Systems and methods for forming large region electronic grade metal chalcogen thin films

Abstract

A vapor deposition system is described. A vapor deposition system includes a reaction chamber and a reactant delivery subsystem coupled with the reaction chamber. The reaction chamber is configured to hold a substrate therein. The reactant delivery subsystem includes an inlet, a pre-reaction zone, and an outlet. The inlet receives a precursor and chalcogen precursor (s). The pre-reaction zone is configured to receive a precursor from a portion of the inlet and to react at least a portion of the precursor to form modified precursor (s). The modified precursor (s) are more thermally stable than the metal-containing precursor (s) used as the precursor (s) to form the modified precursor (s). The outlet is coupled with the reaction chamber and the pre-reaction zone. The outlet separately provides the modified precursor (s) and the chalcogen precursor (s) to the reaction chamber. The modification precursor (s) and the chalcogen precursor (s) react in the reaction chamber and form a chalcogen film on the substrate.

Description

[0001] Cross-references to related applications This application claims priority to U.S. Provisional Patent Application No. 63 / 582708, filed September 14, 2023, entitled “VAPOR DEPOSITION AND DOPING METHOD TO FORM LARGE-AREA ELECTRONIC-GRADE METALCHALCOGEN ULTRATHIN FILMS”, which is incorporated herein by reference for all purposes. Background Technology

[0002] Two-dimensional (2D) transition metal chalcogenide (TMC) materials can include binary, ternary, quaternary, and multi-component oxides, sulfides, selenides, and tellurides. TMCs have applications in a variety of fields. For example, 2D TMCs (such as MoS2, WSe2, WS2, MoTe2, MoSe2, SnSe, and SnS) can be semiconductors. Such films, as well as other TMC materials (e.g., TMCs in metallic form, such as WTe2 and TiSe2), can be used in electronic applications.

[0003] Despite the interest in TMCs, growing TMC films using conventional vapor deposition techniques, such as chemical vapor deposition (CVD) and / or atomic layer deposition (ALD), suffers from various drawbacks. Conventional CVD techniques may require precise temperature control over a narrow range, making processing more difficult and expensive. Such techniques can also suffer from poor processing efficiency due to the low decomposition temperatures of many volatile metal-containing precursors. These precursors may decompose before reaching the reaction temperature for TMC formation. These metal-containing precursors may also have small diffusion lengths, resulting in TMC films growing only on a small area of ​​the substrate (e.g., approximately one or two square centimeters or less). Doping using conventional CVD can also present problems. Although dopants can be introduced into the reaction chamber in gaseous form, the resulting material may not have the desired uniformity or dopant concentration. Carbon residues derived from one or more organic ligands in the precursor can be a serious problem in CVD systems. Therefore, techniques for forming chalcogenides, particularly 2D TMCs, are needed. Attached Figure Description

[0004] Various embodiments of the present invention are disclosed in the following detailed description and accompanying drawings.

[0005] Figure 1 This is a block diagram depicting an embodiment of a vapor deposition system for providing metal chalcogenide materials.

[0006] Figure 2 This is a diagram depicting an embodiment of a vapor deposition system for providing metal chalcogenide materials.

[0007] Figure 3 This is a diagram depicting an embodiment of a vapor deposition system for providing metal chalcogenide materials.

[0008] Figures 4A-4D This is a diagram depicting a portion of a vapor deposition system used to provide metal chalcogenide materials.

[0009] Figure 5 This is a diagram depicting an embodiment of a gas distribution system that can be used in a vapor deposition system for manufacturing metal chalcogenide materials.

[0010] Figures 6A-6D This is a diagram depicting an embodiment of a vapor deposition system that can be used to manufacture metal chalcogenide materials.

[0011] Figure 7 This is a flowchart depicting an embodiment of a method for forming metal chalcogenide materials using vapor deposition.

[0012] Figure 8 This is a flowchart depicting an embodiment of a method for forming metal chalcogenide materials using vapor deposition.

[0013] Figures 9A-9C Examples of metal chalcogenide films fabricated using vapor deposition and their properties are described. Detailed Implementation

[0014] This invention can be implemented in various ways, including as a process; an apparatus; a system; a material composition; a computer program product embodied on a computer-readable storage medium; and / or a processor, such as a processor configured to execute instructions stored on and / or provided thereto in memory coupled to and / or to a processor. In this specification, these implementations or any other forms that the invention may take are referred to as techniques. Generally, the order of steps of the disclosed process can be varied within the scope of this invention. Unless otherwise stated, components such as processors or memory described as being configured to perform a task can be implemented as general-purpose components temporarily configured to perform that task at a given time or manufactured as specific components to perform that task. As used herein, the term 'processor' refers to one or more means, circuits, and / or processing cores configured to process data, such as computer program instructions.

[0015] The following detailed description of one or more embodiments of the invention is provided in conjunction with the accompanying drawings, which illustrate the principles of the invention. The invention is described in conjunction with these embodiments, but is not limited to any particular embodiment. The scope of the invention is limited only by the claims, and the invention covers many alternatives, modifications, and equivalents. Numerous specific details are set forth in the following description to provide a thorough understanding of the invention. These details are provided for illustrative purposes, and the invention may be practiced without some or all of these specific details. For clarity, technical materials known in the art related to the invention have not been described in detail so as not to unnecessarily obscure the invention.

[0016] A vapor deposition system is described. The vapor deposition system includes a reaction chamber and a reactant delivery subsystem coupled to the reaction chamber. The reaction chamber is configured to hold a substrate therein. The reactant delivery subsystem includes an inlet, a pre-reaction zone, and an outlet. The inlet receives a precursor and one or more chalcogenide precursors. The pre-reaction zone is configured to receive the precursor from a portion of the inlet and react at least a portion of the precursor to form a modified precursor. The modified precursor is more thermally stable than a metal-containing precursor that is part of the precursor used to form the modified precursor. The modified precursor may have a higher decomposition temperature and / or a longer diffusion length than the metal-containing precursor. The outlet is coupled to the reaction chamber and the pre-reaction zone. The outlet separately provides the modified precursor and one or more of the chalcogenide precursors to the reaction chamber. Therefore, in some embodiments, the modified precursor and one or more of the chalcogenide precursors are separated before flowing out of the outlet and / or mixing in the reaction chamber. The modified precursor and (one or more) of the chalcogenide precursors react in the reaction chamber to form a chalcogenide film on the substrate.

[0017] The precursor may further include a modifier that reacts with the metal-containing precursor to form the modified precursor. In some embodiments, the precursor includes a dopant precursor. In such embodiments, the chalcogenide film includes a dopant in the dopant precursor. For example, the metal-containing precursor may contain W and / or Mo. The precursor may also include water (e.g., as a modifier that reacts with the metal-containing precursor), Fe (e.g., in the dopant precursor), and / or V (e.g., in the dopant precursor). One or more of the chalcogenide precursors may include S, Se, and / or Te.

[0018] In some embodiments, the reactant delivery subsystem includes a heated pre-reaction chamber and a distribution unit. The heated pre-reaction chamber includes a pre-reaction zone therein. The precursor reacts in the heated pre-reaction chamber in the absence of one or more of the chalcogenide precursors to form the modified precursor. The distribution unit is coupled to the heated pre-reaction chamber via a flow channel. The distribution unit includes the outlet and is coupled to at least one of the plurality of inlets for one or more of the chalcogenide precursors. In some embodiments, the pre-reaction zone is adjacent to the outlet. The precursor reacts in the pre-reaction zone in the absence of one or more of the chalcogenide precursors to form the modified precursor. In some such embodiments, the modified precursor and / or other reactants may be provided directly from the pre-reaction zone to the outlet.

[0019] In some embodiments, the pre-reaction zone includes a heater. The temperature of the pre-reaction zone during use may be lower than the reaction chamber temperature during the formation of the chalcogenide. In other embodiments, the temperature of the pre-reaction zone during use may be equal to or higher than the reaction chamber temperature during the formation of the chalcogenide. The reactant delivery subsystem may also include a cooling zone coupled to the portion of the inlet and the pre-reaction zone. The cooling zone is configured to maintain a temperature below the decomposition temperature of the metal-containing precursor.

[0020] The first portion of the outlet is coupled to the pre-reaction zone and provides the modified precursor to the reaction chamber. The second portion of the outlet separately provides one or more of the chalcogenide precursors from the modified precursor to the reaction chamber.

[0021] The reactant delivery subsystem may further include a gas distribution system. The gas distribution system is coupled to the outlets such that at least a portion of the outlets have individually controllable flow rates. In some embodiments, the flow rates at each outlet are separately controllable.

[0022] The substrate has a substrate region. The outlet is distributed over the region of the pre-reaction zone. The region is at least half of the substrate region. In some embodiments, the outlet is distributed over a region equal to or above the substrate region. At least a portion of the region is aligned with at least a portion of the substrate region.

[0023] An apparatus is also described. The apparatus includes a substrate and a transition metal chalcogenide (TMC) film formed on the substrate by vapor deposition. The TMC film covers an area of ​​at least one square inch of the substrate. In some embodiments, the TMC film covers an area of ​​at least four square inches. In some embodiments, the TMC film covers an area of ​​at least twelve square inches. The TMC film may be a two-dimensional film having a thickness of at least one monolayer. In some embodiments, the TMC film is a doped TMC film.

[0024] A method is described. The method includes reacting at least a portion of a plurality of precursors in a pre-reaction zone to form a modified precursor. The modified precursor is more thermally stable than the metal-containing precursor of the at least a portion thereof. The modified precursor may have a higher decomposition temperature and / or a longer diffusion length than the metal-containing precursor. The precursor may also include a modifier for the metal-containing precursor. The modified precursor and at least one chalcogenide precursor are separately provided to a reaction chamber. The modified precursor and (one or more) of the chalcogenide precursor react to form a chalcogenide film on a substrate in the reaction chamber.

[0025] The method may further include delivering the precursor to the pre-reaction zone. The precursor may include a dopant precursor. In such embodiments, the dopant in the dopant precursor is incorporated into the chalcogenide film. Thus, a doped chalcogenide film is formed on the substrate in the reaction chamber.

[0026] Although the systems(s), methods(s), and apparatus(s)(s) are described in the context of metal precursors, dopant precursors, intermediate precursors, modifiers (as a specific precursor), chalcogenide precursors, and / or similar single-element precursors, this does not preclude the use of other, additional, and / or multiple components. For example, multiple metal precursors, multiple dopant precursors, multiple modifiers, and / or multiple chalcogenide precursors may be used. Furthermore, other components may be present. For example, an inert gas stream (such as Ar gas) may be used as the precursor. Various features are present in the embodiments described herein. In some embodiments, other combinations of features not explicitly shown may also be possible.

[0027] Figure 1This is a block diagram depicting an embodiment of a vapor deposition system 100 for providing metal chalcogenide materials. For clarity, only a portion of the vapor deposition system 100 is shown. The vapor deposition system may be a furnace chemical vapor deposition (CVD) system, a cold-wall CVD system, an atomic layer deposition (ALD) system, or another type of vapor deposition system. The vapor deposition system 100 can be used to form metal chalcogenides, particularly two-dimensional (2D) transition metal chalcogenides (TMCs). Therefore, the vapor deposition system 100 is described in the context of TMCs, particularly 2D TMC films. However, in some embodiments, other metal chalcogenides (2D or other forms) and / or other films can be fabricated.

[0028] The vapor deposition system 100 includes a reaction chamber 110 and a reactant delivery subsystem 120. The reaction chamber 110 houses a substrate 112 on which TMC is to be grown. For example, the reaction chamber 110 may include a substrate support, a vacuum system, a gas flow system, a temperature control system (e.g., heating and / or cooling), and control means for maintaining the desired environment within the reaction chamber 110 for TMC growth. In some embodiments, the reaction chamber 110 may be controlled to maintain a temperature of at least 50°C and no more than 1000°C or no more than 2000°C.

[0029] The reactant delivery subsystem 120 supplies reactants for TMC growth to the reaction chamber 110. The reactant delivery subsystem 120 generates at least some reactants from precursors. More specifically, the reactant delivery subsystem 120 generates some reactants from some precursors, also referred to as modified precursors. Modified precursors have improved thermal stability compared to their corresponding primary precursors. Modified precursors may also have longer diffusion lengths than the precursors. Therefore, modified precursors can flow more effectively to the reaction chamber 110 and form high-quality TMC over a larger area on the substrate 112. For example, the reactant delivery subsystem 120 can generate modified precursors and / or modified dopant precursors from metal-containing precursors and / or dopant-containing precursors. The reactant delivery subsystem 120 supplies other reactants (e.g., chalcogenide-containing precursors) directly to the reaction chamber 110. However, the reactant delivery subsystem 120 supplies modified precursors and chalcogenide-containing precursors separately to the reaction chamber 110. The modified precursor can flow through a channel separate from the sulfide-containing precursor. Therefore, mixing of the modified precursor and the sulfide-containing precursor outside the reaction chamber 110 can be reduced or eliminated, thereby promoting the formation of sulfide materials such as 2D TMC films.

[0030] More specifically, the reactant delivery subsystem 110 includes an inlet 130, a pre-reaction zone 140, and an outlet 150. The pre-reaction zone 140 is coupled to the inlet 130 and the outlet 150. The inlet 130 is also coupled to the outlet 150. The outlet 150 is coupled to the reaction chamber 110. Precursors and chalcogenide precursors are gaseous (e.g., sublimated by heating and carried by an inert gas stream) and are provided to the vapor deposition system 100 via the inlet 130. Some inlets 130 provide precursors to the pre-reaction zone 140. Precursors input to the inlet 130 and provided to the pre-reaction zone 140 include metal-containing precursors and modifiers. The metal-containing precursors contain a metal (e.g., a transition metal for 2D TMC films) for forming chalcogenides in the reaction chamber 110. Modifiers include precursors that react with the metal-containing precursors in the pre-reaction chamber 140 to form modified precursors. In some cases, dopant precursors are also provided to the pre-reaction zone 140 via inlet 130. Additional precursors (such as decarbonized precursors, which may differ from modifiers, metal-containing precursors, and dopant precursors) may also be provided to the pre-reaction zone 140 via inlet 130. The reaction of precursors (e.g., metal-containing precursors, modifiers, and / or dopant precursors) in the pre-reaction zone 140 is carried out in the absence of chalcogenide precursors.

[0031] Examples of metal-containing precursors provided to the pre-reaction zone 140 include single-metal species and / or metal dimer species of the desired metal for the manufacture of one or more chalcogenides. For 2D TMC membranes, such metal-containing precursors may include W and / or Mo. For example, metal-containing precursors may include, but are not limited to: Mo(CO)6, Mo(CO) 6-x Br x , W(CO)6, WCl6, MoCl6, WF6, MoF6, (η 5 -C5H4CH3)2Mo2(CO)6, methylcyclopentadienylmolybdenum tricarbonyl dimer (or other alkyl-cp derivatives; for example, methylcyclopentadienylmolybdenum tricarbonyl dimer or propylcyclopentadienylmolybdenum tricarbonyl dimer), (η 5 -C5H5)2Mo2(CO)6 (the carbonyl group can be replaced by cyanide or PPh3 group), (η 5 -C5H5)2Mo2(CO)4(μ-η 2 -CH3CHO), (η) 5 -C5H5)2Mo2(CO)4(μ-dppm); dppm: 1,1-bis(diphenylphosphino)methane, Mo2(hpp)4, hpp: hexahydropyrimidine, Mo2(tmtaa)2, tmtaa: tetramethyltetraazacyclopentene, (η 5-C5H5)2Mo2(CO)2(μ-SCF3)2、Mo2Cl4(bdppp)2;bdppp:2,6-bis(diphenylphosphine)pyridine and Mo2(CO)(η 5 -C5H5)2(μ-C4(C6H5)4).

[0032] The modifier can react with metal-containing precursors and / or dopant precursors. The modifier is part of the precursors provided to the pre-reaction zone 140. For example, H2O (e.g., water vapor) can be used as a modifier to react with other precursors in the pre-reaction zone 140. Other examples of modifiers include, but are not limited to, Cl2, Br2, I2, O2, H2O2, O3, HCl, HBr, HI, NaCl, NaBr, and / or salts / compounds containing alkali metal ions. For example, the reaction of chlorine with Mo(CO)6 is Mo(CO)6 + HCl -> Mo(CO)6- x Cl x Other reactions involving metal precursors may include, but are not limited to: Mo(CO)6+ (η 5 -C5H4CH3) ->(η 5 -C5H4CH3)2Mo2(CO)6 and (η 5 -C5H4CH3)2Mo2(CO)6+ (η 5 -C5H4CH3)2W2(CO)6->(η 5 -C5H4CH3)3-W-Mo(CO)3(η 5 -C5H4CH3). Some precursors (such as water) perform multiple functions. For example, in addition to its use as a modifier, water can be used to reduce carbon residues in the vapor deposition system 100. Other and / or additional modifying precursors, modifiers, reactants, and / or metal-containing precursors may be possible.

[0033] Dopant precursors are used to incorporate dopants into the forming TMC film. Such dopant precursors are provided to the pre-reaction region 140. The dopant precursors are mixed with remaining precursors (e.g., metal-containing precursors and modifiers) and may react. Thus, modified dopant precursors may be formed. The dopant precursors may have M(CO)6 and / or M(η)6. 5 The form is -C5H5)2, where M represents a transition metal dopant. Examples include Fe(CO)5 and Nb2(CO). 12 Re2(CO) 10 , Ni(CO)4, Ti(CO)6, V(CO)6 and / or Fe(η 5-C5H5)2 can be used as a dopant precursor. One or more organic ligands CO can also be replaced by other aliphatic or aromatic structures. For example, the dopant precursor Fe(CO)5 can be reacted in pre-reaction zone 140 to form a more stable dimer as a modified dopant precursor. For example, Fe-Mo or Fe-W dimer systems can be formed. An example of such a reaction is Fe(CO)5 + 2(η 5 -C5H5) ->(η 5 -C5H5)2Fe2(CO)4. Another such reaction can form a metal dimer with the main precursor. An example of this type of reaction is (η 5 -C5H5)2Fe2(CO)4+ (η 5 -C5H5)2Mo2(CO)6->2[(η 5 -C5H5)2(CO)2Fe - Mo(CO)3(η 5 Therefore, Fe and / or other metal dopants can be added to the formation of TMC.

[0034] Other precursors may be provided to the pre-reaction zone 140. For example, some precursors are used for decarbonization. Such precursors may include H2O, O2, H2, O3, and / or H2O2. The metal-containing precursors, modifiers, dopant precursors, and decarbonization precursors identified above are not intended to be an exhaustive list. Rather, such precursors are for illustrative purposes only.

[0035] A sulfide precursor is also provided to the reactant delivery system 120 via inlet 130. Sulfide precursors may include S, Se, and / or Te. For example, sulfide precursors may include, but are not limited to, H₂S, sulfur powder, dimethyl sulfide (DMS), CS₂, diethyl sulfide (DES), and / or H₂Se.

[0036] Pre-reaction zone 140 and inlet 130 are coupled to outlet 150. Outlet 150 supplies modified precursors, chalcogenide precursors, and / or other precursors (e.g., modifiers, dopant precursors, modified dopant precursors, and / or decarbonization precursors) to reaction chamber 110. Within reactant delivery subsystem 120, the vapor flow from pre-reaction zone 140 is separate from the chalcogenide precursor flow from inlet 130. Therefore, outlet 150 supplies one or more modified precursors and one or more chalcogenide precursors separately to reaction chamber 110. Reaction chamber 110 is configured such that one or more modified precursors and one or more chalcogenide precursors are mixed and reacted to form TMC on substrate 112. If a dopant precursor is supplied to reactant delivery subsystem 120, doped TMC is formed on substrate 112.

[0037] In operation, precursors are provided to pre-reaction zone 140 via inlet 130. These precursors include at least a metal-containing precursor and a modifier. One or more dopant precursors and / or one or more decarbonization precursors may also be provided to pre-reaction zone 140. In pre-reaction zone 140, the metal-containing precursor and the modifier react to form a modified precursor. Therefore, pre-reaction zone 140 is configured to facilitate this reaction. In some embodiments, pre-reaction zone 140 is heated, for example to at least 50°C and no more than 1000°C. In some embodiments, pre-reaction zone 140 is heated to near, equal to, or above the decomposition temperature of the metal-containing precursor (e.g., above 100°C, above 150°C, or above 200°C). The precursors may also be exposed to plasma in pre-reaction zone 140. The resulting modified precursor is more thermally stable than the metal-containing precursor. For example, if the metal-containing precursor has a decomposition temperature of 120°C, the modified precursor may have a decomposition temperature of at least 400°C, at least 600°C, or higher. Other decomposition temperature ranges are possible. Generally, it is desirable that the decomposition temperature of the modified precursor is high enough to facilitate its flow from the pre-reaction chamber 140 to the reaction chamber 110. The resulting modified precursor may also have a longer diffusion length than the metal-containing precursor. For example, Mo(CO)6 may have a diffusion length of approximately 70 micrometers. The corresponding modified precursor is Mo(CO). 6-x (OH) x At one atmosphere and at a temperature of approximately 800°C, a diffusion length greater than 500 micrometers may be present. In some embodiments, the modified precursor has a diffusion length on the order of one thousand times the diffusion length of the metal-containing precursor from which it forms. However, the temperature of the pre-reaction zone 140 is also controlled to be equal to or below the decomposition temperature of the modified precursor. In embodiments where a dopant precursor is provided to the pre-reaction chamber 140, the dopant precursor may react with the metal-containing precursor, the modifier, and / or the modified precursor. The resulting reactants are discharged from the pre-reaction zone 140.

[0038] The modified precursor is supplied from the pre-reaction zone 140 to the outlet 150. The chalcogenide precursor is also supplied from the inlet 130 to the outlet 150. The outlet 150 supplies the modified precursor and the chalcogenide precursor to the reaction chamber 110. However, the outlet 150 is also configured such that the modified precursor remains separate from the chalcogenide precursor within the reactant delivery subsystem 120. Therefore, in some embodiments, the modified precursor and the chalcogenide precursor do not mix before leaving the outlet 150 (and therefore before leaving the reactant delivery subsystem 120). Furthermore, the outlet 150 and any path between the pre-reaction zone 140, the inlet 130, and the outlet 150 can be temperature-controlled to facilitate the arrival of reactants (e.g., the modified precursor, the chalcogenide precursor, and / or any dopant precursor / modified dopant precursor) into the reaction chamber 110. For example, the temperature can be controlled to be high enough that the reactants are unlikely to condense, high enough that the required temperature of reaction chamber 110 can be maintained, and low enough that the reactants are unlikely to decompose or otherwise fail.

[0039] The modified precursor and the chalcogenide precursor are mixed and reacted in reaction chamber 110. Therefore, reaction chamber 110 is configured to form TMC. For example, reaction chamber 110 may be heated to a temperature of at least 50°C. In some embodiments, the temperature of reaction chamber 110 is controlled to be less than 2000°C or more than 1000°C. For example, the temperature of reaction chamber 110 may have a temperature of at least 400°C and no more than 1000°C. In some cases, the temperature of reaction chamber 110 is at least 600°C and no more than 900°C. In some embodiments, the temperature of the pre-reaction zone 140 used to form the modified precursor is lower than the temperature used to form one or more chalcogenides in reaction chamber 110. However, in some cases, the temperature of the pre-reaction zone 140 during use may be higher than the temperature of the reaction chamber 110 during use. For example, the pre-reaction zone 140 may operate at approximately 600°C, while the reaction chamber 110 may operate at approximately 300-400°C. However, in this case, the quality of the TMC membrane may be inferior to that of the TMC membrane grown at high temperatures (e.g., 1000°C).

[0040] Substrate 112 is also oriented in reaction chamber 110 to facilitate TMC growth. For example, substrate 110 may be at least five millimeters and no more than 100 millimeters (and in some embodiments no more than fifty millimeters) from outlet 150. In some embodiments, the surface of substrate 112 is parallel or nearly parallel (e.g., within five degrees of parallelism) to the surface of outlet 150. Other orientations and / or distances are possible. If a dopant precursor is provided to pre-reaction region 140, the resulting reactant, including the dopant, is also provided to reaction chamber 110 via outlet 150. In this case, a doped TMC film is grown.

[0041] For example, the metal-containing precursor Mo(CO)6 can be supplied to the reaction zone 140 via inlet 130. This can be achieved by heating the Mo(CO)6 and passing an inert gas (such as Ar) through the heated Mo(CO)6. Additionally, water vapor can be supplied to the reaction zone 140 via inlet 130 as a modifier and carbon reduction precursor. In the pre-reaction zone 140, Mo(CO)6 reacts with H2O to form Mo(CO). 6-x (OH) x As a modified precursor, Mo(CO) 6-x (OH) x It has a higher degradation temperature and a greater diffusion distance than Mo(CO)6. Therefore, this modified precursor is more likely to reach reaction zone 110 and be able to form TMC. The reaction of water vapor may also help to remove such carbon residues in pre-reaction zone 140 before they reach reaction chamber 110. The modified precursor is provided to reaction chamber 110 via outlet 150. Chalcogenide precursors such as H2S are provided to reaction chamber 110 via inlet 130 and outlet 150. In some embodiments, dopant precursors and / or decarburizers can be provided to reaction chamber 110 via inlet 130 and outlet 150. Reaction chamber 110 may also be heated, for example to 600°C-800°C. The modified precursor and chalcogenide precursor react in reaction chamber 110 to form MoS2 on substrate 112. Although described in the context of a single metal-containing precursor, modifier, and chalcogenide precursor, multiple metal-containing precursors, modifiers, and chalcogenide precursors may be used. Therefore, it is possible to manufacture hybrid TMC membranes (e.g., Mo). x W y S2 and / or Mo x W y Se2). Furthermore, one or more dopant precursors may be provided to the pre-reaction chamber 140. Such dopant can be more easily incorporated into the TMC film compared to providing the dopant directly to the reaction chamber 110. Furthermore, better uniformity and desired amounts of dopant in the TMC film can be achieved. However, in other embodiments, one or more dopant precursors and / or decarbonizing agents may be provided directly to the reaction chamber 110.

[0042] The vapor deposition system 100 can facilitate the growth of materials such as 2D TMC films. The resulting modified precursors may be more stable and / or have longer diffusion lengths than metal-containing precursors. For example, Mo(CO). 6-x (OH) x It may have a decomposition temperature higher than the 120°C decomposition temperature of Mo(CO)6. Mo(CO) 6-x (OH) xThe diffusion length of the modified precursor may also be greater than that of Mo(CO)6 (e.g., greater than one centimeter to several centimeters). Therefore, the modified precursor may be more volatile. These properties allow for higher utilization efficiency. In particular, the modified precursor is less likely to decompose or otherwise adversely affected by its transfer from inlet 130 to reaction chamber 110. A larger proportion of the modified precursor reaches reaction chamber 110 and incorporates into the TMC film. Forming the modified precursor in the pre-reaction zone 140 also allows for the fabrication of new precursors that are not readily available commercially for use in reaction chamber 110. Therefore, the flexibility of the vapor deposition system 100 can be increased. Furthermore, a wider operating temperature range (e.g., 150°C to 1000°C or higher) can be achieved for the vapor deposition system 100. Therefore, robustness to temperature variations and flexibility in fabricating 2D TMC films can be improved. System 100 can also be more easily adapted to different growth requirements. Dopants can also be provided via dopant precursors for the pre-reaction unit 120. The dopant precursor can be provided in a proportion similar to the desired dopant ratio in the TMC being manufactured. Therefore, reliable and more controllable TMC doping can be provided. A decarbonizing agent, such as water (which can also be used as a modifier), can be provided as a precursor to the pre-reaction zone 140. In the example above, water can be both a modifier and a decarbonizing agent. Therefore, carbon can be reduced in the pre-reaction chamber 140, and the quality of the grown TMC can be improved. The modifier precursor and the chalcogenide precursor are also provided separately before being supplied to the reaction chamber 110 via outlet 150. Therefore, the growth of the TMC film can be confined to the reaction chamber 110. Outlet 150 can be distributed such that uniform seeding and growth are achieved over a large area of ​​substrate 112. Therefore, it is possible to grow 2D TMC films with a larger area. For example, in some embodiments, the area of ​​the film may be at least 1 in. 2 In some embodiments, the area of ​​the TMC membrane may be at least 2 inches. 2 At least 8 in 2 At least 12 in 2 or at least 20 in 2 In some cases, 2D TMCs with large areas, thicknesses ranging from a single layer to one hundred micrometers (or more), and low defect densities (e.g., fewer vacancies) can be grown. For example, 2D TMC films fabricated using system 100 may produce films with not only larger areas but also lower defect densities than conventionally formed 2D TMC films. By introducing a pre-reaction zone 140, the initial reaction forming the modified precursor is isolated from the reaction chamber 110. This reduces potential contamination, optimizes precursor use, and facilitates the production of higher quality TMCs. Thus, large-area, electronic-grade metal chalcogenide (e.g., TMC) films can be provided. Therefore, various 2D TMC films with higher quality can be more easily fabricated using the vapor deposition system 100.

[0043] Figure 2 This is a diagram depicting an embodiment of a vapor deposition system 200 for providing metal chalcogenide materials. Figure 2 Not drawn to scale, and not all components may be shown. Vapor deposition system 200 is similar to vapor deposition system 100. Therefore, similar components are similarly labeled. Vapor deposition system 200 is described in the context of TMC, particularly 2D TMC films. However, in some embodiments, other metal chalcogenides (2D or others) and / or other films can be fabricated.

[0044] The vapor deposition system 200 includes a reaction chamber 210 with a substrate 212 and a reactant delivery subsystem 220, which is similar to the reaction chamber 110 and the reactant delivery subsystem 120. The reactant delivery subsystem 220 includes an inlet 230, a pre-reaction zone 240, and an outlet 250, which are similar to the inlet 130, the pre-reaction zone 140, and the outlet 150, respectively.

[0045] Inlet 230 includes a precursor inlet 232 and a sulfide-containing precursor inlet 234. Inlet 232 is connected to and supplies the precursor to the pre-reaction zone 240. Inlet 234 is coupled to outlet 250 and supplies the sulfide-containing precursor thereto. The pre-reaction zone 240 is located within the pre-reaction chamber 242 and includes a temperature control unit 260. The temperature control unit 260 may include, for example, a heater.

[0046] The reactant delivery subsystem 220 also includes a channel 270 and a temperature control unit 280. The channel 270, temperature control unit 280, and outlet 250 can be considered as forming a temperature-controlled gas distribution unit. The temperature control unit 280 can be used to control the temperature of the modified precursors and other reactants before they enter the reaction chamber 210 via outlet 250. For example, the temperature in the reactant delivery system 220 (e.g., in channel 270) can be controlled to be high enough that the reactants do not condense, and low enough that the reactants do not decompose or otherwise damage. Channel 270 allows flow or reactant from the pre-reaction zone 240 to outlet 250. Therefore, the pre-reaction zone 240 can be separated from outlet 250 by a distance.

[0047] Outlets 250 are distributed on some or all of the surface of substrate 212. In some embodiments, outlets 250 are uniformly distributed. In some embodiments, outlets 250 from channel 270 of pre-reaction zone 240 have different dimensions than outlets 250 for chalcogenide precursors. Although outlets 250 from channel 270 are shown concentrated in one region and outlets 250 from inlet 234 are shown concentrated in another region, in some embodiments, outlets 250 carrying gas from channel 270 and inlet 234 are distributed in another manner. For example, outlets 250 carrying gas from channel 270 and inlet 234 may be uniformly distributed. In some embodiments, outlets 250 are distributed in regions close to or larger than the surface of substrate 212. For example, outlets 250 may be distributed in regions at least 1 / 2, at least 3 / 4, approximately equal to, or larger than the substrate region (e.g., no more than 1 1 / 2 or no more than twice the substrate region). Furthermore, outlets 250 are aligned with some or all of substrate 212. Therefore, it can promote the growth of uniform 2D TMC membranes over a larger area.

[0048] The vapor deposition system 200 operates in a manner similar to and shares the benefits of the vapor deposition system 100. The vapor deposition system 200 can facilitate the growth of materials such as 2D TMC films. Modified precursors formed in the pre-reaction zone 240 may be more stable and / or have longer diffusion lengths than metal-containing precursors. Modified precursors are less likely to decompose or otherwise be adversely affected by transfer from the pre-reaction zone 240 to the reaction chamber 210. A larger proportion of modified precursors reach the reaction chamber 210 and can be used for TMC formation, allowing for higher utilization efficiency. Forming modified precursors in the pre-reaction zone 240 also allows for the fabrication of novel precursors that may not be commercially available for use in the reaction chamber 210. Therefore, the flexibility of the vapor deposition system 200 can be increased. Furthermore, a wider operating temperature range (e.g., 150°C to 1000°C or higher) can be achieved for the vapor deposition system 200. Therefore, robustness to temperature variations, adaptability to new growth requirements, and flexibility in fabricating 2D TMC films can be improved. Dopants can also be provided via dopant precursors for pre-reaction unit 220. This allows for reliable and more controllable TMC doping. Decarbonizing agents can be provided as precursors to pre-reaction zone 240. This allows for carbon reduction in pre-reaction chamber 240 and improves the quality of the grown TMC film. Modified precursors and chalcogenide precursors are also provided separately before being supplied to reaction chamber 210 via outlet 250. Outlet 250 can be configured to achieve uniform nucleation and growth over a large area of ​​substrate 212. This allows for the growth of more uniform 2D TMC films with larger areas. In some cases, 2D TMC films with large areas, thicknesses ranging from monolayer to one hundred micrometers (or more), and low defect densities (e.g., fewer or no vacancies) can be grown. Such 2D TMC films may be suitable for electronic applications. Therefore, various 2D TMC films with higher quality can be more easily fabricated using vapor deposition system 200.

[0049] Figure 3 This is a diagram depicting an embodiment of a vapor deposition system 300 for providing metal chalcogenide materials. Figure 3 Not drawn to scale, and not all components may be shown. Vapor deposition system 300 is similar to vapor deposition systems 100 and / or 200. Therefore, similar components are similarly labeled. Vapor deposition system 300 is described in the context of TMC, particularly 2D TMC films. However, in some embodiments, other metal chalcogenides (2D or others) and / or other films can be fabricated.

[0050] The vapor deposition system 300 includes a reaction chamber 310 with a substrate 312 and a reactant delivery subsystem 320, which is similar to the reaction chamber 110 and the reactant delivery subsystem 120. The reactant delivery subsystem 320 includes an inlet 330, a pre-reaction zone 340, and an outlet 350, which are similar to the inlet 130, the pre-reaction zone 140, and the outlet 150, respectively.

[0051] Inlet 330 includes a precursor inlet 332 and a sulfide-containing precursor inlet 334. Precursor inlet 332 is connected to and supplies precursors to the pre-reaction zone 340. The pre-reaction zone 340 is located within the reactant delivery subsystem 320 and includes a temperature control unit 360. Although depicted as adjacent to the pre-reaction zone 340, the temperature control unit 360 may be or include a portion closer to inlet 332. The temperature control unit 360 may, for example, include a heater and / or coolant. For instance, the temperature control unit 360 may include a cooling unit near inlet 332 and a heater adjacent to the pre-reaction zone 340.

[0052] The reactant delivery subsystem 320 also includes a temperature control unit 380. The temperature control unit 380 is used to control the temperature of the modified precursors and other reactants before they enter the reaction chamber 310 via outlet 350. For example, the temperature in the reactant delivery system 320 can be controlled to be high enough that the reactants do not condense (e.g., to prevent or mitigate blockage of the reactant delivery subsystem 320), high enough that the desired temperature of the reactants can be maintained in the reaction chamber 310, and low enough that the reactants do not decompose or otherwise degrade. Outlets 350 are distributed on some or all of the surface of the substrate 312 in a manner similar to outlet 250. For example, outlets 350 carrying gases from the pre-reaction zone 340 and inlet 334 can be uniformly distributed. Furthermore, outlets 350 can be distributed in areas close to or larger than the surface of the substrate 312.

[0053] like Figure 3 As shown, the pre-reaction zone 340 is close to the outlet 350 and therefore close to the reaction chamber 310. Therefore, in some embodiments, the outlet 350 and the pre-reaction zone 340 may be integrated into a single component that both forms the modified precursor, receives the dopant precursor, and supplies the reactants to the reaction chamber 310.

[0054] The vapor deposition system 300 can share the benefits of the vapor deposition system 100. The vapor deposition system 300 can facilitate the growth of materials such as 2D TMC films. The formed modified precursors may be more stable and / or have longer diffusion lengths than metal-containing precursors. The modified precursors are less likely to decompose or otherwise be adversely affected by their transfer to the reaction chamber 310. A larger proportion of the modified precursors reach the reaction chamber 310 and can be used for TMC formation, thus allowing for higher utilization efficiency. Forming modified precursors in the pre-reaction zone 340 also allows for the fabrication of new precursors that may not be commercially available for use in the reaction chamber 310. Therefore, the flexibility of the vapor deposition system 300 can be increased. Furthermore, a wider operating temperature range (e.g., 150°C to 1000°C or higher) can be achieved for the vapor deposition system 300. Therefore, robustness to temperature variations, adaptability to new growth requirements, and flexibility in fabricating 2D TMC films can be improved. Dopants can also be provided via dopant precursors used in the pre-reaction unit 320. Therefore, reliable and more controllable TMC doping can be provided. A decarbonizing agent can be provided as a precursor to the pre-reaction zone 340. Thus, carbon can be reduced in the pre-reaction zone 340, improving the quality of the grown TMC. The modified precursor and the chalcogenide-containing precursor are also provided separately before being supplied to the reaction chamber 310 via outlet 350. Outlet 350 can be configured to achieve the desired (e.g., uniform) nucleation and growth over a large area of ​​substrate 312. Therefore, it is possible to grow more uniform 2D TMC films with larger areas. In some cases, 2D TMCs with large areas, thicknesses ranging from monolayer to one hundred micrometers (or more), and low defect densities (e.g., fewer vacancies) can be grown. For example, a 2D TMC film grown using system 300 may have approximately two orders of magnitude fewer defects per unit area than a conventionally grown 2D TMC film (e.g., some TMC films grown using embodiments of system 300 have 10 fewer defects per unit area). 11 Defects / cm 2 While some TMC films grown using conventional techniques have a relative 10 13 Defects / cm 2 Therefore, using the vapor deposition system 300, it is easier to manufacture various 2DTMC films with higher quality.

[0055] Figures 4A-4D This is a diagram depicting a portion of a vapor deposition system 400 that can be used to form TMC films. Figures 4A-4D Not drawn to scale, and not all components may be shown. Vapor deposition system 400 is similar to vapor deposition systems 100, 200, and / or 300. Vapor deposition system 400 is described in the context of TMC, particularly 2D TMC films. However, in some embodiments, other metal chalcogenides (2D or others) and / or other films can be fabricated. Figure 4A A cross-sectional view of the distribution unit and reaction chamber 410 is depicted. Figure 4B A portion of System 400 is depicted. Figure 4C An outlet 450 is depicted, which takes the form of a plate 450 having holes 452 and 454 therein. Figure 4D This is a perspective view of a portion of the connection between inlet 434 and hole 455. The materials used in system 400 are expected to be heat-resistant. For example, stainless steel, quartz, graphite, Ni, and / or Ni alloys may be used to form various parts of system 400.

[0056] The vapor deposition system 400 is perhaps most similar to the vapor deposition system 200, which includes a temperature-controlled dispensing unit comprising a channel 270 between a pre-reaction zone 240 and an outlet 250. Therefore, similar components are similarly labeled. The vapor deposition system 400 includes a reaction chamber 410 having a substrate 412 and a reactant delivery subsystem comprising a channel 470, an inlet 434, and an outlet 450, which are similar to reaction chambers 110 and 210, and reactant delivery subsystems 120 and 220 comprising channels 270, inlets 234, and outlets 150 and 250, respectively. In some embodiments, the pre-reaction chamber of the vapor deposition system 400 is not shown, but reactants are provided to a mixing chamber 456 via channel 472. In other embodiments, precursors (e.g., one or more metal-containing precursors, modifiers, one or more dopant precursors, and / or other precursors) may be provided to chamber 456. In such embodiments, chamber 456 may serve as a pre-reaction zone.

[0057] Reaction chamber 410 includes a substrate support 414 and an outlet vent 416. Inlet 434 carries one or more chalcogenide precursors. Inlet 434 terminates near passage 451, which carries one or more chalcogenide precursors to region 455 and orifice 454. Channel 472 carries reactants from a pre-reaction zone (not shown), such as one or more modified precursors. Reactants from channel 472 are supplied to mixing chamber 456 and then output via orifice 452 in plate 450.

[0058] In some embodiments, plate 450 includes a series of concentric inner and outer apertures (or pathways) 452 and 454. Some apertures 452 carry modified precursors and other reactants (e.g., for dopants) from mixing chamber 456. Other apertures 454 carry chalcogenide precursors. Apertures 452 and 454 are configured such that the reactants (e.g., modified precursors) and chalcogenide precursors from chamber 456 are separated and uniformly distributed on substrate 412 within reaction chamber 410. The reactants (e.g., modified precursors) and chalcogenide precursors from pre-reaction chambers only meet when exiting apertures 452 and 454 and approaching the surface of substrate 412. Therefore, desired (e.g., uniform) nucleation and growth can be facilitated over a large area of ​​substrate 412.

[0059] In operation, chamber 456 outputs one or more modified precursors via orifice 452. Dopant precursors (or modified dopant precursors) and / or other reactants may also be supplied from chamber 456 via orifice 452. One or more chalcogenide precursors flow from separate inlets 434 to plate 450. More specifically, one or more chalcogenide precursors flow through inlet 434, through passage 451 to passage 455, and out of plate 450 through orifice 454. Thus, 434 / 451 / 455 / 454 and 472 / 456 / 452 form separate, isolated paths for the chalcogenide precursors and reactants from mixing chamber 456. Paths 434 / 451 / 455 / 454 and 472 / 456 / 452 can be considered as part of a gas distribution system that may be able to independently control the reactants and chalcogenide precursors from pre-reaction zone 640. In some embodiments, the airflow through paths 472 / 456 / 452 is controlled separately from the airflow through paths 434 / 451 / 455 / 454. In some embodiments, each path 434 / 451 / 455 / 454 has separately controllable flow. Similarly, each path 472 / 456 / 452 may have separately controllable flow.

[0060] Modified precursors and other reactants from chamber 456, flowing through orifice 452, are mixed with chalcogenide precursors flowing through orifice 454 in reaction chamber 410. Thus, a 2D TMC film can be formed on substrate 412. The distribution and size of orifices 452 and 454 promote uniform nucleation and growth over a large area of ​​substrate 412.

[0061] The vapor deposition system 400 can share the benefits of vapor deposition systems 100, 200, and / or 300. The vapor deposition system 400 can facilitate the growth of more uniform 2D TMC films with larger areas. Therefore, using the vapor deposition system 400, it is easier to fabricate a variety of 2D TMC films with higher quality.

[0062] Figure 5 This is a diagram depicting an embodiment of a gas distribution system 500 that can be used in a vapor deposition system for manufacturing metal chalcogenide materials. The gas flow control system 500 can be used with vapor deposition systems 100, 200, 300, 400, and / or 600. In other embodiments, other gas flow control systems may be used.

[0063] Gas distribution system 500 includes a chalcogenide-containing gas flow subsystem 510 and a precursor flow subsystem 520. Gas flow subsystem 510 is isolated from and independently controlled by gas flow subsystem 520. In gas flow subsystem 520, the flow rates of dopant precursors, metal-containing precursors, and dopant precursors can be controlled separately. In some embodiments, the carrier gas used for gas flow control systems 510 and 520 is an inert gas, such as Ar. In some embodiments, other and / or additional carrier gases may be used. In some embodiments, additional chalcogenide sources and dopant sources may be used (in cases where multiple chalcogenide sources and / or dopant sources are used). Although gas distribution system 500 is depicted with a single line from gas flow subsystem 510 providing chalcogenide precursors, and a single line from gas flow subsystem 510 for precursors (e.g., a single line for metal-containing precursors, modifiers, and dopant precursors), multiple lines and multiple control systems may exist. For example, the gas flow subsystem 520 may have lines for one or more metal-containing precursors, lines for one or more modifiers, and lines for one or more dopant precursors. Furthermore, a single precursor (e.g., a metal-containing precursor or a chalcogenide-containing precursor) may have multiple lines and multiple control subsystems (e.g., multiple valves, mass flow controllers, and / or carrier gases). Therefore, in some embodiments, the gas distribution system 500 can provide a significant degree of control over the reactants.

[0064] By using the valves, carrier gas, and lines shown, the gas distribution system 500 allows for independent control of each precursor. In some embodiments, the gas distribution system 500 can provide additional control over outlets (e.g., orifices 452 and / or 454), inlets (e.g., 232 and 234), and / or other areas of the vapor deposition system (e.g., channel 270) to further control the flow of reactants to the substrate. The gas distribution system 500 facilitates the use of vapor deposition systems 100, 200, 300, 400, and / or 600. Furthermore, the gas flow system 500 can be extended to higher gas flow rates and / or larger substrate (and therefore TMC film) areas.

[0065] Figures 6A-6D This is a diagram depicting a portion of a vapor deposition system 600 that can be used to form TMC films. Figures 6A-6DNot drawn to scale, and not all components may be shown. Vapor deposition system 600 is similar to vapor deposition systems 100, 200, 300, and / or 400. Vapor deposition system 600 is described in the context of TMC, particularly 2D TMC films. However, in some embodiments, other metal chalcogenides (2D or others) and / or other films can be fabricated. Figure 6A A cross-sectional view of system 600 is depicted. Figure 6B and Figure 6D A portion of System 600 is depicted. Figure 6C An outlet 650 is depicted, which takes the form of a plate 650 having holes 652 and 654 therein. The materials used in system 600 are expected to be heat-resistant. For example, stainless steel, quartz, graphite, Ni, and / or Ni alloys can be used to form various parts of system 600.

[0066] The vapor deposition system 600 is perhaps most similar to the vapor deposition system 300, which includes a pre-reaction chamber 340 adjacent to the reaction chamber 310. The vapor deposition system 600 is also configured in a manner similar to that of system 400. Therefore, similar components are similarly labeled. The vapor deposition system 600 includes inlets 632 and 634, a reaction chamber 610 having a substrate 612, a pre-reaction chamber 640, and an outlet 650, which are respectively similar to inlets 330 and 472 and 434, reaction chambers 110, 310 and 410, pre-reaction chambers 140, 340 and (chamber) 456, and outlets 150, 350 and 450.

[0067] The reaction chamber 610 includes a substrate support 614 and an outlet vent 616. Therefore, the reaction chamber 610 is similar to the reaction chamber 410.

[0068] Inlet 634 carries one or more sulfide precursors. Inlet 634 terminates near passage 651, which carries one or more sulfide precursors to region 655 and orifice 654. Passage 651, region 655 and orifice 654 are similar to passage 451, region 455 and orifice 454, respectively.

[0069] Inlet 632 carries a precursor (such as a metal-containing precursor) to pre-reaction zone 640. The precursor passes through cooling zone 661 and insulation zone 663. The temperature of cooling zone 661 is controlled by temperature control unit 662. In the illustrated embodiment, temperature control unit 662 may provide liquid (e.g., water) cooling. In other embodiments, temperature control unit 662 may control the temperature of cooling zone 661 in other ways. The temperature of insulation zone 663 may be controlled by temperature control unit 664. Temperature control unit 664 may be a heater. For example, temperature control unit 664 is shown as a heating coil. Other techniques may be used to control the temperature of insulation zone 663. In some embodiments, temperature control unit 664 may be or include one or more infrared heaters and / or one or more induction heaters. Cooling zone 661 and insulation zone 663 are used to control the temperature of the precursor supplied to pre-reaction zone 640. Therefore, condensation and decomposition of both can be prevented. For example, cooling zone 661 may ensure that the temperature of the precursor is below 100°C before entering insulation zone 663. Therefore, premature decomposition of the metal-containing precursor can be reduced or eliminated. The insulation zone 663 facilitates the precursor reaching the desired temperature in the pre-reaction zone 640. Thus, the temperature of the system 600 can be rapidly increased over a short distance. Using the temperature control unit 664 in the insulation zone 663, this area (and therefore the gas therein) can be easily heated to, for example, 500°C or higher. In some embodiments, the cooling zone 661, the insulation zone 663, and the pre-reaction zone 640 significantly increase the utilization rate of the metal-containing precursor.

[0070] The pre-reaction zone 640 may be heated by coil 660. In some embodiments, other and / or additional temperature control mechanisms may be used. For example, the heating coil 660 may be replaced or supplemented by infrared heating and / or induction heating.

[0071] In some embodiments, plate 650 includes a series of concentric inner and outer vias (or passages) 652 and 654. Some vias 652 carry modified precursors and other reactants (e.g., for dopants) from mixing chamber 656. Other vias 654 carry chalcogenide precursors. Vias 652 and 654 are configured such that reactants (e.g., modified precursors) and chalcogenide precursors from pre-reaction zone 640 are separately distributed on substrate 612 within reaction chamber 610. Therefore, reactants (e.g., modified precursors, dopant precursors, and / or modified dopant precursors) and chalcogenide precursors from pre-reaction zone 640 only meet when exiting vias 652 and 654 and approaching the surface of substrate 612. In the illustrated embodiment (e.g., in…), Figure 6CIn some embodiments, the distribution of holes 652 and 654 near the edges of plate 650 is lower (i.e., holes 652 and 654 are further away from the center of plate 650). In some embodiments, other distributions may be used. For example, holes 652 and / or 654 may be uniformly distributed on the surface of plate 650. In another example, holes 652 and / or 654 may be more densely packed near the edges. Such a distribution may result in more uniform flow of reactants on the surface of substrate 612. In some embodiments, holes 652 and / or 654 may be a rectangular (or other) array rather than radially arranged. In other embodiments, other distributions of holes 652 and / or 654 on the surface of plate 650 may exist. Therefore, desired nucleation (e.g., uniform nucleation) and growth can be facilitated over a large area of ​​substrate 612.

[0072] During operation, the temperature of the precursor is controlled from inlet 632 to pre-reaction zone 640. Therefore, desired heating and flow of the precursor can be achieved. In pre-reaction zone 640, the precursor reacts to form a modified precursor. Pre-reaction zone 640 outputs the modified precursor to reaction chamber 610 via orifice 652. Other reactants (e.g., dopants) can also be supplied from pre-reaction zone 640 via orifice 652. One or more chalcogenide-containing precursors flow from separate inlets 634 to plate 650. More specifically, one or more chalcogenide-containing precursors flow through inlet 634, through pipe 651 to passage 655, and out of plate 650 through orifice 654. Therefore, paths 634 / 651 / 655 / 654 can be configured in a manner similar to passage 434 / 451 / 455 / 454. Therefore, paths 634 / 651 / 655 / 654 and 632 / 640 / 652 form separate, isolated paths for the chalcogenide precursor and the precursor / reactant from the pre-reaction chamber. Thus, paths 634 / 651 / 655 / 654 and 632 / 640 / 652 can be part of a gas distribution system that may be able to independently control the reactants and chalcogenide precursors from the pre-reaction zone 640. In some embodiments, the gas flow through path 632 / 640 / 652 is controlled separately from the gas flow through path 634 / 651 / 655 / 654. In some embodiments, each path 634 / 651 / 655 / 654 and 632 / 640 / 652 has a separately controllable flow. For example, the flow can be controlled such that the flow of reactants from orifices 652 and / or 654 can be uniform, higher at the edges, or can be otherwise configured to provide a desired reactant distribution (e.g., uniform distribution) on the surface of substrate 612.

[0073] Modified precursors and other reactants from pre-reaction zone 640 are mixed with chalcogenide precursors flowing through orifice 654 in reaction chamber 610. In some embodiments, the surface of substrate 612 is at least five millimeters and no more than fifty or one hundred millimeters away from orifices 652 and 654. Furthermore, at least a portion of substrate 612 is aligned with orifices 632 and 634. Thus, a 2D TMC film can be formed on substrate 612. The distribution and size of orifices 652 and 654 can promote uniform nucleation and growth over a large area of ​​substrate 612.

[0074] The vapor deposition system 600 can share the benefits of vapor deposition systems 100, 200, 300 and / or 400. The vapor deposition system 600 can promote the growth of more uniform 2D TMC films with a larger area. Therefore, using the vapor deposition system 600, it is easier to fabricate a variety of 2D TMC films with higher quality.

[0075] Figure 7 This is a flowchart depicting an embodiment of a method 700 for forming metal chalcogenide materials using vapor deposition. Although described in a particular order, an alternative order may be used that does not contradict the description herein. Method 700 is described in the context of vapor deposition system 100. However, other systems, including but not limited to systems 200, 300, 400, and / or 600, may be used.

[0076] At 702, the precursor reacts in the pre-reaction zone to form at least one modified precursor. The precursor reacting at 702 comprises one or more metal-containing precursors and one or more modifiers. The modified precursor is more thermally stable than the metal-containing precursor used to form the modified precursor. The modified precursor may have a higher decomposition temperature and / or a longer diffusion length than the corresponding metal-containing precursor. In some embodiments, the precursor also includes a dopant precursor, which may react with the modifier and / or the metal-containing precursor.

[0077] In step 704, one or more modified precursors and one or more chalcogenide precursors are separately provided to the reaction chamber. The reaction chamber is configured such that the one or more modified precursors and one or more chalcogenide precursors react and form a TMC film on a substrate within the reaction chamber. In some embodiments, the formed TMC film is a 2D TMC film. In embodiments where the dopant precursor is provided in step 702, the dopant in the dopant precursor is incorporated into the chalcogenide film. Thus, a doped chalcogenide film is formed on the substrate within the reaction chamber.

[0078] For example, the metal precursor Mo(CO)6 can be reacted with water (a modifier) ​​in a pre-reaction zone 140 at 702. This can occur by heating Mo(CO)6 and passing an inert gas (such as Ar) through the heated solid. In the pre-reaction zone 140, Mo(CO)6 reacts with H2O to form Mo(CO). 6-x (OH) x As a modification precursor. In 704, Mo(CO) is... 6-x (OH) x The modified precursor and the chalcogenide precursor are provided together with, for example, H2S into the reaction chamber 110. The modified precursor and the chalcogenide precursor are kept separate before meeting in the reaction chamber 110. As part of 704, the reaction chamber 110 can also be heated, for example, to 600°C-800°C. The modified precursor and the chalcogenide precursor react to form MoS2 on the substrate 112. Although described in the context of a single metal-containing precursor, modifier, and chalcogenide precursor, multiple metal-containing precursors, modifiers, and chalcogenide precursors can be used. Therefore, hybrid TMC films can be fabricated.

[0079] Figure 8 This is a flowchart depicting an embodiment of a method for forming metal chalcogenide materials using vapor deposition. Although described in a particular order, an alternative order may be used that does not contradict the description herein. Method 800 is described in the context of vapor deposition system 100. However, other systems may be used, including but not limited to systems 200, 300, 400, and / or 600.

[0080] At 802, one or more metal-containing precursors and one or more modifiers are provided to a pre-reaction zone. In some embodiments, 802 includes passing an inert gas through a heated solid for use with the metal-containing precursor. Modifiers and optional dopants may be similarly provided to the reaction chamber. At 804, the modifier, metal-containing precursor, and optional dopant precursor are reacted in the pre-reaction zone. In some embodiments, this is achieved by heating the pre-reaction zone or otherwise establishing conditions under which the reaction may occur. Thus, a modified precursor can be generated. In some embodiments, the dopant precursor also reacts with the gas. Thus, a modified dopant precursor can also be generated.

[0081] At 806, the modified precursor and the modified dopant precursor are fed into the reaction chamber. Furthermore, at 808, the chalcogenide precursor is separately supplied to the reaction chamber. At 810, the modified precursor, the modified dopant precursor, and the chalcogenide precursor are reacted. In some embodiments, 810 includes establishing conditions in the reaction chamber for the reaction to occur. Therefore, the desired TMC film can be grown.

[0082] For example, in 802, Mo(CO)6 and water can be fed into a pre-reaction chamber 140. This can be achieved by passing an inert gas (such as Ar) through a heated solid for use with Mo(CO)6. Mo(CO)6 reacts with H2O in the pre-reaction chamber 140, where the temperature ranges from approximately 500°C (e.g., 150°C to 750°C). The flow rate of the argon (Ar) carrier gas can be selected (e.g., in the range of approximately 10 sccm to 500 sccm) to dilute the precursor. In 804, the metal-containing precursor and modifier react in the pre-reaction chamber 140. The reaction is: Mo(CO)6 + H2O -> Mo(CO) 6-x (OH) x , where x depends on the ratio of the metal-containing precursor to the modifier and the reaction temperature. Modified precursor Mo(CO) 6-x (OH) x The modified precursor is more stable than the initial precursor Mo(CO)6 and therefore can reach reaction chamber 110 more easily. The temperature of the transport area (e.g., channels 270 and / or outlets 150, 250, 350, 450, or 650) can be set at approximately 400°C to approximately 800°C. In some embodiments, the temperature is in the range of 50°C to 1000°C. Thus, at 806, the modified precursor is provided to reaction chamber 110. Furthermore, at 808, a sulfide-containing precursor (such as H2S) or evaporated sulfur is carried to reaction chamber 110 by Ar gas (e.g., at a flow rate of 10-500 sccm). The modified precursor and the sulfide-containing precursor are transported in two separate paths before reaching reaction unit 110.

[0083] In step 810, the modified precursor and the chalcogenide precursor react in reaction chamber 110 to form a TMC film on substrate 112. This may include heating reaction chamber 140. The temperature of reaction chamber 110 can range from 150 to 1000°C. Reaction chamber 110 can also be evacuated, for example, to pressures ranging from 0.1 Torr to 760 Torr. The growth time can be used to control the film size, ranging from a few nanometers or tens of nanometers to 100 micrometers or more. In some embodiments, the diameter of the film can be at least one inch, at least two inches, at least four inches, or greater (e.g., depending on the diameter of substrate 112). By controlling the flow rate of the precursor, the number of TMC layers can be controlled from single-layer to multi-layer. Therefore, using method 800, a desired 2D TMC film can be achieved.

[0084] Figures 9A-9C These figures depict examples and characteristics of metal chalcogenide films formed using vapor deposition. Specifically, Figure 9A It is a graph 900 depicting the Raman spectra of two 2D TMC films. Figure 9B Figure 910 shows the photoluminescence spectrum of a single-layer 2DTMC film. Figure 9CA micrograph 920 depicts such a 2D TMC film. The film is a MoS2 film formed as described herein. Mo(CO)6 is used as a metal-containing precursor, H2O as a modifier, and S as a chalcogenide element. The Raman spectrum of plot 900 indicates that the MoS2 film can be fabricated as a monolayer and as a multilayer. The low full width at half maximum (FWHM) of the photoluminescence spectrum 910 indicates that a high-quality MoS2 film can be obtained. In some embodiments, electronic-grade thin films can be fabricated. Micrograph 920 is a high-angle annular dark-field scanning transmission microscopy (HAADF-STEM) image. Micrograph 920, from a top view, shows the hexagonal rings of MoS2 without vacancies. Therefore, the desired 2D TMC film can be fabricated using one or more of the vapor deposition systems and / or methods described herein.

[0085] Although the foregoing embodiments have been described in detail for purposes of clarity, the invention is not limited to the details provided. Many alternative ways of implementing the invention exist. The disclosed embodiments are illustrative and not restrictive.

[0086] What is being protected is:

Claims

1. A vapor deposition system, comprising: A reaction chamber configured to hold a substrate therein; A reactant delivery subsystem, coupled to the reaction chamber, and comprising: Multiple inlets, the multiple inlets being used to receive multiple precursors and at least one chalcogenide precursor; A pre-reaction zone configured to receive the plurality of precursors from a portion of the plurality of inlets and react at least a portion of the plurality of precursors to form a modified precursor, the modified precursor being more thermally stable than the metal-containing precursor of the at least a portion of the plurality of precursors; and Multiple outlets coupled to the reaction chamber and the pre-reaction zone, the multiple outlets separately supplying the modified precursor and the at least one chalcogenide precursor to the reaction chamber; The modified precursor and the at least one chalcogenide precursor react to form a chalcogenide film on the substrate in the reaction chamber.

2. The vapor deposition system according to claim 1, wherein, The reactant delivery subsystem includes: A heated pre-reaction chamber, the heated pre-reaction chamber including the pre-reaction zone therein, wherein at least a portion of the plurality of precursors reacts in the heated pre-reaction chamber in the absence of the at least one chalcogenide precursor to form the modified precursor; and A distribution unit coupled to the heated pre-reaction chamber via a flow channel, the distribution unit including the plurality of outlets and coupled to at least one of the plurality of inlets for the at least one chalcogenide precursor.

3. The vapor deposition system according to claim 1, wherein, The pre-reaction zone is adjacent to the plurality of outlets, and the plurality of precursors react in the pre-reaction zone in the absence of the at least one chalcogenide precursor to form the modified precursor.

4. The vapor deposition system according to claim 1, wherein, The pre-reaction zone includes a heater.

5. The vapor deposition system according to claim 4, wherein, The temperature of the pre-reaction zone is lower than the temperature of the reaction chamber.

6. The vapor deposition system according to claim 4, wherein, The reactant delivery subsystem also includes: A cooling zone, coupled to a portion of the plurality of inlets and the pre-reaction zone, is configured to maintain a temperature below the decomposition temperature of the metal-containing precursor.

7. The vapor deposition system according to claim 1, wherein, The plurality of precursors include a modifier for the metal-containing precursor, the modifier reacting with the metal-containing precursor in the pre-reaction zone to form the modified precursor.

8. The vapor deposition system according to claim 1, wherein, The modified precursor has a higher decomposition temperature than the metal-containing precursor.

9. The vapor deposition system according to claim 1, wherein, The plurality of precursors include dopant precursors, and the chalcogenide film includes dopants in the dopant precursors.

10. The vapor deposition system according to claim 1, wherein, The first portion of the plurality of outlets is coupled to the pre-reaction zone and provides the modified precursor to the reaction chamber; and The second portion of the plurality of outlets separately provides the at least one chalcogenide precursor and the modified precursor to the reaction chamber.

11. The vapor deposition system according to claim 1, wherein, The reactant delivery subsystem also includes: A gas distribution system coupled to the plurality of outlets such that at least a portion of the plurality of outlets has an individually controllable flow rate.

12. The vapor deposition system according to claim 1, wherein, The substrate has a substrate region, the plurality of outlets are distributed on the region, the region is at least 1 / 2 of the substrate region, and at least a portion of the region is aligned with at least a portion of the substrate region.

13. The vapor deposition system according to claim 1, wherein, The metal-containing precursor contains at least one of W or Mo, the plurality of precursors contain at least one of water, Fe dopant or V dopant, and the at least one chalcogenide precursor contains at least one of S, Te or Se.

14. An apparatus comprising: Substrate; as well as A transition metal chalcogenide (TMC) film is formed on the substrate by vapor deposition, the TMC film covering an area of ​​at least one square inch of the substrate.

15. The apparatus according to claim 14, wherein, The TMC membrane is a two-dimensional membrane having a thickness of at least one monolayer.

16. The apparatus according to claim 15, wherein, The TMC film is a doped TMC film.

17. The apparatus according to claim 15, wherein, The area is at least four square inches.

18. A method comprising: At least a portion of a plurality of precursors are reacted in a pre-reaction zone to form a modified precursor, said modified precursor being more thermally stable than said at least a portion of the metal-containing precursors of the plurality of precursors; as well as The modified precursor and at least one chalcogenide precursor are separately provided to the reaction chamber; as well as The modified precursor and the at least one chalcogenide precursor react to form a chalcogenide film on a substrate in the reaction chamber.

19. The method of claim 18, further comprising: The plurality of precursors, including a dopant precursor, are delivered to the pre-reaction region; as well as In this process, the dopant in the dopant precursor is incorporated into the chalcogenide film, thereby forming a doped chalcogenide film on the substrate in the reaction chamber.

20. The method according to claim 18, wherein, The plurality of precursors also include modifiers for the metal-containing precursors.

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