In situ generation of H2S or H2Se during growth of two-dimensional films of transition metal disulfides and / or diselenide

Abstract

The presently disclosed and claimed subject matter relates to a method of generating H2S and / or H2Se in situ during the growth of a two-dimensional film containing transition metal disulphides and / or diselenide.

Description

Technical Field

[0001] The disclosed and claimed subject matter relates to a method for in-situ generation of H2S and / or H2Se during the growth of two-dimensional films containing transition metal disulfides and / or diselenides. Background Art

[0002] For transition metal-containing films for semiconductor and electronic applications, chemical vapor deposition (CVD) and atomic layer deposition (ALD) have been used as the main deposition techniques for producing thin films for semiconductor devices. These methods can achieve conformal films (metals, metal oxides, metal nitrides, metal silicides, and the like) through chemical reactions of transition metal-containing compounds (precursors). The chemical reactions occur on surfaces that may include metals, metal oxides, metal nitrides, metal silicides, silicon dioxide, silicon nitride, and other surfaces. In CVD and ALD, precursor molecules play a key role in achieving high-quality films with high conformality and low impurities. The temperature of the substrate in the CVD and ALD processes is an important consideration in selecting precursor molecules. Higher substrate temperatures in the range of 150 to 500 degrees Celsius (°C) promote higher film growth rates. Preferred precursor molecules must be stable in this temperature range. The preferred precursors can be delivered to the reaction vessel in a liquid phase. Liquid phase delivery of precursors generally provides more uniform precursor delivery to the reaction vessel than solid phase precursors.

[0003] CVD and ALD processes are increasingly used because of their advantages of enhanced composition control, high film uniformity, and effective control of doping. In addition, CVD and ALD processes provide excellent conformal step coverage on highly non-planar geometries associated with modern microelectronic devices.

[0004] CVD is a chemical process by which a precursor can be used to form a thin film on a substrate surface. In a typical CVD process, the precursor is passed over the surface of a substrate (e.g., a wafer) in a low pressure or ambient pressure reaction chamber. The precursor reacts and / or decomposes on the substrate surface to produce a thin film of deposited material. Plasma can be used to assist the reaction of the precursor or to modify the material properties. Volatile byproducts are removed by gas flow 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 flow volume and uniformity, chemical loss effects, and time.

[0005] ALD is a chemical process for depositing thin films. It is a self-limiting, sequential, unique film growth technology based on surface reactions that provides precise thickness control and allows conformal thin films of materials provided by precursors to be deposited on surface substrates of varying composition. In ALD, the precursor is separated during the reaction. A first precursor is passed over the substrate surface, producing a monolayer on the substrate surface. Any excess unreacted precursor is pumped out of the reaction chamber. A second precursor or co-reactant is then passed over the substrate surface and reacts with the first precursor, forming a second monolayer on the first formed monolayer on the substrate surface. Plasma can be used to assist the reaction of the precursor or co-reactant or to improve the quality of the material. This cycle is repeated to produce a film of the desired thickness.

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

[0007] In order to grow two-dimensional transition metal disulfide films using H2S and / or to grow two-dimensional transition metal diselenide films using H2Se, it was previously necessary to supply H2S and / or H2Se by means of connecting gas bottles or facilitating the supply of H2S to the growth chamber. However, the use of H2S and / or H2Se supplied externally to the chamber presents many complications due to their toxicity. At a minimum, a significant investment is required to acquire and install the required associated equipment (e.g., gas detectors and safety systems, and go through toxic and fire permit procedures) 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 increase processing time.

[0008] The disclosed and claimed method addresses and largely eliminates these problems by providing in-situ generation of H2S and / or H2Se within a deposition chamber during deposition of two-dimensional metal dichalcogenide films. Summary of the invention

[0009] The disclosed and claimed subject matter relates to a method for growing a two-dimensional film containing transition metal disulfides and / or diselenides by 1 R 2 R 3 Si)2X and NH3 are co-injected into a deposition chamber to generate H2X and in-situ generate H2S and / or H2Se, wherein R 1 , R 2 and R 3 are each independently hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C3-C6 aryl or C2-C6 alkynyl (collectively referred to as "C1-C6 alkyl, alkenyl, aryl or alkynyl") or benzyl, and X is S or Se. In a preferred embodiment, R1 , R 2 and R 3 In one aspect of the disclosed and claimed subject matter relates to a 1 R 2 R 3 Si)2S compound and / or formula (R 1 R 2 R 3 Use of compounds of Si)2Se, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C3-C6 aryl, benzyl or C2-C6 alkynyl, and is used together with NH3 to form a two-dimensional film containing transition metal disulfide and / or diselenide on a substrate.

[0010] In one embodiment, R 1 , R 2 and R 3 Each of them is methyl and X is sulfur (ie, "(Me3Si)2S" or "TMS2S"), which reacts with NH3 to generate H2S according to the following procedure: (Me3Si)2S+NH3→H2S+(Me3Si)2NH.

[0011] In one embodiment, R 1 , R 2 and R 3 Each of them is methyl and X is selenium (ie, "(Me3Si)2Se" or "TMS2Se"), which reacts with NH3 to generate H2Se according to the following procedure: (Me3Si)2Se+NH3→H2Se+(Me3Si)2NH.

[0012] In another embodiment, the disclosed and claimed subject matter includes in-situ generation of H2S and / or H2Se during a CVD deposition process.

[0013] In another embodiment, the disclosed and claimed subject matter includes in-situ generation of H 2 S and / or H 2 Se during an ALD deposition process. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] The accompanying drawings are included to provide a further understanding of the disclosed subject matter and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosed subject matter and together with the description serve to explain the principles of the disclosed subject matter. In the drawings:

[0015] Figure 1The Raman spectrum of the resulting MoS2 film of Example 1 is shown. The inset is the average background-subtracted XRF data of the wafer deposited in the presence and absence of NH3 co-injection during the TMS2S pulse. It should be noted that when XRF data is reported here, it is always background-subtracted XRF;

[0016] Figure 2 The Raman spectrum of the resulting MoS2 film of Example 1 is shown. The inset is the average XRF data for this run, showing that the optimized MoS2 film has a significantly closer XRFS / Mo ratio to stoichiometric. It should be noted that the original XRFS / Mo ratio of the stoichiometric MoS2 film has been calibrated to about 2.1;

[0017] Figure 3 Draw Figure 2 The XPS composition of the film of Example 1 shown in , shows that the S / Mo ratio of this sample is equal to 1.9, while there is negligible Mo-O bonding, as evidenced by the lack of a peak at a binding energy of about 235.5 eV. The Si and O come from the SiO2 substrate, which is measured by x-rays that travel through the two-dimensional atomically thin material to the SiO2 substrate below the MoS2 film and back to the detector. The carbon content in the film is low and all or most of it is exogenous (cannot be splashed away from the surface of the two-dimensional atomically thin film without removing the entire film in the process).

[0018] Figure 4 shows XRF data for both the MoSe2 film in Example 3 deposited by NH3 co-injection during a TMS2SeALD pulse and the MoSe2 film deposited by the same ALD method but without NH3 co-injection;

[0019] Figure 5 The Raman spectrum of the MoSe2 film obtained in Example 3 is shown; and

[0020] Figure 6 The XPS of the MoSe2 film obtained in Example 3 is shown. DETAILED DESCRIPTION

[0021] All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference was individually and specifically indicated to be incorporated by reference and was set forth in its entirety herein.

[0022] Unless otherwise specified herein or clearly contradictory to the content, the use of the terms "one" and "the" and similar indicators in the context of describing the disclosed and claimed subject matter (especially in the context of the following claims) should be interpreted as covering the singular and the plural. Unless otherwise noted, the terms "including", "having", "including" and "containing" should be interpreted as open terms (i.e., meaning "including but not limited to"). Unless otherwise specified herein, the description of the range of values ​​herein is only intended to be used as a shorthand method for each reference to each individual value falling within the range, and each individual value is incorporated into this specification as if it were individually cited in the text. Unless otherwise specified herein or clearly contradictory to the content, all methods described herein can be performed in any suitable order. Unless otherwise required, the use of any and all examples, or exemplary language (e.g., "such as") provided herein is intended only to better illustrate the disclosed and claimed subject matter and does not limit the scope of the disclosed and claimed subject matter. No language in this specification should be construed as indicating any non-claimed element as essential to the practice of the disclosed and claimed subject matter. The use of the terms "comprising" or "including" in this specification and claims includes the narrower language of "consisting essentially of" and "consisting of."

[0023] Embodiments of the disclosed and claimed subject matter are described herein, including the best modes known to the inventors for carrying out the disclosed and claimed subject matter. Those skilled in the art will appreciate variations of those embodiments after reading the foregoing description. The inventors expect those skilled in the art to appropriately adopt such variations, and the inventors expect to practice the disclosed and claimed subject matter in other ways than as specifically described herein. Therefore, the disclosed and claimed subject matter includes all modifications and equivalents of the subject matter listed in the appended claims of the present invention as permitted by applicable law. In addition, unless otherwise specified herein or otherwise clearly contradictory to the content, the disclosed and claimed subject matter covers any combination of the above elements in all possible variations thereof.

[0024] It should be understood that the term "silicon" when deposited as a material on a microelectronic device shall include polysilicon.

[0025] For ease of reference, "microelectronic devices" or "semiconductor devices" correspond to semiconductor wafers having integrated circuits, memory and other electronic structures fabricated thereon, as well as flat panel displays, phase change memory devices, solar panels and other products manufactured for use in microelectronic, integrated circuit or computer chip applications (including solar substrates, photovoltaic devices and microelectromechanical systems (MEMS)). Solar substrates include, but are not limited to, silicon, amorphous silicon, polycrystalline silicon, single crystal silicon, CdTe, copper indium selenide, copper indium sulfide and gallium-on-gallium arsenide. Solar substrates may be doped or undoped. It should be understood that the term "microelectronic device" or "semiconductor device" is not meant to be limiting in any way and includes any substrate that will eventually become a microelectronic device or microelectronic assembly.

[0026] As defined herein, the term "barrier material" corresponds to any material used in the art to seal metal lines (e.g., copper interconnects) to minimize diffusion of the metal (e.g., copper) into dielectric materials. Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium, and other refractory metals and their nitrides and silicides.

[0027] As used herein, the term "about" or "approximately" and the symbol "~" are intended to correspond to ±5% of the stated value.

[0028] Unless otherwise indicated, "alkylene" means a straight-chain saturated divalent hydrocarbon radical having one to six carbon atoms or a branched-chain saturated divalent hydrocarbon radical having three to six carbon atoms (e.g., methylene, ethylene, propylene, 1-methylpropylene, 2-methylpropylene, butylene, pentylene, and the like).

[0029] As used herein, “C x-y " or "C x -C y ” (where x and y are each integers) represents the number of carbon atoms in the chain. For example, C 1-6 Or C1-C6 alkyl refers to an alkyl chain having between 1 and 6 carbons (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl). Unless specifically stated otherwise, the chain may be straight or branched (i.e., branched C3-C6 alkyl).

[0030] Unless otherwise indicated, "alkyl" refers to a hydrocarbon group that can be straight chain, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, and the like), cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, and the like), or polycyclic (e.g., norbornyl, adamantyl, and the like). Suitable non-cyclic groups can be methyl, ethyl, n-propyl or isopropyl, n-butyl, isobutyl or tert-butyl, straight or branched pentyl, hexyl. Unless otherwise stated, alkyl refers to a 1 to 6 carbon atom moiety. Cycloalkyl can be monocyclic. Suitable examples of monocyclic alkyls include substituted cyclopentyl, cyclohexyl, and cycloheptyl.

[0031] "Heteroalkylene" means an -(alkylene)- group as defined above wherein one, two, or three carbons in the alkylene chain are replaced with -O-, N(H, alkyl, or substituted alkyl), S, SO, SO2, or CO. In some preferred embodiments, the carbons are replaced with O or N.

[0032] In all such compositions, where a particular component of the composition is discussed with reference to a weight percent (or "wt %) range (including a zero lower limit), it is understood that such components may or may not be present in various specific embodiments of the composition, and where such components are present, they may be present at a concentration as low as 0.001 weight percent based on the total weight of the composition in which such components are employed. Please note that all percentages of components are weight percentages and are based on the total weight of the composition (i.e., 100%). Any reference to "one or more" or "at least one" includes "two or more" and "three or more" and so on.

[0033] Where applicable, unless otherwise indicated, all weight percentages are "neat," meaning they do not include the aqueous solution in which they are present when added to the composition. For example, "neat" refers to the weight % amount of the undiluted acid or other material (i.e., the content of 100 g of 85% phosphoric acid is composed of 85 g of acid and 15 grams of diluent).

[0034] In addition, when referring to the compositions described herein in wt%, it is understood that in any case, the wt% of all components (including non-essential components, such as impurities) shall not add up to more than 100 wt%. In a composition "essentially consisting of the listed components", such components may add up to 100 wt% of the composition or may add up to less than 100 wt%. In the case where the components add up to less than 100 wt%, such compositions may include some small amounts of non-essential contaminants or impurities. For example, in one such embodiment, the formulation may contain 2 wt% or less impurities. In another embodiment, the formulation may contain 1 wt% or less impurities. In another embodiment, the formulation may contain 0.05 wt% or less impurities. In other such embodiments, the ingredients may account for at least 90 wt%, more preferably at least 95 wt%, more preferably at least 99 wt%, more preferably at least 99.5 wt%, most preferably at least 99.9 wt%, and may include other ingredients that do not substantially affect the performance of the wet etchant. Otherwise, in the absence of significant non-essential impurity components, it is understood that the composition of all essential constituent components will substantially total 100% by weight.

[0035] The headings used herein are not intended to be limiting; rather, they are included for organizational purposes only.

[0036] Exemplary embodiments

[0037] As noted above, the disclosed and claimed subject matter relates to a method of in-situ generation of H2S and / or H2Se during growth of a two-dimensional film containing disulfides and / or diselenides by an ALD and / or CVD deposition process. In other words, the disclosed and claimed subject matter relates to a method of forming a two-dimensional film containing transition metal disulfides and / or diselenides on a substrate, the method comprising generating one or more of H2S and H2Se in-situ 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 that react and / or decompose on the substrate surface to generate a desired deposition, and includes ALD and / or CVD deposition processes.

[0038] In particular, the disclosed and claimed subject matter relates to a method for growing a two-dimensional film containing transition metal disulfides and / or diselenides by removing (R 1 R 2 R 3 Si)2X and NH3 are co-injected into a deposition chamber to generate H2X and in-situ generate H2S and / or H2Se, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl. In one embodiment, R 1 , R 2 and R 3 Each of R is independently hydrogen, linear C1-C6 alkyl, branched C3-C6 alkyl, C3-C6 unsubstituted cycloalkyl, C3-C6 aromatic or benzyl, C2-C6 alkenyl and C2-C6 alkynyl. In one embodiment, R 1 , R 2 and R 3 In one embodiment, R 1 , R 2 and R 3 At least one of them is related to R 1 , R 2 and R 3 Other differences in .

[0039] In one embodiment, X is sulfur and R 1 , R 2 and R 3 Each of the R is independently hydrogen, linear C1-C6 alkyl, branched C3-C6 alkyl, C3-C6 unsubstituted cycloalkyl, C3-C6 aromatic, benzyl, C2-C6 alkenyl, and C2-C6 alkynyl. In one aspect of this embodiment, R1 , R 2 and R 3 In one aspect of this embodiment, R 1 , R 2 and R 3 At least one of them is related to R 1 , R 2 and R 3 In another aspect of this embodiment, X is sulfur, and R 1 , R 2 and R 3 In another aspect of this embodiment, X is sulfur, and R 1 , R 2 and R 3 Each of the above is methyl and reacts with NH3 to generate H2S according to the following procedure: (Me3Si)2S+NH3→H2S+(Me3Si)2NH. In yet another aspect of this embodiment, X is sulfur and R 1 is hydrogen, R 2 and R 3 Each of the above is a methyl group and reacts with NH 3 to generate H 2 S according to the following procedure: (Me 2 HSi) 2 S + NH 3 → H 2 S + (Me 2 HSi) 2 NH.

[0040] In one embodiment, X is selenium and R 1 , R 2 and R 3 Each of the R is independently hydrogen, linear C1-C6 alkyl, branched C3-C6 alkyl, C3-C6 unsubstituted cycloalkyl, C3-C6 aromatic, benzyl, C2-C6 alkenyl, and C2-C6 alkynyl. In one aspect of this embodiment, R 1 , R 2 and R 3 In one aspect of this embodiment, R 1 , R 2 and R 3 At least one of them is related to R 1 , R 2 and R 3 In another aspect of this embodiment, X is selenium, and R 1 , R 2 and R 3 In another aspect of this embodiment, X is selenium, and R 1 , R 2 and R 3Each of the above is methyl and reacts with NH3 to generate H2Se according to the following procedure: (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 Each of the Me2HSi and the H2Se is a methyl group and reacts with NH3 to generate H2Se according to the following procedure: (Me2HSi)2Se+NH3→H2Se+(Me2HSi)2NH.

[0041] In one embodiment, both H2S and H2Se are each generated during the growth of a multicomponent two-dimensional film comprising disulfide and diselenide. 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 generate H2S and H2Se, where R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, R 1 , R 2 and R 3 Each of the above is independently a linear C1-C6 alkyl group, a branched C3-C6 alkyl group, a C3-C6 unsubstituted 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, in the compound (R 1 R 2 R 3 In Si)2S, R 1 , R 2 and R 3 In one aspect of this embodiment, in the compound (R 1 R 2 R 3 In Si)2Se, R 1 , R 2 and R 3 Each of them is a methyl group.

[0042] As used herein, the term "atomic layer deposition process" or ALD refers to self-limiting deposition (e.g., the amount of film material deposited in each reaction cycle is limited by the surface to a constant "saturation" deposition rate), that is, sequential surface chemical reactions that deposit films of material onto substrates of different compositions. Although the precursors, reagents, and sources used herein may sometimes be described as "gases," it should be understood that the precursors may be liquids or solids that are delivered to the reactor via direct vaporization, bubbling, or sublimation with or without an inert gas. In some cases, the vaporized precursor may be passed through a plasma generator. As used herein, the term "reactor" includes, without limitation, a reaction chamber, a reaction vessel, or a deposition chamber.

[0043] Chemical vapor deposition processes in which in-situ generated H2S and / or H2Se can be utilized include, but are not limited to, processes used to fabricate semiconductor-type microelectronic devices, such as ALD and plasma-enhanced ALD (PEALD). Thus, in one embodiment, for example, the metal-containing film is deposited using an ALD process. In another embodiment, for example, the metal-containing film is deposited using a plasma-enhanced ALD (PEALD) process.

[0044] Suitable substrates on which in-situ generated H2S and / or H2Se can be used are not particularly limited and vary depending on the intended end use. For example, the substrate can be selected from oxides such as HfO2-based materials, TiO2-based materials, ZrO2-based materials, rare earth oxide-based materials, ternary oxide-based materials, etc., or from nitride-based films. Other substrates may 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); substrates containing metal nitrides (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 barium strontium titanate); combinations thereof. Preferred substrates include HfO2-based materials, TiO2-based materials, ZrO2-based materials, rare earth oxide-based materials, and silicon oxide-based substrates.

[0045] The deposition method and process may also involve one or more purge gases. The purge gas used to flush away unconsumed reactants and / or reaction byproducts is an inert gas that does not react with the precursor. 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 to the reactor at a flow rate in the range of about 10 to about 2000 sccm for about 0.1 to 10,000 seconds, thereby purging unreacted materials and any byproducts that may remain in the reactor.

[0046] Deposition methods and processes may require the application of energy to at least one of the components used to form the metal-containing film or coating on the substrate. This energy may be provided by, but is not limited to, thermal, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, X-ray, electron beam, photon, remote plasma methods, and combinations thereof. In some processes, a secondary RF frequency source may be used to modify the plasma characteristics at the substrate surface. When utilizing plasma, the plasma generation process may include a direct plasma generation process, in which the plasma is generated directly in the reactor, or a remote plasma generation process, in which the plasma is generated outside the reactor and supplied to the reactor.

[0047] 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 a variety of ways. In some cases, a liquid delivery system can be utilized. In other cases, a combined liquid delivery and flash process unit can be employed, such as a turbo vaporizer manufactured by MSP Corporation of Shoreview, MN, to enable volumetric delivery of low volatility materials that produces reproducible delivery and deposition without thermal decomposition of the precursors. The precursor compositions described herein can be effectively used as source reagents to provide vapor streams of these metal precursors to the ALD reactor via direct liquid injection (DLI).

[0048] In view of the foregoing, one skilled in the art will recognize that the disclosed and claimed subject matter further includes methods of forming two-dimensional films containing transition metal disulfides and / or diselenides on a substrate using H2S and / or H2Se generated in situ in a chemical vapor deposition process as follows.

[0049] CVD

[0050] In one aspect, the disclosed and claimed subject matter includes a method of forming a two-dimensional film containing a transition metal disulfide and / or diselenide via a chemical vapor deposition (CVD) process, the process comprising the steps of:

[0051] (1) contacting a substrate in a deposition chamber with a vapor comprising:

[0052] (a) one or more externally supplied metal precursors, and

[0053] (b) one or more of (i) H2S and (ii) H2Se; and

[0054] (2) optionally purging the vapor with an inert gas,

[0055] Wherein (i) by making the formula (R 1 R 2 R 3 Si)2S compounds react with NH3 to generate H2S in situ, wherein R 1 , R 2 and R 3 are independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl, and / or (ii) by reacting a radical of formula (R 1 R 2 R 3 Si)2Se compounds react with NH3 to generate H2Se in situ, where R 1 , R 2 and R 3 are each independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In another aspect of this embodiment, (i) by allowing a radical of formula (R 1 R 2 R 3 Si)2S compound is reacted with NH3 to generate H2S in situ, wherein a linear C1-C6 alkyl group, a branched C3-C6 alkyl group, a C3-C6 unsubstituted cycloalkyl group, a C3-C6 aromatic group, a C2-C6 alkenyl group and a C2-C6 alkynyl group or a benzyl group, and / or (ii) by reacting a compound of formula (R 1 R 2 R 3 Si)2Se compounds react with NH3 to generate H2Se in situ, where R 1 , R 2 and R 3Each is independently a linear C1-C6 alkyl, a branched C3-C6 alkyl, a C3-C6 unsubstituted cycloalkyl, a C3-C6 aromatic group, a C2-C6 alkenyl group, and a C2-C6 alkynyl group or a benzyl group. In another aspect of this embodiment, (i) H2S is generated in situ by reacting (Me3Si)2S+NH3 in a deposition chamber, and (ii) H2Se is generated in situ by reacting (Me3Si)2Se+NH3 in a deposition chamber. In another aspect of this embodiment, the method consists essentially of steps (i) and (ii). In another aspect of this embodiment, the method consists of steps (i) and (ii).

[0056] ALD

[0057] In one embodiment, the disclosed and claimed subject matter includes a method of forming a two-dimensional film containing a transition metal disulfide and / or diselenide via a thermal atomic layer deposition (ALD) process or a thermal ALD-like process, the process comprising the steps of:

[0058] (1) contacting a substrate in a deposition chamber with a first vapor comprising one of:

[0059] (a) one or more externally supplied metal precursors, or

[0060] (b) one or more of (i) H2S and (ii) H2Se;

[0061] (2) purging the first vapor with an inert gas;

[0062] (3) contacting a second vapor comprising the other of:

[0063] (a) the one or more externally supplied metal precursors, or

[0064] (b) one or more of (i) H2S and (ii) H2Se;

[0065] (4) optionally purging the second vapor with an inert gas; and

[0066] (5) Repeating steps (1) to (4) in sequence until a metal-containing film of a desired thickness is obtained.

[0067] Wherein (i) by making the formula (R 1 R 2 R 3 Si)2S compounds react with NH3 to generate H2S in situ, where R 1 , R 2 and R 3are independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl, and / or (ii) by reacting a radical of formula (R 1 R 2 R 3 Si)2Se compounds react with NH3 to generate H2Se in situ, where R 1 , R 2 and R 3 are each independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In another aspect of this embodiment, (i) by allowing a radical of formula (R 1 R 2 R 3 Si)2S compound reacts with NH3 to generate H2S in situ, where R 1 , R 2 and R 3 are each independently a linear C1-C6 alkyl group, a branched C3-C6 alkyl group, a C3-C6 unsubstituted cycloalkyl group, a C3-C6 aromatic group, a C2-C6 alkenyl group or a C2-C6 alkynyl group, a benzyl group, and / or (ii) by reacting a alkyl radical of the formula (R 1 R 2 R 3 Si)2Se compounds react with NH3 to generate H2Se in situ, where R 1 , R 2 and R 3 Each is independently a linear C1-C6 alkyl, a branched C3-C6 alkyl, a C3-C6 unsubstituted cycloalkyl, a C3-C6 aromatic group, a benzyl group, a C2-C6 alkenyl group or a C2-C6 alkynyl group. In another aspect of this embodiment, (i) H2S is generated in situ by reacting (Me3Si)2S + NH3 in a deposition chamber, and (ii) H2Se is generated in situ by reacting (Me3Si)2Se + NH3 in a deposition 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).

[0068] In another aspect of this embodiment, the method is carried out at a temperature of about 100°C to about 650°C. In another aspect of this embodiment, the method is carried out at a pressure of about 0.1 torr to about 100 torr. In another aspect of this embodiment, the method is carried out at a temperature of about 100°C to about 650°C and a pressure of about 0.1 torr to about 100 torr. In another aspect, the deposition temperature and pressure are adjusted to the selected one or more externally supplied metal precursors. In another aspect of this embodiment, the metal precursor of formula (R 1 R 2 R3 Si)2S compound (where R 1 , R 2 and R 3 Each independently is hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl) + NH3 and / or formula (R 1 R 2 R 3 Si)2Se compound (where R 1 , R 2 and R 3 Each independently C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl) + NH3 are co-injected into the deposition chamber. In another aspect of this embodiment, the formula (R 1 R 2 R 3 Si)2S compound (where R 1 , R 2 and R 3 each independently a linear C1-C6 alkyl group, a branched C3-C6 alkyl group, a C3-C6 unsubstituted cycloalkyl group, a C3-C6 aromatic group, a benzyl group, a C2-C6 alkenyl group or a C2-C6 alkynyl group) + NH3 and / or a group of formula (R 1 R 2 R 3 Si)2Se compound (where R 1 , R 2 and R 3 In another aspect of this embodiment, TMS2S+NH3 and / or TMS2Se+NH3 are co-injected into the deposition chamber. In another aspect of this embodiment, TMS2S+NH3 and / or TMS2Se+NH3 are sequentially injected into the deposition chamber.

[0069] In another aspect of this embodiment, in step (1), the first vapor comprises (a) one or more externally supplied metal precursors. In another aspect of this embodiment, in step (1), the first vapor comprises (b) (i) one or more of H2S and (ii) H2Se. In another aspect of this embodiment, in step (1), the first vapor comprises (i) H2S. In another aspect of this embodiment, in step (1), the first vapor comprises (ii) H2Se. In another aspect of this embodiment, in step (3), the second vapor comprises (a) one or more externally supplied metal precursors. In another aspect of this embodiment, in step (3), the second vapor comprises (b) (i) one or more of H2S and (ii) H2Se. In another aspect of this embodiment, in step (3), the second vapor comprises (i) H2S. In another aspect of this embodiment, in step (3), the second vapor comprises (ii) H2Se.

[0070] Carrier gas

[0071] In one embodiment of the above process, one or more externally supplied metal precursors are introduced (i.e., supplied to) the reaction vessel using a carrier gas flow that is one or more of argon, nitrogen, helium, neon, and / or krypton. When delivering one or more externally supplied precursors, the reaction chamber process pressure is between 1 Torr and 50 Torr, preferably between 5 Torr and 20 Torr.

[0072] Inert gas

[0073] In one embodiment of the above process, the inert gas is one or more of argon, nitrogen, helium, neon, krypton, and combinations thereof.

[0074] Energy Source

[0075] In one embodiment of the above process, the method further includes applying energy to one or more externally supplied metal precursors, one or more of (i) H2S and (ii) H2Se, a carrier gas (if used), a substrate, and combinations thereof, wherein the energy is one or more of thermal, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, X-rays, electron beams, photons, remote plasma methods, and combinations thereof.

[0076] Flow rate

[0077] In one embodiment of the above process, NH3 is reacted with the formula (R 1 R 2 R 3 Si)2S compound reaction period (i.e., during (R 1 R 2 R 3Si)2S pulse period) flows at about 50 sccm to about 2000 sccm, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The compound of Si)2S flows at about 100 sccm to about 1500 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The compound of Si)2S flows at about 250 sccm to about 1250 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The compound of Si)2S flows at about 500 sccm to about 1000 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In another aspect of each of the foregoing embodiments, the formula (R 1 R 2 R 3 Si)2S compound (where R 1 , R 2 and R 3 each independently C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl) includes, consists essentially of or consists of (Me3Si)2S.

[0078] In one embodiment of the above process, NH3 is reacted with the formula (R 1 R 2 R 3 The Si)2S compound flows at about 50 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R1 R 2 R 3 The compound of Si)2S flows at about 100 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The compound Si)2S flows at about 150 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The compound of Si)2S flows at about 200 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The compound Si)2S flows at about 250 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The compound of Si)2S flows at about 300 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The Si)2S compound flows at about 350 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3The compound of Si)2S flows at about 400 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The Si)2S compound flows at about 450 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The compound of Si)2S flows at about 500 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The Si)2S compound flows at about 750 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The compound of Si)2S flows at about 1000 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The compound of Si)2S flows at about 1250 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The compound of Si)2S flows at about 1500 sccm during the reaction, wherein R 1 , R2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The compound of Si)2S flows at about 1750 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The compound of Si)2S flows at about 2000 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In another aspect of each of the foregoing embodiments, the formula (R 1 R 2 R 3 Si)2S compound (where R 1 , R 2 and R 3 each independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl) includes, consists essentially of or consists of (Me3Si)2S.

[0079] In one embodiment of the above process, NH3 is reacted with the formula (R 1 R 2 R 3 Si)2Se compound during the reaction (i.e., during (R 1 R 2 R 3 Si)2Se flows at about 50 sccm to about 2000 sccm during the pulse, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The compound of Si)2Se flows at about 100 sccm to about 1500 sccm during the reaction, wherein R 1 , R 2 and R 3Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The Si)2Se compound flows at about 250 sccm to about 1250 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The compound of Si)2Se flows at about 500 sccm to about 1000 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In another aspect of each of the foregoing embodiments, the formula (R 1 R 2 R 3 Si)2S compound (where R 1 , R 2 and R 3 each independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl) includes, consists essentially of or consists of (Me3Si)2Se.

[0080] In one embodiment of the above process, NH3 is reacted with the formula (R 1 R 2 R 3 The Si)2Se compound flows at about 50 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The compound Si)2Se flows at about 100 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The Si)2Se compound flows at about 150 sccm during the reaction, wherein R1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The compound Si)2Se flows at about 200 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The Si)2Se compound flows at about 250 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The compound Si)2Se flows at about 300 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. 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 flows at about 400 sccm during the TMS2Se pulse. 1 R 2 R 3 The Si)2Se compound flows at about 450 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The Si)2Se compound flows at about 500 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3The Si)2Se compound flows at about 750 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The compound Si)2Se flows at about 1000 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The Si)2Se compound flows at about 1250 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The Si)2Se compound flows at about 1500 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The Si)2Se compound flows at about 1750 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In one embodiment, NH3 is in the same group as the group of formula (R 1 R 2 R 3 The compound Si)2Se flows at about 2000 sccm during the reaction, wherein R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. In another aspect of each of the foregoing embodiments, the formula (R 1 R 2 R 3 Si)2Se compound (where R 1 , R2 and R 3 each independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl) includes, consists essentially of or consists of (Me3Si)2Se.

[0081] In one embodiment of the above process, NH3 is reacted with the formula (R 1 R 2 R 3 Si)2S compound (where R 1 , R 2 and R 3 Each independently is hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl) and reacts with a group of formula (R 1 R 2 R 3 Si)2Se compound (where R 1 , R 2 and R 3 Each independently is hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl) flows at substantially the same rate during the reaction. In one embodiment of the above process, NH3 flows with the formula (R 1 R 2 R 3 Si)2S compound (where R 1 , R 2 and R 3 Each independently is hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl) and reacts with a group of formula (R 1 R 2 R 3 Si)2Se compound (where R 1 , R 2 and R 3 Each independently is hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl) flows at the same rate during the reaction. In one embodiment of the above process, NH3 flows with the formula (R 1 R 2 R 3 Si)2S compound (where R 1 , R 2 and R 3 Each independently is hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl) flows at a rate different from that of the formula (R 1 R 2 R 3 Si)2Se compound (where R 1 , R 2 and R 3Each independently is hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl) flow rate during the reaction. In another aspect of each of the foregoing embodiments, the formula (R 1 R 2 R 3 Si)2S compound (where R 1 , R 2 and R 3 each independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl) includes, consists essentially of or consists of (Me3Si)2S; and the formula (R 1 R 2 R 3 Si)2Se compound (where R 1 , R 2 and R 3 each independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl) includes, consists essentially of or consists of (Me3Si)2Se.

[0082] Formula (R 1 R 2 R 3 Si)2S and / or (R 1 R 2 R 3 Si)2Se compounds

[0083] As described above, various embodiments of the disclosed and claimed processes, formula (R 1 R 2 R 3 Si)2S and / or (R 1 R 2 R 3 Si)2Se, where R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, alkenyl, aryl or alkynyl or benzyl. 1 , R 2 and R 3 In some embodiments, R 1 , R 2 and R 3 In some embodiments, R 1 , R 2 and R 3 The same as in each. Suitable R 1 , R 2 and R 3 The groups include the following.

[0084] hydrogen

[0085] In one embodiment, R 1 , R 2 and R 3 In one embodiment, one or more of R 1 , R 2 and R 3 In one embodiment, two or more of R are hydrogen. 1 , R 2 and R 3 Each of them is hydrogen.

[0086] C1-C6 alkyl

[0087] C1-C6 alkyl includes straight chain C1-C6 alkyl, branched chain C3-C6 alkyl and C3-C6 unsubstituted cycloalkyl. C1-C6 alkyl includes straight chain C1-C6 alkyl, branched chain C3-C6 alkyl and C3-C6 unsubstituted cycloalkyl. Straight chain C1-C6 alkyl includes methyl, ethyl, propyl, butyl, pentyl and hexyl. In some embodiments, R 1 , R 2 and R 3 One or more of contains C1-C6 alkyl selected from these groups. In one embodiment, R 1 , R 2 and R 3 One or more of them is methyl.

[0088] C2-C6 alkenyl

[0089] C2-C6 alkenyl includes straight chain alkenyl and branched chain alkenyl. C2-C6 straight chain alkenyl includes 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. C2-C6 branched alkenyl includes isobutylene, isopentenyl (2-methylbut-1-enyl, 3-methylbut-1-enyl) and isoamylenyl (2-methylbut-2-enyl). In some embodiments, R 1 , R 2 and R 3 One or more of them contains a C2-C6 alkenyl group selected from these groups.

[0090] C3-C6 aryl

[0091] The C3-C6 aryl group includes a C3-C6 aromatic group. In one embodiment, the aromatic group includes a phenyl group.

[0092] Benzyl

[0093] In one embodiment, R 1 , R 2 and R 3 One or more of them is benzyl.

[0094] C2-C6 alkynyl

[0095] The C2-C6 alkynyl group includes ethynyl, propynyl, propargyl, but-1-ynyl, but-2-ynyl and but-3-ynyl.

[0096] Substrate temperature

[0097] In one embodiment, the substrate temperature is from about 150°C to about 650°C. In one embodiment, the substrate temperature is from about 200°C to about 600°C. In one embodiment, the substrate temperature is from about 250°C to about 550°C. In one embodiment, the substrate temperature is from about 300°C to about 500°C. In one embodiment, the substrate temperature is from about 325°C to about 400°C.

[0098] In one embodiment, the substrate temperature is about 150°C. In one embodiment, the substrate temperature is about 200°C. In one embodiment, the substrate temperature is about 250°C. In one embodiment, the substrate temperature is about 300°C. In one embodiment, the substrate temperature is about 350°C. In one embodiment, the substrate temperature is about 400°C. In one embodiment, the substrate temperature is about 450°C. In one embodiment, the substrate temperature is about 500°C. In one embodiment, the substrate temperature is about 550°C. In one embodiment, the substrate temperature is about 600°C. In one embodiment, the substrate temperature is about 650°C.

[0099] Metal Precursors

[0100] In one embodiment of the above process, the metal precursor comprises one or more of the following: 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 embodiment of the above process, the metal precursor comprises MoO2Cl2. In one embodiment of the above process, the metal precursor comprises MoO2Br2. In one embodiment of the above process, the metal precursor comprises MoCl5. In one embodiment of the above process, the metal precursor comprises MoCl6. In one embodiment of the above process, the metal precursor comprises MoOCl4. In one embodiment of the above process, the metal precursor comprises WO2Cl2. In one embodiment of the above process, the metal precursor comprises WCl4. In one embodiment of the above process, the metal precursor comprises WCl6. In one embodiment of the above process, the metal precursor comprises WOCl4. In one embodiment of the above process, the metal precursor comprises TiCl4. In one embodiment of the above process, the metal precursor comprises ZrCl4. In one embodiment of the above process, the metal precursor comprises HfCl4. In one embodiment of the above process, the metal precursor comprises TaCl4. In one embodiment of the above process, the metal precursor comprises TaCl5. In one embodiment of the above process, the metal precursor comprises NbCl4. In one embodiment of the above process, the metal precursor comprises NbCl5.

[0101] In another embodiment of the above process, the metal precursor includes one or more of the following: MoBURE (bis(tert-butylimino)bis(dimethylamino)molybdenum(VI)), TDMAMo (tetrakis(dimethylamino)molybdenum), TDEAMo (tetrakis(diethylamino)molybdenum), TEMAMo (tetrakis(ethylmethylamino)molybdenum), WNBURE (bis(tert-butylimino)bis(dimethylamino)tungsten(VI)), TEMAZ (tetrakis(ethylmethylamino)zirconium), TEMAHf (tetrakis(ethylmethylamino)hafnium), TEMAT (tetrakis(ethylmethylamino)titanium), TDMAT (tetrakis(dimethylamino)titanium), TDEAT (tetrakis(diethylamino)titanium), TBTDMT ((tert-butylimino)tris(dimethylamino)tantalum), TBTDET ((tert-butylimino)tris(diethylamino)tantalum), TEMAV (tetrakis(ethylmethylamino)vanadium), various other precursors of these elements or other TMD forming elements and / or combinations thereof. In another embodiment of the above process, the metal precursor comprises MoBURE (bis(tert-butylimino)bis(dimethylamino)molybdenum(VI)). In another embodiment of the above process, the metal precursor comprises TDMAMo. In another embodiment of the above process, the metal precursor comprises TEMAMo. In another embodiment of the above process, the metal precursor gas comprises WNBURE (bis(tert-butylimino)bis(dimethylamino)tungsten(VI)). In another embodiment of the above process, the metal precursor comprises TEMAZ. In another embodiment of the above process, the metal precursor comprises TEMAHf. In another embodiment of the above process, the metal precursor comprises TEMAT. In another embodiment of the above process, the metal precursor comprises TDMAT. In another embodiment of the above process, the metal precursor comprises TDEAT.

[0102] Example

[0103] Reference will now be made to more specific embodiments of the invention and to experimental results that provide support for these embodiments.The following examples are given to more fully illustrate the disclosed and claimed subject matter and should not be construed as limiting the disclosed subject matter in any way.

[0104] It will be apparent to those skilled in the art that various modifications and changes may be made in the disclosed subject matter and the specific embodiments provided herein without departing from the spirit or scope of the disclosed subject matter. Therefore, the disclosed subject matter (including the description provided by the following embodiments) is intended to cover modifications and changes of the disclosed subject matter that appear within the scope of any claims and their equivalents.

[0105] Materials and Methods

[0106] All reactions and manipulations described in the examples were performed under argon atmosphere using an Intermolecular A30 ALD chamber. All chemicals were received from Versum Materials and Millipore-Sigma (EMD Electronics).

[0107] Specific embodiments

[0108] Example 1: In situ generation of H2S to obtain MoS2 film

[0109] Figure 1 Demonstration of 2D MoS grown over 100 cycles of ALD using MoO2Cl2 as Mo metal precursor and TMS2S and NH3 co-implantation as in-situ H2S source x Raman spectra of the films. The inset box shows the XRF counts in the presence and absence of NH3 co-injection during the TMS2S pulse, showing that MoS x The growth of 2D films increased by 545%, and almost no MoS was present in the absence of NH3 co-injection. x growth, which is also very non-stoichiometric. It should be noted that in the case of NH3 co-injection, MoS x is sulfur deficient (x is about 1.5 instead of 2.0) due to comparing films with the same delivery conditions as deposited without NH3 co-injection (ie, unoptimized ALD process).

[0110] like Figure 2 As shown, the optimized ALD process with NH3 injected during the TMS2S pulse with the same Mo precursor produced MoS 1.9 This is in stark contrast to the fact that MoO2Cl2 and TMS2S hardly react in the absence of NH3 co-injection, demonstrating that H2S is in situ generated by co-injection of NH3 and TMS2S in the same ALD pulse.

[0111] like Figure 3 As shown, Figure 2 The XPS composition of the optimized ALD process with NH3 injected during the TMS2S pulse shown in , shows that the S / Mo ratio of this sample is equal to 1.9, while there is negligible Mo-O bonding, as evidenced by the lack of a peak at about 235.5 eV binding energy. The Si and O are from the SiO2 substrate, which is measured by x-rays that travel through the two-dimensional atomically thin material to the SiO2 substrate below the MoS2 film and back to the detector. The carbon content in the film is low and all or most of it is exogenous (cannot be splashed away from the surface of the two-dimensional atomically thin film without removing the entire film in the process).

[0112] Example 2: In situ generation of H2Se to obtain MoSe2 film

[0113] In-situ H2Se generation using NH3 co-injection during a TMS2Se pulse during an ALD or CVD process is demonstrated by the large change in deposition rate when NH3 is added to the process compared to without any NH3.

[0114] Figure 4 The difference between the XRFMo counts and XRFSe counts in the presence of NH3 co-injection during the TMS2Se pulse and the XRFMo counts and XRFSe counts with only a pure TMS2Se pulse is shown. Figure 4 As shown in Figure 2, the injection of NH3 during the TMS2Se pulse in an ALDMoSe2 process with a Mo precursor greatly increases the yield of MoSe2 thin films. The film thickness increases by 370% with the co-injection of NH3, and Figure 4 The Raman in shows that this can be attributed to in situ H2Se generation. It should be noted that for MoSe2, the original XRFSe / Mo count ratio of the stoichiometric film is about 0.6, so the XPSSe / Mo ratio is also listed on the left side of the table, which is equal to 1.9.

[0115] Figure 5 The resulting MoSe grown using NH3 co-implantation during the TMS2Se pulse in Example 2 is shown. ~1.9-2.1 Raman spectrum of the film. Figure 5 As shown, co-injection of NH3 during the TMS2Se pulse resulted in a 1g Full width at half maximum of 2D MoSe ~1.9-2. 1 membrane.

[0116] Figure 6 The XPS of the MoSe2 film grown in Example 2 is shown. Figure 6 As shown, the XPSSe / Mo ratio of the two-dimensional MoSe2 film of this sample is 1.9.

[0117] The foregoing description is intended primarily for purposes of illustration. Although the disclosed and claimed subject matter has been shown and described with respect to exemplary embodiments thereof, it will be understood by those skilled in the art that the foregoing and various other changes, omissions, and additions in form and detail thereof may be made therein without departing from the spirit and scope of the disclosed and claimed subject matter.

Claims

1. A method for forming a two-dimensional film containing a transition metal disulfide and / or diselenide on a substrate, comprising generating one or more of H2S and H2Se in situ in a deposition chamber.

2. The method according to claim 1, wherein the forming of the two-dimensional film containing transition metal disulfide and / or diselenide comprises a chemical vapor deposition (CVD) process, the process comprising the following steps: (1) contacting a substrate in a deposition chamber with a vapor comprising: (a) one or more externally supplied metal precursors, and (b) one or more of (i) H2S and (ii) H2Se; and (2) optionally purging the vapor with an inert gas, in (i) by applying the formula (R 1 R 2 R 3 Si)2S compound + NH3 reaction to generate the H2S in situ, wherein R 1 , R 2 and R 3 are each independently hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C3-C6 aryl, benzyl or C2-C6 alkynyl, and (ii) by applying the formula (R 1 R 2 R 3 Si)2Se compound + NH3 reaction to generate H2Se in situ, where R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C3-C6 aryl, benzyl or C2-C6 alkynyl.

3. The method according to claim 1, wherein the forming of the two-dimensional film containing transition metal disulfide and / or diselenide comprises 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: (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) 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) Repeating steps (1) to (4) in sequence until a metal-containing film of a desired thickness is obtained. in (i) by applying the formula (R 1 R 2 R 3 Si)2S compound + NH3 reaction to generate the H2S in situ, wherein R 1 , R 2 and R 3 are each independently hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C3-C6 aryl, benzyl or C2-C6 alkynyl, and (ii) by applying the formula (R 1 R 2 R 3 Si)2Se compound + NH3 reaction to generate H2Se in situ, where R 1 , R 2 and R 3 Each is independently hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C3-C6 aryl, benzyl or C2-C6 alkynyl.

4. The method according to any one of claims 1 to 3, wherein R 1 , R 2 and R 3 The ones in are different.

5. The method according to any one of claims 1 to 3, wherein R 1 , R 2 and R 3 The two in are the same.

6. The method according to any one of claims 1 to 3, wherein R 1 , R 2 and R 3 The same for each of them.

7. A method according to any one of claims 1 to 3, wherein R 1 , R 2 and R 3 One or more of them is hydrogen.

8. A method according to any one of claims 1 to 3, wherein R 1 , R 2 and R 3 Two or more of them are hydrogen.

9. The method according to any one of claims 1 to 3, wherein R 1 , R 2 and R 3 Each of them is hydrogen.

10. The method according to any one of claims 1 to 3, wherein R 1 , R 2 and R 3 One or more of the comprises a C1-C6 alkyl group, a branched C3-C6 alkyl group or a C3-C6 unsubstituted cycloalkyl group.

11. The method according to any one of claims 1 to 3, wherein R 1 , R 2 and R 3 One or more of the comprises a C1-C6 alkyl group.

12. The method according to any one of claims 1 to 3, wherein R 1 , R 2 and R 3 One or more of the comprises a branched C3-C6 alkyl group.

13. The method according to any one of claims 1 to 3, wherein R 1 , R 2 and R 3 One or more of the comprises a C3-C6 unsubstituted cycloalkyl group.

14. A method according to any one of claims 1 to 3, wherein R 1 , R 2 and R 3 One or more of the alkyl groups include a C1-C6 alkyl group 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.

15. A method according to any one of claims 1 to 3, wherein R 1 , R 2 and R 3 One or more of the comprises a methyl group.

16. A method according to any one of claims 1 to 3, wherein R 1 , R 2 and R 3 One or more of the above comprises a C2-C6 alkenyl group selected from a linear alkenyl group and a branched alkenyl group.

17. A method according to any one of claims 1 to 3, wherein R 1 , R 2 and R 3 One or more of the above comprises a C2-C6 straight chain alkenyl group.

18. A method according to any one of claims 1 to 3, wherein R 1 , R 2 and R 3 One or more of the above comprises a C2-C6 branched alkenyl group.

19. A method according to any one of claims 1 to 3, wherein R 1 , R 2 and R 3 One or more of the at least one C2-C6 straight chain alkenyl group is 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.

20. The method according to any one of claims 1 to 3, wherein R 1 , R 2 and R 3 One or more of the alkylene groups include a C2-C6 branched alkenyl group selected from the group consisting of isobutylene, isopentenyl (2-methylbut-1-enyl, 3-methylbut-1-enyl) and isoamylenly (2-methylbut-2-enyl).

21. A method according to any one of claims 1 to 3, wherein R 1 , R 2 and R 3 One or more of the comprises a C3-C6 aryl group.

22. A method according to any one of claims 1 to 3, wherein R 1 , R 2 and R 3 One or more of the includes a C3-C6 aryl group, which is an aromatic group.

23. A method according to any one of claims 1 to 3, wherein R 1 , R 2 and R 3 One or more of the phenyl groups comprises a phenyl group.

24. A method according to any one of claims 1 to 3, wherein R 1 , R 2 and R 3 One or more of the comprises a benzyl group.

25. A method according to any one of claims 1 to 3, wherein R 1 , R 2 and R 3 One or more of them contains a C2-C6 alkynyl group.

26. A method according to any one of claims 1 to 3, wherein R 1 , R 2 and R 3 One or more of the alkylene groups include a C2-C6 alkynyl group selected from the group consisting of ethynyl, propynyl, propargyl, but-1-ynyl, but-2-ynyl, and but-3-ynyl.

27. The method according to any one of claims 1 to 3, wherein (i) the H2S is generated in situ by reacting TMS2S + NH3 in the deposition chamber.

28. The method according to any one of claims 1 to 3, wherein (ii) the H2Se is generated in situ by reacting TMS2Se + NH3 in the deposition chamber.

29. The method according to any one of claims 1 to 3, wherein the NH3 in (R 1 R 2 R 3 Si)2S flows at about 50 sccm to about 2000 sccm during the pulse.

30. The method according to any one of claims 1 to 3, wherein the NH3 in (R 1 R 2 R 3 Si)2S flows at about 100 sccm to about 1500 sccm during the pulse.

31. The method according to any one of claims 1 to 3, wherein the NH3 in (R 1 R 2 R 3 Si)2S flows at about 250 seem to about 1250 seem during the pulse.

32. The method according to any one of claims 1 to 3, wherein the NH3 in (R 1 R 2 R 3 Si)2S flows at about 500 sccm to about 1000 sccm during the pulse.

33. according to the method according to any one of claims 1 to 3, wherein the NH3 in (R 1 R 2 R 3 Si)2Se flows at about 50 sccm to about 2000 sccm during the pulse.

34. according to the method according to any one of claims 1 to 3, wherein the NH3 in (R 1 R 2 R 3 Si)2Se flows at about 100 sccm to about 1500 sccm during the pulse.

35. according to the method according to any one of claims 1 to 3, wherein the NH3 in (R 1 R 2 R 3 Si)2Se flows at about 250 seem to about 1250 seem during the pulse.

36. according to the method according to any one of claims 1 to 3, wherein the NH3 in (R 1 R 2 R 3 Si)2Se flows at about 500 sccm to about 1000 sccm during the pulse.

37. The method of any one of claims 1 to 3, wherein the substrate temperature is from about 150°C to about 650°C.

38. The method of any one of claims 1 to 3, wherein the substrate temperature is from about 200°C to about 600°C.

39. The method of any one of claims 1 to 3, wherein the substrate temperature is from about 250°C to about 550°C.

40. The method of any one of claims 1 to 3, wherein the substrate temperature is from about 300°C to about 500°C.

41. The method of any one of claims 1 to 3, wherein the substrate temperature is from about 325°C to about 400°C.

42. The method of any one of claims 1 to 3, wherein the metal precursor gas comprises one or more of MoO2Cl2, MoCl5, MoCl6, MoOCl4, WO2Cl2, WCl4, WCl5, WCl6, WOCl4, TiCl4, ZrCl4, HfCl4, TaCl4, TaCl5, NbCl4, NbCl5, and combinations thereof.

43. The method according to any one of claims 1 to 3, wherein the metal precursor gas comprises MoO2Cl2.

44. A method according to any one of claims 1 to 3, wherein the metal precursor gas comprises MoO2Br2.

45. The method of any one of claims 1 to 3, wherein the metal precursor gas comprises MoCl5.

46. ​​The method of any one of claims 1 to 3, wherein the metal precursor gas comprises MoCl6.

47. A method according to any one of claims 1 to 3, wherein the metal precursor gas comprises MoOCl4.

48. A method according to any one of claims 1 to 3, wherein the metal precursor gas comprises WO2Cl2.

49. The method according to any one of claims 1 to 3, wherein the metal precursor gas comprises WCl4.

50. The method of any one of claims 1 to 3, wherein the metal precursor gas comprises WCl6.

51. A method according to any one of claims 1 to 3, wherein the metal precursor gas comprises WOCl4.

52. The method of any one of claims 1 to 3, wherein the metal precursor gas comprises TiCl4.

53. The method according to any one of claims 1 to 3, wherein the metal precursor gas comprises ZrCl4.

54. The method of any one of claims 1 to 3, wherein the metal precursor gas comprises HfCl4.

55. The method according to any one of claims 1 to 3, wherein the metal precursor gas comprises TaCl4.

56. A method according to any one of claims 1 to 3, wherein the metal precursor gas comprises TaCl5.

57. A method according to any one of claims 1 to 3, wherein the metal precursor gas comprises NbCl4.

58. A method according to any one of claims 1 to 3, wherein the metal precursor gas comprises NbCl5.

59. The method of any one of claims 1 to 3, wherein the metal precursor comprises one or more of the following: MoBURE (bis(tert-butylimino)bis(dimethylamino)molybdenum(VI)), TDMAMo, TDEAMo, TEMAMo, WNBURE (bis(tert-butylimino)bis(dimethylamino)tungsten(VI)), TEMAZ, TEMAHf, TEMAT, TDMAT, TDEAT, and combinations thereof.

60. The method of any one of claims 1 to 3, wherein the metal precursor gas comprises MoBURE (bis(tert-butylimino)bis(dimethylamino)molybdenum(VI)).

61. The method of any one of claims 1 to 3, wherein the metal precursor gas comprises TDMAMo.

62. The method of any one of claims 1 to 3, wherein the metal precursor gas comprises TEMAMo.

63. The method of any one of claims 1 to 3, wherein the metal precursor gas comprises WNBURE (bis(tert-butylimino)bis(dimethylamino)tungsten(VI)).

64. A method according to any one of claims 1 to 3, wherein the metal precursor gas comprises TEMAZ.

65. A method according to any one of claims 1 to 3, wherein the metal precursor gas comprises TEMAHf.

66. The method of any one of claims 1 to 3, wherein the metal precursor gas comprises TEMAT.

67. The method of any one of claims 1 to 3, wherein the metal precursor gas comprises TDMAT.

68. The method of any one of claims 1 to 3, wherein the metal precursor gas comprises TDEAT.

69. The method according to claim 3, wherein the method is carried out at a temperature of about 100°C to about 650°C.

70. The method according to claim 3, wherein the method is performed at a pressure of about 0.1 Torr to about 100 Torr.

71. The method according to claim 3, wherein the method is carried out at a temperature of about 100°C to about 650°C and a pressure of about 0.1 Torr to about 100 Torr.

72. The method according to claim 3, wherein the formula (R 1 R 2 R 3 Si)2S compound + NH3 and / or the formula (R 1 R 2 R 3 A compound of Si)2Se+NH3 is co-injected into the deposition chamber.

73. The method according to claim 3, wherein the formula (R 1 R 2 R 3 Si)2S compound + NH3 and / or the formula (R 1 R 2 R 3 A compound of Si)2S+NH3 is sequentially injected into the deposition chamber.

74. The method according to claim 3, wherein the step (1) first vapor comprises (a) the one or more externally supplied metal precursors.

75. The method according to claim 3, wherein the first vapor of step (1) comprises one or more of (b) (i) H2S and (ii) H2Se.

76. The method according to claim 3, wherein the first steam in step (1) comprises (i) H2S.

77. The method according to claim 3, wherein the first vapor of step (1) comprises (ii) H2Se.

78. The method according to claim 3, wherein the step (3) second vapor comprises (a) the one or more externally supplied metal precursors.

79. The method according to claim 3, wherein the second vapor in step (3) comprises one or more of (b)(i) H2S and (ii) H2Se.

80. The method according to claim 3, wherein the second vapor of step (3) comprises (i) H2S.

81. The method according to claim 3, wherein the second vapor of step (3) comprises (ii) H2Se.

82. A method according to any one of claims 1 to 29 (R 1 R 2 R 3 Si)2S compound and / or formula (R 1 R 2 R 3 Use of a compound of Si)2Se, which is used together with NH3 to form a two-dimensional film containing transition metal disulfides and / or diselenides on a substrate.

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