Periodic deposition method for forming metal-containing materials and films and structures containing metal-containing materials

Abstract

To provide a method for depositing a metal containing material.SOLUTION: A method for depositing a metal containing material includes the use of periodic deposition technology, for example, periodic chemical vapor deposition and atomic layer deposition. The metal containing material can include an intermetallic compound; and a structure including the metal containing material and a system for forming the material are provided.SELECTED DRAWING: Figure 2

Description

[Technical Field]

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

[0002] This disclosure relates, in general terms, to methods for depositing metal-containing materials on the surface of a substrate, to films and structures containing metal-containing materials, and to reactors and systems for depositing metal-containing materials. [Background technology]

[0003] The deposition of metal-containing materials can be used to manufacture various devices, such as semiconductor devices, flat panel display devices, photovoltaic devices, microelectromechanical systems (MEMS), magnetoresistive devices, superconducting devices, energy (e.g., hydrogen) storage devices, lithium or sodium-ion batteries, and / or to form catalytic materials. In many applications, it is desirable to deposit the metal-containing material on a surface that may often include three-dimensional features, such as trenches and / or protrusions. This can be uniform and / or conformal, and have a relatively high aspect ratio.

[0004] In recent years, due to their relatively unique physical and chemical properties, intermetallic compounds, germanides (e.g., nickel germanide (Ni)) have been used in the formation of various devices. x Ge y ) or cobalt germanide (Co x Ge yThere is growing interest in the potential of using metallic materials containing two or more metals, such as intermetallic compounds. Intermetallic compounds generally have a specific ordered crystalline structure that may differ from alloys formed from the same metal. This specific structure may result in superior material properties compared to non-intermetallic compounds. Examples of such properties include magnetoresistance, superconductivity, catalytic activity, and hydrogen storage capacity. For example, intermetallic compounds containing Co or Ni and Sn with altered stoichiometry have been studied as anode materials for Li and Na ion batteries, as ferromagnetic materials for magnetic devices, and for catalytic purposes.

[0005] Metal-containing materials containing intermetallic Co3Sn2 and Ni3Sn2 phases, such as stoichiometric Co-Sn and Ni-Sn, have generally been prepared by methods such as ball milling, arc melting, various solution-based techniques, solvothermal and hydrothermal methods, electrodeposition, sputtering, and electron beam deposition. Co-Sn alloys with a 1:1 stoichiometric ratio and only trace amounts of Co3Sn2 were deposited using chemical vapor deposition (CVD) from two single-source reactants, Me3SnCo(CO)4 and Ph3SnCo(CO)4. Ni3Sn, Ni3Sn2, and Ni3Sn4 were also deposited by CVD using SnMe4 and Ni substrates, followed by hydrogenation at high temperatures. While such techniques can be used to form intermetallic compounds, they are generally not well-suited for forming uniform conformal films of intermetallic materials on the surface of a substrate.

[0006] In recent years, metallic germanides and other Group IIIA and Group IVA metals (IUPAC Group 13 and Group 14 metals) have attracted interest in various applications, particularly low-resistance contacts in equipment fabrication. Group IIIA (IUPAC Group 13) and Group IVA (IUPAC Group 14) metal materials, such as metallic (e.g., nickel) germanides, are typically prepared by physically vapor-deposited (PVD) annealing of a metal (e.g., nickel) onto a germanium substrate or layer. While such techniques can be used to form Group IIIA (IUPAC Group 13) and Group IVA (IUPAC Group 14) metal materials, these techniques are generally not suitable for forming uniform conformal films of Group IIIA and Group IVA metal materials and / or forming these materials at relatively low temperatures.

[0007] Periodic deposition techniques, such as atomic layer deposition, allow for the relatively uniform (e.g., uniform crystalline structure, uniform composition, and / or uniform thickness) conformal deposition of materials onto complex three-dimensional structures on substrate surfaces in a controlled and reproducible manner. However, such techniques have not been commonly used to deposit certain metal-containing materials, including intermetallic compounds and / or Group IIIA metals (IUPAC Group 13 metals) and / or Group IVA metals (IUPAC Group 14 metals). Rather, such compounds and materials are typically formed using alternative techniques and / or often require alternative high-temperature processes. Direct deposition of intermetallic compounds or certain metal-containing films such as germanides, or other pure metals / metalloids containing films, has been challenging to date.

[0008] Therefore, improved methods for forming metal-containing materials, such as intermetallic compounds and Group IIIA (IUPAC Group 13) and Group IVA (IUPAC Group 14) metal materials, are desired. Furthermore, improved techniques for forming uniform and / or conformal films of metal-containing materials are desired.

[0009] The consideration of the issues provided in this section is included in this disclosure solely for the purpose of providing context for the present invention and should not be taken as an acknowledgment that some or all of the considerations at the time the invention was made were known. [Overview of the project]

[0010] This summary of the invention is provided to introduce the selection of concepts in a simplified manner. These concepts are described in more detail in the “Modes for Carrying Out the Invention” of the exemplary embodiments of the present disclosure below. This summary of the invention is not necessarily intended to identify the main or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0011] According to at least one embodiment of this disclosure, a method for depositing intermetallic compounds is disclosed. In various embodiments, the method is a periodic deposition process (method) comprising: supplying a first gas-phase reactant (also referred herein as a precursor) containing a first metal to a reaction chamber and reacting it with the surface of a substrate to form a first metal species; and supplying a second gas-phase reactant containing a second metal to the reaction chamber and reacting it with the first metal species to form an intermetallic compound. Similarly, by using additional reactants, intermetallic compounds containing three or more metals can be formed. As will be described in more detail below, the film of the intermetallic compound can be formed on the substrate surface without any further high-temperature and / or reduction steps. The periodic deposition process may include, for example, atomic layer deposition.

[0012] According to at least one other embodiment of the present disclosure, a method for forming a metal-containing material is disclosed. The metal-containing material can include one, two, or more than two metals as described herein. The method can be a cyclic deposition process, such as an atomic layer deposition or a cyclic chemical vapor deposition process. The cyclic deposition process includes supplying a first gaseous reactant containing a first metal to a reaction chamber to form a first metal species, and supplying a second gaseous reactant, wherein the first and / or second reactants may include a compound having the general formula R-M-H (e.g., R (X-n) -M X -H n ), wherein R is an organic group and M is a metal, which reacts with the first metal species to thereby form a metal-containing material. According to various examples, X is the formal oxidation state of M and n can range from 1 to 5. According to various aspects, the metal-containing material includes one or more elemental metals, metal mixtures, alloys, and intermetallic compounds. A film containing the metal-containing material can be metallic, conductive, non-conductive, or semiconductor. Exemplary films can be superconducting, magnetoresistive, ferromagnetic, or catalytic.

[0013] According to at least one other embodiment of the present disclosure, a first gaseous reactant containing a first metal and a second gaseous reactant containing a second metal (e.g., a compound having the general formula R-M-H (e.g., R (X-n) -M X -H nA method is provided for supplying a first and / or second gas-phase reactant (a gas-phase reactant comprising, in the formula, R being an organic group, X being a formal oxidation state of a metal, n being 1 to 5, and M being a metal). The method comprises providing a second gas-phase reactant source container configured to contain a second gas-phase reactant (e.g., any of the second gas-phase reactants described herein), fluidly connecting the second gas-phase reactant source container to a reaction chamber, heating the second gas-phase reactant contained in the second gas-phase reactant source container to a temperature of about 0°C to about 400°C, about 20°C to about 200°C, or about 20°C to about 100°C, generating a vapor pressure of at least 0.001 mbar for the second gas-phase reactant, and supplying the second gas-phase reactant to the reaction chamber.

[0014] In some embodiments of this disclosure, reactor systems utilizing reactive volatile chemicals are provided. The reactor system may comprise a reaction chamber, a first gas-phase reactant raw material container fluidly communicating with the reaction chamber, and a second gas-phase reactant raw material container fluidly communicating with the reaction chamber. The first and / or second gas-phase reactant is, for example, a compound of the general formula RMH, e.g., R (X-n) -M X -H n The compound may contain (wherein R is an organic group, X is the formal oxidation state of a metal, n is 1 to 5, and M is a metal).

[0015] For the purpose of summarizing the advantages achieved beyond this disclosure and the prior art, certain objectives and advantages may be described above in this specification. Naturally, it should be understood that not all of these objectives or advantages are necessarily achieved by any particular embodiment of this disclosure. Therefore, a person skilled in the art will recognize that embodiments of this disclosure may be carried out in a manner that achieves or optimizes one or a group of advantages taught or suggested herein, without necessarily achieving other objectives or advantages that can be taught or suggested herein.

[0016] The subject matter of this disclosure is specifically pointed out and explicitly asserted in the concluding section of this specification. However, a more complete understanding of this disclosure can be best obtained by referring to the detailed description and claims, when considered in relation to the figures in the drawings, where similar figures indicate similar elements. [Brief explanation of the drawing]

[0017] [Figure 1] This is a process flow of an exemplary periodic deposition method according to at least one embodiment of the present disclosure. [Figure 2] This is another process flow of an exemplary periodic deposition method according to at least one embodiment of the present disclosure. [Figure 3] This is a schematic diagram of an exemplary device structure comprising a deposited metal-containing film according to at least one embodiment of the present disclosure. [Figure 4] An example of a metal halide compound used in a periodic deposition process according to at least one embodiment of the present disclosure. [Figure 5] This is a schematic diagram of an exemplary reactor system according to at least one embodiment of the present disclosure. [Figure 6] An exemplary second gas-phase reactant according to at least one embodiment of the present disclosure. [Modes for carrying out the invention]

[0018] Naturally, the elements in the figures are illustrative for simplification and clarity and are not necessarily drawn to actual size. For example, the dimensions of some elements in the drawings may be exaggerated relative to others to help improve understanding of the illustrated embodiments of the invention.

[0019] The following description of exemplary embodiments of the Disclosure is illustrative and intended for illustrative purposes only, and is not intended to limit the scope of the Invention. Furthermore, the enumeration of multiple embodiments having the described features is not intended to exclude other embodiments having additional features, or other embodiments incorporating different combinations of the described features.

[0020] As will be described in more detail below, exemplary embodiments of this disclosure relate to methods and apparatus for depositing metal-containing materials, such as elemental metals, mixtures, metal alloys, and intermetallic compounds, as well as films and structures comprising metal-containing materials. While this disclosure will be described in more detail below how it addresses various shortcomings of conventional systems and methods, generally speaking, the various systems and methods described herein deposit metal-containing materials having desired properties using improved reactants (sometimes referred to as precursors) and / or improved deposition techniques.

[0021] As used herein, the terms “precursor” and / or “reactant” may refer to one or more gases / vapors that are involved in a chemical reaction, or from which gaseous substances involved in the reaction are induced. The chemical reaction may take place in the gas phase and / or between the gas phase and the surface of the substrate and / or on the surface of the substrate.

[0022] As used herein, the term “periodic deposition” refers to the continuous introduction of reactants into a reaction chamber to deposit a film on a substrate, and includes deposition techniques such as atomic layer deposition and periodic chemical vapor deposition.

[0023] As used herein, the term “periodic chemical vapor deposition” may refer to any process in which a substrate is successively exposed to two or more volatile reactants, the reactants reacting and / or decomposing on the substrate to produce a desired material.

[0024] As used herein, the term “atomic layer deposition” (ALD) refers to a deposition process in which deposition cycles, e.g., multiple consecutive deposition cycles, are carried out within a reaction chamber. Typically, between each cycle, a first reactant is chemisorbed onto the surface of the substrate, forming a monolayer or sub-monolayer that does not readily react with another first reactant (i.e., a self-limiting reaction). Subsequently, another second reactant or reaction gas may be introduced into the process chamber for use in converting the chemisorbed material into a desired material. Furthermore, a purging step may also be utilized during each deposition cycle to remove excess first reactant from the reaction chamber after the conversion of the chemisorbed first and / or second reactants, as well as / or excess second reactant, reaction gas, and / or reaction byproducts from the reaction chamber. Furthermore, as used herein, the term “atomic layer deposition” also means processes represented by related terms, such as chemical vapor deposition atomic layer deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas source MBE, organometallic MBE, and chemical beam epitaxy when carried out with alternating pulses of reactants, reactive gases, and / or purging gases (e.g., inert carriers).

[0025] As used herein, the term “substrate” refers to any material having a surface on which material can be deposited. The substrate may include a bulk material, such as silicon (e.g., single-crystal silicon) or germanium (e.g., single-crystal germanium), and may include one or more layers covering the bulk material, for example, containing chemiadsorbed species from the substrate’s exposure to the TMA. Furthermore, the substrate may have various features, such as grooves, holes, lines, etc., formed in or on at least a portion of the substrate. The features may have an aspect ratio, for example, 5 or more, 10 or more, 15 or more, or 20 or more, which is defined as the height of the feature divided by the width of the feature.

[0026] As used herein, the terms “film,” “thin film,” “layer,” and “thin layer” may mean any continuous or discontinuous material deposited, for example, by the methods disclosed herein. For example, “film,” “thin film,” “layer,” and “thin layer” may include 2D materials, nanorods, nanotubes, or nanoparticles, or partial or complete molecular layers, or partial or complete atomic layers, or clusters of atoms and / or molecules. “Film,” “thin film,” “layer,” and “thin layer” may include materials or layers having pinholes, but are still at least partially continuous.

[0027] As used herein, the terms "metal-containing film" and "metal-containing material" may refer to a film or material containing at least one metal species.

[0028] As used herein, the term "metal" may include metalloids or transmetallic compounds.

[0029] As used herein, the terms “intermetallic” or “intermetallic compound” may refer to a compound containing two or more metallic elements having a defined stoichiometric and regularly arranged crystal structure. Intermetallic compounds differ from metallic alloys in their crystal structure; the crystal structure of an intermetallic compound is arranged in a specific structure, while alloys typically exhibit the crystal structure of one of the metallic components involved. Intermetallic compounds are formed when the bonds between different atoms are stronger than the bonds between atoms of the same element.

[0030] It should be noted that while many illustrative materials are provided through this disclosure, the chemical formulas given for each of the illustrative materials should not be interpreted as restrictive, and the non-restrictive illustrative materials given should not be limited by any particular illustrative stoichiometry.

[0031] This disclosure includes a method for depositing a metal-containing material, such as a film of a metal-containing material, onto a substrate. The method can be carried out using a periodic deposition process to deposit the metal-containing material, such as a metal-containing film, onto the substrate. An exemplary method allows for the deposition of a metal-containing film, such as a film containing an intermetallic compound, substantially composed of an intermetallic compound, or composed of an intermetallic compound, at relatively low temperatures. Additionally or alternatively, the method can deposit a metal-containing material, essentially composed of a metal-containing material, or composed of a metal-containing material, having a large area thickness, crystalline properties, and / or compositional uniformity of the film.

[0032] Referring here to the figures, Figure 1 illustrates a periodic deposition method 100 according to at least one embodiment of the present disclosure. Using method 100, an intermetallic compound, for example, a film of an intermetallic compound, can be formed on the surface of a substrate.

[0033] Method 100 begins with step 110, which includes supplying at least one substrate into a reaction chamber and heating the substrate to a deposition temperature. The deposition temperature may depend, for example, on one or more reactants used to form an intermetallic compound. For example, the reaction chamber may be heated to above 0°C and below 600°C, below 500°C, below 400°C, below 300°C, or below 250°C, or from about 20°C to about 700°C, about 50°C to about 500°C, or from about 50°C to about 400°C, about 75°C to about 300°C, or from about 100°C to about 250°C. In a specific example, the intermetallic compound may include Co3Sn2, in which case the temperature may be in the range of about 170°C to about 200°C. Similarly, if the intermetallic compound includes Ni3Sn2, the temperature may be in the range of about 125°C to about 175°C, or from about 140°C to about 160°C. The pressure inside the reaction chamber may be controlled to provide a desired pressure inside the reaction chamber for the deposition process. For example, the pressure inside the reaction chamber during a periodic deposition process may be less than 1000 mbar, or less than 100 mbar, or less than 10 mbar, or less than 5 mbar, or possibly less than 1 mbar, or about 10 -8 mbar~approx. 1000mbar, approx. 10 -3 mbar~approx. 100mbar, approx. 10 -2 mbar to approximately 50 mbar, or approximately 0.1 mbar to 10 mbar, may also be acceptable.

[0034] Method 100 may continue with step 120, which includes supplying a first gas-phase reactant containing a first metal to a reaction chamber and reacting it with the surface of a substrate to form a first metal species. This step may be performed at the same pressure and temperature as those described above in relation to step 110. The pulse time or the time for which the first gas-phase reactant is supplied to the reaction chamber may be, for example, in the range of about 0.01 seconds to about 60 seconds, or about 0.05 seconds to about 10 seconds, or about 0.1 seconds to about 5 seconds. During step 120, the flow rate of the first gas-phase reactant may be less than 2000 sccm, or less than 1000 sccm, or less than 500 sccm, or less than 200 sccm, or less than 1 to about 5000 sccm, about 5 to about 2000 sccm, or about 10 to about 1000 sccm.

[0035] After the step of supplying the first gas-phase reactant, any excess first gas-phase reactant and any reaction by-products may be removed from the reaction chamber by a purging / pumping process (step 125). The duration of step 125 can be, for example, about 0.01 seconds to about 60 seconds, or about 0.05 seconds to about 10 seconds, or about 0.1 seconds to about 5 seconds. During step 125, the flow rate of the purge gas may be less than 2000 sccm, or less than 1000 sccm, or less than 500 sccm, or less than 200 sccm, or less than 1 to about 5000 sccm, or about 5 to about 2000 sccm, or about 10 to about 1000 sccm. Although illustrated separately, step 125 may be considered part of step 120.

[0036] Method 100 may continue with step 130, in which a second gas-phase reactant containing a second metal is supplied to the reaction chamber to react with the first metal species, thereby forming an intermetallic compound. This step may be the same as or different from the pressure and / or temperature associated with step 110. The pulse time or the time for which the second gas-phase reactant is supplied to the reaction chamber can be in the range of about 0.01 seconds to about 60 seconds, or about 0.05 seconds to about 10 seconds, or about 0.1 seconds to about 5 seconds. During step 130, the flow rate of the second gas-phase reactant may be the same as or similar to the flow rate during step 120.

[0037] As illustrated in Figure 1, when the second gas-phase reactant reacts with a seed on the substrate surface, a film is formed which is essentially composed of an intermetallic compound, such as an intermetallic compound, or composed of an intermetallic compound (step 140).

[0038] After step 140, any excess second gas-phase reactants and any reaction by-products may be removed from the reaction chamber by a purging / pumping process (step 145). The flow rate and / or duration of the purging gas in this step may be the same as or similar to that described above in step 125. Furthermore, although illustrated separately, step 145 may be considered part of step 130.

[0039] Steps 120 and 130 (and purging steps 125 and / or 145, if applicable) may constitute a single deposition cycle. In some embodiments of the present disclosure, method 100 may include repeating the deposition cycle once or more times. For example, method 100 may continue to a decision gate 150, which determines whether the periodic deposition method 100 continues through step 160 or terminates. The decision gate 150 may be determined based on the thickness or amount of the deposited intermetallic compound. For example, if the thickness of the intermetallic compound is insufficient for a desired device structure, method 100 may return to step 120 and repeat steps 120-145. Once the intermetallic compound has been deposited to the desired thickness or amount, the method may terminate in step 160, and the substrate may undergo another process to form one or more devices or device structures.

[0040] According to various aspects of Method 100, an intermetallic compound is formed when a second gas-phase reactant is reacted with a first metal species formed on the surface during step 120. Thus, an intermetallic compound or layer or film containing an intermetallic compound, or consisting essentially of an intermetallic compound, can be formed without a separate reduction step and / or heating step. Furthermore, as described above, the intermetallic compound can be formed at a relatively low temperature.

[0041] The first gas-phase reactant may include any first metal different from the second metal. For example, the first metal may be or may include transition metals (e.g., group 3-12 metals), group 3-6 metals, group 7-12 metals, lanthanide metals, group 8-11 metals, and / or group 9-10 metals, or group 13-15 metals, where the group number refers to the IUPAC group number.

[0042] According to alternative embodiments, such as those described below in relation to Figure 2, the first gas-phase reactant may include a first metal that is identical to the second metal. When the first and second metals are identical, an elemental metal film can be formed. As described above, such an elemental metal film may include a metalloid or a metalloid.

[0043] The first gas-phase reactant is or may contain a metal halide compound, and the metal is or may contain a first metal. The metal halide compound may contain a metal chloride, a metal iodide, a metal fluoride, or a metal bromide. In some embodiments of the disclosure, the metal halide compound may contain, but is not limited to, at least one of cobalt, nickel, or copper. In some embodiments of the disclosure, the metal halide compound may contain at least one of nickel chloride, cobalt chloride, and copper chloride. In some embodiments, the metal halide compound may contain a bidentate nitrogen-containing adduct-forming ligand. In some embodiments, the metal halide compound may contain an adduct-forming ligand containing two nitrogen atoms (e.g., a diamine adduct of the corresponding metal halide), where each nitrogen atom is bonded to at least one carbon atom. In some embodiments of the disclosure, the metal halide compound contains one or more nitrogen atoms bonded to a central metal atom, thereby forming a metal complex. An example of such a compound is illustrated in Figure 4. Another first gas-phase reactant may include an adduct-forming ligand containing phosphorus, oxygen, and / or sulfur.

[0044] In some embodiments, the first gas-phase reactant may include a transition metal compound having an adduct-forming ligand. In some embodiments, the first gas-phase reactant may include a transition metal compound. In some embodiments, the first gas-phase reactant may include a transition metal halide compound. In some embodiments, the first gas-phase reactant may include a transition metal compound having an adduct-forming ligand such as a monodentate, bidentate, or polydentate adduct-forming ligand. In some embodiments, the first gas-phase reactant may include a transition metal halide compound having an adduct-forming ligand such as a monodentate, bidentate, or polydentate adduct-forming ligand. In some embodiments, the first gas-phase reactant may include a transition metal compound having an adduct-forming ligand containing nitrogen, such as a monodentate, bidentate, or polydentate adduct-forming ligand containing nitrogen. In some embodiments, the first gas-phase reactant may include a transition metal compound having an adduct-forming ligand containing phosphorous acid, oxygen, or sulfur, such as a monodentate, bidentate, or polydentate adduct-forming ligand containing phosphorous acid, oxygen, or sulfur. For example, in some embodiments, the transition metal halide compound may include a transition metal chloride, a transition metal iodide, a transition metal fluoride, or a transition metal bromide. In some embodiments of the present disclosure, the transition metal halide compound may include, but is not limited to, at least one of cobalt, nickel, or copper. In some embodiments of the present disclosure, the transition metal halide compound may include at least one of cobalt chloride, nickel chloride, or copper chloride. In some embodiments, the transition metal halide compound may include a bidentate nitrogen-containing adduct-forming ligand. In some embodiments, the transition metal halide compound may include an adduct-forming ligand containing two nitrogen atoms, each of which is bonded to at least one carbon atom. In some embodiments of the present disclosure, the transition metal halide compound includes one or more nitrogen atoms bonded to a central transition metal atom, thereby forming a metal complex.

[0045] In some embodiments of this disclosure, the first gas-phase reactant may include a transition metal compound having the following formula: (Adductor) n -M-Xa In the formula, each of the “adductors” is an adduct-forming ligand, which can be independently selected to be a monodentate, bidentate, or polydentate adduct-forming ligand or a mixture thereof, where n is 1 to 4 for a monodentate ligand, and 1 to 2 for a bidentate or polydentate adduct-forming ligand, where M is a transition metal such as cobalt (Co), copper (Cu), or nickel (Ni), and each of Xa is another ligand, which can be independently selected to be a halide or other ligand, where a is 1 to 4, and in some examples a is 2.

[0046] In some embodiments of this disclosure, the adduct-forming ligand in a transition metal compound, such as a transition metal halide compound, may include a monodentate, bidentate, or polydentate adduct-forming ligand that coordinates to the transition metal atom of the transition metal compound via at least one of a nitrogen atom, a phosphorous acid atom, an oxygen atom, or a sulfur atom. In some embodiments of this disclosure, the adduct-forming ligand in the transition metal compound may include a cyclic adduct ligand. In some embodiments of this disclosure, the adduct-forming ligand in the transition metal compound may include a monoamine, a diamine, or a polyamine. In some embodiments of this disclosure, the adduct-forming ligand in the transition metal compound may include a monoether, a diether, or a polyether. In some embodiments, the adduct-forming ligand in the transition metal compound may include a monophosphine, a diphosphine, or a polyphosphine. In some embodiments, the adduct-forming ligand in the transition metal compound may include carbon in addition to nitrogen, oxygen, phosphorous acid, or sulfur.

[0047] In some embodiments of this disclosure, the adduct-forming ligand in the transition metal compound may include one monodentate adduct-forming ligand. In some embodiments of this disclosure, the adduct-forming ligand in the transition metal compound may include two monodentate adduct-forming ligands. In some embodiments of this disclosure, the adduct-forming ligand in the transition metal compound may include three monodentate adduct-forming ligands. In some embodiments of this disclosure, the adduct-forming ligand in the transition metal compound may include four monodentate adduct-forming ligands. In some embodiments of this disclosure, the adduct-forming ligand in the transition metal compound may include one bidentate adduct-forming ligand. In some embodiments of this disclosure, the adduct-forming ligand in the transition metal compound may include two bidentate adduct-forming ligands. In some embodiments of this disclosure, the adduct-forming ligand in the transition metal compound may include one polydentate adduct-forming ligand. In some embodiments of this disclosure, the adduct-forming ligand in the transition metal compound may include two polydentate adduct-forming ligands.

[0048] In some embodiments of the present disclosure, the adduct-forming ligand includes nitrogen, such as an amine, diamine, or polyamine adduct-forming ligand. In these embodiments, the transition metal compound is triethylamine (TEA), N,N,N',N'-tetramethyl-1,2-ethylenediamine (CAS: 110-18-9) (TMEDA), N,N,N',N'-tetraethylethylenediamine (CAS: 150-77-6) (TEEDA), 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) (TMMDA), N,N,N',N'',N''-pentamethyldiethylenetriamine (CAS: 30 30-47-5)(PMDETA), Diethylenetriamine (CAS:111-40-0)(DIEN), Triethylenetetraamine (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)(H It may contain at least one of the following: MTETA, 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).

[0049] In some embodiments of the present disclosure, the adduct-forming ligand includes phosphorous acid such as a phosphine, diphosphine, or polyphosphine adduct-forming ligand. For example, the transition metal compound may include at least one of triethylphosphine (CAS: 554-70-1), trimethylphosphite (CAS: 121-45-), 1,2-bis(diethylphosphino)ethane (CAS: 6411-21-8) (BDEPE), or 1,3-bis(diethylphosphino)propane (CAS: 29149-93-7).

[0050] In some embodiments of the present disclosure, the adduct-forming ligand contains oxygen, such as an ether, diether, or polyether adduct-forming ligand. For example, the transition metal compound may include at least one of 1,4-dioxane (CAS: 123-91-1), 1,2-dimethoxyethane (CAS: 110-71-4) (DME, monoglyme), diethylene glycol dimethyl ether (CAS: 111-96-6) (diglyme), triethylene glycol dimethyl ether (CAS: 112-49-2) (triglyme), or 1,4,7,10-tetraoxacyclododecane (CAS: 294-93-9) (12-crown-4).

[0051] In some embodiments of the present disclosure, the adduct-forming ligand may include at least one of a thiother or mixed etheramine, such as 1,7-diaza-12-crown-4:1,7-dioxa-4,10-diazacyclododecane (CAS: 294-92-8) or 1,2-bis(methylthio)ethane (CAS: 6628-18-8).

[0052] In some embodiments, the transition metal halide compound may include cobalt chloride N,N,N',N'-tetramethyl-1,2-ethylenediamine (CoCl2(TMEDA)). In some embodiments, the transition metal halide compound may include cobalt bromide tetramethylethylenediamine (CoBr2(TMEDA)). In some embodiments, the transition metal halide compound may include cobalt iodide tetramethylethylenediamine (Col2(TMEDA)). In some embodiments, the transition metal halide compound may include cobalt chloride N,N,N',N'-tetramethyl-1,3-propanediamine (CoCl2(TMPDA)). In some embodiments of the present disclosure, the transition metal halide compound may include at least one of 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)).

[0053] Other preferred first gas-phase reactants may not be substantially halogen-free. A first gas-phase reactant substantially free of halogen species (a halogen-free metal precursor) is M(dmap) x (dmap = dimethylamino-2-propoxide) is included, where M is a metal, β-diketonate, amidinate, and other typical ALD metal precursors. In some embodiments, the halogen-free metal precursor may include at least one of copper, cobalt, and nickel. Thus, the halogen-free metal precursor may include at least one of Cu(dmap)2, Ni(dmap)2, or Co(dmap)2.

[0054] Therefore, in some embodiments, the halogen-free metal precursor may include at least one bidentate ligand to which the central metal atom is bonded via at least one oxygen and at least one nitrogen atom in the bidentate ligand. Therefore, in some embodiments, the halogen-free metal precursor may include at least one bidentate ligand and at least one other ligand, e.g., a monodentate ligand. Therefore, in some embodiments, the halogen-free metal precursor may include at least one bidentate ligand and at least two other ligands, e.g., monodentate ligands. Therefore, in some embodiments, the halogen-free metal precursor may include at least one bidentate ligand and at least one other ligand, e.g., a monodentate ligand bonded to the central metal atom via N or O. Therefore, in some embodiments, the halogen-free metal precursor may include at least one bidentate ligand in which the central metal atom is bonded via at least one nitrogen atom and at least one other atom of the bidentate ligand. Therefore, in some embodiments, the halogen-free metal precursor may include at least one bidentate ligand in which the central metal atom is bonded via at least two nitrogen atoms in the bidentate ligand. In some embodiments, the halogen-free metal precursor includes at least two bidentate ligands. In some embodiments, the halogen-free metal precursor includes two bidentate ligands.

[0055] Some suitable nonhalides containing β-dikethyminate (e.g., Ni(pda)2), (pda = pentane-2,4,-dikethyminate) compounds include at least one β-dikethyminate ligand and have the general formula: [ka] The formula has the following properties, where M is a metal selected from nickel, cobalt, ruthenium, iridium, palladium, platinum, silver, and gold. 1~5Each of these is H and an organic ligand independently selected from an alkyl, alkylsilyl, alkylamide, alkoxide, or alkylsilylamide group, either linear or branched from C1 to C4. Each L is independently selected from hydrocarbons, oxygen-containing hydrocarbons, amines, polyamines, bipyridines, oxygen-containing heterocycles, nitrogen-containing heterocycles, and combinations thereof, and n is an integer in the range of 0 to 4. A specific example is Ni(pda)2.

[0056] Some examples of suitable nonhalides containing amidinate compounds (e.g., Ni(iPr-AMD)2) include compounds having formulas selected from the group consisting of M(I)AMD, M(II)AMD2 and M(III)AMD3 and their oligomers, where M is a metal and AMD is an amidinate moiety, such as amidinate copper(I), amidinate cobalt(II), or nickel amidinate, iron, ruthenium, manganese, chromium, vanadium, niobium, tantalum, titanium, and / or lanthanum.

[0057] In one or more embodiments, the monovalent metal precursor includes volatile metal(I) amide, [M(I)(AMD)]x, (wherein x=2, 3). Some of these compounds have a dimeric structure 1, [ka] In the formula, R 1 , R 2 , R 3 , R 1’ , R 2’ and R 3’ R is a group consisting of one or more nonmetallic atoms. In some embodiments, R 1 , R 2 , R 3 , R 1 ', R 2 ', and R 3' may be independently selected from hydrogen, alkyl, aryl, alkenyl, alkynyl, trialkylsilyl or fluoroalkyl, or other nonmetallic atoms or groups. In some embodiments, R 1 , R 2 , R 3 , R 1 ', R 2 ', and R 3 Each of the ' is independently an alkyl group, fluoroalkyl group, or silylalkyl group containing 1 to 4 carbon atoms. Suitable monovalent metals include copper(I), silver(I), gold(I), and iridium(I). In one or more embodiments, the metal amidinate is a copper amidinate, and the copper amidinate contains R as the isopropyl group in general formula 1. 1 , R 2 , R 1’ , and R 2’ And as a methyl group, R 3 and R 3’ This includes copper(I)N,N'-diisopropylacetamidinate, which corresponds to the case where the material is taken. In one or more embodiments, the metal(I) amidinate is a trimer having the general formula [M(I)(AMD)]3.

[0058] In one or more embodiments, the divalent metal precursor is a volatile metal(II) bis-amidinate, [M(II)(AMD)2] x , (where x=1, 2) are included. These compounds may also have monomeric structure 2, [ka] In the formula, R 1 , R 2 , R 3 , R 1’ , R 2’ and R 3’ is a group consisting of one or more nonmetallic atoms. In one or more embodiments, a dimer of this structure, for example, [M(II)(AMD)2]2, may also be used. In some embodiments, R 1 , R 2 , R 3 , R1’ , R 2’ , and R 3’ R may be independently selected from hydrogen, alkyl, aryl, alkenyl, alkynyl, trialkylsilyl or fluoroalkyl or other nonmetallic atoms or groups. In some embodiments, R 1 , R 2 , R 3 , R 1 ', R 2 ', and R 3 Each of the ' is independently an alkyl group, fluoroalkyl group, or silylalkyl group containing 1 to 4 carbon atoms. Suitable divalent metals include cobalt, iron, nickel, manganese, ruthenium, zinc, titanium, vanadium, chromium, europium, magnesium, and calcium. In one or more embodiments, the metal(II) amidinate is a cobalt amidinate, and the cobalt amidinate contains R as the isopropyl group in general formula 2. 1 , R 2 , R 1’ , and R 2’ And as a methyl group, R 3 and R 3’ It contains cobalt(II) bis(N,N'-diisopropylacetamidinate), which is equivalent to the amount used when obtaining [the substance].

[0059] One or more trivalent metal precursors include volatile metal(III) tris-amidinates, M(III)(AMD)3. Typically, these compounds have monomeric structure 3. [ka] In the formula, R 1 , R 2 , R 3 , R 1’ , R 2’ , R 3’ , R 1’’ , R 2’’ and R 3’’ R is a group consisting of one or more nonmetallic atoms. In some embodiments, R 1 , R 2 , R3 , R 1’ , R 2’ , R 3’ , R 1’’ , R 2’’ and R 3’’ may be independently selected from hydrogen, alkyl, aryl, alkenyl, alkynyl, trialkylsilyl, halogen, or a partially fluorinated alkyl group. In some embodiments, R 1 , R 2 , R 3 , R 1’ , R 2’ , R 3’ , R 1’’ , R 2’’ and R 3’’ are each independently an alkyl group having 1 to 4 carbon atoms. Suitable trivalent metals include lanthanum, praseodymium and other lanthanide series metals, yttrium, scandium, titanium, vanadium, niobium, tantalum, chromium, iron, ruthenium, cobalt, rhodium, iridium, aluminum, gallium, indium, and bismuth. In one or more embodiments, the metal(III) amidinate is a lanthanum amidinate, and the lanthanum amidinate includes, as the t-butyl groups in General Formula 3, R 1 , R 2 , R 1’ , R 2’ , R 1’’ , and R 2’ being taken as methyl groups R 3 , R 3’ , and R 3’’ corresponding to the case where, lanthanum(III) tris(N,N'-di-t-butylacetamidinate) is included.

[0060] As used herein, metal amidinates having the same ratio to the amidinate as a monomer of the metal, but varying in the total number of metal amidinate units in the compound, are called "oligomers" of the monomeric compound. Thus, the oligomers of the monomeric compound M(R)AMD2 include [M(II)(AMD)2] x, (where x=2, 3, etc.) are included. Similarly, the oligomer of the monomer compound M(I)AMD is [M(I)AMD] x The equation includes (x=2, 3, etc.).

[0061] Specific examples include (N,N'-diisopropylacetamidinato)copper ([Cu(iPr-AMD)]2), bis(N,N'-diisopropylacetamidinato)cobalt ([Co(iPr-AMD)2]), cobaltbis(N,N'-di-tert-butylacetamidinate) ([Co(tBu-AMD)2]), lanthantris(N,N'-diisopropylacetamidinate) ([La(iPr-AMD)3]), and lanthantris(N,N'-diisopropyl-2-tert-butylamidinate) ([La(iPr-tBuAMD)3].1 / 2C6H 12 ), bis(N,N'-diisopropylacetamidinate)iron([Fe(iPr-AMD)2]2), bis(N,N'-di-tert-butylacetamidinate)([Fe( t Bu-AMD)2]), bis(N,N'-diisopropylacetamidinato)nickel([Ni( i Pr-AMD)2]), bis(N,N'-diisopropylacetamidinato)manganese([Mn( i Pr-AMD)2]2), manganese bis(N,N'-di-tert-butylacetamidinate)([Mn( t Bu-AMD)2]), Tris(N,N'-diisopropylacetamidinato)titanium([Ti( i Pr-AMD)3]), Tris(N,N'-diisopropylacetamidinato)vanadium([V( i Pr-AMD)3]), Silver (N,N'-di-isopropylacetamidinate) ([Ag( i (Pr-AMD) x(x=2 and x=3), lithium N,N'-di-sec-butylacetamidinate, cobalt bis(N,N'-di-sec-butylacetamidinate) ([Co(sec-Bu-AMD)2]), copper(I)N,N'-di-sec-butylacetamidinate dimer ([Cu(sec-Bu-AMD)]2), bismastris(N,N'-di-tert-butylacetamidinate) dimer ([Bi( t Bu-AMD)3]2), Strontium bis(N,N'-di-tert-butylacetamidinate)([Sr( t Bu-AMD)2] n ), bismuth oxide, Bi2O3, and tris(N,N'-diisopropylacetamidinato)ruthenium ([Ru( i It includes Pr-AMD)3).

[0062] Some examples of suitable nonhalides containing iminoalkoxide compounds are represented by the following formula: [ka] In the formula, M is a metal selected from groups 2 through 12 of the periodic table. R1, R2, R3, and R4 are each independently H or C1-C8 alkyl. In purification, R1, R2, R3, and R4 are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or t-butyl. In another purification, M is Cu, Cr, Mn, Fe, Co, or Ni. Specific examples of compounds having this formula include bis(1-(tert-butylimino)-2,3,3-trimethylbutane-2-oleate)nickel(II), bis(1-(tert-butylimino)-2,3,3-trimethylbutane-2-oleate)cobalt(II), bis(1-(tert-butylimino)-2,3,3-trimethylbutane-2-oleate)iron(II), bis(1-(tert-butylimino)-2,3,3-trimethylbutane-2-oleate)manganese(II), bis(1-(tert-butylimino)-2,3,3-trimethylbutane-2-oleate)chromium(II), and bis(1-(tert-butylimino)-2,3,3- (Dimethylbutane-2-oleate)copper(II), bis(1-(tert-butylimino)-2,3-dimethylbutane-2-oleate)nickel(II), bis(1-(tert-butylimino)-2,3-dimethylbutane-2-oleate)cobalt(II), bis(1-(tert-butylimino)-2,3-dimethylbutane-2-oleate)iron(II), bis(1-(tert-butylimino)-2,3-dimethylbutane-2-oleate)copper(II), bis(3-((tert-butylimino)methyl)-2,2,4,4-tetramethylpentane-3-oleate)manganese(II), bis(3-((tert-butylimino)methyl)-2,2,4,4-tetramethylpentane-3-oleate)copper(II), bis(3-(isopropylimino)-2-methylbutane-2-oleate)nickel(II), bis(3-(isopropylimino)-2-methylbutane-2-oleate)cobalt(II), bis(3-(isopropylimino)-2-methylbutane-2-oleate)iron(II), bis(3-(isopropylimino)-2-methylbutane-2-oleate)manganese(II), bis(3-(isopropylimino)-2-methylbutane-2-oleate)chromium(II), bis(3-(isopropylimino)-2-methylbutane-2-oleate)copper(II), bis(3-(2,2- This includes, but is not limited to, nickel(II) dimethylhydrazono-2-methylbutane-2-oleate, cobalt(II) bis(3-(2,2-dimethylhydrazono)-2-methylbutane-2-oleate), iron(II) bis(3-(2,2-dimethylhydrazono)-2-methylbutane-2-oleate), manganese(II) bis(3-(2,2-dimethylhydrazono)-2-methylbutane-2-oleate), chlorium(II) bis(3-(2,2-dimethylhydrazono)-2-methylbutane-2-oleate), and copper(II) bis(3-(2,2-dimethylhydrazono)-2-methylbutane-2-oleate). Specific examples include bis(1-(tert-butylimino)-2,3,3-trimethylbutane-2-oleate)nickel(H), bis(1-(tert-butylimino)-2,3,3-trimethylbutane-2-oleate)cobalt(II), bis(1-(tert-butylimino)-2,3,3-trimethylbutane-2-oleate)iron(II), bis(1-(tert-butylimino)-2,3,3-trimethylbutane-2-oleate)manganese(II), bis (1-(tert-butylimino)-2,3,3-trimethylbutane-2-oleate)chromium(II), bis(1-(tert-butylimino)-2,3,3-trimethylbutane-2-oleate)copper(II), bis(1-(tert-butylimino)-2,3-dimethylbutane-2-oleate)nickel(II), bis(1-(tert-butylimino)-2,3-dimethylbutane-2-oleate)cobalt(II), bis(1-(tert-butylimino)-2,3-(dimethylbutane-2-oleate) iron(II), bis(1-(tert-butylimino)-2,3-dimethylbutane-2-oleate) copper(II), bis(3-((tert-butylimino)methyl)-2,2,4,4-tetramethylpentane-3-oleate) manganese(II), bis(3-((tert-butylimino)methyl)-2,2,4,4-tetramethylpentane-3-oleate) copper(II), bis(3-(isopropylimino)-2-methylbutane-2-oleate) cobalt(II), bis(3-(isopropylimino)-2-methylbutane-2-oleate) iron(II), bis(3-(isopropylimino)-2-methylbutane-2-oleate) manganese(II), bis(3-( It contains isopropylimino)-2-methylbutane-2-oleate)chromium(II), bis(3-(2,2-dimethylhydrazono)-2-methylbutane-2-oleate)nickel(II), bis(3-(2,2-dimethylhydrazono)-2-methylbutane-2-oleate)cobalt(II), bis(3-(2,2-dimethylhydrazono)-2-methylbutane-2-oleate)iron(II), bis(3-(2,2-dimethylhydrazono)-2-methylbutane-2-oleate)manganese(II), bis(3-(2,2-dimethylhydrazono)-2-methylbutane-2-oleate)chlorium(II), and bis(3-(2,2-dimethylhydrazono)-2-methylbutane-2-oleate)copper(II).

[0063] In some embodiments, the halogen-free metal precursor does not contain metal atoms other than the desired metal (e.g., Co, Ni, Cu). In some embodiments, the metal in the halogen-free metal precursor has an oxidation state of 0. In some embodiments, the metal in the halogen-free metal precursor has an oxidation state of +I. In some embodiments, the metal in the halogen-free metal precursor has an oxidation state of +III. In some embodiments, the metal in the halogen-free metal precursor has an oxidation state of +II. In some embodiments, the oxidation state is the oxidation state of the metal in the precursor at room temperature. The oxidation state can change under different conditions, e.g., under different pressures, temperatures, and / or atmospheres, and when in contact with different surface materials under different conditions. In some embodiments, the halogen-free metal precursor does not contain halides such as F, Cl, Br, and I. In some embodiments, the halogen-free metal precursor contains carbon, hydrogen, nitrogen, and optionally oxygen.

[0064] In some embodiments, the halide-free copper precursor may include, for example, Cu(dmap)2 or copper(I)N,N'-diisopropylacetamidinate. In some embodiments, the copper precursor can be selected from the group consisting of copper β-diketonate compounds, copper β-dikethyminate compounds, copper aminoalkoxide compounds, e.g., Cu(dmae)2, Cu(deap)2 or Cu(dmamb)2, copper amidinate compounds, e.g., Cu(sBu-amd)2, copper cyclopentadienyl compounds, copper carbonyl compounds, and combinations thereof. In some embodiments, X(acac)y or X(thd)y compounds are used, where X is copper, y is generally 2 or 3 but not necessarily, and thd is 2,2,6,6-tetramethyl-3,5-heptanedionate. In some embodiments, the halide-free copper precursor is copper(II) acetate, [Cu(HMDS)]4 or Cu(nhc)HMDS (1,3-di-isopropyl-imidazoline-2-ylidene copper hexamethyldisilazide), or Cu-β-diketiminate, for example, Cu(dki)VTMS (dki = diketiminate).

[0065] In some embodiments, the halide-free nickel precursor may be, for example, bis(4-N-ethylamino-3-pentene-2-N-ethyliminonate)nickel(II). In some embodiments, the nickel precursor can be selected from the group consisting of nickel β-diketonate compounds, nickel β-dikethyminate compounds, nickel aminoalkoxide compounds, nickel amidinate compounds, nickel cyclopentadienyl compounds, nickel carbonyl compounds, and combinations thereof. In some embodiments, X(acac)y or X(thd)y compounds are used, where X is nickel, y is generally 2 or 3 but not necessarily, and thd is 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0066] In some embodiments, the Co precursor is a Coβ-diketoiminate compound. In some embodiments, the Co precursor is a Co-ketoimminate compound. In some embodiments, the Co precursor is a Co-amidinate compound. In some embodiments, the Co precursor is a Coβ-diketoimminate compound. In some embodiments, the Co precursor comprises at least one ketoimine ligand or a derivative thereof. In some embodiments, the Co precursor comprises at least one amidine ligand or a derivative thereof. In some embodiments, the Co precursor comprises at least one ketonate ligand or a derivative thereof. In some embodiments, the Co precursor is Co2(CO)8, CCTBA, CoCp2, Co(Cp-amd), Co(Cp(CO)2), tBu-AllylCo(CO)3, or Co(HMDS)2.

[0067] As a specific example, the first gas-phase reactant is or may contain a metal halide TMPDA compound, where the metal is, for example, Ni or Co, the halide is, for example, Cl or I, and TMPDA is N,N,N',N'-tetramethyl-1,3-propanediamine, such as NiCl2(TMPDA) and CoCl2(TMPDA); and / or the first gas-phase reactant is or may contain a metal halide TMEDA compound, where the metal is, for example, Ni or Co, the halide is, for example, Cl or I, and TMEDA is N,N,N',N'-tetramethyl-1,2-ethylenediamine, such as CoCl2(TMEDA) and NiCl2(TMEDA). Metal hydrides such as alanes can be used as the first gas-phase reactant (for example, for hydride-hydride type reactions).

[0068] The second gas-phase reactant used in Method 100 may include a metal-containing organic compound, an organometallic compound, or a metal-organic compound. For example, the second gas-phase reactant may be of formula RMH (e.g., R (X-n) -M X -H nA compound selected from the group consisting of compounds having the formula (wherein R is an organic group and M is a metal) can be reacted with a first metal species to form a metal-containing material. According to various examples, X is the formal oxidation state of M, and n can be in the range of 1 to 5. In particular examples, M may be or contain Ge, Ga, In, Sn, As, Sb, Pb, and Bi. Alternatively, M may contain Al. For example, M may contain Ge, Ga, In, and / or Sn. R may be or contain an alkyl group, or a cyclopentadienyl, amide, alkoxy, amidinate, guanidinato, imide, carboxylate, β-diketonate, β-ketoimate, malonate, or β-diketimate group, with or without other donor functionality. Exemplary alkyl groups can be independently selected from the group of C1-C10, C1-C8, C1-C7, C1-C6, or C1-C5 alkyl groups. In some cases, the second gas-phase reactant (e.g., an RMH compound) can be a metal reducing agent. Figure 6 shows an example of a specific second gas-phase reactant for tributyl metal hydride, where M can be any metal described herein, such as tributylgermanium hydride (TBGH).

[0069] As described herein, intermetallic films consisting essentially of intermetallic compounds, including intermetallic compounds such as Co3Sn2 or Ni3Sn2, can exhibit magnetic hysteresis with high coercivity values ​​exceeding 500 Oe. The resistivity of such films (as well as films formed according to Method 200) is about 10 to about 10, depending on the thickness and / or stoichiometry of the film. 6 μΩcm, 20~10 4 The impedance can be in the range of μΩcm, or 50-1000 μΩcm, for example, 80-180 μΩcm. Furthermore, the Ni3Sn2 thin film formed according to Method 100 exhibits an intermetallic crystalline structure and high purity. Exemplary intermetallic compounds and films can be used in a variety of applications, such as magnetoresistive devices, superconducting devices, as catalysts, as energy (e.g., hydrogen) storage, etc.

[0070] Figure 2 illustrates another periodic deposition method 200 according to at least one embodiment of the present disclosure. Using method 200, a metal-containing material can be deposited to form a film or layer that is essentially composed of, or made of, a metal-containing material, including, a metal-containing material. The metal-containing material may include any of the intermetallic compounds described above, as well as any other metal-containing compounds described herein. If the film (formed, for example, by either method 100 or 200) is essentially composed of, or made of an intermetallic compound, the film may exhibit the excellent properties described herein. However, unless otherwise specified, films, methods, structures, apparatus, and systems are not limited to intermetallic compounds.

[0071] Method 200 begins with step 210, which may be identical or similar to step 110. For example, the temperature and pressure in the reaction chamber may be identical or similar to those described in step 110.

[0072] Method 200 may be continued in step 220, which includes providing a first gas-phase reactant, such as one of the first gas-phase reactants described above. This step may be at the same pressure and temperature as those described above in relation to step 210. The pulse time or the time for which the first gas-phase reactant is supplied to the reaction chamber may be in the range of about 0.01 seconds to about 60 seconds, or about 0.05 seconds to about 10 seconds, or about 0.1 seconds to about 5 seconds. During step 220, the flow rate of the first gas-phase reactant may be less than 2000 sccm, or less than 1000 sccm, or less than 500 sccm, or less than 200 sccm, or less than 1 to about 5000 sccm, about 5 to about 2000 sccm, or about 10 to about 1000 sccm.

[0073] After step 220, which involves supplying the first gas-phase reactant, any excess first gas-phase reactant and any reaction by-products may be removed from the reaction chamber by a purging / pumping process (step 225). During step 225, the flow rate of the purge gas may be less than 2000 sccm, or less than 1000 sccm, or less than 500 sccm, or less than 200 sccm, or less than 100 sccm, or in the range of about 1 to about 5000 sccm, about 5 to about 2000 sccm, or about 10 to about 1000 sccm. Although illustrated separately, step 225 may be considered part of step 220.

[0074] Method 200 may continue with step 230, which includes supplying a second gas-phase reactant containing a compound having the general formula RMH (wherein R is an organic group and M is a metal) and reacting it with the first metal species (e.g., on the surface of a substrate) to form a metal-containing material. The compound having the general formula RMH may be the same as those described above. The pulse time or the time for which the second gas-phase reactant is supplied to the reaction chamber may be in the range of about 0.01 seconds to about 60 seconds, or about 0.05 seconds to about 10 seconds, or about 0.1 seconds to about 5 seconds. During step 230, the flow rate of the second gas-phase reactant may be less than 2000 sccm, or less than 1000 sccm, or less than 500 sccm, or less than 200 sccm, or less than 1 to about 5000 sccm, about 5 to about 2000 sccm, or about 10 to about 1000 sccm.

[0075] As illustrated in Figure 2, when the second gas-phase reactant reacts with the seeds on the substrate surface, a metal-containing material is formed, for example, a metal-containing material containing a metal-containing material, essentially composed of a metal-containing material, or a film composed of a metal-containing material.

[0076] After step 230, any excess second gas-phase reactants and any reaction by-products may be removed from the reaction chamber by a purging / pumping process (step 245). The flow rate of the purging gas may be the same as that in step 225 above. Furthermore, although illustrated separately, step 245 may be considered part of step 230.

[0077] Steps 220-245 can be repeated as desired in the same or similar manner as steps 120-145 described above in relation to Figure 1. For example, the process can be repeated until a desired thickness or amount of metal-containing material is deposited on the substrate.

[0078] The first gas-phase reactant used in step 220 may be or contain any first gas-phase reactant described herein, and / or the second gas-phase reactant used in step 230 may be or contain any second gas-phase reactant described herein. As described above, the first and second gas-phase reactants may contain the same or different metals. For example, an elemental Ge film can be formed by combining a first gas-phase reactant, e.g., GeCl2 (dioxane) or other Ge precursor, with R3GeH. Furthermore, the use of R3GeH may be advantageous because R3GeH exhibits relatively low toxicity and relatively high stability. Other elemental films (or polymetallic films) can be formed in a similar manner. The metal-containing material may be in the form of an alloy, mixture, intermetallic material, or elemental metal.

[0079] As a specific example, the metal-containing material deposited using Method 200 may contain one or more of M-Ge, M-Ga, and / or M-In, where M is selected from the group consisting of Ni and Co. According to exemplary embodiments of these examples, the first gas-phase reactant includes a metal halide such as a diamine adduct corresponding to the metal halide described above, and the second gas-phase reactant includes a compound having the general formula RMH described above. The temperature during the deposition process to form the M-Ge, M-Ga, and / or M-In metal-containing film may be about 150°C to about 250°C, about 160°C to 200°C, or in the range between the sublimation temperature and the decomposition temperatures of the first and second reactants. The metal-containing material may be formed without annealing at temperatures below 400°C and / or using only the first gas-phase reactant, the second gas-phase reactant, and an optional purging step. Surprisingly and unexpectedly, the exemplary metal-containing material films formed according to methods 100 and 200, particularly the M-Ge, M-Ga, and / or M-In films described above, are relatively pure, with the total amount of contaminants (e.g., nonmetallic materials) being less than 1 atomic percent, and any halide contaminants being less than 0.1 atomic percent. The first and second gas-phase reactants described herein undergo a rapid and complete (or nearly complete) reaction, and the contamination remaining in the resulting material is considered to be relatively small. Due to their high purity, the exemplary materials and films described herein exhibit low resistance, which can result in materials suitable for low-resistance contact layers in microelectronic devices. For example, the M-Ge, M-Ga, and / or M-In materials described herein exhibit relatively low resistance and can therefore be used as contact layers in electronic device structures.

[0080] As mentioned above, Ni x Ge y and Co x Ge y The resistance of films formed according to Method 200, such as metal germanide films, is approximately 10 to approximately 10, based on film thickness and / or stoichiometry. 6 μΩcm, 20~10 4The resistance can be in the range of μΩcm, or 50 to 1000 μΩcm, for example, 80 to 180 μΩcm.

[0081] According to some embodiments of the present disclosure, Method 100 and / or Method 200 may include atomic layer deposition (ALD). ALD is based on a typical self-controlled reaction, thereby depositing approximately one atomic (or molecular) monolayer of material per deposition cycle using sequential and alternating pulses of reactants. The deposition conditions and reactants are typically selected to provide a self-saturating reaction such that an adsorbed layer of one reactant leaves a surface end that is unreactive with the gas-phase reactant of the same reactant. The substrate is then brought into contact with a different reactant that reacts with the previous end, enabling continuous deposition. Thus, each cycle of the alternating pulse typically leaves approximately one monolayer or less of the desired material. However, as described above, multiple monolayers of material can be deposited in one or more ALD cycles, for example, if several gas-phase reactions occur despite the nature of the alternating process.

[0082] In some embodiments, periodic deposition processes are used to form metal-containing films on a substrate, and these processes can be ALD-type processes. In some embodiments, periodic deposition can be a hybrid ALD / CVD or periodic CVD process. For example, in some embodiments, the growth rate of the ALD process may be lower compared to the CVD process. One approach to increase the growth rate is to operate at a substrate temperature higher than that typically used in the ALD process, resulting in a chemical vapor deposition process, but further utilizing the sequential introduction of reactants. Such a process may be called periodic CVD.

[0083] The periodic deposition processes described herein may be carried out using ALD or CVD deposition systems. For example, in some embodiments, the method may include heating the substrate to a temperature of approximately 80°C to approximately 150°C, or further heating the substrate to a temperature between approximately 80°C to approximately 120°C, or approximately 150°C to approximately 250°C, or approximately 160°C to approximately 200°C. Of course, the appropriate temperature window for any given periodic deposition process, such as an ALD reaction, will depend on the surface termination and the types of reactants involved. Here, the temperature will vary depending on the reactants used and is generally below approximately 700°C. In some embodiments, for a vapor deposition process, the deposition temperature is generally above approximately 100°C, in some embodiments the deposition temperature is approximately 100°C to approximately 300°C, and in some embodiments the deposition temperature is approximately 120°C to approximately 200°C. In some embodiments the deposition temperature is below approximately 500°C, or lower than approximately 400°C, or lower than approximately 350°C, or lower than approximately 300°C. In some cases, the deposition temperature may be lower than about 300°C, lower than about 200°C, or lower than about 100°C. In some cases, the deposition temperature may be higher than about 20°C, higher than about 50°C, and higher than about 75°C. In some embodiments of the present disclosure, the deposition temperature, i.e., the temperature of the substrate during deposition, is the same as or similar to the above temperatures related to methods 100 and 200.

[0084] As shown in Figures 1 and 2, the periodic process including the ALD process may include purging steps, e.g., the purging steps 125, 145, 225, and 245 described above. The purging gas used during such steps includes one or more inert gases, e.g., argon (Ar) or nitrogen (N2), which can prevent or mitigate gas-phase reactions between process steps and between reactants, and enable self-saturated surface reactions. However, in some embodiments, the substrate may be additionally or alternatively moved (e.g., to a separate reaction chamber) to come into contact separately with the first gas-phase reactant and the second gas-phase reactant. Thus, steps 120 / 130 and / or steps 220 / 230 do not need to be carried out in the same reaction chamber. Additionally or alternatively, a vacuum pump may be used to facilitate purging.

[0085] Naturally, in some embodiments of this disclosure, the order of supplying the first gas-phase reactant and the second gas-phase reactant may be such that the substrate is first brought into contact with the second gas-phase reactant, followed by contact with the first gas-phase reactant. In other words, steps 120, 130, and 220, 230 can be reversed. Furthermore, in some embodiments, the periodic deposition process may include bringing the substrate into contact with the first gas-phase reactant once or more times before bringing the substrate into contact with the second gas-phase reactant once or more times, or similarly, bringing the substrate into contact with the second gas-phase reactant once or more times before bringing the substrate into contact with the first gas-phase reactant once or more times.

[0086] At least some embodiments of this disclosure (e.g., Methods 100 and / or 200) do not require the inclusion of plasma reactants, for example, the first and second gas-phase reactants substantially contain no ionized reactant species. In some embodiments, the first and second gas-phase reactants substantially contain no ionized reactant species, excited species, or radical species. For example, both the first and second gas-phase reactants may be plasma reactants-free to prevent ionization damage to the underlying substrate and the associated defects that result from it. The use of non-plasma reactants may be particularly useful when the underlying substrate contains a fragile manufacturing or at least partially manufactured semiconductor device structure, as high-energy plasma species can damage and / or degrade the performance characteristics of the device.

[0087] Although not illustrated in Figure 2, in some embodiments of the present disclosure, the exemplary method of the present disclosure may include another process step comprising contacting a substrate with a third gas-phase reactant comprising a reducing agent. In some embodiments, the reducing agent may be hydrogen (H2), hydrogen (H2) plasma, ammonia (NH3), ammonia (NH3) plasma, hydrazine (N2H4), silane (SiH4), disilane (Si2H6), trisilane (Si3H8), germane (GeH4), digermane (Ge2H6), borane (BH3), diborane (B2H6), tertiary butylhydrazine (C4H 12 The material may include at least one of the following: N2), selenium reactant, boron reactant, phosphite reactant, sulfur reactant, organic reactant (e.g., alcohol, aldehyde, or carboxylic acid), or hydrogen reactant. In some embodiments of the present disclosure, the exemplary periodic deposition method of the present disclosure may involve contacting a substrate with a second gas-phase reactant, which is a reducing agent (without any additional precursor / reactant contact step). However, as described above, according to at least some examples, neither a reducing agent nor a reduction reaction (other than the second reactant) is required to form a desired material, e.g., an intermetallic material.

[0088] When used, a third gas-phase reactant containing a reducing agent may be introduced into the reaction chamber and come into contact with the substrate at some process stage of an exemplary periodic deposition method. In some embodiments of the present disclosure, the reducing agent may be introduced into the reaction chamber and come into contact with the substrate separately from the first gas-phase reactant and / or separately from the second gas-phase reactant. For example, the reducing agent may be introduced into the reaction chamber and come into contact with the substrate before the substrate comes into contact with the first gas-phase reactant, after the substrate comes into contact with the first gas-phase reactant and before the substrate comes into contact with the second gas-phase reactant, and / or after the substrate comes into contact with the second gas-phase reactant. In some embodiments of the present disclosure, the reducing agent may be introduced into the reaction chamber and come into contact with the substrate simultaneously with the first gas-phase reactant and / or simultaneously with the second gas-phase reactant. For example, the reducing agent and the first gas-phase reactant may flow into the reaction chamber simultaneously and come into contact with the substrate simultaneously, and / or the reducing agent and the second gas-phase reactant may flow into the reaction chamber simultaneously and come into contact with the substrate simultaneously.

[0089] In some embodiments, the growth rate of metal-containing materials and / or intermetallic compounds is about 0.005 Å / cycle to about 5 Å / cycle, or about 0.01 Å / cycle to about 2.0 Å / cycle. In some embodiments, the growth rate of metal-containing materials and / or intermetallic compounds is greater than about 0.05 Å / cycle, greater than about 0.1 Å / cycle, greater than about 0.15 Å / cycle, greater than about 0.20 Å / cycle, greater than about 0.25 Å / cycle, or greater than about 0.3 Å / cycle. In some embodiments, the growth rate of metal-containing materials and / or intermetallic compounds is less than about 2.0 Å / cycle, less than about 1.0 Å / cycle, less than about 0.75 Å / cycle, less than about 0.5 Å / cycle, or less than 0.2 Å / cycle. In some embodiments of this disclosure, the growth rate of metal-containing materials and / or intermetallic compounds may be about 0.4 Å / cycle or about 0.9 Å / cycle. A specific example is Co3Sn 2の場合The growth rate was in the range of approximately 0.7 to 1.3 Å / cycle at a deposition temperature of approximately 170 to 200°C. In the case of Ni3Sn2, when NiCl2(TMPDA) was used as the first gas-phase reactant, a growth rate of approximately 1.3 Å / cycle was observed at 160°C. x Ge y For membranes, the growth rates are in the range of approximately 0.18 and 1.3 Å / cycle at deposition temperatures of approximately 157–200°C, when NiCl2(TMPDA) is used as the primary gas-phase reactant.

[0090] Figure 3 illustrates a structure 300 comprising a substrate 302 and a layer or film 304. The structure 300 is or may comprise a partially manufactured device structure. As described above, the substrate 302 may comprise a bulk material, such as a bulk semiconductor material, and a layer formed thereon and / or therein. The film 302 may comprise an intermetallic compound or a metal-containing material, such as an intermetallic compound or a metal-containing material deposited according to the embodiments described herein. In some embodiments, the film 304 may be continuous with a thickness of less than about 100 nanometers, or less than about 60 nanometers, or less than about 50 nanometers, or less than about 40 nanometers, or less than about 30 nanometers, or less than about 25 nanometers, or less than about 20 nanometers, or less than about 15 nanometers, or less than about 10 nanometers, or less than about 5 nanometers, or even thinner. The continuity referred to herein may be physical continuity or electrical continuity. In some embodiments, the thickness to which the film 304 can be physically continuous does not have to be the same as the thickness to which the film can be electrically continuous, and the thickness to which the film 304 can be electrically continuous does not have to be the same as the thickness to which the film can be physically continuous.

[0091] In some embodiments, the intermetallic film and / or metal-containing film (e.g., film 304) deposited according to some of the embodiments described herein may have a thickness of about 20 nanometers to about 100 nanometers. In some embodiments, the intermetallic film and / or metal-containing film deposited according to some of the embodiments described herein may have a thickness of about 20 nanometers to about 60 nanometers. In some embodiments, the intermetallic film and / or metal-containing film deposited according to some of the embodiments described herein may have a thickness of more than about 20 nanometers, or more than about 30 nanometers, or more than about 40 nanometers, or more than about 50 nanometers, or more than about 60 nanometers, or more than about 100 nanometers, or more than about 250 nanometers, or more than about 500 nanometers. In some embodiments, the intermetallic film and / or metal-containing film deposited according to some of the embodiments described herein may have a thickness of less than about 50 nanometers, less than about 30 nanometers, less than about 20 nanometers, less than about 15 nanometers, less than about 10 nanometers, less than about 5 nanometers, less than about 3 nanometers, less than about 2 nanometers, or less than about 1 nanometer.

[0092] In some embodiments of the present disclosure, intermetallic films and / or metal-containing films may be deposited on a three-dimensional structure, for example, on a non-planar substrate having a high aspect ratio feature. In some embodiments, the step coverage of the intermetallic films and / or metal-containing films may be about 50% or more, or about 80% or more, or about 90% or more, or about 95% or more, or about 98% or more, or about 99% or more, or greater than that, in structures with an aspect ratio (height / width) of about 2, about 5, about 10, about 25, about 50, or even more than about 100.

[0093] Intermetallic compounds and / or metal-containing materials or their corresponding films include the first and second metals described herein. In specific examples, the first metal may include Ni, Co, Pt, or any other first metal described herein, and the second metal may include Ge, Ga, In, Sn, As, Sb, Pb, and Bi (e.g., Ge, Ga, In, Sn), or any other second metal described herein, including Al. In some cases, the first metal may not contain Al. Exemplary intermetallic and / or metal-containing compounds include (hexagonal) Co3Sn2 or Ni3Sn2, and (e.g., orthorhombic) Ni2Ge, (e.g., monoclinic) Ni5Ge3, N 19 Ge 12 , and / or amorphous or crystalline Ni such as NiGe x Ge y This includes intermetallic compounds and / or metal-containing compounds. Intermetallic compounds and / or metal-containing compounds may also have other stoichiometric or other crystalline structures, which can be obtained, for example, by heat treatment or by adjusting deposition conditions. Other exemplary intermetallic compounds and / or metal-containing materials include In-Sb, Pt-In, Pt-Sn, Pt-Ir, Pd-Pt, Ru-Pt, Ru, Co, Co-W, Ru-Mn, Cu-Mn, and Co-Pt compounds. Other specific examples of intermetallic compounds and / or metal-containing materials include Ni, Co, Cu, and / or Pt, as well as one or more of Ge, Ga, In, Sn, As, Sb, Pb, Al, and Bi. In some cases, films containing intermetallic compounds and / or metal-containing materials do not contain Al, Ga, and / or In, as well as transition metals.

[0094] In some embodiments of this disclosure, intermetallic compounds and / or metal-containing materials and / or films, including those described herein, may contain less than 5 atomic percent of oxygen, less than 2 atomic percent of oxygen, less than 1 atomic percent of oxygen, or less than 0.5 atomic percent of oxygen. In another embodiment, the compound, material, or film may contain less than 5 atomic percent of hydrogen, or less than 2 atomic percent of hydrogen, or less than 1 atomic percent of hydrogen, or even less than 0.5 atomic percent of hydrogen. In yet another embodiment, the compound, material, or film may contain less than 5 atomic percent of carbon, or less than 2 atomic percent of carbon, or less than 1 atomic percent of carbon, or even less than 0.5 atomic percent of carbon. In yet another embodiment, the compound, material, or film may contain less than 5 atomic percent of a halide species, or less than 2 atomic percent of a halide species, or less than 1 atomic percent of a halide species, or less than 0.5 atomic percent of a halide species, or even less than 0.1 atomic percent of a halide species. Furthermore, the total contamination of species (species other than the desired metal) can be less than about 5 atomic percent, less than about 2 atomic percent, or less than 1 atomic percent. In some embodiments, the atomic percent of intermetallic compounds, metal-containing materials, and films containing the same may be determined using time-of-flight elastic recoil particle detection (ToF-ERDA).

[0095] The intermetallic compounds, metal-containing materials, and films described herein can be formed using reactors that can be used to deposit metal-containing films. Such reactors include ALD reactors equipped with appropriate apparatus and means for supplying reactants, as well as CVD reactors. According to some embodiments, high-temperature wall cross-flow reactors can be used. According to some embodiments, other cross-flow, batch, mini-batch, or spatial ALD reactors may be used.

[0096] Examples of suitable reactors that can be used include commercially available single-substrate (or single-wafer) deposition systems available from ASM America, Inc. in Phoenix, Arizona, and ASM Europe BV in Almea, Netherlands, such as Pulsar® reactors (e.g., Pulsar® 2000, Pulsar® 3000, and Pulsar® XP ALD, etc.), as well as EmerALD® XP and EmerALD® reactors. Other commercially available reactors include those traded as Eagle® XP and XP8, manufactured by ASM Japan Co., Ltd. (Tokyo, Japan). In some embodiments, the reactor is a spatial ALD reactor in which the substrate moves or rotates during processing.

[0097] In some embodiments of this disclosure, batch reactors may be used. Suitable batch reactors include, but are not limited to, the Advance® 400 series reactors, commercially available from ASM Europe BV (Almeer, Netherlands) under trade names A400 and A412PLUS. In some embodiments, the wafers are rotated during processing. In other embodiments, the batch reactor comprises a mini-batch reactor configured to accommodate 10 or fewer substrates (e.g., semiconductor wafers), 8 or fewer substrates, 6 or fewer substrates, 4 or fewer substrates, or 2 or fewer substrates. In some embodiments in which the batch reactor is used, the non-uniformity between wafers is less than 3% (1 sigma), less than 2%, less than 1%, or even less than 0.5%.

[0098] The deposition methods described herein can optionally be carried out in reactors or reaction chambers connected to a cluster tool. In a cluster tool, each reaction chamber can be dedicated to one type of process, allowing for a constant temperature to be maintained in the reaction chambers within each module, resulting in improved throughput compared to reactors that heat the substrate to process temperature before each operation. Furthermore, a cluster tool can reduce the time required to evacuate the reaction chambers between substrates to a desired process pressure level. In some embodiments of this disclosure, the deposition process may be carried out in a cluster tool comprising multiple reaction chambers, each individual reaction chamber may be used to expose the substrate to individual reactant gases, or the substrate may be transported between different reaction chambers to expose it to multiple reactant gases, with the transport of the substrate carried out in a controlled environment to avoid oxidation / contamination of the substrate. In some embodiments of this disclosure, the deposition process may be carried out in a cluster tool comprising multiple reaction chambers, each individual reaction chamber may be configured to heat the substrate to different deposition temperatures.

[0099] Standalone reactors are equipped with load locks. In this case, there is no need to cool the reaction space between each operation.

[0100] Figure 5 schematically illustrates a reactor system 500 according to at least one embodiment of the present disclosure. The reactor system 500 can be used, for example, to carry out the periodic deposition (e.g., ALD) method described herein, and / or to form the structures, membranes, compounds and / or materials described herein.

[0101] In the exemplary example, the reactor system 500 comprises an optional substrate handling system 502, a reaction chamber 504, a gas distribution system 506, and a wall 508 optionally positioned between the reaction chamber 504 and the substrate handling system 502. The system 500 may also comprise a first gas-phase reactant source 512, a second gas-phase reactant source 514, and an exhaust source 510. Although two gas sources 512, 514 are exemplified, the reactor system 500 may comprise any suitable number of reactant gas sources. For example, the exemplary reactor system may comprise at least two reactant gas sources (e.g., feed sources containing compounds that become the first or second gas-phase reactants), and optionally one or more carrier gas and / or purge gas sources 516. The reactor system 500 also comprises a susceptor 518 that holds one or more substrates 520 during processing.

[0102] The reactor system 500 may comprise any preferred number of reaction chambers 104 and a substrate handling system 502. For example, the reaction chambers 504 of the reactor system 500 comprise cross-flow high-temperature wall epitaxial reaction chambers. Exemplary reactor systems, including horizontal flow reactors, are available as systems from ASM.

[0103] Figure 5 is a simplified schematic version of the reactor system 500 and should be noted that it does not include all of the elements that may be used in the reactor system 500, such as, but not limited to, valves, electrical connections, mass flow controllers, seals, and gas conduits.

[0104] In some embodiments of the present disclosure, one or more reactant material containers 522, 524 are in fluid communication with a reaction chamber 504 via conduits or other suitable means 526, 528 and may be further connected to a gas distribution system 506 located between the reactant material containers 522, 524 and the reaction chamber 504. The gas distribution system 506 may comprise, for example, a manifold, a valve control system, a mass flow control system, and / or other mechanisms for controlling gaseous reactants originating from the reactant material containers 522 or 524. The reactant material containers 522, 524 may be configured to store metal-containing compounds (e.g., organometallic compounds or metal-organic compounds) which are, respectively, a first gas-phase reactant and a second gas-phase reactant, or which become a first gas-phase reactant and a second gas-phase reactant, respectively, upon heating. In some embodiments, the reactant material containers 522, 524 may contain a quartz material which may be substantially chemically inert to the respective first and second reactants stored in the material containers 522, 524. In another embodiment of the present disclosure, the reactant material containers 522, 524 may be made of a corrosion-resistant metal or metal alloy, such as Hastelloy, Monel, or a combination thereof.

[0105] In some embodiments of the present disclosure, the reactant raw material containers 522, 524 may further comprise one or more heating elements 526, 528 configured to heat the compounds stored in the reactant raw material containers 522, 524 to a desired temperature. In some embodiments, one or more heating elements can be used to heat the compounds to a temperature above about 0°C, or above about 20°C, or above about 100°C, or above about 150°C, or above about 200°C, or above about 300°C, or above about 400°C. In some embodiments, one or more heating elements 526, 528 may be configured to heat the compounds stored in the reactant raw material containers 522, 524 to a temperature of about 25°C to about 200°C, about 25°C to about 300°C, or about 25°C to about 400°C. As a specific example, if the gas-phase reactant contains Bu3SnH or Bu3GeH, the temperature may be in the range of approximately 20°C to approximately 40°C or approximately 30°C; if the reactant contains CoCl2(TMEDA), the temperature may be in the range of approximately 150°C to approximately 190°C or approximately 170°C; if the reactant contains NiCl2(TMPDA), the temperature may be in the range of approximately 140°C to approximately 180°C or approximately 157°C; and if the reactant contains Ni(dmap)2, the temperature may be in the range of approximately 50°C to approximately 70°C or approximately 62°C.

[0106] In some embodiments, one or more heating elements 526, 528 associated with the reactant raw material containers 522, 524 are configured to convert the compound from solid to liquid or gas to form a first gas-phase reactant or a second gas-phase reactant. In some embodiments, one or more heating elements 526, 528 associated with the reactant raw material containers 522, 524 may be used to control the viscosity of the reactant compound stored in the reactant raw material containers 522, 524. In some embodiments, one or more heating elements 526, 528 associated with the reactant raw material containers 522, 524 may be configured to control the vapor pressure generated by the compound stored in the reactant raw material containers 522, 524. In some embodiments of the present disclosure, the compound may have a vapor pressure greater than 0.01 millibars at temperatures above 25°C, above 50°C, or even above 100°C. In some embodiments of this disclosure, the compound may have a vapor pressure greater than 0.01 millibars at temperatures below 350°C, below 250°C, below 200°C, or even below 150°C. In some embodiments of this disclosure, the compound may have a vapor pressure greater than 0.1 millibars at temperatures above 25°C, or even above 100°C. In some embodiments of this disclosure, the compound may have a vapor pressure greater than 0.1 millibars at temperatures below 400°C, below 200°C, or even below 100°C. In some embodiments of this disclosure, the compound may have a vapor pressure greater than 1 millibar at temperatures above 25°C, or even above 100°C. For example, the compound can be heated to a temperature above 150°C to generate a vapor pressure greater than 0.001 millibars.

[0107] In some embodiments of the present disclosure, the steam passage 530 may be connected to the reactant feed container 522 (and / or reactant feed container 524) so ​​that one or more carrier gases (e.g., from source 516 or other sources) may be transferred from the carrier gas storage container through the steam passage 530 into the reactant feed container 522. In some embodiments, a mass flow controller (not shown) may be located on the steam passage 530 and close to the reactant feed container 522. For example, the mass flow controller may be calibrated to control the mass flux of the carrier gas entering the reactant feed container 522, thereby allowing greater control over the subsequent flow rate of reactant vapor from the reactant feed container 522 to the reaction chamber 504.

[0108] In some embodiments, a carrier gas (e.g., hydrogen, nitrogen, helium, argon, or any mixture thereof) may be flowed over an exposed surface of the compound, thereby selectively removing some of the vapor from the compound and transferring the compound (then the first or second gas-phase reactant) together with the carrier gas to the reaction chamber 504. In another embodiment of the present disclosure, the carrier gas may be “bubbled” through the compound, for example, by another vapor passage (not shown), thereby agitating and selectively removing some of the metal-containing compound and transferring the metal-containing compound vapor (then the first or second gas-phase reactant) through a gas conduit 526 to the reaction chamber 504.

[0109] In some embodiments of the present disclosure, the reactor system 500 further comprises a system operation and control mechanism 532 that provides electronic and mechanical components for selectively operating valves, manifolds, pumps and other devices associated with the reactor system 500. Such circuits and components operate to introduce reactants, purge gas, and / or carrier gas from the respective reactant raw material containers 522, 524 and purge gas container 534. The system operation and control mechanism 532 also controls the timing of gas pulse sequences, the temperature of the substrate and / or reaction chamber, and the pressure of the reaction chamber, as well as various other operations necessary for the proper operation of the reactor system 500. The operation and control mechanism 532 may also comprise control software and electrical or air control valves to control the flow rates of reactants, carrier gas, and / or purge gas into and out of the reaction chamber 504. The system operation and control mechanism 532 may comprise modules, e.g., software and / or hardware components, e.g., FPGAs or ASICs, that perform specific tasks. The module is advantageously configured to reside on an addressable storage medium of the system operation and control mechanism 532 and can be configured to run one or more processes.

[0110] Various other configurations of the reactor system are possible, including different numbers and types of reactant sources and purge gas sources. Furthermore, there are many arrangements of valves, conduits, reactant sources, and purge gas sources that can be used to achieve the objective of selectively supplying gas into the reaction chamber 504.

[0111] The examples provided below illustrate specific processes, films, and structures according to exemplary embodiments of the present disclosure. These examples are illustrative and are not intended to limit the scope of the present disclosure.

[0112] Example 1 A periodic deposition process for depositing intermetallic compounds, wherein the periodic deposition method is: A step of supplying a first gas-phase reactant containing a first metal to a reaction chamber in order to react with the surface of a substrate to form a first metal species, A periodic deposition process comprising the steps of supplying a second gas-phase reactant containing a second metal to a reaction chamber and reacting it with a first metal species to form an intermetallic compound.

[0113] Example 2 Furthermore, the periodic deposition process according to Example 1 further comprises repeating the steps of supplying a first gas-phase reactant and supplying a second gas-phase reactant until a desired film thickness is achieved.

[0114] Example 3 The periodic deposition process according to Example 1, further comprising one or more purging steps, at least one of which is performed after the step of supplying a first gas-phase reactant and before the step of supplying a second gas-phase reactant.

[0115] Example 4 A periodic deposition process, including an atomic layer deposition process, as described in Example 1.

[0116] Example 5 A periodic sedimentary process, including periodic chemical vapor deposition, as described in Example 1.

[0117] Example 6 A periodic deposition process as described in Example 1, wherein the temperature in the reaction chamber during the steps of supplying a first gas-phase reactant and supplying a second gas-phase reactant is greater than 0°C and less than 600°C, less than 500°C, less than 400°C, less than 300°C or less than 250°C, or about 20°C to about 700°C, about 50°C to about 500°C, or about 50°C to about 400°C, about 75°C to about 300°C, or about 100°C to about 250°C.

[0118] Example 7 The periodic deposition process described in Example 1, wherein the second gas-phase reactant comprises a metal-containing organic compound.

[0119] Example 8 The periodic deposition process described in Example 1, wherein the second gas-phase reactant is selected from the group consisting of compounds having the formula RMH (wherein R is an organic group and M is a metal).

[0120] Example 9 The periodic deposition process described in Example 1, wherein the second metal is selected from the group consisting of Ge, Ga, In, Sn, Al, As, Sb, Pb, and Bi.

[0121] Example 10 The second metal is selected from the group consisting of Ge, Ga, In, and Sn, in the periodic deposition process described in Example 1.

[0122] Example 11 The second metal is Ge, and the periodic deposition process is as described in Example 1.

[0123] Example 12 The second metal is Ga, and the periodic deposition process is as described in Example 1.

[0124] Example 13 The second metal is In, as described in Example 1, in a periodic deposition process.

[0125] Example 14 The group consisting of compounds having the formula RMH is the group with formula R (X-n) -M X -H n A periodic deposition process as described in Example 8, having the formula (wherein X is the formal oxidation state of the metal and n is 1 to 5).

[0126] Example 15 R comprises an alkyl group or another organic group, as described in Examples 8 and 14, for the periodic deposition process.

[0127] Example 16 R is independently selected from the group consisting of C1-C10 alkyl groups, the periodic deposition process described in either Example 8 or 14.

[0128] Example 17 A periodic deposition process according to any one of Examples 8 and 14, wherein R is a cyclopentadienyl, amide, alkoxy, amidinate, guanidinato, imide, carboxylate, β-diketonate, β-ketoimate, malonate, or β-dikethyminate group having or not having another donor functionality.

[0129] Example 18 The second gas-phase reactant is a metal reducing agent, as described in Example 1, for the periodic deposition process.

[0130] Example 19 The first metal is selected from the group consisting of transition metals and IUPAC Group 13-15 metals, in the periodic deposition process described in Example 1.

[0131] Example 20 The first metal is selected from the group consisting of Groups 3 to 6, in the periodic deposition process described in Example 1.

[0132] Example 21 The first metal is selected from the group consisting of Groups 7-12, in the periodic deposition process described in Example 1.

[0133] Example 22 The first metal is selected from the group consisting of lanthanides, in the periodic deposition process described in Example 1.

[0134] Example 23 The first metal is selected from the group consisting of Groups 8-11, in the periodic deposition process described in Example 1.

[0135] Example 24 The first metal is selected from the group consisting of Groups 13-15, in the periodic deposition process described in Example 1.

[0136] Example 25 The first gas-phase reactant is selected from the group consisting of metal halides, in the periodic deposition process described in Example 1.

[0137] Example 26 The first gas-phase reactant is M(dmap)x A periodic deposition process as described in Example 1, comprising (dmap = dimethylamino-2-propoxide), where M is a metal.

[0138] Example 27 The first gas-phase reactant is selected from the group consisting of metal hydrides, in the periodic deposition process described in Example 1.

[0139] Example 28 The periodic deposition process described in Example 1, wherein the first gas-phase reactant comprises a diamine adduct of the corresponding metal halide.

[0140] Example 29 The periodic deposition process described in Example 1, wherein the first gas-phase reactant comprises a metal halide compound containing a bidentate nitrogen adduct ligand.

[0141] Example 30 The periodic deposition process described in Example 29, wherein the adduct ligand contains two nitrogen atoms, each nitrogen atom being bonded to at least one carbon atom.

[0142] Example 31 The periodic deposition process described in Example 1, wherein the first gas-phase reactant comprises at least one of cobalt chloride (TMEDA) and nickel chloride (TMPDA).

[0143] Example 32 The periodic deposition process described in Example 1, wherein the second gas-phase reactant comprises one or more TBTH and TBGH.

[0144] Example 33 The intermetallic compound is Al, Ga, and / or In, and does not contain transition metals, as described in Example 1, for the periodic deposition process.

[0145] Example 34 A periodic deposition process for forming a metal-containing material, wherein the periodic deposition process is

[0146] To form the first metal species, a first gas phase precursor containing the first metal is supplied to the reaction chamber,

[0147] A periodic deposition process comprising supplying a second gas-phase reactant containing a compound having the general formula RMH (wherein R is an organic group and M is a metal), reacting it with a first metal species, and thereby forming a metal-containing material.

[0148] Example 35 The first and second metals are identical, in the periodic deposition process described in Example 34.

[0149] Example 36 The metal-containing material is a periodic deposition process as described in Example 34, which includes elemental metals.

[0150] Example 37 The periodic deposition process according to either Example 1 or 34, wherein the metal-containing material includes, for example, a mixture of In and Ge or other first and / or second metals.

[0151] Example 38 The periodic deposition process according to claim 34, further comprising repeating the steps of supplying a first gas-phase reactant and supplying a second gas-phase reactant until a desired film thickness is achieved.

[0152] Example 39 The periodic deposition process according to Example 34, further comprising one or more purging steps, at least one of which is performed after the step of supplying a first gas-phase reactant and before the step of supplying a second gas-phase reactant.

[0153] Example 40 A periodic deposition process, including an atomic layer deposition process, as described in Example 34.

[0154] Example 41 The periodic deposition process includes periodic chemical vapor deposition, as described in Example 34.

[0155] Example 42 A periodic deposition process as described in Example 34, wherein the temperature in the reaction chamber during the steps of supplying a first gas-phase reactant and supplying a second gas-phase reactant is greater than 0°C and less than 600°C, less than 500°C, less than 400°C, less than 300°C or less than 250°C, or about 20°C to about 700°C, about 50°C to about 500°C, or about 50°C to about 400°C, about 75°C to about 300°C, or about 100°C to about 250°C.

[0156] Example 43 The second metal is selected from the group consisting of Ge, Ga, In, Sn, Al, As, Sb, Pb, and Bi, in the periodic deposition process described in Example 34.

[0157] Example 44 The second metal is selected from the group consisting of Ge, Ga, In, and Sn, in the periodic deposition process described in Example 34.

[0158] Example 45 The second metal is Ge, and the periodic deposition process is as described in Example 34.

[0159] Example 46 The second metal is In, as described in the periodic deposition process in Example 34.

[0160] Example 47 The second metal is Ga, and the periodic deposition process is as described in Example 34.

[0161] Example 48 The periodic deposition process described in Example 34, wherein the metal-containing material comprises one or more of elemental metals, metal mixtures, alloys, and intermetallic compounds.

[0162] Example 49 The periodic deposition process described in Example 34, wherein the metal-containing material is one or more of the following: metallic, conductive, nonconductive, semiconductor, superconductive, catalytic, ferromagnetic, and magnetoresistive.

[0163] Example 50 Compounds having the general formula RMH are those with the formula R (X-n) -M X -H n A periodic deposition process as described in Example 34, wherein the formula is such that X is the formal oxidation state of the metal and n is 1 to 5.

[0164] Example 51 The periodic deposition process described in Example 34, wherein R comprises an alkyl group or another organic group.

[0165] Example 52 The periodic deposition process described in Example 34, wherein R is independently selected from the group consisting of C1-C10 alkyl groups.

[0166] Example 53 A periodic deposition process according to any of Examples 34-52, wherein R is a cyclopentadienyl, amide, alkoxy, amidinate, guanidinato, imide, carboxylate, β-diketonate, β-ketoimate, malonate, or β-dikethyminate group having or not having another donor functionality.

[0167] Example 54 The second gas-phase reactant is a metal reducing agent, as described in Example 34, for the periodic deposition process.

[0168] Example 55 The first metal is selected from the group consisting of transition metals and IUPAC Group 13-15 metals, in the periodic deposition process described in Example 34.

[0169] Example 56 The first metal is selected from the group consisting of Groups 3 to 6, in the periodic deposition process described in Example 34.

[0170] Example 57 The first metal is selected from the group consisting of Groups 7-12, in the periodic deposition process described in Example 34.

[0171] Example 58 The first metal is selected from the group consisting of lanthanides, in the periodic deposition process described in Example 34.

[0172] Example 59 The first metal is selected from the group consisting of Groups 8-11, in the periodic deposition process described in Example 34.

[0173] Example 60 The first metal is selected from the group consisting of Groups 13-15, in the periodic deposition process described in Example 34.

[0174] Example 61 The first gas-phase reactant is selected from the group consisting of metal halides, in the periodic deposition process described in Example 34.

[0175] Example 62 The first gas-phase reactant is M(dmap) x A periodic deposition process as described in Example 34, comprising (dmap = dimethylamino-2-propoxide), where M is a metal.

[0176] Example 63 The first gas-phase reactant is selected from the group consisting of metal hydrides, in the periodic deposition process described in Example 34.

[0177] Example 64 The periodic deposition process described in Example 34, wherein the first gas-phase reactant comprises a diamine adduct of the corresponding metal halide.

[0178] Example 65 The periodic deposition process described in Example 34, wherein the first gas-phase reactant comprises a metal halide compound containing a bidentate nitrogen adduct ligand.

[0179] Example 66 The periodic deposition process described in Example 65, wherein the adduct ligand contains two nitrogen atoms, each nitrogen atom being bonded to at least one carbon atom.

[0180] Example 67 The periodic deposition process according to Example 34, wherein the first gas-phase reactant comprises at least one of cobalt chloride (TMEDA) and nickel chloride (TMPDA).

[0181] Example 68 The second gas-phase reactant comprises one or more TBTH and TBGH in the periodic deposition process described in Example 34.

[0182] Example 69 A film formed according to a periodic deposition process described in any of Examples 1 to 33.

[0183] Example 70 The film is metallic, conductive, semiconductor, or nonconductive, as described in Example 69.

[0184] Example 71 The film is superconducting, as described in Example 69.

[0185] Example 72 The film is magnetoresistive, as described in Example 69.

[0186] Example 73 The film is ferromagnetic, as described in Example 69.

[0187] Example 74 The membrane is a catalyst, as described in Example 69.

[0188] Example 75 A film formed according to a periodic deposition process described in any of Examples 34-68.

[0189] Example 76 The film is the film according to Example 75, comprising one or more of a metal mixture, an alloy, and an intermetallic compound.

[0190] Example 77 A device structure containing a film according to one or more of the examples 69-76.

[0191] The exemplary embodiments of this disclosure described above are merely examples of embodiments of the invention as defined by the appended claims and their legal equivalents, and therefore do not limit the scope of the invention by these embodiments. Embodiments of any equivalent are intended to be within the scope of the invention. In fact, various modifications of this disclosure, in addition to those shown and described herein, such as alternative useful combinations of the elements described, may become apparent from the description. Such modifications and embodiments are also intended to be within the scope of the appended claims.

Claims

[Claim 1] A periodic deposition method for forming a metal-containing material, A step of supplying a first gas-phase precursor from a first gas-phase reactant source container, which is in fluid communication with the reaction chamber, to the reaction chamber in order to form a first metal species, wherein the first gas-phase precursor includes nickel chloride (TMPDA), The process includes the step of supplying a second gas-phase reactant containing tributylgermanium hydride (TBGH) and reacting it with the first metal species to form the metal-containing material, A periodic deposition method wherein the metal-containing material includes Ni₂Ge.

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