In-situ production of H2S or H2Se during the growth of 2D transition metal dichalcogenide and / or diselenide films

Abstract

The disclosed and claimed invention relates to an in-situ production method of H2S and / or H2Se during the growth of 2D transition metal dichalcogenide and / or diselenide-containing films.

Description

Technical Field

[0001] The disclosed and claimed invention relates to a method for in-situ production of H2S or H2Se during the growth of 2D transition metal dichalcogenide and / or diselenide-containing films.

Background Art

[0002] In transition metal-containing films used in semiconductor and electronics applications, chemical vapor deposition (CVD) and atomic layer deposition (ALD) are used as the main deposition techniques for manufacturing thin films for semiconductor devices. These methods enable the achievement of conformal films (metals, metal oxides, metal nitrides, metal silicides, etc.) through chemical reactions of transition metal-containing compounds (precursors). These chemical reactions occur on surfaces that can include metals, metal oxides, metal nitrides, metal silicides, silicon dioxide, silicon nitride, and other surfaces. In CVD and ALD, the precursor molecules play an important role in achieving high-quality films with high conformality and low impurities. The substrate temperature in CVD and ALD processes is one of the important considerations in selecting precursor molecules. A relatively high substrate temperature in the range from 150 to 500 degrees Celsius (°C) promotes a higher film deposition rate. Preferred precursor molecules need to be stable in this temperature range. Preferred precursors can be delivered into the reaction vessel in the liquid phase. Liquid-phase delivery of precursors generally provides a more uniform delivery of precursors to the reaction vessel compared to solid-phase precursors.

[0003] CVD and ALD processes are increasingly being used because they have the advantages of enhanced composition control, high film uniformity, and effective control of doping. Furthermore, CVD and ALD processes provide excellent conformal step coverage on the highly non-flat geometries associated with modern microelectronic devices.

[0004] CVD is a chemical process in which precursors are used to form thin films on a substrate surface. In a typical CVD process, the precursors are flowed over the surface of a substrate (e.g., a wafer) in a low-pressure or ambient-pressure reaction chamber. The precursors react and / or decompose on the substrate surface to form a thin film of the deposited material. Plasma can be used to assist the reaction of the precursors or to improve the properties of the material. Non-volatile by-products are removed by flowing gases through the reaction chamber. The deposited film thickness can be difficult to control because it depends on the coordination of many parameters such as temperature, pressure, gas volume flow rate and uniformity, chemical depletion effects, and time.

[0005] ALD is one of the chemical methods for thin film deposition. It is a self-limiting, sequential, and unique film growth technique based on surface reactions, which can provide precise thickness control and deposit conformal thin films of materials provided by precursors on surface substrates of various compositions. In ALD, each precursor is separated during the reaction. The first precursor is flowed over the substrate surface to form a monolayer on the substrate surface. Excess unreacted precursor is discharged from the reaction chamber. Then, a second precursor or co-reactant is flowed over the substrate surface, and this reacts with the first precursor to form a second monolayer of the film on the first monolayer of the film formed on the substrate surface. Plasma can be used to assist the reaction of the precursor or co-reactant or to improve the material quality. This cycle is repeated until a film of the desired thickness is formed.

[0006] Thin films, especially metal-containing thin films, have various important applications in nanotechnology and the manufacture of semiconductor devices. Examples of such applications include capacitor electrodes, gate electrodes, adhesive diffusion barriers, and integrated circuits.

[0007] To grow 2D transition metal dichalcogenide films using H2S and / or 2D transition metal diselenide films using H2Se, heretofore it has been necessary to supply H2S and / or H2Se to the growth chamber using a plurality of connected gas bottles or a facility-based H2S supply. However, the use of H2S and / or H2Se supplied to the chamber from the outside has many complications due to their toxicity. At a minimum, there are significant expenses required to obtain and install the associated equipment (e.g., gas detectors and safety systems) and to receive approval for the poison and fire permit procedures necessary to safely use externally supplied H2S and / or H2Se in the deposition process. In addition, the use of externally supplied H2S and / or H2Se can lengthen the process time.

[0008] The disclosed and claimed methods address and largely eliminate these concerns by providing for the in-situ production of H2S and / or H2Se within the deposition chamber during the deposition of 2D metal dichalcogenide films. SUMMARY OF THE INVENTION

[0009] The disclosed and claimed invention relates to a method for in-situ production of H2S and / or H2Se during the growth of 2D transition metal dichalcogenide and / or diselenide-containing films by co-injecting (R 1 R 2 R 3 Si)2X and NH3 into a deposition chamber to produce H2X. In the formula, R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, C2-C6 alkenyl, C3-C6 aryl or C2-C6 alkynyl group (collectively, "C1-C6 alkyl, alkenyl, aryl or alkynyl group") or a benzyl group, and X is either S or Se. In one preferred embodiment, R 1 , R 2 and R 3are identical. In one aspect, the disclosed and claimed invention relates to the use of compounds of the formula (R 1 R 2 R 3 Si)2S and / or compounds of the formula (R 1 R 2 R 3 Si)2Se in combination with NH3 for forming a 2D transition metal disulfide and / or diselenide-containing film on a substrate. In the above formulas, R 1 , R 2 and R 3 are each independently hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C3-C6 aryl, benzyl or a C2-C6 alkenyl group.

[0010] In one embodiment, R 1 , R 2 and R 3 are each a methyl group and X is sulfur (i.e., “(Me3Si)2S” or “TMS2S”), which reacts with NH3 according to the following equation to produce H2S: (Me3Si)2S + NH3 → H2S + (Me3Si)2NH.

[0011] In one embodiment, R 1 , R 2 and R 3 are each a methyl group and X is selenium (i.e., “(Me3Si)2Se” or “TMS2Se”), which reacts with NH3 according to the following equation to produce H2Se: (Me3Si)2Se + NH3 → H2Se + (Me3Si)2NH.

[0012] In one of other aspects, the disclosed and claimed invention includes in-situ generation of H2S and / or H2Se in a CVD deposition process.

[0013] In one of other aspects, the disclosed and claimed invention includes in-situ generation of H2S and / or H2Se in an ALD deposition process.

[0014] The accompanying drawings are intended to provide a further understanding of the disclosed invention and are incorporated herein and constitute a part thereof. These drawings illustrate embodiments of the disclosed invention and are useful for explaining the principles of the disclosed invention together with the detailed description of the invention.

Brief Description of the Drawings

[0015]

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Mode for Carrying Out the Invention

[0016] All documents cited herein, including publications, patent applications, and patents, are hereby incorporated by reference as if each document were individually and specifically indicated to be incorporated by reference and were set forth in its entirety.

[0017] The use of the singular form and similar referents in the context of the description of the disclosed and claimed invention (especially in the context of the dependent claims) shall be construed to include both the singular and plural forms unless otherwise indicated or clearly contradicted by the context. Expressions such as "comprising," "having," "including," and "containing" shall be construed as non-limiting expressions (i.e., "including but not limited to") unless otherwise noted. The recitation of numerical ranges is intended, unless otherwise indicated herein, merely as a convenient way to refer individually to each separate value falling within the range, and each separate value is to be incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise stated herein or clearly contradicted by the context. The use of any and all examples, or exemplary language (e.g., "such as") herein is intended merely to better clarify the disclosed and claimed invention and is not intended to limit the scope of the disclosed and claimed invention. No language in this specification should be construed as indicating that any non-claimed technical matter is essential to the practice of the disclosed and claimed invention. The use of the term "comprising" in this specification and the claims encompasses the more restrictive terms "consisting essentially of" and "consisting of."

[0018] The aspects of the disclosure and claimed invention, including the best mode known to the inventors for practicing the disclosure and claimed invention, are described herein. Variations of these aspects will be apparent to those skilled in the art upon a review of the preceding description. The inventors expect those skilled in the art to appropriately employ such variations, and the inventors also intend that the disclosure and claimed invention be practiced otherwise than as specifically described herein. Accordingly, the disclosure and claimed invention include all improvements and equivalents / fairings of the invention described in the claims to the extent permitted by applicable law. Further, any combination of the above matters in all possible variations is included in the disclosure and claimed invention unless otherwise indicated or clearly inconsistent from the context.

[0019] The term "silicon" as deposited as a material on a microelectronic device is understood to include polysilicon.

[0020] For ease of reference, "microelectronic device" or "semiconductor device" corresponds to a semiconductor wafer with integrated circuits, memory, and other electronic structures formed thereon, and other products including flat panel displays, phase change memory devices, solar panels, and substrates for solar cells, solar power generation devices, and microelectromechanical systems (MEMS) manufactured for use in microelectronics, integrated circuits, or computer chips. Substrates for solar cells include, but are not limited to, silicon, amorphous silicon, polycrystalline silicon, single crystalline silicon, CdTe, copper indium selenide, copper indium sulfide, and gallium arsenide on gallium. Substrates for solar cells may or may not be doped. The term "microelectronic device" or "semiconductor device" is not meant to be limiting in any way and is understood to include any substrate that ultimately becomes a microelectronic device or microelectronic assembly.

[0021] As defined herein, the term "barrier material" corresponds to any material used in the art to encapsulate metal lines, such as copper interconnects, to minimize the diffusion of said metal, such as copper, into the dielectric material. Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium and other refractory metals, and their nitrides and silicides.

[0022] As used herein, the recitations "about" or "approximately" and the symbol "~" are intended to correspond to within ±5% of the recited value.

[0023] "Alkylene", unless otherwise specified, means a linear saturated divalent hydrocarbon residue having 1 to 6 carbon atoms, or a branched saturated divalent hydrocarbon residue having 3 to 6 carbon atoms (e.g., methylene, ethylene, propylene, 1-methylpropylene, 2-methylpropylene, butylene, pentylene, etc.).

[0024] As used herein, "C x-y "(where x and y are each integers) specifies the number of carbon atoms in the chain. For example, C 1-6 or C 1-6 Alkyl refers to an alkyl chain having a chain between 1 and 6 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl and hexyl). Unless specifically stated otherwise, the above chain can be linear or branched (e.g., branched C3-C6 alkyl groups).

[0025] Unless otherwise indicated, "alkyl" refers to a hydrocarbon group, which can be a linear or branched hydrocarbon group (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, etc.), a cyclic hydrocarbon group (e.g., cyclohexyl, cyclopropyl, cyclopentyl, etc.) or a polycyclic hydrocarbon group (e.g., norbornyl, adamantyl, etc.). Suitable acyclic groups can be methyl, ethyl, n- or iso-propyl, n-, iso- or tert-butyl, linear or branched pentyl, hexyl. Unless otherwise specified, alkyl refers to a moiety having 1 to 6 carbon atoms. The cyclic alkyl group may be monocyclic. Suitable examples of monocyclic alkyl groups include substituted cyclopentyl, cyclohexyl and cycloheptyl groups, etc.

[0026] "Heteroalkylene" means the previously defined -(alkylene)- residue in which one, two or three carbons in the alkylene chain are replaced by -O-, N(H, alkyl, or substituted alkyl), S, SO, SO2 or CO. In some preferred embodiments, said carbon is replaced by O or N.

[0027] In all such compositions where a particular component of the composition is described with reference to a weight percentage (or "wt%") range including a lower limit of zero, it is understood that such a component may or may not be present in various particular embodiments of the composition, and if such a component is present, they may be present at a concentration as low as 0.001 wt% based on the total weight of the composition in which such a component is used. It is pointed out that all descriptions of percentages of components are in wt% and are based on the total weight of the composition (i.e., 100%). When referring to "one or more" or "one kind or more" or "at least one" or "at least one kind", in each case, it includes "two or more" or "two kinds or more" or "three or more" or "three kinds or more", etc.

[0028] When applicable, unless otherwise indicated, all weight percentages are "net", meaning that they do not include the aqueous solutions in which they are contained when added to the composition. For example, "net" refers to the amount of weight % of undiluted acid or other material (i.e., when including 100 g of 85% phosphoric acid, it consists of 85 g of said acid and 15 g of diluent).

[0029] Furthermore, when referring to the compositions described herein in terms of weight %, in all cases, it is understood that the weight % of all components, including non-essential components such as impurities, does not exceed 100 weight % in total. In a composition "consisting essentially of" the components described, such components can total up to 100 weight % of the composition or can total less than 100 weight %. When the total of the components is less than 100 weight %, such a composition can contain a small amount of non-essential contaminants or impurities. For example, in one such embodiment, the formulation can contain 2 weight % or less of impurities. In another such embodiment, the formulation can contain 1 weight % or less of impurities. In yet another such embodiment, the formulation can contain 0.05 weight % or less of impurities. In other such embodiments, the constituents can constitute at least 90 weight %, more preferably at least 95 weight %, more preferably at least 99 weight %, more preferably at least 99.5 weight %, most preferably at least 99.9 weight %, and can contain other components that do not substantially affect the performance of the wet etching agent. In other cases, when no significant non-essential impurity components are present, it should be understood that the composition of all essential constituents totals essentially 100 weight %.

[0030] The titles used herein are not intended to be limiting and are described only for the purpose of document organization.

[0031] Exemplary Embodiments As described above, the disclosed and claimed invention relates to a method for in-situ production of H2S and / or H2Se during the growth of 2D disulfide and / or diselenide-containing films by ALD and / or CVD deposition processes. In other words, the disclosed and claimed invention relates to a method for forming a 2D transition metal disulfide and / or diselenide-containing film on a substrate, which includes in-situ generating one or more of H2S and H2Se in a deposition chamber. As used herein, the term "chemical vapor deposition process" generally refers to any process in which a substrate is exposed to one or more volatile precursors, which react and / or decompose on the surface of the substrate to effect the desired deposition, including, for example, ALD and / or CVD deposition processes.

[0032] In particular, the disclosed and claimed invention relates to a method for in-situ production of H2S and / or H2Se during the growth of 2D transition metal disulfide and / or diselenide-containing films by co-injecting (R 1 R 2 R 3 Si)2X and NH3 into a deposition chamber to produce H2X. In the formula, R 1 , R 2 and R 3 are each independently a hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl group. In one embodiment, R1, R2 and R3 are each independently a hydrogen, linear C1-C6 alkyl group, branched C3-C6 alkyl group, unsubstituted C3-C6 cycloalkyl group, C3-C6 aromatic group, benzyl group, C2-C6 alkenyl group and C2-C6 alkynyl group. In one embodiment, R 1 , R 2 and R 3 are the same. In one embodiment, at least one of R 1 , R 2 and R 3 is different from the others of R 1 , R 2 and R 3 .

[0033] In one embodiment, X is sulfur, and R 1 , R 2 and R 3 are each independently hydrogen, a linear C1-C6 alkyl group, a branched C3-C6 alkyl group, an unsubstituted C3-C6 cycloalkyl group, a C3-C6 aromatic group, a benzyl group, a C2-C6 alkenyl group, and a C2-C6 alkynyl group. In one aspect of this embodiment, R 1 , R 2 and R 3 are the same. In one aspect of this embodiment, at least one of R 1 , R 2 and R 3 is different from the others of R 1 , R 2 and R 3 . In yet another aspect of this embodiment, X is sulfur, and R 1 , R 2 and R 3 are each a methyl group. In yet another aspect of this embodiment, X is sulfur, and R 1 , R 2 and R 3 are each a methyl group and react with NH3 according to the following equation to produce H2S: (Me3Si)2S + NH3 → H2S + (Me3Si)2NH. In still yet another aspect of this embodiment, X is sulfur, and R 1 is hydrogen, R 2 and R 3 are each a methyl group and react with NH3 according to the following equation to produce H2S: (Me2HSi)2S + NH3 → H2S + (Me2HSi)2NH.

[0034] In one embodiment, X is selenium, and R 1 , R 2 and R 3 are each independently hydrogen, a linear C1-C6 alkyl group, a branched C3-C6 alkyl group, an unsubstituted C3-C6 cycloalkyl group, a C3-C6 aromatic group, a benzyl group, a C2-C6 alkenyl group, and a C2-C6 alkynyl group. In one aspect of this embodiment, R 1 , R 2 and R3 are identical. In one aspect of this embodiment, R 1 , R 2 and R 3 of which at least one is different from the others of R 1 , R 2 and R 3 . In yet another aspect of this embodiment, X is selenium, and R 1 , R 2 and R 3 are each a methyl group. In yet another aspect of this embodiment, X is selenium, and R 1 , R 2 and R 3 are each a methyl group, and react with NH3 according to the following equation to produce H2Se: (Me3Si)2Se + NH3 → H2Se + (Me3Si)2NH. In yet another aspect of this embodiment, X is sulfur, and R 1 is hydrogen, R 2 and R 3 are each a methyl group, and react with NH3 according to the following equation to produce H2Se: (Me2HSi)2Se + NH3 → H2Se + (Me2HSi)2NH.

[0035] In one embodiment, both H2S and H2Se are each generated during the growth of a multi-component 2D film containing disulfides and diselenides. In this embodiment, (R 1 R 2 R 3 Si)2S, (R 1 R 2 R 3 Si)2Se and NH3 are co-injected into the deposition chamber to produce H2S and H2Se. In each equation, R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group. In one embodiment, R 1 , R 2 and R 3is, independently of one another, a linear C1-C6 alkyl group, a branched C3-C6 alkyl group, an unsubstituted C3-C6 cycloalkyl group, a C3-C6 aromatic group, a benzyl group, a C2-C6 alkenyl group, and a C2-C6 alkynyl group. In one aspect of this embodiment, the compound (R 1 R 2 R 3 Si)2S, R 1 , R 2 and R 3 are each a methyl group. In one aspect of this embodiment, the compound (R 1 R 2 R 3 Si)2Se, R 1 , R 2 and R 3 are each a methyl group.

[0036] As used herein, the term "atomic layer deposition process" or ALD refers to a self-limiting deposition (e.g., the amount of film material deposited in each reaction cycle is surface-limited to a constant "saturation" deposition rate) and a continuous surface chemistry for depositing a film of material on substrates of various compositions. The precursors, reagents, and sources used herein are sometimes described as "gaseous," but it is understood that the precursors can be either liquid or solid and are transported into the reactor via direct vaporization, bubbling, or sublimation, with or without an inert gas. In some cases, the vaporized precursor can be passed through a plasma generator. As used herein, the term "reactor" includes, but is not limited to, a reaction chamber, a reaction vessel, or a deposition chamber.

[0037] Chemical vapor deposition processes that can utilize in-situ generated H2S and / or H2Se include, but are not limited to, processes used in the manufacture of semiconductor-type microelectronic devices, such as ALD and plasma-enhanced ALD (PEALD). Thus, in one embodiment, for example, a metal-containing film is deposited using an ALD process. In one aspect of another embodiment, for example, a metal-containing film is deposited using a plasma-enhanced ALD (PEALD) process.

[0038] Suitable substrates on which H2S and / or H2Se generated in situ can be used are not particularly limited and vary depending on the intended end use. For example, the substrate may be selected from oxides such as HfO2-based materials, TiO2-based materials, ZrO2-based materials, rare earth oxide-based materials, ternary oxide-based materials, or from nitride-based films. Other substrates include solid substrates such as metal substrates (e.g., Au, Pd, Rh, Ru, W, Al, Ni, Ti, Co, Pt) and metal silicides (e.g., TiSi2, CoSi2, and NiSi2); metal nitride-containing substrates (e.g., TaN, TiN, WN, TaCN, TiCN, TaSiN, and TiSiN); semiconductor materials (e.g., Si, SiGe, GaAs, InP, diamond, GaN, and SiC); insulators (e.g., SiO2, Si3N4, SiON, HfO2, Ta2O5, ZrO2, TiO2, Al2O3, and strontium barium titanate); combinations thereof, and the like. Preferred substrates include HfO2-based materials, TiO2-based materials, ZrO2-based materials, rare earth oxide-based materials, and silicon oxide-based substrates.

[0039] The deposition method and process may include one or more purge gases. The purge gas used to purge unconsumed reactants and / or reaction by-products is an inert gas that does not react with the precursors. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N2), helium (He), neon, and mixtures thereof. For example, a purge gas such as Ar is supplied into the reactor at a flow rate in the range of about 10 to about 2000 sccm for up to about 0.1 to 10000 seconds to purge unreacted materials and by-products that may remain in the reactor.

[0040] The deposition method and process may require imparting energy to at least one of the components used to form a metal-containing film or coating on a substrate. Such energy can be provided by, but is not limited to, heat, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, X-rays, electron beams, photons, remote plasma methods, and combinations thereof. In some processes, a secondary RF frequency source can be used to modify plasma characteristics at the substrate surface. When utilizing plasma, plasma generation processes can include a direct plasma generation process in which plasma is generated directly in a reactor, or alternatively a remote plasma generation process in which plasma is generated outside the reactor and supplied into the reactor.

[0041] When used in such deposition methods and processes, suitable precursors and in-situ generated H2S and / or H2Se can be delivered to a reaction chamber, such as an ALD reactor, in various ways. In some cases, a liquid delivery system can be utilized. In other cases, a combined liquid delivery and flash vaporization process unit, such as a turbovaporizer manufactured by MSP Corporation of Shoreview, Minnesota, can be used to enable delivery of low volatility materials on a volume basis, thereby enabling reproducible transport and deposition without thermal decomposition of the precursors. The precursor compositions described herein can be effectively used as source reagents via direct liquid injection (DLI) to supply vapor streams of these metal precursors into an ALD reactor.

[0042] In view of the above, those skilled in the art will recognize that the disclosed and claimed invention further includes a method of forming a 2D transition metal dichalcogenide and / or diselenide-containing film on a substrate using in-situ generated H2S and / or H2Se in a chemical vapor deposition process as follows.

[0043] CVD In one aspect, the disclosed and claimed invention includes a method for forming a 2D transition metal dichalcogenide and / or diselenide-containing film via a chemical vapor deposition (CVD) process, the process comprising the following steps: (1) contacting a substrate in a deposition chamber with a vapor comprising the following (a) and (b): (a) one or more externally supplied metal precursors, and (b) one or more of (i) H2S and (ii) H2Se; (2) optionally purging the vapor with an inert gas; comprising (i) the H2S is generated in situ by reacting a compound of the formula (R 1 R 2 R 3 Si)2S (wherein each R 1 , R 2 and R 3 is independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group or a benzyl group) with NH3 in the deposition chamber, and / or (ii) the H2Se is generated in situ by reacting a compound of the formula (R 1 R 2 R 3 Si)2Se (wherein in each formula, R 1 , R 2 and R 3 is independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group or a benzyl group) with NH3 in the deposition chamber. In yet another aspect of this embodiment, the H2S (i) is a compound of the formula (R 1 R 2 R 3 Si)2S (wherein in each formula, R 1 , R 2 and R 3is, independently of one another, a linear C1-C6 alkyl group, a branched C3-C6 alkyl group, an unsubstituted C3-C6 cycloalkyl group, a C3-C6 aromatic group, a C2-C6 alkenyl group, and a C2-C6 alkynyl group or benzyl group) of the compound is generated in situ by reacting with NH3 in the reaction chamber, and / or said H2Se(ii) is of the formula (R 1 R 2 R 3 Si)2Se (in each formula, R 1 、R 2 and R 3 is, independently of one another, a linear C1-C6 alkyl group, a branched C3-C6 alkyl group, an unsubstituted C3-C6 cycloalkyl group, a C3-C6 aromatic group, a C2-C6 alkenyl group, and a C2-C6 alkynyl group or benzyl group) of the compound is generated in situ by reacting with NH3 in the deposition chamber. In yet another aspect of this embodiment, said H2S(i) is generated in situ by reacting (Me3Si)2S + NH3 in the reaction chamber and said H2Se(ii) is generated in situ by reacting (Me3Si)2Se + NH3 in the reaction chamber. In yet another aspect of this embodiment, the method consists essentially of steps (i) and (ii). In yet another aspect of this embodiment, the method consists of steps (i) and (ii).

[0044] ALD In one embodiment, the disclosed and claimed invention includes a method of forming a 2D transition metal disulfide and / or diselenide-containing film via a thermal atomic layer deposition (ALD) process or a thermal ALD-like process, the process comprising the following steps: (1) contacting a substrate in a deposition chamber with a first vapor comprising one of the following (a) or (b): (a) one or more externally supplied metal precursors, or (b) one or more of (i) H2S and (ii) H2Se; (2) purging the first vapor with an inert gas; (3) contacting the second vapor comprising the other of (a) or (b) below; (a) the one or more externally supplied metal precursors, or (b) one or more of (i) H2S and (ii) H2Se; (4) Optionally, purging the second vapor with an inert gas, and (5) sequentially repeating steps (1) to (4) until a metal-containing film of a desired thickness is obtained, comprising, (i) the H2S is generated in situ by reacting a compound of the formula (R 1 R 2 R 3 Si)2S (wherein R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group or a benzyl group) with NH3 in a deposition chamber, and / or (ii) the H2Se is generated in situ by reacting a compound of the formula (R 1 R 2 R 3 Si)2Se (wherein R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group or a benzyl group) with NH3 in a deposition chamber. In yet another aspect of this embodiment, the H2S (i) is a compound of the formula (R 1 R 2 R 3 Si)2S (wherein R 1 , R 2 and R 3 are each independently a linear C1-C6 alkyl group, a branched C3-C6 alkyl group, an unsubstituted C3-C6 cyclic alkyl group, a C3-C6 aromatic group, a C2-C6 alkenyl group or a C2-C6 alkynyl group or a benzyl group) and is generated in situ by reacting with NH3 in a reaction chamber, and / or the H2Se (ii) is a compound of the formula (R 1 R 2R 3 (Si)2Se (wherein R 1 , R 2 and R 3 are each independently a linear C1-C6 alkyl group, a branched C3-C6 alkyl group, an unsubstituted C3-C6 cyclic alkyl group, a C3-C6 aromatic group, a benzyl group, a C2-C6 alkenyl group, or a C2-C6 alkynyl group) is generated in situ by reacting with NH3 in a deposition chamber. In another aspect of this embodiment, the H2S(i) is generated in situ by reacting (Me3Si)2S + NH3 in a reaction chamber and the H2Se(ii) is generated in situ by reacting (Me3Si)2Se + NH3 in a reaction chamber. In another aspect of this embodiment, the method consists essentially of steps (1), (2), (3), (4) and (5). In another aspect of this embodiment, the method consists of steps (1), (2), (4) and (5).

[0045] In another aspect of this embodiment, the method is carried out at a temperature from about 100°C to about 650°C. In another aspect of this embodiment, the method is carried out at a pressure from about 0.1 Torr to about 100 Torr. In another aspect of this embodiment, the method is carried out at a temperature from about 100°C to about 650°C and a pressure from about 0.1 Torr to about 100 Torr. In yet another aspect, the deposition temperature and pressure are adjusted in accordance with the one or more externally supplied metal precursors selected. In another aspect of this embodiment, a compound of the formula (R 1 R 2 R 3 (Si)2S (wherein R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group or a benzyl group) + NH3, and / or a compound of the formula (R 1 R 2 R 3 (Si)2Se (wherein R 1 , R 2 and R3 Compounds + NH3 (each independently a C1-C6 alkyl, alkenyl, aryl or alkynyl group or benzyl group) are co-injected into the deposition chamber. In yet another aspect of this embodiment, formula (R 1 R 2 R 3 Si)2S (wherein R 1 ,R 2 and R 3 are each independently a linear C1-C6 alkyl group, a branched C3-C6 alkyl group, an unsubstituted C3-C6 cycloalkyl group, a C3-C6 aromatic group, a benzyl group, a C2-C6 alkenyl group or a C2-C6 alkynyl group) compounds + NH3 and / or formula (R 1 R 2 R 3 Si)2Se (wherein R 1 ,R 2 and R 3 are each independently a linear C1-C6 alkyl group, a branched C3-C6 alkyl group, an unsubstituted C3-C6 cycloalkyl group, a C3-C6 aromatic group, a benzyl group, a C2-C6 alkenyl group or a C2-C6 alkynyl group) compounds + NH3 are sequentially injected into the reaction chamber. In yet another aspect of this embodiment, TMS2S + NH3 and / or TMS2Se + NH3 are co-injected into the deposition chamber. In yet another aspect of this embodiment, TMS2S + NH3 and / or TMS2Se + NH3 are sequentially injected into the deposition chamber.

[0046] In yet another aspect of this embodiment, in step (1), the first vapor (a) includes the one or more externally supplied metal precursors. In yet another aspect of this embodiment, in step (1), the first vapor (b) includes one or more of (i) H2S and (ii) H2Se. In yet another aspect of this embodiment, in step (1), the first vapor (i) includes H2S. In yet another aspect of this embodiment, in step (1), the first vapor (ii) includes H2Se. In yet another aspect of this embodiment, in step (3), the second vapor (a) includes the one or more externally supplied metal precursors. In yet another aspect of this embodiment, in step (3), the second vapor (b) includes one or more of (i) H2S and (ii) H2Se. In yet another aspect of this embodiment, in step (3), the second vapor (i) includes H2S. In yet another aspect of this embodiment, in step (3), the second vapor (ii) includes H2Se.

[0047] Carrier gas In one aspect of the above process, the one or more externally supplied metal precursors are introduced (i.e., supplied) into the reaction vessel using a flow of a carrier gas that is one or more of argon, nitrogen, helium, neon, and / or krypton. When delivering the one or more externally supplied precursors, the reaction chamber process pressure can be between 1 and 50 torr, preferably between 5 and 20 torr.

[0048] Inert gas In one aspect of the above process, the inert gas is one or more of argon, nitrogen, helium, neon, krypton, and combinations thereof.

[0049] Energy source In one aspect of the above process, the method further includes imparting energy to one or more externally supplied metal precursors, one or more of (i) H2S and (ii) H2Se, (if used) a carrier gas, the substrate, and combinations thereof, where the energy is one or more of heat, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, X-rays, electron beams, photons, remote plasma methods, and combinations thereof.

[0050] Flow rate In one aspect of the above process, NH3 is flowed at from about 50 sccm to about 2000 sccm during the reaction with a compound of formula (R 1 R 2 R 3 Si)2S (i.e., during a pulse of (R 1 R 2 R 3 Si)2S). In the formula, R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group. In one aspect, NH3 is flowed at from about 100 sccm to about 1500 sccm during the reaction with a compound of formula (R 1 R 2 R 3 Si)2S (wherein R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group). In one aspect, NH3 is flowed at from about 250 sccm to about 1250 sccm during the reaction with a compound of formula (R 1 R 2 R 3 Si)2S (wherein R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group). In one aspect, NH3 is flowed at from about 250 sccm to about 1250 sccm during the reaction with a compound of formula (R 1 R 2R 3 (R 1 R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group) is flowed at from about 500 sccm to about 1000 sccm during the reaction with a compound of. In another aspect of each of the above embodiments, a compound of formula (R 1 R 2 R 3 (R 1 R 2 and R 3 are each independently a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group) contains, consists essentially of, or consists of (Me3Si)2S.

[0051] In one aspect of the above process, NH3 is flowed at about 50 sccm during the reaction with a compound of formula (R 1 R 2 R 3 (R 1 R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group or a benzyl group). In one aspect, NH3 is flowed at about 100 sccm during the reaction with a compound of formula (R 1 R 2 R 3 (R 1 R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group). In one aspect, NH3 is flowed at about 100 sccm during the reaction with a compound of formula (R 1 R 2 R 3 (R 1 R 2 and R 3flows at about 150 sccm during the reaction with a compound (each independently being hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group or a benzyl group). In one embodiment, NH3 is of the formula (R 1 R 2 R 3 Si)2S (wherein R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group or a benzyl group) and flows at about 200 sccm during the reaction with the compound. In one embodiment, NH3 is of the formula (R 1 R 2 R 3 Si)2S (wherein R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group or a benzyl group) and flows at about 250 sccm during the reaction with the compound. In one embodiment, NH3 is of the formula (R 1 R 2 R 3 Si)2S (wherein R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group or a benzyl group) and flows at about 300 sccm during the reaction with the compound. In one embodiment, NH3 is of the formula (R 1 R 2 R 3 Si)2S (wherein R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group or a benzyl group) and flows at about 350 sccm during the reaction with the compound. In one embodiment, NH3 is of the formula (R 1 R 2 R 3 Si)2S (wherein R 1 , R 2 and R 3flows at about 400 sccm during the reaction with a compound (which is independently a hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl group or a benzyl group). In one embodiment, NH3 is of the formula (R 1 R 2 R 3 Si)2S (wherein R 1 , R 2 and R 3 are each independently a hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl group or a benzyl group) and flows at about 450 sccm during the reaction with the compound. In one embodiment, NH3 is of the formula (R 1 R 2 R 3 Si)2S (wherein R 1 , R 2 and R 3 are each independently a hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl group or a benzyl group) and flows at about 500 sccm during the reaction with the compound. In one embodiment, NH3 is of the formula (R 1 R 2 R 3 Si)2S (wherein R 1 , R 2 and R 3 are each independently a hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl group or a benzyl group) and flows at about 750 sccm during the reaction with the compound. In one embodiment, NH3 is of the formula (R 1 R 2 R 3 Si)2S (wherein R 1 , R 2 and R 3 are each independently a hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl group or a benzyl group) and flows at about 1000 sccm during the reaction with the compound. In one embodiment, NH3 is of the formula (R 1 R 2 R 3 Si)2S (wherein R 1 , R 2 and R 3flows at about 1250 sccm during the reaction with a compound that is, independently of each other, hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group or a benzyl group). In one embodiment, NH3 is of the formula (R 1 R 2 R 3 Si)2S (wherein R 1 , R 2 and R 3 are, independently of each other, hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group or a benzyl group) and flows at about 1500 sccm during the reaction with the compound. In one embodiment, NH3 is of the formula (R 1 R 2 R 3 Si)2S (wherein R 1 , R 2 and R 3 are, independently of each other, hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group or a benzyl group) and flows at about 1750 sccm during the reaction with the compound. In one embodiment, NH3 is of the formula (R 1 R 2 R 3 Si)2S (wherein R 1 , R 2 and R 3 are, independently of each other, hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group or a benzyl group) and flows at about 2000 sccm during the reaction with the compound. In yet another aspect of each of the above embodiments, the compound of the formula (R 1 R 2 R 3 Si)2S (wherein R 1 , R 2 and R 3 are, independently of each other, hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group) comprises, consists essentially of, or consists of (Me3Si)2S.

[0052] In one embodiment of the above process, NH3 is of the formula (R 1 R 2 R 3During the reaction with the compound of (Si)2Se (i.e., during the (R 1 R 2 R 3 Si)2Se pulse), it is circulated at about 50 sccm to about 2000 sccm. In the above formula, R 1 、R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group. In one aspect, NH3 is circulated at about 100 sccm to about 1500 sccm during the reaction with the compound of the formula (R 1 R 2 R 3 Si)2Se (wherein R 1 、R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group). In one aspect, NH3 is circulated at about 250 sccm to about 1250 sccm during the reaction with the compound of the formula (R 1 R 2 R 3 Si)2Se (wherein R 1 、R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group). In one aspect, NH3 is circulated at about 500 sccm to about 1000 sccm during the reaction with the compound of the formula (R 1 R 2 R 3 Si)2Se (wherein R 1 、R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group). In another aspect of each of the above aspects, the compound of the formula (R 1 R 2 R 3 Si)2S (wherein R 1 、R 2 and R 3The compound (which is independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group) contains, consists essentially of, or consists of (Me3Si)2Se.

[0053] In one embodiment of the above process, NH3 is flowed at about 50 sccm during the reaction with a compound of the formula (R 1 R 2 R 3 Si)2Se (wherein R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group). In one embodiment, NH3 is flowed at about 100 sccm during the reaction with a compound of the formula (R 1 R 2 R 3 Si)2Se (wherein R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group). In one embodiment, NH3 is flowed at about 150 sccm during the reaction with a compound of the formula (R 1 R 2 R 3 Si)2Se (wherein R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group). In one embodiment, NH3 is flowed at about 200 sccm during the reaction with a compound of the formula (R 1 R 2 R 3 Si)2Se (wherein R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group). In one embodiment, NH3 is flowed at about 200 sccm during the reaction with a compound of the formula (R 1 R 2 R 3 Si)2Se (wherein R 1, R 2 and R 3 flows at about 250 sccm during the reaction with a compound that is, independently of each other, hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group). In one embodiment, NH3 is of the formula (R 1 R 2 R 3 Si)2Se (wherein R 1 , R 2 and R 3 are, independently of each other, hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group) and flows at about 300 sccm during the reaction with the compound. In one embodiment, NH3 flows at about 350 sccm during the TMS2Se pulse. In one embodiment, NH3 flows at about 400 sccm during the TMS2Se pulse. In one embodiment, NH3 is of the formula (R 1 R 2 R 3 Si)2Se (wherein R 1 , R 2 and R 3 are, independently of each other, hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group) and flows at about 450 sccm during the reaction with the compound. In one embodiment, NH3 is of the formula (R 1 R 2 R 3 Si)2Se (wherein R 1 , R 2 and R 3 are, independently of each other, hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group) and flows at about 500 sccm during the reaction with the compound. In one embodiment, NH3 is of the formula (R 1 R 2 R 3 Si)2Se (wherein R 1 , R 2 and R 3 are, independently of each other, hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group) and flows at about 750 sccm during the reaction with the compound. In one embodiment, NH3 is of the formula (R 1R 2 R 3 (R 1 、R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group) is flowed at about 1000 sccm during the reaction with the compound. In one embodiment, NH3 is of the formula (R 1 R 2 R 3 (R 1 、R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group) is flowed at about 1250 sccm during the reaction with the compound. In one embodiment, NH3 is of the formula (R 1 R 2 R 3 (R 1 、R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group) is flowed at about 1500 sccm during the reaction with the compound. In one embodiment, NH3 is of the formula (R 1 R 2 R 3 (R 1 、R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group) is flowed at about 1750 sccm during the reaction with the compound. In one embodiment, NH3 is of the formula (R 1 R 2 R 3 (R 1 、R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group) is flowed at about 2000 sccm during the reaction with the compound. In yet another aspect of each of the above embodiments, the formula (R 1 R 2 R3 (Si)2Se (wherein R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group) The compound contains, consists essentially of, or consists of (Me3Si)2Se.

[0054] In one embodiment of the above process, NH3 is of the formula (R 1 R 2 R 3 (Si)2S (wherein R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group), and the formula (R 1 R 2 R 3 (Si)2Se (wherein R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group). During both reactions with the compounds, it is circulated at substantially the same flow rate. In one embodiment of the above process, NH3 is of the formula (R 1 R 2 R 3 (Si)2S (wherein R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group), and the formula (R 1 R 2 R 3 (Si)2Se (wherein R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group). During both reactions with the compounds, it is circulated at the same flow rate. NH3 is of the formula (R 1 R 2 R 3 (Si)2S (wherein R1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group) during the reaction with a compound of formula (R 1 R 2 R 3 Si)2Se (wherein R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group) is circulated at a flow rate different from the flow rate during the reaction with a compound of formula (R 1 R 2 R 3 Si)2S (wherein R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group) contains, consists essentially of, or consists of (Me3Si)2S, and a compound of formula (R 1 R 2 R 3 Si)2Se (wherein R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group, or a benzyl group) contains, consists essentially of, or consists of (Me3Si)2Se.

[0055] The compounds of formula (R 1 R 2 R 3 Si)2S and / or (R 1 R 2 R 3 Si)2Se As described above, in various aspects of the disclosed and claimed processes, the compounds of formula (R 1 R 2 R 3 Si)2S and / or (R 1 R 2 R 3In (Si)2Se, R 1 , R 2 and R 3 are each independently hydrogen, a C1-C6 alkyl, alkenyl, aryl or alkynyl group or a benzyl group. In some embodiments, R 1 , R 2 and R 3 are each different. In some embodiments, two of R 1 , R 2 and R 3 are the same. In some embodiments, R 1 , R 2 and R 3 are each the same. Suitable R 1 , R 2 and R 3 groups include the following.

[0056] Hydrogen In one embodiment, one or more of R 1 , R 2 and R 3 are hydrogen. In one embodiment, two or more of R 1 , R 2 and R 3 are hydrogen. In one embodiment, R 1 , R 2 and R 3 are each hydrogen.

[0057] C1-C6 alkyl group C1-C6 alkyl groups include linear C1-C6 alkyl groups, branched C3-C6 alkyl groups and unsubstituted C3-C6 cyclic alkyl groups and the like. C1-C6 alkyl groups include linear C1-C6 alkyl groups, branched C3-C6 alkyl groups and unsubstituted C3-C6 cyclic alkyl groups and the like. Linear C1-C6 alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups and the like. In some embodiments, one or more of R 1 , R 2 and R 3 include C1-C6 alkyl selected from these groups. In one embodiment, R 1 , R 2and R 3 One or more of them are methyl.

[0058] C2-C6 alkenyl group The C2-C6 alkenyl group includes linear alkenyl and branched alkenyl, etc. The C2-C6 linear alkenyl includes ethenyl, 1-pyrropenyl, 2-propenyl, 1-butenyl, trans-2-butenyl, cis-2-butenyl, 3-butenyl, 1-pentenyl, trans-2-pentenyl, cis-2-pentenyl, trans-3-pentenyl, cis-3-pentenyl and 4-pentenyl, etc. The C2-C6 branched alkenyl includes isobutene, isopentenyl (2-methylbuta-1-enyl, 3-methylbuta-1-enyl) and isoamylenyl (2-methylbuta-2-enyl), etc. In some cases, R 1 , R 2 and R 3 One or more of them include C2-C6 alkenyl selected from these groups.

[0059] C3-C6 aryl group The C3-C6 aryl group includes C3-C6 aromatic groups, etc. In one aspect, the aromatic group includes a phenyl group, etc.

[0060] Benzyl group In one aspect, one or more of R 1 , R 2 and R 3 are benzyl groups.

[0061] C2-C6 alkynyl group The C2-C6 alkynyl group includes ethynyl, propynyl, propargyl, but-1-ynyl, but-2-ynyl and but-3-ynyl, etc.

[0062] Substrate temperature In one aspect, the substrate temperature is from about 150 °C to about 650 °C. In one aspect, the substrate temperature is from about 200 °C to about 600 °C. In one aspect, the substrate temperature is from about 250 °C to about 550 °C. In one aspect, the substrate temperature is from about 300 °C to about 500 °C. In one aspect, the substrate temperature is from about 325 °C to about 400 °C.

[0063] In one aspect, the substrate temperature is about 150 °C. In one aspect, the substrate temperature is about 200 °C. In one aspect, the substrate temperature is about 250 °C. In one aspect, the substrate temperature is about 300 °C. In one aspect, the substrate temperature is about 350 °C. In one aspect, the substrate temperature is about 400 °C. In one aspect, the substrate temperature is about 450 °C. In one aspect, the substrate temperature is about 500 °C. In one aspect, the substrate temperature is about 550 °C. In one aspect, the substrate temperature is about 600 °C. In one aspect, the substrate temperature is about 650 °C.

[0064] Metal precursor In one aspect of the above process, the metal precursor includes one or more of MoO2Cl2, MoO2Br2, MoCl5, MoCl6, MoOCl4, WO2Cl2, WCl4, WCl5, WCl6, WOCl4, TiCl4, ZrCl4, HfCl4, TaCl4, TaCl5, NbCl4, NbCl5, and / or various other precursors of these elements or other TMD-forming elements, and / or combinations thereof. In one aspect of the above process, the metal precursor includes MoO2Cl2. In one aspect of the above process, the metal precursor includes MoO2Br2. In one aspect of the above process, the metal precursor includes MoCl5. In one aspect of the above process, the metal precursor includes MoCl6. In one aspect of the above process, the metal precursor includes MoOCl4. In one aspect of the above process, the metal precursor includes WO2Cl2. In one aspect of the above process, the metal precursor includes WCl4. In one aspect of the above process, the metal precursor includes WCl6. In one aspect of the above process, the metal precursor includes WOCl4. In one aspect of the above process, the metal precursor includes TiCl4. In one aspect of the above process, the metal precursor includes ZrCl4. In one aspect of the above process, the metal precursor includes HfCl4. In one aspect of the above process, the metal precursor includes TaCl4. In one aspect of the above process, the metal precursor includes TaCl5. In one aspect of the above process, the metal precursor includes NbCl4. In one aspect of the above process, the metal precursor includes NbCl5.

[0065] In one of the other aspects of the process described above, examples of the metal precursor include one or more of MoBURE (bis(t-butylimide)bis(dimethylamino)molybdenum(VI)), TDMAMo (tetrakis(dimethylamino)molybdenum), TDEAMo (tetrakis(diethylamino)molybdenum), TEMAMo (tetrakis(ethylmethylamino)molybdenum), WNBURE (bis(t-butylimide)bis(dimethylamino)tungsten(VI)), TEMAZ (tetrakis(ethylmethylamino)zirconium), TEMAHf (tetrakis(ethylmethylamino)hafnium), TEMAT (tetrakis(ethylmethylamino)titanium), TDMAT (tetrakis(dimethylmethylamino)titanium), TDEAT (tetrakis(diethylmethylamino)titanium), TBTDMT ((t-butylimide)tris(dimethylamino)tantalum), TBTDET ((t-butylimide)tris(diethylamino)tantalum), TEMAV (tetrakis(ethylmethylamino)vanadium), various other precursors of these elements or other TMD-forming elements, and / or combinations thereof. In another aspect of the process described above, the metal precursor includes MoBURE (bis(t-butylimide)bis(dimethylamino)molybdenum(VI)). In another aspect of the process described above, the metal precursor includes TDMAMo. In another aspect of the process described above, the metal precursor includes TEMAMo. In another aspect of the process described above, the metal precursor gas includes WNBURE (bis(t-butylimide)bis(dimethylamino)tungsten(VI)). In one of the other aspects of the process described above, the metal precursor includes TEMAZ. In one of the other aspects of the process described above, the metal precursor includes TEMAHf. In one of the other aspects of the process described above, the metal precursor includes TEMAT. In one of the other aspects of the process described above, the metal precursor includes TDMAT. In one of the other aspects of the process described above, the metal precursor includes TDEAT.

Example

[0066] Hereinafter, more specific embodiments of the present disclosure and the experimental results supporting such embodiments will be described. In the following, examples are described to more fully explain the disclosed and claimed inventions, but these should not be construed as limiting the disclosed inventions in any way.

[0067] It will be apparent to those skilled in the art that various modifications and changes can be made to the disclosed inventions and the specific examples provided herein without departing from the spirit or scope of the disclosed inventions. Therefore, the disclosed inventions, including the descriptions provided by the following examples, are intended to encompass modifications and changes to the disclosed inventions that fall within the scope of any claims and their equivalents.

[0068] Materials and Methods: All reactions and operations described in the examples were carried out under an argon atmosphere using an intermolecular A30 ALD chamber. All chemicals were received from Versum Materials and Millipore-Sigma (EMD Electronics).

[0069] Specific Examples Example 1: In-situ Production of H2S for Generating MoS2 Films Figure 1 shows the Raman spectrum of 2D MoS grown with 100 ALD cycles using MoO2Cl2 as the Mo metal precursor and TMS2S combined with co-injection of NH3 as the in-situ H2S source. The inset shows the XRF counts when NH3 was co-injected during the TMS2S pulse and when NH3 was not co-injected. When NH3 was co-injected, the growth of 2D MoS was 545% higher, and when NH3 was not co-injected during the TMS2S pulse, it was also highly non-stoichiometric and MoS x showed virtually no growth. Note that in order to compare the films with the same delivery conditions as the deposition without co-injection of NH3 (i.e., the unoptimized ALD process), when NH3 was co-injected, MoS x The growth of 2D was 545% more, and when NH3 was not co-injected during the TMS2S pulse, it was also highly non-stoichiometric and MoS x showed virtually no growth. When comparing the films with the same delivery conditions as the deposition without co-injection of NH3 (i.e., the unoptimized ALD process), when NH3 was co-injected, MoS xNote that the sulfur is insufficient (x is not 2.0 but about 1.5).

[0070] As shown in Figure 2, an optimized ALD process in which NH3 was injected during the TMS2S pulse using the same Mo precursor formed MoS 1.9 thin films, which is far from the fact that MoO2Cl2 and TMS2S hardly react without NH3 co-injection. Therefore, it proves that H2S was produced in situ by NH3 co-injection with TMS2S in the same ALD pulse.

[0071] As shown in Figure 3, it shows the XPS composition of the optimized ALD process in which NH3 was injected during the TMS2S pulse shown in Figure 2. This sample shows an S / Mo equal to 1.9, while the Mo-O bond is negligible as evidenced by the absence of a peak at a binding energy of about 235.5 eV. Si and O are from the SiO2 substrate, and these are measured by X-rays that have traveled through the atomically thin 2D material to the SiO2 substrate under the MoS2 film and back to the detector. The carbon content in the film is low and all or most of it is accidental (this cannot escape from the surface of the atomically thin 2D film unless the entire film is removed during the process).

[0072] Example 2: In-situ production of H2Se for generating MoSe2 films In-situ H2Se production using NH3 co-injection during the TMS2Se pulse in an ALD or CVD process is demonstrated by a large change in the deposition rate when NH3 is added to the process compared to when NH3 is not used.

[0073] Figure 4 shows the difference in XRF Mo counts and XRF Se counts between the case where NH3 was co-injected during the TMS2Se pulse and the case where only the TMS2Se pulse was performed. As shown in Figure 4, when NH3 is injected during the TMS2Se pulse in the ALD MoSe2 process using a Mo precursor, the yield of the MoSe2 thin film increases significantly. The 370% increase in film thickness when NH3 was co-injected and the Raman in Figure 4 indicate that this is due to in-situ H2Se production. Note that for MoSe2, the raw XRF Se / Mo count of the stoichiometric film is about 0.6, so the XPS Se / Mo ratio equal to 1.9 is also listed on the left side of the table for your attention.

[0074] Figure 5 shows the Raman spectrum of the as-grown MoSe formed by co-injecting NH3 during the TMS2Se pulse in Example 2. As shown in Figure 5, when NH3 is co-injected during the TMS2Se pulse, a 2D MoSe film with a narrow full width at half maximum (FWHM) is formed. 約1.9-2.1 As shown in Figure 5, when NH3 is co-injected during the TMS2Se pulse, a 2D MoSe film with a narrow A 1g full width at half maximum (FWHM) is formed. 約1.9-2.1 film is formed.

[0075] Figure 6 shows the XPS of the as-grown MoSe2 film grown in Example 2. As shown in Figure 6, the XPS Se / Mo ratio of the 2D MoSe2 film of this sample is 1.9.

[0076] The above description is primarily intended for purposes of illustration. Although the disclosed and claimed invention has been described and illustrated with respect to exemplary embodiments thereof, it should be understood by those skilled in the art that various other changes, omissions, and additions in form and detail may be made without departing from the spirit and scope of the disclosed and claimed invention.

Claims

1. 1. A method for forming a 2D transition metal disulfide and / or diselenide-containing film on a substrate, comprising: ２ S and H ２ and generating one or more of Se in situ. The formation of the 2D transition metal disulfide and / or diselenide-containing film comprises one of the following processes (A) or (B): (A) a chemical vapor deposition (CVD) process comprising the steps of: (1) contacting a substrate in a deposition chamber with a vapor comprising: (a) and (b); (a) one or more externally supplied metal precursors, and (b) one or more of (i) H2S and (ii) H2Se; (2) optionally purging the vapor with an inert gas; or (B) a thermal atomic layer deposition (ALD) or thermal ALD-like process comprising the steps of: (1) contacting a substrate in a deposition chamber with a first vapor comprising one of: (a) or (b); (a) one or more externally supplied metal precursors; or (b) one or more of (i) H2S and (ii) H2Se; (2) purging the first vapor with an inert gas; (3) contacting a second vapor comprising the other of: (a) or (b); (a) said one or more externally supplied metal precursors; or (b) one or more of (i) H2S and (ii) H2Se; (4) optionally purging the second vapor with an inert gas; and (5) sequentially repeating steps (1) through (4) until a metal-containing film of a desired thickness is obtained; however, (i) the H 2 S is generated in situ by reacting a compound of the formula (R 1 R 2 R 3 Si) 2 S, where R 1 , R 2 and R 3 are each independently hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 3 -C 6 aryl, benzyl or C 2 -C 6 alkynyl groups, with NH 3 in a deposition chamber; and (ii) the H 2 Se is generated in situ by reacting a compound of the formula (R 1 R 2 R 3 Si) 2 Se, where R 1 , R 2 and R 3 are each independently hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 3 -C 6 aryl, benzyl or C 2 -C 6 alkynyl groups, with NH 3 in a deposition chamber; The method.

2. R １ , R ２ and R ３ One or more of the following is C １ -C ６ Alkyl group, branched C ３ -C ６ Alkyl group or unsubstituted C ３ -C ６ The method of claim 1 , comprising a cyclic alkyl group.

3. R １ , R ２ and R ３ One or more of the following is C １ -C ６ The method of claim 1 , comprising an alkyl group.

4. R １ , R ２ and R ３ one or more of which are selected from the group consisting of a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group １ -C ６ The method of claim 1 , comprising an alkyl group.

5. R １ , R ２ and R ３ The method of claim 1 , wherein one or more of the following groups comprises a methyl group:

6. R １ , R ２ and R ３ at least one of which is selected from a linear alkenyl group and a branched alkenyl group; ２ -C ６ The method of claim 1 , comprising an alkenyl group.

7. R １ , R ２ and R ３ one or more of which are selected from the group consisting of ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, trans-2-butenyl, cis-2-butenyl, 3-butenyl, 1-pentenyl, trans-2-pentenyl, cis-2-pentenyl, trans-3-pentenyl, cis-3-pentenyl, and 4-pentenyl ２ -C ６ The method of claim 1 comprising a linear alkenyl group.

8. R １ , R ２ and R ３ one or more of which are selected from isobutenyl, isopentenyl (2-methylbut-1-enyl, 3-methylbut-1-enyl) and isoamylenyl (2-methylbut-2-enyl). ２ -C ６ The method of claim 1 comprising a branched alkenyl group.

9. R １ , R ２ and R ３ One or more of the following is C ３ -C ６ The method of claim 1 , comprising an aryl group.

10. R １ , R ２ and R ３ at least one of which is an aromatic group ３ -C ６ The method of claim 1 , comprising an aryl group.

11. R １ , R ２ and R ３ The method of claim 1 , wherein one or more of comprises a phenyl group.

12. R １ , R ２ and R ３ The method of claim 1 , wherein one or more of the following groups comprises a benzyl group:

13. R １ , R ２ and R ３ One or more of the following is C ２ -C ６ The method of claim 1 , comprising an alkynyl group.

14. R １ , R ２ and R ３ one or more of which are selected from the group consisting of ethynyl, propynyl, propargyl, but-1-ynyl, but-2-ynyl and but-3-ynyl ２ -C ６ The method of claim 1 , comprising an alkynyl group.

15. (i) the H ２ S is in the deposition chamber, TMS ２ S to NH ３ 15. The method of any one of claims 1 to 14, wherein the compound is generated in situ by reacting

16. (ii) the H ２ Se is deposited in the deposition chamber using TMS ２ Se to NH ３ 15. The method of any one of claims 1 to 14, wherein the compound is generated in situ by reacting

17. NH ３ However, (R １ R ２ R ３ Si) ２ The method of any one of claims 1 to 14, wherein the S is flowed at about 50 sccm to about 2000 sccm during the S pulse.

18. The method of any one of claims 1 to 14, wherein the substrate temperature is from about 150°C to about 650°C.

19. The metal precursor gas is MoO ２ Cl ２ , MoCl ５ , MoCl ６ , MoOCl ４ , W.O. ２ Cl ２ , WCl ４ , WCl ５ , WCl ６ , WOCl ４ , TiCl ４ , ZrCl ４ , HfCl ４ , TaCl ４ , TaCl ５ , NbCl ４ , NbCl ５ The method of any one of claims 1 to 14, comprising one or more of the following:

20. 15. The method of any one of claims 1 to 14, wherein the metal precursor comprises one or more of MoBURE (bis(t-butylimido)bis(dimethylamino)molybdenum(VI)), TDMAMo, TDEAMo, TEMAMo, WNBURE (bis(t-butylimido)bis(dimethylamino)tungsten(VI)), TEMAZ, TEMAHf, TEMAT, TDMAT, TDEAT, and combinations thereof.

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