plasma step functions to remove undesired deposits on the surface and activate the surface for subsequent deposition of passivation reagents. Such plasma treatments may be most preferably applied after some deposition on the surface has been performed in order to remove non-selectively deposited material from the previously passivated surface and to remove residual passivation reagents after the desired deposition thickness has been achieved.

[0066] Embodiments include a method for passivating silicon nitride comprising:(a) exposing the surface to a vapor comprising at least one passivation molecule (e.g., a diol) having a structure according to Formula I:HO-R-OH (I), wherein, R is a diradical derived from a linear or branched C4 to C20 alkyl group, a C5to C3cyclic alkyl group, a substituted or unsubstituted C4 to Os alkenyl group, a substituted or unsubstituted C4 to C alkynyl group, a C7to C20 arylalkyl group, and a Cg to C20 aryl group by removal of two hydrogen atoms.(b) purging the reactor with inert gas.

[0067] In some embodiments, the steps (a) to (b) can be performed multiple times at one temperature to ensure all available reactive sites are consumed to provide a blocking layer. In other embodiments, the steps (a) to (b) can be performed multiple times at one temperature to ensure all available reactive sites are consumed to provide a blocking layer and then substrate is heated up to a higher temperature to allow further reactions to even provide denser blocking layer. This new family of passivation chemistries that can be used to achieve selective passivation of silicon nitride over silicon oxide.

[0068] This new family of passivation chemistries shows better selective adsorption on silicon nitride over silicon oxide than state of art passivation chemistries reported.

[0069] This new family of passivation chemistries demonstrates better oxide deposition selectivity at 200°C or lower, preferably 150°C or lower, most preferably 100°C or lower.

[0070] This new family of passivation layer on silicon nitride shows good thermal stability up to 250°C and even higher.

[0071] This new passivation method has high potential for high temperature ASD applications.

[0072] In some embodiments, the diol is a C4 to C20 linear alkyl group having a structure selected from the group consisting of CnH2n+i. Preferred diol precursors having a C4 to C20 linear alkyl group include those selected from the group consisting of 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,7-heptanediol, 1 ,8-octanediol, 1 ,9-nonanediol, 1 ,10-decanediol, 1 ,11 -undecanediol, 1 ,12-dodecanediol, 1 ,13- tridecanediol, 1 ,14-tetradecanediol, 1 ,15-pentadecanediol, 1 ,16-hexadecanediol, 1 ,17-heptadecanediol, 1 ,18-octadecanediol, 1 ,19-nonaecanediol, 1 ,20-eicosanediol.

[0073] In other embodiments, R in Formula I is a C4 to C20 branched alkyl group. Preferred diol precursors having a branched alkyl group include those selected from the group consisting of hexane-2,5-diol, heptane-2,6-diol, octane-2, 7-diol, nonane-2,8- diol, decane-2, 9-diol, undecane-2,10-diol, dodecane-2,1 1 -diol, Tridecane-2,12-diol, Tetradecane-2,13-diol, pentadecane-2, 14-diol, hexadecane-2,15-diol, heptadecane- 2,16-diol, octadecane-2,17-diol, nonadecane-2,18-diol, and eicosane-2,19-diol.

[0074] In other embodiments, R in Formula I is a substituted or unsubstituted C5to Cs cyclic alkyl group. In such embodiments, the at least one diol includes those selected from the group consisting of 1 ,3-cyclopentanediol, 1 ,4-cyclohexanediol, 1 ,4- cycloheptanediol, Cyclooctane-1 ,4-diol, and 1-methylcyclohexane-1 ,4-diol.

[0075] In other embodiments, R in Formula I is a substituted or unsubstituted C7 to C20 arylalkyl group. In such embodiments, the at least one diol includes those selected from the group consisting of 1 ,2-benzenedimethanol, 1 ,3-benzenedimethanol, 1 ,4- benzenedimethanol, 3-hydroxybenzyl alcohol, 2-(4-hydroxyphenyl)ethanol, and 3-(4- hydroxyphenyl)-1 -propanol.

[0076] In other embodiments, R in Formula I is a substituted or unsubstituted Ce to C20 aryl group. In such embodiments, the diol includes those selected from the groupconsisting of 1 ,2-dyhydroxybenzene, hydroquinone, 2-methylbenzene-1 , 4-diol, 2- ethylbenzene-1 , 4-diol, 2-propylbenzene-1 , 4-diol, 2-butylbenzene-1 , 4-diol, 2- pentylbenzene-1 , 4-diol, 2-hexylbenzene-1 , 4-diol, 2-heptylbenzene-1 , 4-diol, 4- methylcatechol, 4-ethylcatechol, 4-propylbenzene-1 ,2-diol, 4-butybenzene-1 ,2-diol, 4- pentylbenzene-1 ,2-diol, 4-hexylbenzene-1 ,2-diol, 4-heptylbenzene-1 ,2-diol, 4 octylbenzene-1 ,2-diol, 5-methylbenzene-1 ,3-diol, 5-ethylbenzene-1 ,3-diol, 5 propylbenzene-1 ,3-diol, 5-butylbenzene-1 ,3-diol, 5-pentylbenzene-1 ,3-diol, 5 hexylbenzene-1 ,3-diol, 5-heptylbenzene-1 ,3-diol, and 5-octylbenzene-1 ,3-diol.

[0077] In other embodiments, R in Formula I is an unsubstituted C4 to C20 linear alkyl group or R is a substituted or unsubstituted branched C4 to C20 alkyl group. In such embodiments, the diol includes those selected from the group consisting of 1 ,4- butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,7-heptanediol, 1 ,8-octanediol, 1 ,9- nonanediol, 1 ,10-decanediol, 1 ,11 -undecanediol, 1 ,12-dodecanediol, 1 ,13- tridecanediol, 1 ,14-tetradecanediol, 1 ,15-pentadecanediol, 1 ,16-hexadecanediol,1.17-heptadecanediol, 1 ,18-octadecanediol, 1 ,19-nonaecanediol, 1 ,20-eicosanediol, hexane-2,5-diol, heptane-2,6-diol, octane-2, 7-diol, nonane-2,8-diol, decane-2, 9-diol, undecane-2,10-diol, dodecane-2,1 1-diol, tridecane-2,12-diol, tetradecane-2,13-diol, pentadecane-2,14-diol, hexadecane-2,15-diol, heptadecane-2,16-diol, octadecane-2.17-diol, Nonadecane-2,18-diol, and eicosane-2,19-diol.

[0078] As employed throughout the description, the term “alkyl” means a saturated hydrocarbon group which is straight-chained or branched. In some embodiments, the alkyl group has from 1 to 20 carbon atoms, from 2 to 20 carbon atoms, from 1 to 10 carbon atoms, from 2 to 10 carbon atoms, from 1 to 8 carbon atoms, from 2 to 8 carbon atoms, from 1 to 6 carbon atoms, from 2 to 6 carbon atoms, from 1 to 4 carbon atoms, from 2 to 4 carbon atoms, from 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, t-butyl, isobutyl), pentyl (e.g., n-pentyl, isopentyl, neopentyl), hexyl, isohexyl, heptyl, octyl, nonyl, 4,4dimethylpentyl, 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, and the like.

[0079] As employed throughout the description, the term “cyclic alkyl” denotes a cyclic functional group having from 3 to 10 or from 4 to 10 carbon atoms. Exemplary cyclic alkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

[0080] As used herein, the term “aryl” means a monocyclic, bicyclic, or polycyclic (e.g., having 2, 3 or 4 fused rings) aromatic hydrocarbon. In some embodiments, the aryl group has from 6 to 20 carbon atoms or from 6 to 10 carbon atoms. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, anthracenyl, phenanthrenyl, indanyl, indenyl, and tetrahydronaphthyl, and the like.

[0081] As used herein, the term “arylalkyl” means an alkyl group substituted by an aryl. In some embodiments, the alkyl group is a Ci 6 alkyl group.

[0082] As employed throughout the description, the term “alkenyl group” denotes a group which has one or more carbon-carbon double bonds and has from 2 to 18 or from 2 to 10 carbon atoms. Exemplary alkenyl groups include, but are not limited to, vinyl or allyl groups.

[0083] As used herein, the term “alkynyl” means a straight 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 from 2 to 10 carbon atoms, from 2 to 8 carbon atoms, from 2 to 6 carbon atoms, or from 2 to 4 carbon atoms. Examples of alkynyl groups include, but are not limited to, acetylene, 1 -propylene, 2-propylene, and the like.

[0084] As used herein, the phrase “optionally substituted” means that a substitution is optional and, therefore, includes both unsubstituted and substituted atoms and moieties. A “substituted” atom or moiety indicates that any hydrogen atom on the designated compound or moiety can be replaced with a selection from the indicated substituent groups, provided that the normal valency of the designated compound or moiety is not exceeded, and that the substitution results in a stable compound. For example, if a methyl group is optionally substituted, then 1 , 2, or 3 hydrogen atoms on the carbon atom within the methyl group can be replaced with 1 , 2, or 3 of the recited substituent groups.

[0085] As used herein, the term “phenyl” means -CeHs. A phenyl group can be unsubstituted or substituted with one, two, or three suitable substituents.

[0086] As used herein, the term “cyclic alkyl” means non-aromatic cyclic hydrocarbons including cyclized alkyl, alkenyl, and alkynyl groups that have up to 20 ring-forming carbon atoms. Cycloalkyl groups have from 3 to 15 ring-forming carbon atoms, from 3 to 10 ring-forming carbon atoms, from 3 to 8 ring-forming carbon atoms, from 3 to 6 ring-forming carbon atoms, from 4 to 6 ring-forming carbon atoms, from 3 to 5 ring-forming carbon atoms, or 5 or 6 ring-forming carbon atoms. Ring-forming carbon atoms of a cycloalkyl group can be optionally substituted by oxo or sulfido. Cycloalkyl groups include, but are not limited to, monocyclic or polycyclic ring systems such as fused ring systems, bridged 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, adamantyl, and the like. Cycloalkyl groups can also have one or more aromatic rings fused (having a bond in common with) to the cycloalkyl ring such as, for example, benzo or thienyl derivatives of pentane, pentene, hexane, and the like (e.g., 2,3-dihydro-1 H-indene-1 -yl, or 1 H- inden-2(3H)-one-1 -yl).

[0087] As used herein, the term “halo” means halogen groups and includes, but is not limited to, fluoro, chloro, bromo, and iodo.

[0088] As used herein, the term “heterocycle” or “heterocyclic ring” means a 5- to 7- membered monocyclic or 7- to 10-membered bicyclic ring system, any ring of which may be saturated or unsaturated, and which ring consists of carbon atoms and from one to three heteroatoms chosen from N, O and S, and wherein the N and S heteroatoms may optionally be oxidized, and the N heteroatom may optionally be quaternized, and including any bicyclic group in which any of the above-defined heterocyclic rings is fused to a benzene ring. Heterocycles include rings containing one oxygen or sulfur, one to three nitrogen atoms, or one oxygen or sulfur combined with one or two nitrogen atoms. The heterocyclic ring may be attached at any heteroatom or carbon atom which results in the creation of a stable structure. Examples of heterocyclic groups include, but are not limited to, piperidinyl, piperazinyl, 2-oxopiperazinyl, 2-oxopiperidinyl, 2-oxopyrrolodinyl, 2-oxoazepinyl, azepinyl, pyrrolyl, 4-piperidonyl, pyrrolidinyl, pyrazolyl, pyrazolidinyl, imidazolyl, imidazolinyl, pyridyl, imidazolidinyl, pyrazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolidinyl, isoxazolyl, isoxazolidinyl, morpholinyl, thiazolyl, thiazolidinyl, isothiazolyl, quinuclidinyl, isothiazolidinyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, thiadiazoyl,benzopyranyl, benzothiazolyl, benzoxazolyl, furyl, tetrahydrofuryl, tetrahydropyranyl, thienyl, benzothienyl, thiamorpholinyl, thiamorpholinyl sulfoxide, thiamorpholinyl sulfone, oxadiazolyl, and the like.

[0089] Vapor phase or gas phase reactions include the exposure of the heated substrate to the precursor molecule(s) and / or co-reactants in a suitable chamber that must be capable of providing the necessary pressure control and that can also supply heat to the substrate and / or chamber walls; the chamber should also provide suitable purity for the reactions that will take place, generally through high leak integrity and the use of ultra-high purity carrier and reactive gases.

[0090] As used in this specification and the appended claims, the terms “reactive gas”, “precursor”, “reactant”, and the like, are used interchangeably to mean a gas that includes a species which is reactive with a substrate surface. For example, a first “reactive gas” may simply adsorb onto the surface of a substrate and be available for further chemical reaction with a second reactive gas. They may be used in conjunction with ultra-high purity carrier gases (as defined previously) and in any desired mixtures with one another (i.e. , more than one type of precursor can be used either together or in discrete, independent steps to form the desired passivation layer with whatever order of precursor introduction is desired).

[0091] The precursor(s) and / or co-reactants may be delivered to the reactor using mass flow controllers (perhaps with heated lines), liquid injection vaporizers (perhaps with heated lines) or with no metering device (i.e., neat introduction of the vapor and or gas from a vessel that is isolated from the reactor using a simple valve). Any of the foregoing may also be used in combination with one another. Any means of providing the gas and / or vapor(s) to the reaction chamber that provides sufficient purity and repeatability may be used.

[0092] The precursor(s) and / or co-reactants may be introduced independently to the reactor, mixed prior to introduction to the reactor, mixed in the reactor or in any combination of the preceding in multiple, independent steps that might include differences in how the precursors are introduced between steps.

[0093] The temperature range of the reactions may be between room temperature and 400° C. In some cases, the temperature range of the reactions may be between room temperature and 200 °C. In yet other cases, the temperature range of the reactions may be between room temperature and 100° C. The pressure may range from 1 -10 Torr to 3000 Torr and may be maintained under dynamic flow conditions(i.e., with a valve and a butterfly valve type arrangement) or may be maintained under static conditions (i.e., an evacuated chamber is exposed to the desired precursor(s) and / or co-reactant(s) until a total desired pressure is achieved and then the chamber is isolated from both the precursor(s) and / or co-reactant(s) source(s) and the vacuum pump). The reactor can be evacuated fully and re-exposed to fresh precursor(s) and / or co-reactants as many times as necessary. Precursor(s) and I or co-reactants may be introduced using any mixtures and / or concentrations desired.

[0094] The exposure of the surface can be conducted for 1 second to 60 minutes, preferably in 1 -5 minutes and most preferably for 1 minute. The partial pressure of the diol in the reaction chamber can vary from about 1% of its saturated vapor pressure at the substrate temperature up to almost 100% of its saturation vapor pressure. Most preferably, it will be between 20 and 50% of its saturation vapor pressure. The chamber pressure can be the same as the partial pressure of the diol vapors but can be higher with the balance of the atmosphere comprising a carrier gas. Preferred carrier gases include N2, He, and Ar, but also other gases such as H2, CO2 and dry O2 may be used. The exposure vapors can be static (not flowing) for all or part of the exposure period. The preferred embodiment is to flow the vapors of the diol along with the optional carrier gas through the exposure chamber so that fresh vapors are exposed to the surface of the substrate for at least a portion of the exposure period.

[0095] The exposure chamber can be kept at near ambient temperature or can optionally be heated. Heat can be supplied to the outer walls of the chamber (hot wall) or only to the substrate (cold-wall reactor). Substrate heating in a cold wall reactor can be achieved by use of incident radiation through a transparent window (lamp heating), by resistive heating of the substrate itself or from resistive heating elements in the platform that the substrate is contacting, through induction or by other means known in the art. The temperature of the treatment is preferably between about 20 °C to about 400 °C, preferably between 20°C to about 200 °C, and most preferably between 20 °C to about 100 °C. The temperature can be constant during the exposure period or can vary within the specified temperature range.

[0096] Unreacted vapor of the at least one diol can then optionally be removed by evacuation or purging of the chamber with suitable inert gas before removing the substrate from the chamber or before chemical vapor or atomic-layer deposition processing. Optionally, the exposure chamber might also be used for subsequent processing steps to improve process efficiency so that the process may be repeatedfrom step c), if necessary, to strip the protective film and any non-selective ALD deposit and then re-form a protective film.

[0097] The choice of the at least one diol and the exposing conditions used in this method should be optimized by standard experimentation to optimize selectivity of the protection afforded the silicon nitride surface against potential non-selective passivation, processing time, reagent cost, etc. depending on the requirements imposed by subsequent processing steps. For example, selectivity can be adjusted / optimized by varying the nature of the R group of the at least one diol having the structure represented by Formula I. Typically, since reactivity and selectivity are often inversely related, if the two surfaces are similar in chemistry, experimenting with the R group may be required to optimize the process. There is a difference in reactivity, for example between alkyl R-groups and aryl R-groups; typically, aryl groups are more reactive with active hydrogen bearing surfaces compared to alkyl groups. As a result, in some cases the alkyl groups might be needed to selectively passivate the silicon nitride without also passivating an adjacent surface that also has less reactive active hydrogen atoms.

[0098] Once the silicon nitride surface is passivated the second surface comprising, for example, silicon oxide, is active for further selective reactions, c. Additional materials that may be selectively deposited on the second surface including silicon films comprising oxygen, nitrogen, hydrogen and carbon (i.e., SiOx, SiNx, SiOxNy, SiCxNy, SiOxCy all possibly incorporating H as well), metals, metal nitrides, and metal oxides. In some embodiments, a dielectric film including metal oxide or silicon oxide is selectively deposited on the second surface. In one example, the metal oxide film may serve as a cap layer on the second surface. The dielectric film can, for example, 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 the group consisting of titanium oxide, hafnium oxide, zirconium oxide, aluminum oxide, tantalum oxide, silicon oxide, carbon doped silicon oxide, and combinations thereof. In some examples, the dielectric film such as silicon oxide film may be deposited by ALD using alternating exposures of a silicon precursor (e.g., Tetraisocyanatosilane) and an oxidizer (e.g., H2O). In other examples, the dielectric film such as metal oxide film may be deposited by ALD using alternating exposures of a volatile metal-containing precursor and a mild oxidizer (e.g., H2O, H2O2) as is detailed in U.S. provisional patent application Serial No. 62 / 472,724, filed on March 17, 2017, the entirety of which isincorporated herein by reference. In other examples, the dielectric film such as silicon oxide may be deposited via alternating exposures of a volatile metal-containing precursor catalyst such as trimethylaluminum, triethylaluminum, dimethylaluminum iso-propoxide, diethylaluminum iso-propoxide, and a trialkoxysilanol such as tris(tert- butoxy)silanol, tris(tert-pentoxy)silanol, bis(tert-butoxy)(tert-pentoxy)silanol, and bis(tert-pentoxy)(tert-butoxy)silanol.

[0099] Selective depositions according to the present disclosure can be, for example, metal and metal oxide layers 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 entireties.

[0100] In one particular embodiment, silicon oxide is selectively deposited on the second surface employing a silicon precursor selected from the group consisting of tetraisocyanatosilane (Si(NCO)4), tetraisothiocyanatosilane (Si(NCS)4), tetrathiocyanatosilane (Si(SNC)4), and hexaisocyanatodisiloxne (NCO)sSi-O- Si(NCO)3).

[0101] In some embodiments, a metal oxide is selectively deposited on the second surface employing a metal-containing precursor. The metal-containing precursor should have sufficient vapor pressure and stable enough to be delivered into the reaction chamber, and may have a formula of M(Li)x(L2)y(L3)zwherein M is group 3 to 13 metals; Li, L2, and L3are independently selected from the group consisting of substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted pyrollyl, substituted or unsubstituted imidazolyl, amido, alkoxy, amidinate, linear or branched diene, linear or branched alkyl, hydride, carbon monoxide, nitrosyl, halide (F, Cl, Br, I) and combination thereof; x, y, and z is 0, 1 , 2, 3, 4 depending on the oxidation state of the metal. Examples of metal-containing precursors include, but not limited to, tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), tetrakis(ethylmethylamino)hafnium (TEMAH), cyclopentadienyltris(dimethylamino)hafnium (CpHf(NMe2)3), methylcyclopentadienyltris(dimethylamino)hafnium (MeCpHf(NMe2)3), ethylcyclopentadienyltris(dimethylamino)hafnium (EtCpHf(NMe2)3), cyclopentadienyltris(dimethylamino)hafnium (CpHf(NMeEt)3), methylcyclopentadienyltris(dimethylamino)hafnium (MeCpHf(NMeEt)3),tetrakis(dimethylamino)zirconium (TDMAZ), tetrakis(diethylamino)zirconium (TDEAZ), tetrakis(ethylmethylamino)zirconium (TEMAZ), cyclopentadienyltris(dimethylamino)zirconium (CpZr(NMe2)3), methylcyclopentadienyltris(dimethylamino)zirconium (MeCpZr(NMe2)3), ethylcyclopentadienyltris(dimethylamino)zirconium (EtCpZr(NMe2)3), cyclopentadienyltris(dimethylamino)zirconium (CpZr(NMeEt)3), methylcyclopentadienyltris(dimethylamino)zirconium (MeCpZr(NMeEt)3), tert- butylimino tri(diethylamino)tantalum (TBTDET), tert-butylimino tri(dimethylamino)tantalum (TBTDMT), tert-butylimino tri(ethylmethylamino)tantalum (TBTEMT), ethylimino tri(diethylamino)tantalum (EITDET), ethylimino tri(dimethylamino)tantalum (EITDMT), ethylimino tri(ethylmethylamino)tantalum (EITEMT), tert-amylimino tri(dimethylamino)tantalum (TAIMAT), tert-amylimino tri(diethylamino)tantalum, pentakis(dimethylamino)tantalum, tert-amylimino tri(ethylmethylamino)tantalum, bis(tert-butylimino)bis(dimethylamino)molybdenum (BTBMM), bis(tert-butylimino)bis(diethylamino)molybdenum, bis(tert- butylimino)bis(ethylmethylamino)molybdenum, trimethylaluminum, triethylaluminum, dimethylaluminum iso-propoxide, diethylaluminum iso-propoxide.

[0102] During the selective deposition process, the aforementioned protective surface previously deposited selectively on silicon nitride surfaces with the at least one diol could begin to react or otherwise become less inert. An optional re-application of the at least one diol, either with or without any of the aqueous or plasma or thermal pre-treatment steps may optionally be performed repeatedly to prevent or delay non- selective deposition on the silicon nitride surface.

[0103] In some embodiments passivation on a first surface of a substrate as described herein, such a silicon nitride surface of the substrate, relative to a second surface of the substrate is at least about 90% selective, at least about 95% selective, at least about 96%, 97%, 98% or 99% or greater selective. In some embodiments passivation only occurs on the first surface and does not occur on the second surface. In some embodiments passivation on the first surface of the substrate relative to the second surface of the substrate is at least about 70% selective, or at least about 80% selective, which may be selective enough for some particular applications. In some embodiments passivation on the first surface of the substrate relative to the second surface of the substrate is at least about 30-40% selective, which may be selective enough for some particular applications.

[0104] Wet chemistry cleans may be used to remove the passivation layer. Example wet chemistry cleans include acidic, basic, and oxidative (e.g., peroxide-containing) wet chemistry compositions known in the art and described above for the optional step of contacting the substrate with a wet chemical composition. Another method to remove the passivation layer is via the application of heat or other energy.EXAMPLES

[0105] Example embodiments show diol (linear alkyl diol) selectively passivate the silicon nitride surface versus the silicon oxide surface. This process is depicted in FIG. 1A. The process results in the selectivity to grow thicker silicon oxide film (or metal film) on silicon oxide.

[0106] A substrate 100 containing a first surface 102 (preferably silicon nitride) and a second surface 104 (a material other than silicon nitride). Expose substrates to alkyl diol or aryl diol inhibitor to form a passivated region 106. Subsequently a dielectric film 108 is deposited on the second surface 104.

[0107] The process depicted in FIG. 1 B results in the selectivity to grow thicker silicon oxide film (or metal film) on silicon oxide.

[0108] A substrate 200 containing a first surface 202 (silicon nitride) and a second surface 204 (silicon oxide). Expose substrates to alkyl diol or aryl diol inhibitor to form a passivated region 206, preferably a self-assembled monolayer (SAM), to selectively passivate the SisN4surface 202 by converting the Si-NH2groups to aliphatic or aromatic groups. Subsequently a dielectric film 208 is deposited on the second surface 204.Dielectrics on Dielectrics (DoD)

[0109] ALD silicon nitride and thermal silicon oxide are used to as growth and nongrowth substrates to test the passivation ability of the new chemistries. ALD silicon nitride was grown on thermal oxide substrate treated with oxygen plasma to remove undesired contaminants on the surface, followed by deposition of passivation reagents. The thin organic passivation layer is formed by delivering the precursor(s) to the reactor using mass flow controllers with heated lines. Importantly, a pre-treatment may be performed using hydrogen plasma, argon plasma, helium plasma, ammonia plasma, hydrogen, ammonia, and combination thereof at a temperature ranging from room temperature to 700 °C to provide more Si-NH2groups on at least a first surfacecomprising silicon nitride and at least a second surface comprising a material other than silicon nitride. In a preferred embodiment, the pre-treatment is performed by thermally exposing the substrate to ammonia, hydrogen, and combination thereof at temperature ranging from 450°C to 550°C to provide more Si-NHs groups on at least a first surface comprising silicon nitride and at least a second surface comprising a material other than silicon nitride. Most preferably, the thermal pre-treatment is conducted at temperature ranging from 475°C to 525°C.

[0110] Two distinct representative passivation chemistries have been chosen to showcase the passivation capabilities among HO-R-OH structures where R is linear alkyl group. The passivation layer inhibition ability towards ALD process was tested using Si(NCO)4, triethylamine, and water ALD process. The ALD deposition was conducted at 100°C to achieve silicon oxide film deposition.

[0111] The passivation chemistries are among diols head groups; 1 ,2-ethanediol (ethylene glycol) for the short hydrocarbon chain diol test, and 1 ,8-octanediol for the long hydrocarbon chain diol test.

[0112] FIG. 2 illustrates the saturation of two passivation chemistries. It is apparent that 1 ,8-octanediol demonstrated greater reactivity with silicon nitride surface compared to 1 ,2-ethanediol. This led to the formation of a superior passivation layer on silicon nitride surface, resulting in reduced growth of silicon oxide in the subsequent step.

[0113] FIG. 3 demonstrates applying the same inhibition chemistries on a silicon oxide substrate yielded slight to negligible formation of a passivation layer. This led to immediate growth of silicon oxide on the silicon oxide surface, underscoring the selectivity of the proposed inhibitors.

[0114] FIG. 4 demonstrates the growth of silicon oxide using Si(NCO)4 on passivated silicon nitride using 1 ,2-ethanediol and 1 ,8-octanediol. The thickness of silicon oxide deposited on the passivated silicon nitride substrate with 1 ,8-octanediol as the inhibitor is less than a thickness of silicon oxide deposited on the passivated silicon nitride substrate with 1 ,2-ethanediol as the inhibitor. This confirms the essential role of the hydrocarbon chain length of the inhibitor for passivation.

[0115] FIG 5 demonstrates the growth of silicon oxide using Si(NCO)4 on exposed silicon oxide to 1 ,2-ethanediol and 1 ,8-octanediol. The thickness of silicon oxide deposited on the not exposed silicon oxide substrate and exposed substrates to theinhibitors does not differ significantly, confirming the selective passivation of the inhibitors on silicon nitride substrates over silicon oxide substrates.

[0116] For purposes of this disclosure and claims, selectivity of the second surface to the first surface if found by the following equation: selectivity = (thickness of film on the second surface (silicon oxide) - thickness of film on the first surface (silicon nitride)) / (thickness of film on the second surface (silicon oxide) + thickness of film on the first surface (silicon nitride)). Notably, successful selectivity (preferably greater than about 0.1 , more preferably greater than about 0.2, and most preferably greater than about 0.3) is achieved by passivating with 1 ,8-octanediol. Passivating with 1 ,2-ethanediol was significantly less successful.Table 1 Selectivity of different inhibitors

[0117] As shown in Table 1 , successful selective deposition of dielectric films (silicon oxide at greater than about 0.3 selectivity) was achieved using primary diol: 1 ,8- octanediol, while a smaller alkyl diol such as 1 ,2-ethanediol shows much less selectivity, demonstrating linear diols with C4 to C20 linear alkyl group, preferably Ce to C20 linear alkyl group, most preferable Cs to G linear alkyl group are suitable inhibitors for selective deposition of dielectric film on silicon oxide vs silicon nitride.

[0118] FIG. 6 demonstrates the growth of silicon oxide using Si(NCO)4 on passivated silicon oxide and passivated silicon nitride, respectively, demonstrating up to 67% selectivity for 40 A thermal ALD SiO2 film on silicon oxide vs silicon nitride.

[0119] FIG. 7 demonstrates pre-treatment impact on selectivity of ALD silicon oxide using Si(NCO)4 on passivated silicon nitride and passivated silicon oxide using 1 ,8- octanediol. The pre-treatments are conducted as following: diluted hydrogen fluoride solution (dHF) wet clean, dHF wet clean followed by NH3thermal treatment, and dHFwet clean followed by NH3and hydrogen thermal treatment. All thermal pre-treatments were conducted at 500 °C. The results show the NH3thermal treatment enhances selectivity by -20-30%. Further improvement of -10% was observed when H2is cointroduced with NH3.

[0120] While the principles of the disclosure have been described above in connection with preferred embodiments, it is to be clearly understood that this description is made only by way of example and not as a limitation of the scope of the claimed subject matter.

Claims

CLAIMSWe claim:1 . A method for selectively passivating a substrate, the method comprising: a. providing the substrate, wherein the substrate comprises a first surface comprising silicon nitride and a second surface comprising a material other than silicon nitride; and b. exposing the substrate to at least one passivation molecule having a structure according to Formula I:HO-R-OH (I), wherein R is a diradical derived from a linear or branched C4 to C20 alkyl group, a C5to Cs cyclic alkyl group, a substituted or unsubstituted C4 to Cis alkenyl group, a substituted or unsubstituted C4 to Cis alkynyl group, a C7 to C20 arylalkyl group, a C4 to C20 alkyl group having at least one heteroatom such as oxygen or nitrogen, or a C& to C20 aryl group by removal of two hydrogen atoms, wherein the at least one passivation molecule selectively reacts with the silicon nitride to passivate the first surface, while leaving the second surface substantially unreacted.

2. The method of claim 1 , wherein the second surface comprises at least one selected from the group consisting of silicon oxide, a metal oxide, copper, cobalt, tungsten, amorphous silicon, polysilicon, monocrystalline silicon, germanium, and amorphous hydrogenated germanium, preferably silicon oxide.

3. The method of claim 2, wherein the step of treating the substrate with hydrogen plasma, argon plasma, ammonia plasma, hydrogen, ammonia, or an etchant is conducted prior to step b.

4. The method of claim 1 , wherein R is a C4 to C20 linear alkyl group having a structure CnH2n+i, wherein n is 4 to 20.

5. The method of claim 4, wherein the at least one passivation molecule is a linear Cs to C20 diol selected from the group consisting of 1 ,4-butanediol, 1 ,5- pentanediol, 1 ,6-hexanediol, 1 ,7-heptanediol, 1 ,8-octanediol, 1 ,9-nonanediol, 1 ,10- decanediol, 1 ,11 -undecanediol, 1 ,12-dodecanediol, 1 ,13-tridecanediol, 1 ,14- tetradecanediol, 1 ,15-pentadecanediol, 1 ,16-hexadecanediol, 1 ,17-heptadecanediol, 1 ,18-octadecanediol, 1 ,19-nonaecanediol, and 1 ,20-eicosanediol.

6. The method of claim 1 , wherein R is a branched Cs to C20 alkyl group having a formula CnH2n+i, wherein n is 6 to 20.

7. The method of claim 6, wherein the at least one passivation molecule is selected from the group consisting of hexane-2,5-diol, heptane-2,6-diol, octane- 2,7-diol, nonane-2,8-diol, decane-2, 9-diol, undecane-2,10-diol, dodecane-2,11-diol, tridecane-2, 12-diol, tetradecane-2, 13-diol, pentadecane-2,14-diol, hexadecane-2,15- diol, heptadecane-2, 16-diol, octadecane-2,17-diol, nonadecane-2,18-diol, and eicosane-2,19-diol.

8. The method of claim 1 , wherein R is a substituted or unsubstituted C5to Cs cyclic alkyl group.

9. The method of claim 8, wherein the at least one passivation molecule is selected from the group consisting of 1 ,3-cyclopentanediol, 1 ,4-cyclohexanediol,1 ,4-cycloheptanediol, cyclooctane- 1 , 4-diol, and 1 -methylcyclohexane-1 , 4-diol.

10. The method of claim 1 , wherein R is an unsubstituted C7to C20 arylalkyl group.11 . The method of claim 10, wherein the at least one passivation molecule is selected from the group consisting of 1 ,2-benzenedimethanol, 1 ,3- benzenedimethanol, 1 ,4-benzenedimethanol, 3-hydroxybenzyl alcohol, 2-(4- hydroxyphenyl)ethanol, and 3-(4-hydroxyphenyl)-1 -propanol.

12. The method of claim 1 , wherein R is a substituted or unsubstituted Ce to C20 aryl group.

13. The method of claim 12, wherein the at least one passivation molecule is selected from the group consisting of 1 ,2-dyhydroxybenzene, hydroquinone, 2- methylbenzene-1 ,4-diol, 2-ethylbenzene-1 ,4-diol, 2-propylbenzene-1 ,4-diol, 2- butylbenzene-1 ,4-diol, 2-pentylbenzene-1 ,4-diol, 2-hexylbenzene-1 ,4-diol, 2- heptylbenzene-1 ,4-diol, 4-methylcatechol, 4-ethylcatechol, 4-propylbenzene-1 ,2-diol, 4-butybenzene-1 ,2-diol, 4-pentylbenzene-1 ,2-diol, 4-hexylbenzene-1 ,2-diol, 4- heptylbenzene-1 ,2-diol, 4-octylbenzene-1 ,2-diol, 5-methylbenzene-1 ,3-diol, 5- ethylbenzene-1 ,3-diol, 5-propylbenzene-1 ,3-diol, 5-butylbenzene-1 ,3-diol, 5- pentylbenzene-1 ,3-diol, 5-hexylbenzene-1 ,3-diol, 5-heptylbenzene-1 ,3-diol, and 5- octylbenzene-1 ,3-diol.

14. The method of claim 1 , wherein R is a C4 to C20 alkyl group having at least one heteroatom such as oxygen or nitrogen.

15. The method of claim 14, wherein the at least one passivation molecule is selected from the group consisting of diethylene glycol, bis(hydroxyethyl)amine, bis(3-hydroxypropyl)amine, N-methyldiethanolamine, 3,3’-(methylamino)bis-1 - propanol, 2,2-(phenylamino)bis-ethanol, 3,3’-(phenylamino)bis-propanol, 2,2-(4- methylphenylamino)bis-ethanol, 3,3’-(3-methylphenylamino)bis-ethanol, 2,2-(4- methylphenylamino)bis-ethanol, dipropylene glycol, and pyridine-2,6-diethanol.

16. The method of claim 1 , wherein step b. is conducted with a vapor of the at least one passivation molecule.

17. A method of selectively depositing a dielectric film on a substrate wherein 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, treating the substrate with hydrogen plasma or ammonia plasma or an etchant; b. exposing the substrate to at least one passivation molecule having a structure according to Formula I:HO-R-OH (I), wherein R is a diradical derived from a linear or branched C4 to C20 alkyl group, a C5 to Cs cyclic alkyl group, a substituted or unsubstituted C4 to C18 alkenyl group, a substituted or unsubstituted C4 to C alkynyl group, a C7 to C20 arylalkyl group, a C4 to C20 alkyl group having at least one heteroatom such as oxygen or nitrogen, or a Cs to C20 aryl group by removal of two hydrogen atoms, wherein the at least one passivation molecule is a diol, and wherein the diol selectively reacts with the silicon nitride to passivate the first surface, while leaving the second surface substantially unreacted; and c. exposing the substrate to one or more deposition precursors to deposit a dielectric film on the second surface selectively over the first surface.

18. The method of claim 17, wherein the second surface comprises at least one selected from the group consisting of silicon oxide, a metal oxide, copper, cobalt, ruthenium, tungsten, molybdenum, amorphous silicon, polysilicon, monocrystalline silicon, germanium, and amorphous hydrogenated germanium.

19. The method of claim 18, wherein the second surface comprises silicon oxide.

20. The method of claim 17, wherein R in the at least one passivation molecule is a Cs to C20 linear alkyl group.21 . The method of claim 20, wherein the at least one passivation molecule is selected from the group consisting of 1 ,8-octanediol, 1 ,9-nonanediol, 1 ,10- decanediol, 1 ,11 -undecanediol, 1 ,12-dodecanediol, 1 ,13-tridecanediol, 1 ,14-tetradecanediol, 1 ,15-pentadecanediol, 1 ,16-hexadecanediol, 1 ,17-heptadecanediol, 1 ,18-octadecanediol, 1 ,19-nonaecanediol, and 1 ,20-eicosanediol.

22. The method of claim 17, wherein the dielectric film comprises titanium oxide, hafnium oxide, zirconium oxide, aluminum oxide, tantalum oxide, silicon oxide, carbon doped silicon oxide, or combinations thereof.

23. The method of claim 17, wherein R is a substituted or unsubstituted C5 to Cs cyclic alkyl group.

24. The method of claim 23, wherein the at least one passivation molecule is selected from the group consisting of 1 ,3-cyclopentanediol, 1 ,4-cyclohexanediol,1 ,4-cycloheptanediol, cyclooctane-1 ,4-diol, and 1 -methylcyclohexane-1 ,4-diol.

25. The method of claim 17, wherein R is a substituted or unsubstituted C7to C20 arylalkyl group.

26. The method of claim 25, wherein the at least one passivation molecule is selected from the group consisting of 1 ,2-benzenedimethanol, 1 ,3- benzenedimethanol, 1 ,4-benzenedimethanol, 3-hydroxybenzyl alcohol, 2-(4- hydroxyphenyl)ethanol, and 3-(4-hydroxyphenyl)-1 -propanol.

27. The method of claim 17, wherein R is a substituted or unsubstituted Ce to C20 aryl group.

28. The method of claim 27, wherein the at least one passivation molecule is selected from the group consisting of 1 ,2-dyhydroxybenzene, hydroquinone, 2- methylbenzene-1 ,4-diol, 2-ethylbenzene-1 ,4-diol, 2-propylbenzene-1 ,4-diol, 2- butylbenzene-1 ,4-diol, 2-pentylbenzene-1 ,4-diol, 2-hexylbenzene-1 ,4-diol, 2- heptylbenzene-1 ,4-diol, 4-methylcatechol, 4-ethylcatechol, 4-propylbenzene-1 ,2-diol, 4-butybenzene-1 ,2-diol, 4-pentylbenzene-1 ,2-diol, 4-hexylbenzene-1 ,2-diol, 4-heptylbenzene-1 ,2-diol, 4-octylbenzene-1 ,2-diol, 5-methylbenzene-1 ,3-diol, 5- ethylbenzene-1 ,3-diol, 5-propylbenzene-1 ,3-diol, 5-butylbenzene-1 ,3-diol, 5- pentylbenzene-1 ,3-diol, 5-hexylbenzene-1 ,3-diol, 5-heptylbenzene-1 ,3-diol, and 5- octylbenzene-1 ,3-diol.

29. The method of claim 17, wherein R is a C4 to C20 alkyl group having at least one heteroatom such as oxygen or nitrogen.

30. The method of claim 29, wherein the at least one passivation molecule is selected from the group consisting of diethylene glycol, bis(hydroxyethyl)amine, bis(3-hydroxypropyl)amine, N-methyldiethanolamine, 3,3’-(methylamino)bis-1 - propanol, 2,2-(phenylamino)bis-ethanol, 3,3’-(phenylamino)bis-propanol, 2,2-(4- methylphenylamino)bis-ethanol, 3,3’-(3-methylphenylamino)bis-ethanol, 2,2-(4- methylphenylamino)bis-ethanol, and dipropylene glycol, and pyridine-2,6-diethanol and .31 . The method of claim 17, wherein step b. is conducted with a vapor of the at least one passivation molecule.

32. The method of claim 17, further comprising wherein a thickness of the dielectric film deposited on the first surface is less than a thickness of the dielectric film deposited on the second surface; wherein the second surface comprises silicon oxide; and wherein a 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.

33. The method of claim 17, wherein a thickness of the dielectric film deposited on the first surface is less than a thickness of the dielectric film deposited on the second surface; wherein the second surface comprises silicon oxide; andwherein a 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.

34. The dielectric film of claim 17, wherein the dielectric film is silicon oxide, and wherein the one or more deposition precursors comprising a silicon precursor selected from the group consisting of tetraisocyanatosilane (Si(NCO)4), tetraisothiocyanatosilane (Si(NCS)4), tetrathiocyanatosilane (Si(SNC)4), and hexaisocyanatodisiloxne (NCO)3Si-O-Si(NCO)3).

35. The method of claim 17, wherein in step c, the one or more deposition precursors comprise Si(NCO)4, and wherein the dielectric film has a refractive index ranging from about 1.40 to about 1 .60.

36. The method of claim 17, wherein the dielectric film comprises silicon oxide, and the one or more deposition precursors comprise Si(NCO)4, and wherein a thickness of silicon oxide film on the first surface is less than a thickness of silicon oxide film deposited on the second surface; wherein the first surface comprises silicon nitride; wherein the second surface comprises silicon oxide; and wherein the at least one passivation molecule comprises 1 ,8-octanediol.

37. The method of claim 17, wherein the at least one passivation molecule comprises 1 ,8-octanediol, and a deposition selectivity of the second surface relative to the first surface is greater than about 0.3.

38. A method for selectively passivating a silicon nitride surface of a substrate comprising:a. providing the substrate in a reaction vessel at temperatures ranging from about 20°C to about 300°C; b. forming at least one passivation layer on the silicon nitride surface by exposing the substrate to at least one passivation molecule having a structure according to Formula I:HO-R-OH (I), wherein R is a diradical derived from a linear or branched C4 to C20 alkyl group, a C5 to Cs cyclic alkyl group, a substituted or unsubstituted C4 to G alkenyl group, a substituted or unsubstituted C4 to C18 alkynyl group, a C7to C20 arylalkyl group, a C4 to C20 alkyl group having at least one heteroatom such as oxygen or nitrogen, or a Ce to C20 aryl group by removal of two hydrogen atoms; and c. purging the reactor with inert gas.

39. The method of claim 38, wherein steps (b) to (c) are repeated to provide a fully covered passivation layer on the silicon nitride.

40. The method of claim 38, wherein the steps (b) to (c) are performed at one temperature to ensure all available reactive sites are consumed to provide a blocking layer and then the substrate is heated up to a higher temperature to allow further reactions to provide denser blocking layer.41 . A method for treatment of a substrate, comprising: a. providing the substrate, wherein the substrate comprises at least a first surface comprising silicon nitride and at least a second surface comprising a material other than silicon nitride; and b. thermally exposing the substrate to ammonia, hydrogen, and combination thereof at temperature ranging from 450°C to 550°C to provide more Si- NH2groups on the first surface vs the second surface.P24-105-SEC-W00142. The method of claim 41 , wherein the substrate is cleaned with a diluted hydrogen fluoride solution prior to step b.

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