Protective cap layer for region-selective deposition

Abstract

A method for forming a protective cap layer on a metal layer of a semiconductor substrate is described. The metal layer is deposited using pulses of a metal precursor and reactants to form a metal layer having a reactive surface. The number of cycles can be in the range of 1 to 10 cycles, or 2 to 5 cycles, or 2 to 100 cycles. Next, the metal layer is exposed to a long-chain precursor (e.g., primary amine, alcohol, thiol, phosphine, selenol) and the metal precursor to form a protective cap layer on the metal layer. The number of cycles can be in the range of 1 to 10 cycles, or 2 to 5 cycles, depending on the desired thickness of the protective cap layer.

Description

Technical Field

[0001] Embodiments of the present disclosure relate to a method of forming a protective cap layer on a metal layer so as to be able to perform area-selective deposition (ASD). In particular, embodiments of the present disclosure are directed to a method of depositing a protective cap layer at the end of atomic layer deposition (ALD) of a film that it protects.

Background Art

[0002] The semiconductor processing industry continues to strive for higher production yields while enhancing the uniformity of layers deposited on substrates having larger surface areas. The combination of these same elements with new materials also results in an increase in the integration density of circuits per unit area of the substrate. As the integration density of circuits increases, the need for uniformity and process control with respect to the layer thickness also increases. As a result, various techniques have been developed for depositing layers on substrates in a cost-effective manner while maintaining control over the characteristics of the layers.

[0003] The semiconductor industry faces many challenges in pursuing device miniaturization, including the introduction of complex manufacturing processes such as multiple lithography steps and the integration of high-performance materials. Traditional spacer manufacturing processes include conformal film deposition on 3D structures (e.g., fins, mandrels, etc.) followed by directional plasma dry etching to remove the upper and lower layers while retaining the sidewall film as a spacer. However, it has been found that the dry etching process can gradually damage the sidewall surface and change the film characteristics, ultimately affecting the performance and yield of the device.

[0004] To maintain the pace of device miniaturization, selective deposition is promising because it can reduce costly lithography steps by simplifying the integration scheme.

[0005] Selective deposition of materials can be carried out in various ways. A chemical precursor can react with one surface selectively to another (metal or dielectric). The chemical reaction rate of a particular surface reaction can be adjusted by adjusting process parameters such as pressure, substrate temperature, precursor partial pressure, and / or gas flow rate. Another possible scheme involves surface pretreatment, which can be used to activate or deactivate the target surface for incoming film deposition precursors.

[0006] Region-selective atomic layer deposition (AS-ALD) can be used for the selective deposition of materials. In AS-ALD, SAM deposition on nitrides, oxides, and silicon compounds requires the development of molecules that selectively bond to the surface of the formed layer and have high surface coverage. Often, this requires surface cleaning or pretreatment. Selectivity is often difficult when more film is exposed. Therefore, there is a continuous need in the art to improve deposition selectivity and avoid the problems encountered in AS-ALD. [Overview of the project]

[0007] One or more embodiments of the present disclosure relate to methods for forming semiconductor films. In one or more embodiments, the method includes forming a metal layer on a substrate surface by exposing the substrate surface to a metal precursor and reactants, wherein the metal layer has a reactive surface; and forming a protective cap layer on the metal layer by exposing the metal layer to a metal precursor and a second precursor, wherein the second precursor comprises a functional group and a carbon chain having 2 to 20 carbon atoms, and the functional group is selected from the group consisting of primary amines, thiols, phosphines, alcohols, and selenols.

[0008] Additional embodiments of the present disclosure relate to methods for forming semiconductor films. In one or more embodiments, the method includes carrying out a first process cycle comprising exposing a substrate surface to a metal precursor and reactants to form a metal layer on the substrate surface, wherein the metal layer has a reactive surface; and carrying out a second process cycle comprising exposing the metal layer to a metal precursor and a second precursor to form a protective cap layer on the metal layer, wherein the second precursor comprises a carbon chain having 2 to 20 carbon atoms and a functional group, wherein the functional group is selected from the group consisting of primary amines, thiols, phosphines, alcohols, and selenols.

[0009] A more detailed description of the Disclosure, which is briefly summarized above, can be obtained by referring to embodiments, some of which are shown in the accompanying drawings, so that the above features of the Disclosure can be understood in more detail. However, it should be noted that the accompanying drawings show only typical embodiments of the Disclosure and should not be considered to limit its scope, as the Disclosure may also permit other equally valid embodiments. The embodiments described herein are shown as examples and are not limited to the drawings in the accompanying drawings, where similar references show similar elements. [Brief explanation of the drawing]

[0010] [Figure 1] A process flow diagram of the method according to one or more embodiments is shown. [Figure 2] A cross-sectional view of a substrate processed according to one or more embodiments is shown. [Modes for carrying out the invention]

[0011] Before describing some exemplary embodiments of the present invention, it should be understood that the present invention is not limited to the structural or process details described below. Other embodiments of the present invention are possible and can be implemented or performed in a variety of ways.

[0012] As used herein, the term "approximately" means roughly or nearly, and in the context of the given numbers or ranges, it means a variation of ±15% or less of the number. For example, values ​​that differ by ±14%, ±10%, ±5%, ±2%, or ±1% would satisfy the definition of approximately.

[0013] As used herein and in the appended claims, the terms “substrate” or “wafer” refer to the surface or portion of a surface on which the processing is performed. It will also be understood by those skilled in the art that a reference to a substrate may refer to only a portion of the substrate unless otherwise explicitly stated in the context. Furthermore, a reference to deposition on a substrate may mean both a bare substrate and a substrate on which one or more films or features are deposited or formed.

[0014] As used herein, “substrate” or “substrate surface” means any portion of a substrate or a portion of a material surface formed on a substrate on which a film treatment is performed. For example, substrate surfaces on which treatment can be performed include, depending on the application, materials such as silicon, silicon oxide, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire, and any other material. Substrates include, but are not limited to, semiconductor wafers. Substrates may be subjected to pretreatment processes for polishing, etching, reduction, oxidation, hydroxylation, annealing, UV curing, electron beam curing, and / or baking of the substrate surface. In addition to film treatment directly on the surface of the substrate itself, any film treatment process disclosed herein may also be performed on underlying layers formed on the substrate, as disclosed in more detail below, and the term “substrate surface” is intended to include such underlying layers, as the context indicates. Thus, for example, if a film / layer or partial film / layer is deposited on the substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate surface. The substrate can have various dimensions, such as a wafer with a diameter of 200 mm or 300 mm, and rectangular or square panes. In some embodiments, the substrate includes a rigid discrete material.

[0015] The term "on" indicates that there is direct contact between elements. The term "directly on" indicates that there is direct contact between elements without an intervening element.

[0016] According to one or more embodiments, the method involves forming a metal layer on a substrate surface using an atomic layer deposition (ALD) process, followed by forming a protective cap layer on the metal layer. In such embodiments, the substrate surface is continuously or substantially continuously exposed to the precursor (or reactive gas). As used throughout this specification, “substantially continuous” means that, although there may be some overlap, the majority of the precursor exposure period does not overlap with exposure to the co-reagent.

[0017] As used herein and in the appended claims, terms such as “reactive compound,” “reactive gas,” “reactive species,” “precursor,” and “process gas” are interchangeable to mean a substance having a nuclide capable of reacting with a substrate or material on a substrate in a surface reaction (e.g., chemiadsorption, oxidation, reduction, cycloaddition). The substrate or a portion of the substrate is sequentially exposed to two or more reactive compounds introduced into the reaction zone of a processing chamber.

[0018] As used herein, “atomic layer deposition” or “periodic deposition” refers to the deposition of a layer of material on a substrate surface by successive exposure to two or more reactive compounds. As used herein and in the appended claims, terms such as “reactive compound,” “reactive gas,” “reactive species,” “precursor,” and “process gas” are used interchangeably to mean a substance having a nuclide that can react with the substrate surface or the material on the substrate surface in a surface reaction (e.g., chemiadsorption, oxidation, reduction). The substrate or a portion of the substrate is successively exposed to two or more reactive compounds introduced into the reaction zone of a processing chamber. In a time-domain ALD process, exposure to each reactive compound is separated by a time delay, allowing each compound to adhere to and / or react with the substrate surface. In a spatial ALD process, different portions of the substrate surface or the material on the substrate surface are simultaneously exposed to two or more reactive compounds such that no given point on the substrate is substantially exposed to more than one reactive compound at the same time. As used herein and in the appended claims, the term “substantially” in this regard means, as will be understood by those skilled in the art, that a small portion of the substrate may be simultaneously exposed to multiple reactive gases by diffusion, but simultaneous exposure is not intended.

[0019] In one embodiment of a time-domain ALD process, a first reactive gas (i.e., a first precursor or compound A) is pulsed into the reaction zone, followed by a first time delay. Next, a second precursor or compound B is pulsed into the reaction zone, followed by a second delay. 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 compounds or by-products from the reaction zone. Alternatively, the purge gas may be continuously flowed throughout the entire deposition process so that only the purge gas flows during the time delays between pulses of the reactive compound. Alternatively, the reactive compound is pulsed until the desired film or thickness is formed on the substrate surface. In either scenario, one cycle consists of compound A, the purge gas, compound B, and the ALD process of pulsed purge gas. A cycle can be started with either compound A or compound B, and each sequence of cycles can be continued until a film of the desired thickness is achieved. In some embodiments, there may be two reactants A and B that are pulsed and purged alternately. In other embodiments, there may be three or more reactants A, B, and C that are pulsed and purged alternately.

[0020] In an embodiment of the spatial ALD process, a first reactive gas and a second reactive gas (e.g., hydrogen radicals) are simultaneously supplied to the reaction zone but separated by an inert gas curtain and / or a vacuum curtain. The substrate is moved relative to the gas supply device so that any given point on the substrate is exposed to the first and second reactive gases.

[0021] In one or more embodiments, a strong protective film for region-selective deposition (ASD) is formed, which is deposited in the final stage of atomic layer deposition (ALD) of the layer intended for protection. In the last 1 to 5 cycles of the ALD process, a suitable precursor, such as a long-chain amine or alcohol, is used instead of NH3 or H2O. This yields a protective layer, such as a SAM, which is strongly bonded to the surface and has high coverage.

[0022] In one or more embodiments, by utilizing the reactivity of the ALD precursor, a protective layer, i.e., a protective cap layer, such as a strongly bonded SAM, is deposited at the end of the ALD of the film to be protected. Since this film needs to be removed under more severe conditions than a normal SAM, the protective film can withstand a wider range of process conditions and can be used in combination with other processes using SAMs.

[0023] In one or more embodiments, pulses of a metal precursor and a reactant are used to deposit a metal layer and form a metal layer having a reactive surface. The number of cycles is ideally one cycle, but can range from 1 to 10 cycles, or 2 to 5 cycles, or 2 to 100 cycles. In one or more embodiments, next, the metal layer is exposed to a long-chain precursor (e.g., primary amine, alcohol, thiol, phosphine, selenol) and the metal precursor to form a protective cap layer on the metal layer. Again, the number of cycles is ideally one cycle, but can range from 1 to 10 cycles, or 2 to 5 cycles, depending on the desired thickness of the protective cap layer.

[0024] Embodiments of the present disclosure are illustrated by drawings showing devices (e.g., transistors) and processes for forming semiconductor structures according to one or more embodiments of the present disclosure. The processes shown are merely exemplary possible uses of the disclosed processes, and those skilled in the art will recognize that the disclosed processes are not limited to the illustrated uses.

[0025] FIG. 1 shows a process flow diagram of method 10 according to one or more embodiments. FIG. 2 shows a cross-sectional view of a semiconductor substrate 100 being processed by the method of one or more embodiments. Referring to FIGS. 1 and 2, in one or more embodiments, in operation 12, a substrate 102 is provided. As used herein and in the appended claims, the term "provided" means that the substrate 102 becomes available for processing (e.g., is positioned within a processing chamber).

[0026] Referring to FIG. 2, in one or more embodiments, the substrate 102 can be any suitable material known to those skilled in the art. As used herein and in the appended claims, the term "substrate" refers to the surface or a portion of the surface on which processing is performed. It will also be understood by those skilled in the art that a reference to a substrate may, in the context, refer only to a portion of the substrate, as well as possibly to the entire substrate, unless otherwise explicitly stated. Further, a reference to deposition on a substrate can mean both a bare substrate and a substrate on which one or more films or features have been deposited or formed thereon.

[0027] As used herein, "substrate" refers to any substrate or the surface of a material formed on the substrate on which film processing is performed during the manufacturing process. For example, the substrate surface on which processing can be performed can include materials such as silicon, silicon oxide, strained silicon, silicon on insulator (SOI), carbon-doped silicon oxide, amorphous silicon, doped silicon, germanium, gallium arsenide, glass, sapphire, etc., depending on the application, as well as 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 polish, etch, reduce, oxidize, hydroxylate, anneal, and / or bake the substrate surface. In addition to directly performing film processing on the surface of the substrate itself, in the present disclosure, any of the disclosed film processing steps can also be performed on an underlying layer formed on the substrate, as will be disclosed in more detail below, and the term "substrate surface" is intended to include such underlying layers as the context indicates. Thus, for example, when a film / layer or a partial film / layer is deposited on the substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate surface.

[0028] Referring to Figures 1 and 2, in operation 14, the substrate 102 is exposed to the metal precursor and reactants to form a metal layer 104 on the substrate surface. The metal layer 104 has a reactive surface 106. The metal layer 104 can be any suitable material known to those skilled in the art. In one or more embodiments, the metal layer 104 is one or more of metal nitrides, metal oxides, metal sulfides, metal phosphides, and metal selenides.

[0029] In one or more embodiments, the reactants used to form the metal layer 104 may be any suitable reactants known to those skilled in the art. In one or more embodiments, the reactants include one or more of ammonia (NH3), water (H2O), hydrogen sulfide (H2S), phosphine (PH3), ozone (O3), hydrogen peroxide (H2O2), nitrous oxide (N2O), and hydrogen selenide (H2Se).

[0030] In one or more embodiments, the metal precursor that reacts with the reactants to form the metal layer 104 comprises a metal and a reactive species. In one or more embodiments, the reactive species is any suitable reactive species. In some embodiments, the reactive species is selected from the group consisting of halides, alkyls, arenes, cyclopentadienyls, alkynes, dienes, diketonates, amides, imides, alkoxos, oxos, carbonyls, amidinates, guanidinates, and formamidinates.

[0031] In one or more embodiments, the metal of the metal precursor can be any suitable transition metal. In one or more embodiments, the metal of the metal precursor is selected from one or more of the following: titanium (Ti), silicon (Si), molybdenum (Mo), hafnium (Hf), zirconium (Zr), aluminum (Al), antimony (Sb), boron (B), gallium (Ga), germanium (Ge), indium (In), niobium (Nb), rhenium (Re), tantalum (Ta), tin (Sn), tungsten (W), and zinc (Zn).

[0032] In one or more embodiments, the metal precursor used to form the metal layer 104 may be any suitable metal precursor known to those skilled in the art. The metal precursor may be any inorganic or organometallic precursor. The methods of one or more embodiments are generally applicable to most binary and / or ternary metal films.

[0033] In one or more embodiments, the metal precursor used to form the metal layer 104 may be any suitable metal precursor known to those skilled in the art. In one or more embodiments, the metal precursor may be aluminum chloride, aluminum bromide, aluminum iodide, boron trichloride, boron tribromide, gallium trichloride, germanium tetrachloride, antimony trichloride, antimony pentachloride, indium trichloride, silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, hexachlorodisilane, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, zirconium tetrachloride, hafnium tetrachloride, niobium pentachloride, niobium pentabromide, tantalum pentachloride, tantalum pentabromide, molybdenum pentachloride, or tungsten hexachloride. It contains one or more of the following: rhenium pentachloride, zinc chloride, tin chloride, trimethylaluminum, tetrakis(dimethylamide)titanium, tetrakis(dimethylamide)zirconium, tetrakis(dimethylamide)hafnium, (t-butylimide)tris(diethylamino)niobium, (t-butylimide)tris(diethylamino)tantalum, pentakis(dimethylamide)tantalum, bis(ethylbenzene)molybdenum, hexacarbonylmolybdenum, hexacarbonyltungsten, and diethylzinc.

[0034] Referring to Figures 1 and 2, in operation 16, the metal layer 104 having the reactive surface 106 is exposed to the metal precursor and the second precursor to form a protective cap layer 108. The protective cap layer 108 may have any suitable thickness. In one or more embodiments, the protective cap layer 108 has a thickness in the range of 0.5 nm to 5 nm.

[0035] The second precursor may be any suitable precursor known to those skilled in the art. In one or more embodiments, the second precursor comprises a functional group and a carbon chain having 2 to 20 carbon atoms. In one or more embodiments, the functional group is selected from the group consisting of primary amines, thiols, phosphines, alcohols, and selenols.

[0036] In one or more embodiments, the second precursor is It contains one or more compounds selected from TIFF2026511625000002.tif31170, Here, n is an integer in the range of 1 to 20.

[0037] In one or more embodiments, the second precursor reacts with the metal precursor to form a protective cap layer 108 on the metal layer 104. In one or more embodiments, the metal precursor may be the same metal precursor used to form the metal layer 104. In other embodiments, the metal precursor used to form the protective cap layer 108 is different from the metal precursor used to form the metal layer 104.

[0038] In one or more embodiments, the metal of the metal precursor can be any suitable transition metal. In one or more embodiments, the metal of the metal precursor is selected from one or more of the following: titanium (Ti), silicon (Si), molybdenum (Mo), hafnium (Hf), zirconium (Zr), aluminum (Al), antimony (Sb), boron (B), gallium (Ga), germanium (Ge), indium (In), niobium (Nb), rhenium (Re), tantalum (Ta), tin (Sn), tungsten (W), and zinc (Zn).

[0039] In one or more embodiments, the metal precursor that reacts with the second precursor to form the protective cap layer 108 can be any suitable metal precursor known to those skilled in the art. The metal precursor can be any inorganic or organometallic precursor. The methods of one or more embodiments are generally applicable to most binary and / or ternary metal films.

[0040] In one or more embodiments, the metal precursor used to form the protective cap layer 108 may be any suitable metal precursor known to those skilled in the art. In one or more embodiments, the metal precursor may be aluminum chloride, aluminum bromide, aluminum iodide, boron trichloride, boron tribromide, gallium trichloride, germanium tetrachloride, antimony trichloride, antimony pentachloride, indium trichloride, silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, hexachlorodisilane, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, zirconium tetrachloride, hafnium tetrachloride, niobium pentachloride, niobium pentabromide, tantalum pentachloride, tantalum pentabromide, molybdenum pentachloride, or tungsten hexachloride. It contains one or more of the following: rhenium pentachloride, zinc chloride, tin chloride, trimethylaluminum, tetrakis(dimethylamide)titanium, tetrakis(dimethylamide)zirconium, tetrakis(dimethylamide)hafnium, (t-butylimide)tris(diethylamino)niobium, (t-butylimide)tris(diethylamino)tantalum, pentakis(dimethylamide)tantalum, bis(ethylbenzene)molybdenum, hexacarbonylmolybdenum, hexacarbonyltungsten, and diethylzinc.

[0041] In other embodiments, the method for forming the semiconductor film includes performing a first process cycle and a second process cycle to form a protective cap layer 108 on a metal layer 104 on a substrate. The metal layer 104 may be any suitable material known to those skilled in the art. In one or more embodiments, the metal layer 104 is one or more of metal nitrides, metal oxides, metal sulfides, metal sulfides, metal sulfides, and metal selenides.

[0042] In one or more embodiments, during a first process cycle, the substrate 102 is exposed to a metal precursor and reactants to form a metal layer 104 on the substrate surface. The metal layer 104 has a reactive surface 106. In one or more embodiments, the metal layer 104 comprises one or more of the following: metal nitrides, metal oxides, metal sulfides, metal phosphides, and metal selenides.

[0043] In one or more embodiments, the reactants used to form the metal layer 104 may be any suitable reactants known to those skilled in the art. In one or more embodiments, the reactants include one or more of ammonia (NH3), water (H2O), hydrogen sulfide (H2S), phosphine (PH3), ozone (O3), hydrogen peroxide (H2O2), nitrous oxide (N2O), and hydrogen selenide (H2Se).

[0044] In one or more embodiments, the metal precursor that reacts with the reactants to form the metal layer 104 comprises a metal and a reactive species. In one or more embodiments, the reactive species is any suitable reactive species. In some embodiments, the reactive species is selected from the group consisting of halides, alkyls, arenes, cyclopentadienyls, alkynes, dienes, diketonates, amides, imides, alkoxos, oxos, carbonyls, amidinates, guanidinates, and formamidinates.

[0045] In one or more embodiments, the metal of the metal precursor can be any suitable transition metal. In one or more embodiments, the metal of the metal precursor is selected from one or more of the following: titanium (Ti), silicon (Si), molybdenum (Mo), hafnium (Hf), zirconium (Zr), aluminum (Al), antimony (Sb), boron (B), gallium (Ga), germanium (Ge), indium (In), niobium (Nb), rhenium (Re), tantalum (Ta), tin (Sn), tungsten (W), and zinc (Zn).

[0046] The metal precursor used to form the metal layer 104 can be any suitable metal precursor known to those skilled in the art. The metal precursor can be any inorganic or organometallic precursor. The methods of one or more embodiments are generally applicable to most binary and / or ternary metal films.

[0047] In one or more embodiments, the metal precursor used to form the metal layer 104 may be any suitable metal precursor known to those skilled in the art. In one or more embodiments, the metal precursor may be aluminum chloride, aluminum bromide, aluminum iodide, boron trichloride, boron tribromide, gallium trichloride, germanium tetrachloride, antimony trichloride, antimony pentachloride, indium trichloride, silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, hexachlorodisilane, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, zirconium tetrachloride, hafnium tetrachloride, niobium pentachloride, niobium pentabromide, tantalum pentachloride, tantalum pentabromide, molybdenum pentachloride, or tungsten hexachloride. It contains one or more of the following: rhenium pentachloride, zinc chloride, tin chloride, trimethylaluminum, tetrakis(dimethylamide)titanium, tetrakis(dimethylamide)zirconium, tetrakis(dimethylamide)hafnium, (t-butylimide)tris(diethylamino)niobium, (t-butylimide)tris(diethylamino)tantalum, pentakis(dimethylamide)tantalum, bis(ethylbenzene)molybdenum, hexacarbonylmolybdenum, hexacarbonyltungsten, and diethylzinc.

[0048] The first process cycle can be repeated any number of times, depending on the desired thickness of the metal layer 104. In one or more embodiments, the first process cycle is repeated 2 to 200 times, or 2 to 100 times, or 2 to 50 times.

[0049] In one or more embodiments, during a second process cycle, the metal layer 104 having a reactive surface 106 is exposed to a metal precursor and a second precursor to form a protective cap layer 108 on the metal layer 104. The protective cap layer 108 may have any suitable thickness. In one or more embodiments, the protective cap layer 108 has a thickness in the range of 0.5 nm to 5 nm.

[0050] The second precursor may be any suitable precursor known to those skilled in the art. In one or more embodiments, the second precursor comprises a functional group and a carbon chain having 2 to 20 carbon atoms. In one or more embodiments, the functional group is selected from the group consisting of primary amines, thiols, phosphines, alcohols, and selenols.

[0051] In one or more embodiments, the second precursor is It contains one or more compounds selected from TIFF2026511625000003.tif31170, Here, n is an integer in the range of 1 to 20.

[0052] In one or more embodiments, the second precursor reacts with any suitable metal precursor known to those skilled in the art. In one or more embodiments, the metal precursor may be the same metal precursor used to form the metal layer 104. In other embodiments, the metal precursor used to form the protective cap layer 108 is different from the metal precursor used to form the metal layer 104.

[0053] In one or more embodiments, the metal of the metal precursor can be any suitable transition metal. In one or more embodiments, the metal of the metal precursor is selected from one or more of the following: titanium (Ti), silicon (Si), molybdenum (Mo), hafnium (Hf), zirconium (Zr), aluminum (Al), antimony (Sb), boron (B), gallium (Ga), germanium (Ge), indium (In), niobium (Nb), rhenium (Re), tantalum (Ta), tin (Sn), tungsten (W), and zinc (Zn).

[0054] In one or more embodiments, the metal precursor that reacts with the second precursor to form the protective cap layer 108 can be any suitable metal precursor known to those skilled in the art. The metal precursor can be any inorganic or organometallic precursor. The methods of one or more embodiments are generally applicable to most binary and / or ternary metal films.

[0055] In one or more embodiments, the metal precursor used to form the protective cap layer 108 may be any suitable metal precursor known to those skilled in the art. In one or more embodiments, the metal precursor may be aluminum chloride, aluminum bromide, aluminum iodide, boron trichloride, boron tribromide, gallium trichloride, germanium tetrachloride, antimony trichloride, antimony pentachloride, indium trichloride, silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, hexachlorodisilane, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, zirconium tetrachloride, hafnium tetrachloride, niobium pentachloride, niobium pentabromide, tantalum pentachloride, tantalum pentabromide, molybdenum pentachloride, or tungsten hexachloride. It contains one or more of the following: rhenium pentachloride, zinc chloride, tin chloride, trimethylaluminum, tetrakis(dimethylamide)titanium, tetrakis(dimethylamide)zirconium, tetrakis(dimethylamide)hafnium, (t-butylimide)tris(diethylamino)niobium, (t-butylimide)tris(diethylamino)tantalum, pentakis(dimethylamide)tantalum, bis(ethylbenzene)molybdenum, hexacarbonylmolybdenum, hexacarbonyltungsten, and diethylzinc.

[0056] The second process cycle can be repeated any number of times, depending on the desired thickness of the protective cap layer 108. In one or more embodiments, the second process cycle is repeated 2 to 20 times, or 2 to 10 times, or 2 to 5 times.

[0057] The terms “a,” “an,” and “the,” and similar references in the context describing the materials and methods discussed herein (in particular, in the context of the following claims), should be interpreted as encompassing both singular and plural forms unless otherwise stated herein or unless clearly contradicted by the context. The enumeration of value ranges herein is intended merely as a simple way to refer individually to each individual value falling within the range, unless otherwise stated herein, and each individual value is incorporated herein as if it were individually stated herein. All methods described herein may be carried out in any suitable order unless otherwise stated herein or unless clearly contradicted by the context. Any and all examples or illustrative language provided herein (e.g., “etc.”) are intended merely to further clarify the materials and methods and do not impose limitations on the claims unless specifically stated otherwise. Nothing in the specification should be interpreted as indicating that non-claimed elements are essential to the carrying out of the disclosed materials and methods.

[0058] Throughout this specification, any reference to “one embodiment,” “a particular embodiment,” “one or more embodiments,” or “embodiments” means that any particular feature, structure, material, or property described in relation to an embodiment is included in at least one embodiment of this disclosure. Therefore, any other expression such as “in one or more embodiments,” “in one embodiment,” “in one embodiment,” or “in an embodiment” found elsewhere in this specification does not necessarily refer to the same embodiment of this disclosure. Furthermore, any particular feature, structure, material, or property may be combined in any suitable manner in one or more embodiments.

[0059] While the disclosures herein are described with reference to specific embodiments, these embodiments should be understood as merely illustrative examples of the principles and applications of the disclosure. It will be apparent to those skilled in the art that various modifications and variations can be made to the methods and apparatus of the disclosure without departing from the spirit and scope of the disclosure. Accordingly, the disclosure is intended to include modifications and variations that fall within the scope of the appended claims and their equivalents.

Claims

1. A method for forming a semiconductor film, Forming a metal layer on the substrate surface by exposing the substrate surface to a metal precursor and reactants, wherein the metal layer has a reactive surface, and A protective cap layer is formed on the metal layer by exposing the metal layer to a second metal precursor and a second precursor, wherein the second precursor comprises a functional group and a carbon chain having 2 to 20 carbon atoms, and the functional group is selected from the group consisting of primary amines, thiols, phosphines, alcohols, and selenols. Methods that include...

2. where the reactant is ammonia (NH ３ ), water (H ２ O), hydrogen sulfide (H ２ S), phosphine (PH ３ ), ozone (O ３ ), hydrogen peroxide (H ２ O ２ ), nitrous oxide (N ２ O), and hydrogen selenide (H ２ Se), the method according to claim 1.

3. The method according to claim 1, wherein the metal precursor and the second metal precursor independently comprise a metal and a reactive species.

4. The method according to claim 3, wherein the metal is a transition metal.

5. The method according to claim 4, wherein the metal is selected from one or more of the following: titanium (Ti), silicon (Si), molybdenum (Mo), hafnium (Hf), zirconium (Zr), aluminum (Al), antimony (Sb), boron (B), gallium (Ga), germanium (Ge), indium (In), niobium (Nb), rhenium (Re), tantalum (Ta), tin (Sn), tungsten (W), and zinc (Zn).

6. The method according to claim 3, wherein the reactive species is selected from the group consisting of halides, alkyls, arenes, cyclopentadienyls, alkynes, dienes, diketnates, amides, imides, alkoxos, oxos, carbonyls, amidinates, guanidinates, and formamidinates.

7. The aforementioned metal precursor and the second metal precursor are independently aluminum chloride, aluminum bromide, aluminum iodide, boron trichloride, boron tribromide, gallium trichloride, germanium tetrachloride, antimony trichloride, antimony pentachloride, indium trichloride, silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, hexachlorodisilane, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, zirconium tetrachloride, hafnium tetrachloride, niobium pentachloride, niobium pentabromide, tantalum pentachloride, tantalum pentabromide, molybdenum pentachloride, tungsten hexachloride, and 5 The method according to claim 2, comprising one or more of rhenium chloride, zinc chloride, tin chloride, trimethylaluminum, tetrakis(dimethylamide)titanium, tetrakis(dimethylamide)zirconium, tetrakis(dimethylamide)hafnium, (t-butylimide)tris(diethylamino)niobium, (t-butylimide)tris(diethylamino)tantalum, pentakis(dimethylamide)tantalum, bis(ethylbenzene)molybdenum, hexacarbonylmolybdenum, hexacarbonyltungsten, and diethylzinc.

8. The method according to claim 1, wherein the metal layer comprises one or more of metal nitrides, metal oxides, metal sulfides, metal phosphides, and metal selenides.

9. The method according to claim 1, wherein the protective cap layer has a thickness in the range of 0.5 nm to 5 nm.

10. The second precursor described above is It contains one or more compounds selected from the following: Here, n is an integer in the range of 1 to 20. The method according to claim 1.

11. A method for forming a semiconductor film, Performing a first process cycle, which includes exposing the substrate surface to a metal precursor and reactants to form a metal layer on the substrate surface, wherein the metal layer has a reactive surface, and The process involves carrying out a second process cycle, which includes exposing the metal layer to a second metal precursor and a second precursor to form a protective cap layer on the metal layer, wherein the second precursor has a carbon chain having 2 to 20 carbon atoms and a functional group, and the functional group is selected from the group consisting of primary amines, thiols, phosphines, alcohols, and selenols. Methods that include...

12. The first metal precursor and the second metal precursor independently each comprise a metal and a reactive species, and the reactant is ammonia (NH₄). ３ ), water (H ２ O), hydrogen sulfide (H ２ S), phosphine (PH ３ ), ozone (O ３ ), hydrogen peroxide (H ２ O ２ ), nitrous oxide ( ２ O), and hydrogen selenide (H ２ The method according to claim 11, comprising one or more of Se).

13. The method according to claim 12, wherein the metal is selected from one or more of the following: titanium (Ti), silicon (Si), molybdenum (Mo), hafnium (Hf), zirconium (Zr), aluminum (Al), antimony (Sb), boron (B), gallium (Ga), germanium (Ge), indium (In), niobium (Nb), rhenium (Re), tantalum (Ta), tin (Sn), tungsten (W), and zinc (Zn).

14. The method according to claim 12, wherein the reactive species is selected from the group consisting of halides, alkyls, arenes, cyclopentadienyls, alkynes, dienes, diketnates, amides, imides, alkoxos, oxos, carbonyls, amidinates, guanidinates, and formamidinates.

15. The aforementioned metal precursor and the second metal precursor are independently aluminum chloride, aluminum bromide, aluminum iodide, boron trichloride, boron tribromide, gallium trichloride, germanium tetrachloride, antimony trichloride, antimony pentachloride, indium trichloride, silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, hexachlorodisilane, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, zirconium tetrachloride, hafnium tetrachloride, niobium pentachloride, niobium pentabromide, tantalum pentachloride, tantalum pentabromide, molybdenum pentachloride, tungsten hexachloride, and 5 The method according to claim 12, comprising one or more of rhenium chloride, zinc chloride, tin chloride, trimethylaluminum, tetrakis(dimethylamide)titanium, tetrakis(dimethylamide)zirconium, tetrakis(dimethylamide)hafnium, (t-butylimide)tris(diethylamino)niobium, (t-butylimide)tris(diethylamino)tantalum, pentakis(dimethylamide)tantalum, bis(ethylbenzene)molybdenum, hexacarbonylmolybdenum, hexacarbonyltungsten, and diethylzinc.

16. The method according to claim 11, wherein the metal layer comprises one or more of metal nitrides, metal oxides, metal sulfides, metal phosphides, and metal selenides.

17. The method according to claim 11, wherein the protective cap layer has a thickness in the range of 0.5 nm to 5 nm.

18. The second precursor described above is It contains one or more compounds selected from the following: Here, n is an integer in the range of 1 to 20. The method according to claim 11.

19. The method according to claim 11, wherein the first process cycle is repeated 2 to 100 times.

20. The method according to claim 11, wherein the second process cycle is repeated 2 to 10 times.

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