Selective deposition for pitch EUV patterning below 20 nm

Abstract

Methods of selectively depositing carbon-containing layers are described. An exemplary treatment method may include treating a substrate including 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 carbonaceous layer is then selectively deposited on the carbonaceous surface rather than on the silicon-containing surface by flowing a first precursor over the substrate to form a first portion of the initial carbonaceous film on the carbonaceous surface rather than on the silicon-containing surface. The method may include removing a first precursor effluent from a substrate. The second precursor may then flow over the substrate to react with the first portion of the initial carbonaceous 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 films relative to silicon-containing surfaces (such as silicon and silicon oxide (SiO x ) surface) Method for selectively depositing a carbon-based layer on a carbon-containing surface. Background Art

[0002] Photolithography uses a photoresist (a photosensitive 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 an activating radiation source, 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 radiation-exposed or unexposed areas of the coated substrate.

[0003] Current EUV patterning processes suffer from inefficient underlayer openings. The conical shape of the chemically amplified resist (CAR) and the limited height of the CAR relative to the underlayer may lead to inefficient underlayer etch-through in small-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 underlayer by metal doping. However, these approaches may result in bridging defects or leave CAR residues that are difficult to remove.

[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 for selectively depositing a film includes: flowing a first precursor over a substrate including 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 including a first reactive group; removing a first precursor effluent including the first precursor from the substrate; flowing a second precursor including 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 including the second precursor from the substrate.

[0006] Another embodiment of the present disclosure is directed to a method for selectively depositing a film. In one or more embodiments, the method for selectively depositing a film includes treating a substrate including 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):

[0007] Where R 3 and R 4 independently comprising 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 is flowed over the substrate, the first precursor having the general formula R 1 -(X) n , where R 1 Including one or more of an alkyl group, an alkenyl group, an aryl or aromatic group, and a cycloalkyl group, X n The method comprises the steps of: reacting a first precursor with a reactive group on a carbon-containing surface to form a first portion of a carbon-containing layer on the carbon-containing surface; removing a first precursor effluent including the first precursor from the substrate; and flowing a second precursor over the substrate to form a carbon-containing layer on the carbon-containing surface without being on the passivation surface, wherein the second precursor has a general formula R 2 -(Y) n , where R 2 Including one or more of an alkyl group, an alkenyl group, an aryl or aromatic group, and a cycloalkyl group, Y n comprising 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 in the range of from 1 to 6, wherein a second precursor reacts with the first part to form a carbon-containing layer; and removing a second precursor effluent comprising the second precursor from the substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] In order to be able to understand in detail the manner in which the above-mentioned features of the present disclosure are used, a more specific description of the present disclosure briefly summarized above may be made with reference to embodiments, some of which are shown in the accompanying drawings. However, it will be noted that the drawings only show typical embodiments of the present disclosure and are therefore not to be considered as limiting the scope thereof, as the present disclosure may admit of other equally effective embodiments. The embodiments as described herein are shown by way of example and are not limited in the various figures of the accompanying drawings, in which the same references indicate similar elements.

[0009] Figure 1shows a cross-sectional view of a substrate according to one or more embodiments;

[0010] Figure 2 shows a cross-sectional view of a substrate according to one or more embodiments;

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

[0012] Figure 3B shows a cross-sectional view of a substrate according to one or more embodiments;

[0013] Figure 4 shows a cross-sectional view of a substrate according to one or more embodiments;

[0014] Figure 5 shows a cross-sectional view of a substrate according to one or more embodiments;

[0015] Figure 6 shows a cross-sectional view of a substrate according to one or more embodiments;

[0016] Figure 7 shows a cross-sectional view of a substrate according to one or more embodiments; and

[0017] Figure 8 A process flow diagram of a method for selectively depositing a film on a substrate according to one or more embodiments is shown. DETAILED DESCRIPTION

[0018] Before describing several exemplary embodiments of the present invention, it is to 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.

[0019] As used herein, the term "about" means approximately or nearly, and in the context of a stated 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% will satisfy the definition of about.

[0020] As used in this specification and the appended claims, the term "substrate" or "wafer" refers to a surface, or portion of a surface, on which a process is performed. As will also be understood by those skilled in the art, unless the context clearly indicates otherwise, reference to a substrate may also refer to only a portion of a substrate. In addition, reference to depositing on a substrate may mean both a bare substrate and a substrate having one or more films or features deposited or formed thereon.

[0021] As used herein, "substrate" or "substrate surface" refers to any portion of a substrate on which film processing is performed or a portion of a material surface formed on a substrate. For example, depending on the application, the substrate surface on which processing can be performed includes 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. The substrate may be exposed to a pretreatment process 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, in the present disclosure, as disclosed in more detail below, any film processing step disclosed may also be performed on a bottom layer formed on the substrate, and the term "substrate surface" is intended to include such a bottom layer as indicated in the context. Thus, for example, in the case where a film / layer or a portion of a film / layer has been deposited on the substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate. The substrate may have various sizes, such as 200 mm or 300 mm diameter wafers, and rectangular or square panels. In some embodiments, the substrate comprises a rigid discrete material.

[0022] 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.

[0023] 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 about 13.5 nm is employed.

[0024] As used in this specification and the appended 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.

[0025] 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 mean a material having a substance capable of reacting with a substrate or 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.

[0026] As used in this specification and the appended 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 includes a chemically amplified resist (CAR) layer of an EUV photoresist. In other embodiments, the carbon-containing surface may include an amorphous carbon layer.

[0027] As used in this specification and the appended claims, the term "silicon-containing surface" refers to a surface, layer, or portion of a surface that contains silicon. The silicon-containing surface may contain any suitable amount of silicon. In one or more embodiments, the silicon-containing surface includes a spin-on glass layer below the photoresist layer.

[0028] Carbon-containing materials can be used in several structures and processes in semiconductor device manufacturing, including as mask materials, etch-resistant materials, and trench fill materials, among other applications. More specific examples of applications for carbon-containing materials include forming hot-implantation hard masks, metal gate (MG)-cut hard masks, metal gate manufacturing, and reverse tone patterning, self-aligned patterning, and the like. The present technology includes selectively forming these carbon-containing materials on carbon-containing surfaces using molecular layer deposition (MLD).

[0029] 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, there is inefficient bottom layer etching that may be caused by a tapered CAR shape and a limited CAR height / ES relative to the bottom layer. To address this issue, the CAR thickness may be increased and the CAR etching selectivity relative to the bottom layer may be increased by metal doping before EUV exposure and development. However, these approaches may result in partial development of the CAR and bridging defects, and may result in bridging defects in the bottom layer (when the ES of the CAR is not high enough) or leave CAR residues that are difficult to remove. One or more embodiments advantageously use a selective deposition of a carbon-containing layer on a carbon-containing surface of the substrate but not on a silicon-containing surface (e.g., silicon or silicon oxide) of the substrate to address the discussed issues.

[0030] The method of one or more embodiments advantageously combines silicon or silicon oxide surface passivation with molecular layer deposition (MLD) of carbon-containing films 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 residues, well-controlled process flow, efficient bottom layer etching with controllable non-tapered profile transfer, and high potential for smaller pitch patterning.

[0031] Embodiments of the present technology include methods for selectively forming a carbon-containing material on a carbon-containing surface while substantially eliminating the carbon-containing material on a silicon-containing surface (e.g., a silicon (Si) surface or a silicon oxide (SiO x In one or more embodiments, the carbon-containing film is selectively formed on the carbon-containing surface by molecular layer deposition (MLD).

[0032] 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 and not on the silicon-containing surface.

[0033] In other embodiments, the carbon-containing surface and the silicon-containing surface (e.g., silicon (Si) or silicon oxide (SiO x )) 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 passivated surface on the silicon or silicon oxide surface.

[0034] 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 in which 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 not on or less on the non-metallic surface. 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, and no or less carbon-containing material is deposited on the silicon or silicon oxide surface. Additional compound layers of the first and second layers may accumulate on the deposited layers 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.

[0035] One or more embodiments advantageously provide solutions to problems with conventional methods of forming carbon-containing materials on semiconductor substrates. For example, the present technology forms carbon-containing materials with significantly fewer voids, fractures, and other physical defects than carbon-containing materials formed using spin-on-carbon (SOC) and flowable chemical-vapor-deposition (FCVD) methods. The present technology can also form carbon-containing materials with higher density and lower porosity than materials formed using SOC and FCVD. When the deposited material is processed to form the final material, the high levels of hydrogen found in many SOCs and FCVD precursors result in high levels of shrinkage. 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 stresses on substrate features that are in contact with the material. The present techniques produce treated carbonaceous materials having less than 10 volume percent shrinkage of the deposited material (eg, 5-10 volume percent shrinkage, less than about 5 volume percent shrinkage).

[0036] One or more embodiments advantageously provide solutions to problems 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 produce ion sputtering that causes damage to substrate features on the semiconductor substrate and can also produce re-sputtered ions and other species that may cause defects in the deposited carbon-containing material. In addition, these species often deposit material unevenly in and around substrate features, thereby producing voids in and around substrate trenches and steps, and uneven surfaces in flat substrate areas. The present technology can form carbon-containing materials with high conformality 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 may damage substrate features during deposition.

[0037] Embodiments of the present disclosure are described by way of drawings that illustrate devices (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.

[0038] Figures 1 to 7 A cross-sectional view of a semiconductor substrate processed according to a method of one or more embodiments is shown. Figure 8 A process flow diagram of a method 200 for selectively depositing a film according to one or more embodiments is shown. Figure 1 and Figure 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 (eg, positioned in a processing chamber).

[0039] Reference Figure 1 In one or more embodiments, the substrate 101 includes one or more of a chemically amplified resist (CAR) layer 108 on one or more of the silicon-containing layer 106, the hard mask layer 104, and the target layer 102. In some embodiments, the chemically amplified resist (CAR) layer 108 includes carbon. In one or more embodiments, the silicon-containing layer 106 is a layer including silicon or silicon oxide (SiO x ) of the spin-on glass layer. Those skilled in the art will appreciate that the silicon-containing layer 106 comprises silicon or silicon oxide (SiO x ) surface. In one or more embodiments, the carbon-containing layer grows only on certain carbon-containing surfaces, and no growth or much less growth on passivated silicon or silicon oxide surfaces. The selectivity (ratio of thickness on different surfaces) can be 2:1, 5:1, 10:1, 50:1, 100:1, or absolute selective growth (no growth on undesired surfaces).

[0040] See also Figure 2In one or more embodiments, the substrate 101 on which the carbon-containing material is selectively formed may include a material in which one or more features 107 may be formed. The features of the substrate 101 may be characterized by any shape or configuration according to the present technology. In some embodiments, the feature 107 may be or include a groove structure, a via structure, or an aperture formed in the substrate. Although the substrate features may be characterized by any shape or size, in some embodiments, the substrate features may be characterized by a higher aspect ratio, or a ratio of the depth of the feature to the width across the feature. For example, in some embodiments, the 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. In addition, the feature can be characterized by a narrower width or diameter across the feature between two sidewalls, such as a dimension less than or equal to 20 nm, and can be characterized by a width across the feature 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.

[0041] Reference FIG. 3A to FIG. 3B and Figure 8 In one or more embodiments, at operation 204, the substrate 101 may 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 and not passivate the carbon-containing surface 108. In some embodiments, the substrate 101 may have a carbon-containing surface (i.e., the CAR layer 108) and a silicon-containing layer 106 (comprising silicon (Si) or silicon oxide (SiO x ) surface (ie, the spin-on-glass layer 106)) of the substrate 101 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.

[0042] In one or more embodiments, see Figure 3B The substrate 101 is then exposed to an alkylation precursor that interacts or reacts with the hydroxyl groups (—OH) to form a passivation surface 105 on the silicon or silicon oxide surface of the silicon-containing layer 106 .

[0043] 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 followed by exposure 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. Thus, 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.

[0044] The alkylation precursor may 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):

[0045] Where R 3 and R 4 independently include one or more of hydrogen, alkyl, halide, alkenyl, aryl or aromatic group, cycloalkyl, and trimethylsilyl (Si(CH3)3), and wherein q is an integer in the range of from 0 to 5. In one or more embodiments, R 3 and R 4 In one or more embodiments, the alkylated precursor is selected from one or more of the following: hexamethyldisilazane, N,N-dimethyltrimethylsilylamine, tris(trimethylsilyl)amine, trimethylchlorosilane, 1-(trimethylsilyl)pyrrolidine, and iodotrimethylsilane.

[0046] Unless otherwise indicated, the terms "lower alkyl", "alkyl", or "alk" as used herein alone or as part of another group include straight and branched hydrocarbons containing 1 to 20 carbons in the normal chain, such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, hexyl, isohexyl, heptyl, 4,4-dimethylpentyl, octyl, 2,2,4-trimethyl-pentyl, nonyl, decyl, undecyl, dodecyl, various branched isomers thereof, and the like. Such groups may optionally include up to 1 to 4 substituents. Alkyl groups may be substituted or unsubstituted.

[0047] As used herein, the term "alkoxy" includes any of the above-mentioned alkyl groups linked to an oxygen atom. The alkoxy group may be substituted or unsubstituted.

[0048] As used herein, the term "vinyl" or "vinyl-containing" refers to a group containing a vinyl group (-CH=CH2). The vinyl group may be substituted or unsubstituted.

[0049] 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 may be substituted or unsubstituted.

[0050] As used herein, the term "halide" refers to a binary phase, one part of which is a halogen atom and the other part is an element or radical less electronegative than the halogen, used to prepare fluoride, chloride, bromide, or iodide compounds. Halide ions are halogen atoms with a negative charge. As known to those skilled in the art, halide anions include fluorine (F-), chlorine (Cl-), bromine (Br-), and iodine (I-).

[0051] As used in this specification and the appended 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 is formed on the selective surface at a rate greater than or equal to about 10x, 15x, 20x, 25x, 30x, 35x, 40x, 45x, or 50x the rate of formation 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 greater than or equal to about 10x, 15x, 20x, 25x, 30x, 35x, 40x, 45x, or 50x the rate of formation on the unselected surface (i.e., the passivation surface 105).

[0052] In one or more embodiments, the carbon-containing layer 114 is formed on the carbon-containing surface 108 and not on the passivation surface 105 of the silicon-containing layer 106 with a selectivity ratio of at least 10:1, or at least 100:1, or at least 1000:1.

[0053] Reference Figure 4 and Figure 8 At operation 206, a first type of precursor 110 is introduced / flowed into the substrate processing region of the processing chamber and over the substrate surface. The first precursor 110 strongly binds to the carbon-containing surface 108 and does not bind to the silicon or silicon oxide surface 106.

[0054] 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 that blocks further reactions between the molecules of the first precursor 110 in the first precursor effluent and the substrate.

[0055] 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 a general formula R 1 -(X) n , wherein n is an integer ranging from 1 to 6, and R 1 Includes one or more of the following: alkyl, alkenyl, aryl, or aromatic group, and cycloalkyl. n It includes one or more of the following: hydroxyl group, aldehyde group, ketone group, acid group, amine group, isocyanate group, thiocyanate group, and acyl chloride group.

[0056] Unless otherwise indicated, the terms "lower alkyl", "alkyl", or "alkane" as used herein alone or as part of another group include straight and branched hydrocarbons containing 1 to 20 carbons, or 1 to 10 carbon atoms in the normal chain, such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, hexyl, isohexyl, heptyl, 4,4-dimethylpentyl, octyl, 2,2,4-trimethyl-pentyl, nonyl, decyl, undecyl, dodecyl, various branched chain isomers thereof, and the like. Such groups may optionally include up to 1 to 4 substituents. Alkyl groups may be substituted or unsubstituted.

[0057] Such alkyl groups may optionally include up to 1 to 4 substituents, such as halo, e.g., F, Br, Cl, or I, or CF3, alkyl, alkoxy, aryl, aryloxy, aryl (aryl) or diaryl, aralkyl, arylalkoxy, alkenyl, cycloalkyl, cycloalkylalkyl, cycloalkylalkoxy, amine, hydroxyl, hydroxyalkyl, acyl, heteroaryl, heteroaryloxy, heteroarylalkyl, heteroarylalkoxy, aryloxyalkyl, alkylthio, arylalkylthio, aryloxyaryl, alkylamido, alkanoylamino, arylcarbonylamino, nitro, cyano, thiol, haloalkyl, trihaloalkyl, and / or alkylthio, and the like. In one or more embodiments, R1 Independently selected from C 1-20 In other embodiments, R 1 It is from C 1-12 alkyl.

[0058] 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-heptenyl, 3-octenyl, 3-nonenyl, 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, amine, hydroxy, heteroaryl, cycloheteroalkyl, alkanecarboxyl, alkylamido, alkylamido, arylcarbonyl-amine, nitro, cyano, thiol, alkylthio, and / or any alkyl substituent described herein.

[0059] As used herein, the term "alkynyl" or "lower alkynyl" refers to a straight or branched 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-non ... 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, amine, heteroaryl, cycloheteroalkyl, hydroxy, alkanoylamino, alkanoylamido, arylcarbonylamido, nitro, cyano, thiol, and / or alkylthio, and / or any alkyl substituent described herein.

[0060] As used herein, the term "aryl" refers to monocyclic and bicyclic aromatic groups containing 6 to 10 carbons 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, for example, hydrogen, halo, haloalkyl, alkyl, haloalkyl, alkoxy, haloalkoxy, alkenyl, trifluoromethyl, trifluoromethoxy, alkynyl, and the like, through available carbon atoms.

[0061] Specific examples of the first precursor 110 include, but are not limited to, one or more of the following: terephthalaldehyde, phenylenediamine, ethylenediamine, hexamethylenediamine, terephthaloyl chloride, 1,3,5-benzenetricarbonyl trichloride, pyromellitic dianhydride, benzene-1,3,5-tricarbaldehyde, 1,4-phenylene diisocyanate, 4,4′-oxydiphenylamine, tris(2-aminoethyl)amine, and the like.

[0062] 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 forming 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.

[0063] The outflow of the first precursor 110 may be maintained in the substrate processing region for a period of time to almost or completely form the first portion 108 of the carbon-containing layer 114. The precursors may 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 may 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.

[0064] Reference Figure 8At operation 208, the first precursor 110 is purged or removed from the substrate processing area after forming the first portion 110 of the carbon-containing layer 114. The effluent of the first precursor 110 can be removed by pumping it out of the substrate deposition area 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, as well as 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 area to assist in removing the effluent. Exemplary purge gases include argon (Ar), helium (He), and nitrogen (N2), as well as other purge gases.

[0065] See also Figure 5 and Figure 8 At operation 210, the 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.

[0066] In one or more embodiments, the second precursor 111 may be a carbon-containing precursor having at least two reactive groups that can form bonds with unreacted reactive groups of the first precursor 110 to form a 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 precursor molecules and the 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 deposition precursor is formed that 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.

[0067] The second precursor 111 may include any suitable precursor known to those skilled in the art. In one or more embodiments, the second precursor 111 may have a general formula R 2 -(Y) n , wherein n is an integer ranging from 1 to 6, and R 2 Including one or more of the following: alkyl, alkenyl, aryl, or aromatic group, and cycloalkyl. In one or more embodiments, R 2 Independently selected from C 1-20In other embodiments, R 2 It is from C 1-12 Alkyl. n It includes one or more of the following: hydroxyl group, aldehyde group, ketone group, acid group, amine group, isocyanate group, thiocyanate group, and acyl chloride group.

[0068] Without intending to be bound by theory, it is believed that the second precursor 111 includes reactive groups that can form covalent bonds with reactive groups of the first precursor 110 .

[0069] Specific examples of the second precursor 111 include, but are not limited to, one or more of the following: terephthalaldehyde, phenylenediamine, ethylenediamine, hexamethylenediamine, terephthaloyl 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.

[0070] See also Figure 8 In one or more embodiments, method 200 also includes operation 212 for purging or removing effluent of 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 may be introduced into the substrate processing region to assist in removing the effluent. Exemplary purge gases include argon, helium, and nitrogen, among other purge gases.

[0071] 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 vary from about 1 mTorr to about 20 Torr. Additional exemplary ranges include 5 Torr to 15 Torr, and 9 Torr to 12 Torr, among other exemplary ranges.

[0072] Reference Figure 8In one or more embodiments of the method 200, there is a determination point / decision point 214: whether a target thickness of the deposited carbon-containing layer 114 on the carbon-containing surface 108 of the substrate is reached after one or more cycles of forming the carbon-containing layer 114 (e.g., after forming the first portion and the second portion 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 portion and the second portion of the carbon-containing layer 114 is performed. If the target thickness of the deposited carbon-containing layer 114 has been reached, another cycle for forming another carbon-containing layer 114 is not started. 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.

[0073] Thus, in one or more embodiments, 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.

[0074] In one or more embodiments, see Figure 6 , the selective 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 a compound layer include about 10 nm to about 500 nm. Additional exemplary thickness ranges may include about 5 nm to about 20 nm, about 50 nm to about 300 nm, and 100 nm to about 200 nm, as well as other exemplary thickness ranges.

[0075] exist Figure 8 In the embodiment illustrated in the method 200 of FIG. 1 , the deposited carbon-containing layer 114 on the carbon-containing surface 108 of the substrate may be post-processed at operation 216 as appropriate, such as Figure 7 The optional post-processing operation 216 may be, for example, a process to etch through the bottom layer (the hard mask layer 104 and the target layer 102) to pattern the substrate 101 for EUV development.

[0076] In some embodiments, the processing area is in a modular system including 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 accommodate 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 moving substrates from one chamber to another and / or to a load lock chamber positioned at the front end of a cluster tool. Two well-known modular systems that may be applicable to the present disclosure are and All are available from Applied Materials, Inc., Santa Clara, California, USA. However, the exact arrangement and combination of chambers may vary for the purpose of performing specific steps of the process as described herein. Other processing chambers that may 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 the process in the processing chambers of the modular system, surface contamination of the substrate by atmospheric impurities can be avoided without oxidation prior to deposition of subsequent films.

[0077] According to one or more embodiments, the substrate remains under vacuum or "load lock" conditions and is not exposed to ambient air when moving 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 of the reactants (e.g., reactants). According to one or more embodiments, an 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 the inert gas forms a curtain at the outlet of the chamber.

[0078] Substrates can be processed in a single substrate deposition chamber, where a single substrate is loaded, processed, and unloaded before processing another substrate. Similar to a conveyor system, 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 shape of the chamber and associated conveyor system can form a straight path or a curved path. In addition, the processing chamber can be a turntable, where multiple substrates are moved around a central axis throughout the turntable path and exposed to deposition, etching, annealing, cleaning, etc. processes.

[0079] During processing, the substrate may be heated or cooled. Such heating or cooling may be achieved by any suitable means, including but not limited to changing the temperature of the substrate support and flowing the 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 in a conductive manner. In one or more embodiments, the gas (reactive gas or inert gas) used is heated or cooled to locally change the substrate temperature. In some embodiments, the heater / cooler is located in the chamber adjacent to the substrate surface to change the substrate temperature convectively.

[0080] The substrate may also be fixed or rotated during processing. The rotating substrate may be rotated continuously or in discrete steps (about the substrate axis). For example, the substrate may be rotated throughout the process, or the substrate may be rotated a small amount between exposures to different reactive gases or purge gases. Rotating the substrate during processing (continuously or in steps) may help produce a more uniform deposition or etch by minimizing the effects of regional variability in, for example, gas flow geometry.

[0081] In the spatial ALD process, reactive gases flow into different processing areas within the processing chamber. Different processing areas are separated from adjacent processing areas so that the reactive gases do not mix. The substrate can be moved between processing areas to expose the substrate to reactive gases separately. During the movement of the substrate, different parts of the substrate surface, or materials on the substrate surface, are exposed to two or more reactive gases so that at any given point on the substrate, they are not substantially exposed to more than one reactive gas at the same time. Those skilled in the art will understand that there is the possibility that due to the diffusion of gases in the processing chamber, a small portion of the substrate may be exposed to multiple reactive gases at the same time, and simultaneous exposure is unintentional unless otherwise specified.

[0082] In another aspect of the 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 moves relative to the gas delivery apparatus so that any given point on the substrate is exposed to only one reactive gas.

[0083] As used herein, "pulse" or "dose" refers to the amount of source gas that is intermittently or discontinuously introduced into a process chamber. Depending on the duration of the pulse, the amount of a particular compound in each pulse may vary over time. A particular process gas may include a single compound or a mixture / combination of two or more compounds.

[0084] In a time-domain ALD process, in some embodiments, exposure to each reactive gas (including but not limited to metals and dielectric materials to be used for the ALD film) is separated by a time delay to allow each compound to adhere to and / or react on the substrate surface and then be purged from the processing chamber. Mixing of reactive gases is prevented by purging the processing chamber between subsequent exposures.

[0085] In another aspect of the time-domain ALD process of some embodiments, there are time delays between pulses of 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 or reaction products or byproducts from the reaction zone. Alternatively, the purge gas may flow continuously throughout the deposition process, such that only the purge gas flows during the time delay between pulses of reactive gas. The reactive gas is pulsed multiple times alternately with pulses of purge gas in between. Purging may also be accomplished using a vacuum pump with or without an inert gas.

[0086] The duration of each pulse / dose is variable and can be adjusted to accommodate, for example, the volumetric capacity of the processing chamber and the capacity of the vacuum system coupled to the processing chamber. In addition, the dosage time of the reactive gas can vary depending on the flow rate of the reactive gas, the temperature of the process gas, the type of control valve, the type of process chamber employed, and the ability of the components of the process gas to adsorb onto the substrate. The dosage time can also vary based on the type of layer being formed and the geometry of the device being formed. The dosage time should be long enough to provide a volume of the compound sufficient to adsorb / chemisorb onto substantially the entire surface of the substrate and form a layer of the process gas component thereon.

[0087] Once the carbon-containing layer is deposited, the method may optionally include further processing (eg, EUV patterning and bottom etching).

[0088] The present disclosure provides that the process can be stored as a software program in memory in general, and when executed by a processor, the software program causes the processing chamber to perform the process of the present disclosure. The software program can also be stored and / or executed by a second processor (not shown), which is located at the hardware remote end controlled by the processor. Some or all methods of the present disclosure can also be executed in hardware. Therefore, the process can be implemented in software and executed using a computer system, implemented in hardware as, for example, a dedicated 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 program converts a general-purpose computer into a special-purpose computer (controller), which controls the chamber operation so that the process can be executed. 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 following operations: 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; 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.

[0089] 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 further operations: 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 further operations: 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)

[0090] Where R 3 and R 4 Independently includes one or more of hydrogen, alkyl, halide, alkenyl, aryl or aromatic group, cycloalkyl, and trimethylsilyl (Si(CH3)3), and wherein q is an integer in the range from 0 to 5.

[0091] References throughout this specification to "one embodiment," "certain embodiments," "one or more embodiments," or "an embodiment" mean that a particular feature, structure, material, or characteristic described in conjunction 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 an embodiment," or "in an embodiment" in various places throughout this specification do not necessarily refer to the same embodiment of the present disclosure. Furthermore, particular features, structures, materials, or characteristics may be combined in one or more embodiments in any suitable manner.

[0092] 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 may be made to the methods and apparatus of the disclosure without departing from the spirit and scope of the disclosure. Therefore, the disclosure is intended to include modifications and variations within the scope of the appended claims and their equivalents.

Claims

1. A method for selectively depositing a film, the method comprising the following steps: flowing a first precursor over a substrate including 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 including a first reactive group; removing a first precursor effluent including the first precursor from the substrate; flowing a second precursor including 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 A second precursor effluent including the second precursor is removed from the substrate.

2. The method of claim 1, further comprising 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 comprising the steps of: The silicon-containing surface and the hydroxyl groups are exposed to an alkylation precursor to form a passivated surface.

4. The method of claim 3, wherein the alkylated precursor has the general formula (A) Where R 3 and R 4 Independently includes one or more of hydrogen, alkyl, halide, alkenyl, aryl or aromatic group, cycloalkyl, and trimethylsilyl (Si(CH3)3), and wherein q is an integer in the range from 0 to 5.

5. The method of claim 4, wherein the alkylated 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 substrate comprises a chemically amplified resist (CAR) layer on one or more of a spin-on-glass layer, a hard mask layer, and a target layer.

7. The method of claim 1, wherein the first precursor has the general formula R 1 -(X) n Where R 1 Includes one or more of the following: alkyl, alkenyl, aryl or aromatic group, and cycloalkyl, X n One or more of the following are included: 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.

8. The method of claim 1, wherein the second precursor has the general formula R 2 -(Y) n Where R 2 includes one or more of the following: alkyl, alkenyl, aryl or aromatic group, and cycloalkyl, Y n One or more of the following are included: 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.

9. 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, terephthaloyl chloride, 1,3,5-benzenetricarbonyltrichloride, pyromellitic dianhydride, benzene-1,3,5-tricarbaldehyde, 1,4-phenylene diisocyanate, 4,4′-oxydiphenylamine, and tris(2-aminoethyl)amine.

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

11. The method of claim 1, further comprising the steps of: At least one additional carbon-containing layer is deposited on the carbon-containing layer, wherein the carbon-containing layer and the at least one additional carbon-containing layer form the carbon-containing layer on the carbon-containing surface of the substrate.

12. The method of claim 1, wherein the step of removing the first precursor comprises the steps of: flowing a purge gas over the substrate; and The mixture of the first precursor effluent and the purge gas is removed from the substrate.

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

14. The method of claim 6, further comprising the steps of: The substrate is patterned to expose the hard mask layer.

15. A method for selectively depositing a film, the method comprising the following steps: treating a substrate including 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 alkylation precursor to form a passivated surface, wherein the alkylation precursor has the general formula (A) Where R 3 and R 4 independently comprising one or more of hydrogen, alkyl, halide, alkenyl, aryl or aromatic group, cycloalkyl, and trimethylsilyl (Si(CH3)3), and wherein q is an integer in the range from 0 to 5; A first precursor is flowed over the substrate, wherein the first precursor has a general formula R 1 -(X) n Where R 1 Includes one or more of the following: alkyl, alkenyl, aryl or aromatic group, and cycloalkyl, X n 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, and n is an integer ranging from 1 to 6, wherein the first precursor reacts with 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 including the first precursor from the substrate; A second precursor is flowed over the substrate to form a carbon-containing layer on the carbon-containing surface but not on the passivating surface, the second precursor having a general formula R 2 -(Y) n Where R 2 includes one or more of the following: alkyl, alkenyl, aryl or aromatic group, and cycloalkyl, Y n 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, and n is an integer ranging from 1 to 6, wherein the second precursor reacts with the first portion to form the carbon-containing layer; and A second precursor effluent including the second precursor is removed from the substrate.

16. The method of claim 15, wherein the substrate comprises a chemically amplified resist (CAR) layer on one or more of a spin-on-glass layer, a hard mask layer, and a target layer.

17. The method of claim 15, wherein the first precursor and the second precursor are independently selected from one or more of the following: terephthalaldehyde, phenylenediamine, ethylenediamine, hexamethylenediamine, terephthaloyl chloride, 1,3,5-benzenetricarbonyltrichloride, pyromellitic dianhydride, benzene-1,3,5-tricarbaldehyde, 1,4-phenylene diisocyanate, 4,4′-oxydiphenylamine, and tris(2-aminoethyl)amine.

18. The method of claim 15, further comprising the steps of: At least one additional carbon-containing layer is deposited on the carbon-containing layer, wherein the carbon-containing layer and the at least one additional carbon-containing layer form the carbon-containing layer on the carbon-containing surface of the substrate.

19. The method of claim 15, wherein the step of removing the first precursor comprises the steps of: flowing a purge gas over the substrate, wherein the purge gas is selected from argon (Ar), helium (He), and nitrogen (N2); and The mixture of the first precursor effluent and the purge gas is removed from the substrate.

20. The method of claim 15, further comprising the steps of: The substrate is patterned to expose the hard mask layer.

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