Method and apparatus for stabilizing vanadium compounds

Abstract

To provide methods of stabilizing a vanadium compound in solution, compositions including a vanadium compound and a stabilizing agent, apparatus including the composition, systems that use the composition, and methods of using the compositions, apparatus, and systems.SOLUTION: Use of the stabilizing agent allows for use of desired precursors, while mitigating unwanted decomposition of the precursors.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates generally to methods and apparatus suitable for gas phase reactor systems. More specifically, the present disclosure relates to methods, compounds, and apparatus that can be used to stabilize precursors in gas phase reactor systems. [Background technology]

[0002] A precursor is a compound that can be used to form another material. For example, a precursor can be used in a gas-phase reaction to form a thin film or layer of material. Unfortunately, some precursors, which may have desirable properties, such as a desirable vapor pressure at normal pressure and temperature and / or a desired reactivity, e.g., with surfaces or other compounds, can thermally decompose into other compounds. In particular, some precursors can decompose to produce corrosive gases that can corrode reactor system components and / or result in undesirable etching during processing. Decomposition can reduce the precursor's shelf life, complicate manufacturing, require additional purification steps, cause storage and / or shipping issues, and limit the amount of desired material in a supply vessel available for reaction in the reactor system. Furthermore, corrosion of reactor system components can shorten the life of the reactor system and / or its components, thereby increasing the cost of operating such equipment. Furthermore, corrosion can cause reactor system etch products to become incorporated into the deposited film and / or etch the film on the substrate, which in turn can result in a decrease in the quality and / or uniformity of such films. Furthermore, the rate of precursor decomposition generally accelerates with temperature, thus inhibiting the ability to increase precursor flow into the reaction chamber by heating the precursor.

[0003] Efforts to reduce precursor decomposition can result in precursors that produce films with undesirably high carbon content, require undesirably high temperatures to achieve desired flow rates, result in chemical vapor deposition (CVD) of materials when atomic layer deposition (ALD) is desired, lack desired growth rate control, and / or exhibit relatively poor step coverage. Therefore, improved methods, apparatus, and compositions for providing precursors for gas-phase reactions are desirable.

[0004] All descriptions, including descriptions of the problems and solutions described in this section, are included in this disclosure solely for the purpose of providing a context for the disclosure, and such descriptions should not be construed as an admission that any or all of the information was known at the time the invention was made or constitutes prior art. Summary of the Invention [Means for solving the problem]

[0005] This Summary introduces selected concepts in a simplified form that may be described in more detail below. This Summary is not necessarily intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0006] Various embodiments of the present disclosure relate to methods for stabilizing vanadium compounds in solution, compositions comprising vanadium compounds and stabilizers, devices comprising the compositions, systems using the compositions, and methods of using the compositions, devices, and systems.

[0007] According to an exemplary embodiment of the present disclosure, a method for stabilizing a vanadium compound in a solution is provided. The method may include incorporating an effective amount of one or more stabilizing agents into the solution, the solution including the vanadium compound and the one or more stabilizing agents. An exemplary vanadium compound includes a vanadium halide. The one or more stabilizing agents may include an organic molecule. The organic molecule may include one or more of nitrogen, oxygen, sulfur, and / or oxygen heteroatoms. The one or more stabilizing agents may include an adduct-forming compound. Additionally or alternatively, the one or more stabilizing agents may include an aprotic compound. Additionally or alternatively, the one or more stabilizing agents may include a compound containing one or more heteroatoms with lone pairs of electrons. By way of example, at least one of the one or more stabilizers may be a tertiary amine of formula NR3, where all -R groups are independently C1-C20 alkyl or C1-C20 aryl groups; a tertiary phosphine of formula PR3, where all -R groups are independently C1-C20 alkyl or C1-C20 aryl groups; an ether of formula OR2, where all -R groups are independently C1-C20 alkyl or C1-C20 aryl groups; a dialkyl sulfide, diaryl sulfide, or mixed alkyl / aryl sulfide of formula SR2, where all -R groups are independently C1-C20 alkyl or C1-C20 aryl groups; an aromatic heterocyclic amine such as pyridine, pyridazine, pyrimidine, pyrazine, or 1,2,4-triazine, and alkyl or aryl sulfides thereof. aprotic non-aromatic heterocyclic amines such as N-alkylpiperidines, N,N'-dialkylpiperazines, N-alkylpyrrolidines, N-alkylpyrroles, N-alkylpyrrolines, N,N'-dialkylimidazolidines, and similar compounds, where alkyl can be a C1-C20 hydrocarbon group; heterocyclic ethers such as furan, tetrahydrofuran, pyran, tetrahydropyran, 1,4-dioxane, 1,4-dioxine, and similar compounds, and alkyl or aryl substituted versions thereof; heterocyclic thioethers such as thiophene, tetrahydrothiophene, thiazole, thiane, thiopyran, dithiane, and similar compounds, and the common alkyl or aryl substituted versions thereof.The stabilizer or stabilizers may be added or present in an amount of 0.001 mol % to 300 mol %, or 0.1 mol % to 100 mol % of the amount of vanadium compound present in the solution.

[0008] According to a further example of the present disclosure, a composition is provided. An exemplary composition includes a vanadium compound and an effective amount of one or more stabilizers, e.g., an amount that reduces decomposition of the vanadium compound. The vanadium compound can be any vanadium compound, such as those described herein. Similarly, the one or more stabilizers can include any suitable stabilizer, such as those described herein.

[0009] In yet additional embodiments of the present disclosure, a container for providing precursors for gas phase (e.g., semiconductor) processing is provided. The container may contain a vanadium compound and / or composition and / or solution described herein. The container may include a base and a removable lid.

[0010] According to additional examples of the present disclosure, an apparatus for manufacturing a device is provided. The apparatus can include a container (e.g., a container described herein) that can be attached to a reactor of a reactor system. The container can be configured to transport, store, and / or deliver a composition, such as a composition described herein, to the reactor.

[0011] According to a further exemplary embodiment of the present disclosure, a method for fabricating a device is provided. The method includes providing a composition to a reaction chamber, the composition including a vanadium compound and one or more stabilizers. The vanadium compound and / or the one or more stabilizers may be as described above and elsewhere herein. The reactor may be a gas-phase reactor designed for fabricating semiconductor devices. According to an example of the present disclosure, the reactor is designed for deposition of thin films. The composition may be a composition described above or elsewhere herein.

[0012] According to a further example of the present disclosure, a system is provided. An exemplary system may include one or more reaction chambers, a source including a composition including a vanadium compound and one or more stabilizers, and a controller, the controller configured to control flow of the composition or the vanadium compound into at least one of the one or more reaction chambers. The composition, vanadium compound, and one or more stabilizers may be as described above and elsewhere herein.

[0013] According to still further examples of the present disclosure, there is provided the use of one or more stabilizers to stabilize a vanadium compound. The vanadium compound and / or the one or more stabilizers may be as described above and elsewhere herein.

[0014] According to yet further examples of the present disclosure, systems are disclosed for performing the methods described herein and / or forming structures, devices, or portions of any thereof.

[0015] These and other embodiments will become readily apparent to those skilled in the art from the following detailed description of certain embodiments, taken in conjunction with the accompanying drawings, in which: The invention is not limited to any particular embodiment disclosed.

[0016] A more complete understanding of the embodiments of the present disclosure can be obtained by reference to the detailed description and claims when considered in conjunction with the following illustrative drawings. [Brief explanation of the drawings]

[0017] [Figure 1] 1 illustrates a reactor system according to an additional exemplary embodiment of the present disclosure. [Figure 2] 1 illustrates a container and apparatus according to an additional exemplary embodiment of the present disclosure; DETAILED DESCRIPTION OF THE INVENTION

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

[0019] The descriptions of exemplary embodiments of methods, compositions, containers, devices, systems, and uses thereof provided below are merely exemplary and for illustrative purposes only, and the following descriptions are not intended to limit the scope of the present disclosure or the claims. Moreover, the recitation of multiple embodiments having stated features is not intended to exclude other embodiments having additional features or other embodiments incorporating different combinations of the stated features. For example, various embodiments may be described as exemplary embodiments and recited in the dependent claims. Unless otherwise specified, exemplary embodiments or components thereof may be combined or applied separately from each other.

[0020] As described in more detail below, various embodiments of the present disclosure provide methods, systems, compositions, and apparatus that allow for the transport, storage, and / or delivery of compositions and / or vanadium compounds to (e.g., gas-phase) reactors of a reactor system. Exemplary compositions include one or more stabilizers to mitigate undesired decomposition of the vanadium compounds. The methods, compositions, vessels, apparatus, systems, and uses thereof described herein can be used in a variety of applications, including those described in the Appendix.

[0021] In this disclosure, "gas" can include materials that are gases at ambient temperature and pressure (NTP), vaporized solids, and / or vaporized liquids, and can consist of a single gas or a mixture of gases, depending on the circumstances. Gases other than process gases, i.e., gases introduced without passing through a gas distribution assembly, other gas distribution devices, etc., can be used, for example, to seal the reaction space and can include seal gases, such as noble gases. In some cases, the term "precursor" can refer to a compound that participates in a chemical reaction to produce another compound, and specifically, a compound that constitutes the film matrix or main framework of the film. The term "reactant" can be used interchangeably with the term precursor. The term "inert gas" can refer to a gas that does not participate in a chemical reaction and / or does not become part of the film matrix to a significant extent. Exemplary inert gases include helium, argon, and any combination thereof. In some examples, the inert gas can include nitrogen and / or hydrogen.

[0022] As used herein, the term "substrate" may refer to any underlying material or materials that can be used to form a device, circuit, or film, or any underlying material or materials on which a device, circuit, or film can be formed. The substrate can include bulk materials such as silicon (e.g., monocrystalline silicon), other Group IV materials such as germanium, or other semiconductor materials such as Group II-VI or Group III-V semiconductor materials, and can include one or more layers overlying or underlying the bulk material. Additionally, the substrate can include various features (such as recesses, protrusions, and the like) formed in or on at least a portion of the layers of the substrate. Illustratively, the substrate can include a bulk semiconductor material and an insulating or dielectric material layer overlying at least a portion of the bulk semiconductor material.

[0023] As used herein, the terms "film" and / or "layer" can refer to any continuous or discontinuous structure and material, such as materials deposited by the methods disclosed herein. For example, films and / or layers can include two-dimensional materials, three-dimensional materials, nanoparticles, or partial or complete molecular layers, partial or complete atomic layers, or even clusters of atoms and / or molecules. A film or layer may include a material or layer with pinholes and may be at least partially continuous. As used herein, a "vanadium nitride layer" can be a material layer that can be represented by a chemical formula including vanadium and nitrogen. A vanadium nitride layer can include additional elements such as oxygen (e.g., a vanadium oxynitride layer). As used herein, a "layer including vanadium boride" can be a material layer that can be represented by a chemical formula including vanadium and boron. In some cases, the vanadium boride layer includes vanadium diboride (VB2). As used herein, a "vanadium phosphide-containing layer" may be a material layer that can be represented by a chemical formula that includes vanadium and phosphorus. The vanadium phosphide-containing layer may include vanadium(III) phosphide (VP).

[0024] As used herein, a "structure" can be or include a substrate as described herein. A structure can include one or more layers overlying a substrate, such as one or more layers formed according to the methods described herein. Devices and device portions can be, include, or be formed using structures.

[0025] The term "cyclic deposition process" or "cyclical deposition process" can refer to the sequential introduction of precursors (and / or reactants) into a reaction chamber to deposit layers on a substrate, and includes processing techniques such as atomic layer deposition (ALD), cyclical chemical vapor deposition (cyclic CVD), and hybrid cyclic deposition processes that include ALD and cyclic CVD components.

[0026] The term "atomic layer deposition" can refer to a vapor deposition process in which deposition cycles, typically multiple consecutive deposition cycles, are performed in a process chamber. As used herein, the term atomic layer deposition is also meant to include processes denoted by related terms, such as chemical vapor deposition, atomic layer deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas source MBE, or metalorganic MBE, and chemical beam epitaxy, when performed with alternating pulses of precursor / reactive gases and purge (e.g., inert carrier) gases.

[0027] As used herein, "vanadium compounds" includes compounds that can be represented by a chemical formula that includes vanadium.

[0028] Furthermore, in this disclosure, any two variables can constitute a workable range for that variable, and any stated range may include or exclude endpoints. Furthermore, any value of a stated variable (whether or not it is indicated as "about") may refer to an exact or approximate value, including equivalents, and may refer to a mean, median, representative value, or majority, etc. Furthermore, in this disclosure, the terms "comprising," "comprising," and "having" independently refer, in some embodiments, to "typically or broadly comprising," "comprising," "consisting essentially of," or "consisting of." Furthermore, whether explicitly stated or not, the compositions and compounds described herein can comprise, consist essentially of, or consist of the compounds and agents described herein. In this disclosure, any defined meaning does not necessarily exclude the ordinary and customary meaning in some embodiments.

[0029] Referring now to the figures, FIG. 1 illustrates a system 100 according to an exemplary embodiment of the present disclosure. The system 100 can be used to perform the methods described herein and / or to form the structures or device portions described herein. The vanadium precursors and compositions described herein can be used to form layers such as vanadium nitride layers, vanadium boride layers, and / or vanadium phosphide layers. Layers including one or more of vanadium boride and vanadium phosphide can be used in metal-oxide-semiconductor (MOS) applications (e.g., as work function layers and / or dipole or flatband shifters). The vanadium boride and / or vanadium phosphide layers can be used in various applications, such as gate stack metal layers, logic or memory (e.g., NAND, V-NAND, DRAM) electrode layer applications, etch stop layers (as front-end (FEOL), middle-end (MEOL), and / or back-end (BEOL) end of line processing), and / or diffusion barrier layers or liners. As specific examples, vanadium boride and / or vanadium phosphide layers may be used as work function metals (e.g., for NMOS devices), as work function adjusting layers, as voltage threshold adjusting layers, as (e.g., p) dipole or flatband shifter layers, or the like.

[0030] The structures described herein may be or form part of CMOS structures, such as one or more of PMOS and NMOS structures, or other device structures. In some embodiments, the structures may be gate electrodes. Furthermore, structures and devices according to the present disclosure may include vertical and / or three-dimensional structures and devices, such as FinFET devices.

[0031] In the illustrated example, the system 100 includes one or more reaction chambers 102 , a precursor gas source 104 , a reactant source 106 , a purge gas source 108 , an exhaust source 110 , and a controller 112 .

[0032] The reaction chamber 102 may include any suitable reaction chamber, such as an ALD or CVD reaction chamber.

[0033] The precursor gas source 104 may include a container and one or more vanadium compounds described herein, one or more stabilizers described herein, and / or a composition described herein. As described in more detail below, the composition may be a liquid at ambient temperature and pressure.

[0034] The reactant gas source 106 may include a container and one or more reactants (e.g., boron reactant, phosphorus reactant, nitrogen reactant, carbon reactant, sulfur reactant), alone or mixed with other compounds. The purge gas source 108 may include one or more inert gases described herein. Although shown with three gas sources 104-108, the system 100 may include any suitable number of gas sources. The gas sources 104-108 may be connected to the reaction chamber 102 via lines 114-118, each of which may include flow controllers, valves, heaters, etc.

[0035] The exhaust source 110 may include one or more vacuum pumps.

[0036] The controller 112 includes electronic circuitry and software that selectively operate the valves, manifolds, heaters, pumps, and other components included in the system 100. Such circuitry and components operate to introduce precursor, reactant, and purge gases from their respective sources 104-108. By way of example, the controller 112 may be configured to control the flow of a composition or vanadium compound to at least one of the one or more reaction chambers. The controller 112 may control the timing of gas pulse sequences, the temperature of the substrate and / or reaction chamber, the pressure within the reaction chamber, and various other operations to properly operate the system 100. The controller 112 may include control software that electrically or pneumatically controls valves to control the flow of precursor, reactant, and purge gases into and out of the reaction chamber 102. The controller 112 may include software or hardware components, such as modules, such as FPGAs or ASICs, that perform specific tasks. The modules may advantageously be configured to reside on addressable storage media in the control system and be configured to perform one or more processes.

[0037] Other configurations of the system 100 are possible, including different numbers and types of precursor and reactant sources and purge gas sources. It will be appreciated that there are numerous arrangements of valves, conduits, precursor sources, and purge gas sources that can be used to achieve the goal of selectively delivering gases into the reaction chamber 102. Furthermore, as a schematic representation of the system, many components have been omitted for ease of illustration. Such components may include, for example, various valves, manifolds, purifiers, heaters, reservoirs, vents, and / or bypasses.

[0038] During operation of reactor system 100, a substrate (not shown), such as a semiconductor wafer, is transferred, for example, from a substrate handling system to reaction chamber 102. Once the substrate is transferred to reaction chamber 102, one or more gases, such as precursors, reactants, carrier gases, and / or purge gases, from gas sources 104-108 are introduced into reaction chamber 102.

[0039] 2 shows an apparatus 200. The apparatus 200 may be attached to a reactor of a reactor system. For example, the apparatus 200 may be used as or form part of, for example, the gas source 104.

[0040] In the illustrated example, apparatus 200 comprises a vessel 203 including a base 202 and a lid 204 for containing composition 214 within vessel 203. Vessel 203 may be configured to transport, store, and / or deliver reactor composition 214.

[0041] The container 203 may be formed of any suitable material. By way of example, the base 202 and / or lid 204 of the container 203 may be formed of stainless steel. In other embodiments, the base 202 and / or lid 204 may be formed of a high nickel alloy, aluminum, or titanium. Of course, the base 202 and / or lid 204 may be formed of any other material that is substantially inert or non-reactive with the composition 214 within the container 203.

[0042] The lid 204 may be removably attached to the base 202. Once the lid 204 is removably attached to the base 202, a seal (not shown) may be disposed between the lid 204 and the base 202 such that the contents within the container 203 are secured therein. In one embodiment, the base 202 and the lid 204 are formed of the same material such that both have substantially the same thermal conductivity and the same coefficient of thermal expansion. In another embodiment, the base 202 may be formed of a different material than the material used to form the lid 204.

[0043] The device 200 may also include one or more valves 206, 208 coupled to the lid 204 and in fluid communication with the interior of the base 202. The device 200 may optionally include one or more blocks 210, 212 that may include internal gas passages.

[0044] Compositions suitable for use as composition 214 may include a vanadium compound and an effective amount of one or more stabilizers. The composition may be referred to herein as a solution. The stabilizer may reduce or facilitate the reduction of undesired thermal decomposition of the vanadium compound, such as decomposition that may otherwise occur during transportation or storage of the vanadium compound. By way of example, the stabilizer may combine with and / or form an adduct with the vanadium compound and / or may include a solvent that stabilizes the vanadium compound. Existing solutions for stabilizing compounds such as vanadium tetrachloride (VCl4) include the use of strong chlorinating agents to prevent decomposition. However, strong chlorinating agents such as acetyl chloride or phosphorus trichloride are corrosive, and the use of such compounds may raise environmental, health, and / or safety concerns and / or deposit impurities in layers formed using the composition.

[0045] The vanadium precursor may include, for example, one or more of vanadium halides, vanadium oxyhalides, vanadium organometallic compounds, vanadium metal organic compounds, vanadium beta-diketone compounds, vanadium cyclopentadienyl compounds, vanadium alkoxide compounds, vanadium dialkylamide compounds, vanadium amidinate compounds, DAD ligand compounds (where DAD is represented by 1,4-diaza-1,3-butadiene (RN=CR'CR'=NR, R=alkyl, aryl, R'=H, alkyl)), and vanadium heteroleptic or mixed ligand compounds or the like.

[0046] As a specific example, the vanadium halide may be selected from one or more of vanadium fluoride, vanadium chloride, vanadium bromide, and vanadium iodide. The vanadium halide may contain only vanadium and one or more halogens, such as vanadium tetrachloride. The vanadium oxyhalide may be selected from one or more vanadium oxyhalides, such as vanadium oxyfluoride, vanadium oxychloride, vanadium oxybromide, and vanadium oxyiodide. The vanadium oxyhalide may contain only vanadium, oxygen, and one or more halogens. By way of example, the vanadium halides and oxyhalides may be selected from the group consisting of and including one or more of VCl, VBr, VI, VOCl, VOBr, and VOI (referred to as vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide, vanadium trichloride, vanadium oxytribromide, and vanadium oxytriiodide, respectively).

[0047] Exemplary vanadium beta-diketone compounds include VO(acac), VO(thd), V(acac), and V(thd) (referred to as oxobis(2,4-pentanedione)vanadium(IV), oxobis(2,2,6,6-tetramethyl-3,5-heptanedione)vanadium(IV), tris(2,4-pentanedione)vanadium(IV), and tris(2,2,6,6-tetramethyl-3,5-heptanedione)vanadium(IV), respectively), and / or VO(hfac) or V(hfac), where hfac is a hexafluoroacetylacetonate ligand, and the like.

[0048] Exemplary vanadium cyclopentadienyl compounds include VCp2Cl2, VCp2, VCp2(CO)4, and VCpCl3 (referred to as bischlorobis(cyclopentadienyl)vanadium(IV), bis(cyclopentadienyl)vanadium(II), cyclopentadienylvanadium tetracarbonyl, and trichloro(cyclopentadienyl)vanadium(IV), respectively. Additional exemplary vanadium cyclopentadienyl compounds include variations of these compounds, where Cp is unsubstituted or bears one or more alkyl groups, such as, for example, MeCp, EtCp, iPrCp, etc.

[0049] Exemplary vanadium alkoxide compounds are V(OMe)4, V(OEt)4, V(OiPr)4, V(OtBu)4, VO(OMe)3, VO(OEt)3, VO(OiPr)3, and VO(OtBu)3 (referred to as tetrakis(methoxy)vanadium(IV), tetrakis(ethoxy)vanadium(IV), tetrakis(isopropoxy)vanadium(IV), tetrakis(t-butoxy)vanadium(IV), oxotris(methoxy)vanadium(IV), oxotris(ethoxy)vanadium(IV), oxotris(isopropoxy)vanadium(IV), and oxotris(t-butoxy)vanadium(IV), respectively). Additional vanadium alkoxide compounds include variations of these compounds in which other alkoxy ligands are used.

[0050] Exemplary vanadium dialkylamide compounds include V(NMe2)4, V(NEt2)4, and V(NEtMe)4, (referred to as tetrakis(dimethylamido)vanadium(IV), tetrakis(diethylamido)vanadium(IV), and tetrakis(ethylmethylamido)vanadium(IV), respectively).

[0051] Exemplary amidinate compounds include V(iPrFMD), V(iPrAMD), V(tBuFMD), and V(tBuAMD), where iPrFMD is an N,N'-diisopropylformamide ligand, iPrAMD is an N,N'-diisopropylacetamide ligand, tBuFMD is an N,N'-di-tert-butylformamidinate ligand, and tBuAMD is an N,N'-di-tert-butylacetamidinate ligand.

[0052] Examples of precursors containing DAD ligands include V(DAD)2, V(DAD)(CO)4, VCp(DAD)(CO)2, V(DAD)Cl3, and V(DAD)2(NO)2, where DAD is 1,4-diaza-1,3-butadiene (RN=CR'CR'=NR, where R=alkyl or aryl group, and R'=H or alkyl group).

[0053] Additionally, exemplary vanadium precursors can include "heteroleptic" or mixed-ligand precursors, where any combination of exemplary ligand types can be attached to the vanadium atom in any achievable number (typically 3-5 ligands, but there are exceptions). Examples include V(Cl) x (NMe) 4‐x and V(Cl) x (iPrAMD) x could be included.

[0054] The use of vanadium halide precursors may be advantageous compared to methods using other precursors, such as vanadium organometallic precursors, because vanadium halide precursors may be relatively inexpensive, may result in vanadium layers with lower concentrations of impurities such as carbon, and / or processes using such precursors may be more controllable compared to processes using organometallic or other vanadium precursors. Furthermore, such reactants can be used to form excited species without the aid of a plasma. Also, processes using vanadium halide precursors may be easier to scale up compared to methods using organometallic vanadium precursors.

[0055] According to examples of the present disclosure, the composition is liquid at ambient temperature and pressure.

[0056] According to examples of the present disclosure, the vanadium compound includes a vanadium halide, which may be or may include a vanadium chloride, such as vanadium tetrachloride.

[0057] Exemplary stabilizers may include adduct-forming compounds. Additionally or alternatively, one or more of the stabilizers may include compounds having one or more of the following characteristics: 1) being aprotic (e.g., an aprotic compound) and lacking a hydrogen atom that can be protonated by the vanadium compound; 2) containing one or more heteroatoms with lone pairs of electrons that can form modified bonds to the vanadium to form adducts; 3) being selected so as not to affect the delivery of vanadium compound vapor or vanadium compound adduct vapor; 4) being selected to minimize incorporation of the stabilizer as an impurity into the vanadium-containing film; and / or 5) being incorporated in amounts ranging from trace "catalyst inhibitor" amounts up to a 1:1 stoichiometric amount. The desired ratio may depend, for example, on the particular vanadium compound and the desired stabilization.

[0058] According to embodiments of the present disclosure, at least one of the one or more stabilizers may be or include an organic molecule, which may include one or more of nitrogen, oxygen, sulfur, and / or oxygen heteroatoms.

[0059] According to further examples of the present disclosure, at least one of the one or more stabilizers may be selected from the group consisting of tertiary amines of formula NR3, where all -R groups are independently C1-C20 alkyl groups or C1-C20 aryl groups; tertiary phosphines of formula PR3, where all -R groups are independently C1-C20 alkyl groups or C1-C20 aryl groups; ethers of formula OR2, where all -R groups are independently C1-C20 alkyl groups or C1-C20 aryl groups; dialkyl sulfides, diaryl sulfides, or mixed alkyl / aryl sulfides of formula SR2, where all -R groups are independently C1-C20 alkyl groups or C1-C20 aryl groups; aromatic heterocyclic amines such as pyridine, pyridazine, pyrimidine, pyrazine, or 1,2,4-triazine; The alkyl or aryl substituted heterocyclic amines may be selected from the group consisting of aprotic non-aromatic heterocyclic amines such as N-alkylpiperidines, N,N'-dialkylpiperazines, N-alkylpyrrolidines, N-alkylpyrroles, N-alkylpyrrolines, N,N'-dialkylimidazolidines, and similar compounds, where alkyl can be a C1-C20 hydrocarbon group; heterocyclic ethers such as furan, tetrahydrofuran, pyran, tetrahydropyran, 1,4-dioxane, 1,4-dioxine, and similar compounds, and alkyl or aryl substituted versions thereof; and heterocyclic thioethers such as thiophene, tetrahydrothiophene, thiazoles, thianes, thiopyrans, dithianes, and similar compounds, and common alkyl or aryl substituted versions thereof. The solution or composition may contain any suitable number of stabilizers, such as two or more stabilizers, where one or more of the two or more stabilizers may be selected from the list above. The two or more stabilizers may include any combination of two or more stabilizers, including at least one stabilizer from the examples above.

[0060] According to a further example of the present disclosure, there is provided a method for stabilizing a vanadium compound in a solution (also referred to herein as a composition). The method may include incorporating an effective amount of one or more stabilizers into the solution. By way of example, the one or more stabilizers may be added in an amount of 0.001 mol% to 300 mol%, or 0.1 mol% to 100 mol% of the amount of vanadium compound present in the solution. Thus, the one or more stabilizers may be added in an amount of 1 mol%, 25 mol%, 50 mol%, or 200 mol% of the vanadium compound present in the solution. The ratio of the vanadium compound and one or more stabilizers present in the solution may be calculated according to the amounts present in the solution when the solution is prepared.

[0061] According to a further embodiment of the present disclosure, a method for fabricating a device is provided. The method may include applying a process that includes providing a composition, such as a composition or solution described herein, to a reaction chamber. According to an example of the present disclosure, the reactor is designed for the fabrication of semiconductor devices. According to a further example of the present disclosure, the reactor is designed for the deposition of a thin film or layer, such as one or more layers comprising vanadium. Exemplary vanadium layers are described in the appendix that forms a part of this disclosure.

[0062] According to yet further embodiments of the present disclosure, there is provided the use of one or more stabilizers to stabilize a vanadium compound. The stabilizers may include at least one, and in some cases at least two of the stabilizers described herein. The vanadium compound may include, for example, the vanadium compounds described herein.

[0063] The exemplary embodiments of the present disclosure described above are merely examples of embodiments of the present invention, as defined by the appended claims and their legal equivalents, and therefore do not limit the scope of the present invention. Any equivalent embodiments are intended to be within the scope of the present invention. Indeed, various modifications of the present disclosure in addition to those shown and described herein may become apparent to those skilled in the art from the description, including alternative useful combinations of the described elements. Such modifications and embodiments are also intended to be included within the scope of the appended claims.

Claims

1. 1. A method for stabilizing vanadium compounds in solution, comprising incorporating into said solution an effective amount of one or more stabilizing agents; the vanadium compound comprises a vanadium halide; At least one of the one or more stabilizers is all —R groups are independently a C1-C20 alkyl group or a C1-C20 aryl group; ３ and a tertiary amine of Formula PR ３ and a tertiary phosphine of all —R groups are independently a C1-C20 alkyl group or a C1-C20 aryl group; ２ ether and Formula SR, where every —R group is independently a C1-C20 alkyl group or a C1-C20 aryl group. ２ and a dialkyl sulfide, diaryl sulfide, or mixed alkyl / aryl sulfide of pyridine, pyridazine, pyrimidine, pyrazine, 1,2,4-triazine, or alkyl or aryl substituted derivatives thereof; N-alkylpiperidine, N,N'-dialkylpiperazine, N-alkylpyrrolidine, N-alkylpyrrole, N-alkylpyrroline, or N,N'-dialkylimidazolidine, in which alkyl is a C1-C20 hydrocarbon group; Furan, tetrahydrofuran, pyran, tetrahydropyran, 1,4-dioxane, 1,4-dioxine, or alkyl or aryl substituted derivatives thereof; Thiophene, tetrahydrothiophene, thiazole, thiane, thiopyran, dithiane, alkyl or aryl substituted derivatives thereof; The method is selected from the group consisting of:

2. The method of claim 1 , wherein the vanadium halide comprises vanadium chloride.

3. 10. The method of claim 1, wherein the one or more stabilizers comprise organic molecules containing one or more of nitrogen, oxygen, and / or sulfur heteroatoms.

4. The method of claim 1 , wherein the one or more stabilizing agents comprise an adduct-forming compound.

5. The method of claim 1 , wherein the one or more stabilizing agents comprise an aprotic compound.

6. 10. The method of claim 1, wherein the one or more stabilizers comprise a compound containing one or more heteroatoms with lone pairs of electrons.

7. 7. The method of any one of claims 1 to 6, wherein the one or more stabilizers are added in an amount of 0.001 mol % to 300 mol %, or 0.1 mol % to 100 mol % of the amount of vanadium compounds present in the solution.

8. a vanadium compound and an effective amount of one or more stabilizers, the vanadium compound comprises a vanadium halide; At least one of the one or more stabilizers is all —R groups are independently a C1-C20 alkyl group or a C1-C20 aryl group; ３ and a tertiary amine of Formula PR ３ and a tertiary phosphine of all —R groups are independently a C1-C20 alkyl group or a C1-C20 aryl group; ２ ether and Formula SR, where every —R group is independently a C1-C20 alkyl group or a C1-C20 aryl group. ２ and a dialkyl sulfide, diaryl sulfide, or mixed alkyl / aryl sulfide of pyridine, pyridazine, pyrimidine, pyrazine, 1,2,4-triazine, or alkyl or aryl substituted derivatives thereof; N-alkylpiperidine, N,N'-dialkylpiperazine, N-alkylpyrrolidine, N-alkylpyrrole, N-alkylpyrroline, or N,N'-dialkylimidazolidine, in which alkyl is a C1-C20 hydrocarbon group; Furan, tetrahydrofuran, pyran, tetrahydropyran, 1,4-dioxane, 1,4-dioxine, or alkyl or aryl substituted derivatives thereof; Thiophene, tetrahydrothiophene, thiazole, thiane, thiopyran, dithiane, alkyl or aryl substituted derivatives thereof; A composition selected from the group consisting of:

9. 9. The composition of claim 8, wherein the composition is a liquid at ambient temperature and pressure.

10. 10. The composition of claim 8, wherein the one or more stabilizers comprise organic molecules containing one or more of nitrogen, oxygen, and / or sulfur heteroatoms.

11. The composition of claim 8 , wherein the one or more stabilizing agents comprise an adduct-forming compound.

12. 12. The composition of claim 8, wherein the one or more stabilizers comprise an aprotic compound.

13. 13. The composition of any one of claims 8 to 12, wherein the one or more stabilizers comprise a compound containing one or more heteroatoms with lone pairs of electrons.

14. a vessel for providing a precursor for a vapor phase process, the vessel containing a vanadium compound and one or more stabilizers; the vanadium compound comprises a vanadium halide; At least one of the one or more stabilizers is all —R groups are independently a C1-C20 alkyl group or a C1-C20 aryl group; ３ and a tertiary amine of Formula PR ３ and a tertiary phosphine of all —R groups are independently C1-C20 alkyl or C1-C20 aryl groups; ２ ether and Formula SR, where every —R group is independently a C1-C20 alkyl group or a C1-C20 aryl group. ２ and a dialkyl sulfide, diaryl sulfide, or mixed alkyl / aryl sulfide of pyridine, pyridazine, pyrimidine, pyrazine, 1,2,4-triazine, or alkyl or aryl substituted derivatives thereof; N-alkylpiperidine, N,N'-dialkylpiperazine, N-alkylpyrrolidine, N-alkylpyrrole, N-alkylpyrroline, or N,N'-dialkylimidazolidine, in which alkyl is a C1-C20 hydrocarbon group; Furan, tetrahydrofuran, pyran, tetrahydropyran, 1,4-dioxane, 1,4-dioxine, or alkyl or aryl substituted derivatives thereof; Thiophene, tetrahydrothiophene, thiazole, thiane, thiopyran, dithiane, alkyl or aryl substituted derivatives thereof; A container selected from the group consisting of:

15. 15. The container of claim 14, wherein the one or more stabilizing agents comprise a stabilizing agent according to any one of claims 3 to 6.

16. 1. A system comprising: one or more reaction chambers; a source comprising a composition comprising a vanadium compound and one or more stabilizers; a controller; the controller is configured to control flow of the composition or the vanadium compound into at least one of the one or more reaction chambers; the vanadium compound comprises a vanadium halide; At least one of the one or more stabilizers is all —R groups are independently a C1-C20 alkyl group or a C1-C20 aryl group; ３ and a tertiary amine of Formula PR ３ and a tertiary phosphine of all —R groups are independently a C1-C20 alkyl group or a C1-C20 aryl group; ２ ether and Formula SR, where every —R group is independently a C1-C20 alkyl group or a C1-C20 aryl group. ２ and a dialkyl sulfide, diaryl sulfide, or mixed alkyl / aryl sulfide of pyridine, pyridazine, pyrimidine, pyrazine, 1,2,4-triazine, or alkyl or aryl substituted derivatives thereof; N-alkylpiperidine, N,N'-dialkylpiperazine, N-alkylpyrrolidine, N-alkylpyrrole, N-alkylpyrroline, or N,N'-dialkylimidazolidine, in which alkyl is a C1-C20 hydrocarbon group; Furan, tetrahydrofuran, pyran, tetrahydropyran, 1,4-dioxane, 1,4-dioxine, or alkyl or aryl substituted derivatives thereof; Thiophene, tetrahydrothiophene, thiazole, thiane, thiopyran, dithiane, alkyl or aryl substituted derivatives thereof; The system is selected from the group consisting of:

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