Method of forming carbon-based spacers for EUV photoresist patterns

Abstract

Methods of depositing a conformal carbon-containing spacer layer are described. An exemplary processing method may include flowing a first precursor over a patterned surface and a substrate to form a first portion of an initial carbon-containing film on a structure. The method may include removing a first precursor effluent from a substrate. A second precursor may then be flowed over the substrate to react with the first portion of the initial carbon-containing film. The method may include removing the second precursor effluent from the substrate. The method may include etching the substrate to remove a portion of the carbon-containing film and to expose top surfaces of the patterned surfaces and to expose the substrate between the patterned surfaces. The patterned surface may be an EUV photoresist pattern, and a carbon-containing film may be formed on the sidewalls and act as a spacer to reduce critical dimension (CD). The carbon-containing film may act as an etch protection layer or an etch resist layer for sidewalls of the nanostructure. When the etch is not performed, the carbon-containing film may act as a liner material.

Description

Technical Field

[0001] Embodiments of the present disclosure relate to methods for depositing a carbon-based film as a liner or spacer on a nanostructure. Specifically, embodiments of the present disclosure relate to methods for depositing a carbon-based layer as a spacer layer on a patterned EUV photoresist. Background Art

[0002] The semiconductor processing industry is continually striving to achieve greater throughput while improving the uniformity of layers deposited on substrates with larger surface areas. These same factors combined with new materials also provide for higher circuit integration per unit area of ​​the substrate. As circuit integration increases, the need for greater uniformity and process control related to layer thickness increases. Therefore, various techniques have been developed to deposit layers on substrates in a more cost-effective manner while maintaining control over the layer properties.

[0003] Integrated circuits are made possible by processes that create intricately patterned layers of material on a substrate surface. Creating patterned material on a substrate requires controlled methods of forming and removing exposed material. As device sizes continue to shrink, material formation can affect subsequent operations.

[0004] The semiconductor industry faces many challenges in the pursuit of device miniaturization, which involves rapid scaling of nanoscale features. These issues include the introduction of complex manufacturing steps, such as multiple lithography steps and the integration of high-performance materials. Conventional spacer manufacturing processes include conformal film deposition on 3D structures (e.g., fins, mandrels, and the like), followed by directional plasma dry etching to remove the top and bottom layers while retaining the sidewall film as a spacer. However, it has been found that the dry etching process may inadvertently damage the sidewall surface and change the film properties; ultimately affecting device performance and yield.

[0005] Therefore, there is a continuing need in the art for methods of depositing carbon-based films as spacers or liners on nanostructures. Summary of the invention

[0006] One or more embodiments of the present disclosure relate to a method of depositing a film. The method includes: flowing a first precursor over a substrate including a patterned surface to form a first portion of a carbon-containing film on the patterned surface, the first precursor including a first reactive group, and the patterned surface including a sidewall and a top surface; 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 conformally form a carbon-containing film on the patterned surface, wherein the carbon-containing film serves as an etch protection layer or as a liner; and removing a second precursor effluent including the second precursor from the substrate.

[0007] Another embodiment of the present disclosure is directed to a method of depositing a spacer film. The method includes flowing a first precursor having a general formula R 1 -(X) n , where R 1 Including one or more of alkyl, alkenyl, aryl, aromatic and cycloalkyl, X n The method comprises: forming a first precursor effluent comprising the first precursor from a substrate; and flowing a second precursor over the substrate, wherein the second precursor has a general formula R 2 -(Y) n , where R 2 Including one or more of alkyl, alkenyl, aryl, aromatic and cycloalkyl, Y n comprising one or more of a hydroxyl group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group and an acyl chloride group, and n is an integer in the range from 1 to 6, wherein a second precursor reacts with the first portion to form a conformal carbon-containing film; a second precursor effluent comprising the second precursor is removed from the substrate; and the substrate is etched to remove a portion of the carbon-containing film from the top surface of the patterned surface to form a spacer layer on the first sidewall and the second sidewall of the patterned surface.

[0008] Further embodiments of the present disclosure relate to a non-transitory computer-readable medium comprising instructions that, when executed by a controller of a processing chamber, cause the processing chamber to perform the following operations: flowing a first precursor over a substrate comprising a patterned surface to form a first portion of a carbon-containing film on the patterned surface, the first precursor comprising a first reactive group, and the patterned surface comprising a sidewall and a top 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 film on the patterned surface; removing the second precursor effluent comprising the second precursor from the substrate; and etching the substrate to remove a portion of the carbon-containing film from the top surface of the patterned surface to form a spacer layer on the first sidewall and the second sidewall of the patterned surface. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] Thus, the manner in which the above-described features of the present disclosure may be understood in detail, a more particular description of the present disclosure briefly summarized above may be obtained by reference to the embodiments, some of which are illustrated in the accompanying drawings. It should be noted, however, that the drawings illustrate only typical embodiments of the present disclosure and therefore should not be considered limiting of the scope of the present disclosure, as the disclosure may admit to other equally effective embodiments. Embodiments as described herein are illustrated by way of example and not limitation in the figures of the accompanying drawings, wherein like reference numerals indicate similar components.

[0010] Figure 1A A cross-sectional view of a substrate is shown according to one or more embodiments.

[0011] Figure 1B A cross-sectional view of a substrate is shown according to one or more embodiments.

[0012] Figure 1C A cross-sectional view of a substrate is shown according to one or more embodiments.

[0013] Figure 1D A cross-sectional view of a substrate is shown according to one or more embodiments.

[0014] Figure 2 A process flow diagram of a method of depositing a film on a substrate according to one or more embodiments is shown.

[0015] Figure 3 A process flow diagram of a method of depositing a film on a substrate according to one or more embodiments is shown. DETAILED DESCRIPTION

[0016] 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 can be practiced or carried out in various ways.

[0017] As used herein, the term "about" means substantially or almost, 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% would satisfy the definition of about.

[0018] As used in this specification and the appended claims, the term "substrate" or "wafer" refers to a surface, or a portion of a surface, on which a process acts. It will also be understood by those of ordinary skill in the art that reference to a substrate may refer to only a portion of a substrate unless the context clearly indicates otherwise. In addition, references to depositing on a substrate may refer to a bare substrate and a substrate having one or more films or features deposited or formed thereon.

[0019] As used herein, the term "substrate" or "substrate surface" represents any portion of a substrate or a portion of a surface of a material formed on the substrate on which film processing is performed. For example, depending on the application, the substrate surface on which processing may be performed includes materials such as silicon, silicon oxide, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire, and any other materials such as metals, metal nitrides, metal alloys and other conductive materials. Substrates include, but are not limited to, semiconductor wafers. The substrate may be exposed to a pretreatment process to grind, etch, reduce, oxidize, hydroxylate, anneal, UV cure, electron beam cure, and / or bake the substrate surface. In addition to performing film processing directly on the surface of the substrate itself, in the present disclosure, any of the disclosed film processing steps may also be performed on an underlying layer (as disclosed in more detail below) formed on the substrate, and the term "substrate surface" is intended to include such an underlying layer, as indicated in the context. Thus, for example, where a film / layer or portion of a film / layer has been deposited onto a substrate surface, the exposed surface of the most recently deposited film / layer becomes the substrate. The substrate may be of 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.

[0020] The term "on" indicates that there is direct contact between components. The term "directly on" indicates that there is direct contact between components without intervening components.

[0021] As used in this specification and the appended claims, the terms "precursor," "reactant," "reactive gas," and the like are used interchangeably to represent any gaseous species that can react with a substrate surface.

[0022] As used in this specification and the appended claims, the terms "reactive compound," "reactive gas," "reactive substance," "precursor," "process gas," and the like are used interchangeably to refer to substances having species 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 introduced into a reaction zone of a processing chamber.

[0023] Carbon-containing materials can be used in the manufacture of semiconductor components of many structures and processes, including as mask materials, etch-resistant materials and trench filling materials, among other applications. More specific examples of applications of carbon-containing materials include, among others, forming thermal implant hardmasks, metal gate (MG) cutting hardmasks, metal gate manufacturing and anti-tone patterning, self-aligned patterning, and others. One or more embodiments include forming these carbon-containing materials as spacers or liners on patterned nanostructures using molecular layer deposition (MLD).

[0024] Embodiments of the present disclosure provide methods for depositing films (e.g., carbon-containing films) on features having small dimensions. Some embodiments advantageously provide conformal films to completely cover features. Other embodiments advantageously provide conformal films that completely or partially cover features. The carbon-containing films of one or more embodiments have high conformality. In one or more embodiments, the conformal carbon-containing film is deposited on a logic component comprising alternating layers of silicon and silicon germanium. In some embodiments, the logic component is a transistor, such as a FinFET or GAA. In other embodiments, the conformal carbon-containing film is deposited on an EUV photoresist.

[0025] Embodiments of the present technology include molecular layer deposition (MLD) methods and systems for forming carbon-containing materials on patterned nanostructures. An exemplary MLD method may include providing a first deposition precursor to a surface of a semiconductor 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 effluents are removed from a processing area where the semiconductor substrate is exposed, which may include unbound molecules of the first deposition precursor. A second deposition precursor may then be introduced to the semiconductor 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 patterned nanostructure surface. During or after forming the second layer, unbound deposition effluents are removed from the processing area, which may include unbound molecules of the second deposition precursor. The semiconductor substrate now has a layer of carbon-containing material bound to the patterned nanostructure surface of the semiconductor substrate. Additional compound layers of the first and second layers may be deposited on the deposited layer until the number of deposited compound layers reaches the desired thickness of the carbon-containing material on the patterned surface of the semiconductor substrate. The compound layer may then be annealed or plasma treated to form a carbon-containing material on the surface of the semiconductor substrate.

[0026] 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 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 by SOC and FCVD. The high hydrogen content found in many SOC and FCVD precursors results in high shrinkage levels when the as-deposited material is processed to form the final material. It is not uncommon for as-deposited SOC and FCVD materials to shrink by as much as 50 vol.% after processing, which can create cracks, fractures, and voids in the processed material, as well as stress on substrate features that contact the material. The present techniques produce carbonaceous materials having a shrinkage of less than 10 vol. % (eg, a shrinkage of 5 vol. % - 10 vol. %, a shrinkage of less than about 5 vol. %) of the as-deposited material.

[0027] One or more embodiments advantageously provide solutions to problems associated 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 semiconductor substrates, and may also produce re-sputtered ions and other species that may cause defects in the deposited carbon-containing material. In addition, they often deposit material unevenly in and around substrate features, thereby creating voids in and around substrate trenches and steps, and producing uneven surfaces in planar substrate areas. The present technology can form carbon-containing materials with high consistency in narrow substrate features (e.g., dimension widths less than about 25 nm) and high aspect ratios (e.g., AR of 10:1 or greater) without the need for plasma that may damage substrate features during deposition.

[0028] Embodiments of the present disclosure are described with the aid of figures 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 one of ordinary skill in the art will recognize that the disclosed processes are not limited to the illustrated applications.

[0029] Figures 1A to 1D A cross-sectional view of a semiconductor substrate processed according to a method of one or more embodiments is shown. Figure 2 FIG. 2 is a process flow diagram of a method 200 for depositing a spacer film according to one or more embodiments. Figures 1A to 1D and Figure 2 In one or more embodiments, at operation 202, a patterned substrate is provided. As used in this specification and the appended claims, the term "providing" means making the substrate available for processing (eg, positioned in a processing chamber).

[0030] refer to Figure 1A In one or more embodiments, the substrate 104 includes a patterned surface 102. In one or more embodiments, the patterned surface 102 includes one or more of a photoresist, a mandrel, a groove, a via, a hole, and the like. In a specific embodiment, the patterned surface 102 includes a patterned photoresist. The photoresist can be patterned using EUV radiation and a developer to form the patterned surface 102 to expose portions and leave residues of the photoresist. As used herein, "photoresist" represents any photosensitive material used in these processes for photolithography and photolithography to form a patterned coating on a surface.

[0031] In one or more embodiments, the patterned surface 102 includes a top surface 110, a first sidewall 109, and a second surface 111. As one of ordinary skill in the art will recognize, there may be more than one patterned surface 102 on the substrate 104. In some embodiments, there are at least two patterned surfaces 102 separated by features 101.

[0032] In one or more embodiments, the substrate on which the carbonaceous material is formed may include a material in which one or more features 101 may be formed. According to the present technology, the substrate features 101 may be characterized as any shape or configuration. In some embodiments, the features 101 may be or include a groove structure, a through-hole structure, or a pore formed in the substrate. Although the substrate features may be characterized as any shape or size, in some embodiments, the substrate features 101 may be characterized as a higher aspect ratio, or a ratio of the feature depth to the width across the feature 101. For example, in some embodiments, the substrate features may be characterized as an aspect ratio greater than or equal to 5:1, and may be characterized as 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, feature 101 may be characterized by a narrow width or diameter across the feature (including between two sidewalls), such as a critical dimension in a range from 5 nm to 500 nm, or in a range from 10 nm to 200 nm, or in a range from 20 nm to 100 nm.

[0033] In one or more embodiments, the distance d1 between each of the patterned surfaces 102 is in a range from 5 nm to 500 nm, or in a range from 10 nm to 200 nm, or in a range from 20 nm to 100 nm.

[0034] refer to Figure 1B In one or more embodiments, an optional liner layer 106 may be formed on the patterned surface 102. In some embodiments, the liner layer 106 is not present, and the carbon-containing film 108 is formed directly on the patterned surface 102. In other embodiments, the liner layer 106 is present, and the carbon-containing film 108 is formed on the liner layer 106. The liner layer 106 may include a liner. In one or more embodiments, the liner layer 106 may include any suitable material. In some embodiments, the liner layer 106 includes a metal. As used herein, "metal" means a metal, a metallization, a metal alloy, a metal oxide, a metal nitride, or a combination thereof.

[0035] refer to Figure 2 In one or more embodiments, at operation 204, the substrate 104 and the patterned surface 102 may be exposed to a pretreatment process to grind, coat, dope, etch, reduce, oxidize, hydroxylate, anneal, UV cure, e-beam cure, and / or bake the substrate as appropriate. In addition to pretreatments directly on the substrate 104 and the patterned surface 102 themselves, in the present disclosure, any of the disclosed treatments or pretreatments may also be performed on the underlying metal surface or liner layer 106.

[0036] In one or more embodiments, the carbon-containing film 108 is substantially conformally formed on the substrate 104 and the patterned surface 102. As used herein, a "substantially conformal" layer represents a layer in which the thickness is approximately the same throughout, for example, on the top, middle, and bottom of the sidewalls and on the bottom of the feature 101. A substantially conformal layer has a thickness variation of less than or equal to about 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, or 0.5%.

[0037] refer to Figure 2 At operation 206 , a first type of precursor is introduced / flowed into the substrate processing region of the processing chamber and onto the substrate surface. The first precursor is strongly bound to the substrate 104 and the patterned surface 102 .

[0038] In one or more embodiments, the first precursor may be a carbon-containing precursor having at least two reactive groups that can form bonds with groups attached to the substrate 104 and the patterned surface 102. The molecules of the first precursor react with the surface groups of the substrate 104 and the patterned surface 102 to form bonds that link the first precursor molecules to the substrate 104 and the patterned surface 102. The reaction between the first precursor molecules and the groups on the substrate 104 and the patterned surface 102 continues until most or all of the surface groups are bonded to the reactive groups on the first precursor molecules. A first portion of the carbon-containing film 108 is formed that prevents further reaction between the first precursor molecules in the first precursor effluent and the substrate.

[0039] The first precursor may include any suitable precursor known to those skilled in the art. In one or more embodiments, the first precursor may have a general formula R 1 -(X) n , wherein n is an integer in the range of 1 to 6, and R 1 Includes one or more of an alkyl group, an alkenyl group, an aryl group or an aromatic group and a cycloalkyl group. n It includes one or more of a hydroxyl group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group and an acyl chloride group.

[0040] 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, tertiary butyl, isobutyl, pentyl, hexyl, isohexyl, heptyl, 4,4-dimethylpentyl, octyl, 2,2,4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl, various branched isomers thereof, and the like. These groups may optionally include up to 1 to 4 substituents. Alkyl groups may be substituted or unsubstituted.

[0041] These alkyl groups may optionally include 1 to 4 substituents such as halo (e.g., F, Br, Cl or I, or CF3), alkyl, alkoxy, aryl, aryloxy, aryl (aryl) or diaryl, arylalkyl, arylalkoxy, alkenyl, cycloalkyl, cycloalkylalkyl, cycloalkylalkoxy, amino, hydroxy, 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, R 1 Independently selected from C 1-20 In other embodiments, R 1 From C 1-20 alkyl.

[0042] As used herein, the term "alkene" or "alkenyl" or "lower alkenyl" represents 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 vinyl, 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 which may be optionally substituted with 1 to 4 substituents, i.e., halogen, haloalkyl, alkyl, alkoxy, alkenyl, alkynyl, aryl, arylalkyl, cycloalkyl, amino, hydroxy, heteroaryl, cycloheteroalkyl, alkanoylamino, alkylamido, arylcarbonyl-amino, nitro, cyano, thiol, alkylthio and / or any of the alkyl substituents described herein.

[0043] As used herein, the term "alkynyl" or "lower alkynyl" represents 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-nonynyl, 4-decynyl, 3-undecyl, 4-dodecyl and the like, and which may be optionally substituted with 1 to 4 substituents, i.e., halogen, haloalkyl, alkyl, alkoxy, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, amino, heteroaryl, cycloheteroalkyl, hydroxy, alkanoylamino, alkylacylamino, arylcarbonylamino, nitro, cyano, thiol and / or alkylthio, and / or any of the alkyl substituents listed herein.

[0044] As used herein alone or as part of another group, the term "halogen" or "halo" represents chlorine, bromine, fluorine and iodine, as well as CF3.

[0045] As used herein, the term "aryl" represents 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 be optionally substituted with 1, 2 or 3 substituents, for example, hydrogen, halogen, haloalkyl, alkyl, haloalkyl, alkoxy, haloalkoxy, alkenyl, trifluoromethyl, trifluoromethoxy, alkynyl and the like, through available carbon atoms.

[0046] Specific examples of the first precursor include, but are not limited to, one or more of terephthalaldehyde, phenylenediamine, ethylenediamine, hexamethylenediamine, terephthaloyl chloride, 1,3,5-benzenetricarbonyltrichloride, pyromellitic dianhydride, benzene-1,3,5-tricarbaldehyde, 1,4-phenylenediisocyanate, 4,4'-oxydiphenylamine, tris(2-aminoethyl)amine, and the like.

[0047] 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 precursors flowed 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 the substrate temperature elevated, such as, in some embodiments, above or about 100° C., a greater number of nucleation sites may be obtained along the substrate 104 and the patterned surface 102, which may improve formation and reduce void formation by improving coverage at each location.

[0048] The first precursor effluent may remain in the substrate processing region for a period of time to almost or completely form the first portion of the carbon-containing film 108. The precursors may be pulsed alternately to grow the material. In some embodiments, the pulse time of either or both of the first and second precursors 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.

[0049] refer to Figure 2At operation 208, after forming the first portion 110 of the carbon-containing film 108, the first precursor is purged or removed from the substrate processing area. The effluent of the first precursor can be removed by pumping the effluent of the first precursor 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. Therefore, 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.

[0050] refer to Figure 1C and Figure 2 At operation 210, a second type of precursor reacts with the first precursor to form a second portion of the carbon-containing film 108. The second precursor may advantageously have a functional group on one end that increases the thickness of the carbon-containing film 108.

[0051] In one or more embodiments, the second precursor may be a carbon-containing precursor having at least two reactive groups that can form bonds with unreacted reactive groups of the first precursor that forms the first portion of the carbon-containing film 108. Molecules of the second precursor react with the unreacted reactive groups of the first precursor to form bonds linking the second precursor molecules to the first precursor molecules. The reaction between the second and first precursor molecules continues until most or all of the unreacted reactive groups on the first precursor have reacted with the second precursor molecules. A second portion of the carbon-containing film 108 of the deposited precursor is formed that prevents further reaction between the second precursor molecules in the second precursor effluent and the first portion of the carbon-containing film 108.

[0052] The second precursor may include any suitable precursor known to those skilled in the art. In one or more embodiments, the second precursor may have a general formula R 2 -(Y) n , wherein n is an integer in the range of 1 to 6, and R 2 Including one or more of alkyl, alkenyl, aryl or aromatic and cycloalkyl. In one or more embodiments, R 2 Independently selected from C 1-20 In other embodiments, R 2 From C 1-20 Alkyl. nIt includes one or more of a hydroxyl group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group and an acyl chloride group.

[0053] Without intending to be limited by theory, it is believed that the second precursor includes a reactive group that can form a covalent bond with a reactive group of the first precursor.

[0054] Specific examples of the second precursor include, but are not limited to, one or more of terephthalaldehyde, phenylenediamine, ethylenediamine, hexamethylenediamine, terephthaloyl chloride, 1,3,5-benzenetricarbonyltrichloride, pyromellitic dianhydride, benzene-1,3,5-tricarbaldehyde, 1,4-phenylenediisocyanate, 4,4′-oxydiphenylamine, tris(2-aminoethyl)amine, and the like.

[0055] refer to Figure 2 In one or more embodiments, method 200 also includes an operation 212 of purging or removing the second precursor effluent from the substrate processing region after forming the second portion of the carbon-containing film 108. The effluents may be removed by pumping the effluents 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, as well as other exemplary time ranges. In some embodiments, a purge gas may be introduced into the substrate processing region to assist in removing the effluents. Exemplary purge gases include argon, helium, and nitrogen, as well as other purge gases.

[0056] In one or more embodiments, the formation rate of the second portion of the carbon-containing film 108 may also depend on the pressure of the second precursor effluent in the substrate processing region. Exemplary effluent pressures in the substrate processing region may range 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.

[0057] refer to Figure 2 In one or more embodiments of the method 200, there is a determination / decision point 214, which is whether a target thickness of the carbon-containing film 108 as deposited on the substrate 104 and the patterned surface 102 has been achieved after one or more cycles of forming the carbon-containing film 108 (e.g., after forming the first and second portions of the compound layer). If the target thickness of the carbon-containing film 108 as deposited has not been achieved, another cycle of forming the first and second portions of the carbon-containing film 108 is performed. If the target thickness of the carbon-containing film 108 as deposited has been achieved, another cycle of forming another carbon-containing film 108 is not initiated. An exemplary number of cycles to form a carbon-containing film may include 1 cycle to 2000 cycles. Additional exemplary ranges of the number of cycles may include, among others, 50 cycles to 1000 cycles, and 100 cycles to 750 cycles, among others.

[0058] Therefore, in one or more embodiments, the method 200 further includes depositing at least one additional carbon-containing film on the initial carbon-containing film, wherein the initial carbon-containing film and the at least one additional carbon-containing film form a carbon-containing film 108 on the metal surface of the substrate.

[0059] In one or more embodiments, the carbon-containing film 108 may have any suitable thickness. In one or more embodiments, the carbon-containing film 108 has a thickness in a range from 0.1 nm to 200 nm, or in a range from 1 nm to 20 nm, or in a range from 1 nm to 10 nm.

[0060] exist Figure 2 In the embodiment shown in the method 200 of , the as-deposited carbon-containing film 108 on the substrate 104 and the patterned surface 102 may be optionally post-processed at operation 216. The optional post-processing operation 216 may be, for example, a process to modify film properties (e.g., annealing or plasma treatment) or another film deposition process to grow additional films (e.g., additional ALD or CVD processes). In some embodiments, the optional post-processing operation 216 may be a process to modify the properties of the deposited film. In some embodiments, the optional post-processing operation 216 includes annealing the carbon-containing film 108. In some embodiments, the annealing is performed at a temperature in the range of about 300° C., 400° C., 500° C., 600° C., 700° C., 800° C., 900° C., or 1000° C. The annealing environment of some embodiments includes one or more of an inert gas (e.g., molecular nitrogen (N2), argon (Ar)) or a reducing gas (e.g., molecular hydrogen (H2) or ammonia (NH3)) or an oxidant (such as, but not limited to, oxygen (O2), ozone (O3), or a peroxide). The annealing may be performed for any suitable duration. In some embodiments, the carbon-containing film is annealed for a predetermined time in the range of about 15 seconds to about 90 minutes or in the range of about 1 minute to about 60 minutes. In some embodiments, annealing the carbon-containing film as deposited increases density, reduces resistivity, and / or increases purity of the film.

[0061] refer to Figure 1D In one or more embodiments, the carbon-containing film 108 undergoes an etching process to remove a portion of the carbon-containing film 108 and expose a top surface 110 of the patterned surface 102 and a portion of the substrate 104 between the patterned surfaces 102. The etching process can be any suitable etching process known to those of ordinary skill in the art. In one or more embodiments, the etching process is a dry etching process.

[0062] In one or more embodiments, removing the portion of the carbon-containing film from the top surface 110 of the patterned surface forms spacers on the patterned structure. The critical dimension d2 between adjacent spacers on the patterned surface 102 is less than the critical dimension d1 before forming the carbon-containing film 108. In one or more embodiments, the critical dimension d2 after removing the carbon-containing film from the top surface 110 of the patterned surface 102 is in a range from 5 nm to 500 nm, or in a range from 10 nm to 200 nm, or in a range from 20 nm to 100 nm.

[0063] Figure 3 A process flow diagram of a method 300 for depositing a spacer film is shown according to one or more embodiments. In one or more embodiments, the spacer film formed according to the method 300 is a metal-doped carbon-containing film. In one or more embodiments, the carbon-containing film 108 may be doped with a metal selected from one or more of aluminum (Al), tin (Sn), zinc (Zn), titanium (Ti), and the like. Figures 1A to 1D and Figure 3 In one or more embodiments, at operation 302, a patterned substrate is provided.

[0064] refer to Figure 3 In one or more embodiments, at operation 304, the substrate 104 and the patterned surface 102 may be exposed to a pretreatment process to grind, coat, dope, etch, reduce, oxidize, hydroxylate, anneal, UV cure, e-beam cure, and / or bake the substrate as appropriate, as described above with respect to Figure 2 Discussed.

[0065] At operation 306 , a first type of precursor is introduced / flowed into the substrate processing region of the processing chamber and onto the substrate surface. The first precursor is strongly bound to the substrate 104 and the patterned surface 102 .

[0066] In one or more embodiments, the first precursor may be a carbon-containing precursor having at least two reactive groups that can form bonds with groups attached to the substrate 104 and the patterned surface 102, as described above with respect to Figure 2 The molecules of the first precursor react with the surface groups of the substrate 104 and the patterned surface 102 to form bonds linking the first precursor molecules to the substrate 104 and the patterned surface 102. The reaction between the first precursor molecules and the groups on the substrate 104 and the patterned surface 102 continues until most or all of the surface groups are bonded to the reactive groups on the first precursor molecules. A first portion of the carbon-containing film 108 is formed that prevents further reaction between the first precursor molecules in the first precursor effluent and the substrate.

[0067] The first precursor may include any suitable precursor known to those skilled in the art, such as those discussed above. In other embodiments, the first precursor may include one or more of trimethylaluminum (TMA), titanium tetrachloride (TiCl4), tin tetrachloride (SnCl4), diethylzinc ((C2H5)2Zn), and mixtures thereof.

[0068] refer to Figure 3 At operation 308, after forming the first portion 110 of the carbon-containing film 108, the first precursor is purged or removed from the substrate processing region. The effluent of the first precursor may be removed by pumping the effluent of the first precursor out of the substrate deposition region for a time period ranging from about 10 seconds to about 100 seconds. Exemplary purge gases include argon (Ar), helium (He), and nitrogen (N2), among other purge gases.

[0069] At operation 310, a second type of precursor reacts with the first precursor to form a second portion of the carbon-containing film 108. The second precursor may advantageously have a functional group on one end that increases the thickness of the carbon-containing film 108.

[0070] In one or more embodiments, the second precursor may be a carbon-containing precursor having at least two reactive groups that can form bonds with unreacted reactive groups of the first precursor (which forms the first portion of the carbon-containing film 108), as described above with respect to Figure 2 The molecules of the second precursor react with the unreacted reactive groups of the first precursor to form bonds linking the second precursor molecules to the first precursor molecules. The reaction between the second and first precursor molecules continues until most or all of the unreacted reactive groups on the first precursor have reacted with the second precursor molecules. A second portion of the carbon-containing film 108 of the deposited precursor is formed that prevents further reaction between the second precursor molecules in the second precursor effluent and the first portion of the carbon-containing film 108.

[0071] The second precursor may include any suitable precursor known to those skilled in the art, such as those discussed above. In other embodiments, the second precursor may include one or more of trimethylaluminum (TMA), titanium tetrachloride (TiCl4), tin tetrachloride (SnCl4), diethylzinc ((C2H5)2Zn), and mixtures thereof.

[0072] Without intending to be limited by theory, it is believed that the second precursor includes a reactive group that can form a covalent bond with a reactive group of the first precursor.

[0073] refer to Figure 3In one or more embodiments, the method 300 also includes an operation 312 of purging or removing the second precursor effluent from the substrate processing region after forming the second portion of the carbon-containing film 108. The effluent may be removed by pumping the effluent out of the substrate deposition region for a time period ranging from about 10 seconds to about 100 seconds. Exemplary purge gases include argon, helium, and nitrogen, among other purge gases.

[0074] At operation 314, the third type of precursor reacts with the second precursor to form a third portion of the carbon-containing film 108. The third precursor may advantageously have a functional group on one end that increases the thickness of the carbon-containing film 108.

[0075] In one or more embodiments, the third precursor may be a carbon-containing precursor having at least two reactive groups that can form bonds with unreacted reactive groups of the second precursor (which forms the second portion of the carbon-containing film 108). Molecules of the third precursor react with unreacted reactive groups of the second precursor to form bonds linking the third precursor molecules to the second precursor molecules. The reaction between the third and second precursor molecules continues until most or all of the unreacted reactive groups on the second precursor have reacted with the third precursor molecules. A third portion of the carbon-containing film 108 of the deposited precursor is formed that prevents further reaction between the third precursor molecules in the third precursor effluent and the first portion of the carbon-containing film 108.

[0076] The third precursor may include any suitable precursor known to those skilled in the art, including but not limited to Figure 2 In one or more embodiments, the third precursor may include one or more of TMA, titanium chloride (TiCl4), tin chloride (SnCl4), diethyl zinc (Et2Zn), and the like.

[0077] Without intending to be bound by theory, it is believed that the third precursor includes a reactive group that can form a covalent bond with a reactive group of the second precursor.

[0078] Specific examples of the second precursor include, but are not limited to, one or more of 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, trimethylaluminum (TMA), titanium tetrachloride (TiCl4), tin tetrachloride (SnCl4), diethylzinc ((C2H5)2Zn), and the like, and mixtures thereof.

[0079] refer to Figure 3In one or more embodiments, the method 300 also includes an operation 316 of purging or removing the third precursor effluent from the substrate processing area after forming the third portion of the carbon-containing film 108. The effluents may be removed by pumping the effluents 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, among other exemplary time ranges. In some embodiments, a purge gas may be introduced into the substrate processing area to assist in removing the effluents. Exemplary purge gases include argon, helium, and nitrogen, among other purge gases.

[0080] refer to Figure 3 In one or more embodiments of the method 300, there is a determination / decision point 318, which is whether a target thickness of the as-deposited carbon-containing film 108 (which may now be a metal-doped carbon-containing film) on the substrate 104 and the patterned surface 102 has been achieved after one or more cycles of forming the carbon-containing film 108 (e.g., after forming the first and second portions of the compound layer). If the target thickness of the as-deposited carbon-containing film 108 has not been achieved, another cycle of forming the first and second portions of the carbon-containing film 108 is performed. If the target thickness of the as-deposited carbon-containing film 108 has been achieved, another cycle of forming another carbon-containing film 108 is not initiated. An exemplary number of cycles of forming a carbon-containing film 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, as well as other exemplary ranges.

[0081] Therefore, in one or more embodiments, the method 300 further includes depositing at least one additional carbon-containing film on the initial carbon-containing film, wherein the initial carbon-containing film and the at least one additional carbon-containing film form the carbon-containing film 108 on the metal surface of the substrate.

[0082] In one or more embodiments, the carbon-containing film 108 may have any suitable thickness. In one or more embodiments, the carbon-containing film 108 has a thickness in a range from 0.1 nm to 200 nm, or in a range from 1 nm to 20 nm, or in a range from 1 nm to 10 nm.

[0083] exist Figure 3 In the embodiment shown in the method 300 of , the substrate 104 and the as-deposited carbon-containing film 108 on the patterned surface 102 may be post-processed at operation 320 as appropriate. The optional post-processing operation 320 may be as described above with respect to Figure 2 Any of the optional post-processing operations described.

[0084] refer to Figure 1DIn one or more embodiments, the carbon-containing film 108 undergoes an etching process to remove a portion of the carbon-containing film 108 and expose the top surface 110 of the patterned surface 102 and expose the substrate 104 between the patterns. The etching process can be any suitable etching process known to those of ordinary skill in the art. In one or more embodiments, the etching process is a dry etching process.

[0085] Some embodiments of the present disclosure relate to electronic components including nanostructures having a carbon-containing film 108 as a spacer layer that remains after an etching process removes the carbon-containing film 108 and an optional liner layer 106 from the bottom portion of the trench between the structures. The carbon-containing film 108 may act as an etch protection layer or an anti-etching layer for the sidewalls of the nanostructures. In some embodiments, the carbon-containing film 108 acts as a liner material when etching is not performed. In some embodiments, when formed on an EUV photoresist pattern, the carbon-containing film 108 acts as a spacer to reduce the critical dimension (CD) or for CD shrinkage.

[0086] 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 shuttle substrates between the processing chambers and the load lock chamber. The transfer chamber is typically maintained under vacuum conditions and provides an intermediate stage for shuttling substrates from one chamber to another and / or to a load lock chamber located at the front end of the cluster tool. However, the exact arrangement and combination of chambers may be modified 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 treatment (such as RTP), plasma nitridation, degassing, orientation, hydroxylation, and other substrate processes. By performing the process in a processing chamber of a modular system, surface contamination of the substrate by atmospheric impurities can be avoided without oxidation prior to deposition of subsequent films.

[0087] According to one or more embodiments, the substrate is continuously 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 under vacuum and is "evacuated" 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.

[0088] Substrates may be processed in a single substrate deposition chamber, where a single substrate is loaded, processed, and unloaded before another substrate is processed. Substrates may also be processed in a continuous manner (similar to a conveyor belt system), where multiple substrates are individually 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 belt system may form a straight path or a curved path. Additionally, the processing chamber may be a turntable, where multiple substrates are moved about a central axis and exposed to deposition, etching, annealing, cleaning, etc. processes throughout the turntable path.

[0089] 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 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) employed is heated or cooled to locally change the substrate temperature. In some embodiments, the heater / cooler is positioned within the chamber, adjacent to the substrate surface, to change the substrate temperature convectively.

[0090] The substrate may also be stationary or rotated during processing. A rotating substrate may be rotated continuously or in discrete steps (about a substrate axis). For example, the substrate may be rotated throughout the entire process, or the substrate may be rotated a small amount between exposures to different reactive 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 local variability in, for example, gas flow geometry.

[0091] 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 any given point on the substrate is not substantially exposed to more than one reactive gas at the same time. As will be understood by those skilled in the art, there is a possibility that due to the diffusion of gases within the processing chamber, a small part of the substrate may be exposed to multiple reactive gases at the same time, and unless otherwise indicated, the simultaneous exposure is unintentional.

[0092] In another aspect of the spatial ALD process, reactive gases are delivered simultaneously to the reaction region but separated by an inert gas curtain and / or a vacuum curtain. The gas curtain may be a combination of an inert gas flow into the processing chamber and a vacuum flow out of the processing chamber. The substrate moves relative to the gas delivery device so that any given point on the substrate is exposed to only one reactive gas.

[0093] As used herein, "pulse" or "dose" refers to the amount of source gas that is intermittently or non-continuously introduced into a process chamber. Depending on the duration of the pulse, the amount of a particular compound within each pulse may vary over time. A particular process gas may include a single compound or a mixture / combination of two or more compounds.

[0094] 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 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.

[0095] In another aspect of the time-domain ALD process of some embodiments, there is a time delay 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 region or otherwise remove any residual reactive gas or reaction products or byproducts from the reaction region. Alternatively, the purge gas may flow continuously throughout the deposition process so that only the purge gas flows during the time delay between pulses of reactive gas. Between multiple times, pulses of reactive gas and purge gas are alternated. Purging may also be accomplished by a vacuum pump with or without an inert gas.

[0096] The duration of each pulse / dose may vary and may be adjusted to accommodate, for example, the spatial capacity of the processing chamber and the capacity of the vacuum system coupled to the processing chamber. Additionally, the dose time of the reactive gas may 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 dose time may also vary based on the type of layer being formed and the geometry of the component being formed. The dose time should be long enough to provide a volume of compound sufficient to adsorb / chemisorb onto substantially the entire surface of the substrate and form a layer of the process gas component thereon.

[0097] Once the carbon-containing film is deposited, the method may optionally include further processing (eg, bulk deposition of a dielectric film). In some embodiments, the further processing may be an ALD process.

[0098] The present disclosure provides that the process can be generally stored in a memory as a software routine, and when executed by a processor, the software routine causes the process chamber to perform the process of the present disclosure. The software routine can also be stored and / or executed by a second processor (not shown), and the second processor is located away from the hardware controlled by the processor. Part or all of the method of the present disclosure can also be executed in hardware. In this way, the process can be implemented in software and executed using a computer system, implemented in hardware as (for example) a special application 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 routine transforms a general-purpose computer into a special-purpose computer (controller), which controls the operation of the chamber so that the process can be performed. 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 patterned surface to form a first portion of a carbon-containing film on the patterned surface, the first precursor comprising a first reactive group, and the patterned surface comprising a sidewall and a top 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 film on the patterned surface; removing a second precursor effluent comprising the second precursor from the substrate; and etching the substrate to remove a portion of the carbon-containing film from a top surface of the patterned surface to form a spacer layer on a first sidewall and a second sidewall of the patterned surface.

[0099] 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 connection with the embodiment is included in at least one embodiment of the present disclosure. Thus, phrases such as "in one or more embodiments," "in certain embodiments," "in an embodiment," or "in an embodiment" appearing throughout this specification do not necessarily refer to the same embodiment of the present disclosure. Additionally, particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments.

[0100] Although the disclosure herein has been described with reference to specific embodiments, it should be understood that these embodiments are merely illustrative of the principles and applications of the disclosure. It will be apparent to one of ordinary skill 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, it is contemplated that the disclosure includes modifications and variations within the scope of the appended claims and their equivalents.

Claims

1. A method for depositing a spacer film, the method comprising the following steps: flowing a first precursor over a substrate including a patterned surface to form a first portion of a carbon-containing film on the patterned surface, the first precursor including a first reactive group, and the patterned surface including sidewalls and a top surface; 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 conformally form the carbon-containing film on the patterned surface, wherein the carbon-containing film serves as an etch protection layer or as a liner; as well as A second precursor effluent including the second precursor is removed from the substrate.

2. The method of claim 1, wherein the first precursor has the general formula R 1 -(X) n Where R 1 Including one or more of alkyl, alkenyl, aryl, aromatic and cycloalkyl, X n Includes one or more of a hydroxyl group, an aldehyde group, a keto group, an acid group, an amino group, an isocyanate group, a thiocyanate group, and an acyl chloride group, and n is an integer ranging from 1 to 6.

3. The method of claim 1, wherein the second precursor has the general formula R 2 -(Y) n Where R 2 Including one or more of alkyl, alkenyl, aryl, aromatic and cycloalkyl, Y n Includes one or more of a hydroxyl group, an aldehyde group, a keto group, an acid group, an amino group, an isocyanate group, a thiocyanate group, and an acyl chloride group, and n is an integer ranging from 1 to 6.

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

5. The method of claim 4, wherein the first precursor comprises terephthalaldehyde and the second precursor comprises phenylenediamine.

6. The method of claim 1, further comprising the steps of: The patterned surface is etched to remove a portion of the carbon-containing film from the top surface of the patterned surface and from the substrate to form a spacer layer on the sidewalls of the patterned surface, wherein the carbon-containing film serves as an etch protection layer.

7. The method of claim 1, further comprising the steps of: The method is repeated to form the carbon-containing film having a thickness in a range from 1 nm to 20 nm.

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

9. The method of claim 1, wherein the patterned surface is an EUV photoresist pattern, and the carbon-containing film is formed on the sidewalls and acts as a spacer to reduce the critical dimension (CD).

10. The method of claim 1, further comprising the steps of: A third precursor is flowed over the substrate to form a third portion of the carbon-containing film on the patterned surface, wherein one or more of the first precursor, the second precursor, or the third precursor includes trimethylaluminum (TMA), titanium tetrachloride (TiCl4), tin tetrachloride (SnCl4), diethylzinc ((C2H5)2Zn), and the carbon-containing film is doped with a metal.

11. The method of claim 10, further comprising the steps of: A third precursor effluent including the third precursor is removed from the substrate.

12. A method of depositing a spacer film, the method comprising the steps of: A first precursor is flowed over a substrate comprising a patterned surface, the first precursor having a general formula R 1 -(X) n Where R 1 including one or more of alkyl, alkenyl, aryl, aromatic and cycloalkyl, X n includes one or more of a hydroxyl group, an aldehyde group, a keto group, an acid group, an amino 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 patterned surface to form a first portion of a carbon-containing film; removing a first precursor effluent including the first precursor from the substrate; A second precursor is flowed over the substrate, wherein the second precursor has a general formula R 2 -(Y) n Where R 2 including one or more of alkyl, alkenyl, aryl, aromatic and cycloalkyl, Y n includes one or more of a hydroxyl group, an aldehyde group, a keto group, an acid group, an amino 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 a conformal carbon-containing film; removing a second precursor effluent including the second precursor from the substrate; and The substrate is etched to remove a portion of the carbon-containing film from a top surface of the patterned surface to form a spacer layer on a first sidewall and on a second sidewall of the patterned surface.

13. The method of claim 12, wherein the first precursor and the second precursor are independently selected from one or more of terephthalaldehyde, phenylenediamine, ethylenediamine, hexamethylenediamine, terephthaloyl chloride, 1,3,5-benzenetricarbonyltrichloride, pyromellitic dianhydride, benzene-1,3,5-tricarbaldehyde, 1,4-phenylenediisocyanate, 4,4'-oxydiphenylamine and tris(2-aminoethyl)amine.

14. The method of claim 13, wherein the first precursor comprises terephthalaldehyde and the second precursor comprises phenylenediamine.

15. The method of claim 12, further comprising the steps of: A liner is deposited on the patterned surface prior to flowing the first precursor over the substrate.

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

17. The method of claim 12, wherein the patterned surface is an EUV photoresist pattern, and the carbon-containing film is formed on the sidewalls and acts as a spacer to reduce the critical dimension (CD).

18. The method of claim 12, further comprising the steps of: A third precursor is flowed over a substrate including a patterned surface to form a third portion of the carbon-containing film on the patterned surface, wherein the third precursor is selected from a group consisting of trimethylaluminum (TMA), titanium tetrachloride (TiCl4), tin tetrachloride (SnCl4), diethylzinc ((C2H5)2Zn) and mixtures thereof, and wherein the carbon-containing film is doped with a metal.

19. The method of claim 18, further comprising the steps of: A third precursor effluent including the third precursor is removed from the substrate.

20. A non-transitory computer readable medium comprising instructions which, when executed by a controller of a processing chamber, cause the processing chamber to perform the following operations: flowing a first precursor over a substrate including a patterned surface to form a first portion of a carbon-containing film on the patterned surface, the first precursor including a first reactive group, and the patterned surface including sidewalls and a top surface; 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 conformally form the carbon-containing film on the patterned surface; removing a second precursor effluent including the second precursor from the substrate; as well as The substrate is etched to remove a portion of the carbon-containing film from a top surface of the patterned surface to form a spacer layer on a first sidewall and on a second sidewall of the patterned surface.

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