Cyclic deposition methods and films and structures for forming metal-containing materials

Abstract

A method of depositing a metal-containing material is disclosed. The methods may include the use of cyclic deposition techniques, such as cyclic chemical vapor deposition and atomic layer deposition. The metal-containing material may include an intermetallic compound. A structure including the metal-containing material and a system for forming the material are also disclosed.

Description

[0001] This application is a divisional application of the invention patent application with application date of June 21, 2019, application number 201980041932.1, and invention name “Cyclic deposition method for forming metal-containing materials and films and structures containing metal-containing materials”.

[0002] Partners in the Joint Research Agreement

[0003] The invention claimed herein was made pursuant to, on behalf of, and / or in connection with a joint research agreement between the University of Helsinki and ASM Microchemistry Oy. Said agreement was in effect on and before the date on which the claimed invention was made, and the claimed invention was made as a result of activities carried out within the scope of said agreement. Technical Field

[0004] The present disclosure generally relates to methods for depositing metal-containing materials on a surface of a substrate, films and structures comprising metal-containing materials, and reactors and systems for depositing metal-containing materials. Background Art

[0005] The deposition of metal-containing materials can be used in the manufacture of various devices such as semiconductor devices, flat panel display devices, photovoltaic devices, micro-electromechanical systems (MEMS), magnetoresistive devices, superconducting devices, energy storage (e.g., hydrogen storage) devices, lithium or sodium ion batteries, etc., and / or for forming catalytic materials. For many applications, it is often desirable to deposit the metal-containing material in a uniform and / or conformal manner over a surface, which may include three-dimensional features such as trenches and / or protrusions, which may have relatively high aspect ratios.

[0006] Recently, interest in the potential use of intermetallic compounds in the formation of various devices has grown due to their relatively unique physical and chemical properties. Intermetallic compounds typically possess a specific, ordered crystalline structure that can differ from alloys formed from the same metal; this specific structure can 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. For example, intermetallic compounds containing Co or Ni and Sn in varying stoichiometries have been studied as anode materials for Li- and Na-ion batteries, as ferromagnetic materials for magnetic devices, and for catalytic purposes.

[0007] Metal-containing materials, such as Co-Sn and Ni-Sn, with different stoichiometries, including intermetallic Co3Sn2 and Ni3Sn2 phases of the materials, have typically been prepared by methods such as ball milling, arc melting, various solution-based techniques, solvothermal and hydrothermal routes, electrodeposition, sputtering, and electron beam evaporation. Chemical vapor deposition (CVD) from two single-source reactants, Me3SnCo(CO)4 and Ph3SnCo(CO)4, has been used to deposit alloys of Co and Sn with a 1:1 stoichiometry and containing only trace amounts of Co3Sn2. Ni3Sn, Ni3Sn2, and Ni3Sn4 have also been deposited by CVD using SnMe4 and a Ni substrate, followed by hydrogen treatment at high temperatures. Although such techniques can be used to form intermetallic compounds, such techniques are generally not well suited for forming uniform, conformal films of intermetallic materials on the surface of a substrate.

[0008] Cyclic deposition techniques, such as atomic layer deposition, can be used to deposit materials in a relatively uniform (e.g., uniform crystalline structure, uniform composition, and / or uniform thickness) and conformal manner over complex three-dimensional structures on a substrate surface in a controlled and reproducible manner. However, such techniques have not generally been used to deposit several metal-containing materials, including intermetallic compounds. Instead, intermetallic compounds, in particular, are typically formed using other techniques and / or require additional, often high-temperature processing.

[0009] Accordingly, there is a need for improved methods for forming metal-containing materials, such as intermetallic compounds. Additionally, there is a need for improved techniques for forming uniform and / or conformal films of metal-containing materials.

[0010] Any discussion of issues provided in this section is introduced solely for the purpose of providing context for the present invention and should not be taken as an admission that any or all of these discussions were known at the time the present invention was made. Summary of the Invention

[0011] This summary is provided to introduce a series of concepts in a simplified form. These concepts are described in more detail below in the detailed description of the example embodiments of the present disclosure. This summary is not intended to necessarily 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.

[0012] 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 comprising: providing a first gaseous reactant (also referred to herein as a precursor) comprising a first metal to a reaction chamber to react with a surface of a substrate to form a first metal species; and providing a second gaseous reactant comprising a second metal to the reaction chamber to react with the first metal species to thereby form an intermetallic compound. Additional reactants may similarly be used to form an intermetallic compound comprising more than two metals. As described in more detail below, a film of the intermetallic compound may be formed on the substrate without the need for additional high temperature and / or reduction steps. The cyclic deposition process may comprise, for example, atomic layer deposition.

[0013] According to at least one other embodiment of the present disclosure, a method for forming a metal-containing material is disclosed. The metal-containing material may comprise one, two, or three or more metals as described herein. The method may be a cyclic deposition process, such as atomic layer deposition or a cyclic chemical vapor deposition process. The cyclic deposition process may include providing a first gaseous reactant comprising a first metal to a reaction chamber to form a first metal species and providing a gaseous reactant comprising a general formula RMH (e.g., R (X-n) -M X -H n ) to react with the first metal species to form a metal-containing material, wherein in the general formula, R is an organic group and M is a metal. According to various examples, X is a formal oxidation state of M, and n can range from 1 to 5. According to various aspects, the metal-containing material comprises one or more of a metal mixture, an alloy, and an intermetallic compound. Films comprising the metal-containing material can be metallic, conductive, non-conductive, or semiconductive. Exemplary films can be superconducting, magnetoresistive, ferromagnetic, or catalytic.

[0014] According to at least one further embodiment of the present disclosure, a method for supplying a first gas-phase reactant comprising a first metal and a second gas-phase reactant comprising a second metal (e.g., comprising a gas having a general formula of RMH (e.g., R (X-n) -M X -H n), wherein R is an organic group, X is a formal oxidation state of a metal, n is 1 to 5, and M is a metal). The method may include providing a second gas-phase reactant source container configured to contain a second gas-phase reactant (e.g., any of the second gas-phase reactants described herein), fluidly connecting the second gas-phase reactant source container to a reaction chamber; heating the second gas-phase reactant contained in the second gas-phase reactant source container to a temperature of about 0° C. to about 400° C., about 20° C. to about 200° C., or about 20° C. to about 100° C.; generating a second gas-phase reactant vapor pressure of at least 0.001 mbar; and supplying the second gas-phase reactant to the reaction chamber.

[0015] In some embodiments of the present disclosure, a reactor system utilizing reactive volatile chemicals is provided. The reactor system may include a reaction chamber, a first gaseous reactant source container in fluid communication with the reaction chamber, and a second gaseous reactant source container in fluid communication with the reaction chamber. The second gaseous reactant may include, for example, a gaseous reactant having the general formula RMH—e.g., R (X-n) -M X -H n A compound wherein R is an organic group, X is a formal oxidation state of a metal, n is 1 to 5, and M is a metal.

[0016] For the purpose of summarizing the present disclosure and the advantages achieved over the prior art, certain objectives and advantages may have been described herein above. Of course, it should be understood that not all such objectives or advantages may be achieved according to any particular embodiment of the present disclosure. Thus, for example, those skilled in the art will recognize that embodiments of the present disclosure may be performed in a manner that achieves or optimizes one advantage or group of advantages as taught or suggested herein without necessarily achieving other objectives or advantages as may be taught or suggested herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The subject matter of the present disclosure is particularly pointed out and distinctly claimed in the concluding portion of the specification. However, a more complete understanding of the disclosure may be best obtained by referring to the detailed description and claims when considered in conjunction with the accompanying drawings, in which like reference numerals represent like elements, and in which:

[0018] Figure 1 illustratively illustrates a process flow of an exemplary cyclic deposition method according to at least one embodiment of the present disclosure;

[0019] Figure 2 Another process flow of an exemplary cyclic deposition method according to at least one embodiment of the present disclosure is illustrated;

[0020] Figure 3 illustrates a schematic diagram of an exemplary device structure including a metal-containing film deposited according to at least one embodiment of the present disclosure;

[0021] Figure 4 illustrates examples of metal halide compounds employed in a cyclic deposition process according to at least one embodiment of the present disclosure;

[0022] Figure 5 a schematic diagram illustrating an exemplary reactor system according to at least one embodiment of the present disclosure; and

[0023] Figure 6 Illustrated are exemplary second gas-phase reactants according to at least one embodiment of the present disclosure.

[0024] It should be understood that the elements in the figures are illustrated for simplicity and clarity only and are not necessarily drawn to scale. For example, the dimensions of some elements in the figures may be exaggerated relative to other elements to help improve understanding of the illustrated embodiments of the present invention. DETAILED DESCRIPTION

[0025] The description of exemplary embodiments of the present disclosure provided below is merely exemplary and is intended for illustrative purposes only; the following description is not intended to limit the scope of the invention. Furthermore, the recitation of multiple embodiments having recited features is not intended to exclude other embodiments having additional features or other embodiments incorporating different combinations of the recited features.

[0026] As described in greater detail below, exemplary embodiments of the present disclosure relate to methods and apparatus for depositing metal-containing materials, such as intermetallic compounds, and to films and structures comprising metal-containing materials. While the following describes in greater detail how the present disclosure addresses various shortcomings of existing systems and methods, generally speaking, the various systems and methods described herein employ improved reactants (sometimes generally referred to as precursors) and / or improved deposition techniques to deposit metal-containing materials having desired properties.

[0027] 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 gaseous substance participating in the reaction originates. The chemical reaction may occur in the gas phase and / or between the gas phase and the substrate surface and / or species on the substrate surface.

[0028] As used herein, the term "cyclic deposition" may refer to the sequential introduction of reactants into a reaction chamber to deposit a film over a substrate and includes deposition techniques such as atomic layer deposition and cyclic chemical vapor deposition.

[0029] As used herein, the term "cyclic chemical vapor deposition" may 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.

[0030] As used herein, the term "atomic layer deposition" (ALD) may refer to a vapor deposition process in which deposition cycles, such as multiple consecutive deposition cycles, are performed in a reaction chamber. Typically, during each cycle, a first reactant is chemisorbed onto the surface of the substrate, forming a monolayer or sub-monolayer that is not readily reactive with additional first reactant (i.e., a self-limiting reaction). Thereafter, another second reactant or reactive gas may be subsequently introduced into the process chamber for converting the chemisorbed species into the desired material. Additionally, a purge step may be utilized during each deposition cycle to remove excess first reactant from the reaction chamber following conversion of the chemisorbed first and / or second reactant and / or to remove excess second reactant, reactive gas, and / or reaction byproducts from the reaction chamber. In addition, as used herein, the term "atomic layer deposition" is also intended to include processes designated by related terms such as chemical vapor atomic layer deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas source MBE, metalorganic MBE, and chemical beam epitaxy when performed using alternating pulses of reactants, reactive gases, and / or purge gases (e.g., inert carrier gases).

[0031] As used herein, the term "substrate" may refer to any material having a surface onto which a material may be deposited. A substrate may include a bulk material such as silicon (e.g., single crystal silicon) and may include one or more layers applied to the bulk material, including, for example, chemisorbed species. Additionally, a substrate may include various features, such as channels, vias, lines, and the like, formed within or on at least a portion of the substrate. The features may have an aspect ratio, for example, of greater than or equal to 5, greater than or equal to 10, greater than or equal to 15, or greater than or equal to 20, where the aspect ratio is defined as the height of the feature divided by the width of the feature.

[0032] As used herein, the terms "film," "thin film," "layer," and "thin layer" may refer to any continuous or non-continuous material that is deposited, for example, by the methods disclosed herein. For example, a "film," "thin film," "layer," and "thin layer" may include 2D materials, nanorods, nanotubes, or nanoparticles, or even a partial or complete molecular layer, or a partial or complete atomic layer, or clusters of atoms and / or molecules. A "film," "thin film," "layer," and "thin layer" may include a material or layer that has pinholes, but is still at least partially continuous.

[0033] As used herein, the terms "metal-containing film" and "metal-containing material" may refer to a film or material containing at least one metal species.

[0034] As used herein, the term "metal" may include semimetals or metalloids.

[0035] As used herein, "intermetallic" or "intermetallic compound" may refer to a compound containing two or more metallic elements with a defined stoichiometry and an ordered crystal structure. Intermetallic compounds differ from metal alloys in their crystal structure; the crystalline structure of an intermetallic compound is arranged in a specific structure, while alloys generally exhibit the crystal structure of one of the participating metallic components. Intermetallic compounds form when the bonds between dissimilar atoms are stronger than the bonds between atoms of the same element.

[0036] Numerous example materials are given throughout this disclosure; it should be noted that the chemical formula given for each example material should not be construed as limiting, and that the non-limiting example materials given should not be limited to the example stoichiometries given.

[0037] The present disclosure includes methods for depositing a metal-containing material, e.g., a film of the metal-containing material, onto a substrate. The methods can be performed using a cyclic deposition process to deposit the metal-containing material, e.g., to form a metal-containing film on a substrate. Exemplary methods can deposit a metal-containing film, e.g., a film comprising, consisting essentially of, or consisting of an intermetallic compound, at a relatively low temperature. Additionally or alternatively, the methods can deposit a metal-containing material, wherein the film comprising, consisting essentially of, or consisting of the metal-containing material has a large-area thickness, crystallinity, and / or compositional uniformity.

[0038] Now turning to the accompanying drawings, Figure 1 A cyclic deposition method 100 is illustrated in accordance with at least one embodiment of the present disclosure. The method 100 can be used to form an intermetallic compound, such as a film of the intermetallic compound, on a surface of a substrate.

[0039] Method 100 begins with step 110, which includes providing at least one substrate into a reaction chamber and heating the substrate to a deposition temperature. The deposition temperature may depend, for example, on the one or more reactants used to form the intermetallic compound. As examples, the reaction chamber may be heated to a temperature above 0°C and below 600°C, below 500°C, below 400°C, below 300°C, or below 250°C, or between about 20°C and about 700°C, about 50°C and about 500°C, or about 50°C and about 400°C, about 75°C and about 300°C, or about 100°C and about 250°C. As a specific example, the intermetallic compound may comprise Co3Sn2, in which case the temperature may be in the range of about 170°C to about 200°C; similarly, when the intermetallic compound comprises Ni3Sn2, the temperature may be in the range of about 125°C to about 175°C, or about 140°C to about 160°C. The pressure within the reaction chamber may be controlled to provide a desired pressure within the reaction chamber for the deposition process. For example, the pressure within 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 even in some cases less than 1 mbar, or about 10 -8 mbar to about 1000 mbar, about 10 -3 mbar to about 100 mbar, about 10 -2 mbar to about 50 mbar, or about 0.1 mbar to about 10 mbar.

[0040] Method 100 may continue with step 120, which includes providing a first gas-phase reactant comprising a first metal to the reaction chamber to react 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 conjunction with step 110. The pulse time or time for providing the first gas-phase reactant to the reaction chamber may be, for example, in the range of about 0.01 seconds to about 60 seconds, or about 0.05 seconds to about 10 seconds, or about 0.1 seconds to about 5 seconds. During step 120, the flow rate of the first gas-phase reactant may be less than 2000 sccm, or less than 1000 sccm, or less than 500 sccm, or less than 200 sccm, or even less than 100 sccm, or may be in the range of about 1 to about 5000 sccm, about 5 to about 2000 sccm, or about 10 to about 1000 sccm.

[0041] After providing the first gaseous reactant, any excess first gaseous reactant and any reaction byproducts may be removed from the reaction chamber by a purge / pump process (step 125). The duration of step 125 may, for example, be between about 0.01 seconds and about 60 seconds, or between about 0.05 seconds and about 10 seconds, or between about 0.1 seconds and 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 even less than 100 sccm, or may be in the range of about 1 to about 5000 sccm, about 5 to about 2000 sccm, or about 10 to about 1000 sccm. Although shown separately, step 125 may be considered part of step 120.

[0042] Method 100 may continue with step 130 by providing a second gaseous reactant comprising a second metal to the reaction chamber to react with the first metal species to form an intermetallic compound. This step may be performed at the same or different pressure and / or temperature as described above in connection with step 110. The pulse duration or time for providing the second gaseous reactant to the reaction chamber may be in the range of about 0.01 seconds to about 60 seconds, or about 0.05 seconds to about 10 seconds, or about 0.1 seconds to about 5 seconds. During step 130, the flow rate of the second gaseous reactant may be the same or similar to the flow rate described above during step 120.

[0043] like Figure 1 As shown in , as the second gas-phase reactant reacts with species on the substrate surface, an intermetallic compound—eg, a film comprising, consisting essentially of, or consisting of the intermetallic compound—is formed (step 140 ).

[0044] After step 140, any excess second gaseous reactant and any reaction byproducts may be removed from the reaction chamber via a purge / pump process (step 145). The flow rate and / or duration of the purge gas in this step may be the same or similar to those described above in step 125. Furthermore, although illustrated separately, step 145 may be considered part of step 130.

[0045] Steps 120 and 130 (and optionally purge steps 125 and / or 145) may constitute a 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 the cyclic deposition method 100 continues or exits via step 160. Decision gate 150 may make a decision based on the thickness or amount of the deposited intermetallic compound. 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 be subjected to additional processing to form one or more devices or device structures.

[0046] According to various aspects of method 100, an intermetallic compound is formed when the second gas-phase reactant reacts with the first metal species formed on the surface during step 120. Thus, an intermetallic compound, or a layer or film comprising, consisting essentially of, or consisting of an intermetallic compound, can be formed without an additional reduction step and / or heating step. Furthermore, as explained above, the intermetallic compound can be formed at a relatively low temperature.

[0047] The first gas-phase reactant can include any first metal that is different from the second metal. As an 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.

[0048] According to an alternative embodiment, as follows in conjunction with Figure 2 As described above, the first gas-phase reactant may include a first metal that is the same as the second metal. When the first metal and the second metal are the same, an elemental metal film may be formed. As described above, such an elemental metal film may include a semimetal or a metalloid.

[0049] The first gas-phase reactant may be or may include a metal halide compound, wherein the metal is or includes the 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 cobalt chloride, nickel 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 including two nitrogen atoms, wherein 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. Figure 4 An example of such a compound is illustrated in Additional first gas phase reactants may include adduct forming ligands comprising phosphorus, oxygen and / or sulfur.

[0050] In some embodiments, the first gas-phase reactant may comprise a transition metal compound having an adduct-forming ligand. In some embodiments, the first gas-phase reactant may comprise a transition metal compound. In some embodiments, the first gas-phase reactant may comprise a transition metal halide compound. In some embodiments, the first gas-phase reactant may comprise a transition metal compound having an adduct-forming ligand, such as a monodentate, bidentate, or multidentate adduct-forming ligand. In some embodiments, the first gas-phase reactant may comprise a transition metal halide compound having an adduct-forming ligand, such as a monodentate, bidentate, or multidentate adduct-forming ligand. In some embodiments, the first gas-phase reactant may comprise a transition metal compound having an adduct-forming ligand, such as a monodentate, bidentate, or multidentate adduct-forming ligand comprising nitrogen. In some embodiments, the first gas-phase reactant may comprise a transition metal compound having an adduct-forming ligand comprising phosphorus, oxygen, or sulfur, such as a monodentate, bidentate, or multidentate adduct-forming ligand comprising phosphorus, oxygen, or sulfur. For example, in some embodiments, the transition metal halide compound may comprise 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 comprise 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 comprise at least one of cobalt chloride, nickel chloride, or copper chloride. In some embodiments, the transition metal halide compound may comprise a bidentate nitrogen-containing adduct-forming ligand. In some embodiments, the transition metal halide compound may comprise an adduct-forming ligand comprising two nitrogen atoms, wherein 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 comprises one or more nitrogen atoms bonded to a central transition metal atom, thereby forming a metal complex.

[0051] In some embodiments of the present disclosure, the first gas-phase reactant may comprise a transition metal compound having the formula:

[0052] (Adduct) n -M-Xa

[0053] 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 a mixture thereof; in the case of a monodentate adduct-forming ligand, n is 1 to 4, in the case of a bidentate or polydentate adduct-forming ligand, n is 1 to 2; M is a transition metal, such as cobalt (Co), copper (Cu) or nickel (Ni); wherein each of the Xa is another ligand and can be independently selected to be a halide or other ligand; wherein a is 1 to 4, and in some cases a is 2.

[0054] In some embodiments of the present disclosure, the adduct-forming ligand in the transition metal compound, such as a transition metal halide compound, may comprise a monodentate, bidentate, or polydentate adduct-forming ligand coordinated to the transition metal atom of the transition metal compound through at least one of a nitrogen atom, a phosphorus atom, an oxygen atom, or a sulfur atom. In some embodiments of the present disclosure, the adduct-forming ligand in the transition metal compound may comprise a cyclic adduct ligand. In some embodiments of the present disclosure, the adduct-forming ligand in the transition metal compound may comprise a monoamine, a diamine, or a polyamine. In some embodiments of the present disclosure, the adduct-forming ligand in the transition metal compound may comprise a monoether, a diether, or a polyether. In some embodiments, the adduct-forming ligand in the transition metal compound may comprise a monophosphine, a diphosphine, or a polyphosphine. In some embodiments, the adduct-forming ligand in the transition metal compound may comprise carbon and / or carbon in addition to the nitrogen, oxygen, phosphorus, or sulfur in the adduct-forming ligand.

[0055] In some embodiments of the present disclosure, the adduct-forming ligand in the transition metal compound may include one monodentate adduct-forming ligand. In some embodiments of the present disclosure, the adduct-forming ligand in the transition metal compound may include two monodentate adduct-forming ligands. In some embodiments of the present disclosure, the adduct-forming ligand in the transition metal compound may include three monodentate adduct-forming ligands. In some embodiments of the present disclosure, the adduct-forming ligand in the transition metal compound may include four monodentate adduct-forming ligands. In some embodiments of the present disclosure, the adduct-forming ligand in the transition metal compound may include one bidentate adduct-forming ligand. In some embodiments of the present disclosure, the adduct-forming ligand in the transition metal compound may include two bidentate adduct-forming ligands. In some embodiments of the present disclosure, the adduct-forming ligand in the transition metal compound may include one polydentate adduct-forming ligand. In some embodiments of the present disclosure, the adduct-forming ligand in the transition metal compound may include two polydentate adduct-forming ligands.

[0056] In some embodiments of the present disclosure, the adduct-forming ligand comprises nitrogen, such as an amine, diamine, or polyamine adduct-forming ligand. In such embodiments, the transition metal compound may include at least one 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-propylenediamine (CAS: 110-95-2) (TMPDA), N,N,N',N'-tetramethylmethanediamine (CAS: 51-80-9) (TMMDA), N,N,N',N'',N''-pentamethyldiethylenetriamine (CAS: 3030-47-5) (PMDETA), diethylenetriamine (CAS: 111-40-0) (DIEN), triethylenetetramine (CAS: 112-24-3) (TRIEN), tris(2-aminoethyl)amine (CAS: 4097-89-6) (TREN, TAEA), 1,1,4,7,10,10-hexamethyltriethylenetetramine (CAS: 3083-10-1) (HMTETA), 1,4,8,11-tetraazacyclotetradecane (CAS: 295-37-4) (Cyclam), 1,4,7-trimethyl-1,4,7-triazacyclononane (CAS: 96556-05-7) or 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (CAS: 41203-22-9).

[0057] In some embodiments of the present disclosure, the adduct-forming ligand comprises phosphorus, 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), trimethyl phosphite (CAS: 121-45-), 1,2-bis(diethylphosphino)ethane (CAS: 6411-21-8) (BDEPE), or 1,3-bis(diethylphosphino)propane (CAS: 29149-93-7).

[0058] 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 may 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).

[0059] In some embodiments of the present disclosure, the adduct-forming ligand may comprise a thioether or mixed etheramine, such as, for example, at least one of 1,7-diaza-12-crown-4,10-diazacyclododecane (CAS: 294-92-8) or 1,2-bis(methylthio)ethane (CAS: 6628-18-8).

[0060] In some embodiments, the transition metal halide compound may include cobalt chloride N,N,N',N'-tetramethyl-1,2-ethylenediamine (CoCl2(TMEDA)). In some embodiments, the transition metal halide compound may include cobalt bromide tetramethylethylenediamine (CoBr2(TMEDA)). In some embodiments, the transition metal halide compound may include cobalt iodide tetramethylethylenediamine (CoI2(TMEDA)). In some embodiments, the transition metal halide compound may include cobalt chloride N,N,N',N'-tetramethyl-1,3-propylenediamine (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-propylenediamine (NiCl2(TMPDA)), or nickel iodide tetramethyl-1,3-propylenediamine (NiI2(TMPDA)).

[0061] Other suitable first gas-phase reactants may be substantially free of halogen species. Examples of substantially halogen-free first gas-phase reactants (halogen-free metal precursors) include M(dmap)x (dmap = dimethylamino-2-propanolate), where M is a metal, a β-diketonate anion, an amidine anion, and other typical ALD metal precursors. In some embodiments, the halogen-free metal precursor may comprise at least one of copper, cobalt, and nickel. Thus, the halogen-free metal precursor may comprise at least one of Cu(dmap)2, Ni(dmap)2, or Co(dmap)2.

[0062] In some embodiments, the halogen-free metal precursor may therefore include at least one bidentate ligand, wherein the metal central atom is bonded to at least one oxygen and at least one nitrogen atom in the bidentate ligand. In some embodiments, the halogen-free metal precursor may therefore include at least one bidentate ligand, wherein the metal central atom is bonded to at least one nitrogen atom in the bidentate ligand. In some embodiments, the halogen-free metal precursor may therefore include at least one bidentate ligand and at least one other ligand, such as a monodentate ligand. In some embodiments, the halogen-free metal precursor may therefore include at least one bidentate ligand and at least two other ligands, such as a monodentate ligand. In some embodiments, the halogen-free metal precursor may therefore include at least one bidentate ligand and at least one other ligand, such as a monodentate ligand, which is bonded to the metal central atom through N or O. In some embodiments, the halogen-free metal precursor may therefore include at least one bidentate ligand, wherein the metal central atom is bonded to at least one nitrogen atom in the bidentate ligand and bonded to at least one other atom other than nitrogen in the bidentate ligand. In some embodiments, the halogen-free metal precursor may thus comprise at least one bidentate ligand, wherein the metal central atom is bonded via at least two nitrogen atoms in the bidentate ligand. In some embodiments, the halogen-free metal precursor comprises at least two bidentate ligands. In some embodiments, the halogen-free metal precursor comprises two bidentate ligands.

[0063] Some examples of suitable halide-free β-diketimine anion ligands (e.g., Ni(pda)2) (pda = pentane-2,4,-diketimine anion ligand) compounds comprise at least one β-diketimine anion ligand and have the general formula:

[0064]

[0065] wherein M is a metal selected from nickel, cobalt, ruthenium, iridium, palladium, platinum, silver and gold. 1-5 Each of the ligands is independently selected from H and a C1-C4 linear or branched alkyl group, an alkylsilyl group, an alkylamide group, an alkoxide group, or an 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, inclusive. Specific examples include Ni(pda)2.

[0066] Some examples of suitable halide-free amidine anion 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, wherein M is a metal and AMD is an amidine anion moiety, such as an amidine anion copper(I) salt, an amidine anion cobalt(II) salt, or an amidine anion salt of nickel, iron, ruthenium, manganese, chromium, vanadium, niobium, tantalum, titanium, and / or lanthanum.

[0067] In one or more embodiments, the monovalent metal precursor comprises a volatile amidine anion metal (I) salt [M (I) (AMD)] x, where x = 2, 3. Some of these compounds have a dimer structure 1,

[0068]

[0069] where R 1 、R 2 、R 3 、R 1 ′、R 2 ′ and R 3 ' is a group consisting of one or more non-metal atoms. In some embodiments, R 1 、R 2、 R 3 、R 1 ′、R 2 ′ and R 3 ' can 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 ' are each independently an alkyl or fluoroalkyl or silyl group containing 1 to 4 carbon atoms. Suitable monovalent metals include copper (I), silver (I), gold (I) and iridium (I). In one or more embodiments, the amidine anion metal salt is an amidine anion copper salt, and the amidine anion copper salt comprises N,N'-diisopropylacetamidine anion copper (I) salt, which corresponds to R in Formula 1 1 、R 2 、R 1 ′ and R 2 ' is taken as an isopropyl group and R 3 and R 3 In one or more embodiments, the metal (I) amidine anion salt is a trimer having the general formula [M(I)(AMD)]3.

[0070] In one or more embodiments, the divalent metal precursor comprises a volatile metal (II) salt of a bisamidine anion [M(II)(AMD)2] x , where x = 1, 2. These compounds may have a monomer structure 2,

[0071]

[0072] where R 1 、R 2 、R 3 、R 1 ′、R 2 ′ and R 3 ' is a group consisting of one or more non-metal atoms. In one or more embodiments, a dimer of this structure may also be used, such as [M(II)(AMD)2] 2。 In some embodiments, R 1 、R 2、 R 3 、R 1 ′、R 2 ′ and R 3 ' can 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 ' are each independently an alkyl or fluoroalkyl or silyl group containing 1 to 4 carbon atoms. Suitable divalent metals include cobalt, iron, nickel, manganese, ruthenium, zinc, titanium, vanadium, chromium, europium, magnesium and calcium. In one or more embodiments, the amidine anion metal (II) salt is an amidine anion cobalt salt, and the amidine anion cobalt salt comprises bis (N, N'-diisopropylacetamidine anion) cobalt (II) salt, which corresponds to R in Formula 2 1 、R 2 、R 1 ′ and R 2 ' is taken as an isopropyl group and R 3 and R 3 ' is taken as a methyl group.

[0073] In one or more embodiments, the trivalent metal precursor comprises a volatile metal (III) triamidine anion salt [M(III)(AMD)3]. Typically, these compounds have a monomeric structure 3,

[0074]

[0075] where R 1 、R 2 、R3 、R 1 ′、R 2 ′、R 3 ′、R 1 ″、R 2 ″ and R 3 " is a group consisting of one or more non-metal atoms. In some embodiments, R 1 、R 2 、R 3 、R 1 ′、R 2 ′、R 3 ′、R 1 ″、R 2 ″ and R 3 " may be independently selected from hydrogen, alkyl, aryl, alkenylalkynyl, trialkylsilyl, halogen, or partially fluorinated alkyl groups. 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 containing 1 to 4 carbon atoms. Suitable trivalent metals include lanthanum, praseodymium and other lanthanide metals, yttrium, scandium, titanium, vanadium, niobium, tantalum, chromium, iron, ruthenium, cobalt, rhodium, iridium, aluminum, gallium, indium and bismuth. In one or more embodiments, the amidine anion metal (III) salt is an amidine anion lanthanum salt, and the amidine anion lanthanum salt comprises tris (N, N'-di-tert-butylacetamidine anion) lanthanum (III) salt, which corresponds to R in Formula 3. 1 、R 2 、R 1 ′、R 2 ′、R 1 ″ and R 2 ' is taken as the tert-butyl group and R 3 、R 3 ′ and R 3 " is taken as a methyl group.

[0076] As used herein, amidine anion metal salts having the same metal to amidine anion ratio as the monomer but differing in the total number of metal-amidine anion 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 , wherein x is 2, 3, etc. Similarly, oligomers of the monomeric compound M(I)AMD include [M(I)AMD] x , where x is 2, 3, etc.

[0077] Specific examples include (N,N′-diisopropylacetamidine anion ligand) copper ([Cu(iPr-AMD)]2), bis(N,N′-diisopropylacetamidine anion ligand) cobalt ([Co(iPr-AMD)2]), bis(N,N′-di-tert-butylacetamidine anion) cobalt salt ([Co(tBu-AMD)2]), tris(N,N′-diisopropylacetamidine anion) lanthanum salt ([La(iPr-AMD)3]), tris(N,N′-diisopropyl-2-tert-butylamidine anion) lanthanum salt ([La(iPr-tBuAMD)3]. ½C6H 12 )、bis(N,N′-diisopropylacetamidine anion ligand) iron ([Fe(iPr-AMD)2]2), bis(N,N′-di-tert-butylacetamidine anion) iron salt ([Fe( t Bu-AMD)2]), bis(N,N′-diisopropylacetamidine anion ligand) nickel ([Ni( i Pr-AMD)2]), bis(N,N′-diisopropylacetamidine anion ligand) manganese ([Mn( i Pr-AMD)2]2), bis(N,N′-di-tert-butylacetamidine anion) manganese salt ([Mn( t Bu-AMD)2]), tris(N,N′-diisopropylacetamidine anion ligand)titanium ([Ti( i Pr-AMD)3]), tris(N,N′-diisopropylacetamidine anion ligand)vanadium ([V( i Pr-AMD)3])、(N,N′-diisopropylacetamidine anion) silver salt([Ag( i Pr-AMD)] x (x = 2 and x = 3), N, N'-di-sec-butylacetamidine anion lithium salt, bis(N, N'-di-sec-butylacetamidine anion) cobalt salt ([Co(sec-Bu-AMD)2]), N, N'-di-sec-butylacetamidine anion copper (I) salt dimer ([Cu(sec-Bu-AMD)]2), tris(N, N'-di-tert-butylacetamidine anion) bismuth salt dimer ([Bi( t Bu-AMD)3]2), strontium bis(N,N′-di-tert-butylacetamidine anion) salt ([Sr( t Bu-AMD)2] n ), bismuth oxide Bi2O3 and tris(N,N′-diisopropylacetamidine anion ligand)ruthenium ([Ru( i Pr-AMD)3]).

[0078] Some examples of suitable non-halide containing iminoalkoxide compounds are described by the following formula:

[0079]

[0080] wherein M is a metal selected from Groups 2 to 12 of the Periodic Table; and R1, R2, R3, and R4 are each independently H or a C1-C8 alkyl group. In one refinement, R1, R2, R3, and R4 are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl. In another refinement, M is Cu, Cr, Mn, Fe, Co, or Ni. Specific examples of compounds having the formula include, but are not limited to, bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-ol)nickel(II), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-ol)cobalt(II), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-ol)iron(II), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-ol)manganese(II), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-ol)chromium(II), bis(1-(tert-butylimino)-2 ,3,3-trimethylbutan-2-ol)copper(II), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-ol)nickel(II), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-ol)cobalt(II), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-ol)iron(II), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-ol)copper(II), bis(3-((tert-butylimino)methyl)-2,2,4,4-tetramethylpentan-3-ol)manganese(II), bis(3-((tert-butylimino)methyl)-2,2,4,4-tetramethylpentan-3-ol) Bis(3-(isopropylimino)-2-methylbutan-2-ol)copper(II), bis(3-(isopropylimino)-2-methylbutan-2-ol)cobalt(II), bis(3-(isopropylimino)-2-methylbutan-2-ol)iron(II), bis(3-(isopropylimino)-2-methylbutan-2-ol)manganese(II), bis(3-(isopropylimino)-2-methylbutan-2-ol)chromium(II), bis(3-(isopropylimino)-2-methylbutan-2-ol)copper(II), bis(3-(isopropylimino)-2-methylbutan-2-ol) (3-(2,2-dimethylhydrazine)-2-methylbutan-2-ol)nickel(II), bis(3-(2,2-dimethylhydrazine)-2-methylbutan-2-ol)cobalt(II), bis(3-(2,2-dimethylhydrazine)-2-methylbutan-2-ol)iron(II), bis(3-(2,2-dimethylhydrazine)-2-methylbutan-2-ol)manganese(II), bis(3-(2,2-dimethylhydrazine)-2-methylbutan-2-ol)chromium(II), and bis(3-(2,2-dimethylhydrazine)-2-methylbutan-2-ol)copper(II).Specific examples include bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-ol)nickel(H), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-ol)cobalt(II), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-ol)iron(II), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-ol)manganese(II), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-ol)chromium(II), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-ol) Bis(1-(tert-butylimino)-2,3-dimethylbutan-2-ol)copper(II), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-ol)nickel(II), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-ol)cobalt(II), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-ol)iron(II), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-ol)copper(II), bis(3-((tert-butylimino)methyl)-2,2,4,4-tetramethylpentan-3- Bis(3-((tert-butylimino)methyl)-2,2,4,4-tetramethylpentan-3-ol)copper(II), bis(3-(isopropylimino)-2-methylbutan-2-ol)cobalt(II), bis(3-(isopropylimino)-2-methylbutan-2-ol)iron(II), bis(3-(isopropylimino)-2-methylbutan-2-ol)manganese(II), bis(3-(isopropylimino)-2-methylbutan-2-ol)chromium(II), bis(3-(2,2-dimethylhydrazino)-2- bis(3-(2,2-dimethylhydrazine)-2-methylbutan-2-olate)nickel(II), bis(3-(2,2-dimethylhydrazine)-2-methylbutan-2-olate)cobalt(II), bis(3-(2,2-dimethylhydrazine)-2-methylbutan-2-olate)iron(II), bis(3-(2,2-dimethylhydrazine)-2-methylbutan-2-olate)manganese(II), bis(3-(2,2-dimethylhydrazine)-2-methylbutan-2-olate)chromium(II), bis(3-(2,2-dimethylhydrazine)-2-methylbutan-2-olate)copper(II).

[0081] In some embodiments, the halogen-free metal precursor does not contain any 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 such different conditions. In some embodiments, the halogen-free metal precursor does not contain halides, such as F, Cl, Br, or I. In some embodiments, the halogen-free metal precursor contains carbon, hydrogen, and nitrogen, and optionally oxygen.

[0082] In some embodiments, the halide-free copper precursor may include, for example, Cu(dmap)2 or N,N′-diisopropylacetamidine anion copper(I) salt. In some embodiments, the copper precursor may be selected from β-diketone anion copper salt compounds; β-diketimine anion ligand copper compounds; amino alcohol copper compounds such as Cu(dmae)2, Cu(deap)2, or Cu(dmamb)2; amidine anion copper salt compounds such as Cu(sBu-amd)]2; cyclopentadienyl copper compounds; carbonyl copper 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 a 2,2,6,6-tetramethyl-3,5-heptanedione anion ligand. In some embodiments, the halide-free copper precursor is copper(II) acetate, [Cu(HMDS)]4 or Cu(nhc)HMDS (1,3-diisopropylimidazolin-2-ylidene copper hexamethyldisilazide), or a Cu-β diketimine anion salt such as Cu(dki)VTMS (dki = diketimine anion).

[0083] In some embodiments, the halide-free nickel precursor may be, for example, bis(4-N-ethylamino-3-pentenyl-2-N-ethylimine anion ligand) nickel(II). In some embodiments, the nickel precursor may be selected from β-diketone anion nickel salt compounds, β-diketone imine anion ligand nickel compounds, amino alcohol nickel compounds, amidine anion nickel salt compounds, cyclopentadienyl nickel compounds, carbonyl nickel compounds, and combinations thereof. In some embodiments, an X(acac)y or X(thd)y compound is used, where X is nickel, y is typically, but not necessarily, 2 or 3, and thd is 2,2,6,6-tetramethyl-3,5-heptanedione anion ligand.

[0084] In some embodiments, the Co precursor is a Co compound with a β-diketoimine anion ligand. In some embodiments, the Co precursor is a Co salt compound with a ketimine anion. In some embodiments, the Co precursor is a Co salt compound with an amidine anion. In some embodiments, the Co precursor is a Co salt compound with a β-diketoimine anion. In some embodiments, the Co precursor contains at least one ketimine ligand or a derivative thereof. In some embodiments, the Co precursor contains at least one amidine ligand or a derivative thereof. In some embodiments, the Co precursor contains at least one ketone anion ligand or a derivative thereof. In some embodiments, the Co precursor is Co2(CO)8, CCTBA, CoCp2, Co(Cp-amd), Co(Cp(CO)2), tBu-AllylCo(CO)3, or Co(HMDS)2. Alternatively, a metal hydride and / or aluminum reagent may be used as the first gas-phase reactant (e.g., for a hydride-hydride type reaction).

[0085] The second gaseous reactant used in method 100 may include a metal-containing organic compound. For example, the second gaseous reactant may include a metal selected from the group consisting of a metal having the formula RMH (e.g., R (X-n) -M X -H n ), wherein R is an organic group and M is a metal, to react with the 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 Sn, In, Ga, Ge, As, Sb, Pb, and Bi. Alternatively, M can include Al. For example, M can include Sn, In, or Ga. R can be or include an alkyl group or a cyclopentadienyl, amino, alkoxy, amidine anion ligand, guanidine anion ligand, imino, carboxylate ligand, β-diketone anion ligand, β-ketoimine anion ligand, malonate ligand, or β-diketoimine anion ligand group, with or without additional donor functional groups. Exemplary alkyl groups can be independently selected from C1-C5 alkyl groups. In some cases, the second gas-phase reactant (e.g., the RMH compound) can be a metal reducing agent. Figure 6 A specific example of a second gas phase reactant of tributyltin hydride (TBTH) is illustrated.

[0086] Intermetallic films comprising, consisting essentially of, or consisting of intermetallic compounds such as Co3Sn2 or Ni3Sn2 as described herein can exhibit hysteresis with high coercivity values ​​exceeding 500 Oe. Such films (and films formed according to method 200) can have resistivity values ​​between about 10 and about 10 6 µΩcm, 20 to 10 4The Ni3Sn2 thin film formed according to method 100 exhibits an intermetallic crystal structure and high purity. The exemplary intermetallic compounds and films can be used in various applications, including, for example, magnetoresistive devices, superconducting devices, as catalysts, as energy (e.g., hydrogen) storage, and the like.

[0087] Figure 2 Another cyclic deposition method 200, in accordance with at least one embodiment of the present disclosure, is illustrated. Method 200 can be used to deposit a metal-containing material, for example, to form a film or layer comprising, consisting essentially of, or consisting of the 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 via method 100 or 200) consists essentially of or consists of the intermetallic compound, the film can exhibit excellent properties as described herein.

[0088] The method 200 begins at step 210, which may be the same as or similar to step 110. For example, the temperature and pressure within the reaction chamber may be the same as or similar to those set forth in step 110.

[0089] Method 200 may continue with step 220, which includes providing a first gas phase, such as any of the first gas phase reactants described above. This step may be at the same pressure and temperature as described above in conjunction with step 210. The pulse time or time for providing the first gas phase reactant to the reaction chamber may be in the range of about 0.01 seconds to about 60 seconds, or about 0.05 seconds to about 10 seconds, or about 0.1 seconds to about 5 seconds. During step 220, the flow rate of the first gas phase reactant may be less than 2000 sccm, or less than 1000 sccm, or less than 500 sccm, or less than 200 sccm, or even less than 100 sccm, or may be in the range of about 1 to about 5000 sccm, about 5 to about 2000 sccm, or about 10 to about 1000 sccm.

[0090] After step 220 of providing the first gas-phase reactant, any excess first gas-phase reactant and any reaction byproducts may be removed from the reaction chamber via 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 even less than 100 sccm, or may be in the range of about 1 to about 5000 sccm, about 5 to about 2000 sccm, or about 10 to about 1000 sccm. Although illustrated separately, step 125 may be considered part of step 120.

[0091] Method 200 may continue with step 230, which includes providing a second gas-phase reactant to react with the first metal species (e.g., on the substrate surface) to form a metal-containing material, wherein the second gas-phase reactant comprises a compound having the general formula RMH, where R is an organic group and M is a metal. The compound having the general formula RMH may be the same as described above. The pulse duration or time for providing the second gas-phase reactant to the reaction chamber may be in the range of about 0.01 seconds to about 60 seconds, or about 0.05 seconds to about 10 seconds, or about 0.1 seconds to about 5 seconds. During step 230, the flow rate of the second gas-phase reactant may be less than 2000 sccm, or less than 1000 sccm, or less than 500 sccm, or less than 200 sccm, or even less than 100 sccm, or may be in the range of about 1 to about 5000 sccm, about 5 to about 2000 sccm, or about 10 to about 1000 sccm. Although illustrated separately, step 225 may be considered part of step 220.

[0092] like Figure 2 As illustrated in , as the second gas-phase reactant reacts with species on the substrate surface, a metal-containing material—eg, a film comprising, consisting essentially of, or consisting of—is formed.

[0093] After step 230, any excess second gaseous reactant and any reaction byproducts may be removed from the reaction chamber by a purge / pump process (step 245). The flow rate of the purge gas may be the same as described above in step 225. Furthermore, although shown separately, step 245 may be considered part of step 230.

[0094] Steps 220-245 can be combined with the above as needed. Figure 1 The steps 120-145 described are repeated in the same or similar manner. For example, the steps may be repeated until a desired film thickness or a desired amount of metal-containing material is deposited on the substrate.

[0095] The first gas-phase reactant used in step 220 can be or include any of the first gas-phase reactants 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 GeCl3 (dioxane) or some other Ge precursor with R3GeH. Other elemental films (or multi-metal films) can be formed similarly.

[0096] The second gas-phase reactant comprising a compound having the general formula RMH can be or include any RMH compound described herein, such as those described above in connection with method 100, wherein in RMH, R is an organic group and M is a metal.

[0097] According to some embodiments of the present disclosure, method 100 and / or method 200 may include atomic layer deposition (ALD). ALD is typically based on self-limiting reactions, whereby sequential and alternating pulses of reactants are used to deposit approximately one atomic (or molecular) monolayer of a material in each deposition cycle. 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 that does not react with gas-phase reactants of the same reactant. The substrate is then contacted with a different reactant, which reacts with the previous termination to effect continued deposition. Thus, each cycle of alternating pulses typically leaves no more than approximately one monolayer of the desired material. However, as mentioned above, in one or more ALD cycles, more than one monolayer of material may be deposited (e.g., if some gas-phase reactions occur) regardless of the alternating nature of the process.

[0098] In some embodiments, a cyclic deposition process is used to form a metal-containing film on a substrate and the cyclic deposition process can be an ALD-type process. In some embodiments, the cyclic deposition can be a hybrid ALD / CVD or cyclic CVD process. For example, in some embodiments, the growth rate of an ALD process can be low compared to a CVD process. One way to increase the growth rate can be to operate at a higher substrate temperature than is typically used in an ALD process, resulting in a chemical vapor deposition process, but still utilizing the sequential introduction of reactants. Such a process can be referred to as cyclic CVD.

[0099] The cyclic deposition processes described herein can be performed in an ALD or CVD deposition system with a heated substrate. For example, in some embodiments, the method may include heating the substrate to a temperature between approximately 80°C and approximately 150°C, or even between approximately 80°C and approximately 120°C. Of course, the appropriate temperature window for any given cyclic deposition process (e.g., for an ALD reaction) will depend on the surface termination state and reactant species involved. Here, the temperature varies depending on the reactants used and is typically at or below approximately 700°C. In some embodiments, for vapor deposition processes, the deposition temperature is typically at or above approximately 100°C, in some embodiments between approximately 100°C and approximately 300°C, and in some embodiments between approximately 120°C and approximately 200°C. In some embodiments, the deposition temperature is below approximately 500°C, or below approximately 400°C, or below approximately 350°C, or below approximately 300°C. In some cases, the deposition temperature may be below approximately 300°C, below approximately 200°C, or below approximately 100°C. In some cases, the deposition temperature may be greater than about 20° C., greater than about 50° C., or greater than about 75° C. In some embodiments of the present disclosure, the deposition temperature (ie, the temperature of the substrate during deposition) is the same or similar to the temperature described above in connection with methods 100 and 200 .

[0100] like Figure 1 and 2 As shown in FIG, a cyclic process including an ALD process may include a purge step, such as purge steps 125, 145, 225, and 245 described above. The purge gas 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 achieve self-saturating surface reactions. However, in some embodiments, the substrate may be moved (e.g., to another reaction chamber) to contact the first gas-phase reactant and the second gas-phase reactant, respectively. Therefore, steps 120 / 130 and / or steps 220 / 230 do not need to be performed in the same reaction chamber. Additionally or alternatively, a vacuum pump may be used to assist in the purge.

[0101] It should be understood that in some embodiments of the present disclosure, the order of providing the first gas-phase reactant and providing the second gas-phase reactant can be such that the substrate is first contacted with the second gas-phase reactant and then with the first gas-phase reactant. In other words, steps 120, 130 and 220, 230 can be reversed. In addition, in some embodiments, the cyclic deposition process may include contacting the substrate with the first gas-phase reactant one or more times, then contacting the substrate with the second gas-phase reactant one or more times, and similarly, as an alternative, may include contacting the substrate with the second gas-phase reactant one or more times, then contacting the substrate with the first gas-phase reactant one or more times.

[0102] At least some embodiments of the present disclosure (e.g., method 100 and / or method 200) may include non-plasma reactants, for example, 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, or radical species. For example, both the first and second gas-phase reactants may include non-plasma reactants to prevent ionization damage to the underlying substrate and associated defects. The use of non-plasma reactants may be particularly useful when the underlying substrate contains fragile fabricated or at least partially fabricated semiconductor device structures, as energetic plasma species may damage and / or degrade device performance characteristics.

[0103] Although Figure 2 Although not shown, in some embodiments of the present disclosure, the exemplary methods of the present disclosure may include an additional process step comprising contacting the substrate with a third gaseous reactant comprising a reducing agent. In some embodiments, the reducing agent may comprise at least one of 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), tert-butylhydrazine (C4H 12 N2), a selenium reactant, a boron reactant, a phosphorus 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 methods 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 described above, according to at least some examples, a reducing agent or reduction reaction is not required to form a desired material, such as an intermetallic material.

[0104] If used, in an exemplary cyclic deposition method, a third gas-phase reactant containing a reducing agent may be introduced into the reaction chamber and contacted with the substrate at multiple process stages. 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 the substrate is contacted with the first gas-phase reactant, after the substrate is contacted with the first gas-phase reactant and before the substrate is contacted with the second gas-phase reactant, and / or after the substrate is contacted 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 be flowed into the reaction chamber together and contacted with the substrate simultaneously, and / or the reducing agent and the second gas-phase reactant may be flowed into the reaction chamber together and contacted with the substrate simultaneously.

[0105] In some embodiments, the growth rate of the metal-containing material and / or intermetallic compound is from about 0.005 Å / cycle to about 5 Å / cycle, from about 0.01 Å / cycle to about 2.0 Å / cycle. In some embodiments, the growth rate of the metal-containing material and / or 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 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 about 0.2 Å / cycle. In some embodiments of the present disclosure, the growth rate of the metal-containing material and / or intermetallic compound may be about 0.4 Å / cycle. As specific examples, in the case of Co3Sn2, growth ranges from about 0.7 to 1.3 Å / cycle at deposition temperatures of about 170-200°C, while in the case of Ni3Sn2, a growth rate of about 1.3 Å / cycle is observed at 160°C when NiCl2(TMPDA) is used as the first gas-phase reactant.

[0106] Figure 3A structure 300 comprising a substrate 302 and a layer or film 304 is illustrated. Structure 300 may be or may comprise a partially fabricated device structure. As described above, substrate 302 may comprise a bulk material, such as a bulk semiconductor material, and a layer formed thereon and / or therein. Film 302 may comprise an intermetallic compound or a metal-containing material, such as an intermetallic compound or a metal-containing material deposited according to the embodiments described herein. In some embodiments, film 304 may be continuous at a thickness of less than approximately 100 nanometers, or less than approximately 60 nanometers, or less than approximately 50 nanometers, or less than approximately 40 nanometers, or less than approximately 30 nanometers, or less than approximately 25 nanometers, or less than approximately 20 nanometers, or less than approximately 15 nanometers, or less than approximately 10 nanometers, or less than approximately 5 nanometers or less. The continuity mentioned herein may be physical continuity or electrical continuity. In some embodiments, the thickness that makes film 304 physically continuous may be different from the thickness that makes the film electrically continuous, and the thickness that makes film 304 electrically continuous may be different from the thickness that makes the film physically continuous.

[0107] In some embodiments, the thickness of intermetallic and / or metal-containing films (e.g., film 304) deposited according to some embodiments described herein may be from about 20 nanometers to about 100 nanometers. In some embodiments, the thickness of intermetallic and / or metal-containing films deposited according to some embodiments described herein may be from about 20 nanometers to about 60 nanometers. In some embodiments, the thickness of intermetallic and / or metal-containing films deposited according to some embodiments described herein may be 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 thickness of intermetallic and / or metal-containing films deposited according to some embodiments described herein may be 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 even less than about 1 nanometer.

[0108] In some embodiments of the present disclosure, intermetallic and / or metal-containing films can be deposited on three-dimensional structures, such as non-planar substrates, that include high-aspect-ratio features. In some embodiments, the step coverage of the intermetallic and / or metal-containing films can be equal to or greater than about 50%, or greater than about 80%, or greater than about 90%, or greater than about 95%, or greater than about 98%, or greater than about 99%, or higher, in structures having an aspect ratio (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.

[0109] Intermetallic compounds and / or metal-containing materials, or their corresponding films, comprise a first metal and a second metal as described herein. As specific examples, the first metal may include Co, Ni, Pt, or any other first metal mentioned herein, and the second metal may include Sn, In, Ga, Ge, As, Sb, Pb, and Bi (e.g., Sn, In, or Fe), or any other second metal mentioned herein, including Al. Exemplary intermetallic and / or metal-containing compounds include (hexagonal) Co3Sn2 or Ni3Sn2. Intermetallic 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 Co, Ni, Cu, and / or Pt and one or more of Sn, In, Ga, Ge, As, Sb, Pb, Al, and Bi. In some cases, the film containing the intermetallic compound and / or metal-containing material does not contain Al, Ga, and / or In and a transition metal.

[0110] In some embodiments of the present disclosure, intermetallic compounds and / or metal-containing materials and / or films containing 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 further embodiments, the compounds, materials, or films may contain less than about 5 atomic % hydrogen, less than about 2 atomic % hydrogen, less than about 1 atomic % hydrogen, or even less than about 0.5 atomic % hydrogen. In still further embodiments, the compounds, materials, or films may contain less than about 5 atomic % carbon, less than about 2 atomic % carbon, less than about 1 atomic % carbon, or even less than about 0.5 atomic % carbon. In still further embodiments, the compounds, materials, and films may contain less than about 5 atomic % halide species, less than about 2 atomic % halide species, less than about 1 atomic % halide species, or even less than about 0.5 atomic % halide species. In some embodiments, time of flight elastic recoil detection analysis (ToF-ERDA) may be utilized to determine the atomic % composition of intermetallic compounds, metal-containing materials, and films containing the same.

[0111] Reactors capable of depositing metal-containing films can be used to form the intermetallic compounds, metal-containing materials, and films described herein. Such reactors include ALD reactors and CVD reactors equipped with appropriate equipment and means for providing reactants. According to some embodiments, a hot-wall cross-flow reactor can be used. According to some embodiments, other cross-flow, batch, mini-batch, or spatial ALD reactors can be used.

[0112] 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), and EmerALD® XP and EmerALD® reactors, available from ASM America, Inc., Phoenix, Arizona, USA, and ASM Europe BV, Almere, The Netherlands. Other commercially available reactors include those sold under the Eagle® XP and XP8 designations from ASM Japan KK (Tokyo, Japan). In some embodiments, the reactor is a spatial ALD reactor, in which the substrate is moved or rotated during processing.

[0113] In some embodiments of the present disclosure, a batch reactor may be used. Suitable batch reactors include, but are not limited to, the Advance® 400 series reactors commercially available from ASM Europe BV (Almere, The Netherlands) under the trade names A400 and A412 PLUS. In some embodiments, the wafers are rotated during processing. In other embodiments, the batch reactor includes a mini-batch reactor configured to accommodate 10 or fewer substrates (e.g., semiconductor wafers), 8 or fewer substrates, 6 or fewer substrates, 4 or fewer substrates, or 2 or fewer substrates. In some embodiments using a batch reactor, the inter-wafer non-uniformity is less than 3% (1 sigma), less than 2%, less than 1%, or even less than 0.5%.

[0114] The deposition processes described herein may optionally be performed in a reactor or reaction chamber connected to a cluster tool. In a cluster tool, because each reaction chamber is dedicated to one process type, the temperature of the reaction chamber in each module can be maintained constant, which increases throughput compared to reactors in which the substrates are heated to the process temperature before each run. Additionally, the time to bring the reaction chamber pressure to the desired process pressure level between substrates can be shortened in a cluster tool. In some embodiments of the present disclosure, a deposition process may be performed in a cluster tool comprising multiple reaction chambers, wherein each individual reaction chamber may be used to expose the substrate to an individual reactant gas, and the substrates may be transferred between different reaction chambers for exposure to multiple reactant gases, the transfer of the substrates being performed in a controlled environment to prevent oxidation / contamination of the substrates. In some embodiments of the present disclosure, a deposition process may be performed in a cluster tool comprising multiple reaction chambers, wherein each individual reaction chamber may be configured to heat the substrate to a different deposition temperature.

[0115] Individual reactors can be equipped with a load lock. In this case, cooling of the reaction space between runs is unnecessary.

[0116] Figure 5 Schematically depicts a reactor system 500 in accordance with at least one embodiment of the present disclosure. Reactor system 500 can be used, for example, to perform cyclic deposition (eg, ALD) methods as described herein and / or to form structures, films, compounds, and / or materials as described herein.

[0117] In the illustrated example, reactor system 500 includes an optional substrate processing system 502, a reaction chamber 504, a gas distribution system 506, and optionally a wall 508 disposed between reaction chamber 504 and substrate processing system 502. System 500 may also include a first gas-phase reactant source 512, a second gas-phase reactant source 514, and an exhaust source 510. Although illustrated as having two gas sources 512, 514, reactor system 500 may include any suitable number of reactant gas sources. As an example, the exemplary reactor system may include at least two reactant gas sources (e.g., sources including compounds that will become first or second gas-phase reactants) and optionally one or more carrier gas and / or purge gas sources 516. Reactor system 500 also includes a susceptor 518 for holding one or more substrates 520 during processing.

[0118] Reactor system 500 may include any suitable number of reaction chambers 104 and substrate processing systems 502. As an example, reaction chamber 504 of reactor system 500 includes a cross-flow hot wall epitaxy reaction chamber. An exemplary reactor system includes a horizontal flow reactor available as a system from ASM.

[0119] It should be pointed out that Figure 5This is a simplified schematic version of the reactor system 500 and does not include every element that may be utilized in the reactor system 500, such as, but not limited to, valves, electrical connections, mass flow controllers, seals, and gas conduits.

[0120] In some embodiments of the present disclosure, one or more reactant source containers 522, 524 are in fluid communication with the reaction chamber 504 via conduits or other suitable means 526, 528 and may be further coupled to a gas distribution system 506 disposed between the reactant source containers 522, 524 and the reaction chamber 504. The gas distribution system 506 may include, for example, a manifold, a valve control system, a mass flow control system, and / or other mechanisms to control the gaseous reactants originating from the reactant source container 522 or 524. The reactant source containers 522, 524 may be configured to store metal-containing compounds (e.g., organometallic or metal-organic compounds), which may be first and second gaseous reactants, respectively, or may become first and second gaseous reactants, respectively, upon heating. In some embodiments, the reactant source containers 522, 524 may comprise a quartz material that is substantially chemically inert to the respective first and second reactants stored within the source containers 522, 524. In alternative embodiments of the present disclosure, reactant source vessels 522, 524 may be made of corrosion-resistant metals or metal alloys such as, for example, Hastelloy, Monel, or combinations thereof.

[0121] In some embodiments of the present invention, the reactant source containers 522, 524 may further include one or more heating units 526, 528 configured to heat the compounds stored in the reactant source containers 522, 524 to a desired temperature. In some embodiments, the one or more heating units may be utilized to heat the compounds to a temperature of approximately above 0° C., or approximately above 20° C., or approximately above 100° C., or approximately above 150° C., or approximately above 200° C., or approximately above 200° C., or approximately above 300° C., or even approximately above 400° C. In some embodiments, the one or more heating units 526, 528 may be configured to heat the compounds stored in the reactant source containers 522, 524 to a temperature of approximately about 25° C. to about 200° C., about 25° C. to about 300° C., or about 25° C. to about 400° C. As specific examples, when the gas-phase reactant includes Bu3SnH, the temperature may be in the range of about 20°C to about 40°C, or about 30°C; when the reactant includes CoCl2(TMEDA), the temperature may be in the range of about 150°C to about 190°C, or about 170°C; when the reactant includes NiCl2(TMPDA), the temperature may be in the range of about 140°C to about 180°C, or about 157°C; and when the reactant includes Ni(dmap)2, the temperature may be in the range of about 50°C to about 70°C, or about 62°C.

[0122] In some embodiments, one or more heating units 526, 528 associated with reactant source containers 522, 524 are configured to convert a compound from a solid into a liquid or gas to form a first gas-phase reactant or a second gas-phase reactant. In some embodiments, the viscosity of the reactant compound stored in each of the reactant source containers 522, 524 can be controlled using the one or more heating units 526, 528 associated with each of the reactant source containers 522, 524. In some embodiments, the one or more heating units 526, 528 associated with each of the reactant source containers 522, 524 can be configured to control the vapor pressure generated by the compound stored in the reactant source containers 522, 524. In some embodiments of the present disclosure, the compound can have a vapor pressure greater than 0.01 millibar at a temperature greater than 25°C, greater than 50°C, or even greater than 100°C. In some embodiments of the present disclosure, the compound can have a vapor pressure greater than 0.01 millibar at a temperature less than 350°C, less than 250°C, less than 200°C, or even less than 150°C. In some embodiments of the present disclosure, the compound may have a vapor pressure greater than 0.1 mbar at a temperature greater than 25° C., or even greater than 100° C. In some embodiments of the present disclosure, the compound may have a vapor pressure greater than 0.1 mbar at a temperature less than 400° C., or less than 200° C., or even less than 100° C. In some embodiments of the present disclosure, the compound may have a vapor pressure greater than 1 mbar at a temperature greater than 25° C., or even greater than 100° C. For example, the compound may be heated to a temperature greater than 150° C., thereby generating a vapor pressure greater than 0.001 mbar.

[0123] In some embodiments of the present disclosure, vapor passage 530 can be connected to reactant source container 522 (and / or reactant source container 524) so ​​that one or more carrier gases (e.g., from source 516 or another source) can be delivered from a carrier gas storage container to reactant source container 522 via vapor passage 530. In some embodiments, a mass flow controller (not shown) can be disposed on vapor passage 530 and positioned proximate to reactant source container 522. For example, the mass flow controller can be calibrated to control the mass flux of the carrier gas entering reactant source container 522, thereby allowing for better control of the subsequent flow of reactant vapor out of reactant source container 522 and into reaction chamber 504.

[0124] In some embodiments, a carrier gas (e.g., hydrogen, nitrogen, helium, argon, or any mixture thereof) may flow over the exposed surface of the compound, thereby picking up a portion of the vapor from the compound and, along with the carrier gas, delivering the compound (now the first or second gas-phase reactant) to the reaction chamber 504. In alternative embodiments of the present disclosure, the carrier gas may be "bubbled" through the compound, for example, through an optional vapor passageway (not shown), thereby agitating and picking up a portion of the metal-containing compound, and delivering the metal-containing compound vapor (now the first or second gas-phase reactant) to the reaction chamber 504 via gas conduit 526.

[0125] In some embodiments of the present disclosure, the reactor system 500 may also include a system operation and control mechanism 532, which provides electronic circuitry and mechanical components to selectively operate valves, manifolds, pumps, and other equipment associated with the reactor system 500. Such circuitry and components are used to introduce reactants, purge gases, and / or carrier gases from the corresponding reactant source containers 522, 524 and purge gas container 534. The system operation and control mechanism 532 may also control the timing of gas pulse sequences, the temperature of the substrate and / or reaction chamber, the pressure of the reaction chamber, and various other operations necessary to provide proper operation of the reactor system 500. The operation and control mechanism 532 may include control software and electrically or pneumatically controlled 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 include modules that perform certain tasks, such as software and / or hardware components, such as FPGAs or ASICs. The modules may be advantageously configured to reside on an addressable storage medium of the system operation and control mechanism 532 and configured to perform one or more processes.

[0126] Various other configurations of the reactor system are possible, including different numbers and types of reactant sources and purge gas sources. In addition, there are many arrangements of valves, conduits, reactant sources, and purge gas sources that can be used to achieve the goal of selectively feeding gases into the reaction chamber 504.

[0127] Examples

[0128] The examples provided below illustrate specific processes, films, and structures according to exemplary embodiments of the present disclosure. These examples are illustrative and are not intended to limit the scope of the present disclosure.

[0129] 1. A cyclic deposition process for depositing an intermetallic compound, the cyclic deposition method comprising the following steps:

[0130] providing a first gaseous reactant comprising a first metal to the reaction chamber to react with the surface of the substrate to form a first metal species; and

[0131] A second gas-phase reactant comprising a second metal is provided to the reaction chamber to react with the first metal species to thereby form the intermetallic compound.

[0132] 2. The cyclic deposition process of Example 1, further comprising repeating the steps of providing the first gas-phase reactant and providing the second gas-phase reactant until a desired film thickness is achieved.

[0133] 3. The cyclic deposition process of Example 1, further comprising one or more purge steps, wherein at least one of the purge steps is performed after the step of providing the first gas-phase reactant and before the step of providing the second gas-phase reactant.

[0134] 4. The cyclic deposition process of Example 1, wherein the cyclic deposition process comprises atomic layer deposition.

[0135] 5. The cyclic deposition process of Example 1, wherein the cyclic deposition process comprises cyclic chemical vapor deposition.

[0136] 6. The cyclic deposition process of Example 1, wherein the temperature within 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 between about 20°C and about 700°C, about 50°C and about 500°C, or about 50°C and about 400°C, about 75°C and about 300°C, or about 100°C and about 250°C.

[0137] 7. The cyclic deposition process of Example 1, wherein the second gas-phase reactant comprises a metal-containing organic compound.

[0138] 8. The cyclic deposition process of Example 1, wherein the second gas phase reactant is selected from compounds having the formula RMH, wherein R is an organic group and M is a metal.

[0139] 9. The cyclic deposition process of Example 1, wherein the second metal is selected from Sn, In, Al, Ga, Ge, As, Sb, Pb and Bi.

[0140] 10. The cyclic deposition process of Example 1, wherein the second metal is selected from Sn, Ge, As, Sb, Pb and Bi.

[0141] 11. The cyclic deposition process of Example 1, wherein the second metal comprises Sn.

[0142] 12. The cyclic deposition process of Example 1, wherein the second metal comprises In.

[0143] 13. The cyclic deposition process of Example 1, wherein the second metal comprises Ga.

[0144] 14. The cyclic deposition process of Example 8, wherein the compound having the formula RMH has 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.

[0145] 15. The cyclic deposition process of any one of Examples 8 and 14, wherein R comprises an alkyl group or other organic group.

[0146] 16. The cyclic deposition process of any one of examples 8 and 14, wherein R is independently selected from C1-C5 alkyl groups.

[0147] 17. The cyclic deposition process of any one of Examples 8 and 14, wherein R is a cyclopentadienyl, amino, alkoxy, amidine anion ligand, guanidine anion ligand, imino, carboxylate ligand, β-diketone anion ligand, β-ketoiminine anion ligand, malonate ligand, β-diketiminine anion ligand group, with or without additional donor functional groups.

[0148] 18. The cyclic deposition process of Example 1, wherein the second gas-phase reactant comprises a metal reducing agent.

[0149] 19. The cyclic deposition process of Example 1, wherein the first metal is selected from transition metals.

[0150] 20. The cyclic deposition process of Example 1, wherein the first metal is selected from Group 3-6 metals.

[0151] 21. The cyclic deposition process of Example 1, wherein the first metal is selected from Group 7-12 metals.

[0152] 22. The cyclic deposition process of Example 1, wherein the first metal is selected from the lanthanide series.

[0153] 23. The cyclic deposition process of Example 1, wherein the first metal is selected from Group 8-11 metals.

[0154] 24. The cyclic deposition process of Example 1, wherein the first metal is selected from Group 9-10 metals.

[0155] 25. The cyclic deposition process of Example 1, wherein the first gas-phase reactant is selected from metal halides.

[0156] 26. The cyclic deposition process of Example 1, wherein the first gas phase reactant comprises M(dmap) x (dmap = dimethylamino-2-propanolate), where M is a metal.

[0157] 27. The cyclic deposition process of Example 1, wherein the first gas phase reactant is selected from metal hydrides and aluminum reagents.

[0158] 28. The cyclic deposition process of Example 1, wherein the first gas phase reactant comprises a diamine adduct of a corresponding metal chloride.

[0159] 29. The cyclic deposition process of example 1, wherein the first gas-phase reactant comprises a metal halide compound comprising a bidentate nitrogen-containing adduct ligand.

[0160] 30. The cyclic deposition process of Example 29, wherein the adduct ligand comprises two nitrogen atoms, and wherein each nitrogen atom is bonded to at least one carbon atom.

[0161] 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).

[0162] 32. The cyclic deposition process of Example 1, wherein the second gas-phase reactant comprises TBTH.

[0163] 33. The cyclic deposition process of Example 1, wherein the intermetallic compound does not contain Al, Ga and / or In and transition metals.

[0164] 34. A cyclic deposition process for forming a metal-containing material, the cyclic deposition process comprising:

[0165] providing a first vapor-phase precursor comprising a first metal to the reaction chamber to form a first metal species; and

[0166] A second gas-phase reactant is provided to react with the first metal species to thereby form a metal-containing material, wherein the second gas-phase reactant comprises a compound having the general formula RMH, wherein R is an organic group and M is a metal.

[0167] 35. The cyclic deposition process of Example 34, wherein the first metal and the second metal are the same.

[0168] 36. The cyclic deposition process of Example 34, wherein the metal-containing material comprises elemental metal.

[0169] 37. The cyclic deposition process of example 1 or 34, wherein the metal-containing material comprises, for example, a mixture of In and Ge or other first metal and / or second metal.

[0170] 38. The cyclic deposition process of example 34, further comprising repeating the steps of providing the first gas-phase reactant and providing the second gas-phase reactant until a desired film thickness is achieved.

[0171] 39. The cyclic deposition process of example 34, further comprising one or more purge steps, wherein at least one of the purge steps is performed after the step of providing the first gas-phase reactant and before the step of providing the second gas-phase reactant.

[0172] 40. The cyclic deposition process of Example 34, wherein the cyclic deposition process comprises atomic layer deposition.

[0173] 41. The cyclic deposition process of Example 34, wherein the cyclic deposition process comprises cyclic chemical vapor deposition.

[0174] 42. The cyclic deposition process of Example 34, wherein the temperature within 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 between about 20°C and about 700°C, about 50°C and about 500°C, or about 50°C and about 400°C, about 75°C and about 300°C, or about 100°C and about 250°C.

[0175] 43. The cyclic deposition process of Example 34, wherein the first metal is selected from Sn, In, Ga, Al, Ge, As, Sb, Pb and Bi.

[0176] 44. The cyclic deposition process of Example 34, wherein the second metal is selected from Sn, Ge, As, Sb, Pb and Bi.

[0177] 45. The cyclic deposition process of Example 34, wherein the second metal comprises Sn.

[0178] 46. ​​The cyclic deposition process of Example 34, wherein the second metal comprises In.

[0179] 47. The cyclic deposition process of Example 34, wherein the second metal comprises Ga.

[0180] 48. The cyclic deposition process of Example 34, wherein the metal-containing material comprises one or more of a metal mixture, an alloy, and an intermetallic compound.

[0181] 49. The cyclic deposition process of Example 34, wherein the metal-containing material is one or more of a metallic, conductive, non-conductive, semiconductive, superconductive, catalytic, ferromagnetic, and magnetoresistive material.

[0182] 50. The cyclic deposition process of Example 34, wherein the compound having the general formula RMH has 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.

[0183] 51. The cyclic deposition process of Example 34, wherein R comprises an alkyl group or other organic group.

[0184] 52. The cyclic deposition process of Example 34, wherein R is independently selected from a C1-C5 alkyl group.

[0185] 53. The cyclic deposition process of any one of Examples 34-52, wherein R is a cyclopentadienyl, amino, alkoxy, amidine anion ligand, guanidine anion ligand, imino, carboxylate ligand, β-diketone anion ligand, β-ketoiminine anion ligand, malonate ligand, β-diketiminine anion ligand group, with or without additional donor functional groups.

[0186] 54. The cyclic deposition process of Example 34, wherein the second gas-phase reactant comprises a metal reducing agent.

[0187] 55. The cyclic deposition process of Example 34, wherein the first metal is selected from transition metals.

[0188] 56. The cyclic deposition process of Example 34, wherein the first metal is selected from Group 3-6 metals.

[0189] 57. The cyclic deposition process of Example 34, wherein the first metal is selected from Group 7-12 metals.

[0190] 58. The cyclic deposition process of Example 34, wherein the first metal is selected from the lanthanide series.

[0191] 59. The cyclic deposition process of Example 34, wherein the first metal is selected from Group 8-11 metals.

[0192] 60. The cyclic deposition process of Example 34, wherein the first metal is selected from Group 9-10 metals.

[0193] 61. The cyclic deposition process of Example 34, wherein the first gas phase reactant is selected from metal halides.

[0194] 62. The cyclic deposition process of Example 34, wherein the first gas phase reactant comprises M(dmap) x (dmap = dimethylamino-2-propanolate), where M is a metal.

[0195] 63. The cyclic deposition process of Example 34, wherein the first gas phase reactant is selected from metal hydrides and aluminum reagents.

[0196] 64. The cyclic deposition process of Example 34, wherein the first gas phase reactant comprises a diamine adduct of a corresponding metal chloride.

[0197] 65. The cyclic deposition process of example 34, wherein the first gas phase reactant comprises a metal halide compound comprising a bidentate nitrogen-containing adduct ligand.

[0198] 66. The cyclic deposition process of Example 65, wherein the adduct ligand comprises two nitrogen atoms, and wherein each nitrogen atom is bonded to at least one carbon atom.

[0199] 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).

[0200] 68. The cyclic deposition process of Example 34, wherein the second gas phase reactant comprises TBTH.

[0201] 69. A film formed according to the process of any of Examples 1-33.

[0202] 70. The film of Example 69, wherein the film is metallic, conductive, semiconductive, or non-conductive.

[0203] 71. The membrane of Example 69, wherein the membrane is superconducting.

[0204] 72. The film of Example 69, wherein the film is magnetoresistive.

[0205] 73. The film of Example 69, wherein the film is ferromagnetic.

[0206] 74. The membrane of Example 69, wherein the membrane is a catalyst.

[0207] 75. A membrane formed according to the process of any of Examples 34-68.

[0208] 76. The film of Example 75, wherein the film comprises one or more of a metal mixture, an alloy, and an intermetallic compound.

[0209] 77. A device structure comprising a film according to one or more of Examples 69 and 76.

[0210] The example embodiments of the present disclosure described above do not limit the scope of the present invention, as these embodiments are merely examples of embodiments of the present invention, which are defined by the appended claims and their legal equivalents. Any equivalent embodiments are intended to be included within the scope of the present invention. Indeed, various modifications of the present disclosure, such as alternative available combinations of the elements described, in addition to those shown and described herein, will be apparent to those skilled in the art from the description. Such modifications and embodiments are also intended to fall within the scope of the appended claims.

Claims

1. A cyclic deposition process for depositing an intermetallic compound, the cyclic deposition method comprising the following steps: providing a first gaseous reactant comprising a first metal to the reaction chamber to react with the surface of the substrate to form a first metal species; providing a second gaseous reactant comprising a second metal to the reaction chamber to react with the first metal species to thereby form the intermetallic compound, Wherein the intermetallic compound has a different crystal structure than the corresponding alloy, the corresponding alloy exhibiting the crystal structure of one of the participating metallic components, the intermetallic compound is formed when the bonds between different atoms are stronger than the bonds between atoms of the same element.

2. The cyclic deposition process of claim 1, wherein the second gas-phase reactant comprises a metal-containing organic compound.

3. The cyclic deposition process of claim 1, wherein the second gas phase reactant is selected from compounds having the formula RMH, wherein R is an organic group and M is a metal.

4. The cyclic deposition process of claim 1, wherein the second metal is selected from Sn, In, Al, Ga, Ge, As, Sb, Pb, and Bi.

5. The cyclic deposition process of claim 3, wherein the compound of formula RMH has formula R (X-n) -M X -H n , wherein X is the formal oxidation state of the metal and n is 1 to 5.

6. The cyclic deposition process according to any one of claims 3 and 5, wherein R is independently selected from C1-C5 alkyl groups.

7. A cyclic deposition process according to any one of claims 3 and 5, wherein R is a cyclopentadienyl, amino, alkoxy, amidine anion ligand, guanidine anion ligand, imino, carboxylate ligand, β-diketone anion ligand, β-ketoiminine anion ligand, malonate ligand, β-diketiminine anion ligand group, which may or may not have additional donor functional groups.

8. The cyclic deposition process of claim 1, wherein the second gas-phase reactant comprises a metal reducing agent.

9. The cyclic deposition process of claim 1, wherein the first gas phase reactant comprises a diamine adduct of a corresponding metal chloride.

10. The cyclic deposition process of claim 1, wherein the first gas-phase reactant comprises a metal halide compound comprising a bidentate nitrogen-containing adduct ligand.

11. The cyclic deposition process of claim 1, wherein the first gas-phase reactant comprises at least one of cobalt chloride (TMEDA) and nickel chloride (TMPDA).

12. The cyclic deposition process of claim 1, wherein the second gas-phase reactant comprises TBTH.

13. A cyclic deposition process for forming a metal-containing material, the cyclic deposition process comprising: providing a first vapor-phase precursor comprising a first metal to a reaction chamber to form a first metal species; as well as providing a second gas-phase reactant to react with the first metal species to thereby form the metal-containing material, wherein the second gas-phase reactant comprises a compound having the general formula RMH, wherein R is an organic group and M is a metal, wherein the temperature in the reaction chamber is higher than 0°C and lower than 600°C, wherein the metal-containing material is an intermetallic compound, Wherein the intermetallic compound has a different crystal structure than the corresponding alloy, the corresponding alloy exhibiting the crystal structure of one of the participating metallic components, the intermetallic compound is formed when the bonds between different atoms are stronger than the bonds between atoms of the same element.

14. The cyclic deposition process of claim 13, wherein the metal-containing material comprises elemental metal.

15. The cyclic deposition process of claim 13, wherein the first metal is selected from Sn, In, Ga, Al, Ge, As, Sb, Pb, and Bi.

16. The cyclic deposition process of claim 13, wherein the compound of formula RMH has formula R (X-n) -M X -H n , wherein X is the formal oxidation state of the metal and n is 1 to 5.

17. The cyclic deposition process of claim 13, wherein the first gas phase reactant comprises a diamine adduct of a corresponding metal chloride.

18. The cyclic deposition process of claim 13, wherein the first gas-phase reactant comprises at least one of cobalt chloride (TMEDA) and nickel chloride (TMPDA).

19. The cyclic deposition process of claim 13, wherein the second gas-phase reactant comprises TBTH.

20. A device structure comprising a film according to one or more of claims 1-19.

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