Cyclic deposition methods for forming metal-containing materials and films and structures including metal-containing materials - Patents.com

Abstract

Methods for depositing metal-containing materials are disclosed. The methods can include the use of cyclic deposition techniques, such as cyclic chemical vapor deposition and atomic layer deposition. The metal-containing materials can include intermetallic compounds. Structures including the metal-containing materials and systems for forming the materials are also disclosed.

Description

[Technical field]

[0001] Parties to the Joint Research Agreement The invention claimed in this application was made by, for, and / or in connection with a Joint Research Agreement between the University of Helsinki and ASM Microchemistry Oy, which was in effect on or before the date the claimed invention was made, and which was made as a result of activities undertaken within the scope of the Agreement.

[0002] The present disclosure generally relates to methods for depositing metal-containing materials on the surface of a substrate, films and structures including metal-containing materials, and reactors and systems for depositing metal-containing materials. [Background technology]

[0003] Deposition of metal-containing materials can be used to fabricate a variety of 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 often desirable to deposit metal-containing materials onto surfaces that may include three-dimensional features, such as trenches and / or protrusions, which 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 x Ge y ) or cobalt germanide (Co x Ge yThere has been growing interest in the possibility of using metallic materials containing two or more metals such as Co, Ni, and Sn. Intermetallic compounds generally have a specific ordered crystal structure that may differ from alloys formed with the same metals. The specific structure may result in material properties that are superior to those of non-intermetallic compounds. Such properties include, for example, magnetoresistance, superconductivity, catalytic activity, and hydrogen storage capacity. As an example, intermetallic compounds containing Co or Ni and Sn with varying stoichiometry have been investigated as anode materials in Li and Na-ion batteries, as ferromagnetic materials in magnetic devices, and for catalytic purposes.

[0005] Metal-containing materials, including the intermetallic Co3Sn2 and Ni3Sn2 phases of material, e.g., Co-Sn and Ni-Sn of varying stoichiometry, have commonly been prepared by, e.g., ball milling, arc melting, various solution-based techniques, solvothermal and hydrothermal methods, electrodeposition, sputtering, and electron beam evaporation. Chemical vapor deposition (CVD) from two single-source reactants, Me3SnCo(CO)4 and Ph3SnCo(CO)4, was used to deposit alloys of Co and Sn with 1:1 stoichiometry and only a minor component of Co3Sn2. Ni3Sn, Ni3Sn2, and Ni3Sn4 were also deposited by CVD using SnMe4 and Ni substrates, followed by hydrogen treatment at high temperatures. Although such techniques can be used to form intermetallic compounds, they are generally not well suited to forming uniform conformal films of intermetallic materials on the surface of a substrate.

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

[0007] Cyclic deposition techniques, such as atomic layer deposition, can be used to deposit materials conformally, relatively uniformly (e.g., uniform crystal structure, uniform composition, and / or uniform thickness) onto complex three-dimensional structures on a substrate surface in a controlled and reproducible manner. However, such techniques have not been commonly used to deposit some metal-containing materials, including intermetallic compounds and / or Group IIIA metal (IUPAC Group 13 metals) and / or Group IVA metal (IUPAC Group 14 metals) materials. Rather, such compounds and materials are typically formed using separate techniques and / or often require separate high temperature processes. Direct deposition of certain metal-containing films, such as intermetallic compounds or germanides, or other pure metal / metalloid containing films, has been difficult until now.

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

[0009] The discussion of problems provided in this section is included in the present disclosure solely for the purpose of providing a context for the invention, and should not be taken as an admission that any or all of the discussion was known at the time the invention was made. Summary of the Invention

[0010] This Summary is provided to introduce a selection of concepts in a simplified form that are described in further detail below in the Detailed Description of Exemplary Embodiments of this Disclosure. This Summary is not necessarily intended to identify key features 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 the present disclosure, a method for depositing an intermetallic compound is disclosed. According to various aspects, the method is a cyclic deposition process (method) that includes supplying a first gas-phase reactant (also referred to herein as a precursor) containing a first metal to a reaction chamber to react with a 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 to react with the first metal species, thereby forming an intermetallic compound. Similarly, additional reactants can be used to form an intermetallic compound containing three or more metals. As described in more detail below, a film of an intermetallic compound can be formed on a substrate surface without a separate high temperature and / or reduction step. The cyclic deposition process can include, for example, atomic layer deposition.

[0012] In accordance with 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 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 providing a first gas-phase reactant including a first metal to a reaction chamber to form a first metal species, and providing a second gas-phase reactant, where the first and / or second reactant has the general formula RMH (e.g., R (X-n) -M X -H n ), where R is an organic group and M is a metal, reacts with the first metal species, thereby forming 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 embodiments, the metal-containing material includes one or more elemental metals, metal mixtures, alloys, and intermetallic compounds. Films including metal-containing materials can be metallic, conductive, non-conductive, or semiconducting. Exemplary films can be superconducting, magnetoresistive, ferromagnetic, or catalytic.

[0013] In accordance with at least one alternative embodiment of the present disclosure, a first vapor phase reactant including a first metal and a second vapor phase reactant including a second metal (e.g., a compound having the general formula RMH (e.g., R (X-n) -M X -H nA method is provided for delivering a first and / or second gas phase reactant comprising: R is an organic group, X is a formal oxidation state of a metal, n is 1-5, and M is a metal. The method includes providing a second gas phase reactant source vessel 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 vessel to a reaction chamber, heating the second gas phase reactant contained in the second gas phase reactant source vessel 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 the second gas phase reactant of at least 0.001 mbar, and delivering the second gas phase reactant to the reaction chamber.

[0014] In some embodiments of the present disclosure, a reactor system is provided that utilizes a reactive volatile chemical. The reactor system can include a reaction chamber, a first gas phase reactant source vessel in fluid communication with the reaction chamber, and a second gas phase reactant source vessel in fluid communication with the reaction chamber. The first and / or second gas phase reactants can be, for example, of the general formula RMH, e.g., R (X-n) -M X -H n In one embodiment, the compound may include a compound having the formula: (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 over the present disclosure and the prior art, certain objects and advantages may be described herein above. Of course, it should be understood that not all such objects or advantages may be achieved by any particular embodiment of the present disclosure. Thus, for example, one skilled in the art will recognize that an embodiment of the present disclosure may be implemented in a manner that achieves or optimizes one advantage or a group of advantages taught or suggested herein, without necessarily achieving other objects or advantages that may be taught or suggested herein.

[0016] The subject matter of the present disclosure is particularly pointed out and distinctly claimed in the concluding portion of this specification, however, a more complete understanding of the present disclosure can best be obtained by reference to the detailed description and claims when considered in connection with the drawing figures, in which like numerals refer to like elements. [Brief description of the drawings]

[0017] [Figure 1] 1 is a process flow for an exemplary cyclic deposition method in accordance with at least one embodiment of the present disclosure. [Diagram 2] 1 is another process flow for an exemplary cyclic deposition method in accordance with at least one embodiment of the present disclosure. [Diagram 3] 1 is a schematic diagram of an exemplary device structure comprising a deposited metal-containing film in accordance with at least one embodiment of the present disclosure. [Figure 4] 1 is an example of a metal halide compound utilized in a cyclic deposition process according to at least one embodiment of the present disclosure. [Diagram 5] FIG. 1 is a schematic diagram of an exemplary reactor system according to at least one embodiment of the present disclosure. [Figure 6] 1 is an exemplary second gas phase reactant according to at least one embodiment of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] It will be appreciated that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help improve understanding of illustrated embodiments of the present invention.

[0019] The description of exemplary embodiments of the present disclosure provided below is merely exemplary and intended for purposes of explanation only, and the following description is not intended to limit the scope of the invention. Moreover, the recitation of multiple embodiments having described features is not intended to exclude other embodiments having additional features or incorporating different combinations of the described features.

[0020] As described in more detail below, exemplary embodiments of the present 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 that include metal-containing materials. The present disclosure describes in more detail below how it addresses various shortcomings of conventional systems and methods, but generally, the various systems and methods described herein use improved reactants (sometimes commonly referred to as precursors) and / or improved deposition techniques to deposit metal-containing materials with desired properties.

[0021] As used herein, the terms "precursor" and / or "reactant" may refer to one or more gases / vapors that participate in a chemical reaction or from which a gas phase material that participates in a reaction is derived. The chemical reaction may take place in the gas phase and / or between the gas phase and the surface of the substrate and / or with species on the surface of the substrate.

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

[0023] As used herein, the term "cyclic chemical vapor deposition" can refer to any process in which a substrate is sequentially exposed to two or more volatile reactants that react and / or decompose on the substrate to produce a desired material.

[0024] The term "atomic layer deposition" (ALD) as used herein refers to a vapor deposition process in which a deposition cycle, e.g., multiple successive deposition cycles, is carried out in a reaction chamber. Typically, during each cycle, a first reactant is chemisorbed on the surface of the substrate to form a monolayer or submonolayer that does not readily react with another first reactant (i.e., a self-limiting reaction). Another second reactant or reactant gas may then be subsequently introduced into the process chamber for use in converting the chemisorbed material to a desired material. Additionally, a purge step may also be utilized during each deposition cycle to remove excess first reactant from the reaction chamber after conversion of the chemisorbed first and / or second reactants, and / or to remove excess second reactant, reactant gas, and / or reaction by-products from the reaction chamber. Additionally, the term "atomic layer deposition" as used herein is also meant to include processes denoted by related terms, such as chemical vapor deposition atomic layer deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas source MBE, metalorganic MBE, and chemical beam epitaxy when performed with alternating pulses of reactant, reactive gases, and / or purge (e.g., inert carrier) gases.

[0025] The term "substrate" as used herein refers to any material having a surface on which a 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 overlying the bulk material, including chemisorbed species, for example, from exposure of the substrate to TMA. Additionally, the substrate may include 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, defined as the height of the feature divided by the width of the feature, for example, 5 or more, 10 or more, 15 or more, or 20 or more.

[0026] As used herein, the terms "film," "thin film," "layer," and "thin layer" may refer to any continuous or non-continuous material, for example, deposited by the methods disclosed herein. For example, "film," "thin film," "layer," and "thin layer" can 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" can include materials or layers that have 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 that includes at least one metal species.

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

[0029] As used herein, the term "intermetallic" or "intermetallic compound" may refer to a compound containing two or more metallic elements with a defined stoichiometry and ordered crystal structure. Intermetallic compounds differ in crystal structure from metal alloys in that the crystal structure of an intermetallic compound is arranged in a specific configuration, whereas an alloy typically exhibits 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 many example materials are provided throughout this disclosure, and the chemical formulas provided for each of the example materials should not be construed as limiting, nor should the non-limiting example materials provided be limited by any example stoichiometry.

[0031] The present disclosure includes a method for depositing a metal-containing material, e.g., a film of a metal-containing material, on a substrate. The method can be carried out using a cyclic deposition process to deposit a metal-containing material, e.g., a metal-containing film, to form on the substrate. An exemplary method can deposit a metal-containing film, e.g., a film that includes, consists essentially of, or consists of an intermetallic compound, at a relatively low temperature. Additionally or alternatively, the method can deposit a metal-containing material with large area thickness, crystallinity, and / or composition uniformity of a film that includes, consists essentially of, or consists of a metal-containing material.

[0032] 1 illustrates a cyclic deposition method 100 in accordance with at least one embodiment of the present disclosure. Method 100 can be used to form an intermetallic compound, such as a film of an intermetallic compound, on a substrate surface.

[0033] The method 100 begins with step 110, which includes providing at least one substrate in a reaction chamber and heating the substrate to a deposition temperature. The deposition temperature may depend, for example, on the reactant or reactants used to form the intermetallic compound. By way of example, the reaction chamber may be heated to a temperature 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 from about 20° C. to about 700° C., from about 50° C. to about 500° C., or from about 50° C. to about 400° C., from about 75° C. to about 300° C., or from about 100° C. to about 250° C. As a specific example, the intermetallic compound may include Co3Sn2, in which case the temperature may range from about 170° C. to about 200° C. Similarly, if the intermetallic compound includes Ni3Sn2, the temperature may range from about 125° C. to about 175° C., or from about 140° C. to about 160° C. The pressure in the reaction chamber may be controlled to provide a desired pressure in the reaction chamber for the deposition process. For example, the pressure in the reaction chamber during the cyclic deposition process may be less than 1000 mbar, or less than 100 mbar, or less than 10 mbar, or less than 5 mbar, or in some cases less than 1 mbar, or about 10 -8 mbar~approx. 1000mbar, approx. 10 -3 mbar~about 100mbar, about 10 -2 It may be from about 0.1 mbar to about 50 mbar, or from about 0.1 mbar to 10 mbar.

[0034] Method 100 may continue with step 120, which includes supplying a first gas phase reactant including a first metal to the reaction chamber and reacting with the surface of the substrate to form a first metal species. This step may be at the same pressure and temperature as described above in connection with step 110. The pulse time or the time that the first gas phase reactant is supplied to the reaction chamber may range, for example, from about 0.01 seconds to about 60 seconds, or from about 0.05 seconds to about 10 seconds, or from 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 100 sccm, or may range from about 1 to about 5000 sccm, from about 5 to about 2000 sccm, or from about 10 to about 1000 sccm.

[0035] After the step of providing 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 purge / pump process (step 125). The duration of step 125 may be, for example, from about 0.01 seconds to about 60 seconds, or from about 0.05 seconds to about 10 seconds, or from 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 100 sccm, or may range from about 1 to about 5000 sccm, from about 5 to about 2000 sccm, or from about 10 to about 1000 sccm. Although illustrated separately, step 125 may be considered as part of step 120.

[0036] The method 100 may continue with step 130 of supplying a second gas phase reactant including a second metal to the reaction chamber to react with the first metal species, thereby forming an intermetallic compound. This step may be at the same or different pressure and / or temperature as described above in connection with step 110. The pulse time or the time that the second gas phase reactant is supplied to the reaction chamber may range from about 0.01 seconds to about 60 seconds, or from about 0.05 seconds to about 10 seconds, or from about 0.1 seconds to about 5 seconds. The flow rate of the second gas phase reactant during step 130 may be the same as or similar to the flow rate during step 120 described above.

[0037] As illustrated in FIG. 1 , when the second gas-phase reactant reacts with the species on the substrate surface, an intermetallic compound is formed (step 140), e.g., a film that includes, consists essentially of, or consists of an intermetallic compound.

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

[0039] Steps 120 and 130 (as well as optional purging steps 125 and / or 145) may comprise one deposition cycle. In some embodiments of the present disclosure, method 100 may include repeating the deposition cycle one or more times. For example, method 100 may continue with decision gate 150, which determines whether cyclic deposition method 100 continues through step 160 or ends. Decision gate 150 can be determined based on the thickness or amount of intermetallic compound deposited. For example, if the thickness of the intermetallic compound is insufficient for the desired device structure, method 100 may return to step 120 and may repeat steps 120-145. Once the intermetallic compound has been deposited to the desired thickness or amount, the method may end at step 160, and the substrate may undergo another process to form one or more devices or device structures.

[0040] According to various embodiments of method 100, an intermetallic compound is formed when a second gas phase reactant is reacted with the first metal species that forms on the surface during step 120. Thus, an intermetallic compound or a layer or film that comprises, consists essentially of, or consists of an intermetallic compound can be formed without a separate reduction and / or heating step. Moreover, as noted above, the intermetallic compound can be formed at relatively low temperatures.

[0041] The first gas-phase reactant can include any first metal that is different from the second metal. By way of example, the first metal can be or include a transition metal (e.g., a Group 3-12 metal), a Group 3-6 metal, a Group 7-12 metal, a Lanthanide metal, a Group 8-11 metal, and / or a Group 9-10 metal, or a Group 13-15 metal, where the Group numbers refer to IUPAC Group numbers.

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

[0043] The first gas-phase reactant may be or include a metal halide compound, and the metal is or includes a first metal. The metal halide compound may include a metal chloride, a metal iodide, a metal fluoride, or a metal bromide. In some embodiments of the present disclosure, the metal halide compound may include a metal species including, but not limited to, at least one of cobalt, nickel, or copper. In some embodiments of the present disclosure, the metal halide compound may include at least one of nickel chloride, cobalt chloride, and copper chloride. In some embodiments, the metal halide compound may include a bidentate nitrogen-containing adduct-forming ligand. In some embodiments, the metal halide compound may include an adduct-forming ligand that includes two nitrogen atoms (e.g., a diamine adduct of the corresponding metal halide), where each of the nitrogen atoms is bonded to at least one carbon atom. In some embodiments of the present disclosure, the metal halide compound includes 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 FIG. 4. Alternative first vapor phase reactants can include adduct forming ligands that contain 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 a nitrogen-containing adduct forming ligand, such as a nitrogen-containing monodentate, bidentate, or polydentate adduct forming ligand. In some embodiments, the first gas phase reactant may include a transition metal compound having a phosphorous, oxygen, or sulfur-containing adduct forming ligand, such as a phosphorous, oxygen, or sulfur-containing monodentate, bidentate, or polydentate adduct forming ligand. 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 a transition metal species including, but 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 that includes two nitrogen atoms, where each of the nitrogen atoms 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 the present disclosure, the first vapor phase reactant may include a transition metal compound having the formula: (adduct) n -M-Xa wherein each of the "adducts" is an adduct-forming ligand and can be independently selected to be a monodentate, bidentate, or polydentate adduct-forming ligand or mixture thereof, where for a monodentate forming ligand, n is 1-4, and for a bidentate or polydentate adduct-forming ligand, n is 1-2; M is a transition metal such as, for example, cobalt (Co), copper (Cu), or nickel (Ni); and each of the Xa is another ligand and can be independently selected to be a halide or other ligand, where a is 1-4, and in some examples, a is 2.

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

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

[0048] In some embodiments of the present disclosure, the adduct forming ligands include nitrogen, such as amine, diamine, or polyamine adduct forming ligands. In such embodiments, the transition metal compound may be selected from the group consisting of 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), triethylenetetramine (CAS:112-24-3)(TRIEN), tris(2-aminoethyl)amine (CAS:4097-89-6)(TREN, TAEA), 1,1,4,7,10,10-hexamethyltriethylenetetramine (CAS:3083-10-1)(H 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 comprises a phosphorous acid, such as a phosphine, diphosphine, or polyphosphine adduct-forming ligand. For example, the transition metal compound may comprise 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 comprises oxygen, such as an ether, diether, or polyether adduct-forming ligand. For example, the transition metal compound can comprise 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 ether amine, 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 can include cobalt chloride N,N,N',N'-tetramethyl-1,2-ethylenediamine (CoCl2(TMEDA)). In some embodiments, the transition metal halide compound can include cobalt bromide tetramethylethylenediamine (CoBr2(TMEDA)). In some embodiments, the transition metal halide compound can include cobalt iodide tetramethylethylenediamine (Col2(TMEDA)). In some embodiments, the transition metal halide compound can 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 suitable first gas phase reactants may be substantially free of halogen species. A first gas phase reactant that is substantially free of halogen species (non-halogen-containing metal precursor) has a M(dmap) x (dmap = dimethylamino-2-propoxide), 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] Thus, in some embodiments, the halogen-free metal precursor can include at least one bidentate ligand, in which the central metal atom is bonded through at least one oxygen and at least one nitrogen atom in the bidentate ligand. Thus, in some embodiments, the halogen-free metal precursor can include at least one bidentate ligand, in which the central metal atom is bonded through at least one nitrogen atom in the bidentate ligand. Thus, in some embodiments, the halogen-free metal precursor can include at least one bidentate ligand and at least one other ligand, such as a monodentate ligand. Thus, in some embodiments, the halogen-free metal precursor can include at least one bidentate ligand and at least two other ligands, such as a monodentate ligand, that are bonded to the central metal atom through N or O. Thus, in some embodiments, the halogen-free metal precursor can include at least one bidentate ligand and at least one other ligand, such as a monodentate ligand that is bonded to the central metal atom through N or O. Thus, in some embodiments, the halogen-free metal precursor may include at least one bidentate ligand, in which the central metal atom is bonded through at least one nitrogen atom and at least one atom other than the nitrogen of the bidentate ligand. Thus, in some embodiments, the halogen-free metal precursor may include at least one bidentate ligand, in which the central metal atom is bonded through 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 examples of suitable non-halogenated containing β-diketiminato (e.g., Ni(pda)2), (pda=pentane-2,4,-diketiminato) compounds include at least one β-diketiminato ligand and have the general formula: [ka] where M is a metal selected from nickel, cobalt, ruthenium, iridium, palladium, platinum, silver, and gold. 1~5Each of is an organic ligand independently selected from H and a C1-C4 linear or branched alky, alkylsilyl, alkylamide, alkoxide, or alkylsilylamide group. Each L is independently selected from a hydrocarbon, an oxygen-containing hydrocarbon, an amine, a polyamine, a bipyridine, an oxygen-containing heterocycle, a nitrogen-containing heterocycle, and combinations thereof, and n is an integer ranging from 0 to 4. A specific example includes Ni(pda)2.

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

[0057] In one or more embodiments, the precursors of monovalent metals include volatile metal(I) amides, [M(I)(AMD)]x, where x=2, 3. Some of these compounds have the dimeric structure 1, [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 non-metallic 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 groups, or other non-metallic atoms or groups. In some embodiments, R 1 , R 2 , R 3 , R 1 ', R 2 ', and R 3 Each ' is independently an alkyl group containing 1 to 4 carbon atoms, or a fluoroalkyl group, or a silylalkyl group. 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 includes R as the isopropyl group in general formula 1. 1 , R 2 , R 1’ , and R 2’ and R as a methyl group. 3 and R 3’ In one or more embodiments, the metal(I) amidinate is a trimer having the general formula [M(I)(AMD)].

[0058] In one or more embodiments, the divalent metal precursor is a volatile metal(II) bis-amidinate, [M(II)(AMD)] x , (wherein x=1, 2). These compounds may have the monomer 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 non-metallic atoms. In one or more embodiments, dimers of this structure may also be used, e.g., [M(II)(AMD)2]2. In some embodiments, R 1 , R 2 , R 3 , R1’ , R 2’ , and R 3’ may be independently selected from hydrogen, alkyl, aryl, alkenyl, alkynyl, trialkylsilyl, or fluoroalkyl groups, or other non-metallic atoms or groups. In some embodiments, R 1 , R 2 , R 3 , R 1 ', R 2 ', and R 3 Each ' is independently an alkyl group containing 1 to 4 carbon atoms, or a fluoroalkyl group, or a silylalkyl group. 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 includes R as the isopropyl group in general formula 2. 1 , R 2 , R 1’ , and R 2’ and R as a methyl group. 3 and R 3’ This includes cobalt(II) bis(N,N'-diisopropylacetamidinate), which corresponds to the above.

[0059] The precursor of the trivalent metal(s) includes volatile metal(III) tris-amidinates, M(III)(AMD). Typically, these compounds have the 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’’ is a group consisting of one or more non-metallic 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 lanthanum 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, which includes R as the t-butyl group in general formula 3. 1 , R 2 , R 1’ , R 2’ , R 1’’ , and R 2’ R as a methyl group 3 , R 3’ , and R 3’’ This includes lanthanum(III) tris(N,N'-di-t-butylacetamidinate), which corresponds to the above.

[0060] As used herein, metal amidinates that have the same ratio of metal to amidinate as the monomer, but vary in the total number of metal amidinate units in the compound, are referred to as "oligomers" of the monomeric compound. Thus, oligomers of the monomeric compound M(R)AMD2 include [M(II)(AMD)2] x, where x=2, 3, etc. Similarly, oligomers of the monomeric compound M(I)AMD include [M(I)AMD] x , (where 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]), cobalt bis(N,N'-di-tert-butylacetamidinate) ([Co(tBu-AMD)2]), lanthanum tris(N,N'-diisopropylacetamidinate) ([La(iPr-AMD)3]), lanthanum tris(N,N'-diisopropyl-2-tert-butylamidinate) ([La(iPr-tBuAMD)3].1 / 2CH 12 ), bis(N,N'-diisopropylacetamidinato)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'-diisopropylacetamidinate) ([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), bismuth tris(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 Pr-AMD)3]).

[0062] Some examples of suitable non-halogenated, including iminoalkoxide compounds are represented by the formula: [ka] wherein M is a metal selected from Groups 2-12 of the Periodic Table. R1, R2, R3, and R4 are each independently H or C1-C8 alkyl. In one embodiment, R1, R2, R3, and R4 are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or t-butyl. In another embodiment, M is Cu, Cr, Mn, Fe, Co, or Ni. Specific examples of compounds having this formula include bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-oleate)nickel(II), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-oleate)cobalt(II), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-oleate)iron(II), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-oleate)manganese(II), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-oleate)chromium(II), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-oleate)chromium(II), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-oleate) bis(1-(tert-butylimino)-2,3-dimethylbutan-2-oleate)copper(II), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-oleate)nickel(II), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-oleate)cobalt(II), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-oleate)iron(II), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-oleate)copper(II), bis(3-((tert-butylimino)methyl)-2,2,4,4-tetramethylpentan-3-oleate)manganese(II), bis(3-((tert-butylimino)methyl)-2,2,4,4-Tetramethylpentane-3-olate) copper(II), bis(3-(isopropylimino)-2-methylbutane-2-olate) nickel(II), bis(3-(isopropylimino)-2-methylbutane-2-olate) cobalt(II), bis(3-(isopropylimino)-2-methylbutane-2-olate) iron(II), bis(3-(isopropylimino)-2-methylbutane-2-olate) manganese(II), bis(3-(isopropylimino)-2-methylbutane-2-olate) chromium(II), bis(3-(isopropylimino)-2-methylbutane-2-olate) copper(II), bis(3-(2,2- bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate)nickel(II), bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate)cobalt(II), bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate)iron(II), bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate)manganese(II), bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate)chlorium(II), and bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate)copper(II). 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-trimethylbutan-2-olate)chromium(II), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-olate)copper(II), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-olate)nickel(II), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-olate)cobalt(II), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-olate)iron(II), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-olate)copper(II), bis(3-((tert-butylimino)methyl)-2,2,4,4-tetramethylpentan-3-olate)manganese(II), bis(3-((tert-butylimino)methyl)-2,2,4,4-tetramethylpentan-3-olate)copper(II), bis(3-(isopropylimino)-2-methylbutan-2-olate)cobalt(II), bis(3-(isopropylimino)-2-methylbutan-2-olate)iron(II), bis(3-(isopropylimino)-2-methylbutan-2-olate)manganese(II), bis(3-( isopropylimino)-2-methylbutan-2-olate) chromium(II), bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate) nickel(II), bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate) cobalt(II), bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate) iron(II), bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate) manganese(II), bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate) chlorium(II), bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate) 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 may change under different conditions, such as at 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, and 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 may be selected from the group consisting of copper β-diketonate compounds, copper β-diketiminato compounds, copper aminoalkoxide compounds such as Cu(dmae)2, Cu(deap)2 or Cu(dmamb)2, copper amidinate compounds such as 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 typically but not necessarily 2 or 3, and thd is 2,2,6,6-tetramethyl-3,5-heptanedionato. In some embodiments, the halide-free copper precursor is copper(II) acetate, [Cu(HMDS)] or Cu(nhc)HMDS (1,3-di-isopropyl-imidazolin-2-ylidenecopper hexamethyldisilazide), or a Cu-β-diketiminate, such as Cu(dki)VTMS (dki = diketiminate).

[0065] In some embodiments, the halide-free nickel precursor can be, for example, bis(4-N-ethylamino-3-pentene-2-N-ethyliminonato)nickel(II). In some embodiments, the nickel precursor can be selected from the group consisting of nickel β-diketonate compounds, nickel β-diketiminato 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 typically but not necessarily 2 or 3, and thd is 2,2,6,6-tetramethyl-3,5-heptanedionato.

[0066] In some embodiments, the Co precursor is a Coβ-diketoiminate compound. In some embodiments, the Co precursor is a Co ketoiminate compound. In some embodiments, the Co precursor is a Co amidinate compound. In some embodiments, the Co precursor is a Coβ-diketoiminate compound. In some embodiments, the Co precursor comprises at least one ketoimine ligand or derivative thereof. In some embodiments, the Co precursor comprises at least one amidine ligand or derivative thereof. In some embodiments, the Co precursor comprises at least one ketonate ligand or 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 may be or include 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, for example, N,N,N',N'-tetramethyl-1,3-propanediamine, such as NiCl2(TMPDA) and CoCl2(TMPDA), and / or the first gas phase reactant may be or include 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, for example, N,N,N',N'-tetramethyl-1,2-ethylenediamine, such as CoCl2(TMEDA) and NiCl2(TMEDA). Metal hydrides, such as alanes, may be used as the first gas phase reactant (e.g., for hydride-hydride type reactions).

[0068] The second gas phase reactant used in the method 100 can include a metal-containing organic compound, an organometallic, or a metal-organic compound. For example, the second gas phase reactant can be a compound of the formula RMH (e.g., R (X-n) -M X -H n) where R is an organic group and M is a metal, and 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 range from 1 to 5. As specific examples, M can be or include Ge, Ga, In, Sn, As, Sb, Pb, and Bi. Or, M can include Al. For example, M can include Ge, Ga, In, and / or Sn. R can be or include an alkyl group, or a cyclopentadienyl, amido, alkoxy, amidinato, guanidinato, imido, carboxylato, β-diketonato, β-ketoiminato, malonato, β-diketiminato group, with or without another 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 vapor phase reactant (e.g., an RMH compound) can be a metal reducing agent. Figure 6 shows an example of a particular second vapor phase reactant of tributyl metal hydride, where M can be any metal described herein, such as, for example, tributyl germanium hydride (TBGH).

[0069] As described herein, intermetallic films that consist essentially of, or consist of, intermetallic compounds, such as Co3Sn2 or Ni3Sn2, can exhibit magnetic hysteresis with high coercivity values ​​of over 500 Oe. The resistivity of such films (as well as films formed according to method 200) can range from about 10 to about 10, depending on the thickness and / or stoichiometry of the film. 6 μΩcm, 20-10 4 The resistivity can range from 0.1 μΩcm, or from 50 to 1000 μΩcm, e.g., from 80 to 180 μΩcm. Additionally, the Ni3Sn2 thin films formed according to method 100 exhibit an intermetallic crystal structure and high purity. Exemplary intermetallic compounds and films can be used in a variety of applications including, for example, magnetoresistive devices, superconducting devices, as catalysts, as energy (e.g., hydrogen) storage, and the like.

[0070] FIG. 2 illustrates another cyclical deposition method 200 according to at least one embodiment of the present disclosure. Method 200 can be used to deposit metal-containing materials, for example, to form a film or layer that includes, consists essentially of, or consists of a metal-containing material. The metal-containing material can include any of the intermetallic compounds described above, as well as other metal-containing compounds described herein. When a film (e.g., formed by either method 100 or 200) consists essentially of, or consists of, an intermetallic compound, the film may exhibit superior properties as described herein. However, unless otherwise specified, the films, methods, structures, devices, and systems are not limited to intermetallic compounds.

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

[0072] Method 200 may continue with step 220, which includes providing a first gas phase reactant, such as any of the first gas phase reactants described above. This step may be at the same pressure and temperature as those described above in connection with step 210. The pulse time or the time that the first gas phase reactant is delivered to the reaction chamber may range from about 0.01 seconds to about 60 seconds, or from about 0.05 seconds to about 10 seconds, or from 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 100 sccm, or may range from about 1 to about 5000 sccm, from about 5 to about 2000 sccm, or from about 10 to about 1000 sccm.

[0073] After step 220 of providing 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 purge / pump 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 may range from about 1 to about 5000 sccm, from about 5 to about 2000 sccm, or from 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 providing a second gas-phase reactant comprising a compound having the general formula RMH, where R is an organic group and M is a metal, to react with the first metal species (e.g., on the substrate surface), thereby forming a metal-containing material. The compound having the general formula RMH can be the same as described above. The pulse time or the time that the second gas-phase reactant is provided to the reaction chamber can range from about 0.01 seconds to about 60 seconds, or from about 0.05 seconds to about 10 seconds, or from about 0.1 seconds to about 5 seconds. During step 230, the flow rate of the second gas-phase reactant can 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 can range from about 1 to about 5000 sccm, from about 5 to about 2000 sccm, or from about 10 to about 1000 sccm.

[0075] As illustrated in FIG. 2, when the second gas-phase reactant reacts with species on the substrate surface, a metal-containing material is formed, e.g., a film that includes, consists essentially of, or consists of a metal-containing material.

[0076] After step 230, any excess second gas phase reactant and any reaction by-products may be removed from the reaction chamber by a purge / pump process (step 245). The flow rate of the purge gas can be the same as in step 225 above. Additionally, although illustrated separately, step 245 can 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 connection with Figure 1. For example, the steps can be repeated until a desired film thickness or amount of metal-containing material has been deposited on the substrate.

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

[0079] As a particular example, the metal-containing material deposited using method 200 can include 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 an exemplary embodiment of these examples, the first gas phase reactant includes a metal halide, such as a diamine adduct corresponding to the metal halide, such as the metal halide described above, and the second gas phase reactant includes a compound having the general formula of RMH described above. The temperature during the deposition process to form the M-Ge, M-Ga, and / or M-In metal-containing film can range from about 150° C. to about 250° C., about 160° C. to 200° C., or between the sublimation temperature and the decomposition temperature of the first and second reactants. The metal-containing material can be formed without an annealing process at a temperature below 400° C. and / or using only the first gas phase reactant, the second gas phase reactant, and an optional purge 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 less than 1 atomic % of total contaminants (e.g., non-metallic materials) and less than 0.1 atomic % of any halide contaminants. It is believed that the first and second gas-phase reactants described herein undergo rapid and complete (or near complete) reactions, thereby leaving relatively little contamination in the formed material. Due to their high degree of purity, the exemplary materials and films described herein exhibit low resistivity, which may 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 resistivity and thus may be used as contact layers in electronic device structures.

[0080] As mentioned above, Ni x Ge y and Co x Ge y The resistivity of films formed according to the method 200, such as metal germanide films, may range from about 10 to about 10 based on film thickness and / or stoichiometry. 6 μΩcm, 20-10 4μΩcm, or may be in the range of 50 to 1000 μΩcm, for example 80 to 180 μΩcm.

[0081] According to some embodiments of the present disclosure, the method 100 and / or the method 200 can include atomic layer deposition (ALD). ALD is based on a typical self-limiting reaction whereby sequential and alternating pulses of reactants are used to deposit approximately one atomic (or molecular) monolayer of material per deposition cycle. 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 termination unreactive with the gas-phase reactant of the same reactant. The substrate is then contacted with a different reactant that reacts with the previous termination, allowing for successive depositions. Thus, each cycle of alternating pulses typically leaves approximately one monolayer or less of the desired material. However, as described above, in one or more ALD cycles, multiple monolayers of material can be deposited, for example, if some gas-phase reactions occur despite the nature of the alternating process.

[0082] In some embodiments, a cyclical deposition process is used to form a metal-containing film on a substrate, and the cyclical deposition process can be an ALD-type process. In some embodiments, the cyclical deposition can be a hybrid ALD / CVD or cyclical CVD process. For example, in some embodiments, the growth rate of an ALD process can be low compared to a CVD process. One approach to increase the growth rate is to operate at a higher substrate temperature than typically used in an ALD process, resulting in a chemical vapor deposition process, but which may further utilize sequential introduction of reactants. Such a process may be referred to as a cyclical CVD.

[0083] The cyclic deposition processes described herein may be carried out in an ALD or CVD deposition system. For example, in some embodiments, the method may include heating the substrate to a temperature of about 80° C. to about 150° C., or further heating the substrate to a temperature between about 80° C. to about 120° C., or about 150° C. to about 250° C., or between about 160° C. to 200° C. Of course, the appropriate temperature window for any given cyclic deposition process, such as an ALD reaction, will depend on the surface termination and reactant species involved, where the temperature varies depending on the reactants used and is generally about 700° C. or less. In some embodiments, for vapor deposition processes, the deposition temperature is generally about 100° C. or more, in some embodiments, the deposition temperature is about 100° C. to about 300° C., and in some embodiments, the deposition temperature is about 120° C. to about 200° C. In some embodiments, the deposition temperature is less than about 500° C., or less than about 400° C., or less than about 350° C., or less than about 300° C. In some cases, the deposition temperature may be less than about 300° C., less than about 200° C., or less than about 100° C. In some cases, the deposition temperature may be greater than about 20° C., greater than about 50° C., and greater 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 those temperatures described above in connection with methods 100 and 200.

[0084] As shown in Figures 1 and 2, cyclic processes including ALD processes may include purge steps, such as purge steps 125, 145, 225, and 245 described above. Purge gases used during such steps may include one or more inert gases, such as argon (Ar) or nitrogen (N2), to prevent or mitigate gas-phase reactions between reactants between process steps and to allow self-saturating surface reactions. However, in some embodiments, the substrate may additionally or alternatively be moved (e.g., to separate reaction chambers) to contact the first and second gas-phase reactants separately. Thus, steps 120 / 130 and / or steps 220 / 230 need not be performed in the same reaction chamber. Additionally or alternatively, a vacuum pump may be used to facilitate purging.

[0085] Of course, in some embodiments of the present disclosure, the order of providing the first gas-phase reactant and providing the second gas-phase reactant may be such that the substrate is first contacted with the second gas-phase reactant followed by contact with the first gas-phase reactant. In other words, steps 120, 130, and 220, 230 may be reversed. Furthermore, in some embodiments, the cyclic deposition process may include contacting the substrate with the first gas-phase reactant one or more times before contacting the substrate with the second gas-phase reactant one or more times, or equivalently, contacting the substrate with the second gas-phase reactant one or more times before contacting the substrate with the first gas-phase reactant one or more times.

[0086] At least some embodiments of the present disclosure (e.g., methods 100 and / or 200) may be free of plasma reactants, e.g., the first and second gas phase reactants are substantially free of ionized reactive species. In some embodiments, the first and second gas phase reactants are substantially free of ionized reactive species, excited species, and radical species. For example, both the first and second gas phase reactants may be free of plasma reactants to prevent ionization damage of the underlying substrate and associated defects thereby generated. The use of non-plasma reactants may be particularly useful when the underlying substrate includes fragile fabricated or at least partially fabricated semiconductor device structures, as energetic plasma species may damage and / or degrade performance characteristics of the device.

[0087] 2, in some embodiments of the present disclosure, the exemplary method of the present disclosure may include another process step that includes contacting the substrate with a third gas phase reactant that includes a reducing agent. In some embodiments, the reducing agent is 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 butyl hydrazine (C4H 12 The reactant may include at least one of a selenium reactant, a boron reactant, a phosphorous reactant, a sulfur reactant, an organic reactant (e.g., an alcohol, an aldehyde, or a carboxylic acid), or a hydrogen reactant. In some embodiments of the present disclosure, the exemplary cyclic deposition method of the present disclosure may include contacting the substrate with a second gas-phase reactant that is a reducing agent (without any additional precursor / reactant contacting step). However, as noted above, according to at least some examples, no reducing agent or reduction reaction (other than the second reactant) is required to form the desired material, e.g., an intermetallic material.

[0088] When used, a third gas-phase reactant including a reducing agent may be introduced into the reaction chamber and contacted with the substrate at some process stages of the exemplary cyclical deposition method. In some embodiments of the present disclosure, the reducing agent may be introduced into the reaction chamber and contacted 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 contacted with the substrate before contacting the substrate with the first gas-phase reactant, after contacting the substrate with the first gas-phase reactant and before contacting the substrate with the second gas-phase reactant, and / or after contacting the substrate with the second gas-phase reactant. In some embodiments of the present disclosure, the reducing agent may be introduced into the reaction chamber and contacted 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 contact the substrate simultaneously, and / or the reducing agent and the second gas-phase reactant may flow into the reaction chamber simultaneously and contact the substrate simultaneously.

[0089] In some embodiments, the growth rate of the metal-containing material and / or the intermetallic compound 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 the metal-containing material and / or the intermetallic compound 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 the metal-containing material and / or the intermetallic compound 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 the present disclosure, the growth rate of the metal-containing material and / or the intermetallic compound may be about 0.4 Å / cycle or about 0.9 Å / cycle. As a specific example, Co3Sn 2の場合The growth rates range from about 0.7 to 1.3 Å / cycle at deposition temperatures of about 170 to 200 °C, and for Ni3Sn2, a growth rate of about 1.3 Å / cycle was observed at 160 °C when NiCl2(TMPDA) was used as the first gas-phase reactant. x Ge y For films, growth rates range between about 0.18 and 1.3 Å / cycle at deposition temperatures between about 157 and 200 °C when NiCl2(TMPDA) is used as the first gas-phase reactant.

[0090] FIG. 3 illustrates a structure 300 comprising a substrate 302 and a layer or film 304. The structure 300 can be or comprise a partially fabricated device structure. As described above, the substrate 302 can comprise a bulk material, such as a bulk semiconductor material, and layers formed thereon and / or therein. The film 302 can comprise an intermetallic or metal-containing material, such as an intermetallic or metal-containing material deposited according to embodiments described herein. In some embodiments, the film 304 can be continuous at 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 less. The continuity referred to herein can be physical continuity or electrical continuity. In some embodiments, the thickness at which the film 304 can be physically continuous may not be the same as the thickness at which the film is electrically continuous, and the thickness at which the film 304 can be electrically continuous may not be the same as the thickness at which the film is physically continuous.

[0091] In some embodiments, the intermetallic and / or metal-containing films (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 and / or metal-containing films 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 and / or metal-containing films deposited according to some of the embodiments described herein may have a thickness of greater than about 20 nanometers, or greater than about 30 nanometers, or greater than about 40 nanometers, or greater than about 50 nanometers, or greater than about 60 nanometers, or greater than about 100 nanometers, or greater than about 250 nanometers, or greater than about 500 nanometers. In some embodiments, the intermetallic and / or metal-containing films 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 and / or metal-containing films may be deposited on three-dimensional structures, such as non-planar substrates including high aspect ratio features. In some embodiments, the step coverage of the intermetallic 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 more, in structures with aspect ratios (height / width) greater than about 2, greater than about 5, greater than about 10, greater than about 25, greater than about 50, or even greater than about 100.

[0093] The intermetallic compound and / or metal-containing material or its corresponding film includes a first metal and a second metal as described herein. As a specific example, the first metal can include Ni, Co, Pt, or any of the other first metals described herein, and the second metal can include Ge, Ga, In, Sn, As, Sb, Pb, and Bi (e.g., Ge, Ga, In, Sn), or any of the other second metals described herein, including Al. In some cases, the first metal does not include 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 The intermetallic compounds and / or metal-containing compounds may also have other stoichiometries or other crystal structures, which may 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, and one or more of Ge, Ga, In, Sn, As, Sb, Pb, Al, and Bi. In some cases, the films including intermetallic compounds and / or metal-containing materials do not include Al, Ga, and / or In, and transition metals.

[0094] In some embodiments of the present disclosure, the intermetallic compounds and / or metal-containing materials and / or films, including the same, as described herein, may contain less than about 5 atomic % oxygen, less than about 2 atomic % oxygen, less than about 1 atomic % oxygen, or less than about 0.5 atomic % oxygen. In another embodiment, the compound, material, or film may contain less than about 5 atomic % hydrogen, or less than about 2 atomic % hydrogen, or less than about 1 atomic % hydrogen, or even less than about 0.5 atomic % hydrogen. In yet another embodiment, the compound, material, or film may contain less than about 5 atomic % carbon, or less than about 2 atomic % carbon, or less than about 1 atomic % carbon, or even less than about 0.5 atomic % carbon. In yet another embodiment, the compound, material, or film may contain less than about 5 atomic % halide species, or less than about 2 atomic % halide species, or less than about 1 atomic % halide species, or less than about 0.5 atomic % halide species, or even less than about 0.1 atomic % halide species. Additionally, the total contamination of species (other than the desired metal) may be less than about 5 atomic %, or less than about 2 atomic %, or less than about 1 atomic %. In some embodiments, the atomic % of intermetallic compounds, metal-containing materials, and films containing the same may be determined utilizing Time-of-Flight Elastic Recoil Detection (ToF-ERDA).

[0095] Reactors that can be used to deposit metal-containing films can be used to form the intermetallic compounds, metal-containing materials, and films described herein. Such reactors include ALD reactors with appropriate devices and means for supplying reactants, as well as CVD reactors. According to some embodiments, hot-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 equipment, such as Pulsar® reactors (e.g., Pulsar® 2000, Pulsar® 3000, and Pulsar® XP ALD, etc.), and EmerALD® XP and EmerALD® reactors, available from ASM America, Inc., Phoenix, Arizona, and ASM Europe BV, Almere, The Netherlands. Other commercially available reactors include reactors under the trade names 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 the present disclosure, a batch reactor may be used. Suitable batch reactors include, but are not limited to, Advance® 400 series reactors available from ASM Europe BV (Almere, The Netherlands) under the trade names A400 and A412PLUS. In some embodiments, the wafer rotates during processing. In other embodiments, the batch reactor comprises a mini-batch reactor configured to accommodate 10 or less substrates (e.g., semiconductor wafers), 8 or less substrates, 6 or less substrates, 4 or less substrates, or 2 or less substrates. In some embodiments where a batch reactor is used, the wafer-to-wafer non-uniformity 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 be optionally performed in a reactor or reaction chamber connected to a cluster tool. In a cluster tool, each reaction chamber can be dedicated to one type of process, so the temperature of the reaction chambers in each module can be kept constant, improving throughput compared to reactors that heat the substrate to a process temperature before each run. Additionally, a cluster tool can reduce the time to evacuate the reaction chamber to a desired process pressure level between substrates. In some embodiments of the present disclosure, the deposition process can be performed in a cluster tool including multiple reaction chambers, each individual reaction chamber can be used to expose the substrate to an individual reactant gas, and the substrate can be transported between different reaction chambers to be exposed to multiple reactant gases, with the substrate transport being performed under a controlled environment to avoid oxidation / contamination of the substrate. In some embodiments of the present disclosure, the deposition process can be performed in a cluster tool with multiple reaction chambers, each individual reaction chamber can be configured to heat the substrate to a different deposition temperature.

[0099] A stand-alone reactor is equipped with a load lock, in which case there is no need to cool the reaction space between each run.

[0100] 5 illustrates a schematic of a reactor system 500 in accordance with at least one embodiment of the present disclosure. The reactor system 500 can be used, for example, to perform cyclic deposition (e.g., ALD) methods described herein and / or to form structures, films, compounds, and / or materials described herein.

[0101] In the illustrated example, the reactor system 500 includes an optional substrate handling system 502, a reaction chamber 504, a gas distribution system 506, and optionally a wall 508 disposed between the reaction chamber 504 and the substrate handling system 502. The system 500 can also include 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 illustrated, the reactor system 500 can include any suitable number of reactant gas sources. By way of example, the illustrative reactor system can include at least two reactant gas sources (e.g., sources including compounds that become the first or second gas phase reactants), as well as one or more carrier gas and / or purge gas sources 516, as required. The reactor system 500 also includes a susceptor 518 that holds one or more substrates 520 during processing.

[0102] The reactor system 500 may include any suitable number of reaction chambers 104 and a substrate handling system 502. By way of example, the reaction chambers 504 of the reactor system 500 include a cross-flow hot-wall epitaxial reaction chamber. An exemplary reactor system including a horizontal flow reactor is available as a system from ASM.

[0103] It should be noted that FIG. 5 is a simplified schematic version of reactor system 500 and does not include all of the elements that may be utilized in 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 source vessels 522, 524 are in fluid communication with the reaction chamber 504 through conduits or other suitable means 526, 528 and may be further coupled to a gas distribution system 506 disposed between the reactant source vessels 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 from the reactant source vessels 522 or 524. The reactant source vessels 522, 524 may be configured to store metal-containing compounds (e.g., organometallic compounds or metal-organic compounds) that are, or become, first and second gas phase reactants, respectively, upon heating. In some embodiments, the reactant source vessels 522, 524 may comprise a quartz material, which may be substantially chemically inert to the respective first and second reactants stored in the source vessels 522, 524. In another embodiment of the present disclosure, the reactant source vessels 522, 524 may be fabricated from a corrosion resistant metal or metal alloy, such as, for example, Hastelloy, Monel, or combinations thereof.

[0105] In some embodiments of the present disclosure, the reactant source vessels 522, 524 may further comprise one or more heating elements 526, 528 configured to heat the compounds stored in the reactant source vessels 522, 524 to a desired temperature. In some embodiments, the one or more heating elements may be utilized to heat the compounds to a temperature greater than about 0° C., or greater than about 20° C., or greater than about 100° C., or greater than about 150° C., or greater than about 200° C., or greater than about 200° C., or greater than about 300° C., or greater than about 400° C. In some embodiments, the one or more heating elements 526, 528 may be configured to heat the compounds stored in the reactant source vessels 522, 524 to a temperature between about 25° C. and about 200° C., between about 25° C. and about 300° C., or between about 25° C. and about 400° C. As specific examples, when the gas phase reactant includes Bu3SnH or Bu3GeH, the temperature may range from about 20°C to about 40°C or about 30°C; when the reactant includes CoCl2(TMEDA), the temperature may range from about 150°C to about 190°C or about 170°C; when the reactant includes NiCl2(TMPDA), the temperature may range from about 140°C to about 180°C or about 157°C; and when the reactant includes Ni(dmap)2, the temperature may range from about 50°C to about 70°C or about 62°C.

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

[0107] In some embodiments of the present disclosure, a vapor passage 530 may be coupled to the reactant source vessel 522 (and / or reactant source vessel 524) such that one or more carrier gases (e.g., from source 516 or other sources) may be transferred from a carrier gas storage vessel through the vapor passage 530 and into the reactant source vessel 522. In some embodiments, a mass flow controller (not shown) may be disposed on the vapor passage 530 and in close proximity to the reactant source vessel 522. For example, the mass flow controller may be calibrated to control the mass flux of the carrier gas entering the reactant source vessel 522, thereby allowing greater control over the subsequent flow rate of the reactant vapor after exiting the reactant source vessel 522 and into 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 the exposed surface of the compound, thereby picking up a portion of the vapor from the compound and transporting the compound (then the first or second vapor-phase reactant) along 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 a separate vapor passage (not shown), thereby agitating and picking up a portion of the metal-containing compound and transporting the metal-containing compound vapor (then the first or second vapor-phase reactant) through 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 circuitry and mechanical components for selectively operating valves, manifolds, pumps and other devices associated with the reactor system 500. Such circuitry and components operate to introduce reactants, purge gases, and / or carrier gases from the respective reactant source vessels 522, 524 and purge gas vessel 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 to properly operate the reactor system 500. The operation and control mechanism 532 may comprise control software and electrical or pneumatic control valves to control the flow of reactants, carrier gases, and / or purge gases 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. A module may be advantageously configured to reside on an addressable storage medium of the system operation and control mechanism 532 and configured to execute one or more processes.

[0110] Various other configurations of reactor systems are possible, with different numbers and types of reactant and purge gas sources. Additionally, there are many arrangements of valves, conduits, reactant sources, and purge gas sources that can be used to achieve the goal of selectively delivering gases into the reaction chamber 504.

[0111] The examples provided below illustrate certain 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 1. A cyclic deposition process for depositing an intermetallic compound, the cyclic deposition method comprising: providing a first gas-phase reactant comprising a first metal to a reaction chamber for reaction with a surface of the substrate to form a first metal species; and supplying a second gas phase reactant comprising a second metal to the reaction chamber to react with the first metal species, thereby forming an intermetallic compound.

[0113] Example 2 The cyclic deposition process of Example 1, 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.

[0114] Example 3 The cyclic deposition process of Example 1, further comprising one or more purge steps, at least one of the purge steps occurring after the step of providing a first gas-phase reactant and before the step of providing a second gas-phase reactant.

[0115] Example 4 The cyclic deposition process described in Example 1, wherein the cyclic deposition process comprises an atomic layer deposition process.

[0116] Example 5 The cyclic deposition process described in Example 1, wherein the cyclic deposition process comprises cyclic chemical vapor deposition.

[0117] Example 6 The cyclic deposition process described in Example 1, wherein the temperature in the reaction chamber during the steps of providing the first gas phase reactant and providing the 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 from about 20°C to about 700°C, from about 50°C to about 500°C, or from about 50°C to about 400°C, from about 75°C to about 300°C, or from about 100°C to about 250°C.

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

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

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

[0122] Example 11 The cyclic deposition process described in Example 1, wherein the second metal comprises Ge.

[0123] Example 12 The cyclic deposition process described in Example 1, wherein the second metal comprises Ga.

[0124] Example 13 The cyclic deposition process described in Example 1, wherein the second metal comprises In.

[0125] Example 14 The group consisting of compounds having the formula RMH is represented by the formula R (X-n) -M X -H n wherein X is the formal oxidation state of the metal and n is 1 to 5.

[0126] Example 15 The cyclic deposition process of Examples 8 and 14, wherein R comprises an alkyl group or another organic group.

[0127] Example 16 The cyclic deposition process of any of Examples 8 and 14, wherein R is independently selected from the group consisting of C1 to C10 alkyl groups.

[0128] Example 17 The cyclic deposition process of any of Examples 8 and 14, wherein R is a cyclopentadienyl, amido, alkoxy, amidinato, guanidinato, imido, carboxylato, β-diketonato, β-ketoiminato, malonato, β-diketiminato group with or without additional donor functionality.

[0129] Example 18 The cyclic deposition process described in Example 1, wherein the second gas phase reactant comprises a metal reducing agent.

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

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

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

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

[0134] Example 23 The cyclic deposition process of Example 1, wherein the first metal is selected from the group consisting of Groups 8 to 11 metals.

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

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

[0137] Example 26 The first gas phase reactant is M(dmap)x (dmap=dimethylamino-2-propoxide), where M is a metal.

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

[0139] Example 28 The cyclic 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 cyclic deposition process described in Example 1, wherein the first gas phase reactant comprises a metal halide compound comprising a bidentate nitrogen adduct ligand.

[0141] Example 30 30. The cyclic deposition process of Example 29, wherein the adduct ligand comprises two nitrogen atoms, each of which is bonded to at least one carbon atom.

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

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

[0144] Example 33 The cyclic deposition process described in Example 1, wherein the intermetallic compound does not include Al, Ga, and / or In, and transition metals.

[0145] Example 34 1. A cyclic deposition process for forming a metal-containing material, the cyclic deposition process comprising:

[0146] providing a first vapor phase precursor comprising a first metal to a reaction chamber to form a first metal species;

[0147] providing a second gas-phase reactant comprising a compound having the general formula RMH, where R is an organic group and M is a metal, to react with the first metal species, thereby forming a metal-containing material.

[0148] Example 35 The cyclic deposition process of Example 34, wherein the first metal and the second metal are the same.

[0149] Example 36 The cyclic deposition process of Example 34, wherein the metal-containing material comprises an elemental metal.

[0150] Example 37 The cyclic deposition process of any of Examples 1 or 34, wherein the metal-containing material comprises, for example, a mixture of In and Ge or other first and / or second metals.

[0151] Example 38 35. The cyclic deposition process of 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 cyclic deposition process of Example 34, further comprising one or more purge steps, at least one of the purge steps occurring after the step of providing a first gas-phase reactant and before the step of providing a second gas-phase reactant.

[0153] Example 40 The cyclic deposition process of Example 34, wherein the cyclic deposition process comprises an atomic layer deposition process.

[0154] Example 41 The cyclic deposition process of Example 34, wherein the cyclic deposition process comprises cyclic chemical vapor deposition.

[0155] Example 42 The cyclic deposition process of Example 34, wherein the temperature in the reaction chamber during the steps of providing the first gas phase reactant and providing the 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 from about 20°C to about 700°C, from about 50°C to about 500°C, or from about 50°C to about 400°C, from about 75°C to about 300°C, or from about 100°C to about 250°C.

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

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

[0158] Example 45 The cyclic deposition process of Example 34, wherein the second metal comprises Ge.

[0159] Example 46 The cyclic deposition process of Example 34, wherein the second metal comprises In.

[0160] Example 47 The cyclic deposition process of Example 34, wherein the second metal comprises Ga.

[0161] Example 48 35. The cyclic deposition process of example 34, wherein the metal-containing material comprises one or more of an elemental metal, a mixture of metals, an alloy, and an intermetallic compound.

[0162] Example 49 35. The cyclic deposition process of example 34, wherein the metal-containing material is one or more of metallic, conductive, non-conductive, semiconductive, superconductive, catalytic, ferromagnetic, and magnetoresistive.

[0163] Example 50 Compounds having the general formula RMH are of the formula R (X-n) -M X -H n wherein X is the formal oxidation state of the metal and n is 1 to 5.

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

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

[0166] Example 53 The cyclic deposition process of any of Examples 34-52, wherein R is a cyclopentadienyl, amido, alkoxy, amidinato, guanidinato, imido, carboxylato, β-diketonato, β-ketoiminato, malonato, β-diketiminato group with or without additional donor functionality.

[0167] Example 54 The cyclic deposition process of Example 34, wherein the second gas phase reactant comprises a metal reducing agent.

[0168] Example 55 The cyclic deposition process of Example 34, wherein the first metal is selected from the group consisting of transition metals and IUPAC Groups 13-15 metals.

[0169] Example 56 The cyclic deposition process of Example 34, wherein the first metal is selected from the group consisting of Groups 3-6 metals.

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

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

[0172] Example 59 The cyclic deposition process of Example 34, wherein the first metal is selected from the group consisting of Groups 8 to 11 metals.

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

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

[0175] Example 62 The first gas phase reactant is M(dmap) x The cyclic deposition process of Example 34 comprising (dmap=dimethylamino-2-propoxide) where M is a metal.

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

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

[0178] Example 65 The cyclic deposition process of Example 34, wherein the first gas phase reactant comprises a metal halide compound comprising a bidentate nitrogen adduct ligand.

[0179] Example 66 66. The cyclic deposition process of Example 65, wherein the adduct ligand comprises two nitrogen atoms, each of the nitrogen atoms being bonded to at least one carbon atom.

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

[0181] Example 68 The cyclic deposition process of Example 34, wherein the second gas phase reactant comprises one or more of TBTH and TBGH.

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

[0183] Example 70 The membrane of Example 69, wherein the membrane is metallic, conductive, semiconducting, or nonconductive.

[0184] Example 71 The membrane of Example 69, wherein the membrane is superconducting.

[0185] Example 72 The film of Example 69, wherein the film is magnetoresistive.

[0186] Example 73 The membrane of Example 69, wherein the membrane is ferromagnetic.

[0187] Example 74 The membrane of Example 69, wherein the membrane is a catalyst.

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

[0189] Example 76 76. The film of example 75, wherein the film comprises one or more of a metal mixture, an alloy, and an intermetallic compound.

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

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

Claims

1. 1. A cyclic deposition method for forming a metal-containing material, comprising: providing a first vapor phase precursor to a reaction chamber from a first vapor phase reactant source vessel in fluid communication with the reaction chamber to form a first metal species, the first vapor phase precursor comprising nickel chloride (TMPDA); providing a second gas phase reactant comprising tributyl germanium hydride (TBGH) to react with the first metal species to form the metal-containing material; The pressure in the reaction chamber is 10 －８ mbar to 10 mbar, The cyclic deposition method, wherein the temperature in the reaction chamber is from 140° C. to 200° C.

2. 10. The cyclical deposition method of claim 1, further comprising one or more purge steps, at least one of said purge steps occurring after the step of delivering the first gas phase precursor and before the step of delivering the second gas phase reactant.

3. The cyclic deposition method of claim 1 , wherein the second gas phase reactant comprises a metal reducing agent.

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