Compositions and vessels including vanadium compounds, and methods and systems for stabilizing vanadium compounds

Abstract

A method is provided for stabilizing a vanadium compound in solution. The method comprises: incorporating an effective amount of one or more stabilizers into the solution. The one or more stabilizers comprise one or more of the following: an organic molecule containing a sulfur heteroatom, an ether of formula OR12, a tertiary amine of formula NR23, pyran, tetrahydropyran, pyridazine, pyrimidine, pyrazine, 1,2,4-triazine, and aprotic non-aromatic heterocyclic amines. All R1 groups are independently C1-C20 alkyl or C1-C20 aryl, and all R2 groups are independently C1-C20 aryl.

Description

[Technical Field]

[0001] This disclosure generally relates to methods and apparatus suitable for gas-phase reactor systems. More specifically, this disclosure relates to methods, compounds, and apparatus that can be used to stabilize precursors in gas-phase reactor systems. [Previous 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 that may possess desired properties (such as desired vapor pressure at ambient pressure and temperature) and / or desired reactivity (e.g., reactivity with a surface or another compound) may thermally decompose into other compounds. Specifically, some precursors may decompose to produce corrosive gases that can corrode parts of the reactor system during processing and / or cause undesirable etching. Decomposition reduces the shelf life of the precursor, complicates manufacturing, requires additional purification steps, causes storage and / or transportation problems, and can limit the amount of material required in the source vessel that can be used for the reaction in the reactor system. Furthermore, corrosion of reactor system components can shorten the lifespan of the reactor system and / or its components, thereby increasing the cost of operating such equipment. In addition, corrosion can lead to the incorporation of reactor system etching products into the deposited film and / or lead to etching of the film on the substrate, which can in turn lead to a reduction in the quality and / or uniformity of such films. Furthermore, since the precursor decomposition rate generally increases with temperature, the ability to increase the flux of precursor to the reaction chamber by heating the precursor is hindered.

[0003] Efforts to reduce precursor decomposition have resulted in the production of precursors with undesirably high carbon content that may require undesirable high temperatures to achieve desired flux rates. When atomic layer deposition (ALD) is required, chemical vapor deposition (CVD) of the material may result in undesirable control over the growth rate and / or exhibit relatively poor step coverage. Therefore, it is desirable to provide improved methods, apparatus, and compositions for gas-phase reaction precursors.

[0004] Any discussion presented in this section (including discussions of problems and solutions) is included in this invention solely for the purpose of providing background information. Such discussions should not be construed as an admission that any or all of the information was known at the time of completion of this invention or otherwise constituted prior art. [Summary of the Invention]

[0005] The present invention provides a simplified description of the selected concepts, which will be further described in detail below. The present invention is not intended to necessarily identify key or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.

[0006] The various embodiments disclosed herein relate to methods for stabilizing vanadium compounds in solution, including compositions of vanadium compounds and stabilizers, apparatus including the composition, systems using the composition, and methods for using the composition, apparatus, and systems.

[0007] According to exemplary embodiments of the present disclosure, a method for stabilizing a vanadium compound in solution is provided. The method may include incorporating an effective amount of one or more stabilizers into the solution, wherein the solution includes the vanadium compound and the one or more stabilizers. Exemplary vanadium compounds include vanadium halides. The one or more stabilizers may comprise an organic molecule. The organic molecule may include one or more of nitrogen, oxygen, sulfur, and / or oxygen heteroatoms. The one or more stabilizers may include an adduct-forming compound. Alternatively or additionally, the one or more stabilizers may comprise an aprotic compound. Alternatively or additionally, the one or more stabilizers may include compounds containing one or more heteroatoms with a lone pair of electrons. For example, at least one of the stabilizers is selected from the group consisting of: a tertiary amine of formula NR3, wherein all -R groups are independently C1-C20 alkyl or C1-C20 aryl; a tertiary phosphine of formula PR3, wherein all -R groups are independently C1-C20 alkyl or C1-C20 aryl; an ether of formula OR2, wherein all -R groups are independently C1-C20 alkyl or C1-C20 aryl; a dialkyl sulfide, diaryl sulfide, or mixed alkyl / aryl sulfide of formula SR2, wherein... All -R groups are independently C1-C20 alkyl or C1-C20 aryl groups; aromatic heterocyclic amines, such as pyridine, pyridazine, pyrimidine, pyrazine, or 1,2,4-triazine, and their alkyl or aryl substituted forms; aprotic non-aromatic heterocyclic amines, such as N-alkylpiperidine, N,N'-dialkylpiperazine, N-alkylpyrrolidine, N-alkylpyrrole, N-alkylpyrroline, N,N'-dialkylimidazolidine, and similar compounds, wherein the alkyl group may be C1-C20 hydrocarbon; heterocyclic ethers, such as furan. Tetrahydrofuran, pyran, tetrahydropiperan, 1,4-dioxane, 1,4-dioxine, and similar compounds, and their alkyl or aryl substituted forms; heterocyclic sulfides, such as thiophene, tetrahydrothiophene, thiazole, thiane, thiopiperan, dithiane, and similar compounds, and their common alkyl or aryl substituted forms.One or more stabilizers may be added or present in amounts ranging from 0.001 mol-% to 300 mol-% of the vanadium compound present in the solution, or in amounts ranging from 0.1 mol-% to 100 mol-%.

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

[0009] According to yet another embodiment of this disclosure, a container is provided for providing precursors for gas-phase (e.g., semiconductor) processing. The container may contain vanadium compounds and / or compositions and / or solutions as described herein. The container may include a base and a removable lid.

[0010] According to an additional example of this disclosure, an apparatus for manufacturing a device is provided. The apparatus may include a container (e.g., a container as described herein) that can be attached to a reactor of a reactor system. The container may be configured to convey, store, and / or supply a component (such as a component described herein) to the reactor.

[0011] According to a further exemplary embodiment of the present disclosure, a method for manufacturing an apparatus is provided. The method may include performing a process comprising: providing a composition to a reactor chamber comprising 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 manufacturing semiconductor devices. According to an example of the present disclosure, the reactor is designed for depositing thin films. The composition may be as described above and elsewhere herein.

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

[0013] According to a further example of this disclosure, one or more stabilizers are provided for use in stabilizing vanadium compounds. Such vanadium compounds and / or one or more stabilizers may be as described above and elsewhere herein.

[0014] In addition to the examples disclosed herein, a system is disclosed for carrying out the methods described herein and / or for forming a structure, apparatus, or part thereof.

[0015] Those skilled in the art will readily understand these and other embodiments from the following detailed description of certain embodiments with reference to the accompanying drawings. The invention is not limited to any of the specific embodiments disclosed.

Implementation Method

[0017] The illustrative descriptions of methods, components, containers, devices, systems, and uses thereof provided below are merely illustrative and intended for purposes of explanation only; the following descriptions are not intended to limit the scope of this disclosure or the claims. Furthermore, the listing of multiple embodiments having the 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 are presented as illustrative examples and may be enumerated in the appendix. Unless otherwise stated, illustrative embodiments or their components may be combined or used separately.

[0018] As described in more detail below, various embodiments of this disclosure provide methods, systems, compositions, and apparatus for conveying, storing, and / or supplying a composition and / or vanadium compound to one of a reactor system (e.g., a gas-phase reactor) or for facilitating such conveying, storage, and / or supply. Exemplary compositions include one or more stabilizers for mitigating undesirable decomposition of vanadium compounds. The methods, compositions, containers, apparatus, systems, and uses described herein are applicable to a variety of applications, including those described in the appendix.

[0019] In this invention, "gas" may include materials that are gaseous at room temperature and atmospheric pressure (NTP), vaporized solids, and / or vaporized liquids, and may consist of a single gas or a mixture of gases depending on the context. Gases other than process gases (i.e., gases not introduced by a gas distribution assembly, other gas distribution device, or the like) may be used, for example, to seal the reaction space, and may include sealing gases such as rare gases. In some cases, the term "precursor" may refer to a compound that participates in a chemical reaction to form another compound, and in some cases, to a compound that constitutes the membrane matrix or the main framework of the membrane; the term "reactant" may be used interchangeably with the term "precursor". The term "inert gas" may refer to a gas that does not participate in a chemical reaction and / or does not become part of the membrane matrix to a perceptible extent. Exemplary inert gases include helium, argon, and any combination thereof. In some cases, inert gases may include nitrogen and / or hydrogen.

[0020] As used herein, the term "substrate" can refer to any (or more) underlying materials on which devices, circuits, or films can be formed or formed. Substrate may include bulk materials (such as silicon (e.g., single-crystal silicon)), other group IV materials (such as germanium), or other semiconductor materials (such as group II-VI or III-V semiconductor materials), and may include one or more layers overlying or underlying the bulk material. Further, substrate may include various features such as recesses, protrusions, and the like formed within or on at least a portion of a layer of the substrate. As an example, a substrate may include a bulk semiconductor material and an insulating or dielectric material layer overlying at least a portion of the bulk semiconductor material.

[0021] 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 even partial or complete molecular layers, or partial or complete atomic layers or atomic and / or molecular clusters. Films or layers may contain materials or layers with pinholes, and may be at least partially continuous. As used herein, "vanadium nitride layer" can be a material layer represented by a chemical formula including vanadium and nitrogen. Vanadium nitride layers may include additional elements, such as oxygen (e.g., vanadium oxynitride layer) and the like. As used herein, "layer containing vanadium boride" can be a material layer represented by a chemical formula including vanadium and boron. In some cases, the vanadium boride layer includes vanadium diboride (VB2). As used herein, "a layer containing vanadium phosphide" may refer to a layer of material represented by a chemical formula including vanadium and phosphorus. The layer containing vanadium phosphide may include vanadium phosphide (III) (VP).

[0022] As used herein, "structure" may be or may include a substrate as described herein. A structure may 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 may be or may include a structure or be formed using such a structure.

[0023] The term "cyclic deposition process" can refer to the process of sequentially introducing precursors (and / or reactants) into a reaction chamber to deposit a layer over a substrate, and includes processing techniques such as atomic layer deposition (ALD), cyclic chemical vapor deposition (cyclic CVD), and hybrid cyclic deposition processes including ALD configurations and cyclic CVD configurations.

[0024] The term "atomic layer deposition" can refer to a vapor deposition process in which deposition cycles (generally multiple consecutive deposition cycles) are performed in a process chamber. When performed using alternating pulses of (multiple) precursor / (multiple) reactive gases and (multiple) flushing (e.g., inert carrier) gases, the term atomic layer deposition as used herein also means processes specified by the relevant terms, such as chemical vapor deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas source MBE, organometallic MBE, and chemical beam epitaxy.

[0025] As used herein, "vanadium compound" includes compounds that can be represented by a chemical formula including vanadium.

[0026] Further, in this invention, any two numbers of a variable may constitute a working range of the variable, and any indicated range may include or exclude endpoints. Additionally, any numerical value of the indicated variable (whether or not such numerical value is indicated by "about") may refer to an exact value or an approximate value and include equivalent values, and may refer to an average value, median value, representative value, multiple values, or the like. Further, in this disclosure, in some embodiments, the terms "including," "constituted by," and "having" independently mean "typically or broadly comprising," "comprising," "consisting essentially of," or "consisting of." Furthermore, whether explicitly stated or not, the compositions and compounds described herein may include, substantially consist of, or be composed of the compounds and agents mentioned herein. In this disclosure, in some embodiments, any defined meaning does not necessarily exclude ordinary and conventional meaning.

[0027] Turning now to the drawings, Figure 1 illustrates a system 100 according to an exemplary embodiment of the present disclosure. System 100 can be used to perform the methods described herein and / or form structural or device portions as described herein. 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 containing 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 flat-band shifters). These vanadium boride and / or vanadium phosphide layers can be used in a variety of applications, including gate stack metal layers, logic or memory (e.g., NAND, V-NAND, DRAM) electrode layer applications, as etch stop layers (in front-end (FEOL), middle-end (MEOL), and / or back-end (BEOL) processes), and / or as diffusion barrier layers or pads. For specific examples, vanadium boride and / or vanadium phosphide layers can be used as work function metals (e.g., for NMOS devices), as work function adjustment layers, as voltage threshold adjustment layers, as (e.g., p) dipole or flat-band shifter layers, or similar.

[0028] The structures described herein may be or may form part of a CMOS structure (such as one or more PMOS and NMOS structures) or other device structures. In some embodiments, the structure may be a gate electrode. Furthermore, the structures and devices according to this disclosure may include vertical and / or three-dimensional structures and devices, such as finned FET devices.

[0029] In the illustrated example, system 100 includes one or more reaction chambers 102, precursor gas source 104, reactant gas source 106, flushing gas source 108, exhaust source 110, and controller 112.

[0030] Reaction chamber 102 may include any suitable reaction chamber, such as an ALD or CVD reaction chamber.

[0031] The precursor gas source 104 may include a container and one or more vanadium compounds as described herein, one or more stabilizers as described herein, and / or a composition as described herein. As described in more detail below, the composition may be a liquid at room temperature and pressure.

[0032] The reactant gas source 106 may include a container and one or more reactants (e.g., boron reactants, phosphorus reactants, nitrogen reactants, carbon reactants, sulfur reactants) (either alone or in mixture with another compound). The purging gas source 108 may include one or more inert gases as described herein. Although illustrated with three gas sources 104 to 108, the system 100 may include any suitable number of gas sources. Gas sources 104 to 108 may be coupled to the reaction chamber 102 via lines 114 to 118, each of which may include a flow controller, valve, heater, and the like.

[0033] The exhaust source 110 may include one or more vacuum pumps.

[0034] Controller 112 includes electronic circuitry and software to selectively operate valves, manifolds, heaters, pumps, and other components included in system 100. Such circuitry and components operate to introduce precursors, reactants, and purge gases from individual sources 104 to 108. For example, controller 112 may be configured to control the flow of a component or vanadium compound to at least one of one or more reaction chambers. 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 provide appropriate operation of system 100. Controller 112 may include control software to electrically or pneumatically control valves to control the flow of precursors, reactants, and purge gases into and out of reaction chamber 102. Controller 112 may include modules, such as software or hardware components, like FPGAs or ASICs, to perform certain tasks. The module can be advantageously configured to reside on an addressable storage medium of the control system and to execute one or more processes.

[0035] Other configurations of system 100 are possible, including different numbers and types of precursor and reactant sources and purge gas sources. Furthermore, it will be understood that valves, conduits, precursor sources, and purge gas sources exist in many configurations, which can be used to achieve the objective of selectively feeding gases into reaction chamber 102. Further, as a system schematic diagram, many components have been omitted for simplicity, and such components may include, for example, various valves, manifolds, purifiers, heaters, containers, vents, and / or bypasses.

[0036] During the operation of reactor system 100, substrates (such as semiconductor wafers (not shown)) are transferred from, for example, a substrate handling system to reaction chamber 102. Once the substrates are transferred to reaction chamber 102, one or more gases (such as precursors, reactants, carrier gases, and / or purging gases) from gas sources 104 to 108 are introduced into reaction chamber 102.

[0037] Figure 2 illustrates device 200. Device 200 may be attached to a reactor in a reactor system. For example, device 200 may be used as, for example, a gas source 104 or form part of it.

[0038] In the illustrated example, the apparatus 200 includes a container 203, which includes a base 202 and a lid 204 for containing composition 214 within the container 203. The container 203 can be configured to deliver, store and / or supply composition 214 to a reactor.

[0039] Container 203 may be formed of any suitable material. For example, the base 202 and / or lid 204 of 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. It should be understood that the base 202 and / or lid 204 may be formed of any other inert material or material that does not react with the components 214 in container 203 to any perceptible degree.

[0040] The lid 204 may be removably attached to the base 202. When the lid 204 is removably attached to the base 202, a seal (not shown) may be provided between the lid 204 and the base 202 to ensure that the contents of the container 203 are securely held therein. In one embodiment, the base 202 and the lid 204 are formed of the same material, such that they 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.

[0041] The device 200 may also include one or more valves 206, 208 coupled to the cover 204 and in fluid communication with the interior of the base 202. The device 200 may include one or more blocks 210, 212, which may include an internal gas flow channel.

[0042] A composition suitable for use as composition 214 may include a vanadium compound and an effective amount of one or more stabilizers. The composition may sometimes be referred to herein as a solution. Stabilizers may reduce or help reduce undesirable thermal decomposition of the vanadium compound, such as decomposition that would otherwise occur during the transport or storage of the vanadium compound. For example, stabilizers may bond to and / or form adducts with the vanadium compound and / or include solvents that stabilize the vanadium compound. Existing solutions for stabilizing compounds such as vanadium tetrachloride (VCl4) include the use of strong chlorinating agents to inhibit 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 may cause impurities to deposit in the layer formed by using the composition.

[0043] The vanadium precursor may include, for example, one or more of the following: vanadium halide, vanadium oxyhalide, organometallic vanadium compound, organometallic vanadium compound, β-diketovanadium compound, cyclopentadienylvanadium compound, vanadium alkoxide compound, dialkylamide vanadium compound, vanadium amidinate compound, DAD ligand compound (where DAD is represented by 1,4-diaza-1,3-butadiene (RN=CR'CR'=NR, R=alkyl, aryl, R'=H, alkyl)), and vanadium isocoordinated or mixed ligand compound, or similar.

[0044] As a specific example, vanadium halide may be selected from one or more of vanadium fluoride, vanadium chloride, vanadium bromide, and vanadium iodide. Vanadium halide may consist only of vanadium and one or more halogens (e.g., vanadium tetrachloride or similar). Vanadium oxyhalide may be selected from one or more of vanadium oxyhalides, such as vanadium oxyfluoride, vanadium oxychloride, vanadium oxybromide, and vanadium oxyiodide. Vanadium oxyhalide may consist only of vanadium, oxygen, and one or more halides. As an example, vanadium halide and vanadium oxyhalide may be selected from the group consisting of and include one or more of the following: VCl4, VBr4, VI4, VOCl4, VOBr3, and VOI3 (named vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide, vanadium oxytrichloride, vanadium oxytribromide, and vanadium oxytriiodide, respectively).

[0045] Exemplary β-diketone vanadium compounds include VO(acac)2, VO(thd)2, V(acac)3, V(thd)3 (named respectively 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)), and / or VO(hfac)2 or V(hfac)3, wherein hfac is a hexafluoroacetyl acetone ligand and the like.

[0046] Exemplary cyclopentadienylvanadium compounds include VCP2Cl2, VCP2, VCP2(CO)4, and VCPCl3 (named bis(cyclopentadienyl)vanadium(IV), bis(cyclopentadienyl)vanadium(II), tetracarbonylcyclopentadienylvanadium, and trichloro(cyclopentadienyl)vanadium(IV), respectively). Additional exemplary cyclopentadienylvanadium compounds include variants of these compounds in which Cp is unsubstituted or supported by one or more alkyl groups (e.g., MeCp, EtCp, iPrCp, and the like).

[0047] Exemplary vanadium alkoxide compounds include 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 (named tetra(methoxy)vanadium(IV), tetra(ethoxy)vanadium(IV), tetra(isopropoxy)vanadium(IV), tetra(tert-butoxy)vanadium(IV), oxotris(methoxy)vanadium(IV), oxotris(ethoxy)vanadium(IV), oxotris(isopropoxy)vanadium(IV), and oxotris(tert-butoxy)vanadium(IV) respectively). Additional vanadium alkoxide compounds include variants of these compounds in which other alkoxy ligands are used.

[0048] Exemplary dialkyl nitrovanadium compounds include V(NMe2)4, V(NEt2)4, and V(NEtMe)4 (named tetra(dimethylnitrovanadium(IV), tetra(diethylnitrovanadium(IV), and tetra(ethylmethylnitrovanadium(IV)) respectively).

[0049] Exemplary amidinate compounds include V(iPrFMD)3, V(iPrAMD)3, V(tBuFMD)3, and V(tBuAMD)3, wherein iPrFMD is an N,N'-diisopropylmethylamicyl ligand, iPrAMD is an N,N'-diisopropylethylamicyl ligand, tBuFMD is an N,N'-di-tert-butylmethylamicyl ligand, and tBuAMD is an N,N'-di-tert-butylethylamicyl ligand.

[0050] Examples of precursors including DAD ligands include V(DAD)2, V(DAD)(CO)4, VCp(DAD)(CO)2, V(DAD)Cl3, and V(DAD)2(NO)2, wherein DAD is 1,4-diaza-1,3-butadiene (RN=CR'CR'=NR, where R=alkyl or aryl and R'=H or alkyl).

[0051] Further, exemplary vanadium precursors may include "heterocoordinated" or mixed ligand precursors, wherein any combination of any number (generally 3 to 5 ligands, but exceptions may exist) of exemplary ligand types may be attached to vanadium atoms. Examples may include V(Cl)x(NMe)4-x and V(Cl)x(iPrAMD)x.

[0052] Using vanadium halide precursors is advantageous compared to methods using other precursors (such as vanadium organometallic precursors) because vanadium halide precursors are relatively inexpensive, produce vanadium layers with lower impurity (such as carbon) concentrations, and / or are more controllable than processes using organometallic or other vanadium precursors. Furthermore, such reactants can be used without plasma assistance to form excited species. In addition, processes using vanadium halide precursors are easier to scale up than methods using organometallic vanadium precursors.

[0053] According to the examples disclosed herein, the composition is a liquid at room temperature and normal pressure.

[0054] According to examples of this disclosure, vanadium compounds include vanadium halides. Vanadium halides may be or include vanadium chloride, such as vanadium tetrachloride.

[0055] Exemplary stabilizers may include adduct-forming compounds. Alternatively or concurrently, one or more stabilizers may comprise compounds having one or more of the following properties: 1) aprotic (e.g., an aprotic compound lacking hydrogen that can be protonated by the vanadium compound); 2) containing one or more heteroatoms having a lone pair of electrons that can coordinate with vanadium to form an adduct; 3) selected in a manner that does not affect the delivery of vanadium compound vapor or vanadium compound adduct vapor; 4) selected in a manner that minimizes the inclusion of the stabilizer in the vanadium-containing film as an impurity; and / or 5) introduced in amounts ranging from trace amounts of "catalytic inhibitors" up to a 1:1 stoichiometric ratio. The desired ratio may, for example, depend on the specific vanadium compound and the desired stabilizing effect.

[0056] According to embodiments of this disclosure, at least one of the one or more stabilizers may be or include an organic molecule. The organic molecule may include one or more of nitrogen, oxygen, sulfur and / or oxygen heteroatoms.

[0057] According to further examples of this disclosure, at least one of the one or more stabilizers may be selected from the group consisting of: a tertiary amine of formula NR3, wherein all -R groups are independently C1-C20 alkyl or C1-C20 aryl; a tertiary phosphine of formula PR3, wherein all -R groups are independently C1-C20 alkyl or C1-C20 aryl; an ether of formula OR2, wherein all -R groups are independently C1-C20 alkyl or C1-C20 aryl; a dialkyl sulfide, a diaryl sulfide, or a mixed alkyl / aryl sulfide of formula SR2, wherein all -R groups are independently C1-C20 alkyl or C1-C20 aryl; or an aromatic heterocyclic amine, such as pyridine, pyrazine, pyrimidine, etc. Pyridine, pyridine, or 1,2,4-triazine, and their alkyl or aryl substituted forms; aprotic nonaromatic heterocyclic amines, such as N-alkylpiperidine, N,N'-dialkylpiperidine, N-alkylpyrrolidine, N-alkylpyrrole, N-alkylpyrrolline, N,N'-dialkylimidazolidine, and similar compounds, wherein the alkyl group may be a C1-C20 hydrocarbon group; heterocyclic ethers, such as furan, tetrahydrofuran, piperan, tetrahydropiperan, 1,4-diane, 1,4-diazine, and similar compounds, and their alkyl or aryl substituted forms; heterocyclic sulfides, such as thiophene, tetrahydrothiophene, thiazole, thiocyclohexane, thiopiperan, dithiocyclohexane, and similar compounds, and their common alkyl or aryl substituted forms, or the like. The solution or composition may include any suitable number of stabilizers, such as two or more stabilizers, wherein one or more of the two or more stabilizers may be selected from the list above. The two or more stabilizers may comprise any combination of two or more stabilizers, including at least one stabilizer from the examples provided above.

[0058] According to a further example of this disclosure, a method for stabilizing a vanadium compound in a solution (also referred to herein as a composition) is provided. The method may include incorporating an effective amount of one or more stabilizers into the solution. For example, the one or more stabilizers may be added in amounts from 0.001 mol-% to 300 mol-% of the vanadium compound present in the solution, or in amounts from 0.1 mol-% to 100 mol-% of the vanadium compound present in the solution. Therefore, the one or more stabilizers may be added in amounts of 1 mol-%, 25 mol-%, 50 mol-%, or 200 mol-% of the vanadium compound present in the solution. The proportions of the vanadium compound and the one or more stabilizers present in the solution can be calculated based on the amount present in the solution during solution preparation.

[0059] According to additional embodiments of the present disclosure, a method for manufacturing an apparatus is provided. The method may include performing a process comprising: providing a composition, such as a composition or solution described herein, to a reactor chamber. According to an example of the present disclosure, the reactor is designed to manufacture a semiconductor device. According to a further example of the present disclosure, the reactor is designed to deposit a thin film or layer, such as one or more vanadium-containing layers. Exemplary vanadium layers are described in the appendix, which forms part of this disclosure.

[0060] According to further embodiments of this disclosure, one or more stabilizers are provided for use in stabilizing vanadium compounds. The stabilizer may include at least one, and in some cases may include at least two stabilizers mentioned herein. The vanadium compound may include, for example, vanadium compounds as mentioned herein.

[0061] The exemplary embodiments described above do not limit the scope of the present invention, as these embodiments are merely examples of embodiments of the present invention, the scope of which is defined by the appended claims and their legal equivalents. Any equivalent embodiments are intended to be within the scope of the present invention. In fact, in addition to what is shown and described herein, various modifications to the present disclosure (such as alternative combinations of described elements) will be apparent to those skilled in the art from this specification. Such modifications and embodiments are also intended to fall within the scope of the appended claims. [Simplified Explanation of the Diagram]

[0016] A more complete understanding of the embodiments of this disclosure can be obtained by referring to the embodiments and the claims when considered in conjunction with the following illustrative drawings. Figure 1 illustrates a reactor system according to an additional exemplary embodiment of this disclosure. Figure 2 illustrates a container and apparatus according to an additional exemplary embodiment of this disclosure. It should be understood that the elements in the drawings are drawn for simplicity and clarity and are not necessarily drawn to scale. For example, the dimensions of some of the elements in the drawings may be enlarged relative to other elements to help improve the understanding of the illustrated embodiments of this disclosure.

Claims

1. A method for stabilizing a vanadium compound in solution, comprising: adding an effective amount of one or more stabilizers to the solution, wherein the one or more stabilizers comprise one or more of the following: an organic molecule containing a sulfur heteroatom, an ether of formula OR12, a tertiary amine of formula NR23, pyran, tetrahydropyran, pyridazine, pyrimidine, pyrazine, 1,2,4-triazine, and an aprotic non-aromatic heterocyclic amine, wherein all R1 groups are independently C1-C20 alkyl or C1-C20 aryl, and wherein all R2 groups are independently C1-C20 aryl, wherein the vanadium compound comprises vanadium halide.

2. The method of claim 1, wherein the one or more stabilizers comprise the organic molecule, the organic molecule comprising sulfur heteroatoms.

3. The method of claim 2, wherein the one or more stabilizers comprise a dialkyl sulfide, a diaryl sulfide, or a mixed alkyl / aryl sulfide of formula SR32, wherein all R3 groups are independently C1-C20 alkyl or C1-C20 aryl.

4. The method of claim 2, wherein the one or more stabilizers comprises a heterocyclic sulfide selected from thiophene, tetrahydrothiophene, thiazole, thiane, thiopiperanone, and dithiane.

5. The method of claim 1, wherein the one or more stabilizers comprise an ether of formula OR12, wherein all R1 groups are independently C1-C20 alkyl or C1-C20 aryl.

6. The method of claim 1, wherein the one or more stabilizers comprise one or more of the following: pyran, tetrahydropyran, pyridazine, pyrimidine, pyrazine, 1,2,4-triazine.

7. The method of claim 1, wherein the one or more stabilizers are added in an amount from 0.001 mol-% to 300 mol-% of the amount of the vanadium compound present in the solution.

8. The method of claim 1, wherein the one or more stabilizers comprise a tertiary amine of formula NR23, wherein all R2 groups are independently C1-C20 aryl groups.

9. The method of claim 1, wherein the one or more stabilizers comprises two or more stabilizers.

10. A composition comprising a vanadium compound and an effective amount of one or more stabilizers, wherein the one or more stabilizers comprise one or more of the following: an organic molecule containing a sulfur heteroatom, an ether of formula OR12, a tertiary amine of formula NR23, pyran, tetrahydropyran, pyridazine, pyrimidine, pyrazine, 1,2,4-triazine, and an aprotic nonaromatic heterocyclic amine, wherein all R1 groups are independently C1-C20 alkyl or C1-C20 aryl, and wherein all R2 groups are independently C1-C20 aryl, wherein the vanadium compound comprises vanadium halide.

11. The composition of claim 10, wherein the composition is a liquid at room temperature and pressure.

12. The composition of claim 10, wherein the one or more stabilizers comprises two or more stabilizers.

13. A container for providing a precursor for gas-phase processing, wherein the container comprises a vanadium compound and one or more stabilizers, wherein the one or more stabilizers comprise one or more of the following: an organic molecule containing a sulfur heteroatom, an ether of formula OR12, a tertiary amine of formula NR23, pyran, tetrahydropyran, pyridazine, pyrimidine, pyrazine, 1,2,4-triazine, and an aprotic non-aromatic heterocyclic amine, wherein all R1 groups are independently C1-C20 alkyl or C1-C20 aryl, and wherein all R2 groups are independently C1-C20 aryl, wherein the vanadium compound comprises vanadium halide.

14. The container of claim 13, wherein the container comprises a base and a lid, the base and the lid being formed of a material selected from stainless steel, high-nickel alloy, aluminum and titanium; and one or more valves coupled to the lid and in fluid communication with the interior of the base.

15. The container of claim 13, wherein the one or more stabilizers contain the organic molecule, the organic molecule containing sulfur heteroatoms.

16. A system for stabilizing a vanadium compound, comprising: one or more reaction chambers; a source containing a composition comprising a vanadium compound and one or more stabilizers; and a controller, wherein the one or more stabilizers comprise one or more of the following: an organic molecule containing a sulfur heteroatom, an ether of formula OR12, a tertiary amine of formula NR23, pyran, tetrahydropyran, pyridazine, pyrimidine, pyrazine, 1,2,4-triazine, and an aprotic nonaromatic heterocyclic amine, wherein all R1 groups are independently C1-C20 alkyl or C1-C20 aryl, and wherein all R2 groups are independently C1-C20 aryl, wherein the vanadium compound comprises vanadium halide.

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