Deposition of transition metal materials

Abstract

This disclosure relates to the fabrication of semiconductor devices. Specifically, this disclosure relates to a method for forming a transition metal-containing material on a substrate via a cyclic deposition process. The method includes providing a substrate in a reaction chamber, providing a transition metal precursor comprising a transition metal compound in the reaction chamber, and providing a second precursor in the reaction chamber, wherein the transition metal compound comprises a transition metal halide bound to an adduct ligand, and the second precursor comprises a chalcogenide or a nitrogen-group element. This disclosure also relates to a method for forming a transition metal layer and a semiconductor device. Furthermore, a vapor deposition assembly is disclosed.

Description

[0001] Parties to the Joint Research Agreement

[0002] The invention claimed herein was made, represented, or related to a joint research agreement between the University of Helsinki and ASM Microchemistry. This agreement was in effect on or prior to the date of the claimed invention, and the claimed invention is a result of activities carried out within the scope of the agreement. Technical Field

[0003] This disclosure relates to methods and apparatus for manufacturing semiconductor devices. More specifically, this disclosure relates to methods and systems for depositing a transition metal-containing material on a substrate, and to layers including the transition metal-containing material. This disclosure also relates to semiconductor device structures including transition metal-containing materials deposited by the methods disclosed herein. Background Technology

[0004] Transition metals such as manganese, iron, cobalt, nickel, and copper form a series of chalcogenides with different compositions and properties. For example, most cobalt sulfide and nickel sulfide phases are highly conductive. Therefore, they may offer promise for microelectronics, including as barrier layers and seed layers for cobalt-copper interconnects. They may also be promising materials for other applications, such as electrocatalysts for water splitting and electrodes in lithium-ion and other batteries, solar cells, and supercapacitors. The potential of other chalcogenides, such as selenides and tellurides, in various microelectronic applications has also been explored. In addition to chalcogenides, Group 15 elements (nitrogen group elements), most notably antimony (Sb), arsenic (As), and bismuth (Bi), offer potential for future semiconductor materials.

[0005] Transition metal sulfides are also potential precursors for cobalt and nickel layers. Furthermore, cobalt and nickel sulfides are more stable to oxidize and easier to synthesize than metallic 2D sulfides. As sulfides, they may be more chemically compatible with semiconductor 2D sulfides such as MoS2 compared to metals, oxides, and other material groups, for example, as contacts.

[0006] Most potential future applications require the deposition of ultrathin, continuous layers on desired substrates and structures. In other cases, nanoparticles with controlled sizes may be preferred. In either case, methods for providing the necessary level of control are rarely known, and each known method contains drawbacks that may reduce the material's attractiveness in new applications.

[0007] Therefore, there is a need in the art for alternative methods for depositing transition metal chalcogenides, such as sulfides, and transition metal nitrides (pnicides), such as antimonides.

[0008] Any discussion set forth in this section (including discussions of problems and solutions) is included in this disclosure only to provide background for this disclosure. Such discussion should not be construed as an admission that any or all information was known at the time the invention was made or otherwise constituted prior art. Summary of the Invention

[0009] This invention provides a simplified overview of some concepts, which will be described in further detail below. This invention is not necessarily intended to identify key or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.

[0010] Various embodiments of this disclosure relate to methods for depositing transition metal-containing materials on a substrate via a cyclic vapor deposition process, vapor deposition assemblies, and semiconductor device structures.

[0011] On one hand, a method for forming a transition metal-containing material on a substrate through a cyclic deposition process is disclosed. This method may include providing a substrate and a transition metal precursor in a reaction chamber, and providing a second precursor in the reaction chamber. The transition metal precursor may include a transition metal compound comprising a transition metal halide bound to an adduct ligand.

[0012] On the other hand, a method for forming a transition metal-containing material on a substrate through a cyclic deposition process is disclosed. This method may include providing a substrate in a reaction chamber, providing a transition metal precursor comprising a transition metal compound containing a transition metal halide bound to an adduct ligand in the reaction chamber, providing a second precursor in the reaction chamber, and contacting the transition metal-containing material with a reducing agent to form an elemental transition metal.

[0013] On the other hand, a semiconductor device structure containing a transition metal material and a transition metal material deposited according to the present disclosure is disclosed.

[0014] In another aspect, a vapor deposition assembly for depositing transition metal-containing materials on a substrate using a cyclic deposition method is disclosed. The vapor deposition assembly according to this disclosure may include: one or more reaction chambers configured and arranged to hold a substrate; and a precursor injector system configured and arranged to provide, in the reaction chamber, a transition metal precursor and / or a second precursor comprising a transition metal compound containing a transition metal halide bound to an adduct ligand in the gas phase. The vapor deposition assembly may further include a transition metal precursor container configured and arranged to contain and evaporate the transition metal precursor comprising a transition metal compound containing a transition metal halide bound to an adduct ligand; and a second precursor container configured and arranged to contain and evaporate a second precursor. The vapor deposition assembly according to this disclosure may be configured and arranged to provide the transition metal precursor and / or the second precursor to the reaction chamber via the precursor injector system to deposit a transition metal-containing material on a substrate.

[0015] In this disclosure, any two numbers of a variable may constitute a feasible range of that variable, and any range indicated may include or exclude endpoints. Furthermore, any value of the indicated variable (whether or not it is indicated by “about”) may refer to an exact value or an approximate value, and includes equivalents, and may refer to the mean, median, representativeness, majority, etc. Additionally, in this disclosure, the terms “comprising,” “consisting of,” and “having” independently mean, in some embodiments, “generally or broadly comprising,” “including,” “substantially constitutes,” or “consisting of.” The meaning of any definition in this disclosure does not necessarily exclude the common and customary meaning in some embodiments.

[0016] The chemical formulas given for each example material should not be interpreted as restrictive, and the non-restrictive example materials given should not be limited by the given example stoichiometry. Attached Figure Description

[0017] The accompanying drawings are included to provide a further understanding of this disclosure and form part of this specification. The drawings illustrate exemplary embodiments and, together with the description, help to explain the principles of this disclosure. In the drawings:

[0018] Figure 1 Figure 1A and 1B This is a process flow diagram of an exemplary embodiment of a method for depositing a transition metal material on a substrate according to the present disclosure.

[0019] Figure 2 An exemplary embodiment of a method for selectively depositing a transition metal-containing material on a substrate according to the present disclosure is shown.

[0020] Figure 3 This is a schematic diagram of a vapor deposition assembly according to the present disclosure. Detailed Implementation

[0021] The following description of exemplary embodiments of methods, structures, devices, and apparatuses is merely illustrative and for purposes of explanation only. The following description is not intended to limit the scope of this disclosure or the claims. Furthermore, the description of multiple embodiments having the indicated features is not intended to exclude other embodiments having additional features or other embodiments comprising different combinations of said features. For example, various embodiments are set forth as exemplary embodiments and may be stated in the dependent claims. Unless otherwise stated, exemplary embodiments or their components may be combined or applied separately from each other.

[0022] The illustrations presented herein are not intended to be actual views of any particular material, structure, or device, but are merely idealized representations used to describe embodiments of this disclosure.

[0023] In various methods according to this disclosure, a substrate is provided in a reaction chamber. In other words, the substrate is brought into a space where deposition conditions can be controlled. The reaction chamber may be part of a combination tool in which different processes are performed to form an integrated circuit. In some embodiments, the reaction chamber may be a flow reactor, such as a cross-flow reactor. In some embodiments, the reaction chamber may be a spray head reactor. In some embodiments, the reaction chamber may be a space-separated reactor. In some embodiments, the reaction chamber may be a single-wafer ALD reactor. In some embodiments, the reaction chamber may be a high-volume manufacturing single-wafer ALD reactor. In some embodiments, the reaction chamber may be a batch reactor for simultaneously manufacturing multiple substrates.

[0024] substrate

[0025] As used herein, the term substrate can refer to any one or more underlying materials that can be used to form or on which devices, circuits, materials, or material layers are formed. Substrates can include bulk materials, such as silicon (e.g., single-crystal silicon), other Group 4 materials, such as germanium, or other semiconductor materials, such as Group 2-6 or Group 3-5 semiconductor materials. Substrates can include one or more layers covering the bulk material. Substrates can include various topologies, such as gaps, including spaces between recesses, lines, trenches, or protrusions formed within or on at least a portion of the substrate layer, such as fins. Substrates can include nitrides, such as TiN, oxides, insulating materials, dielectric materials, conductive materials, metals, such as tungsten, ruthenium, molybdenum, cobalt, aluminum, or copper, or metallic materials, crystalline materials, epitaxial materials, heteroepitaxial materials, and / or single-crystal materials. In some embodiments of this disclosure, the substrate includes silicon. As described above, in addition to silicon, the substrate can include other materials. Other materials can form layers.

[0026] In some embodiments, the substrate includes –OH groups, such as a silicon oxide-based surface. In some embodiments, the substrate surface may additionally include –H terminals, such as HF-impregnated Si (Si-H) or HF-impregnated Ge surfaces. In such embodiments, the surface of interest will be considered to include the –H terminals and the material beneath them.

[0027] Cyclic deposition

[0028] Cyclic deposition processes are used to deposit transition metal materials. As used herein, the term "cyclic deposition" can refer to the sequential introduction of precursors (reactants) into a reaction chamber to deposit a layer on a substrate, encompassing processing techniques such as atomic layer deposition (ALD) and cyclic chemical vapor deposition (cyclic CVD). CVD-type processes typically involve a gas-phase reaction between two or more precursors. Precursors can be simultaneously provided to a reaction chamber containing a substrate on which material is to be deposited. Precursors can be provided in partially or completely separate pulses. The substrate and / or reaction chamber can be heated to facilitate the reaction between the gaseous precursors. In some embodiments, precursors are provided until a layer of desired thickness is deposited. In some embodiments, cyclic CVD-type processes can be used with multiple cycles to deposit a thin film of desired thickness. In cyclic CVD-type processes, precursors can be provided to the reaction chamber in non-overlapping or partially or completely overlapping pulses.

[0029] ALD-type processes are based on controlled, typically self-limiting, precursor surface reactions. Gas-phase reactions are avoided by alternately and sequentially feeding the precursors into the reaction chamber. For example, gas-phase precursors are separated from each other in the reaction chamber by removing excess precursors and / or reaction byproducts from the chamber between precursor pulses. This can be achieved through a purging step and / or inert gas pulses or purging. In some embodiments, the substrate is contacted with a purging gas, such as an inert gas. For example, the substrate may be contacted with a purging gas between precursor pulses to remove excess precursors and reaction byproducts.

[0030] In some embodiments, each reaction is self-limiting, and monolayer-to-monolayer growth is achieved. These may be referred to as “true ALD” reactions. In some such embodiments, a transition metal precursor can be adsorbed onto the substrate surface in a self-limiting manner. A second precursor can then react sequentially with the adsorbed transition metal precursor to form a monolayer containing the transition metal material on the substrate. A third reactant, such as a reducing agent, can be introduced to reduce the transition metal in the material to an elemental transition metal.

[0031] In some embodiments, the deposition process containing transition metal materials has one or more non-self-limiting phases. For example, in some embodiments, at least one precursor may be at least partially decomposed on the substrate surface. Therefore, in some embodiments, the process may be operated within process conditions close to CVD conditions, or in some cases, entirely under CVD conditions.

[0032] The method according to this disclosure can also be used in a space atomic layer deposition apparatus. In space ALD, precursors are continuously supplied in different physical sections, and a substrate moves between these sections. At least two sections can be provided, where a half-reaction can occur in the presence of a substrate. If a substrate is present in such a half-reaction region, a monolayer can be formed from a first or second precursor. The substrate is then moved to a second half-reaction region, where an ALD cycle is completed with the first or second precursor to form the target material. Alternatively, the substrate position can be fixed, the gas supply can be mobile, or some combination of both. To obtain a thicker film, this sequence can be repeated.

[0033] Purging refers to the removal of gaseous precursors and / or gaseous byproducts from the substrate surface, such as by evacuating the reaction chamber with a vacuum pump and / or replacing the gas in the reaction chamber with an inert gas such as argon or nitrogen. Purging can be performed between two precursor pulses. Typical purging times are approximately 0.05 to 20 seconds, but can be approximately 0.2 to 10 seconds, or approximately 0.5 to 5 seconds. However, other purging times can be used if desired, for example, where highly conformal step coverage is required on structures with very high aspect ratios or other structures with complex surface morphologies, or where different reactor types can be used, such as batch reactors. As described above for ALD, purging can be performed in temporal or spatial modes.

[0034] In this disclosure, "gas" can include materials that are gaseous at normal temperature and pressure (NTP), evaporated solids and / or evaporated liquids, and can consist of a single gas or a mixture of gases, depending on the circumstances. The term "inert gas" can refer to a gas that does not participate in the chemical reaction to a considerable extent. Exemplary inert gases include He and Ar and any combination thereof. In some cases, nitrogen and / or hydrogen can be inert gases. Gases other than process gases, i.e., gases introduced without passing through gas distribution components, other gas distribution devices, etc., can be used, for example, to seal the reaction space, and may include sealing gases, such as rare gases.

[0035] The term "precursor" can refer to a compound that participates in a chemical reaction to produce another compound, particularly a compound that constitutes the deposited material. The term "reactant" is used interchangeably with "precursor." However, reactants can also be used to modify the chemical composition of the deposited material. For example, a reducing agent that reduces transition metal chalcogenides to elemental metals can be called a reactant.

[0036] Deposition materials

[0037] Transition metal-containing materials can be deposited by the methods according to this disclosure. In some embodiments, the transition metal is a first-row transition metal. In some embodiments, the transition metal is selected from the group consisting of manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn). The transition metal can be selected from the group consisting of cobalt (Co), nickel (Ni), and copper (Cu). In some embodiments, the transition metal is selected from the group consisting of Co and Ni. Therefore, the transition metal-containing material deposited by the methods disclosed herein can contain one or more transition metals, such as Co, Ni, and / or Cu, and one or more other chalcogen or nitrogen elements. Chalcogen elements, except for oxygen, are considered to be elements in group 16 of the periodic table. In some embodiments, the chalcogen elements are selected from the group consisting of sulfur (S), selenium (Se), and tellurium (Te). The transition metal-containing material according to this disclosure can include, for example, Co and S, Co and Se, or Co and Te. In some embodiments, the transition metal-containing material according to this disclosure can include Cu and S, Cu and Se, or Cu and Te. In some embodiments, the transition metal-containing material according to this disclosure can include Ni and S, Ni and Se, or Ni and Te. The transition metal-containing materials according to this disclosure may include, for example, Mn and S, Mn and Se, or Mn and Te. The transition metal-containing materials according to this disclosure may include, for example, Fe and S, Fe and Se, or Fe and Te.

[0038] In this disclosure, except for nitrogen, the nitrogen group elements are considered to be elements in group 15 of the periodic table.

[0039] In some embodiments, the nitrogen group elements are selected from the group consisting of arsenic (As), antimony (Sb), and bismuth (Bi). Therefore, the transition metal-containing materials according to this disclosure may include, for example, Co and As, Co and Sb, or Co and Bi. In some embodiments, the transition metal-containing materials according to this disclosure may include, for example, Mn and As, Mn and Sb, or Mn and Bi. In some embodiments, the transition metal-containing materials according to this disclosure may include, for example, Fe and As, Fe and Sb, or Fe and Bi. In some embodiments, the transition metal-containing materials according to this disclosure may include, for example, Ni and As, Ni and Sb, or Ni and Bi. In some embodiments, the transition metal-containing materials according to this disclosure may include, for example, Cu and As, Cu and Sb, or Cu and Bi.

[0040] Transition metal chalcogenides can exist in a variety of phases. Unless otherwise stated, transition metal chalcogenides are referred to in general terms without specifying a general phase. For example, CoS... xIt can represent any cobalt sulfide phase, such as Co4S3, Co9S8, CoS, Co3S4, or CoS2, or combinations thereof. NiS x It can represent any nickel sulfide phase, such as Ni3S2, Ni3S8, β-NiS, Ni3S4, or NiS2, or combinations thereof. Additionally, CuS... x This can refer to any copper sulfide phase, such as CuS2, CuS, Cu9S8, or combinations thereof. However, in some embodiments, the transition metal-containing material comprises, is substantially composed of, or is composed of Co9S8 (cobalt pyrite). In some embodiments, the transition metal-containing material comprises, is substantially composed of, or is composed of β-NiS. In some embodiments, the transition metal-containing material may comprise, is substantially composed of, or is composed of Ni9S8. However, in some embodiments, the transition metal chalcogenides deposited according to this disclosure comprise a mixture of different phases. Exemplary phases that may be present in the material are Cu2S, Cu... 31 S 16 Cu 58 S 32 Cu9S5, Cu7S4, Cu8S5, Cu 39 S 28 Cu9S8, CuS, and CuS2. In some embodiments, the S / Co ratio of the transition metal material can be 0.9-1.0.

[0041] In some embodiments, the transition metal-containing material may include, for example, about 70 to about 99.5 atomic percent of a transition metal chalcogenide or a transition metal nitride, or about 80 to about 99.5 atomic percent of a transition metal chalcogenide or a transition metal nitride, or about 90 to about 99.5 atomic percent of a transition metal chalcogenide or a transition metal nitride. The transition metal-containing material deposited by the method according to this disclosure may include, for example, about 80 atomic percent, about 83 atomic percent, about 85 atomic percent, about 87 atomic percent, about 90 atomic percent, about 95 atomic percent, about 97 atomic percent, or about 99 atomic percent of a transition metal chalcogenide or a transition metal nitride.

[0042] In some embodiments, the transition metal-containing material deposited according to the present disclosure contains less than about 3 atomic% or less than about 1 atomic% of chlorine. In some embodiments, the transition metal-containing material deposited according to the present disclosure contains less than about 1 atomic% or less than about 0.5 atomic% of oxygen. In some embodiments, the transition metal-containing material deposited according to the present disclosure contains less than about 2 atomic% or less than about 1 atomic% or less than about 0.5 atomic% of carbon. In some embodiments, the transition metal-containing material deposited according to the present disclosure contains less than about 0.5 atomic% or less than about 0.2 atomic% or less than about 0.1 atomic% of nitrogen. In some embodiments, the transition metal-containing material deposited according to the present disclosure contains less than about 1.5 atomic% or less than about 1 atomic% of hydrogen.

[0043] In some embodiments, the transition metal-containing material is substantially composed of or composed of a transition metal-containing material. In some embodiments, the transition metal-containing material is substantially composed of or composed of cobalt sulfide. In some embodiments, the transition metal-containing material is substantially composed of or composed of nickel sulfide. In some embodiments, the transition metal-containing material is substantially composed of or composed of copper sulfide. In some embodiments, the transition metal-containing material is substantially composed of or composed of cobalt selenide. In some embodiments, the transition metal-containing material is substantially composed of or composed of nickel selenide. In some embodiments, the transition metal-containing material is substantially composed of or composed of copper selenide. In some embodiments, the transition metal-containing material is substantially composed of or composed of cobalt telluride. In some embodiments, the transition metal-containing material is substantially composed of or composed of nickel telluride. In some embodiments, the transition metal-containing material is substantially composed of or composed of copper telluride.

[0044] In some embodiments, the transition metal-containing material deposited according to this disclosure may form a layer. As used herein, the terms "layer" and / or "film" may refer to any continuous or discontinuous structure and material, such as materials deposited by the methods disclosed herein. For example, layers and / or films may include two-dimensional materials, three-dimensional materials, nanoparticles, or even partially or entirely molecular layers or partially or entirely atomic layers or atomic and / or molecular clusters. Films or layers may include materials or layers with pinholes, which may be at least partially continuous. Seed layers may be discontinuous layers used to increase the nucleation rate of another material. However, seed layers may also be substantially or completely continuous. In some embodiments, the transition metal-containing material forms a substantially continuous layer with a thickness of 10 nm or less.

[0045] On the one hand, a semiconductor device structure comprising a material deposited according to the method presented herein is disclosed.

[0046] As used herein, "structure" can be or includes the substrate described herein. A structure can include one or more layers covering the substrate, such as one or more layers formed according to the method of this disclosure.

[0047] Selective deposition

[0048] In some embodiments, the substrate includes a first surface comprising a first material and a second surface comprising a second material, wherein the transition metal material is selectively deposited on the first surface relative to the second surface. By appropriately selecting deposition conditions, the transition metal material can be selectively deposited on the first surface relative to the second surface. The methods according to this disclosure can be performed without pretreatment, such as passivation or other surface treatments to produce selectivity. Therefore, in some embodiments of the methods of this disclosure, deposition is inherently selective. However, as those skilled in the art will understand, selectivity may be affected by processes such as cleaning the substrate surface, etching, etc.

[0049] Selectivity can be given as a percentage calculated as [(deposition on the first surface) - (deposition on the second surface)] / (deposition on the first surface). Deposition can be measured using any of a variety of methods. In some embodiments, deposition can be given as a measured thickness of the deposited material. In some embodiments, deposition can be given as a measured quantity of the deposited material.

[0050] In some embodiments, the selectivity is greater than about 30%, greater than about 50%, greater than about 75%, greater than about 85%, greater than about 90%, greater than about 93%, greater than about 95%, greater than about 98%, greater than about 99%, or even greater than about 99.5%. In embodiments, the selectivity may vary with the duration or thickness of the deposition.

[0051] In some embodiments, deposition occurs only on the first surface and not on the second surface. In some embodiments, deposition on the first surface of the substrate is at least about 80% selective relative to the second surface of the substrate, which may be sufficiently selective for some specific applications. In some embodiments, deposition on the first surface of the substrate is at least about 50% selective relative to the second surface of the substrate, which may be sufficiently selective for some specific applications. In some embodiments, deposition on the first surface of the substrate is at least about 10% selective relative to the second surface of the substrate, which may be sufficiently selective for some specific applications.

[0052] In some embodiments, the thickness of the transition metal material deposited on the first surface of the substrate may be less than about 50 nm, less than about 20 nm, less than about 10 nm, less than about 5 nm, less than about 3 nm, less than about 2 nm, or less than about 1 nm, and the ratio of the transition metal material deposited on the first surface of the substrate to the second surface of the substrate may be greater than or equal to about 2:1, greater than or equal to about 20:1, greater than or equal to about 15:1, greater than or equal to about 10:1, greater than or equal to about 5:1, greater than or equal to about 3:1, or greater than or equal to about 2:1.

[0053] In some embodiments, the selectivity of the selective deposition process described herein may depend on the materials comprising the first and / or second surfaces. For example, in some embodiments, where the first surface comprises a Cu surface and the second surface comprises a silicon dioxide surface, the selectivity may be greater than about 10:1 or greater than about 20:1. In some embodiments, where the first surface comprises a metal or metal oxide and the second surface comprises a silicon dioxide surface, the selectivity may be greater than about 5:1.

[0054] Transition metal precursors

[0055] Transition metals are introduced into transition metal-containing materials via transition metal precursors. In some embodiments, the transition metal precursor may comprise a transition metal compound having an adduct-forming ligand. In some embodiments, the transition metal precursor may comprise a transition metal halide. In some embodiments, the transition metal precursor may comprise a transition metal compound having an adduct-forming ligand, such as a monodentate, bidentate, or multidentate adduct-forming ligand. In some embodiments, the transition metal precursor may comprise a transition metal compound having a nitrogen-containing adduct-forming ligand, such as a nitrogen-containing monodentate, bidentate, or multidentate adduct-forming ligand. In some embodiments, the transition metal precursor may comprise a transition metal compound having an adduct-forming ligand comprising phosphorus, oxygen, or sulfur, such as a monodentate, bidentate, or multidentate adduct-forming ligand comprising phosphorus, oxygen, or sulfur. For example, in some embodiments, the transition metal halide may comprise a transition metal chloride, a transition metal iodide, a transition metal fluoride, or a transition metal bromide. In some embodiments, the transition metal halide may include a transition metal substance, including but not limited to at least one of manganese, iron, cobalt, nickel, copper, or zinc. In some embodiments, the transition metal halide may include at least one of cobalt chloride, nickel chloride, or copper chloride. In some embodiments, the transition metal halide may include at least one of cobalt bromide, nickel bromide, or copper bromide. In some embodiments, the transition metal halide may include at least one of cobalt fluoride, nickel fluoride, or copper fluoride. In some embodiments, the transition metal halide may include at least one of cobalt iodide, nickel iodide, or copper iodide.

[0056] In some embodiments, the transition metal halide may comprise a bidentate nitrogen-containing adduct-forming ligand. In some embodiments, the transition metal halide may comprise an adduct-forming ligand comprising two nitrogen atoms, wherein each nitrogen atom is bonded to at least one carbon atom. In some embodiments of this disclosure, the transition metal halide comprises one or more nitrogen atoms bonded to a central transition metal atom, thereby forming a metal complex.

[0057] In some embodiments of this disclosure, the transition metal precursor may include a transition metal compound having formula (I):

[0058] (adduct) n -MX a (I)

[0059] Each “adduct” is an adduct-forming ligand and can be independently selected as a monodentate, bidentate, or multidentate adduct-forming ligand or a mixture thereof: for monodentate ligands, n is 1-4, and for bidentate or multidentate adduct-forming ligands, n is 1-2; M is a transition metal, such as cobalt (Co), copper (Cu), or nickel (Ni); where each X a It is another ligand and can be independently selected as a halide or other ligands; where a is 1 to 4, and in some cases a is 2.

[0060] In some embodiments of this disclosure, the adduct-forming ligand in a transition metal compound, such as a transition metal halide, may include a monodentate, bidentate, or polydentate adduct-forming ligand that coordinates to a transition metal atom of the transition metal compound via at least one of a nitrogen atom, phosphorus atom, oxygen atom, or sulfur atom. In some embodiments of this disclosure, the adduct-forming ligand in a transition metal compound may comprise a cyclic adduct ligand. In some embodiments of this disclosure, the adduct-forming ligand in a transition metal compound may comprise a monoamine, diamine, or polyamine. In some embodiments of this disclosure, the adduct-forming ligand in a transition metal compound may comprise a monoamine, diamine, or polyether. In some embodiments, the adduct-forming ligand in a transition metal compound may comprise a monophosphine, diamine, or polyphosphine. In some embodiments, the adduct-forming ligand in a transition metal compound may comprise carbon and / or elements other than nitrogen, oxygen, phosphorus, or sulfur in the adduct-forming ligand.

[0061] In some embodiments, the adduct-forming ligand in the transition metal compound may comprise one monodentate adduct-forming ligand. In some embodiments of this disclosure, the adduct-forming ligand in the transition metal compound may comprise two monodentate adduct-forming ligands. In some embodiments of this disclosure, the adduct-forming ligand in the transition metal compound may comprise three monodentate adduct-forming ligands. In some embodiments of this disclosure, the adduct-forming ligand in the transition metal compound may comprise four monodentate adduct-forming ligands. In some embodiments of this disclosure, the adduct-forming ligand in the transition metal compound may comprise one bidentate adduct-forming ligand. In some embodiments of this disclosure, the adduct-forming ligand in the transition metal compound may comprise two bidentate adduct-forming ligands. In some embodiments of this disclosure, the adduct-forming ligand in the transition metal compound may comprise one polydentate adduct-forming ligand. In some embodiments of this disclosure, the adduct-forming ligand in the transition metal compound may comprise two polydentate adduct-forming ligands.

[0062] In some embodiments, the adduct-forming ligand comprises nitrogen, such as an amine, diamine, or polyamine adduct-forming ligand. In such embodiments, the transition metal compound may comprise at least one of the following: triethylamine (TEA), N,N,N',N'-tetramethyl-1,2-ethylenediamine (CAS: 110-18-9, TMEDA), N,N,N',N'-tetraethylethylenediamine (CAS: 150-77-6, TMEDA), N,N'-diethyl-1,2-ethylenediamine (CAS: 111-74-0, DEEDA), N,N'-diisopropylethylenediamine (CAS: 4013-94-9), N,N,N',N'-tetramethyl-1,3-propanediamine (CAS: 110-95-2, TMPDA), N,N,N',N'-tetramethylmethanediamine (CAS: 51-80-9, TMPDA), N,N,N',N",N"-pentamethyldiethylenetriamine Amines (CAS: 3030-47-5, PMDETA), diethylenetriamine (CAS: 111-40-0, DIEN), triethylenetetramine (CAS: 112-24-3, TRIEN), tris(2-aminoethyl)amine (CAS: 4097-89-6, TREN, TAEA), 1,1,4,7,10,10-hexamethyltriethylenetetramine (CAS: 3083-10-1, HMTETA), 1,4,8,11-tetraazacyclotetradecane (CAS: 295-37-4, Cyclam), 1,4,7-trimethyl-1,4,7-triazacyclononane (CAS: 96556-05-7) or 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (CAS: 41203-22-9).

[0063] In some embodiments, the adduct-forming ligand comprises phosphorus, such as phosphine, diphosphine, or polyphosphine adduct-forming ligand. For example, the transition metal compound may include at least one of the following: triethylphosphine (CAS: 554-70-1), trimethyl phosphite (CAS: 121-45-9), 1,2-bis(diethylphospho)ethane (CAS: 6411-21-8, BDEPE), or 1,3-bis(diethylphospho)propane (CAS: 29149-93-7).

[0064] In some embodiments of this disclosure, the adduct-forming ligand comprises oxygen, such as an ether, diether, or polyether adduct-forming ligand. For example, the transition metal compound may comprise at least one of the following: 1,4-dioxane (CAS: 123-91-1), 1,2-dimethoxyethane (CAS: 110-71-4, DME, monoethylene glycol dimethyl ether), diethylene glycol dimethyl ether (CAS: 111-96-6, diethylene glycol dimethyl ether), triethylene glycol dimethyl ether (CAS: 112-49-2, triethylene glycol dimethyl ether), or 1,4,7,10-tetraoxane-dodecane (CAS: 294-93-9, 12-Crown-4).

[0065] In some embodiments, the adduct-forming ligand may comprise a thioether or a mixed etheramine, such as at least one of the following: 1,7-diaza-12-crown-4:1,7-dioxa-4,10-diazacyclodecane (CAS:294-92-8) or 1,2-bis(methylthio)ethane (CAS:6628-18-8).

[0066] In some embodiments, the bidentate nitrogen-containing ligand is N,N,N',N'-tetramethylethylenediamine (TMEDA) or N,N,N',N'-tetramethyl-1,3-propanediamine (TMPDA). In some embodiments, the transition metal halide may include cobalt chloride N,N,N',N'-tetramethyl-1,2-ethylenediamine (CoCl2(TMEDA)). In some embodiments, the transition metal halide may include cobalt bromide N,N,N',N'-tetramethyl-1,2-ethylenediamine (CoBr2(TMEDA)). In some embodiments, the transition metal halide may include cobalt iodide N,N,N',N'-tetramethyl-1,2-ethylenediamine (CoI2(TMEDA)). In some embodiments, the transition metal halide may include cobalt chloride N,N,N',N'-tetramethyl-1,3-propanediamine (CoCl2(TMPDA)). In some embodiments, the transition metal halide may include at least one of the following: cobalt chloride N,N,N',N'-tetramethyl-1,2-ethylenediamine (CoCl2(TMEDA)), nickel chloride tetramethyl-1,3-propanediamine (NiCl2(TMPDA)), or nickel iodide tetramethyl-1,3-propanediamine (NiI2(TMPDA)).

[0067] In some embodiments, the transition metal precursor comprises cobalt bromide N,N,N',N'-tetramethyl-1,3-propanediamine (CoBr2(TMPDA)). In some embodiments, the transition metal precursor comprises cobalt iodide N,N,N',N'-tetramethyl-1,3-propanediamine (CoI2(TMPDA)). In some embodiments, the transition metal precursor comprises cobalt iodide N,N,N',N'-tetraethylethylenediamine (CoI2(TEEDA)).

[0068] In some embodiments of this disclosure, contacting the substrate with the transition metal precursor may include providing the transition metal precursor in a reaction chamber for a period of about 0.01 seconds to about 60 seconds, about 0.05 seconds to about 10 seconds, about 0.1 seconds to about 5.0 seconds, about 0.5 seconds to about 10 seconds, or about 1 second to about 30 seconds. For example, the transition metal precursor may be provided in the reaction chamber for about 0.5 seconds, about 1 second, about 1.5 seconds, about 2 seconds, or about 3 seconds. Furthermore, during the pulse of the transition metal precursor, the flow rate of the transition metal precursor may be less than 2000 sccm, less than 500 sccm, or even less than 100 sccm. Additionally, during the provision of the transition metal precursor on the substrate, the current flow rate of the transition metal precursor may be in the range of about 1 to 2000 sccm, about 5 to 1000 sccm, or about 10 to about 500 sccm.

[0069] Excess transition metal precursors and reaction byproducts (if any) can be removed from the surface, for example, by pumping with an inert gas. For instance, in some embodiments of this disclosure, the method may include a purging cycle in which the substrate surface is purged for a period of less than about 2.0 seconds. Excess transition metal precursors and any reaction byproducts can be removed with the aid of a vacuum generated by a pump system in fluid communication with the reaction chamber.

[0070] In some embodiments, heterogeneous transition metal precursors may be used. As an example, a Co(btsa)₂(THF)-containing transition metal precursor may be used. In another example, a Ni(btsa)₂(THF)-containing transition metal precursor may be used. These transition metal precursors comprise a tetrahydrofuran (THF) ring attached to the transition metal atom via an epoxy ring. The transition metal precursor also comprises two bis(trimethylsilyl)amide ligands attached to the same transition metal atom via a nitrogen atom.

[0071] Second precursor

[0072] In some embodiments, the second precursor may refer to a precursor compound comprising a chalcogenide, wherein the chalcogenide is an element from Group 16 of the periodic table, including sulfur, selenium, and tellurium. In some embodiments, the second precursor comprises a chalcogenide. Various second precursors may be used in the methods according to this disclosure. In some embodiments, the second precursor comprises a chalcogenide hydride. In some embodiments, the second precursor is selected from the following list: H₂S, H₂Se, H₂Te, (CH₃)₂S, (NH₄)₂S, dimethyl sulfoxide ((CH₃)₂SO), (CH₃)₂Se, (CH₃)₂Te, element or atom S, other precursors comprising a chalcogenide-hydrogen bond, such as H₂S₂, H₂Se₂, H₂Te₂, or a chalcogenide having the formula RYH, wherein R may be a substituted or unsubstituted hydrocarbon, such as a C1-C8 alkyl or a substituted alkyl, such as an alkylsilyl, such as a straight-chain or branched C1-C5 alkyl, and Y may be S, Se, or Te. In some embodiments, the second precursor comprises a thiol having the formula RSH, wherein R can be a substituted or unsubstituted hydrocarbon, such as a C1-C8 alkyl, such as a more straight-chain or branched C1-C5 alkyl. In some embodiments, the second precursor comprises a selenol having the formula R-Se-H, wherein R can be a substituted or unsubstituted hydrocarbon, such as a C1-C8 alkyl, such as a more straight-chain or branched C1-C5 alkyl.

[0073] In some embodiments, the second precursor may comprise a compound having formula (II):

[0074] (R3Si)2Y (II)

[0075] R3Si is an alkylsilyl group, and Y can be S, Se, or Te.

[0076] In some embodiments, the second precursor comprises S or Se. In some embodiments, the second precursor comprises S. In some embodiments, the second precursor does not comprise S. In some embodiments, the second precursor may comprise an elemental chalcogenide, such as elemental sulfur. In some embodiments, the second precursor comprises Te. In some embodiments, the second precursor does not comprise Te. In some embodiments, the second precursor comprises Se. In some embodiments, the second precursor does not comprise Se. In some embodiments, the second precursor is selected from precursors comprising S, Se, or Te. In some embodiments, the second precursor comprises a compound having formula (III):

[0077] H2S n (III)

[0078] Where n is between 4 and 10.

[0079] In some embodiments, a suitable second precursor may include any number of chalcogenide compounds. In some embodiments, the second precursor may include at least one chalcogenide hydrogen bond. In some embodiments, the second precursor may include a chalcogenide plasma, chalcogenide atoms, or chalcogenide radicals. In some embodiments requiring an energized second precursor, the plasma may be generated in or upstream of the reaction chamber. In some embodiments, the second precursor does not include an energized second precursor, such as plasma, atoms, or radicals. In some embodiments, the second precursor may include a chalcogenide plasma, chalcogenide atoms formed from a second precursor including chalcogenide hydrogen bonds, or chalcogenide radicals, such as H₂S. In some embodiments, the second precursor may include a chalcogenide plasma, chalcogenide atoms, or chalcogenide radicals, such as a plasma containing sulfur, selenium, or tellurium, preferably a plasma containing sulfur. In some embodiments, the plasma, atoms, or radicals include tellurium. In some embodiments, the plasma, atoms, or radicals include selenium. In some embodiments, the second precursor does not include a tellurium precursor.

[0080] In some embodiments, the purity of the chalcogen elements comprising the gaseous precursor can affect the composition of the deposited material; therefore, a high-purity source of the chalcogen element-containing gaseous precursor can be used. In some embodiments, the chalcogen element-containing gaseous precursor may have a purity greater than or equal to 95.0%, or greater than or equal to 98.0%, or greater than or equal to 99.0%, or greater than or equal to 99.5%. As a non-limiting example, the second precursor may comprise hydrogen sulfide (H2S) with a purity greater than or equal to 99.0% or greater than or equal to 99.5%.

[0081] In some embodiments, the second precursor comprises a nitrogen group element. In some embodiments, the nitrogen group element is selected from the group consisting of As, Sb, and Bi. In some embodiments, the nitrogen group element is selected from the group consisting of As and Sb. In some embodiments, the nitrogen group element is Sb. In some embodiments, the nitrogen group element is As. In some embodiments, the nitrogen group element is Bi. For example, the nitrogen group-containing second precursor may comprise an alkylsilyl nitride.

[0082] In some embodiments, in addition to utilizing a high-purity second precursor, the second precursor gas may be further purified to remove unwanted impurities. Therefore, some embodiments of this disclosure may further include passing the second precursor through a gas purifier before it enters the reaction chamber to reduce the concentration of at least one of water or oxygen within the second precursor.

[0083] In some embodiments, the water or oxygen concentration in the second precursor may be reduced to less than 5 atomic%, or less than 1 atomic%, or less than 1000 parts per million, or less than 100 parts per million, or less than 10 parts per million, or less than one part per million, or less than 100 parts per billion, or less than 10 parts per billion, or even less than one part per billion.

[0084] Without limiting this disclosure to any particular theory, a reduction in at least one of the water or oxygen concentrations in the second precursor can allow the deposition of transition metal chalcogenide materials with the desired composition, while preventing the deposition of transition metal oxide phases at a suitable deposition temperature.

[0085] In some embodiments, providing a second precursor in the reaction chamber (i.e., exposing the substrate to the second precursor) may include pulsed application of the second precursor (e.g., hydrogen sulfide) onto the substrate for a duration of 0.1 to 2.0 seconds, or about 0.01 to about 20 seconds, or about 0.01 to about 60 seconds, or about 0.01 to about 10 seconds. In some embodiments, the second precursor may be provided in the reaction chamber for less than about 40 seconds, or less than about 30 seconds, or less than about 20 seconds, or less than about 10 seconds, or less than about 5 seconds, or less than about 3 seconds. During the provision of the second precursor in the reaction chamber, the flow rate of the second precursor may be less than about 100 sccm, or less than about 50 sccm, or less than about 25 sccm. For example, the flow rate of the second precursor may be between about 10 sccm and about 20 sccm, such as about 15 sccm. Furthermore, during the provision of the second precursor on the substrate, the flow rate of the second precursor can be from about 1 sccm to about 2000 sccm, or from about 5 sccm to about 1000 sccm, or from about 10 sccm to about 500 sccm.

[0086] The second precursor can react with transition metal-containing molecules on the substrate. In some embodiments, the second precursor may include hydrogen sulfide, and the reaction may deposit a transition metal sulfide on the substrate.

[0087] reducing agent

[0088] In some embodiments of this disclosure, the exemplary cyclic deposition method may include an additional process step of contacting a substrate with a reducing agent. In such embodiments, a method for forming a transition metal-containing material on a substrate via a cyclic deposition process is disclosed. The method includes providing a substrate in a reaction chamber and providing a transition metal precursor comprising a transition metal halide bound to an adduct ligand in the reaction chamber. The method further includes providing a second precursor in the reaction chamber and contacting the transition metal-containing material with a reducing agent to form an elemental transition metal.

[0089] Therefore, in some embodiments, the transition metal material on the substrate is in contact with the reducing agent. In some embodiments, the reducing agent precursor includes at least one of the following: forming gas (H2+N2), ammonia (NH3), ammonia (NH3) plasma, hydrazine (N2H4), molecular hydrogen (H2), hydrogen atom (H), hydrogen plasma, hydrogen radical, hydrogen excitation substance, alcohol, aldehyde, carboxylic acid, borane or amine, tert-butylhydrazine (C4H ... 12 N2), silane (SiH4), disilane (Si2H6), trisilane (Si3H8), germanane (GeH4), digermanane (Ge2H6), borane (BH3), and diborane (B2H6) or organic reducing agents. Organic reducing agents may include, for example, alcohols, aldehydes, or carboxylic acids.

[0090] A reducing agent may be provided in the reaction chamber and contacted with the substrate in each deposition cycle, i.e., after each transition metal precursor and second precursor are provided in the reaction chamber. Alternatively, the reducing agent may be provided in the reaction chamber and contacted with the substrate after a predetermined number of deposition cycles have been performed. For example, the reducing agent may be provided in the reaction chamber after every 5, 10, 20, 40, 50, or 100 cycles of depositing a transition metal chalcogenide or transition metal nitride on the substrate. Alternatively, the reducing agent may be provided in the reaction chamber at the end of the deposition process. Thus, the desired amount of transition metal-containing material is deposited first, and then the deposited material is exposed to the reducing agent. In some embodiments, the reducing agent may be provided in the reaction chamber and contacted with the substrate separately from the transition metal precursor and separately from the second precursor.

[0091] In some embodiments, the transition metal-containing material may be exposed to a reducing agent at temperatures below 500°C, or below 400°C, or below 300°C, or below 250°C, or below 200°C, or even below 150°C. In some embodiments, the transition metal-containing material may be exposed to a reducing agent in a reduced-pressure atmosphere, wherein the pressure may be from about 0.001 mbar to about 10 bar, or from about 1 mbar to about 1000 mbar. The substrate may be exposed to the reducing agent in the same reaction chamber in which the transition metal-containing material is deposited. Alternatively, the substrate may be exposed to the reducing agent in different reaction chambers. The different reaction chambers may be part of the same combination of tools as the reaction chamber used for depositing the transition metal-containing material.

[0092] Attached Figure

[0093] This disclosure is further explained by the following exemplary embodiments depicted in the accompanying drawings. The illustrations presented herein are not intended to be actual views of any particular material, structure, or device, but are merely schematic representations illustrating embodiments of this disclosure. It should be understood that the elements in the drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the dimensions of some elements in the drawings may be enlarged relative to other elements to aid in understanding the illustrated embodiments of this disclosure. The structures and devices depicted in the drawings may include additional elements and details, which may be omitted for clarity.

[0094] Figure 1A This is a process flow diagram of an exemplary embodiment of a method 100 for depositing a transition metal-containing material on a substrate according to the present disclosure. In this method, the transition metal-containing material is deposited on the substrate through a cyclic deposition process. The method includes providing a substrate 102 in a reaction chamber. In some embodiments, the substrate may include silicon. In some embodiments, the substrate may include, be substantially composed of, or be composed of silicon oxide.

[0095] The reaction chamber may form part of an atomic layer deposition (ALD) reactor. The reactor may be a single-wafer reactor. Alternatively, the reactor may be a batch reactor. The various stages of method 100 may be performed in a single reaction chamber, or they may be performed in multiple reaction chambers, such as the reaction chamber of a tooling assembly. In some embodiments, method 100 is performed in a single reaction chamber of a tooling assembly, but other, preceding or subsequent fabrication steps of the structure or device are performed in additional reaction chambers of the same tooling assembly. Optionally, the reactor including 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.

[0096] During step 102, the substrate may be brought to a desired temperature and pressure to provide a transition metal precursor 104 and / or a second precursor 106 in the reaction chamber. The temperature within the reaction chamber (e.g., the temperature of the substrate or substrate support) may be, for example, about 50°C to about 350°C, about 100°C to about 300°C, about 120°C to about 170°C, or about 150°C to about 200°C. As another example, the temperature within the reaction chamber may be about 275°C to about 325°C, or about 100°C to about 225°C. The temperature used may be selected depending on the precursor. For example, if a transition metal precursor containing CoCl2 (TMEDA) is used, the deposition temperature may be in the range of about 175°C to about 325°C. For example, the deposition temperature may be 180°C, 200°C, 225°C, 250°C, 275°C, or 300°C. If NiCl2 (TMPDA) is used as the transition metal precursor, the deposition temperature can be in the range of about 150°C to about 280°C, for example, 165°C, 175°C, 185°C, 225°C or 250°C can be used.

[0097] In some embodiments, the pressure in the reaction chamber during deposition according to this disclosure is less than 50 mbar or less than 10 mbar. In some embodiments, the pressure in the reaction chamber during deposition according to this disclosure is about 5 mbar.

[0098] In the first deposition stage 104 of the method according to this disclosure, a transition metal precursor is provided in a reaction chamber. The transition metal precursor may include a transition metal compound. The transition metal compound may comprise a transition metal halide bound to an adduct ligand. In some embodiments, the adduct ligand may comprise a bidentate nitrogen-containing adduct ligand. In some embodiments, the bidentate nitrogen-containing adduct ligand may comprise two nitrogen atoms, each nitrogen atom bonded to at least one carbon atom. In some embodiments, the bidentate nitrogen-containing ligand is N,N,N',N'-tetramethylethylenediamine (TMEDA) or N,N,N',N'-tetramethyl-1,3-propanediamine (TMPDA). In some embodiments, the transition metal halide comprises a transition metal chloride. In some embodiments, the transition metal halide is a transition metal chloride. In some embodiments, the transition metal compound comprises one of CoCl2 (TMEDA) and NiCl2 (TMPDA). In some embodiments, the transition metal compound is one of CoCl2 (TMEDA) and NiCl2 (TMPDA).

[0099] In the second deposition stage 106 of the method according to this disclosure, a second precursor is provided in a reaction chamber. In some embodiments, the second precursor comprises a chalcogenide element selected from the group consisting of sulfur, selenium, and tellurium. In some embodiments, the second precursor comprises a chalcogenide element and hydrogen. In some embodiments, the second precursor comprises a chalcogenide-hydrogen bond. For example, the second precursor may be H2S, or the second precursor may be H2Se. In some embodiments, the second precursor comprises an alkyl group. In some embodiments, the second precursor is selected from the group consisting of H2S, H2Se, H2Te, (CH3)2S, (NH4)2S, (CH3)2SO, (CH3)2Se, and (CH3)2Te.

[0100] In some embodiments, the transition metal precursor may be heated before being supplied to the reaction chamber. For example, the transition metal precursor may be heated from about 60°C to about 180°C, such as to about 100°C, about 110°C, about 120°C, about 150°C, or about 170°C. As a non-limiting example, transition metal halides such as CoCl2 (TMEDA) or NiCl2 (TMPDA) bound to a bidentate nitrogen-containing adduct ligand precursor may be heated to about 150°C, about 160°C, or about 170°C. For some other transition metal precursors, such as those containing silylamide ligands, the temperature may be lower, such as to about 60°C or about 80°C.

[0101] In some embodiments, the second precursor may be heated before being supplied to the reaction chamber. In some embodiments, the second precursor may be maintained at ambient temperature before being supplied to the reaction chamber. In some embodiments, the flow of the second precursor may be regulated by a pressure regulator and / or a needle valve. This is particularly advantageous for highly volatile second precursors such as H2S. In some embodiments, the second precursor may be heated from about 40°C to about 60°C, for example to about 50°C. For example, in embodiments where the second precursor comprises selenium or tellurium, the second precursor may be heated.

[0102] The stages of providing transition metal precursor 104 and providing second precursor 106 can be performed in any order. The stages of providing transition metal precursor 104 and providing second precursor 106 can constitute a deposition cycle, resulting in the deposition of a transition metal-containing material. In some embodiments, the two stages of deposition of the transition metal-containing material (loop 108) can be repeated, i.e., providing the transition metal precursor and the second precursor (104 and 106) in the reaction chamber. Such embodiments involve multiple deposition cycles. The thickness of the deposited transition metal can be adjusted by regulating the number of deposition cycles. The deposition cycle (loop 108) can be repeated until the desired transition metal thickness is obtained. For example, approximately 50, 100, 200, 300, 400, 500, 700, 800, 1000, 1200, 1500, 2000, 2400, or 3000 deposition cycles can be performed.

[0103] In a non-limiting example, cobalt sulfide can be deposited on a silicon oxide-containing material, such as a natural oxide or thermal oxide surface. CoCl2 (TMEDA) can be used as a transition metal precursor, and H2S (e.g., at a flow rate of 14 sccm) as a second precursor. A 1-second pulse duration can be used for CoCl2 (TMEDA), and a 2-second pulse duration can be used for H2S, with each subsequent precursor pulse separated by a 1-second purge. The substrate can comprise natural silicon oxide or soda-lime glass, and the deposition temperature can range from 180°C to 275°C. Deposition can be performed at approximately 5 mbar N2 pressure.

[0104] For example, the deposited cobalt sulfide material can have a resistivity of 70 μΩcm. In some embodiments, the resistivity of the material can increase as the deposition temperature decreases. Furthermore, the material uniformity can depend on the deposition temperature, and in some embodiments, 275°C may be a suitable temperature for obtaining a uniform cobalt sulfide layer. The cobalt sulfide may contain the Co9S8 phase.

[0105] The growth rate of cobalt sulfide material can be, for example, about 0.1 to about 1. / cycle. For example, at a temperature of 180°C, the growth rate of cobalt sulfide can be, for example, approximately / cycle, at a temperature of 275℃ for approximately / Loop to approximately / cycle. However, in some embodiments, for example, approximately The growth rate of the deposition cycle can vary during deposition. Longer H2S pulses can increase the growth rate of the deposited material. For example, the pulse length can vary from 1 second to 6 seconds. Longer pulse lengths also decrease the resistivity of the deposited material. For example, with a shorter pulse length, the resistivity of cobalt sulfide can be approximately 100 μΩcm, while using a longer pulse duration can reduce the resistivity to approximately 70 μΩcm. The S / Co ratio of the deposited material can remain constant (approximately 0.9), independent of the pulse length.

[0106] In some embodiments, the deposited material may consist essentially of or solely of cubic Co9S8 (cobalt nickel pyrite). Layer crystallinity may increase with increasing deposition temperature. Low levels of oxygen (less than 1 atomic% or less than 0.5 atomic%), carbon (less than 2 atomic% or less than 1 atomic%), nitrogen (less than 0.5 atomic%), and hydrogen (less than 1.5 atomic%) may be present in the deposited material. Oxygen may originate from post-deposition oxidation.

[0107] In some embodiments, continuous material layers of varying thicknesses can be observed. For example, in some embodiments, a continuous layer of material approximately 3 nm thick can be formed. This can be observed, for example, after 10 deposition cycles. In some embodiments, a continuous layer of material approximately 7 nm thick can be formed. This can be observed, for example, after 50 deposition cycles. The cobalt sulfide material according to this disclosure can also be grown on chemically different substrates, including sapphire, mica, GaN, and various ALD growth surfaces such as Al₂O₃, Ir, and TiO₂.

[0108] Compared to silicon oxide surfaces, cobalt sulfide deposition can exhibit a significant nucleation delay on Si-H surfaces. For example, approximately 250 deposition cycles may be required to obtain a continuous layer.

[0109] In some embodiments, a cobalt sulfide layer can be grown on a silicon surface to a thickness of approximately 60 nm at 275 °C and then heat-treated to test the stability of the deposited material. No changes in crystallinity or phase composition were observed when heated to at least 750 °C in a flowing N2 atmosphere with a total pressure of 30 mbar. Therefore, the Co9S8-containing layer deposited according to the method of this disclosure can be used as a seed layer or barrier layer for other applications, such as cobalt or copper deposition and high-temperature processing. Under dynamic high vacuum (approximately 10... –5At 1000 mbar, the Co9S8 layer can be stable up to at least 600 °C. In a reducing gas (10% H2 / 90% N2) environment at atmospheric pressure, the Co9S8 layer can be stable up to at least about 400 °C. At higher temperatures, metallic cobalt can begin to form. The layer can be almost completely converted to elemental cobalt (mainly fcc Co with a small amount of hcp Co) at about 475 °C. In an ambient (oxidizing) atmosphere, Co9S8 in the deposited material can remain stable up to about 225 °C, and it can begin to transform into Co3S4 at about 250 °C. The formation of Co3S4 can begin at 275 °C, and the oxide can coexist with various phases during the measurement, for example, Co3S4 up to about 300 °C, Co3S4 and CoS2 from about 325 °C to about 375 °C, and CoSO4 from about 400 °C to about 550 °C, until Co3S4 may become the only phase present at about 575 °C to about 725 °C. Under atmospheric pressure with pure oxygen, high-temperature behavior may resemble that of ambient air, although some phase transitions may occur at slightly lower temperatures.

[0110] As a further example, nickel sulfide materials can be deposited according to the methods presented herein. Many nickel sulfides are suitable for applications similar to CoS… x Highly conductive materials are used in this application. Therefore, NiCl2 (TMPDA) (Tsource = 157°C) can be used as a transition metal precursor, deposited with H2S as a second precursor at temperatures ranging from 165°C to 250°C. A 2-second pulse time can be used for both NiCl2 (TMPDA) and H2S. For example, nickel sulfide can be deposited at a temperature of 165°C. The growth rate of the cyclic deposition is high, and the resulting nickel sulfide material can have a resistivity of 40 μΩcm.

[0111] At temperatures of approximately 165°C to approximately 175°C, nickel sulfide-containing materials can, for example... The material grows at a rate of approximately 1 / 2 cycle, and the resulting material can have a resistivity of, for example, about 40 μΩcm. For example, a lower growth rate can be observed at temperatures from about 200 °C to about 250 °C, while the resistivity of the material can increase to about 100 μΩcm. The sulfur / nickel ratio can be maintained at about 1.0 over the entire temperature range from about 165 °C to about 250 °C. The material can contain β-NiS and Ni9S8 phases.

[0112] Layers deposited at the lowest temperatures may primarily consist of β-NiS, while increasing the temperature may increase the amount of the Ni9S8 phase. Low levels of oxygen (less than 0.5 atomic%), carbon (about 0.5 atomic% or less), nitrogen (less than 0.5 atomic%), and hydrogen (less than 1.5 atomic% or less than 1 atomic%) may be present in the deposited material. In some embodiments, the total level of O, C, N, and H impurities may be about 2 atomic% or less. In some embodiments, the deposited nickel sulfide material may not contain a distinct surface oxide, even if the material is stored in the ambient atmosphere.

[0113] NiS x It can be deposited on a range of substrates, including Si, SiO2, SLG, sapphire (α-Al2O3), mica, and ALD-deposited r, SnS2, and TiN as the first surface. However, nickel sulfide materials may not be readily grown as the second surface on Si-H, ALD-grown Al2O3, ALD-grown Ta2O5, ALD-grown ZrO2, ALD-grown Nb2O5, ALD-grown TiO2, or ALD-grown ZnS. In some embodiments, 50 nm NiS can be grown on the first surface. x On the second surface, no material is deposited. In some embodiments, some nanometers, such as 4 or 6 nm, may be deposited on the second surface, while about 50 nm of material is deposited on the first surface.

[0114] In some embodiments, a layer approximately 6 nm thick with a conductivity of 250 μΩcm can be deposited on silicon oxide containing a natural oxide in 100 deposition cycles. The resistivity of this layer can decrease with increasing layer thickness. For example, at a layer thickness of approximately 20 nm, the resistivity can be approximately 60 μΩcm, while at a layer thickness of approximately 45 nm, the resistivity can be approximately 40 μΩcm.

[0115] In some embodiments, a layer approximately 50 nm thick deposited at 165 °C may initially consist primarily of β-NiS with a Ni9S8 component. In an N2 atmosphere at atmospheric pressure, the β-NiS phase may be present at a temperature of approximately 400 °C, and Ni9S8 may be present at a temperature of approximately 475 °C. Above these temperatures, α-Ni7S6 may form, and at temperatures of approximately 575 °C and above, α-Ni7S6 may be the essentially unique phase. NiSi may form at temperatures above 600 °C, and its presence may be due to a reaction with the substrate without limiting this disclosure to any particular theory. Sulfur may not be completely lost from the nickel sulfide layer, as Ni3S2 also forms and is present when the material cools to room temperature.

[0116] In about 10 –5In a dynamic high vacuum of millibars, phase transitions may occur at lower temperatures compared to N2. The β-NiS and Ni9S8 phases can disappear, for example, at approximately 350 °C and 375 °C, respectively, and α-Ni7S6 can be observed between approximately 375 °C and approximately 475 °C, while NiSi begins to form at approximately 450 °C. After heating the deposited material to approximately 750 °C and cooling it back to room temperature, Ni3S2 may also exist in addition to NiSi.

[0117] In a reducing gas environment (10% H2, 90% N2) at atmospheric pressure, β-NiS may begin to reduce at approximately 300 °C to form Ni9S8. Metallic nickel (fcc structure) may begin to form at approximately 350 °C and exists as the sole phase above approximately 425 °C. Therefore, NiS... x The layer may be more easily reduced to an elemental metal than Co9S8.

[0118] In some embodiments, Ni9S8 may disappear at approximately 250°C, leaving essentially only β-NiS before reaching 300°C, while the Ni3S4 component may begin to form at 300°C. Hexagonal α-NiS may begin to form at 325°C, and the layer may primarily consist of α-NiS between approximately 375°C and 450°C, although NiO may begin to appear in ambient air above approximately 350°C. The α-NiS phase may disappear at approximately 475°C, while the NiSO4 phase may be present between approximately 500°C and approximately 550°C. At higher temperatures, the sulfur-containing phase may not be present in the layer after the decomposition of NiSO4. A similar phase transition may occur when pure O2 is used instead of ambient air, although the temperature is approximately 25°C to approximately 50°C lower than ambient air.

[0119] Under oxidizing conditions, NiS x The NiS layer may be more stable than Co9S8, which may begin to transform into other sulfide phases at around 275°C. x The oxide formation threshold temperature may be about 100°C higher than that of Co9S8 (375°C compared to 275°C).

[0120] In another non-limiting example, transition metal selenides and transition metal tellurides can be deposited. CoCl2 (TMEDA) and NiCl2 (TMPDA) can be used together with Se(SiEt3)2 and Te(SiEt3)2 as second precursors to deposit the corresponding selenides and tellurides.

[0121] CoCl2 (TMEDA) can be used to deposit cobalt selenide layers with a Se / Co atomic ratio close to 1.0. At a deposition temperature of 180°C, the resistivity of this layer is approximately 50 μΩcm. Using higher deposition temperatures of 225°C or 275°C yields materials primarily composed of crystalline Co9Se8 and some CoSe.

[0122] CoCl2(TMEDA) and Te(SiEt3)2 can be used to deposit cobalt telluride materials on a substrate at temperatures ranging from about 180°C to about 275°C. This material can be crystalline and can include, for example, a hexagonal CoTe phase and possibly Co... 1.67 Te2 phase. The resistivity of the deposited material can be approximately 120 μΩcm.

[0123] NiCl2 (TMPDA) and Te(SiEt3)2 can be used to deposit nickel telluride materials on substrates. The deposition temperature can vary from about 165°C to about 200°C.

[0124] In some embodiments, the cyclic deposition process includes alternately and sequentially providing a transition metal precursor and a second precursor in a reaction chamber. In some embodiments, such as... Figure 1B As shown, the reaction chamber is purged between precursors 105 and 107. In such an embodiment, the deposition cycle can be considered to include steps 104, 105, 106, and 107. As described above, the deposition cycle can be repeated 108 times to obtain the desired thickness of the transition metal material.

[0125] The amount of transition metal material deposited during a single growth cycle (each growth cycle) varies depending on process conditions, such as temperature, precursor pulse length, and flow rate. The growth rate per cycle can be, for example, approximately / Loop to approximately / cycle, or approximately / Loop to approximately / cycle, / Loop to approximately / Loop, for example, about / Loop to approximately / cycle or approximation / Loop to approximately / cycle. For example, the growth rate might be approximately / cycle, / cycle, / cycle, / cycle, / loop or / cycle. Depending on the deposition conditions, number of deposition cycles, etc., layers containing transition metal materials of varying thicknesses can be deposited. For example, the thickness of the transition metal material can be from about 0.2 nm to 90 nm, or about 1 nm to 50 nm, or about 0.5 nm to 25 nm, or about 1 nm to 50 nm, or about 10 nm to 120 nm. The thickness of the transition metal material can be, for example, about 0.5 nm, 1 nm, 2 nm, 3 nm, 5 nm, 6 nm, 8 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 50 nm, 70 nm, 85 nm, or 100 nm. The desired thickness can be selected according to the application discussed. In some embodiments, a thin, essentially continuous layer can be deposited by the method according to this disclosure.

[0126] In some applications, a thin, substantially continuous layer is required. In some embodiments, a substantially continuous layer containing a transition metal material is formed at a thickness of 10 nm or less. In some embodiments, a substantially continuous layer containing a transition metal material is formed at a thickness of 10 nm or less. In some embodiments, a substantially continuous layer can be formed in about 10 deposition cycles. In some embodiments, a substantially continuous layer can be formed at a thickness of less than 5 nm. For example, a substantially continuous cobalt sulfide layer can be formed at a thickness of less than 4 nm.

[0127] The transition metal precursor and the second precursor can be provided in the reaction chamber in separate steps (104 and 106). Figure 1B An embodiment according to this disclosure is shown, wherein steps 104 and 106 are separated by purging steps 105 and 107. In such an embodiment, the deposition cycle includes one or more purging steps 103, 105. During the purging steps, the precursors and / or reactants may be temporarily separated from each other by an inert gas such as argon (Ar), nitrogen (N2), or helium (He) and / or vacuum pressure. Separation of the transition metal precursor and the second precursor may alternatively be spatial.

[0128] Purging reaction chambers 103 and 105 can prevent or mitigate gas-phase reactions between the transition metal precursor and the second precursor, and enable possible self-saturating surface reactions. Excess chemicals and reaction byproducts (if any) can be removed from the substrate surface before the substrate comes into contact with the next reactive chemical, for example, by purging the reaction chamber or by moving the substrate. However, in some embodiments, the substrate can be moved to contact the transition metal precursor and the second precursor separately. Because the reaction may be self-saturating in some embodiments, strict temperature control of the substrate and precise dosage control of the precursor may not be necessary. However, the substrate temperature is preferably such that the incident gaseous material does not condense into a monolayer or multiple monolayers, nor does it thermally decompose on the surface.

[0129] When method 100 is performed, a transition metal material is deposited onto a substrate. The deposition process can be a cyclic deposition process and can include cyclic CVD, ALD, or a hybrid cyclic CVD / ALD process. For example, in some embodiments, the growth rate of a particular ALD process may be lower compared to a CVD process. One way to increase the growth rate is to operate at a deposition temperature higher than that typically used in ALD processes, resulting in certain portions of the chemical vapor deposition process, but still utilizing the sequential introduction of a transition metal precursor and a second precursor. This process can be referred to as cyclic CVD. In some embodiments, a cyclic CVD process may include introducing two or more precursors into a reaction chamber, wherein there may be a period of overlap between the two or more precursors in the reaction chamber, resulting in the deposition of both the ALD component and the CVD component. This is referred to as a mixing process. According to a further example, a cyclic deposition process may include a continuous flow of one reactant or precursor and periodic pulses of another chemical component entering the reaction chamber. The temperature and / or pressure within the reaction chamber during step 104 may be the same as or similar to any of the pressures and temperatures mentioned above in conjunction with step 102.

[0130] In some embodiments, a transition metal precursor is contacted with a substrate surface 104, excess transition metal precursor is partially or substantially completely removed by an inert gas or vacuum 105, and a second precursor is contacted with the substrate surface containing the transition metal precursor. The transition metal precursor may be contacted with the substrate surface 104 by one or more pulses. In other words, the pulses 104 of the transition metal precursor may be repeated. The transition metal precursor on the substrate surface may react with the second precursor to form a transition metal-containing material on the substrate surface. The pulses 106 of the second precursor may also be repeated. In some embodiments, the second precursor may be provided first in the reaction chamber 106. Thereafter, the reaction chamber 105 may be purged and the transition metal precursor 104 may be provided in the reaction chamber with one or more pulses.

[0131] The suitability of a material can depend on its electrical properties, such as resistivity. In some embodiments, the resistivity of a transition metal-containing layer according to this disclosure can be less than 200 μΩcm. For example, the resistivity of a transition metal-containing layer according to this disclosure can be less than 150 μΩcm, less than 100 μΩcm, less than 70 μΩcm, or less than 50 μΩcm. The thickness of the layer having said resistivity can be, for example, about 20 nm, about 30 nm, about 40 nm, about 50 nm, or about 80 nm. For example, a resistivity of less than 100 μΩcm can be achieved for a transition metal chalcogenide-containing layer by depositing cobalt sulfide using CoCl2 (TMEDA) and H2S. The thickness of such a layer can range from about 40 nm to about 70 nm. The transition metal-containing material can include, is substantially composed of, or is composed of Co9S8. As another non-limiting example, a resistivity of less than 50 μΩcm can be achieved for a transition metal chalcogenide-containing layer by depositing nickel sulfide using NiCl2 (TMPDA) and H2S. The thickness of such layers can range from about 25 nm to about 60 nm. The transition metal-containing material may include, is substantially composed of, or is composed of β-NiS and / or Ni9S8. In some embodiments, the resistivity of the transition metal chalcogenide-containing layer may depend on the deposition temperature. In some cases, a lower deposition temperature yields a lower resistivity. In other cases, the opposite effect occurs, and the resistivity increases as the deposition temperature decreases. In some embodiments, the resistivity of the transition metal chalcogenide-containing layer according to this disclosure is less than 100 μΩcm at a layer thickness of 50 nm. In some embodiments, the resistivity of the nickel sulfide-containing layer according to this disclosure is less than 100 μΩcm at a layer thickness of 20 nm. In some embodiments, the resistivity of the nickel sulfide-containing layer according to this disclosure is less than 50 μΩcm at a layer thickness of 50 nm.

[0132] Following deposition, the transition metal-containing material can be subjected to additional processing steps, such as reduction or annealing. For example, in some embodiments, annealing can be performed to convert the transition metal chalcogenides into the desired phase. For example, annealing a nickel sulfide layer at a temperature of about 400°C to about 500°C can allow the acquisition of a layer that essentially contains only Ni9S8 and / or α-Ni7S6. In some embodiments, the transition metal chalcogenide-containing layer according to this disclosure, such as a cobalt sulfide layer, can be stabilized at high temperatures. In some embodiments, the transition metal-containing material according to this disclosure can be used as a seed layer for cobalt or copper. In some embodiments, the transition metal-containing material according to this disclosure can be used as a barrier layer for cobalt or copper. Generally, transition metal-containing materials deposited by the methods according to this disclosure can be used in high-heat-budget applications.

[0133] Figure 2This is a schematic diagram of a selective embodiment of the present disclosure. The substrate 200 provided during step 102 may include a first surface 202 comprising a first material and a second surface 204 comprising a second material. Figure 2 In an exemplary embodiment, a substrate 200 is depicted including a first surface 202 having a first material and a second surface 204 having a second material. The substrate 200 may include an additional layer beneath the surface. In FIG. a), the surfaces of the substrate are formed by the first surface 202 and the second surface 204. The first surface 202 comprises, is substantially composed of, or is made of the first material. The second surface 204 comprises, is substantially composed of, or is made of the second material. The first material and the second material are different materials. Figure 2 In the illustration, the first surface 202 and the second surface 204 are at the same vertical level. However, in reality, the first and second surfaces 202 and 204 can be at different levels.

[0134] exist Figure 2 In Figure b), the transition metal-containing material 206 according to the present disclosure has been selectively deposited on the first surface 202. The deposition of the transition metal-containing material 206 can be completed in one or more deposition cycles.

[0135] In some embodiments, the first material includes a first dielectric material. In some embodiments, the first material includes a first metal. In some embodiments, the second material includes a second dielectric material. The second dielectric material is different from the first dielectric material. In some embodiments, the second material includes a second metal. The second metal is different from the first metal. Therefore, in some embodiments, the first material includes either the first dielectric material or the first metal, and the second material includes either the second dielectric material or the second metal. In some embodiments, the first surface 202 is substantially composed of or made of the first material. In some embodiments, the second surface 204 is substantially composed of or made of the second material.

[0136] In some embodiments, the first material includes natural silicon dioxide, thermal silicon dioxide, soda-lime glass, a metal such as iridium, a metal sulfide such as tin sulfide, or a metal nitride such as titanium nitride. In some embodiments, the first surface may include ruthenium (Ru), rhodium (Rh), osmium (Os), palladium (Pd), platinum (Pt), or gold (Au).

[0137] In some embodiments, the second material includes Si-H, metal oxides such as alumina, tantalum oxide, zirconium oxide, niobium oxide, or titanium oxide, and metal sulfides such as zinc sulfide. In some embodiments, the second material is an in-situ deposited material. An in-situ deposited material is defined herein as a material that is not exposed to an atmosphere other than the atmosphere in which it is deposited. For example, the in-situ deposited material is not exposed to the ambient atmosphere. As another example, the in-situ deposited material is kept under a nitrogen atmosphere. In one embodiment, the second material is in-situ deposited alumina (Al2O3).

[0138] Figure 3 This is a schematic diagram of an embodiment of a vapor deposition assembly 30 for depositing a transition metal material on a substrate, according to the present disclosure.

[0139] The deposition assembly 30 can be used to perform methods according to this disclosure and / or form structural or device portions according to this disclosure. In the illustrated example, the deposition assembly 30 includes one or more reaction chambers 32 configured and arranged to hold a substrate, and a precursor injector system 33 configured and arranged to provide a transition metal precursor and / or a second precursor into the reaction chambers 32. The reaction chambers 32 can include any suitable reaction chamber, such as an ALD or CVD reaction chamber. The deposition assembly 30 can include a heater configured and arranged to control the temperature in the reaction chamber between 50°C and 350°C.

[0140] The deposition assembly also includes a precursor container 331 configured and arranged to contain and evaporate transition metal precursor addition features. According to this disclosure, the deposition assembly 400 is configured and arranged to supply a precursor to the reaction chamber 402 via a precursor injector system 401 for depositing silicon oxide on a substrate.

[0141] The precursor injector system 33 of the deposition assembly 30 also includes a second precursor source 332, an optional purge gas source 333, an exhaust source 34, and a controller 35. The transition metal precursor source 331 may include a container and one or more transition metal precursors as described herein—either alone or mixed with one or more carrier gases (e.g., inert gases). The second precursor source 332 may include a container and one or more second precursors according to the present disclosure—either alone or mixed with one or more carrier gases. According to the present disclosure, one or both containers may include evaporators configured and arranged to evaporate the transition metal precursor or the second precursor, respectively. The evaporators may be configured and arranged to evaporate the transition metal precursor or the second precursor, respectively, at a suitable temperature. A suitable temperature for the transition metal precursor may be, for example, from 50°C to 350°C. The purge gas source 333 may include one or more inert gases as described herein. Although three gas sources 331-333 are illustrated, the deposition assembly 30 may include any suitable number of gas sources. Gas sources 331-333 can be connected to reaction chamber 32 via pipelines 334-336, each pipeline including a flow controller, valve, heater, etc. Deposition apparatus 30 may include a pump configured and arranged to reduce pressure within reaction chamber 30. The pump may be included in exhaust source 34. Exhaust source 34 may include one or more vacuum pumps.

[0142] Controller 35 includes electronic circuitry and software to operate valves, manifolds, heaters, pumps, and other components included in deposition assembly 30. This circuitry and components operate to introduce one or more precursors, reactants, and purge gases from respective sources 331-333. Controller 35 can control the timing of gas pulse sequences, the temperature of the substrate and / or reaction chamber, the pressure within the reaction chamber, and various other operations to provide proper operation of deposition assembly 30. Controller 35 may include control software to electrically or pneumatically control valves to control the inflow and outflow of precursors, reactants, and purge gases from reaction chamber 32. Controller 35 may include modules, such as software or hardware components, that perform specific tasks. Modules may advantageously be configured to reside on an addressable storage medium of the control system and configured to perform one or more processes.

[0143] Other configurations of the deposition assembly 30 are also possible, including different numbers and types of precursor sources and purge gas sources. Furthermore, it should be understood that numerous arrangements of valves, conduits, precursor sources, and purge gas sources can be used to achieve the goal of properly supplying gases to the reaction chamber 32. Additionally, as a schematic representation of the assembly, many components are omitted for simplicity, and these components may include, for example, various valves, manifolds, purifiers, heaters, containers, vents and / or bypasses, as well as safety features.

[0144] During operation of the deposition assembly 30, a substrate, such as a semiconductor wafer (not shown), is transferred from, for example, a substrate processing system to a reaction chamber 32. Once the substrate is transferred to the reaction chamber 32, one or more gases, such as precursors, carrier gases, and / or purge gases, from gas sources 331-333 are introduced into the reaction chamber 32.

[0145] The exemplary embodiments disclosed above do not limit the scope of the invention, as these embodiments are merely examples of embodiments of the invention, which is defined by the appended claims and their legal equivalents. Any equivalent embodiments are within the scope of the invention. In addition to those shown and described herein, various modifications to this disclosure, such as alternative useful combinations of the described elements, will become apparent to those skilled in the art from the description. Such modifications and embodiments are also intended to fall within the scope of the appended claims.

Claims

1. A method of forming a transition metal-containing material on a substrate by a cyclic deposition process, the method comprising: providing a substrate in a reaction chamber; providing a transition metal precursor comprising a transition metal compound in the reaction chamber; and providing a second precursor in the reaction chamber, wherein the transition metal compound comprises a transition metal halide bound to an addend ligand, and the second precursor comprises a chalcogen or pnictogen, wherein the substrate comprises a first surface comprising a first material and a second surface comprising a second material, the first material being different from the second material, wherein the second material comprises Si-H, wherein the transition metal-containing material is selectively deposited on the first surface relative to the second surface, wherein the addend ligand is a bidentate nitrogen-containing addend ligand, wherein the bidentate nitrogen-containing addend ligand comprises two nitrogen atoms, each nitrogen atom being bonded to at least one carbon atom, wherein the chalcogen is selected from the group consisting of sulfur, selenium, and tellurium; and the second precursor comprises a pnictogen selected from the group consisting of arsenic, antimony, and bismuth.

2. The method of claim 1, wherein, the transition metal is a first row transition metal.

3. The method of claim 1 or 2, wherein, the transition metal is selected from the group consisting of Mn, Fe, Co, Ni, Cu, and Zn.

4. The method of claim 1 or 2, wherein, the transition metal is selected from the group consisting of Co and Ni.

5. The method of claim 1 or 2, wherein, the transition metal halide comprises a transition metal chloride.

6. The method of claim 1 or 2, wherein, the transition metal compound comprises one of CoCl2(TMEDA) and NiCl2(TMPDA).

7. The method of claim 1 or 2, wherein, the second precursor comprises a chalcogen.

8. The method of claim 1, wherein, the second precursor is selected from the group consisting of H2S, H2Se, H2Te, (CH3)2S, (NH4)2S, (CH3)2SO, (CH3)2Se, (CH3)2Te, Se(SiEt3)2, and Te(SiEt3)2.

9. The method of claim 1 or 2, wherein, the second precursor comprises an alkyl group.

10. The method of claim 1 or 2, wherein, the cyclic deposition process comprises alternating and sequentially providing the transition metal precursor and the second precursor in the reaction chamber.

11. The method of claim 1, wherein, the first material comprises native silicon oxide, thermal silicon oxide, soda-lime glass, a metal, a metal sulfide, or a metal nitride.

12. The method of claim 11, wherein, the metal is iridium, the metal sulfide is tin sulfide, and the metal nitride is titanium nitride.

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