Selective deposition for sub 20 nm pitch EUV patterning

Abstract

A method for selectively depositing a carbon-containing layer is described. Exemplary processing methods may include treating a substrate comprising a carbon-containing surface and a silicon-containing surface with one or more of ozone or hydrogen peroxide to passivate the silicon-containing surface. In one or more embodiments, a carbon-containing layer is then selectively deposited on the carbon-containing surface but not on the silicon-containing surface by flowing a first precursor over the substrate to form a first portion of an initial carbon-containing film on the carbon-containing surface but not on the silicon-containing surface. The method may include removing the first precursor effluent from the substrate. A second precursor may then flow over the substrate to react with the first portion of the initial carbon-containing layer. The method may include removing the second precursor effluent from the substrate.

Description

Technical Field

[0001] Embodiments of the present disclosure relate to methods for selectively depositing carbon-based films. In particular, embodiments of the present disclosure relate to methods for selectively depositing carbon-based layers on carbon-containing surfaces relative to silicon-containing surfaces, such as silicon and silicon oxide (SiOx) surfaces. Prior Art

[0002] Photolithography uses a photoresist (a light-sensitive film) to transfer a negative or positive image onto a substrate (e.g., a semiconductor wafer). After coating the substrate with the photoresist, the coated substrate is exposed to a source of activating radiation, which causes a chemical transformation in the exposed areas of the surface. Depending on the type of photoresist employed, the photoresist-coated substrate is then treated with a developer solution to dissolve or otherwise remove the radiation-exposed or unexposed areas of the coated substrate.

[0003] Current EUV patterning processes suffer from inefficient bottom-layer opening. The tapered shape of the chemically amplified resist (CAR) and the limited height of the CAR relative to the bottom layer can lead to inefficient bottom-layer etching during fine-pitch EUV patterning. Current approaches to address these issues involve increasing the CAR thickness before EUV exposure and development, and increasing the CAR etch selectivity relative to the bottom layer through metal doping. However, these approaches can result in bridging defects or leave difficult-to-remove CAR residues.

[0004] Thus, there is a continuing need in the art for methods to improve deposition selectivity and avoid the problems encountered during EUV patterning. Summary of the Invention

[0005] One or more embodiments of the present disclosure relate to a method for selectively depositing a film. The method includes flowing a first precursor comprising a first reactive group over a substrate comprising a carbon-containing surface and a silicon-containing surface to form a first portion of a carbon-containing layer on the carbon-containing surface; removing a first precursor effluent comprising the first precursor from the substrate; flowing a second precursor comprising a second reactive group over the substrate to react with the first reactive group to form a carbon-containing layer on the carbon-containing surface of the substrate but not on the silicon-containing surface; and removing a second precursor effluent comprising the second precursor from the substrate.

[0006] Another embodiment of the present disclosure relates to a method for selectively depositing a film. In one or more embodiments, the method for selectively depositing a film comprises treating a substrate comprising a carbon-containing surface and a silicon-containing surface with one or more of ozone or hydrogen peroxide to form hydroxyl groups on the silicon-containing surface; exposing the silicon-containing surface and the hydroxyl groups to an alkylating precursor to form a passivated surface, wherein the alkylating precursor has the general formula (A): wherein R 3 and R 4 independently comprise one or more of hydrogen, an alkyl group, a halide, an alkenyl group, an aryl or aromatic group, a cycloalkyl group, and a trimethylsilyl group (Si(CH 3) 3), and wherein q is an integer ranging from 0 to 5; flowing a first precursor over the substrate, the first precursor having the formula R 1-(X) n, wherein R 1 comprises one or more of an alkyl group, an alkenyl group, an aryl or aromatic group, and a cycloalkyl group, X n comprises one or more of a hydroxyl group, an aldehyde group, a ketone group, an acid group, an amine group, an isocyanate group, a thiocyanate group, and an acyl chloride group, and n is an integer ranging from 1 to 6, wherein the first precursor reacts with the reactive groups on the carbon-containing surface to form a first portion of a carbon-containing layer on the carbon-containing surface; removing a first precursor effluent comprising the first precursor from the substrate; flowing a second precursor over the substrate to form a carbon-containing layer on the carbon-containing surface but not on the passivating surface, the second precursor having the formula R 2-(Y) n, wherein R 2 comprises one or more of an alkyl group, an alkenyl group, an aryl or aromatic group, and a cycloalkyl group, Y n comprises one or more of a hydroxyl group, an aldehyde group, a ketone group, an acid group, an amine group, an isocyanate group, a thiocyanate group, and an acyl chloride group, and n is an integer ranging from 1 to 6, wherein a second precursor reacts with the first portion to form a carbon-containing layer; and removing a second precursor effluent comprising the second precursor from the substrate. Simple diagram description

[0007] In order to enable a detailed understanding of the manner in which the above-described features of the present disclosure are employed, a more particular description of the present disclosure, briefly summarized above, may be had with reference to embodiments, some of which are illustrated in the accompanying drawings. It should be noted, however, that the accompanying drawings illustrate only typical embodiments of the present disclosure and are not to be considered limiting of its scope, as the disclosure may admit to other equally effective embodiments. The embodiments as described herein are illustrated by way of example and not limitation in the figures of the accompanying drawings, in which like references indicate similar elements.

[0008] Figure 1 shows a cross-sectional view of a substrate according to one or more embodiments;

[0009] Figure 2 shows a cross-sectional view of a substrate according to one or more embodiments;

[0010] Figure 3A shows a cross-sectional view of a substrate according to one or more embodiments;

[0011] Figure 3B shows a cross-sectional view of a substrate according to one or more embodiments;

[0012] Figure 4 shows a cross-sectional view of a substrate according to one or more embodiments;

[0013] Figure 5 shows a cross-sectional view of a substrate according to one or more embodiments;

[0014] Figure 6 shows a cross-sectional view of a substrate according to one or more embodiments;

[0015] FIG7 illustrates a cross-sectional view of a substrate according to one or more embodiments; and

[0016] FIG. 8 illustrates a process flow diagram of a method for selectively depositing a film on a substrate according to one or more embodiments. Implementation Method

[0017] Before describing several exemplary embodiments of the present invention, it should be understood that the present invention is not limited to the details of construction or process steps set forth in the following description. The present invention is capable of other embodiments and of being practiced or carried out in various ways.

[0018] As used herein, the term "about" means approximately or nearly, and in the context of a recited numerical value or range, means a variation of ±15% or less of the value. For example, values ​​that differ by ±14%, ±10%, ±5%, ±2%, or ±1% would meet the definition of about.

[0019] As used in this specification and the accompanying claims, the term "substrate" or "wafer" refers to a surface, or portion of a surface, upon which a process is performed. As will also be understood by those skilled in the art, reference to a substrate may also refer to only a portion of a substrate, unless the context clearly indicates otherwise. Furthermore, reference to depositing on a substrate may refer to both a bare substrate and a substrate upon which one or more films or features are deposited or formed.

[0020] As used herein, "substrate" or "substrate surface" refers to any portion of a substrate or portion of the surface of a material formed on a substrate on which film processing is performed. For example, depending on the application, substrate surfaces on which processing may be performed include materials such as silicon, silicon oxide, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire, and any other material. Substrates include, but are not limited to, semiconductor wafers. Substrates may be exposed to pretreatment processes to polish, etch, reduce, oxidize, hydroxylate, anneal, UV cure, electron beam cure, and / or bake the substrate surface. In addition to film processing directly on the surface of the substrate itself, as described in more detail below, any of the disclosed film processing steps may also be performed on underlying layers formed on the substrate, and the term "substrate surface" is intended to include such underlying layers as indicated by the context. Thus, for example, where a film / layer or portion of a film / layer has already been deposited onto a substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate. Substrates may have various sizes, such as 200 mm or 300 mm diameter wafers, as well as rectangular or square panels. In some embodiments, the substrate comprises a rigid, discrete material.

[0021] The term “on” indicates that there is direct contact between elements. The term “directly on” indicates that there is direct contact between elements without intervening elements.

[0022] As used herein, "extreme UV," "EUV," or the like refers to radiation in the approximate range of 10 nm to 124 nm. In some embodiments, EUV radiation, extreme ultraviolet light (also referred to as EUV light), is in the range of 10 nm to 15 nm. In one or more embodiments, EUV light having a wavelength of approximately 13.5 nm is used.

[0023] As used in this specification and the accompanying claims, the terms "precursor," "reactant," "reactive gas," and the like are used interchangeably to refer to any gaseous species that can react with a substrate surface.

[0024] As used in this specification and the appended claims, the terms "reactive compound," "reactive gas," "reactive substance," "precursor," "processing gas," and the like are used interchangeably to refer to a material having a substance capable of reacting with a substrate or a material on the substrate in a surface reaction (e.g., chemisorption, oxidation, reduction, cycloaddition). The substrate, or portion of the substrate, is sequentially exposed to two or more reactive compounds, which are introduced into a reaction zone of a processing chamber.

[0025] As used in this specification and the accompanying claims, the term "carbon-containing surface" refers to a surface, layer, or portion of a surface that contains carbon. The carbon-containing surface may contain any suitable amount of carbon. For example, in some embodiments, the carbon-containing surface is a photoresist composed of a polymeric material containing carbon. In one or more embodiments, the carbon-containing surface comprises a chemically amplified resist (CAR) layer of an EUV photoresist. In other embodiments, the carbon-containing surface may comprise an amorphous carbon layer.

[0026] As used in this specification and the accompanying claims, the term "silicon-containing surface" refers to a surface, layer, or portion of a surface that contains silicon. The silicon-containing surface can contain any suitable amount of silicon. In one or more embodiments, the silicon-containing surface comprises a spin-on-glass layer beneath a photoresist layer.

[0027] Carbon-containing materials can be used in a variety of structures and processes during semiconductor device fabrication, including as mask materials, etch resists, and trench fill materials, among other applications. More specific examples of carbon-containing material applications include forming thermal implant hardmasks, metal gate (MG)-cut hardmasks, metal gate fabrication, and reverse-tone patterning and self-aligned patterning. This technology involves selectively forming these carbon-containing materials on carbon-containing surfaces using molecular layer deposition (MLD).

[0028] In one or more embodiments, the substrate is an EUV substrate for EUV development and processing. Therefore, in one or more embodiments, the substrate includes a chemically amplified resist (CAR) layer on one or more of a spin-on-glass layer, a hard mask layer, and a target layer. In fine-pitch EUV patterning, inefficient bottom layer etch-through can occur due to the tapered CAR shape and limited CAR height / ES relative to the bottom layer. To address this issue, the CAR thickness can be increased prior to EUV exposure and development, and the CAR etch selectivity relative to the bottom layer can be increased through metal doping. However, these approaches can result in partial CAR development and bridging defects, and can also lead to bridging defects in the bottom layer (when the CAR ES is not high enough) or leave difficult-to-remove CAR residue. One or more embodiments advantageously utilize selective deposition of a carbon-containing layer on carbon-containing surfaces of the substrate, but not on silicon-containing surfaces (e.g., silicon or silicon oxide), to address the aforementioned issues.

[0029] The method of one or more embodiments advantageously combines silicon or silicon oxide surface passivation with molecular layer deposition (MLD) of a carbon-containing film to achieve controlled profile repair and height replenishment of CAR. In one or more embodiments, the method advantageously results in no bridging effect, no difficult-to-remove CAR residue, well-controlled process flow, efficient bottom layer etching with controlled non-tapered profile transfer, and high potential for finer pitch patterning.

[0030] Embodiments of the present technology include processes for selectively forming a carbon-containing material on a carbon-containing surface while substantially eliminating the deposition of carbon-containing material on a silicon-containing surface (e.g., a silicon (Si) surface or a silicon oxide (SiOx) surface). In one or more embodiments, the carbon-containing film is selectively formed on the carbon-containing surface by molecular layer deposition (MLD).

[0031] In one or more embodiments, the carbon-containing surface may be pre-treated or passivated and molecular layer deposition (MLD) may be used to selectively form a carbon-containing layer on the carbon-containing surface but not on the silicon-containing surface.

[0032] In other embodiments, a substrate having a carbon-containing surface and a silicon-containing surface (e.g., silicon (Si) or silicon oxide (SiOx)) is treated with one or more of ozone (O3) or hydrogen peroxide (H2O2) to form hydroxyl groups (-OH) on the silicon or silicon oxide surface. The substrate is then exposed to an alkylating precursor that interacts or reacts with the hydroxyl groups (-OH) to form a passivating surface on the silicon or silicon oxide surface.

[0033] An exemplary MLD method may include providing a first deposition precursor to a carbon-containing surface of a substrate, wherein the precursor forms a first layer (e.g., a first monolayer) on the surface. During or after forming the first layer, unbound deposition effluent (which may include unbound molecules of the first deposition precursor) is removed from a processing region where the semiconductor substrate is exposed. A second deposition precursor may then be introduced to the substrate, wherein molecules of the second deposition precursor bind to reactive moieties on the first layer to form a second layer (e.g., a second monolayer) on the carbon-containing surface and less, or no, non-metallic surfaces. During or after forming the second layer, unbound deposition effluent, which may include unbound molecules of the second deposition precursor, is removed from the processing region. The substrate now has a layer of carbon-containing material bound to the carbon-containing surface of the substrate, with no, or less, carbon-containing material deposited on silicon or silicon oxide surfaces. Additional compound layers of the first and second layers may be accumulated on the deposited layer until the number of accumulated compound layers reaches the desired thickness of the carbon-containing material on the carbon-containing surface of the substrate. The compound layer may then be annealed or plasma treated to form a carbon-containing material on the carbon-containing surface of the substrate.

[0034] One or more embodiments advantageously provide solutions to problems associated with conventional methods of forming carbon-containing materials on semiconductor substrates. For example, the present technique forms carbon-containing materials with significantly fewer voids, cracks, and other physical defects compared to carbon-containing materials formed using spin-on-carbon (SOC) and flowable chemical vapor deposition (FCVD) methods. The present technique can also form carbon-containing materials with higher density and lower porosity compared to materials formed using SOC and FCVD. High levels of hydrogen found in many SOC and FCVD precursors lead to high levels of shrinkage when the deposited material is processed to form the final material. Shrinkage of up to 50% by volume after processing is not uncommon for deposited SOC and FCVD materials, which creates gaps, features, and voids in the processed material, as well as stress on substrate features that come into contact with the material. The present techniques produce treated carbonaceous materials having less than 10% shrinkage by volume of the deposited material (eg, 5-10% shrinkage by volume, less than about 5% shrinkage by volume).

[0035] One or more embodiments advantageously provide solutions to problems encountered with conventional plasma deposition methods for forming carbon-containing materials on semiconductor substrates. Conventional plasma deposition methods, such as plasma-enhanced chemical vapor deposition (PECVD) and high-density plasma chemical vapor deposition (HDPCVD), often generate ion sputtering, which damages substrate features on the semiconductor substrate and can also generate re-sputtered ions and other species that can cause defects in the deposited carbon-containing material. Furthermore, these species often deposit material unevenly in and around substrate features, creating voids in and around substrate trenches and steps, and producing uneven surfaces in planar substrate areas. The present technique can form carbon-containing materials with highly conformal levels and high aspect ratios (e.g., AR of 10:1 or greater) in narrow substrate features (e.g., dimensions less than about 25 nm in width) without requiring plasma that can damage substrate features during deposition.

[0036] Embodiments of the present disclosure are described with reference to drawings that illustrate components (e.g., transistors) and processes for forming semiconductor structures according to one or more embodiments of the present disclosure. The processes shown are merely illustrative of possible uses of the disclosed processes, and those skilled in the art will recognize that the disclosed processes are not limited to the applications shown.

[0037] Figures 1 through 7 illustrate cross-sectional views of a semiconductor substrate processed according to one or more embodiments. Figure 8 illustrates a process flow diagram of a method 200 for selective film deposition according to one or more embodiments. Referring to Figures 1 and 8, in one or more embodiments, at operation 202, a substrate 101 is provided. As used in this specification and the appended claims, the term "provided" means that the substrate 101 is available for processing (e.g., positioned in a processing chamber).

[0038] Referring to FIG. 1 , in one or more embodiments, substrate 101 includes one or more chemical amplification resist (CAR) layers 108 on one or more of a silicon-containing layer 106, a hard mask layer 104, and a target layer 102. In some embodiments, CAR layer 108 comprises carbon. In one or more embodiments, silicon-containing layer 106 is a spin-on-glass layer comprising silicon or silicon oxide (SiO x ). Those skilled in the art will appreciate that silicon-containing layer 106 has a silicon or silicon oxide (SiO x ) surface. In one or more embodiments, the carbon-containing layer grows only on certain carbon-containing surfaces, while not growing or growing much less on passivated silicon or silicon oxide surfaces. The selectivity (the ratio of thickness on different surfaces) can be 2:1, 5:1, 10:1, 50:1, 100:1, or absolutely selective growth (no growth on undesired surfaces).

[0039] Referring to FIG. 2 , in one or more embodiments, a substrate 101 on which a carbon-containing material is selectively formed may include a material in which one or more features 107 may be formed. Features of substrate 101 may be characterized by any shape or configuration according to the present technology. In some embodiments, feature 107 may be or include a trench structure, a via structure, or a hole formed within the substrate. While substrate features may be characterized by any shape or size, in some embodiments, substrate features may be characterized by a high aspect ratio, or the ratio of the depth of the feature to the width across the feature. For example, in some embodiments, substrate features may be characterized by an aspect ratio greater than or equal to 5:1, and may be characterized by an aspect ratio greater than or equal to 10:1, greater than or equal to 15:1, greater than or equal to 20:1, greater than or equal to 25:1, greater than or equal to 30:1, greater than or equal to 40:1, greater than or equal to 50:1, or greater. Additionally, a feature may be characterized by a narrower width or diameter across the feature, including between two sidewalls, such as a dimension of less than or equal to 20 nm, and may be characterized by a width across the feature of less than or equal to 15 nm, less than or equal to 12 nm, less than or equal to 10 nm, less than or equal to 9 nm, less than or equal to 8 nm, less than or equal to 7 nm, less than or equal to 6 nm, less than or equal to 5 nm, or less.

[0040] 3A-3B and 8 , in one or more embodiments, at operation 204, the substrate 101 may optionally be exposed to a treatment process to passivate the substrate 101. Specifically, in one or more embodiments, the substrate 101 may be exposed to a treatment process to passivate the silicon-containing layer 106 without passivating the carbon-containing surface 108. In some embodiments, the substrate 101 having the carbon-containing surface (i.e., the CAR layer 108) and the silicon-containing layer 106 (including a silicon (Si) or silicon oxide (SiOx) surface (i.e., the spin-on-glass layer 106)) is treated with one or more of ozone (O₃) or hydrogen peroxide (H₂O₂) to form hydroxyl groups (—OH) 103 on the silicon or silicon oxide surface of the silicon-containing layer 106.

[0041] In one or more embodiments, referring to FIG. 3B , the substrate 101 is then exposed to an alkylation precursor that interacts or reacts with hydroxyl groups (—OH) to form a passivation surface 105 on the silicon or silicon oxide surface of the silicon-containing layer 106 .

[0042] Without intending to be bound by theory, it is believed that passivating the silicon or silicon oxide surface of the silicon-containing layer 106 with ozone or hydrogen peroxide and then exposing it to the alkylating precursor produces a passivated surface 105, such that a carbon-containing layer cannot form on the passivated silicon or silicon oxide surface. Therefore, in one or more embodiments, the carbon-containing layer 114 is selectively deposited on the carbon-containing surface 108 of the substrate and substantially not on the silicon or silicon oxide surface of the silicon-containing layer 106.

[0043] The alkylation precursor can be any suitable alkylation precursor known to those skilled in the art. In one or more embodiments, the alkylation precursor has the general formula (A):

[0044] wherein R 3 and R 4 independently comprise one or more of hydrogen, an alkyl group, a halide, an alkenyl group, an aryl or aromatic group, a cycloalkyl group, and a trimethylsilyl group (Si(CH 3) 3), and wherein q is an integer ranging from 0 to 5. In one or more embodiments, R 3 and R 4 are independently selected from the group consisting of H, an alkyl group, a chloride, and a trimethylsilyl group. In one or more embodiments, the alkylation precursor is selected from one or more of the following: hexamethyldisilazane, N,N-dimethyltrimethylsilylamine, tris(trimethylsilyl)amine, trimethylchlorosilane, 1-(trimethylsilyl)pyrrolidine, and iodotrimethylsilane.

[0045] Unless otherwise indicated, the term "lower alkyl," "alkyl," or "alkane," as used herein alone or as part of another group, includes straight and branched hydrocarbons containing from 1 to 20 carbons in the normal chain, such as methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, isobutyl, pentyl, hexyl, isohexyl, heptyl, 4,4-dimethylpentyl, octyl, 2,2,4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl, their various branched isomers, and the like. Such groups may optionally include from 1 to 4 substituents. Alkyl groups may be substituted or unsubstituted.

[0046] As used herein, the term "alkoxy" includes any of the above-mentioned alkyl groups linked to an oxygen atom. Alkoxy groups may be substituted or unsubstituted.

[0047] As used herein, the term "vinyl" or "vinyl-containing" refers to a group containing a vinyl group (-CH=CH 2). The vinyl group may be substituted or unsubstituted.

[0048] As used herein, the term "silane" refers to the compound SiR' 3, wherein R' is independently selected from hydrogen (H) or an alkyl group. The alkyl group of the silane can be substituted or unsubstituted.

[0049] As used herein, the term "halide" refers to a binary phase, one portion of which is a halogen atom and the other portion is an element or radical less electronegative than the halogen, used to prepare fluoride, chloride, bromide, or iodide compounds. A halide ion is a negatively charged halogen atom. As known to those skilled in the art, halide anions include fluorine (F-), chlorine (Cl-), bromine (Br-), and iodine (I-).

[0050] As used in this specification and the accompanying claims, the phrase "selectively relative to" or similar phrases means that the target material is deposited on the surface to a greater extent than on another surface. In some embodiments, "selectively" means that the target material forms on the selected surface at a rate that is greater than or equal to about 10x, 15x, 20x, 25x, 30x, 35x, 40x, 45x, or 50x the rate at which the target material forms on the unselected surface. Thus, in one or more embodiments, the carbon-containing layer 114 is selectively formed on the carbon-containing surface 108 at a rate that is greater than or equal to about 10x, 15x, 20x, 25x, 30x, 35x, 40x, 45x, or 50x the rate at which the target material forms on the unselected surface (i.e., the passivation surface 105).

[0051] In one or more embodiments, the carbon-containing layer 114 is formed on the carbon-containing surface 108 but not on the passivation surface 105 of the silicon-containing layer 106, wherein the selectivity ratio is at least 10:1, or at least 100:1, or at least 1000:1.

[0052] 4 and 8 , a first type of precursor 110 is introduced / flowed into the substrate processing region of the processing chamber and over the substrate surface at operation 206. The first precursor 110 strongly bonds to the carbon-containing surface 108 and does not bond to the silicon or silicon oxide surface 106.

[0053] In one or more embodiments, the first precursor 110 may be a carbon-containing precursor having at least two reactive groups that can form bonds with groups attached to the carbon-containing surface 108 of the substrate 101. The molecules of the first precursor 110 react with the surface groups of the carbon-containing surface 108 to form bonds linking the molecules of the first precursor 110 to the carbon-containing surface 108 of the substrate. The reaction between the molecules of the first precursor 110 and the groups on the carbon-containing surface 108 of the substrate continues until most or all of the surface groups are linked to the reactive groups on the molecules of the first precursor 110. A first portion of the carbon-containing layer 114 is formed, which blocks further reactions between the molecules of the first precursor 110 in the first precursor effluent and the substrate.

[0054] The first precursor 110 may include any suitable precursor known to those skilled in the art. In one or more embodiments, the first precursor 110 may have the general formula R1-(X)n, where n is an integer ranging from 1 to 6, and R1 includes one or more of the following: an alkyl group, an alkenyl group, an aryl group, an aromatic group, and a cycloalkyl group. Xn includes one or more of the following: a hydroxyl group, an aldehyde group, a ketone group, an acid group, an amine group, an isocyanate group, a thiocyanate group, and an acyl chloride group.

[0055] Unless otherwise indicated, the term "lower alkyl," "alkyl," or "alkane," as used herein alone or as part of another group, includes straight and branched hydrocarbons containing 1 to 20 carbon atoms, or 1 to 10 carbon atoms, in the normal chain, such as methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, isobutyl, pentyl, hexyl, isohexyl, heptyl, 4,4-dimethylpentyl, octyl, 2,2,4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl, their various branched isomers, and the like. Such groups may optionally include up to 1 to 4 substituents. Alkyl groups may be substituted or unsubstituted.

[0056] Such alkyl groups may optionally include up to 1 to 4 substituents, such as halogen, for example, F, Br, Cl, or I, or CF3, alkyl, alkoxy, aryl, aryloxy, aryl (aryl) or diaryl, aralkyl, arylalkoxy, alkenyl, cycloalkyl, cycloalkylalkyl, cycloalkylalkoxy, amino, hydroxy, hydroxyalkyl, acyl, heteroaryl, heteroaryloxy, heteroarylalkyl, heteroarylalkoxy, aryloxyalkyl, alkylthio, arylalkylthio, aryloxyaryl, alkylamido, alkylamido, arylcarbonylamido, nitro, cyano, thiol, haloalkyl, trihaloalkyl, and / or alkylthio, and the like. In one or more embodiments, R1 is independently selected from C1-20 alkyl. In other embodiments, R1 is selected from C1-12 alkyl.

[0057] As used herein, the term "alkene" or "alkenyl" or "lower alkenyl" refers to a straight or branched chain radical of 2 to 20 carbons or 2 to 12 carbons and 1 to 8 carbons in the normal chain, which includes one to six double bonds in the normal chain, such as ethenyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 2-heptenyl, 3-heptenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-heptenyl, 4 ... 4-decenyl, 3-undecenyl, 4-dodecenyl, 4,8,12-tetradecatrienyl, and the like, and optionally substituted with 1 to 4 substituents, i.e., halogen, haloalkyl, alkyl, alkoxy, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, amino, hydroxy, heteroaryl, cycloheteroalkyl, alkylamido, alkylamido, arylcarbonyl-amino, nitro, cyano, thiol, alkylthio, and / or any alkyl substituent described herein.

[0058] As used herein, the term "alkynyl" or "lower alkynyl" refers to a straight or branched chain radical of 2 to 20 carbons, or 2 to 12 carbons, or 2 to 8 carbons in the normal chain, which includes a triple bond in the normal chain, such as 2-propynyl, 3-butynyl, 2-butynyl, 4-pentynyl, 3-pentynyl, 2-hexynyl, 3-hexynyl, 2-heptynyl, 3-heptynyl, 4-heptynyl, 3-octynyl, 3-nonynyl, 4-but ...hexynyl, 4-hexynyl, 3-hexynyl, 2-heptynyl, 3-heptynyl, 4-heptynyl, 3-octynyl, 3-nonynyl, 4-hexynyl, 4-hexynyl, 3-hexynyl, 2-heptynyl, 3-h 4-decynyl, 3-undecynyl, 4-dodecynyl, and the like, and optionally substituted with 1 to 4 substituents, i.e., halogen, haloalkyl, alkyl, alkoxy, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, amino, heteroaryl, cycloheteroalkyl, hydroxy, alkanoylamino, alkanoylamino, arylcarbonylamino, nitro, cyano, thiol, and / or alkylthio, and / or any alkyl substituent described herein.

[0059] As used herein, the term "aryl" refers to monocyclic and bicyclic aromatic groups containing 6 to 10 carbon atoms in the ring portion (such as phenyl, biphenyl or naphthyl, including 1-naphthyl and 2-naphthyl) and may optionally include 1 to 3 additional rings fused to a carbocyclic or heterocyclic ring (such as an aryl, cycloalkyl, heteroaryl, or cycloheteroalkyl ring). The aryl group may optionally be substituted with 1, 2, or 3 substituents, such as hydrogen, halo, haloalkyl, alkyl, haloalkyl, alkoxy, haloalkoxy, alkenyl, trifluoromethyl, trifluoromethoxy, alkynyl, and the like, through available carbon atoms.

[0060] Specific examples of the first precursor 110 include, but are not limited to, one or more of the following: terephthalaldehyde, phenylenediamine, ethylenediamine, hexamethylenediamine, terephthalyl chloride, 1,3,5-benzenetricarbonyltrichloride, pyromellitic dianhydride, benzene-1,3,5-tricarbaldehyde, 1,4-phenylene diisocyanate, 4,4'-oxydianiline, tris(2-aminoethyl)amine, and the like.

[0061] In one or more embodiments, the rate of formation of the first portion of the carbon-containing film may depend on the temperature of the substrate and the temperature of the deposition precursor flowing into the substrate processing region. Exemplary substrate temperatures during the formation operation may be greater than or equal to 50°C, greater than or equal to 60°C, greater than or equal to 70°C, greater than or equal to 80°C, greater than or equal to 90°C, greater than or equal to 100°C, greater than or equal to 110°C, greater than or equal to 120°C, greater than or equal to 130°C, greater than or equal to 140°C, greater than or equal to 150°C, or higher. By maintaining an elevated substrate temperature, such as greater than or about 100°C, in some embodiments, an increased number of nucleation sites may be available along the carbon-containing surface 108 of the substrate, which may improve formation and reduce void formation by improving coverage at each location.

[0062] The outflow of the first precursor 110 can be maintained in the substrate processing region for a period of time to nearly or completely form the first portion 108 of the carbon-containing layer 114. The precursors can be delivered in alternating pulses to grow the material. In some embodiments, the pulse time of either or both of the first precursor 110 and the second precursor 111 can be greater than or equal to 0.1 seconds, greater than or equal to 1 second, greater than or equal to 2 seconds, greater than or equal to 3 seconds, greater than or equal to 4 seconds, greater than or equal to 5 seconds, greater than or equal to 10 seconds, greater than or equal to 20 seconds, greater than or equal to 40 seconds, greater than or equal to 60 seconds, greater than or equal to 80 seconds, greater than or equal to 100 seconds, or greater.

[0063] Referring to FIG. 8 , at operation 208 , the first precursor 110 is purged or removed from the substrate processing region after forming the first portion 110 of the carbon-containing layer 114 . Effluent from the first precursor 110 may be removed by pumping it out of the substrate deposition region for a time period ranging from about 10 seconds to about 100 seconds. Additional exemplary time ranges may include about 20 seconds to about 50 seconds, and 25 seconds to about 45 seconds, among other exemplary time ranges. However, in some embodiments, increasing the purge time may begin to remove reactive sites, which may reduce uniform formation. Thus, in some embodiments, the purge may be performed for less than or equal to 60 seconds, and may be performed for less than or equal to 50 seconds, less than or equal to 40 seconds, less than or equal to 30 seconds, or less. In some embodiments, a purge gas may be introduced into the substrate processing region to facilitate removal of the effluent. Exemplary purge gases include argon (Ar), helium (He), and nitrogen (N 2 ), among other purge gases.

[0064] 5 and 8 , in operation 210, a second type of precursor 111 reacts with the first precursor 110 to form a second portion 112 of the carbon-containing layer 114. The second precursor 111 may advantageously have a functional group on one end that increases the thickness of the carbon-containing layer 114.

[0065] In one or more embodiments, the second precursor 111 can be a carbon-containing precursor having at least two reactive groups that can form bonds with unreacted reactive groups of the first precursor 110, thereby forming the first portion 108 of the carbon-containing layer 114. Molecules of the second precursor 111 react with the unreacted reactive groups of the first precursor 110 to form bonds linking the molecules of the second precursor 111 to the molecules of the first precursor 110. The reaction between the second and first precursor molecules continues until most or all of the unreacted reactive groups on the molecules of the first precursor 110 have reacted with molecules of the second precursor 111. A second portion 112 of the carbon-containing layer 114 of the deposited precursor is formed, which blocks further reaction between molecules of the second precursor 111 in the second precursor effluent and the first portion 108 of the carbon-containing layer 114.

[0066] The second precursor 111 may comprise any suitable precursor known to those skilled in the art. In one or more embodiments, the second precursor 111 may have the general formula R2-(Y)n, where n is an integer ranging from 1 to 6, and R2 comprises one or more of the following: an alkyl group, an alkenyl group, an aryl group, an aromatic group, and a cycloalkyl group. In one or more embodiments, R2 is independently selected from a C1-20 alkyl group. In other embodiments, R2 is selected from a C1-12 alkyl group. Yn comprises one or more of the following: a hydroxyl group, an aldehyde group, a ketone group, an acid group, an amine group, an isocyanate group, a thiocyanate group, and an acyl chloride group.

[0067] Without intending to be bound by theory, it is believed that the second precursor 111 includes reactive groups that can form covalent bonds with the reactive groups of the first precursor 110 .

[0068] Specific examples of the second precursor 111 include, but are not limited to, one or more of the following: terephthalaldehyde, phenylenediamine, ethylenediamine, hexamethylenediamine, terephthalyl chloride, 1,3,5-benzenetricarbonyltrichloride, pyromellitic dianhydride, benzene-1,3,5-tricarbaldehyde, 1,4-phenylene diisocyanate, 4,4'-oxydianiline, tris(2-aminoethyl)amine, and the like.

[0069] Referring to FIG. 8 , in one or more embodiments, method 200 also includes operation 212 for purging or removing effluent from the second precursor 111 from the substrate processing region after forming the second portion of the carbon-containing layer 114. The effluent can be removed by pumping it out of the substrate deposition region for a time period ranging from about 10 seconds to about 100 seconds. Additional exemplary time ranges may include about 20 seconds to about 50 seconds, and 25 seconds to about 45 seconds, among other exemplary time ranges. In some embodiments, a purge gas can be introduced into the substrate processing region to facilitate removal of the effluent. Exemplary purge gases include argon, helium, and nitrogen, among others.

[0070] In one or more embodiments, the formation rate of the second portion of the carbon-containing layer 114 may also depend on the pressure of the effluent of the second precursor 111 in the substrate processing region. Exemplary effluent pressures in the substrate processing region may range from approximately 1 mTorr to approximately 20 Torr. Additional exemplary ranges include 5 Torr to 15 Torr and 9 Torr to 12 Torr, among other exemplary ranges.

[0071] Referring to FIG. 8 , in one or more embodiments of method 200 , there is a determination point 214: whether a target thickness of the deposited carbon-containing layer 114 on the carbon-containing surface 108 of the substrate has been reached after one or more cycles of forming the carbon-containing layer 114 (e.g., after forming the first and second portions of the compound layer). If the target thickness of the deposited carbon-containing layer 114 has not been reached, another cycle of forming the first and second portions of the carbon-containing layer 114 is performed. If the target thickness of the deposited carbon-containing layer 114 has been reached, another cycle of forming another carbon-containing layer 114 is not initiated. An exemplary number of cycles for forming the carbon-containing layer may include 1 cycle to 2000 cycles. Additional exemplary ranges of the number of cycles may include 50 cycles to 1000 cycles, and 100 cycles to 750 cycles, among other exemplary ranges.

[0072] Thus, in one or more embodiments, the method 200 further includes depositing at least one additional carbon-containing layer on the initial carbon-containing layer, wherein the initial carbon-containing layer and the at least one additional carbon-containing layer form a carbon-containing layer 114 on the metal surface of the substrate.

[0073] In one or more embodiments, referring to FIG. 6 , the optional carbon-containing layer 114 can have any suitable thickness. In one or more embodiments, the thickness is at least 1 nm, or at least 10 nm, or at least 100 nm, or at least 200 nm, or at least 500 nm, or at least 1000 nm. Exemplary ranges of target thicknesses for interrupting further cycles of forming the compound layer include approximately 10 nm to approximately 500 nm. Additional exemplary thickness ranges may include approximately 5 nm to approximately 20 nm, approximately 50 nm to approximately 300 nm, and 100 nm to approximately 200 nm, among other exemplary thickness ranges.

[0074] In the embodiment illustrated in method 200 of FIG8 , the deposited carbon-containing layer 114 on the carbon-containing surface 108 of the substrate may be optionally post-processed at operation 216, as shown in FIG7 . The optional post-processing operation 216 may be, for example, a process that etches through the underlying layers (the hard mask layer 104 and the target layer 102) to pattern the substrate 101 for EUV development.

[0075] In some embodiments, the processing area is housed in a modular system comprising multiple chambers that perform various functions, including substrate centering and orientation, degassing, annealing, deposition, and / or etching. According to one or more embodiments, the modular system includes at least a first processing chamber and a central transfer chamber. The central transfer chamber can house a robot that can move substrates between and within the processing chambers and the load lock chamber. The transfer chamber is typically maintained under vacuum conditions and provides an intermediate stage for transferring substrates from one chamber to another and / or to the load lock chamber positioned at the front end of the cluster tool. Two well-known modular systems suitable for use in the present disclosure are Centura® and Endura®, both available from Applied Materials, Inc., Santa Clara, California. However, the exact arrangement and combination of chambers may vary depending on the specific steps of the process described herein. Other process chambers that can be used include, but are not limited to, cyclical layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etching, pre-cleaning, chemical cleaning, thermal treatments such as RTP, plasma nitridation, degassing, orientation, hydroxylation, and other substrate processes. By performing processes in a modular system's process chambers, surface contamination of the substrate by atmospheric impurities can be avoided, preventing oxidation prior to subsequent film deposition.

[0076] According to one or more embodiments, the substrate remains under vacuum or "load lock" conditions and is not exposed to ambient air while being moved from one chamber to the next. The transfer chamber is thus "evacuated" under vacuum and at vacuum pressure. An inert gas may be present in the processing chamber or the transfer chamber. In some embodiments, the inert gas is used to purge or remove some or all reactants (e.g., reactants). According to one or more embodiments, the inert gas is injected at the outlet of the processing chamber to prevent reactants (e.g., reactants) from moving from the processing chamber to the transfer chamber and / or additional processing chambers. Thus, the flow of inert gas forms a curtain at the chamber outlet.

[0077] Substrates can be processed in a single substrate deposition chamber, where a single substrate is loaded, processed, and unloaded before another substrate is processed. Similar to conveyor systems, substrates can also be processed in a continuous manner, where multiple substrates are independently loaded into a first portion of the chamber, moved through the chamber, and unloaded from a second portion of the chamber. The chamber and associated conveyor system can be shaped to form a straight or curved path. Furthermore, the processing chamber can be a turntable, where multiple substrates are moved around a central axis throughout the turntable path and exposed to processes such as deposition, etching, annealing, and cleaning.

[0078] During processing, the substrate may be heated or cooled. This heating or cooling can be achieved by any suitable means, including but not limited to changing the temperature of the substrate support and flowing a heated or cooled gas to the substrate surface. In some embodiments, the substrate support includes a heater / cooler that can be controlled to change the substrate temperature conductively. In one or more embodiments, the gas (reactive or inert) employed is heated or cooled to locally change the substrate temperature. In some embodiments, the heater / cooler is located within the chamber adjacent to the substrate surface to convectively change the substrate temperature.

[0079] The substrate can be stationary or rotated during processing. Rotation can occur continuously or in discrete steps (around the substrate axis). For example, the substrate can be rotated throughout the entire process, or it can be rotated slightly between exposures to different reactive and purge gases. Rotating the substrate during processing (continuously or in steps) can help produce more uniform deposition or etching by minimizing the effects of regional variability, such as gas flow geometry.

[0080] In a spatial ALD process, reactive gases flow into different processing zones within a process chamber. Different processing zones are isolated from adjacent processing zones, preventing the reactive gases from mixing. A substrate can be moved between processing zones to expose the substrate to the reactive gases separately. During this movement, different portions of the substrate surface, or materials on the substrate surface, are exposed to two or more reactive gases, such that no given point on the substrate is substantially simultaneously exposed to more than one reactive gas. Those skilled in the art understand that due to diffusion of gases within the process chamber, small portions of the substrate may be exposed to multiple reactive gases simultaneously, and that such simultaneous exposure is unintentional unless otherwise specified.

[0081] In another aspect of a spatial ALD process, reactive gases are delivered simultaneously to the reaction zone but separated by an inert gas curtain and / or a vacuum curtain. The gas curtain can be a combination of an inert gas flow into the processing chamber and a vacuum vapor flow out of the processing chamber. The substrate is moved relative to the gas delivery apparatus so that any given point on the substrate is exposed to only one reactive gas.

[0082] As used herein, "pulse" or "dose" refers to the amount of a source gas that is intermittently or discontinuously introduced into a processing chamber. Depending on the duration of the pulse, the amount of a particular compound in each pulse can vary over time. A particular process gas can include a single compound or a mixture / combination of two or more compounds.

[0083] In a time-domain ALD process, in some embodiments, exposure to each reactive gas (including, but not limited to, the metal and dielectric materials to be used in the ALD film) is separated by a time delay to allow each precursor to adhere to and / or react on the substrate surface and then be purged from the processing chamber. Mixing of the reactive gases is prevented by purging the processing chamber between subsequent exposures.

[0084] In another aspect of the time-domain ALD process of some embodiments, a time delay exists between pulses of the reactive gas. During each time delay, a purge gas (such as argon) is introduced into the processing chamber to purge the reaction zone or otherwise remove any residual reactive gas, reaction products, or byproducts from the reaction zone. Alternatively, the purge gas may flow continuously throughout the deposition process, with the purge gas flowing only during the time delays between pulses of the reactive gas. The reactive gas is pulsed multiple times, alternating with pulses of the purge gas in between. Purging may also be accomplished using a vacuum pump, with or without an inert gas.

[0085] The duration of each pulse / dose is variable and can be adjusted to accommodate, for example, the volumetric capacity of the process chamber and the capacity of the vacuum system coupled to the process chamber. Furthermore, the dose time of the reactive gas can vary depending on the reactive gas flow rate, the temperature of the process gas, the type of control valve, the type of process chamber employed, and the ability of the process gas components to adsorb onto the substrate. The dose time can also vary based on the type of layer being formed and the geometry of the device being formed. The dose time should be long enough to provide a sufficient volume of the compound to adsorb / chemisorb onto substantially the entire surface of the substrate and form a layer of the process gas component thereon.

[0086] Once the carbon-containing layer is deposited, the method may optionally include further processing (eg, EUV patterning and bottom etching).

[0087] The present disclosure provides that processes can generally be stored as software routines in memory. When executed by a processor, the software routines cause a processing chamber to perform the disclosed process. The software routines can also be stored and / or executed by a second processor (not shown) located remotely from the hardware controlled by the processor. Some or all of the methods of the present disclosure can also be implemented in hardware. Thus, the processes can be implemented in software and executed using a computer system, implemented in hardware, such as an application-specific integrated circuit or other type of hardware implementation, or implemented as a combination of software and hardware. When executed by a processor or controller, the software routines transform a general-purpose computer into a special-purpose computer (controller) that controls chamber operations to enable the process to be performed. A process may be stored on a non-transitory computer-readable medium comprising instructions that, when executed by a controller of a substrate processing chamber, cause the substrate processing chamber to: flow a first precursor comprising a first reactive group over a substrate comprising a carbon-containing surface and a silicon-containing surface to form a first portion of a carbon-containing layer on the carbon-containing surface; remove a first precursor effluent comprising the first precursor from the substrate; flow a second precursor comprising a second reactive group over the substrate to react with the first reactive group to form a carbon-containing layer on the carbon-containing surface of the substrate but not on the silicon-containing surface; and remove a second precursor effluent comprising the second precursor from the substrate.

[0088] In one or more embodiments, the process may be stored on a non-transitory computer-readable medium comprising instructions that, when executed by a controller of a substrate processing chamber, cause the substrate processing chamber to perform the further operation of treating the carbon-containing surface and the silicon-containing surface with one or more of ozone or hydrogen peroxide to form hydroxyl groups on the silicon-containing surface. In some embodiments, the process may be stored on a non-transitory computer-readable medium comprising instructions that, when executed by a controller of a substrate processing chamber, cause the substrate processing chamber to perform the further operation of exposing the silicon-containing surface and the hydroxyl groups to an alkylating precursor to form a passivated surface, wherein the alkylating precursor has the general formula (A): wherein R 3 and R 4 independently comprise one or more of hydrogen, alkyl, halide, alkenyl, aryl or aromatic group, cycloalkyl, and trimethylsilyl (Si(CH 3) 3), and wherein q is an integer ranging from 0 to 5.

[0089] Reference throughout this specification to "one embodiment," "certain embodiments," "one or more embodiments," or "an embodiment" means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the present disclosure. Thus, the appearance of phrases such as "in one or more embodiments," "certain embodiments," "in one embodiment," or "in an embodiment" in various places throughout this specification are not necessarily referring to the same embodiment of the present disclosure. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments.

[0090] Although the disclosure herein has been described with reference to specific embodiments, it will be understood that these embodiments are merely illustrative of the principles and applications of the disclosure. It will be apparent to those skilled in the art that various modifications and variations can be made to the methods and apparatuses of the disclosure without departing from the spirit and scope of the disclosure. Therefore, the disclosure is intended to include such modifications and variations as come within the scope of the appended claims and their equivalents.

[0091] 101:Substrate 102: Target layer 103: Hydroxyl (-OH) 104: Hard Mask Layer 105: Passivated surface 106: Silicon-containing layer 107: Features 108: Carbon surface 110: First Precursor 111: Second Precursor 112: Part 2 114: Carbon-containing layer 200:Method 202: Operation 204: Operation 206: Operation 208: Operation 210: Operation 212: Operation 214: Operation 216: Operation OH: hydroxyl

[0092] Domestic storage information (please note the order of storage institution, date, and number) none Overseas deposit information (please note the order of deposit country, institution, date, and number) none

Claims

1. A method for selectively depositing a film, the method comprising the steps of: flowing a first precursor over a substrate comprising a carbon-containing surface and a silicon-containing surface to form a first portion of a carbon-containing layer on the carbon-containing surface, the first precursor comprising a first reactive group, wherein the carbon-containing surface is a chemical amplification inhibitor (CAR) layer, and the silicon-containing surface is a spin-coated glass layer on a hard mask layer on a target layer, and wherein the carbon-containing surface has at least one feature formed therein, the at least one feature having a bottom surface, the bottom surface being the silicon-containing surface; removing a first precursor effluent comprising the first precursor from the substrate; flowing a second precursor comprising a second reactive group over the substrate to react with the first reactive group to form the carbon-containing layer on the carbon-containing surface of the substrate but not on the silicon-containing surface; and removing a second precursor effluent comprising the second precursor from the substrate.

2. The method of claim 1 further comprises the step of treating the carbon-containing surface and the silicon-containing surface with one or more of ozone or hydrogen peroxide to form hydroxyl groups on the silicon-containing surface.

3. The method of claim 2 further comprises the step of exposing the silicon-containing surface and the hydroxyl group to an alkylation precursor to form a passivated surface.

4. The method of claim 3, wherein the alkylation precursor has a general formula (A) wherein R3 and R4 independently comprise one or more of hydrogen, an alkyl group, a halide, an alkenyl group, an aryl or aromatic group, a cycloalkyl group, and a trimethylsilyl group (Si(CH3)3), and wherein q is an integer in the range from 0 to 5.

5. The method of claim 4, wherein the alkylation precursor is selected from one or more of the following: hexamethyldisilazane, N,N-dimethyltrimethylsilylamine, tris(trimethylsilyl)amine, trimethylchlorosilane, 1-(trimethylsilyl)pyrrolidine, and iodotrimethylsilane.

6. The method of claim 1, wherein the first precursor has a general formula R1-(X)n, wherein R1 comprises one or more of the following: an alkyl group, an alkenyl group, an aryl or aromatic group, and a cycloalkyl group, and Xn comprises one or more of the following: a hydroxyl group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group, and a chlorohydrin group, and n is an integer in a range from 1 to 6.

7. The method of claim 1, wherein the second precursor has a general formula R2-(Y)n, wherein R2 comprises one or more of the following: an alkyl group, an alkenyl group, an aryl or aromatic group, and a cycloalkyl group, and Yn comprises one or more of the following: a hydroxyl group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group, and a chlorohydrin group, and n is an integer in the range from 1 to 6.

8. The method of claim 1, wherein the first precursor and the second precursor are independently selected from one or more of the following: terephthalaldehyde, phenylenediamine, ethylenediamine, hexamethylenediamine, terephthalic chloride, 1,3,5-phenyltricarbonyltrichloro, benzopyrene dianhydride, benzene-1,3,5-tricarboxaldehyde, 1,4-phenylene diisocyanate, 4,4'-oxodiphenylamine, and tris(2-aminoethyl)amine.

9. The method of claim 8, wherein the first precursor comprises terephthalaldehyde and the second precursor comprises phenylenediamine.

10. The method of claim 1, further comprising the step of: depositing at least one additional carbon-containing layer on the carbon-containing layer, wherein the carbon-containing layer and the at least one additional carbon-containing layer are formed on the carbon-containing surface of the substrate.

11. The method of claim 1, wherein the step of removing the first precursor comprises the following steps: flowing a purifying gas over the substrate; and removing a mixture of the first precursor effluent and the purifying gas from the substrate.

12. The method of claim 11, wherein the purifying gas is selected from argon (Ar), helium (He), and nitrogen (N2).

13. The method of claim 1, further comprising the step of: patterning the substrate to expose the hard mask layer.

14. A method for selectively depositing a film, the method comprising the steps of: treating a substrate comprising a carbon-containing surface and a silicon-containing surface with one or more of ozone or hydrogen peroxide to form hydroxyl groups on the silicon-containing surface, wherein the carbon-containing surface is a chemical amplification inhibitor (CAR) layer, and the silicon-containing surface is a spin-coated glass layer on a hard mask layer on a target layer, and wherein the carbon-containing surface has at least one feature formed therein, the at least one feature having a bottom surface, the bottom surface being the silicon-containing surface; exposing the silicon-containing surface and the hydroxyl groups to an alkylation precursor to form a passivated surface, wherein the alkylation precursor has a general formula (A) wherein R3 and R4 independently comprise one or more of hydrogen, an alkyl group, a halide, an alkenyl group, an aryl or aromatic group, a cycloalkyl group, and a trimethylsilyl group (Si(CH3)3), and wherein q is an integer in the range from 0 to 5; A first precursor flows over the substrate. The first precursor has a general formula R1-(X)n, wherein R1 includes one or more of the following: an alkyl group, an alkenyl group, an aryl or aromatic group, and a cycloalkyl group; Xn includes one or more of the following: a hydroxyl group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group, and a chlorohydrin group; and n is an integer in the range of 1 to 6. The first precursor reacts with a reactive group on the carbon-containing surface to form a first portion of a carbon-containing layer on the carbon-containing surface. A first precursor effluent containing the first precursor is removed from the substrate. A second precursor flows over the substrate to form a carbon-containing layer on the carbon-containing surface but not on the passivated surface. The second precursor has a general formula R2-(Y)n. R2 comprises one or more of the following: an alkyl group, an alkenyl group, an aryl group or an aromatic group, and a cycloalkyl group; Yn comprises one or more of the following: a hydroxyl group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group, and a chlorohydrin group; and n is an integer in the range from 1 to 6; wherein the second precursor reacts with the first portion to form the carbon-containing layer; and a second precursor effluent containing the second precursor is removed from the substrate.

15. The method of claim 14, wherein the first precursor and the second precursor are independently selected from one or more of the following: terephthalaldehyde, phenylenediamine, ethylenediamine, hexamethylenediamine, terephthalic chloride, 1,3,5-phenyltricarbonyltrichloro, benzopyrene dianhydride, benzene-1,3,5-tricarboxaldehyde, 1,4-phenylene diisocyanate, 4,4'-oxodiphenylamine, and tris(2-aminoethyl)amine.

16. The method of claim 14 further comprises the step of: depositing at least one additional carbon-containing layer on the carbon-containing layer, wherein the carbon-containing layer and the at least one additional carbon-containing layer are formed on the carbon-containing surface of the substrate.

17. The method of claim 14, wherein the step of removing the first precursor comprises the following steps: flowing a purging gas over the substrate, wherein the purging gas is selected from argon (Ar), helium (He), and nitrogen (N2); and removing a mixture of the first precursor effluent and the purging gas from the substrate.

18. The method of claim 14 further comprises the step of: patterning the substrate to expose a hard mask layer.

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