Method and system for depositing transition metal-containing films

Abstract

The present invention provides a method and apparatus for depositing a transition metal-containing material onto a substrate by a periodic deposition process. [Solution] The method of the present disclosure comprises providing a substrate in a reaction chamber, providing a transition metal halide precursor in the gas phase in the reaction chamber, and providing a second precursor in the gas phase in the reaction chamber to form a layer containing a transition metal on the substrate. The transition metal halide precursor comprises a transition metal tetrahalide.

Description

[Technical Field]

[0001] [Parties to the Joint Research Agreement] The inventions claimed herein were made under, for, and / or in connection with, a joint research agreement between the University of Helsinki and ASM Microchemistry Oy. This agreement was in effect on and before the date the claimed inventions were made, and the claimed inventions are the result of activities undertaken within the scope of this agreement.

[0002] The present invention relates to a method and system for manufacturing semiconductor devices. More specifically, the present disclosure relates to a method and assembly for depositing a transition metal-containing material onto a substrate by a periodic deposition process, as well as to a layer comprising the transition metal-containing material. [Background technology]

[0003] Transition metal carbides (TMCs) are widely used in catalytic and wear-resistant applications, exhibiting excellent chemical and thermal stability, very high hardness, and low resistivity. In addition, TMCs typically possess good electromigration resistance. The properties of TMCs allow their metal wire dimensions to shrink to below 10 nm, making them relatively good conductors. The development of ALD processes for TMCs opens up the possibility of using carbides in semiconductor applications. However, ALD of metal carbides is still in its early stages, and current challenges include the lack of thermal ALD processes, high process temperatures, and low growth rates. Transition metal carbides such as molybdenum carbide (MoCx) have the potential to improve the performance, efficiency, and reliability of semiconductor devices. In recent years, these transition metal carbides have been considered potential candidates for diffusion barriers, interconnects, and gate electrodes.

[0004] All discussions, including those concerning the problems and solutions described herein, are included in this disclosure solely for the purpose of providing background to this disclosure. Such discussions should not be construed as acknowledging that any or all of the information was known at the time the invention was made, or otherwise constitutes prior art. [Overview of the project]

[0005] This summary is provided to introduce selected concepts in a simplified form. These concepts are described in more detail in the following detailed description of exemplary embodiments of the disclosure. This summary is not intended to identify any major or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter. [Means for solving the problem]

[0006] Various embodiments of the present disclosure are disclosed of a method for forming a layer containing a transition metal on a substrate by a periodic deposition process. The method of the present disclosure includes providing a substrate in a reaction chamber and performing at least one deposition cycle. Each deposition cycle includes providing a gaseous transition metal halide precursor in the reaction chamber and providing a second gaseous precursor in the reaction chamber to form a layer containing a transition metal on the substrate. In the method, the transition metal halide precursor includes a transition metal tetrahalide.

[0007] In some embodiments, the transition metal halide precursor comprises a transition metal selected from the group of transition metals from Group IV to VIII. In some embodiments, the transition metal halide precursor comprises a transition metal selected from the group consisting of molybdenum, chromium, tungsten, nickel, cobalt, niobium, copper, titanium, palladium, platinum, zirconium, hafnium, vanadium, tantalum, manganese, rhodium, iron, iridium, and rhenium. In some embodiments, the transition metal halide precursor comprises a transition metal selected from the group of transition metals from Group VI. In some embodiments, the halogen in the transition metal halide precursor is selected from the group consisting of chlorine, iodine, fluorine, and bromine. In some embodiments, the transition metal halide precursor comprises molybdenum tetrachloride.

[0008] In another embodiment, a transition metal carbide layer produced by a periodic deposition process is disclosed. The method comprises providing a substrate in a reaction chamber and performing at least one deposition cycle. Each deposition cycle comprises providing a gaseous transition metal halide precursor in the reaction chamber and providing a second gaseous precursor in the reaction chamber to form a layer containing the transition metal on the substrate. In this method, the transition metal halide precursor comprises a transition metal tetrahalide.

[0009] In some embodiments, the second precursor acts as a reducing agent and / or carbon donor. In some embodiments, the second precursor comprises a cyclic diene compound comprising a substituent containing a metalloid. In some embodiments, the metalloid comprises a trialkyl metalloid. In some embodiments, the second precursor may also include those in which the metalloid of the second precursor is germanium or silicon. In some embodiments, the second precursor may include those in which the cyclic diene is a 5-membered or 6-membered cyclic diene. In some embodiments, the second precursor comprises a cyclohexadiene compound selected from the compounds of formula (I).

[0010] [ka]

[0011] In Formula (I), M is either Ge or Si, Z 1 and Z 2 are each independently selected from CR 11 and N, and R 1 to R 11 are each independently selected from the group consisting of H, C1 to C7 linear or branched alkyl, C6 to C10 aryl, and C6 to C14 heteroaryl. In some embodiments, the second precursor may also include those wherein R 11 is H. In some embodiments, the second precursor may include those wherein each of R 7 to R 10 is independently selected from the group consisting of H, C1 to C4 linear and branched alkyl, and phenyl. In some embodiments, the second precursor may include those wherein all of R 7 to R 10 are H. In some embodiments, the second precursor may include those wherein each of R 1 to R 6 is independently selected from the group consisting of H, methyl, ethyl, n-propyl, and isopropyl. In some embodiments, the second precursor may include those wherein all of R 1 to R 6 are methyl. In some embodiments, the second precursor comprises a cyclohexadiene compound selected from compounds of Formula (II).

[0012]

Chemical Formula

[0013] In Formula (II), M is either Ge or Si, Z 1 and Z 2 are each independently selected from CR 15 and N, and R 1 to R 15each is independently selected from the group consisting of H, C1-C7 linear or branched alkyl, C6-C10 aryl, and C6-C14 heteroaryl. In some embodiments, the second precursor comprises R 15 that is H. In some embodiments, the second precursor comprises R 7 to R 14 each of which is independently selected from the group consisting of H, C1-C4 linear and branched alkyl, and phenyl. In some embodiments, the second precursor comprises R 7 to R 14 all of which are H. In some embodiments, the second precursor comprises R 1 to R 6 each of which is independently selected from the group consisting of H, methyl, ethyl, n-propyl, and isopropyl. In some embodiments, the second precursor comprises R 1 to R 6 all of which are methyl. In some embodiments, the second precursor is selected from the group consisting of 1,4-bis(trimethylgermyl)-1,4-dihydropyrazine, 1,4-bis(trimethylsilyl)-1,4-dihydropyrazine, 1,1'-bis(trimethylsilyl)-1,1'-dihydro-4,4'-bipyridine, and 1,1'-bis(trimethylgermyl)-1,1'-dihydro-4,4'-bipyridine.

[0014] In some embodiments, the transition metal-containing layer comprises an elemental transition metal. In some embodiments, the second precursor comprises a metal selected from the group consisting of zinc, sodium, magnesium, and aluminum. Other technical arrangements may be readily apparent to those skilled in the art from the following drawings, description, and claims.

[0015] In yet another embodiment, a method for producing a transition metal tetrahalide precursor is disclosed. The method includes mixing a transition metal pentahalide, diethyl ether, and tin in a container to form a mixture; washing the mixture with diethyl ether to remove tin chloride from the mixture to form an intermediate product; and heating the intermediate product to obtain a transition metal tetrahalide.

[0016] In some embodiments, the transition metal comprises molybdenum. In some embodiments, the halide in the transition metal tetrahalide and transition metal pentahalide comprises chloride. In some embodiments, the intermediate product comprises MoCl4(Et2O)2. In some embodiments, heating is carried out under vacuum at about 90°C for more than 90 minutes. Other technical configurations may be readily apparent to those skilled in the art from the following drawings, description, and claims.

[0017] In another embodiment, a vapor supply vessel containing a transition metal tetrahalide precursor for depositing a layer containing a transition metal is disclosed. The vapor supply vessel comprises an outer wall enclosing a cavity for storing the film-forming composition and a gas outlet for allowing vapor of the film-forming composition to exit the cavity. The vessel is configured to supply precursor vapor to a semiconductor processing chamber.

[0018] In some embodiments, the steam supply vessel further comprises a gas inlet and a conduit extending within a cavity to a fixed point. The conduit may extend within the cavity and into the film-forming composition to allow the carrier gas to pass through the film-forming composition. Alternatively, the conduit may extend within the cavity to a point above the film-forming composition to allow the carrier gas to pass over the surface of the film-forming composition.

[0019] In some embodiments, the steam supply vessel further comprises a probe member. The probe member may comprise one or more temperature sensors and / or one or more level sensors and one or more pressure sensors.

[0020] In some embodiments, the outer wall and cavity of the steam supply vessel are formed from stainless steel. In some embodiments, the vessel is suitable for mounting to a vapor deposition reactor.

[0021] In one embodiment, a deposition assembly for depositing a layer containing a transition metal on a substrate is disclosed. The deposition assembly includes one or more reaction chambers constructed and positioned to hold a substrate, and a precursor injector system constructed and positioned to provide a transition metal halide precursor and a second precursor in the gas phase into the reaction chambers. The deposition assembly comprises a first precursor container containing a transition metal halide precursor containing a transition metal tetrahalide and constructed and positioned to evaporate, and a second precursor container containing a second precursor and constructed and positioned to evaporate, wherein the assembly is constructed and positioned to provide the transition metal halide precursor and the second precursor to the reaction chambers via the precursor injector system and to deposit a layer containing the transition metal on the substrate.

[0022] In some embodiments, the assembly further includes a temperature controller for controlling the temperature of the reaction chamber.

[0023] Those skilled in the art will readily see these and other embodiments from the following detailed description of certain embodiments with reference to the accompanying drawings. The present invention is not limited to any particular embodiment disclosed. [Brief explanation of the drawing]

[0024] [Figure 1] This is a flowchart of a method according to one embodiment. [Figure 2] This is a block diagram of a device according to one embodiment. [Modes for carrying out the invention]

[0025] A more complete understanding of the embodiments of this disclosure is obtained by referring to the following exemplary drawings, the detailed description and the claims. To facilitate the identification of any particular component or operation, the most significant digit of the reference number refers to the figure number in which that component is first introduced.

[0026] It should be understood that the components in the drawings are illustrative for simplification and clarity and are not necessarily drawn to actual size. For example, the dimensions of some components in the drawings may be exaggerated relative to others to help improve understanding of the illustrated embodiments of this disclosure.

[0027] Although certain embodiments and examples are disclosed below, it will be understood by those skilled in the art that the present invention extends beyond the embodiments and / or uses of the invention specifically disclosed, as well as their obvious modifications and equivalents. Therefore, the scope of the disclosed invention is not intended to be limited by the specific embodiments described below.

[0028] The descriptions of exemplary embodiments of methods, structures, devices, and systems provided below are illustrative and descriptive only, and are not intended to limit the scope of this disclosure or the claims. Furthermore, the enumeration of multiple embodiments having the described features is not intended to exclude other embodiments having additional features or incorporating different combinations of the described features. For example, various embodiments may be described as exemplary embodiments and enumerated in dependent claims. Unless otherwise stated, exemplary embodiments or their components may be used in combination or separately.

[0029] In this disclosure, “gas” can enclose materials that are gases at room temperature and pressure (NTP), vaporized solids and / or vaporized liquids, and may, depending on the context, consist of a single gas or a mixture of gases. Gases other than process gases, i.e., gases introduced without passing through gas distribution assemblies, other gas distribution devices, etc., can be used, for example, to seal reaction spaces, and include sealing gases, such as noble gases. In some cases, the term “precursor” refers to a compound involved in a chemical reaction that produces another compound, specifically a compound that constitutes the matrix or main skeleton of a membrane. The term “reactant” may be used interchangeably with the term “precursor.” Exemplary gases may include precursors and reactants.

[0030] Where used herein, the term “includes / composes” indicates that a particular feature is included, but does not exclude the presence of other features unless it renders the claims or embodiments unfeasible. In some embodiments, the term “includes / composes” includes the meaning of “consists of.” Where used herein, the term “consists of” indicates that, apart from the feature following this term, the apparatus / method / product has no other features. When the term “consists of” is used in reference to a compound or substance, it indicates that the chemical compound contains only the listed components.

[0031] As used herein, the term “substrate” may refer to any underlying material or material that can be used to form a device, circuit, or film, or any underlying material or material on which a device, circuit, or film can be formed. A substrate may include a bulk material such as silicon (e.g., single-crystal silicon), another Group IV material such as germanium, or another semiconductor material such as Group II-VI or Group III-V semiconductor material, and may include one or more layers that overlap or lie beneath the bulk material. Furthermore, a substrate may include various features such as recesses, protrusions, and similar features formed within or on at least a portion of the layers of the substrate. For example, a substrate may include a bulk semiconductor material and an insulating or dielectric material layer on at least a portion of the bulk semiconductor material. As an additional or alternative configuration, an exemplary substrate may include a bulk semiconductor material and a conductive layer on at least a portion of the bulk semiconductor material.

[0032] As used herein, “step coverage” refers to the percentage obtained by dividing the growth rate of the layer on the distal end face relative to the opening of the recess by the growth rate of the same layer on the proximal end face relative to the opening of the recess. Step coverage provides a measure of layer suitability.

[0033] As used herein, “vapor supply vessel” refers to a vessel suitable for or configured for vapor supply of a substance contained within the vessel. A vapor supply vessel comprises an outer wall enclosing a cavity for storing and / or holding a substance, and a fluid outlet for allowing vapor of the substance to exit the cavity. The substance contained within the cavity may be a composition suitable for a vapor deposition or etching method. For example, the substance contained within the cavity may optionally include one or more precursors, one or more reactants, one or more etchants, or one or more surface treatment agents. The substance contained within the cavity may be a homogeneous or heterogeneous mixture. The substance contained within the cavity may be in solid form, liquid form, gaseous form, or a combination thereof. A vapor supply vessel may be a vapor suction vessel, a carrier gas vessel, a double-walled vessel, a sublimation vessel, and / or other configurations.

[0034] As used herein, the terms “film” and / or “layer” may refer to any continuous or discontinuous structure and material, such as material deposited by the methods disclosed herein. Examples of films and / or layers include two-dimensional materials, three-dimensional materials, nanoparticles, partial or complete molecular layers, partial or complete atomic layers, and clusters of atoms and / or molecules. A film or layer may consist partially or completely of a plurality of atoms dispersed on the surface of a substrate and / or be embedded within the substrate and / or embedded in a device manufactured on that substrate. A film or layer may comprise a material or layer having pinholes and / or isolated islands. A film or layer may be at least partially continuous. A film or layer may be patterned, for example, subdivided, and may be contained within a plurality of semiconductor devices.

[0035] As used herein, “structure” may be or include a substrate as described herein. A structure may include one or more layers on a substrate, such as one or more layers formed according to the methods described herein. Device portions and interconnects may be or include a structure.

[0036] As used in this disclosure, the term “deposition process” may refer to the process of introducing a precursor (and / or reactant) into a reaction chamber and depositing a layer over a substrate. A “periodic deposition process” is an example of a “deposition process.”

[0037] In this disclosure, the deposition process may include, for example, a periodic deposition process such as an atomic layer deposition (ALD) process or a periodic chemical vapor deposition (CVD) process. The term “periodic deposition process” may refer to the sequential introduction of precursors and / or reactants into a reaction chamber in order to deposit a material, such as a metal or metalloid-containing material, onto a substrate. Periodic deposition includes processing techniques such as atomic layer deposition (ALD), periodic chemical vapor deposition (periodic CVD), and hybrid periodic deposition processes that include ALD components and periodic CVD components. The aforementioned processes may include a purging step between providing a plurality of precursors or between providing precursors and reactants in the reaction chamber.

[0038] The process may include one or more periodic steps. For example, pulses of a transition metal halide precursor and a second precursor may be repeated. In some embodiments, the process includes one or more non-periodic steps. In some embodiments, the deposition process includes a continuous flow of at least one precursor. In some embodiments, the reactants may be continuously supplied into the reaction chamber. In such embodiments, the process includes a continuous flow of a precursor or reactants. In some embodiments, one or more of the precursors and / or reactants are continuously supplied into the reaction chamber. In some embodiments, auxiliary reactants may be continuously supplied into the reaction chamber.

[0039] The term "atomic layer deposition" (ALD) can refer to a deposition process in which deposition cycles, such as multiple consecutive deposition cycles, are carried out in a reaction chamber. Generally, in an ALD process, during each cycle, a precursor is introduced into the reaction chamber and chemisorbed onto the deposition surface (e.g., a substrate surface that may contain previously deposited material from a previous ALD cycle or other materials) to form a monolayer or quasi-monolayer of material that does not readily react with additional precursors (i.e., a self-limiting reaction). Subsequently, another precursor or reactant may be introduced into the process chamber for use in converting the chemisorbed precursor onto the deposition surface into a desired material. The second precursor or reactant can further react with the precursor. A purging step may be utilized between one or more cycles, for example, between each step of each cycle, to remove excess precursor from the process chamber and / or excess reactant and / or reaction byproducts from the reaction chamber. Thus, in some embodiments, the periodic deposition process includes purging the reaction chamber after providing transition metal halide precursors into the reaction chamber. In some embodiments, the periodic deposition process includes purging the reaction chamber after providing a second precursor into the reaction chamber. In some embodiments, the periodic deposition process includes purging the reaction chamber after providing any precursor or reactant into the reaction chamber.

[0040] CVD-type processes typically involve gas-phase reactions between two or more precursors and / or reactants. The precursors or reactants can be supplied to the reaction space or substrate simultaneously, or in partially or completely separated pulses. The substrate and / or reaction space may be heated to facilitate the reaction between the gaseous precursors and / or reactants. In some embodiments, the precursors and reactants are supplied until a layer of the desired thickness is deposited. In some embodiments, a periodic CVD process can be used in multiple cycles to deposit a thin film of the desired thickness. In a periodic CVD process, the precursors and / or reactants can be supplied to the reaction chamber in non-overlapping, partially or completely overlapping pulses.

[0041] As used herein, the term “purge” may refer to the procedure of providing a purge gas to the reaction chamber between a precursor pulse and a plasma pulse, or between a precursor pulse and a reactant pulse. It should be understood that during purging, the substrate is not exposed to plasma-generating species. For example, when using a DC plasma, the plasma can be turned off during purging. For example, purging uses a purge gas, such as nitrogen or a noble gas, and is provided between the precursor pulse and the reactant pulse, thereby avoiding, or at least minimizing, gas-phase interaction between the precursor and the reactant. Naturally, purging can be achieved temporally, spatially, or both. For example, in the case of temporal purging, the purging process may be used chronologically, for example, by providing a first precursor to the reaction chamber, providing a purge gas to the reaction chamber, and then providing a second precursor to the reaction chamber, while the substrate on which the layer is deposited does not move. For example, in the case of spatial purging, the purging process may take the following form: moving the substrate from a first position where a first precursor is continuously supplied to a second position where a second precursor is continuously supplied, through a purge gas curtain.

[0042] As used herein, “precursor” includes a gas or material that may be in gaseous form and can be represented by a chemical formula that includes elements that may be incorporated during the deposition process as described herein.

[0043] Furthermore, in this disclosure, any two numbers of a variable can constitute a viable range of that variable, and any range shown may include or exclude the endpoints. In addition, any value of a variable shown (whether shown with “approximately” or not) may refer to an exact value or an approximate value, may include its equivalent, or may refer to the mean, median, measure of central tendency, major value, etc. Furthermore, in this disclosure, the terms “contains,” “constitutes,” and “have” independently refer to “typically or broadly contain,” “contains,” “essentially consists of,” or “consists of.”

[0044] "At least one," "one or more," and "and / or" are open-ended expressions that function as both conjunctions and disjunctions. For example, the expressions "at least one of A, B, and C," "at least one of A, B, or C," "one or more of A, B, and C," "one or more of A, B, or C," and "A, B, and / or C" mean A alone, B alone, C alone, a combination of A and B, a combination of A and C, a combination of B and C, or a combination of A, B, and C. Each of A, B, and C in the above expressions can be an element such as X, Y, Z, or X1-X n Y1-Y m , and Z1-Z o When referring to classes of elements such as X, Y, and Z, the phrase can refer to a single element selected from X, Y, and Z, a combination of elements selected from the same class (e.g., X1 and X2), and a combination of elements selected from two or more classes (e.g., Y1 and Z). O It is intended to refer to )

[0045] In this disclosure, any defined meaning does not necessarily exclude the ordinary and common meanings in some embodiments.

[0046] In the deposition methods according to this disclosure, layers containing transition metals are deposited. In some embodiments, the material deposited according to this disclosure contains transition metal carbides, in other words, carbidic transition metals. Herein, carbidic transition metal means carbon bonded to a transition metal. This means, for example, that the deposited material does not contain carbon impurities. In some embodiments, the material deposited according to this disclosure consists of or comprises transition metal carbides. In some embodiments, at least 60% of the transition metal carbides are deposited as carbidic transition metals. In some embodiments, at least 80% or at least 90% of the transition metal carbides are deposited as carbidic transition metals. In one embodiment, the transition metal carbide has a structure according to the general formula MC, where M is a transition metal in formulas (I) and (II). In one embodiment, the transition metal carbide has a structure according to the general formula M2C, where M is a transition metal in the aforementioned general formula.

[0047] In some embodiments, the material deposited according to this disclosure includes elemental transition metals. In some embodiments, the material deposited according to this disclosure is essentially made of or consists of elemental transition metals. In some embodiments, at least 60% of the transition metal is deposited as elemental transition metals. In some embodiments, at least 80% or at least 90% of the transition metal is deposited as elemental transition metals.

[0048] Without limiting the present disclosure to any particular theory, in some embodiments it may be possible to produce layers with low resistivity, particularly when transition metal carbides are deposited. The resistivity of the metal layer according to the present disclosure may be less than 400 μΩcm, or less than 320 μΩcm, or less than 250 μΩcm, or less than 170 μΩcm. For example, the resistivity of the transition metal carbide layer according to the present disclosure may be about 5 μΩcm to about 520 μΩcm, about 5 μΩcm to about 350 μΩcm, or about 5 μΩcm to about 300 μΩcm, or about 5 μΩcm to about 250 μΩcm.

[0049] In another embodiment, a method for preparing a transition metal tetrahalide precursor is disclosed. The method comprises mixing a transition metal pentahalide, diethyl ether, and tin in a container to form a mixture; washing the mixture with diethyl ether to remove tin chloride from the mixture to form an intermediate product; and heating the intermediate product to obtain a transition metal tetrahalide.

[0050] In some embodiments, the transition metal comprises molybdenum. In some embodiments, the halide in the transition metal tetrahalide and transition metal pentahalide comprises chloride. In some embodiments, the intermediate product comprises MoCl4(Et2O)2. In some embodiments, heating is carried out under vacuum at about 90°C for more than 90 minutes. Other technical configurations may be readily apparent to those skilled in the art from the following drawings, description, and claims.

[0051] In another embodiment, a vapor supply vessel containing a transition metal tetrahalide precursor for depositing a layer containing a transition metal is disclosed. The vapor supply vessel comprises an outer wall enclosing a cavity for storing the film-forming composition and a gas outlet for allowing vapor of the film-forming composition to exit the cavity. The vessel is configured to supply precursor vapor to a semiconductor processing chamber.

[0052] In some embodiments, the steam supply vessel further comprises a gas inlet and a conduit extending within a cavity to a fixed point. The conduit may extend within the cavity and into the film-forming composition to allow the carrier gas to pass through the film-forming composition. Alternatively, the conduit may extend within the cavity to a point above the film-forming composition to allow the carrier gas to pass over the surface of the film-forming composition.

[0053] In some embodiments, the steam supply vessel further comprises a probe member. The probe member may comprise one or more temperature sensors and / or one or more level sensors and one or more pressure sensors.

[0054] In some embodiments, the outer wall and cavity of the steam supply vessel are formed from stainless steel. In some embodiments, the vessel is suitable for mounting to a vapor deposition reactor.

[0055] This disclosure is further described by the following exemplary embodiments illustrated in the drawings. The drawings presented herein are not intended to be actual drawings of any particular material, structure, device, or apparatus, but are merely schematic diagrams illustrating embodiments of the disclosure. Elements in the drawings are illustrative for simplification and clarity and are not necessarily drawn to actual size. For example, the dimensions of some components in the drawings may be exaggerated compared to other components to help improve understanding of the illustrated embodiments of the disclosure. Structures and devices illustrated in the drawings may include additional elements and details that are omitted for clarity.

[0056] The specific embodiments described are illustrative of the present invention and are not intended to limit the scope of the aspects and embodiments in any way. Indeed, for the sake of brevity, conventional manufacturing, connection, preparation, and other functional aspects of the system may not be described in detail. Furthermore, the connection lines shown in various figures are intended to represent exemplary functional relationships and / or physical connections between various components. Many alternative or additional functional relationships or physical connections may exist in a practical system and / or may not exist in some embodiments.

[0057] It should be understood that the configurations and / or approaches described herein are illustrative in nature, and these particular embodiments or examples should not be considered restrictively, as numerous variations are possible. A particular routine or method described herein may represent one or more of any number of processing strategies. Thus, the various actions illustrated may be performed in the illustrated order, in other orders, or, in some cases, omitted.

[0058] The subject matter of this disclosure includes all novel and non-obvious combinations and partial combinations of the various processes, systems, and configurations disclosed herein, as well as all their equivalents.

[0059] Figure 1 shows a flowchart of an exemplary embodiment of flow 100 of a method for depositing a layer containing a transition metal on a substrate. In step 102, method flow 100 provides the substrate into a reaction chamber. The substrate according to this disclosure may contain an oxide such as silicon oxide (e.g., thermal silicon oxide or native silicon oxide). The substrate may also contain nitrides, such as silicon nitride or titanium nitride, metals such as copper, cobalt or tungsten, or chalcogenide materials such as molybdenum sulfide. The transition metal-containing material according to this disclosure may be deposited on the aforementioned surface.

[0060] The reaction chamber can form part of an atomic layer deposition (ALD) assembly. The reaction chamber can form part of a chemical vapor deposition (CVD) assembly. The assembly may be a single-wafer reactor. Alternatively, the reactor may be a batch reactor. The assembly may comprise one or more multi-station deposition chambers. The various steps of method flow 100 can be performed in a single reaction chamber, or they can be performed in multiple reaction chambers, such as a cluster tool reaction chamber. In some embodiments, method flow 100 is performed in a single reaction chamber of a cluster tool, while other pre- or post-construction steps for a structure or device are performed in additional reaction chambers of the same cluster tool. Optionally, the assembly comprising the reaction chamber may be equipped with a heater to activate the reaction by raising the temperature of one or more of the substrate, and / or reactants, and / or precursors. The transition metal-containing material according to this disclosure may be deposited in a cross-flow reaction chamber. The transition metal-containing material according to this disclosure may be deposited in a showerhead reaction chamber. In some embodiments, the reaction chamber may be a spatially divided reactor. In some embodiments, the reaction chamber may be a single-wafer ALD reactor. In some embodiments, the reaction chamber may be a single-wafer ALD reactor capable of mass production. In some embodiments, the reaction chamber may be a batch reactor for simultaneously manufacturing multiple substrates. The reaction chamber according to this disclosure may further be a deposition station in a multi-station chamber.

[0061] In step 104, a gaseous transition metal halide precursor is introduced into the reaction chamber. Without limiting this disclosure to any particular theory, the transition metal halide precursor may chemiadsorb onto the substrate while it is being introduced into the reaction chamber. The duration for which the transition metal halide precursor is introduced into the reaction chamber (transition metal halide precursor pulse time) may be, for example, 0.1 seconds, 0.5 seconds, 1 second, 1.5 seconds, 2 seconds, 3 seconds, 4 seconds, and 5 seconds.

[0062] In the method according to this disclosure, the transition metal halide precursor may be in the gaseous phase while in the reaction chamber. The transition metal halide precursor may be partially gaseous or liquid, or may be solid at some point before being supplied to the reaction chamber. In other words, the transition metal halide precursor may be solid, liquid, or gaseous in a precursor container or other containment vessel, for example, before being introduced into the reaction chamber. Various means of bringing the precursor into the gaseous phase are applicable when introducing the precursor into the reaction chamber. Such means may include, for example, a heater, a vaporizer, the application of a gas flow or reduced pressure, or any combination thereof. Thus, the method according to this disclosure may include heating the transition metal halide precursor before providing it to the reaction chamber.

[0063] In some embodiments, the deposition of the transition metal-containing material according to the Disclosure is carried out at a temperature of less than about 450°C, or less than about 380°C, or less than about 360°C. In some embodiments, deposition is carried out at a temperature of about 240°C to about 310°C, for example, about 200°C to about 300°C, for example, about 350°C to about 420°C, for example, at a temperature of about 250°C, about 275°C, about 300°C, or about 420°C. In some embodiments, deposition is carried out at a temperature of about 250°C to about 450°C, for example, about 300°C to about 400°C, for example, at any of the following temperatures: about 325°C, about 350°C, about 375°C, 400°C, about 425°C, and about 450°C.

[0064] In some embodiments, the transition metal halide precursor is heated to a temperature of at least 30°C, at least 50°C, or at least 70°C, or at least 90°C, or at least 110°C, or at least 140°C, or at least 200°C before being supplied to the reaction chamber. In some embodiments, the transition metal halide precursor is heated to at least 100°C, or at least 130°C. Heating may be performed in the precursor vessel. In some embodiments, the transition metal halide precursor is heated to a maximum of 180°C, or a maximum of 170°C, or a maximum of 160°C, or at a maximum of 250°C before being supplied to the reaction chamber. The injector system of the deposition assembly may be heated to improve gas-phase delivery of the transition metal precursor to the reaction chamber.

[0065] In some embodiments, the transition metal halide precursor includes a transition metal for depositing a layer containing the transition metal on a substrate. In some embodiments, the transition metal halide precursor includes a Group IV to Group VIII transition metal for depositing a Group IV to Group VIII layer containing the transition metal on a substrate. In some embodiments, the transition metal in the transition metal halide precursor is selected from the group consisting of molybdenum (Mo), chromium (Cr), tungsten (W), nickel (Ni), cobalt (Co), niobium (Nb), copper (Cu), titanium (Ti), palladium (Pd), platinum (Pt), zirconium (Zr), hafnium (Hf), vanadium (V), tantalum (Ta), manganese (Mn), rhodium (Rh), iron (Fe), iridium (Ir), and rhenium (Re). In some embodiments, the transition metal in the transition metal halide precursor is selected from the group consisting of chromium (Cr), molybdenum (Mo), and tungsten (W). In some embodiments, the transition metal in the transition metal halide precursor is selected from the group consisting of scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), rhenium (Re), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), and cadmium (Cd). In some embodiments, the transition metal in the transition metal precursor is selected from the group consisting of molybdenum (Mo), chromium (Cr), tungsten (W), nickel (Ni), cobalt (Co), niobium (Nb), rhenium (Re), copper (Cu), gold (Au), titanium (Ti), palladium (Pd), platinum (Pt), rhodium (Rh), and ruthenium (Ru). In some embodiments, the metal precursor includes lanthanide metals for depositing lanthanide series metals on a substrate. In some embodiments, the transition metal in the transition metal precursor is selected from the group consisting of chromium (Cr), molybdenum (Mo), niobium (Nb), and tungsten (W).In some embodiments, the transition metal in the transition metal precursor may be molybdenum (Mo). In some embodiments, the transition metal precursor consists only of a transition metal and a halogen.

[0066] In some embodiments, the halogen in the transition metal halide precursor is selected from the group consisting of chlorine, iodine, fluorine, and bromine. In some embodiments, the transition metal halide precursor includes molybdenum tetrachloride.

[0067] In some embodiments, the transition metal precursor is provided as a mixture of two or more compounds. In the mixture, the other compounds in addition to the transition metal precursor may be inert compounds or elements. In some embodiments, the transition metal precursor is provided as a composition. A composition suitable for use as a composition may contain a transition metal compound and an effective amount of one or more stabilizers. The composition may be a solution or a gas under standard conditions.

[0068] Step 106 provides an optional purging step. During the purging step, the precursors and / or reactants may be temporally separated from each other by an inert gas such as argon (Ar), nitrogen (N2), or helium (He), and / or vacuum pressure. The separation of the transition metal halide precursor and / or the second precursor may alternatively be spatial. For example, in the case of spatial purging, the purging step may take the form of moving the substrate from a first position where the transition metal halide precursor is continuously supplied, through a purge gas curtain, to a second position where the second precursor is continuously supplied. The purging time may be, for example, about 0.01 seconds to about 20 seconds, about 0.05 seconds to about 20 seconds, or about 1 second to about 20 seconds, or about 0.5 seconds to about 10 seconds, or about 1 second to about 7 seconds, and may be any of 1 second, 2 seconds, and 3 seconds. However, other purging times may be employed as needed, for example, when highly conformal step coverage is required to cover structures with very high aspect ratios or other structures with complex surface morphologies, or in certain reactor types such as batch reactors.

[0069] Step 106, purging the reaction chamber, may prevent or mitigate the gas-phase reaction between the transition metal halide precursor and the second precursor, potentially leading to a self-saturated surface reaction. If there are any excess chemicals and reaction byproducts, these may be removed from the substrate surface before contact with the next reactive chemical, for example, by purging the reaction chamber or by moving the substrate. However, in some embodiments, the substrate may be moved so that the transition metal halide precursor and the second precursor come into contact separately. In some embodiments, the reaction may self-saturate, so strict temperature control of the substrate and precise dosage control of the precursors may not be required. However, the substrate temperature is preferably such that the incident gas species do not condense into a single or multiple single layer, nor do they undergo thermal decomposition on the surface.

[0070] In step 108, a second precursor in the gas phase is introduced into the reaction chamber. In some embodiments, the second precursor comprises a cyclic diene compound comprising a substituent containing a metalloid semimetal. In some embodiments, the metalloid semimetal comprises a trialkyl metalloid. In some embodiments, the second precursor may also comprise a compound in which the metalloid semimetal of the second precursor is germanium or silicon. In some embodiments, the second precursor may comprise a compound in which the cyclic diene is a 5-membered or 6-membered cyclic diene.

[0071] In some embodiments, the second precursor includes a reducing agent and / or a carbon donor for reducing a transition metal halide precursor and optionally depositing a transition metal carbide onto a substrate. In some embodiments, the second precursor includes a reducing agent, a carbon donor, and a nitrogen donor for simultaneously reducing the transition metal halide precursor and the deposited transition metal carbonitride on the substrate. In some embodiments, the second precursor includes a carbon precursor for depositing a transition metal carbide onto a substrate. The duration for providing the second precursor in the reaction chamber (second precursor pulse time) may be, for example, 0.5 seconds, 1 second, 1.5 seconds, 2 seconds, 3 seconds, 4 seconds, and 5 seconds.

[0072] In some embodiments, the second precursor is a reducing agent. The reducing agent can reduce the transition metal of the transition metal halide precursor to the elemental metal. In some embodiments, the second precursor is a carbon donor. The carbon donor may donate carbon atoms to the transition metal of the transition metal halide precursor to form a transition metal carbide. In some embodiments, the second precursor acts as both a reducing agent and a carbon donor. In some embodiments, the second precursor is a nitrogen donor. The nitrogen donor may donate nitrogen atoms to the transition metal of the transition metal halide precursor to form a transition metal nitride. In some embodiments, the second precursor acts as both a reducing agent and a nitrogen donor. In some embodiments, the second precursor acts as both a reducing agent, a carbon donor, and a nitrogen donor.

[0073] For the sake of simplification of terminology, the term cyclic diene encompasses not only ring structures containing only carbon atoms, but also ring structures containing one or two nitrogen atoms. In some embodiments, the cyclic diene is a five-membered or six-membered cyclic diene. Thus, in addition to the metalloid group, the cyclic diene ring may have additional substituents. In some embodiments, one or more of the ring carbons have alkyl substituents. The alkyl substituents may be linear or branched. In some embodiments, one ring carbon has a C1-C7 alkyl substituent. In some embodiments, two ring carbons have C1-C7 alkyl substituents. In some embodiments, three ring carbons have C1-C7 alkyl substituents. In some embodiments, four ring carbons have C1-C7 alkyl substituents. If a germanium or silicon atom is bonded to the cyclic diene via a carbon atom, the same carbon atom may have additional alkyl substituents. In some embodiments, all additional substituents to the ring carbons are C1-C4 alkyls. In some embodiments, all additional substituents are methyl or ethyl groups. In some embodiments, all additional substituents are methyl groups. In some embodiments, all of the additional substituents are ethyl groups. In some embodiments, the cyclohexadiene compound has one additional substituent, which is a methyl group. In some embodiments, the cyclic diene compound has one additional substituent, which is an ethyl group. In some embodiments, the methyl group is bonded to a carbon adjacent to the carbon atom to which the germanium group is bonded. However, in some embodiments, none of the ring carbons have additional substituents.

[0074] Increasing the molecular weight of a cyclic diene compound generally negatively affects its volatility. Therefore, the more substituents a cyclic diene ring contains, the fewer substituents are needed to maintain sufficient volatility.

[0075] In some embodiments, the two metalloid groups of the cyclohexadiene compound are trialkyl metalloid groups. In some embodiments, the two trialkyl metalloid groups include C1-C7 alkyl groups. The alkyl groups may be linear or branched. In some embodiments, the two metalloid groups of the cyclic diene compound are trimethyl metalloid groups. In some embodiments, the two metalloid groups of the cyclohexadiene compound are triethyl metalloid groups.

[0076] In some embodiments, the cyclohexadiene compound according to this disclosure has the structure of formula (VI), where M is a metalloid. In some embodiments, the cyclohexadiene compound according to this disclosure has the structure of formula (VII), where M is a metalloid. In some embodiments, the cyclohexadiene compound according to this disclosure has the structure of formula (VIII), where M is a metalloid. In some embodiments, the cyclohexadiene compound according to this disclosure has the structure of formula (IX), where M is a metalloid. In some embodiments, the cyclohexadiene compound according to this disclosure has the structure of formula (X), where M is a metalloid. In some embodiments, the cyclohexadiene compound according to this disclosure has the structure of formula (XI), where M is a metalloid. In some embodiments, the metalloid is selected from the group consisting of germanium and silicon.

[0077] [ka]

[0078] [ka]

[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082] [ka]

[0083] In some embodiments, the cyclohexadiene compounds according to this disclosure have a structure of formula (XII).

[0084] [ka]

[0085] In equation (XII), M is a semimetal, and Z 1 and Z 2 Each of them is independently CR 14 and selected from N, R 1 ~R 14 Each of these is independently selected from the group consisting of H, C1-C7 linear or branched alkyl, C6-C10 aryl, and C6-C14 heteroaryl. In one embodiment, R 11 is H. In one embodiment, R 7 ~R 14 Each of these is independently selected from the group consisting of H, C1-C4 linear and branched alkyl groups, and phenyl. In one embodiment, all of R7-R14 are H. In one embodiment, each of R1-R6 is independently selected from the group consisting of H, methyl, ethyl, n-propyl, and isopropyl. In one embodiment, all of R1-R6 are methyl.

[0086] In one embodiment, the second precursor is 1,4-bis(trimethylgermyl)-1,4-dihydropyrazine. In one embodiment, the second precursor is 1,4-bis(trimethylsilyl)-1,4-dihydropyrazine. In one embodiment, the second precursor is 1,1'-bis(trimethylsilyl)-1,1'-dihydro-4,4'-bipyridine. In one embodiment, the second precursor is 1,1'-bis(trimethylgermyl)-1,1'-dihydro-4,4'-bipyridine.

[0087] In some embodiments, the layer containing the transition metal contains an elemental transition metal. In these embodiments, the second precursor acts as a reducing agent for reducing the transition metal halide precursor to the metal. In some embodiments, the second precursor contains a metal selected from the list consisting of zinc and aluminum. In some embodiments, the second precursor contains zinc. In some embodiments, the second precursor may be in the form of an elemental metal. In some embodiments, the second precursor may be part of a compound such as a metal halide.

[0088] Similar to the transition metal halide precursor, the second precursor may be heated before being supplied to the reaction chamber. The temperature at which the second precursor is heated depends on the properties of the second precursor. As will be understood by those skilled in the art, the vaporization temperatures of the transition metal precursor and the second precursor may need to be compatible.

[0089] In some embodiments, the second precursor is heated to at least 20°C, at least 25°C to at least 50°C, or at least 70°C, or at least 90°C, or at least 100°C, or at least 110°C before being supplied to the reaction chamber. Heating may be performed in the precursor container. In some embodiments, the second precursor is heated to a maximum of 120°C, or a maximum of 100°C, or a maximum of 80°C, or a maximum of 60°C before being supplied to the reaction chamber. In some embodiments, the second precursor is heated to at least 350°C, or at least 370°C, or at least 390°C before being supplied to the reaction chamber. Heating may be performed in the precursor container. In some embodiments, the second precursor is heated to a maximum of 450°C, or at least 430°C, or at least 410°C before being supplied to the reaction chamber. The injector system of the deposition assembly may be heated to improve the gas phase delivery of the second precursor to the reaction chamber.

[0090] Step 110 provides an optional purging step. This purging step may be the same as that of step 106 described above.

[0091] Step 104, providing the transition metal halide precursor, and Step 108, providing the second precursor, may be performed in any order. Steps 104 and 108, providing the transition metal halide precursor and providing the second precursor, constitute a deposition cycle, which may result in the deposition of the transition metal-containing material. In some embodiments, the two steps of deposition of the transition metal-containing material, namely providing the transition metal halide precursor and the second precursor to the reaction chamber (steps 104 and 106), may be repeated (step 120 in the loop). Such embodiments include several deposition cycles. The thickness of the deposited transition metal carbide-containing material may be controlled by adjusting the number of deposition cycles. The deposition cycle (step 120 in the loop) may be repeated until a desired thickness of the transition metal-containing material is achieved. For example, the deposition cycle may be performed for any of the following numbers: approximately 50, 100, 200, 300, 400, 500, 700, 800, 1000, 1200, 1500, 2000, 2400, and 3000. Periodic deposition can result in the formation of a transition metal-containing layer. The layer may be substantially continuous or continuous. Once the desired thickness is formed on the surface of the substrate, the flow 100 of the method is completed (termination step 112).

[0092] When method flow 100 is performed, the transition metal-containing material is deposited on the substrate. The deposition process may be a periodic deposition process and may include periodic CVD, ALD, or hybrid periodic CVD / ALD processes. For example, in some embodiments, the growth rate of a particular ALD process may be lower compared to a CVD process. One approach to increase the growth rate may be to operate at a deposition temperature higher than the temperatures typically used in ALD processes, thereby still taking advantage of the benefits of the sequential introduction of the transition metal halide precursor and the second precursor in some part of the chemical deposition process. Such a process may be called periodic CVD. In some embodiments, the periodic CVD process may include the introduction of two or more precursors into the reaction chamber, with overlapping time periods between the two or more precursors in the reaction chamber, which may result in both the ALD component and the CVD component of the deposition. This is called a hybrid process. According to further embodiments, the periodic deposition process may include a continuous flow of one reactant or precursor and periodic pulses of other chemical components into the reaction chamber. The temperature and / or pressure in the reaction chamber during step 104 may be the same as or similar to any of the pressures and temperatures described above in relation to step 102.

[0093] In some embodiments, a transition metal halide precursor is brought into contact with the substrate surface (step 104), any excess transition metal halide precursor is partially or substantially completely removed by an inert gas or vacuum (step 106), and a second precursor is brought into contact with the substrate surface containing the transition metal halide precursor. The transition metal halide precursor may be brought into contact with the substrate surface in one or more pulses (step 104). In other words, the pulses of the transition metal precursor may be repeated. The transition metal halide precursor on the substrate surface may react with the second precursor to form a transition metal-containing material on the substrate surface. The pulses of the second precursor may also be repeated. In some embodiments, the second precursor may be initially supplied to the reaction chamber (step 104). The reaction chamber may then be purged (step 106), and the transition metal halide precursor may be supplied into the reaction chamber in one or more pulses (step 108).

[0094] Figure 2 is a schematic block diagram showing the deposition assembly 200 according to this disclosure. The deposition assembly 200 can be used to carry out the methods described herein and / or to form the structures or devices described herein, or parts thereof.

[0095] In the example described above, the deposition assembly 200 includes one or more reaction chambers 202, a precursor injector system 208, a transition metal halide precursor container 204, a second precursor container 206, an exhaust source 210, and a controller 212. The deposition assembly 200 may also include one or more additional gas sources (not shown), such as an inert gas source, a carrier gas source, and / or a purge gas source.

[0096] The reaction chamber 202 may include any preferred reaction chamber, such as an ALD or CVD reaction chamber as described herein.

[0097] The transition metal halide precursor container 204 may contain the container and one or more transition metal halide precursors described herein, either alone or in combination with one or more carrier (e.g., inert) gases. The second precursor container 206 may contain the container and a second precursor described herein, either alone or in combination with one or more carrier gases. Although exemplified by the two source containers, the transition metal halide precursor container 204 and the second precursor container 206, the deposition assembly 200 may contain any suitable number of source containers. The transition metal halide precursor container 204 and the second precursor container 206 can be coupled to the reaction chamber 202 via lines 214, 216, which may each contain flow controllers, valves, heaters, and the like. In some embodiments, the transition metal halide precursor in the transition metal halide precursor container 204 and the second precursor in the second precursor container 206 may be heated. In some embodiments, the container is heated so that the precursor or reactant reaches a temperature of, for example, about 20°C to about 450°C, depending on the properties of the chemical substance.

[0098] The exhaust source 210 may include one or more vacuum pumps.

[0099] The controller 212 includes electronic circuits and software for selectively operating valves, manifolds, heaters, pumps, and other components included in the deposition assembly 200. Such circuits and components operate to introduce precursors, reactants, and purge gases from their respective sources. The controller 212 can provide proper operation of the deposition assembly 200 by controlling the timing of gas pulse sequences, the temperature of the substrate and / or the reaction chamber 202, the pressure within the reaction chamber 202, and various other operations. The controller 212 may include control software that electrically or pneumatically controls valves to control the flow of precursors, reactants, and purge gases into and out of the reaction chamber 202. The controller 212 may include modules, such as software or hardware components, that perform certain tasks. Modules may be configured to reside on an addressable storage medium of the control system, or they may be configured to perform one or more processes.

[0100] Other configurations of the deposition assembly 200 are possible, including different numbers and types of precursor and reactant sources. Furthermore, there are, of course, many arrangements and configurations of valves, conduits, precursor sources, and auxiliary reactant sources that may be used to achieve the objective of selectively and controlledly supplying gas into the reaction chamber 202. In addition, for the sake of simplicity, many components have been omitted from the schematic representation of the deposition assembly, and these components may include, for example, various valves, manifolds, purifiers, heaters, vessels, vents, and / or bypasses.

[0101] During the operation of the deposition assembly 200, a substrate, such as a semiconductor wafer (not shown), is transferred, for example, from a substrate handling system to a reaction chamber 202. Once the substrate is transferred to the reaction chamber 202, one or more gases from a gas source, such as a precursor, reactant, carrier gas, and / or purge gas, are introduced into the reaction chamber 202.

[0102] In some embodiments, a transition metal halide precursor is supplied in pulses, a second precursor is supplied in pulses, and the reaction chamber is purged between the pulses of the successive transition metal halide precursors and the second precursor.

[0103] The exemplary embodiments of this disclosure described above are merely examples of embodiments of the invention as defined by the appended claims and their legal equivalents, and do not limit the scope of the invention. Any equivalent embodiment is intended to fall within the scope of the invention. Various modifications of this disclosure, including alternative useful combinations of the described elements, may be apparent to those skilled in the art from the description, in addition to those shown and described herein. Various modifications and embodiments are also intended to fall within the scope of the appended claims.

Claims

1. A method for forming a layer containing a transition metal on a substrate, To provide the substrate inside the reaction chamber, To carry out at least one sedimentation cycle, the sedimentation cycle is To provide a gaseous transition metal halide precursor into the reaction chamber, and A method comprising providing a second gas-phase precursor into a reaction chamber for forming a layer containing a transition metal on a substrate, wherein the transition metal halide precursor contains a transition metal tetrahalide.

2. The method according to claim 1, wherein the transition metal halide precursor comprises a transition metal selected from transition metals of Group IV to Group VIII.

3. The method according to claim 1, wherein the transition metal halide precursor comprises a transition metal selected from the group consisting of molybdenum, chromium, tungsten, nickel, cobalt, niobium, copper, titanium, palladium, platinum, zirconium, hafnium, vanadium, tantalum, manganese, rhodium, iron, iridium, and rhenium.

4. The method according to any one of claims 1 to 3, wherein the transition metal halide precursor comprises a transition metal selected from transition metals of group VI.

5. The method according to any one of claims 1 to 3, wherein the halogen in the transition metal halide precursor is selected from the group consisting of chlorine, iodine, fluorine, and bromine.

6. The method according to any one of claims 1 to 3, wherein the transition metal halide precursor comprises molybdenum tetrachloride.

7. The method according to claim 1, wherein the layer contains a transition metal carbide.

8. The method according to claim 7, wherein the second precursor acts as a reducing agent and / or carbon donor.

9. The method according to claim 7 or 8, wherein the second precursor comprises a cyclic diene compound containing a substituent that includes a semimetallic compound.

10. The method according to claim 9, wherein the substituent includes a trialkyl metalloid.

11. The method according to claim 9, wherein the metalloid semimetal is germanium or silicon.

12. The method according to claim 9, wherein the cyclic diene of the cyclic diene compound is a 5-membered or 6-membered cyclic diene.

13. The method according to claim 7 or 8, wherein the second precursor comprises a cyclohexadiene compound selected from the compounds of formula (I). 【Chemistry 1】 In equation (I), M is Ge or Si, and Z １ and Z ２ Each of them independently, CR １１ and selected from N, R １ ~R １１ Each of these is independently selected from the group consisting of H, C1-C7 linear or branched alkyl groups, C6-C10 aryl groups, and C6-C14 heteroaryl groups.

14. R １１ The method according to claim 13, wherein H is

15. R ７ ~R １０ The method according to claim 13, wherein each of is independently selected from the group consisting of H, C1-C4 linear and branched alkyl groups, and phenyl.

16. R ７ to R １０ are all H, the method according to claim 13.

17. R １ ~R ６ The method according to claim 13, wherein each of is independently selected from the group consisting of H, methyl, ethyl, n-propyl, and isopropyl.

18. R １ ~R ６ The method according to claim 13, wherein all of them are methyl.

19. A deposition assembly for depositing a layer containing a transition metal on a substrate, One or more reaction chambers constructed and positioned to hold the substrate, A precursor injector system constructed and arranged to supply a transition metal halide precursor and a second precursor in the gas phase into the reaction chamber, A first precursor vessel containing a transition metal halide precursor including a transition metal tetrahalide, and constructed and arranged to allow evaporation, A second precursor vessel comprising a second precursor and constructed and arranged to evaporate the second precursor, A deposition assembly is constructed and arranged to supply the transition metal halide precursor and the second precursor to the reaction chamber via the precursor injector system, and to deposit a layer containing the transition metal on the substrate.

20. The deposition assembly according to claim 19, further comprising a temperature controller for controlling the temperature of the reaction chamber.

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