Method of selectively depositing a film

Abstract

Methods for selectively depositing carbon-containing layers are described. Exemplary processing methods may include passing a first precursor through a substrate comprising a metallic surface and a non-metallic surface to form a first portion of an initial carbon-containing film on the metallic surface. These methods may include removing the first precursor effluent from the substrate. A second precursor may then be passed through the substrate to react with the first portion of the initial carbon-containing layer. These methods may include removing the second precursor effluent from the substrate. These methods may include pretreating the metallic surface of the substrate to form a metal oxide surface on the metallic surface.

Description

Technical Field

[0001] The embodiments of this disclosure relate to a method for selectively depositing carbon-based films. In particular, the embodiments of this disclosure relate to a method for selectively depositing a carbon substrate on a metal surface above a non-metallic surface. Prior Technology

[0002] The semiconductor processing industry continues to seek higher throughput while simultaneously improving the uniformity of layers deposited on substrates with larger surface areas. These same factors, combined with new materials, also provide higher circuit integration per unit area of ​​substrate. As circuit integration increases, the demand for greater uniformity and process control regarding layer thickness also increases. Therefore, various technologies have been developed to deposit layers on substrates cost-effectively while maintaining control over layer properties.

[0003] The semiconductor industry faces numerous challenges in its pursuit of device miniaturization, which involves the rapid scaling of nanometer-level features. These challenges include the introduction of complex manufacturing steps, such as multiple lithography steps and the integration of high-performance materials. To maintain the pace of device miniaturization, selective deposition has shown promise because it has the potential to eliminate costly lithography steps by simplifying the integration process.

[0004] Selective deposition of materials can be accomplished in a variety of ways. A chemical precursor can selectively react with a surface relative to another surface (metal or dielectric). Process parameters such as pressure, substrate temperature, precursor partial pressure, and / or gas flow can be modulated to alter the chemical kinetics of the reaction on a particular surface. Another possible approach involves surface pretreatment, which can be used to enable or disable surfaces beneficial to the incoming film deposition precursor.

[0005] Area-selective atomic layer deposition (AS-ALD) can be used for the selective deposition of materials. During AS-ALD, when the deposited ALD film becomes thicker than the self-assembled monolayer (SAM) used to passivate non-grown surfaces, the ALD film may grow laterally (this can be referred to as mushrooming), thereby reducing selectivity. Therefore, there is a continued need in the art for methods to improve deposition selectivity and avoid the problems encountered during AS-ALD. Summary of the Invention

[0006] One or more embodiments of this disclosure relate to a method of depositing a film. A method of selectively depositing a film includes: passing a first precursor through a substrate including a metal surface and a non-metal surface to form a first portion of a carbon-containing layer on the metal surface, the first precursor comprising a first reactive group; removing a first precursor effluent containing the first precursor from the substrate; passing a second precursor comprising a second reactive group through the substrate to react with the first reactive group to form the carbon-containing layer on the metal surface of the substrate but not on the non-metal surface; and removing a second precursor effluent containing the second precursor from the substrate.

[0007] Another embodiment of this disclosure relates to a method for selectively depositing a film. In one or more embodiments, a method for selectively depositing a film includes: passing a first precursor through a substrate comprising a metal surface and a non-metal surface, the first precursor having the general formula R1-(X)n, wherein R1 comprises one or more of alkyl, alkenyl, aryl or aromatic groups and cycloalkyl, Xn comprises one or more of hydroxyl, aldehyde, ketone, acid, amino, isocyanate, thiocyanate and chlorohydrin, and n is an integer ranging from 1 to 6, wherein the first precursor reacts with reactive groups on the metal surface to form a first portion of a carbon-containing layer on the metal surface; removing the first precursor effluent containing the first precursor from the substrate; and passing a second precursor through the substrate, the second precursor having the general formula R2-(Y)n, wherein R2 comprises one or more of alkyl, alkenyl, aryl or aromatic groups and cycloalkyl, Yn... n includes one or more of hydroxyl, aldehyde, ketone, acid, amino, isocyanate, thiocyanate and chlorohydrin groups, and n is an integer ranging from 1 to 6, wherein the second precursor reacts with the first portion to form a carbon-containing layer; and the second precursor effluent containing the second precursor is removed from the substrate. Simple Explanation of the Diagram

[0008] To gain a more detailed understanding of the features described above, reference can be made to the embodiments for a more specific description of the disclosure, some of which are illustrated in the accompanying drawings. However, it should be noted that the drawings illustrate only typical embodiments of the disclosure and should not be considered as limiting its scope, as the disclosure may allow for other equally effective embodiments. The embodiments described herein are illustrated in the drawings by way of example rather than limitation, and the same reference numerals denote similar elements in the drawings.

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

[0010] Figure 1B illustrates a cross-sectional view of a substrate according to one or more embodiments;

[0011] Figure 1C illustrates a cross-sectional view of a substrate according to one or more embodiments;

[0012] Figure 1D illustrates a cross-sectional view of a substrate according to one or more embodiments; and

[0013] Figure 2 illustrates a process flow diagram of a method for selectively depositing a film on a substrate according to one or more embodiments. Implementation

[0014] Before describing several exemplary embodiments of the present invention, it should be understood that the present invention is not limited to the details of the construction or processing steps set forth in the following description. The present invention can have other embodiments and can be practiced or carried out in various ways.

[0015] As used herein, the term "about" means approximately or close to, and in the context of a numerical value or range, it means a variation of ±15% or less of that value. For example, values ​​differing by ±14%, ±10%, ±5%, ±2%, or ±1% would satisfy the definition of about.

[0016] As used in this specification and the appended claims, the terms "substrate" or "wafer" refer to the surface or part of the surface on which the process is performed. Those skilled in the art will also understand that, unless the context clearly indicates otherwise, reference to substrate may also refer to only a portion of the substrate. Furthermore, reference to deposition on a substrate may refer to both a bare substrate and a substrate on which one or more films or features are deposited or formed.

[0017] As used herein, "substrate" or "substrate surface" means any portion of the substrate on which a film treatment is performed or a portion of the surface of a material formed on the substrate. For example, depending on the application, a substrate surface on which a treatment can be performed may include 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. Substrates may be exposed to pretreatment processes such as polishing, etching, reduction, oxidation, hydroxylation, annealing, UV curing, electron beam curing, and / or baking of the substrate surface. In addition to performing film treatments directly on the surface of the substrate itself, any of the film treatment steps disclosed in this disclosure may also be performed on an underlayer formed on the substrate, as disclosed in more detail below, and the term "substrate surface" is intended to include such an underlayer as the context suggests. Thus, for example, where a film / layer or a portion of a film / layer has already been deposited on the substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate. The substrate can have various sizes, such as wafers with a diameter of 200 mm or 300 mm, and rectangular or square panels. In some embodiments, the substrate comprises a rigid discrete material.

[0018] The term "on" indicates that there is direct contact between elements. The term "directly on" indicates that there is direct contact between elements without any intermediary elements.

[0019] As used in this specification and the appended claims, the terms "precursor," "reactant," "reactive gas," etc., are used interchangeably to represent any gaseous substance that can react with the substrate surface.

[0020] As used in this specification and the appended claims, the terms "reactive compound," "reactive gas," "reactive substance," "precursor," "process gas," etc., are used interchangeably to refer to substances having species capable of reacting with a substrate or material on a substrate in surface reactions (e.g., chemisorption, oxidation, reduction, cycloaddition). The substrate or a portion of the substrate is sequentially exposed to two or more reactive compounds introduced into a reaction zone of a processing chamber.

[0021] Carbon-containing materials can be used in the fabrication of semiconductor devices with many structures and processes, including as masking materials, etch-resistant materials, and trench-filling materials, among other applications. More specific examples of applications for carbon-containing materials include the formation of thermally implanted hard masks, metal gate (MG) dicing hard masks, metal gate fabrication and inverted-tone patterning, self-aligned patterning, etc. This technology involves the selective formation of such carbon-containing materials on metal / metal surfaces using molecular layer deposition (MLD).

[0022] Embodiments of this technology include molecular layer deposition (MLD) methods and systems for selectively forming carbon-containing materials on metal / metal surfaces. An exemplary MLD method may include providing a first deposition precursor to a metal / metal surface of a semiconductor substrate, wherein the precursor forms a first layer (e.g., a first monolayer) on the surface. During or after the formation of the first layer, unbound deposition effluent, which may include unbound molecules of the first deposition precursor, is removed from a processing area of ​​the exposed semiconductor substrate. A second deposition precursor may then be introduced into the semiconductor substrate, wherein molecules of the second deposition precursor bind to reactive portions on the first layer to form a second layer (e.g., a second monolayer) on the metal / metal surface, with little or no such layer on the non-metallic surface. During or after the formation of the second layer, unbound deposition effluent, which may include unbound molecules of the second deposition precursor, is removed from the processing area. The semiconductor substrate now has a carbon-containing material layer bonded to the metal / metal surface of the semiconductor substrate, and little or no carbon-containing material is deposited on the non-metallic surface. Additional compound layers, having a first and a second layer, can be deposited on top of the deposited layers until the number of deposited compound layers reaches the desired thickness of the carbon-containing material on the metal / metal surface of the semiconductor substrate. The compound layers can then be annealed or plasma-treated to form the carbon-containing material on the metal / metal surface of the semiconductor substrate.

[0023] One or more embodiments advantageously provide a solution to the problems of conventional methods for forming carbon-containing materials on semiconductor substrates. For example, the carbon-containing materials formed by this technique have significantly fewer voids, cracks, and other physical defects than those formed using spin-on-carbon (SOC) and flowable chemical-vapor-deposition (FCVD) methods. This technique can also form carbon-containing materials with higher density and lower porosity than those formed using SOC and FCVD. When processing as-deposited materials to form the final material, the high levels of hydrogen present in many SOC and FCVD precursors lead to high levels of shrinkage. Shrinkage of up to 50% by volume is not uncommon for processed as-deposited SOC and FCVD materials, resulting in gaps, cracks, and voids in the processed material, as well as stress on substrate features in contact with the material. The processed carbon-containing materials produced by this technique have a shrinkage rate of less than 10% by volume of the as-deposited material (e.g., 5-10% by volume, less than about 5% by volume).

[0024] One or more embodiments advantageously provide a solution to the problems of 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), tend to produce ion sputtering that can damage substrate features on the semiconductor substrate, and can also produce re-sputtered ions and other substances that can cause defects in the deposited carbon-containing material. Furthermore, they tend to deposit material unevenly in and around substrate features, creating voids in and around substrate trenches and steps, and producing uneven surfaces in flat substrate regions. This technique can form carbon-containing materials with a high level of consistency, having narrow substrate features (e.g., a width of less than about 25 nm) and a high aspect ratio (e.g., 10:1 or greater AR), without requiring plasma that can damage substrate features during deposition.

[0025] Embodiments of this disclosure are described with reference to accompanying drawings illustrating elements (e.g., transistors) and processes for forming semiconductor structures according to one or more embodiments of this disclosure. The processes shown are merely illustrative possible uses of the disclosed processes, and those skilled in the art will recognize that the disclosed processes are not limited to the illustrated applications.

[0026] Figures 1A through 1D illustrate cross-sectional views of a semiconductor substrate processed according to one or more embodiments. Figure 2 illustrates a process flow diagram of a selective film deposition method 200 according to one or more embodiments. Referring to Figures 1A through 1D and Figure 2, in one or more embodiments, a substrate is provided at operation 202. As used in this specification and the appended claims, the term "provided" means that the substrate is made for processing (e.g., positioned in a processing chamber).

[0027] Referring to Figure 1A, in one or more embodiments, the substrate includes a metal surface 102 and a non-metallic surface 104. In some embodiments, the non-metallic surface 104 includes a dielectric surface. In other embodiments, the non-metallic surface 104 includes one or more of the following: a dielectric surface, a semiconductor surface, a non-metallic surface, or a metal surface in which the metal is different from the metal of the metal surface 102. Those skilled in the art will understand that the carbon-containing layer has only been grown on some metal surfaces, while it has not grown or grown much less on other second surfaces. The selectivity (thickness ratio on different surfaces) can be 2:1, 5:1, 10:1, 50:1, 100:1, or absolutely selective growth (no growth on undesirable surfaces).

[0028] In one or more embodiments, a substrate on which a carbon-containing material is selectively formed may include a material in which one or more features may be formed. According to the present technology, the features of the substrate may be of any shape or configuration. In some embodiments, the features may be or include trench structures, via structures, or pores formed within the substrate. Although the features of the substrate may be of any shape or size, in some embodiments, the features of the substrate may be characterized by a high aspect ratio, or a ratio of the depth of the feature to the width of 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 the features 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. Furthermore, the features may be characterized by a narrow width or diameter on the feature (including between the two sidewalls), such as a size less than or equal to 20 nm, and the features may be characterized by a width 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 smaller.

[0029] As used herein, "metal" means metal, metal-made, metal alloy, metal oxide, metal nitride, or a combination thereof. As used herein, "metal surface" means any portion of a substrate or a portion of the surface of a material formed of metal. Metal surfaces may be exposed to pretreatment processes for polishing, coating, doping, etching, reduction, oxidation, hydroxylation, annealing, UV curing, electron beam curing, and / or baking of the substrate. In addition to pretreatment directly on the metal surface itself, any metal surface treatment disclosed in this disclosure, as disclosed in more detail below, may also be performed on the underlying metal surface, and the term "metal surface" is intended to include such an underlying surface as indicated by the context. Thus, for example, where a film / layer or portion of a film / layer has already been deposited on a metal surface, the exposed surface of the newly deposited film / layer becomes the metal surface.

[0030] In one or more embodiments, the metal surface 102 comprises a metal, a metal alloy, a metal oxide, a metal nitride, or a combination thereof. Non-limiting examples of metals include copper (Cu), cobalt (Co), nickel (Ni), tungsten (W), ruthenium (Ru), chromium (Cr), iron (Fe), platinum (Pt), gold (Au), silver (Ag), molybdenum (Mo), gallium (Ga), indium (In), tungsten (W), titanium (Ti), tantalum (Ta), aluminum (Al), nickel (Ni), their oxides, or combinations thereof. In one or more specific embodiments, the metal surface 102 comprises one or more of copper (Cu), cobalt (Co), ruthenium (Ru), tungsten (W), molybdenum (Mo), titanium nitride (TiN), tantalum nitride (TaN), titanium (Ti), tantalum (Ta), aluminum (Al), nickel (Ni), or their oxides.

[0031] As used herein, "dielectric surface" refers to any part of a substrate or a portion of the surface of a material formed of a dielectric material. Non-limiting examples of dielectric materials include silicon oxide (SiOx), silicon nitride (SixNy), silicon (Si), silicon oxynitride (SiON), carbides, carbon oxides, nitrides, nitrogen oxides, carbonitrides, polymers, phosphosilate glasses, fluorosilate (SiOF) glasses, organosilicon glasses (SiOCH), aluminum oxide (AlOx), hafnium oxide (HfOx), zirconium oxide (ZrO2), titanium oxide (TiOx), titanium nitride (TiN), tantalum oxide (TaxO5), yttrium oxide (Y2O3), lanthanum oxide (La2O3), aluminum nitride (AlN), magnesium oxide (MgO), calcium fluoride (CaF2), lithium fluoride (LiF2), strontium oxide (SrO2), silicon carbide (SiC), barium oxide (BaO), hafnium silicate (HfSiO4), and lanthanum aluminate (LaAlO2). 3) Niobium pentoxide (Nb₂O₅), barium titanate (BaTiO₃), strontium titanate (SrTiO₃), bismuth titanate (Bi₄Ti₃O₁₂), lead zirconium titanate (Pb(Zr,Ti)O₃), calcium copper titanate (CaCu₃Ti₄O₁₂), lithium niobate (LiNbO₃), barium titanate (BaTiO₃), and potassium niobate (KNbO₃). In one or more specific embodiments, the non-metallic surface 104 comprises one or more of silicon oxide (SiO x), silicon carbide (SiOC), silicon oxycarbonitride (SiOCN), silicon nitride (SiN), silicon oxynitride (SiON), silicon (Si), germanium (Ge), silicon germanium (SiGe), silicon carbide (SiC), indium gallium zinc oxide (InGaZnO), aluminum oxide (AlO x), aluminum nitride (AlN), and hafnium oxide (HfO x).

[0032] In one or more embodiments, at operation 204, the non-metallic surface 104 may be exposed to pretreatment processes for polishing, coating, doping, etching, reduction, oxidation, hydroxylation, annealing, UV curing, electron beam curing, and / or baking of the substrate. In addition to pretreatment directly on the non-metallic surface 104 itself, in this disclosure, as disclosed in more detail below, any of the disclosed processes or pretreatments may also be performed on the underlying metallic surface, and the term "dielectric surface" is intended to include such an underlying surface as indicated by the context. Thus, for example, where a film / layer or a portion thereof has already been deposited on a metallic surface, the exposed surface of the newly deposited film / layer becomes the metallic surface.

[0033] In one or more embodiments, the substrate is pretreated with one or more of the following: high-temperature annealing, plasma treatment, and gas annealing. Plasma treatment may include treatment with one or more of the following: hydrogen (H₂), oxygen (O₂), amine (NH₃), nitrogen (N₂), carbon dioxide (CO₂), nitrous oxide (N₂O), argon (Ar). Gas annealing may include annealing in an atmosphere of one or more of the following: hydrogen (H₂), oxygen (O₂), ozone (O₃), nitrous oxide (N₂O), water (H₂O), hydrogen peroxide (H₂O₂).

[0034] In one or more embodiments, the pretreatment process of operation 204 removes a layer from the substrate. In some embodiments, the pretreatment process of operation 204 creates a metal oxide layer on the metal surface 102. In one or more embodiments, the pretreatment process of operation 204 is critical for forming a metal oxide on the metal surface, enabling selective molecular layer deposition (MLD) on the metal surface.

[0035] In some embodiments, the metal surface 102 is cleaned / pretreated with plasma. In some embodiments, the plasma is conductively coupled plasma (CCP). In some embodiments, the plasma is inductively coupled plasma (ICP).

[0036] As used in this specification and the appended claims, the phrase "relatively...selectively" or similar phrases indicate that the material is deposited to a greater extent on the surface than on another surface. In some embodiments, the material indicated by "selectively" is formed on the selective surface at a rate of about 10x, 15x, 20x, 25x, 30x, 35x, 40x, 45x, or 50x greater than or equal to the formation rate on the non-selected surface.

[0037] In one or more embodiments, the carbon-containing layer 114 is formed on a metal / metal surface 102 rather than a non-metal surface 104, with a selectivity ratio of at least 10:1, at least 100:1, or at least 1000:1.

[0038] Referring to Figures 1B and 2, at operation 206, a first-type precursor 106 is introduced / flowed into the substrate processing area of ​​the processing chamber and above the substrate surface. The first precursor 106 is firmly bonded to the metal surface 102, but not to the non-metallic surface 104.

[0039] In one or more embodiments, the first precursor 106 may be a carbon-containing precursor having at least two reactive groups capable of forming bonds with groups attached to the metal surface 102 of the substrate. Molecules of the first precursor 106 react with surface groups (e.g., metal ions) of the metal surface 102 to form bonds connecting the first precursor 106 molecules to the metal surface 102 of the substrate. The reaction between the first precursor 106 molecules and the groups on the metal surface 102 of the substrate continues until most or all of the surface groups are bonded to the reactive groups on the first precursor 106 molecules. A first portion 108 of the carbon-containing layer 114 is formed, which prevents further reaction between the first precursor 106 molecules in the first precursor effluent and the substrate.

[0040] The first precursor 106 may include any suitable precursor known to those skilled in the art. In one or more embodiments, the first precursor 106 may have the general formula R1-(X)n, where n is an integer ranging from 1 to 6, and R1 includes one or more of alkyl, alkenyl, aryl or aromatic groups and cycloalkyl groups. Xn includes one or more of hydroxyl, aldehyde, ketone, acid, amino, isocyanate, thiocyanate, and chlorohydrin groups.

[0041] Unless otherwise stated, the terms "lower alkyl," "alkyl," or "alkane," as used alone or as part of another group herein, include straight-chain and branched hydrocarbons containing 1 to 20 carbon atoms or 1 to 10 carbon atoms in the positive chain, such as methyl, ethyl, propyl, isopropyl, butyl, tributyl, isobutyl, pentyl, hexyl, isohexyl, heptyl, 4,4-dimethylpentyl, octyl, 2,2,4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl, and their various branched isomers. Such groups may contain up to 1 to 4 substituents, as appropriate. Alkyl groups may be substituted or unsubstituted.

[0042] Such alkyl groups may, depending on the context, contain up to one to four substituents, such as halogens (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, acetyl, heteroaryl, heteroaryloxy, heteroarylalkyl, heteroarylalkoxy, aryloxyalkyl, alkylthio, arylalkylthio, aryloxyaryl, alkylamino, alkylamino, arylcarbonylamino, nitro, cyano, thiol, haloalkyl, trihaloalkyl, and / or alkylthio, etc. In one or more embodiments, R1 is independently selected from C1-20 alkyl groups. In other embodiments, R1 is derived from C1-12 alkyl groups.

[0043] As used herein, the terms "olefin" or "alkenyl" or "lower alkenyl" refer to a straight-chain or branched group having 2 to 20 carbons, or 2 to 12 carbons, and 1 to 8 carbon atoms in the positive chain, and containing one to six double bonds in the positive 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-tetradectrienyl, etc., and may be substituted with one to four substituents, namely halogen, haloalkyl, alkyl, alkoxy, alkenyl, alkynyl, aryl, arylalkyl, cycloalkyl, amino, hydroxyl, heteroaryl, cyclohexaalkyl, alkylamino, alkylamino, arylcarbonyl-amino, nitro, cyano, thiol, alkylthio and / or any alkyl substituent listed herein.

[0044] As used herein, the term "alkynyl" or "lower alkynyl" refers to a straight-chain or branched group having 2 to 20 carbons, 2 to 12 carbons, or 2 to 8 carbons in the positive chain and containing one triple bond in the positive chain, such as 2-propynyl, 3-butynyl, 2-butynyl, 4-pentynyl, 3-pentynyl, 2-hexynyl, 3-hexynyl, 2-hepynyl, 3-hepynyl, 4-hepynyl, 3-octyynyl, 3-nonynyl Alkynyl, 4-decynyl, 3-undecynyl, 4-dodecynyl, etc., and may be substituted with one to four substituents, namely halogen, haloalkyl, alkyl, alkoxy, alkenyl, alkynyl, aryl, arylalkyl, cycloalkyl, amino, heteroaryl, cyclohexaalkyl, hydroxyl, alkylamino, alkylamino, arylcarbonylamino, nitro, cyano, thiol and / or alkylthio, and / or any alkyl substituent listed herein.

[0045] The term "halogen" or "halogen group" as used alone or as part of another group in this document refers to chlorine, bromine, fluorine, and iodine, as well as CF3.

[0046] As used herein, the term "aryl" refers to a monocyclic or bicyclic aromatic group (such as phenyl, biphenyl, or naphthyl, including 1-naphthyl and 2-naphthyl) containing 6 to 10 carbon atoms in the ring moiety, and may, depending on the case, include 1 to 3 additional rings fused to a carbocyclic or heterocyclic ring (such as an aromatic ring, cycloalkyl ring, heteroaromatic ring, or cyclohexaalkyl ring). The aryl group may, depending on the case, be substituted by one, two, or three substituents, such as hydrogen, halogen, haloalkyl, alkyl, haloalkyl, alkoxy, haloalkoxy, alkenyl, trifluoromethyl, trifluoromethoxy, alkynyl, etc.

[0047] Unwilling to be bound by theory, it is assumed that the metal surface 102 contains metal ions, such as, for example, Cu+ or Cu2+, which act as catalysts to accelerate reactions or generate new reactions between two precursors on the metal surface to form a first portion of the initial carbon-containing film on the metal surface. In one or more embodiments, pretreating the metal surface 102 to form a metal oxide surface can generate metal ions that are crucial for the selective deposition of the carbon-containing layer 114.

[0048] Specific examples of the first precursor 106 include, but are not limited to, one or more of the following: terephthalaldehyde, phenylenediamine, ethylenediamine, hexamethylenediamine, terephthalic chloride, 1,3,5-benzenetrimethylchloro, pyromellitic dianhydride, benzene-1,3,5-tricarboxaldehyde, 1,4-epenylphenyl diisocyanate, 4,4'-oxodiphenylamine, tris(2-aminoethyl)amine, etc.

[0049] In one or more embodiments, the formation rate 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 area. Indicative substrate temperatures during the formation operation may be greater than or equal to 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, or higher. By maintaining an elevated substrate temperature, such as above or about 100°C in some embodiments, an increased number of nucleation sites can be obtained along the metal surface 102 of the substrate, which can improve formation and reduce void formation by improving coverage at each location.

[0050] The first precursor 106 effluent may be retained in the substrate processing area for a period of time to almost or completely form a first portion 108 of the carbon-containing layer 114. The precursor may be delivered in alternating pulses to allow material growth. In some embodiments, the pulse duration of one or both of the first precursor 106 and the second precursor 110 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 longer.

[0051] Referring to Figure 2, at operation 208, after the formation of the first portion 110 of the carbon-containing layer 114, the first precursor 106 is cleaned or removed from the substrate processing area. Effluent from the first precursor 106 can be removed by pumping it out of the substrate deposition area for a period ranging from about 10 seconds to about 100 seconds. Additional exemplary time ranges may include about 20 seconds to about 50 seconds, and 25 seconds to about 45 seconds, among other exemplary time ranges. However, in some embodiments, the increased cleanup time may begin to remove reactive sites, which could reduce uniform formation. Therefore, in some embodiments, cleanup 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 cleanup gas may be introduced into the substrate processing area to aid in the removal of effluent. Exemplary cleanup gases include argon (Ar), helium (He), and nitrogen (N2), among other cleanup gases.

[0052] Referring to Figures 1C and 2, at operation 210, the second type of precursor 110 reacts with the first precursor 106 to form a second portion 112 of the carbon-containing layer 114. The second precursor 110 may advantageously have functional groups at one end that increase the thickness of the carbon-containing layer 114.

[0053] In one or more embodiments, the second precursor 110 may be a carbon-containing precursor having at least two reactive groups capable of forming bonds with unreacted reactive groups of the first precursor 106 forming the first portion 108 of the carbon-containing layer 114. Molecules of the second precursor 110 react with the unreacted reactive groups of the first precursor 106 to form bonds linking the second precursor 110 molecules to the first precursor 106 molecules. The reaction between the second precursor molecules and the first precursor molecules continues until most or all of the unreacted reactive groups on the first precursor 106 molecules have reacted with the second precursor 110 molecules. A second portion 112 of the carbon-containing layer 114 of the deposited precursor is formed, which prevents further reaction between the second precursor 110 molecules in the second precursor effluent and the first portion 108 of the carbon-containing layer 114.

[0054] The second precursor 110 may include any suitable precursor known to those skilled in the art. In one or more embodiments, the second precursor 110 may have the general formula R2-(Y)n, where n is an integer ranging from 1 to 6, and R2 includes one or more of alkyl, alkenyl, aryl or aromatic groups and cycloalkyl groups. In one or more embodiments, R2 is independently selected from C1-20 alkyl groups. In other embodiments, R2 is derived from C1-12 alkyl groups. Yn includes one or more of hydroxyl, aldehyde, ketone, acid, amino, isocyanate, thiocyanate, and chlorohydrin groups.

[0055] Unwilling to be bound by theory, it is believed that the second precursor 110 contains reactive groups that can form covalent bonds with the reactive groups of the first precursor 106.

[0056] Specific examples of the second precursor 110 include, but are not limited to, one or more of the following: terephthalaldehyde, phenylenediamine, ethylenediamine, hexamethylenediamine, terephthalic chloride, 1,3,5-benzenetrimethylchloro, pyromellitic dianhydride, benzene-1,3,5-tricarboxaldehyde, 1,4-epenylphenyl diisocyanate, 4,4'-oxodiphenylamine, and tris(2-aminoethyl)amine.

[0057] Referring to Figure 2, in one or more embodiments, method 200 also includes operation 212 to purify or remove second precursor 110 effluent from the substrate processing area after the formation of the second portion of the carbon-containing layer 114. The effluent can be removed by pumping it out of the substrate deposition area for a 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 purging gas may be introduced into the substrate processing area to aid in the removal of the effluent. Exemplary purging gases include argon, helium, and nitrogen, among other purging gases.

[0058] 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 from the second precursor 110 in the substrate processing region. Exemplary effluent pressures in the substrate processing region may range from about 1 millitor to about 20 tors. Other exemplary ranges include 5 tors to 15 tors, and 9 tors to 12 tors, among others.

[0059] Referring to Figure 2, in one or more embodiments of method 200, there is a determination / judgment point 214 indicating whether a target thickness of the deposited carbon-containing layer 114 on the metal surface 102 of the substrate has been reached after one or more cycles of forming the carbon-containing layer 114 (e.g., after forming the first and second portions of the compound layer). If the target thickness of the deposited carbon-containing layer 114 has not been reached, another cycle of forming the first and second portions of the carbon-containing layer 114 is performed. If the target thickness of the deposited carbon-containing layer 114 has been reached, another cycle of forming another carbon-containing layer 114 is not initiated. The exemplary number of cycles used to form the carbon-containing layer may include 1 to 2000 cycles. Additional exemplary ranges of the number of cycles may include 50 to 1000 cycles, and 100 to 750 cycles, among other exemplary ranges.

[0060] Therefore, 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 at least one additional carbon-containing layer form a carbon-containing layer 114 on the metal surface of the substrate.

[0061] In one or more embodiments, the selective carbon-containing layer 114 may 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 target thickness ranges for interrupting further cycles of compound layer formation include about 10 nm to about 500 nm. Additional exemplary thickness ranges may include about 50 nm to about 300 nm, and 100 nm to about 200 nm, among other exemplary thickness ranges.

[0062] In the embodiment shown in method 200 of Figure 2, the deposited carbon-containing layer 114 on the metal surface 102 of the substrate is post-treated at operation 216, as shown in Figure 1D. Optional post-treatment operation 216 may be, for example, a process for modifying film properties (e.g., annealing or plasma treatment) or a further film deposition process for growing additional films (e.g., additional ALD or CVD processes). In some embodiments, optional post-treatment operation 216 may be a process for modifying the properties of the deposited film. In some embodiments, optional post-treatment operation 216 includes annealing the carbon-containing layer 114. In some embodiments, annealing is performed at a temperature ranging from about 300°C, 400°C, 500°C, 600°C, 700°C, 800°C, 900°C, or 1000°C. The annealing environment in 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 amine (NH₃)) or an oxidizing agent (such as, but not limited to, oxygen (O₂), ozone (O₃) or peroxide). Annealing can be performed for any suitable duration. In some embodiments, the carbon-containing layer is annealed for a predetermined time ranging from about 15 seconds to about 90 minutes, or from about 1 minute to about 60 minutes. In some embodiments, annealing the deposited carbon-containing layer increases density, reduces resistivity, and / or increases the purity of the film.

[0063] In other embodiments, the carbon-containing layer 114 is subjected to a plasma treatment process at operation 216. The plasma may include one or more of hydrogen (H2), argon (Ar), amine (NH3), or oxygen (O2).

[0064] In some embodiments, the processing area is a modular system comprising multiple chambers that perform various functions, including substrate centering and orientation, degassing, annealing, deposition, and / or etching. According to one or more embodiments, the modular system includes at least a first processing chamber and a central transfer chamber. The central transfer chamber may house a robot that can move substrates between and among the processing chambers and loading gate chambers. The transfer chamber is typically maintained under vacuum and provides an intermediate stage for moving substrates from one chamber to another and / or to a loading gate chamber located at the front end of a cluster tool. Two well-known modular systems applicable to this disclosure are Centura® and Endura®, both available from Applied Materials, Inc., of Santa Clara, California. However, the exact arrangement and combination of the chambers can be varied for the purpose of performing specific steps of the processes described herein. Other processing chambers that can be used include, but are not limited to, cyclical layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etching, pre-cleaning, chemical cleaning, thermal treatments such as RTP, plasma nitriding, degassing, orientation, hydroxylation, and other substrate processes. By processing within the chambers of a modular system, contamination of the substrate surface by atmospheric impurities can be avoided without oxidation before subsequent film deposition.

[0065] According to one or more embodiments, the substrate remains under vacuum or "loading gate" conditions and is not exposed to ambient air as it moves from one chamber to the next. Therefore, the transfer chamber is under vacuum and is "evacuated" under 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 purify 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. Therefore, the inert gas flow forms a curtain at the chamber outlet.

[0066] Substrates can be processed in a single-substrate deposition chamber, where a single substrate is loaded, processed, and unloaded before another substrate is processed. Alternatively, substrates can be processed continuously, similar to a conveyor system, where multiple substrates are individually loaded into a first portion of a chamber, the chamber is moved, and unloaded from a second portion of the chamber. The shapes of the chambers and the associated conveyor system can form straight or curved paths. Furthermore, the processing chamber can be a rotating rack in which multiple substrates move around a central axis and are exposed to processes such as deposition, etching, annealing, and cleaning along the entire rotating rack path.

[0067] During processing, the substrate may be heated or cooled. Such heating or cooling can 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 conductively change the substrate temperature. In one or more embodiments, the gas used (reactive gas or inert gas) is heated or cooled to locally change the substrate temperature. In some embodiments, the heater / cooler is positioned in a chamber adjacent to the substrate surface to convectively change the substrate temperature.

[0068] The substrate can be stationary or rotating during processing. A rotating substrate can rotate continuously or in discontinuous steps (around the substrate axis). For example, the substrate can rotate throughout the entire process, or it can rotate slightly between exposures to different reactive or purge gases. Rotating the substrate (continuously or in stages) during processing can help produce more uniform deposition or etching by minimizing the effects of local variability, such as gas flow geometry.

[0069] In the spatial ALD process, reactive gases flow into different processing zones within a processing chamber. These different processing zones are separated from adjacent zones, preventing the reactive gases from mixing. The substrate can be moved between processing zones to expose it individually to the reactive gases. During substrate movement, different portions of the substrate surface or materials on the substrate surface are exposed to two or more reactive gases, ensuring that no given point on the substrate is substantially exposed to more than one reactive gas simultaneously. As those skilled in the art will understand, it is possible that a small portion of the substrate may be simultaneously exposed to multiple reactive gases due to gas diffusion within the processing chamber, and such simultaneous exposure is unintentional unless otherwise stated.

[0070] In another embodiment of the space ALD process, reactive gases are simultaneously delivered to the reaction zone, but separated by an inert gas curtain and / or a vacuum curtain. The gas curtain can be a combination of inert gas flowing into the processing chamber and vacuum feed flowing out of the processing chamber. The substrate moves relative to the gas delivery equipment such that any given point on the substrate is exposed to only one reactive gas.

[0071] As used herein, "pulse" or "dose" refers to the amount of source gas introduced into the processing chamber intermittently or discontinuously. Depending on the duration of the pulse, the amount of a particular compound within each pulse may vary over time. The customized process gas may contain a single compound or a mixture / combination of two or more compounds.

[0072] In some embodiments of the time-domain ALD process, exposure to each reactive gas system is separated by a time delay to allow each compound to adhere to and / or react on the substrate surface. These reactive gases include, but are not limited to, metals and dielectric materials used in the ALD film; and are subsequently purged from the processing chamber. Mixing of reactive gases is prevented by purging the processing chamber between subsequent exposures.

[0073] In another aspect of the time-domain ALD process in some embodiments, there is a time delay between the pulses of the reactive gas. During each time delay, a purge gas, such as argon, is introduced into the processing chamber to purge the reaction zone or otherwise remove any residual reactive gas, reaction products, or byproducts from the reaction zone. Alternatively, the purge gas can flow continuously throughout the deposition process, such that only the purge gas flows during the time delay between reactive gas pulses. The reactive gas is pulsed alternately with purge gas pulses between multiple pulses. Purge can also be achieved using a vacuum pump with or without an inert gas.

[0074] The duration of each pulse / dose is variable and can be adjusted to suit, for example, the volumetric capacity of the processing chamber and the capabilities of the vacuum system coupled thereto. Furthermore, 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 processing chamber employed, and the ability of the process gas components to adsorb onto the substrate. The dosage time can also be varied based on the type of layer being formed and the geometry of the element being formed. The dosage time should be long enough to provide sufficient compound volume to adsorb / chemisorb onto substantially the entire surface of the substrate and form a layer of process gas components thereon.

[0075] Once the carbon-containing layer is deposited, the method may, as appropriate, include further processing (e.g., bulk deposition of the dielectric film). In some embodiments, the further processing may be an ALD process. This disclosure provides that the process can generally be stored in memory as a software routine, which, when executed by a processor, causes a processing chamber to perform the process of this disclosure. The software routine can also be stored and / or executed by a second processor (not shown) located remotely from hardware controlled by the processor. Some or all of the methods in this disclosure can also be executed in hardware. Thus, the process can be implemented in software and executed in hardware using a computer system as, for example, application-specific integrated circuits or other types of hardware implementation, or as a combination of software and hardware. When executed by a processor, the software routine transforms a general-purpose computer into a dedicated computer (controller) that controls the operation of the chamber, causing the process to be executed. The process can be stored on a non-transitory computer-readable medium containing 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 through a substrate including a metal surface and a non-metal surface to form a first portion of an initial carbon-containing film on the metal surface, the first precursor containing a first reactive group; removing the first precursor effluent containing the first precursor from the substrate; flowing a second precursor containing a second reactive group through the substrate to react with the first reactive group to form a second portion of the initial carbon-containing film on the metal surface; removing the second precursor effluent containing the second precursor from the substrate; and annealing the initial carbon-containing film to form an annealed carbon-containing layer on the metal surface of the substrate, but not on the non-metal surface.

[0076] Throughout this specification, references to "one embodiment," "some embodiments," "one or more embodiments," or "an embodiment" mean that a particular feature, structure, material, or characteristic described in connection with that embodiment is included in at least one embodiment of this disclosure. Therefore, the appearance of terms such as "in one or more embodiments," "in some embodiments," "in one embodiment," or "in one embodiment" throughout this specification does not necessarily refer to the same embodiment of this disclosure. Furthermore, in one or more embodiments, a particular feature, structure, material, or characteristic may be combined in any suitable manner.

[0077] Although this disclosure has been described with reference to specific embodiments, it should be understood that these embodiments are merely illustrative of the principles and applications of this disclosure. It will be apparent to those skilled in the art that various modifications and variations can be made to the methods and apparatus of this disclosure without departing from the spirit and scope of this disclosure. Therefore, this disclosure is intended to include modifications and variations within the scope of the appended claims and their equivalents.

[0078] 102: Metal surface 104: Non-metallic surface 106: First Precursor 108: Part One 110: Second front-wheel drive 112: Part Two 114: Carbonaceous layer 200: Method 202: Operation 204: Operation 206: Operation 208: Operation 210: Operation 212: Operation 214: Operation 216: Operation

[0079] Domestic storage information (please note in order of storage institution, date, and number) none Overseas storage information (please note in the order of storage country, institution, date, and number) none

Claims

1. A method for selectively depositing a film, the method comprising the steps of: passing a first precursor through a substrate including a metal surface and a non-metal surface to form a first portion of a carbon-containing layer on the metal surface, the first precursor comprising a first reactive group; removing a first precursor effluent comprising the first precursor from the substrate; passing a second precursor comprising a second reactive group through the substrate to react with the first reactive group to form the carbon-containing layer on the metal surface of the substrate but not on the non-metal surface; and removing a second precursor effluent comprising the second precursor from the substrate, wherein the first precursor and the second precursor are independently selected from one or more of phenylenediamine, hexamethylenediamine, terephthalic acid chloride, 1,3,5-benzenetrichlorochloride, benzene-1,3,5-tricarboxaldehyde, 1,4-epenylphenyl diisocyanate, 4,4'-oxodiphenylamine, and tris(2-aminoethyl)amine.

2. The method as described in claim 1 further includes the step of: pretreating the metal surface to form a metal oxide surface on the metal surface.

3. The method as described in claim 1, further comprising the step of: depositing at least one additional carbon-containing layer on the carbon-containing layer, wherein the carbon-containing layer and the at least one additional carbon-containing layer form the carbon-containing layer on the metal surface of the substrate.

4. The method as described in claim 1, wherein the step of removing the first precursor includes the following steps: passing a purge gas through the substrate; and removing a mixture of the first precursor effluent and the purge gas from the substrate.

5. The method as described in claim 4, wherein the purifying gas is selected from argon (Ar), helium (He) and nitrogen (N2).

6. The method as described in claim 1, further comprising the step of annealing the carbon-containing layer at a temperature in the range of 100°C to 600°C.

7. The method as described in claim 1, further comprising the step of exposing the carbon-containing layer to a plasma treatment.

8. A method for selectively depositing a film, the method comprising the steps of: passing a first precursor through a substrate comprising a metal surface and a non-metal surface, the first precursor being selected from phenylenediamine, hexamethylenediamine, terephthalic acid chloride, 1,3,5-benztrichlorophenyl, benzene-1,3,5-tricarboxaldehyde, 1,4-epenylphenyl diisocyanate, 4,4'-oxodiphenylamine, tris(2-aminoethyl)amine, or one or more of a general formula R1-(X)n, wherein R1 comprises one or more of aryl or aromatic groups and cycloalkyl groups, Xn comprises one or more of aldehyde, ketone, acid, amino, isocyanate, thiocyanate, and chlorohydrin groups, and n is an integer in the range of 1 to 6, wherein the first precursor reacts with a reactive group on the metal surface to form a first portion of a carbon-containing layer on the metal surface; and removing a first precursor effluent comprising the first precursor from the substrate; A second precursor is passed through the substrate, the second precursor being selected from one or more of phenylenediamine, hexamethylenediamine, terephthalic acid chloride, 1,3,5-benztrichlorophenyl, benzene-1,3,5-tricarboxaldehyde, 1,4-epenylphenyl diisocyanate, 4,4'-oxodiphenylamine, tris(2-aminoethyl)amine, or a general formula R2-(Y)n, wherein R2 includes one or more of aryl or aromatic groups and cycloalkyl groups, Yn includes one or more of aldehyde, ketone, acid, amino, isocyanate, thiocyanate, and chlorohydrin groups, and n is an integer in the range of 1 to 6, wherein the second precursor reacts with the first portion to form a carbon-containing layer; and a second precursor effluent containing the second precursor is removed from the substrate.

9. The method as described in claim 8 further includes the step of: pretreating the metal surface to form a metal oxide surface on the metal surface.

10. The method as described in claim 8, further comprising the step of: depositing at least one additional carbon-containing layer on the carbon-containing layer, wherein the carbon-containing layer and the at least one additional carbon-containing layer form the carbon-containing layer on the metal surface of the substrate.

11. The method as described in claim 8, wherein the step of removing the first precursor includes the following steps: passing a purifying gas through the substrate; and removing a mixture of the first precursor effluent and the purifying gas from the substrate.

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

13. The method as described in claim 8 further includes the step of annealing the carbon-containing layer at a temperature ranging from 100°C to 600°C.

14. The method as described in claim 8 further includes the step of exposing the carbon-containing layer to a plasma treatment.

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