Niobium, vanadium, tantalum film-forming compositions and deposition of group 5 metal-containing films using the same

Abstract

The invention relates to a Metal-containing film forming composition comprising a precursor having the formula M(=NR)X2L, in which M = V or Nb or Ta; R = H or C1-C10 alkyl group; X = Substituted or unsubstituted diketones, aminoketones, alkoxyalcohols, alkoxyalkanes, alkanediols, alkanolamines, aminoaldehydes, diimines, dienes; and L = Substituted or unsubstituted cyclopentadienes, cyclohexadienes, cycloheptadienes, cyclooctadienes, fluorenes, indenes, fused ring systems, propenes, butadienes, pentadienes, hexadienes, heptadienes.

Description

[0001]2021P00136 NIOBIUM, VANADIUM, TANTALUM FILM-FORMING COMPOSITIONS AND DEPOSITION OF GROUP 5 METAL-CONTAINING FILMS USING THE SAME Cross Reference to Related Applications This application claims the benefit of priority to U.S. Provisional Patent Application No.63 / 526,730, filed July 14, 2023, the entire contents of which are incorporated herein by reference. Technical Field The invention relates to metal-containing film forming composition comprising a precursor of Niobium or Vanadium or Tantalum and a method of forming a Niobium or Vanadium or Tantalum containing film on one or more substrates via vapor deposition processes using the Niobium or Vanadium or Tantalum containing film forming compositions. Background Art Metal Oxide films, such as Niobium Oxide (Nb2O5), have been extensively utilized in various fields of technology. Traditionally these oxides have been applied as resistive films used as high-k materials for insulating layers. For instance, a thin layer of Nb2O5between two ZrO2 dielectric layers is expected to help significantly reduce leakage current and stabilize the cubic / tetragonal phase of the ZrO2, affording higher k values in the current MIM capacitor of a DRAM (Alumina, J. Vac. Sci. Technol A 4 (6), 1986 and Microelectronic Engineering 86 (2009) 1789-1795). A thin layer of V2O5 may behave similarly. Metal Nitride films, such as Niobium Nitride, Vanadium Nitride (NbNx, VNxwherein x is approximately 1) have been extensively utilized in various fields of technology. Traditionally these nitrides have been applied as hard and decorative coatings but during the past decade they have increasingly been used as diffusion barrier and adhesion / glue layers in microelectronic devices [Applied Surface Science 120 (1997) 199-212]. Mixed oxides containing Nb is also of high interest in energy storage applications for instance as thin, highly ionic conductive, interface layers between active cathode material and electrolyte in all-solid-state batteries and Li-ion batteries [US7993782B2]. For instance, a thin layer of Lithium Niobate deposited on active cathode materials in the right crystalline phase has been reported to reduce reaction resistance and increase battery 2021P00136 power output [US 2020 / 0075956 A1]. Lithium Niobate is of particular interest as an interface layer because it displays a significantly higher ionic conductivity [Electrochem. Commun.2007, 9, 1486−1490]. Vapor phase deposition such as Atomic Layer Deposition has been reported to be a viable technique to deposit such stabilizing interface layers onto low Cobalt Cathodes Materials [ACS Appl. Mater. Interfaces 2018, 10, 1654−1661]. NbCl5for instance has been examined as a niobium source for Atomic Layer Epitaxial growth of NbNx, but the process required Zn as a reducing agent [Applied Surface Science 82 / 83 (1994) 468-474]. NbNx, films were also deposited by atomic layer deposition using NbCl5and NH3[Thin Solid Films 491 (2005) 235-241]. The chlorine content showed strong temperature dependence, as the film deposited at 500oC was almost chlorine free, while the chlorine content was 8% when the deposition temperature was as low as 250oC. The high melting point of NbCl5also makes this precursor difficult to use in the vapor deposition process. As an example for VNx, V(NMe2)4has been examined as a vanadium source for chemical vapor deposition of VNx[Chemical Vapor Deposition of Vanadium, Niobium, and Tantalum Nitride Thin Films by Fix et al., Chem. Mater.1993, 5, 614-619]. VNxfilms were also deposited by plasma enhanced atomic layer deposition using V(NEtMe)4and NH3. [Low Temperature Plasma-Enhanced Atomic Layer Deposition of Thin Vanadium Nitride Layers for Copper Diffusion Barriers by Rampelberg et al., Appl. Phys. Lett., 102, 111910 (2013)]. Gust et al. disclose the synthesis, structure, and properties of niobium and tantalum imido complexes bearing pyrazolato ligands and their potential use for the growth of tantalum nitride films by CVD [Polyhedron 20 (2001) 805-813]. Elorriaga et al. disclose asymmetric niobium guanidinates as intermediates in the catalytic guanylation of amines (Dalton Transactions, 2013, Vol. 42, Issue 23 pp. 8223- 8230). Tomson et al. disclose the synthesis and reactivity of the cationic Nb and Ta monomethyl complexes [(BDI)MeM(NtBu)][X](BDI=2,6-iPr2C6H3-N-C(Me)CH-C(Me)- N(2,6-iPr2C6H3); X=MeB(C6F5)3or B(C6F5)4) (Dalton Transactions 2011 Vol.40, Issue 30, pp.7718-7729). US20080038466A1 discloses tantalum- and niobium-compounds having the formula R4R5R6M(R1NNR2R3)2, wherein M is Ta or Nb; R1-R3=C1-12alkyl, C5-12cycloalkyl, C6-10aryl, alkenyl, C1-4triorganosilyl; and R4-R6=halo, (cyclo)alkoxy, aryloxy, siloxy, BH4, allyl, indenyl, benzyl, cyclopentadienyl, CH2SiMe3, silylamido, amido, or imino. Maestre et al. discloses the reaction of the cyclopentadienyl-silyl-amido titanium 2021P00136 compound with group 5 metal monocyclopentadienyl complexes to form NbCp(NH(CH2)2- NH2)CI3and NbCpCI2(N-(CH2)2-N). Gibson et al. discloses the ligand exchange reaction and kinetic study with Mo, Nb complexes including the Nb(=NtBu)Cp(OiPr)2, Nb(=NtBu)Cp(OtBu)2(Dalton Transactions (2003), (23), 4457-4465). Today, there is a need for providing liquid or low melting point (<50oC. at standard pressure), highly thermally stable, Niobium or Vanadium or Tantalum containing precursor molecules suitable for vapor phase film deposition with controlled thickness and composition at high temperature. Summary According to the invention, certain precursors have been found suitable for the deposition of Nb or V or Ta containing thin films by ALD processes and to have the following advantages: ● They are liquid at room temperature or having a melting point lower than 50°C. ● They are thermally stable to enable proper distribution (gas phase or direct liquid injection) without particle generation. ● They are thermally stable to allow a wide self-limited ALD window, allowing deposition of a variety of Nb or V or Ta containing films, by using one or a combination of co-reactants. ○ The co-reactant can typically be selected from an oxidizing agent, such as O2, O3, H2O, H2O2, alcohols, or a nitriding agent such as ammonia, amines, polyamines, hydrazines, NO. Such co-reactant may be plasma activated or not. ● They can also be used in combination with another precursor to deposit mixed films. ○ More particularly, these precursors are suitable to be used with precursors of group IV and other group V elements, as well as with phosphorous or lithium compounds for energy storage applications for instance. Brief Description of the Drawings For a further understanding of the nature and objects for the present invention, reference should be made to the following detailed description, taken in conjunction with the accompanying drawings, in which like elements are given the same or analogous reference numbers and wherein: 2021P00136 Fig. 1. is a ThermoGravimetric Analysis (TGA) graph demonstrating the percentage of weight with increasing temperature of Nb(=NtBu)(Cp)(mmp)2. Fig.2. is a Differential Scanning Calorimetry(DSC) of Nb(=NtBu)(Cp)(mmp)2. Fig.3. is a vapor pressure of Nb(=NtBu)(Cp)(mmp)2. Fig.4. is a ALD window of Nb(=NtBu)(Cp)(mmp)2. Fig. 5. is a step coverage image of patterned wafer of Nb2O5film deposited by Nb(=NtBu)(Cp)(mmp)2at 300oC (measured by SEM) Detailed Description of Preferred Embodiments According to a first embodiment, the invention relates to a chemical and metal- containing film forming compositions comprising the chemical. The chemical has the general formula: M(=NR)X2L wherein: M = V or Nb or Ta; R = independently H or C1-C10alkyl group; X = a substituted or unsubstituted diketones, aminoketones, alkoxyalcohols, alkoxyalkanes, alkanediols, alkanolamines, aminoaldehydes, diimines, dienes; and L = a substituted or unsubstituted cyclopentadienes, cyclohexadienes, cycloheptadienes, cyclooctadienes, fluorenes, indenes, fused ring systems, propenes, butadienes, pentadienes, hexadienes, heptadienes. According to other particular embodiments, the invention concerns: - A chemical of formula: Formula 1: wherein X1is independently OR10or NR11R12; X2is independently O or NR13or CR14R15; X3is independently OR16or NR17R18; X4is independently O or NR19or CR20R21; each R1to R21is independently H or C1-C10alkyl group; R22is independently H or C1-C10alkyl 2021P00136 group or fluoroalkyl group; n≦5. Formula 2: wherein X1is independently OR10or NR11R12; X2is independently O or NR13or CR14R15; X3is independently OR16or NR17R18; X4is independently O or NR19or CR20R21; each R1to R21is independently H or C1-C10alkyl group; each R22to R28is independently H or C1- C10alkyl group or fluoroalkyl group. Formula 3: wherein X1is independently OR10or NR11R12; X2is independently O or NR13or CR14R15; X3is independently OR16or NR17R18; X4is independently O or NR19or CR20R21; each R1to R21is independently H or C1-C10alkyl group; each R22to R25is independently H or C1- C10alkyl group or fluoroalkyl group. 2021P00136 Formula 4: wherein X1is independently OR10or NR11R12; X2is independently O or NR13or CR14R15; X3is independently OR16or NR17R18; X4is independently O or NR19or CR20R21; each R1to R21is independently H or C1-C10alkyl group; each R22to R26is independently H or C1- C10alkyl group or fluoroalkyl group. Formula 5: wherein X1is independently O or NR6or CR7R8; X2is independently O or NR9or CR10R11; X3is independently O or NR12or CR13R14; X4is independently O or NR15or CR16R17; each R1to R17is independently H or C1-C10alkyl group; R18is independently H or C1-C10alkyl group or fluoroalkyl group; n≦5. 2021P00136 Formula 6: wherein X1is independently O or NR6or CR7R8; X2is independently O or NR9or CR10R11; X3is independently O or NR12or CR13R14; X4is independently O or NR15or CR16R17; each R1to R17is independently H or C1-C10alkyl group; each R18to R24is independently H or C1-C10alkyl group or fluoroalkyl group. Formula 7: wherein X1is independently O or NR6or CR7R8; X2is independently O or NR9or CR10R11; X3is independently O or NR12or CR13R14; X4is independently O or NR15or CR16R17; each R1to R17is independently H or C1-C10alkyl group; each R18to R21is independently H or C1-C10alkyl group or fluoroalkyl group. 2021P00136 Formula 8: wherein X1is independently O or NR6or CR7R8; X2is independently O or NR9or CR10R11; X3is independently O or NR12or CR13R14; X4is independently O or NR15or CR16R17; each R1to R17is independently H or C1-C10alkyl group; each R18to R22is independently H or C1-C10alkyl group or fluoroalkyl group. Formula 9: wherein X1is independently OR4or NR5R6; X2is independently O or NR7or CR8R9; wherein X3is independently OR10or NR11R12; X4is independently O or NR13or CR14R15; X5is independently CR16or N; X6is independently CR17or N; each R1to R17is independently H or C1-C10alkyl group; R18is independently H or C1-C10alkyl group or fluoroalkyl group; n≦5. 2021P00136 Formula 10: wherein X1is independently OR4or NR5R6; X2is independently O or NR7or CR8R9; wherein X3is independently OR10or NR11R12; X4is independently O or NR13or CR14R15; X5is independently CR16or N; X6is independently CR17or N; each R1to R17is independently H or C1-C10alkyl group; each R18to R24is independently H or C1-C10alkyl group or fluoroalkyl group. Formula 11: wherein X1is independently OR4or NR5R6; X2is independently O or NR7or CR8R9; wherein X3is independently OR10or NR11R12; X4is independently O or NR13or CR14R15; X5is independently CR16or N; X6is independently CR17or N; each R1to R17is independently H or C1-C10alkyl group; each R18to R21is independently H or C1-C10alkyl 2021P00136 group or fluoroalkyl group. Formula 12: wherein X1is independently OR4or NR5R6; X2is independently O or NR7or CR8R9; wherein X3is independently OR10or NR11R12; X4is independently O or NR13or CR14R15; X5is independently CR16or N; X6is independently CR17or N; each R1to R17is independently H or C1-C10alkyl group; each R18to R22is independently H or C1-C10alkyl group or fluoroalkyl group. Chemicals of the foregoing formulae are useful as volatile precursors for vapor phase deposition of M containing films such as Niobium Oxide. Vapor phase dispositions include chemical vapor depositions (CVD) and atomic layer depositions (ALD). Often, co- reactants are used in combination with the chemicals to produce a desired atomic composition of the deposited material. Such co-reactants can be, for example, O2, O3, H2O, H2O2, NO, N2O, NO2, TMPO, oxygen radicals thereof, and mixtures thereof. Plasma enhanced or assisted CVD or ALD may be particularly preferred. The target substrate may be a partially fabricated semiconductor or a cathode active material in powder form. The substrate may be a cathode material having a cathode active material powder, a conductive carbon and a binder material deposited onto a current collector foil. The substrate may be ZrO2 or HfO2 or TiO2 or Al2O3 or TiN, and the Niobium or Vanadium or Tantalum containing film forming composition is used to form a DRAM capacitor. According to another embodiment, the invention relates to a method of manufacturing a thin interface layer into a Lithium-ion or into an all-solid-state-batteries 2021P00136 device. The thin layer is generally a Niobium containing oxide layer deposited by Atomic Layer Deposition using the chemicals of the foregoing formulae in which M is Nb. These depositions generally use a co-reactant selected from O2, O3, H2O, H2O2, NO, NO2, or a NOx, trimethylphosphate, diethyl phosphoramidate, a sulfate or any other oxygen containing species. The thin layer can be a niobium containing ternary or quaternary oxide, such as LiNbO, LiNb(M)O, NbMO with M being selected from the list consisting of Zr, Ti, Co, W, Ta, V, Sr, Ba, La, Y, Sc, Mn, Ni, Mo. The thin interface layer can be deposited directly onto the cathode active material for instance in a fluidized bed ALD-reactor. The cathode active material is the main element in the composition of cathode battery cells. The cathode materials are for example Cobalt, Nickel and Manganese in the crystal structure such as the layered structure forms a multi-metal oxide material in which lithium is inserted. The cathode active material may preferably be a “NMC” (a lithium nickel manganese cobalt oxide), a NCA (a lithium nickel cobalt aluminum oxide), a LNO (a lithium nickel oxide) a LMNO (a lithium manganese nickel oxide), or a LFP (a lithium iron phosphate). For instance, the cathode active material can be NMC622 or NMC811. The thin interface layer may be done on the electrode active material powder, on electrode active material porous materials, on different shapes of electrode active materials, or in pre-formed electrodes in which the electrode active material may be already associated with conductive carbons and / or binders and may already be supported by a current collector foil. Examples The following examples are an illustration of the various embodiments of the present invention, without being a limitation. Example 1: Synthesis of Nb(=NtBu)(Cp)(mmp)2To a solution of Nb(=NtBu)(Cp)(NMe2)2(40g, 126mmol) in 500mL of Toluene at - 78oC, was added dropwise a solution of 1-Methoxy-2-methyl-2-propanol (27.6g, 265mmol). After stirring the mixture at room temperature for 12h, the solvent was removed under vacuum to give yellow oil. The material was then purified by distillation up to 110oC at 25mTorr to give 51.8g (94.5%) of yellow oil. The material was characterized by NMR1H (δ, ppm, C6D6): 6.23 (s, 5H), 3.27 (dd, 4H), 3.23 (s, 6H), 1.43 (s, 12H), 1.21 (s, 9H). The purified product left a 1.7% residual mass during open-cup TGA analysis measured at a temperature rising rate of 10oC / min in an atmosphere which flows nitrogen 2021P00136 at 200mL / min. These results are shown in Fig. 1, which is a TGA graph illustrating the percentage of weight upon temperature increase. Onset temperature of decomposition (310oC) of the product were measured by Differential Scanning Calorimetry (DSC), which are shown in Fig.2. Example 2: Synthesis of Nb(=NtBu)(Cp)(tmhd)2To a solution of Nb(=NtBu)(Cp)(NEt2)2(2g, 5.4mmol) in 30mL of Toluene at -78oC, was added dropwise a solution of 2,2,6,6-Tetramethyl-3,5-heptanedione (2.1g, 11.25mmol). After stirring the mixture at room temperature for 12h, the solvent was removed under vacuum to give yellow solid. The material was then purified by sublimation up to 130oC at 25mTorr to give 1.2g (38%) of yellow solid. The material was characterized by NMR1H (δ, ppm, C6D6): 6.4 (s, 5H), 5.77 (s, 1H), 5.70 (s, 1H), 1.28 (s, 9H), 1.24(s, 9H), 1.16 (s, 9H), 1.07 (s, 9H), 1.03 (s, 9H). Example 3: ALD of Nb2O5using Nb(=NtBu)(Cp)(mmp)2Nb(=NtBu)(Cp)(mmp)2is stored into a container. The container is heated at 110oC and Ar is used as carrier gas at a flow of 200sccm. The pressure of the container is controlled at 0.8Torr. O3is used as an oxygen source. The substrate is heated at 250- 400oC. During the first step, Nb(=NtBu)(Cp)(mmp)2is introduced into the reaction chamber during 3s. A N2purge of 30s is performed afterwards as a second step. As third step, a pulse of O3is then introduced into the reaction chamber during 1s, followed by a 30s N2purge as fourth step. All four steps are repeated 80 times to obtain a Nb2O5film. Fig. 4 shows the ALD window was observed from 300 to 350oC with a consistent growth rate. Fig.5 shows a step coverage image of patterned wafer having 1:30 aspect ratio of Nb2O5film deposited by Nb(=NtBu)(Cp)(mmp)2at 300oC. Industrial Applicability The present invention is at least industrially applicable to producing Niobium Oxide (Nb2O5) in semiconductor applications. While the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications, and variations as fall within the spirit and broad scope of the appended claims. The present invention may suitably comprise, 2021P00136 consist or consist essentially of the elements disclosed and may be practiced in the absence of an element not disclosed. Furthermore, if there is language referring to order, such as first and second, it should be understood in an exemplary sense and not in a limiting sense. For example, it can be recognized by those skilled in the art that certain steps can be combined into a single step. The singular forms "a", "an" and "the" include plural referents, unless the context clearly dictates otherwise. "Comprising" in a claim is an open transitional term which means the subsequently identified claim elements are a nonexclusive listing (i.e., anything else may be additionally included and remain within the scope of “comprising”). “Comprising” as used herein may be replaced by the more limited transitional terms "consisting essentially of" and “consisting of” unless otherwise indicated herein. “Providing” in a claim is defined to mean furnishing, supplying, making available, or preparing something. The step may be performed by any actor in the absence of express language in the claim to the contrary. Optional or optionally means that the subsequently described event or circumstances may or may not occur. The description includes instances where the event or circumstance occurs and instances where it does not occur. Ranges may be expressed herein as from about one particular value, and / or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and / or to the other particular value, along with all combinations within said range. All references identified herein are each hereby incorporated by reference into this application in their entireties, as well as for the specific information for which each is cited. Technical Definitions As used herein, “room temperature" in the text or in a claim means from approximately 20°C to approximately 25°C. The term “ambient conditions” refers to an environment temperature (i.e., ambient temperature) approximately 20°C to approximately 25°C and an environment pressure (ambient temperature) approximately 1 atm or 1 bar. The term “substrate” refers to a material or materials on which a process is conducted. The substrate may also have one or more layers of differing materials already deposited upon it from a previous manufacturing step. One of ordinary skill in the art will recognize that the terms “film” or “layer” used 2021P00136 herein refer to a thickness of some material laid on or spread over a surface and that the surface may be a trench or a line. The standard abbreviations of the elements from the periodic table of elements are used herein. It should be understood that elements may be referred to by these abbreviations (e.g., Si refers to silicon, N refers to nitrogen, O refers to oxygen, C refers to carbon, H refers to hydrogen, F refers to fluorine, etc.). The unique CAS registry numbers (i.e., “CAS”) assigned by the Chemical Abstract Service are provided to help better identify the molecules disclosed. The Aspect Ratio of a geometric shape is the ratio of its sizes in different dimensions. The aspect ratio is most often expressed as two integer numbers separated by a colon (x:y). The values x and y do not represent actual widths and heights but, rather, the proportion between width and height. As an example, 8:5, 16:10, 1.6:1 are all ways of representing the same aspect ratio. In objects of more than two dimensions, such as hyperrectangles, the aspect ratio can still be defined as the ratio of the longest side to the shortest side. Conformality and Step Coverage both refer to the degree of variability in the thickness of a film on a surface, especially topologically different areas of a surface. This is especially relevant to surfaces with microstructures having various aspect ratios. Complete (100%) conformality for the above example means there is zero cusping and the top surface, the trench sidewall and when applicable the trench bottom, have all identical thicknesses. If a single conformality percentage is given, it is the least conformal measurement corresponding to the greatest deviation in relative thickness of the overall film at two selected points on the surface. The two points may correspond to the highest Aspect Ratio points or, for example, points having a specific Aspect Ratio such as 6:1 or less. Thicknesses of films are assessed by a number of methods, for example scanning electron microscopy of sectioned substrates. A film is generally “conformal” if the film is at least 20% conformality, preferably at least 50%.

Claims

2021P00136 CLAIMS:

1. A chemical having the formula M(=NR1)X2L, wherein: M = V or Nb or Ta; R1= H or a C1-C10alkyl group; X = substituted or unsubstituted diketones, aminoketones, alkoxyalcohols, alkoxyalkanes, alkanediols, alkanolamines, aminoaldehydes, diimines, dienes; and L = a cyclopentadiene, cyclohexadiene, cycloheptadienes, cyclooctadiene, fluorene, indene, fused ring system, propene, butadiene, pentadiene, hexadiene, heptadiene; or a substituted analog of the foregoing.

2. The chemical of claim 1, wherein each pair of X2are selected from the group consisting of: a), wherein X1is independently OR10or NR11R12; X2is independently O or NR13or CR14R15; X3is independently OR16or NR17R18; X4is independently O or NR19or CR20R21; each R1to R21is independently H or C1-C10alkyl group,, wherein X1is independently O or NR6or CR7R8; X2is independently O or NR9or CR10R11; X3is independently O or NR12or CR13R14; X4is independently O or NR15or CR16R17; each R1to R17is independently H or C1-C10alkyl group, and2021P00136, wherein X1is independently OR4or NR5R6; X2is independently O or NR7or CR8R9; wherein X3is independently OR10or NR11R12; X4is independently O or NR13or CR14R15; X5is independently CR16or N; X6is independently CR17or N; each R1to R17is independently H or C1-C10alkyl group.

3. The chemical of claim 1 or 2, wherein L is selected from the group consisting of:, wherein R22is independently H or C1-C10alkyl group or fluoroalkyl group; n≦5,, wherein each R22to R28is independently H or C1-C10alkyl group or fluoroalkyl group,, wherein each R22to R26is independently H or C1-C10alkyl group or fluoroalkyl group,2021P00136wherein each R22to R25is independently H or C1-C10alkyl group or fluoroalkyl group.

4. The chemical of claims 1-2, selected from the group consisting of:, wherein X1is independently OR10or NR11R12; X2is independently O or NR13or CR14R15; X3is independently OR16or NR17R18; X4is independently O or NR19or CR20R21; each R1to R21is independently H or C1-C10alkyl group; R22is independently H or C1-C10alkyl group or fluoroalkyl group; and n≦5,, wherein X1is independently OR10or NR11R12; X2is independently O or NR13or CR14R15; X3is independently OR16or NR17R18; X4is independently O or NR19or CR20R21; each R1to R21is independently H or C1-C10alkyl group; each R22to R28is independently H or C1- C10alkyl group or fluoroalkyl group,2021P00136, wherein X1is independently OR10or NR11R12; X2is independently O or NR13or CR14R15; X3is independently OR16or NR17R18; X4is independently O or NR19or CR20R21; each R1to R21is independently H or C1-C10alkyl group; each R22to R25is independently H or C1- C10alkyl group or fluoroalkyl group,, wherein X1is independently OR10or NR11R12; X2is independently O or NR13or CR14R15; X3is independently OR16or NR17R18; X4is independently O or NR19or CR20R21; each R1to R21is independently H or C1-C10alkyl group; each R22to R26is independently H or C1- C10alkyl group or fluoroalkyl group,, wherein X1is independently O or NR6or CR7R8; X2is independently O or NR9or2021P00136 CR10R11; X3is independently O or NR12or CR13R14; X4is independently O or NR15or CR16R17; each R1to R17is independently H or C1-C10alkyl group; R18is independently H or C1-C10alkyl group or fluoro group; and n≦5,, wherein X1is independently O or NR6or CR7R8; X2is independently O or NR9or CR10R11; X3is independently O or NR12or CR13R14; X4is independently O or NR15or CR16R17; each R1to R17is independently H or C1-C10alkyl group; each R18to R24is independently H or C1-C10alkyl group or fluoroalkyl group,, wherein X1is independently O or NR6or CR7R8; X2is independently O or NR9or CR10R11; X3is independently O or NR12or CR13R14; X4is independently O or NR15or CR16R17; each R1to R17is independently H or C1-C10alkyl group; each R18to R21is independently H or C1-C10alkyl group or fluoroalkyl group,2021P00136, wherein X1is independently O or NR6or CR7R8; X2is independently O or NR9or CR10R11; X3is independently O or NR12or CR13R14; X4is independently O or NR15or CR16R17; each R1to R17is independently H or C1-C10alkyl group; each R18to R22is independently H or C1-C10alkyl group or fluoroalkyl group,, wherein X1is independently OR4or NR5R6; X2is independently O or NR7or CR8R9; wherein X3is independently OR10or NR11R12; X4is independently O or NR13or CR14R15; X5is independently CR16or N; X6is independently CR17or N; each R1to R17is independently H or C1-C10alkyl group; R18is independently H or C1-C10alkyl group or fluoroalkyl group; and n≦5,2021P00136, wherein X1is independently OR4or NR5R6; X2is independently O or NR7or CR8R9; wherein X3is independently OR10or NR11R12; X4is independently O or NR13or CR14R15; X5is independently CR16or N; X6is independently CR17or N; each R1to R17is independently H or C1-C10alkyl group; each R18to R24is independently H or C1-C10alkyl group or fluoro group, k), wherein X1is independently OR4or NR5R6; X2is independently O or NR7or CR8R9; wherein X3is independently OR10or NR11R12; X4is independently O or NR13or CR14R15; X5is independently CR16or N; X6is independently CR17or N; each R1to R17is independently H or C1-C10alkyl group; each R18to R21is independently H or C1-C10alkyl group or fluoro group,2021P00136wherein X1is independently OR4or NR5R6; X2is independently O or NR7or CR8R9; wherein X3is independently OR10or NR11R12; X4is independently O or NR13or CR14R15; X5is independently CR16or N; X6is independently CR17or N; each R1to R17is independently H or C1-C10alkyl group; each R18to R22is independently H or C1-C10alkyl group or fluoroalkyl group.

5. A composition comprising the chemical of any one of claims 1-4.

6. The composition of claim 5, further comprising a solvent such as toluene.

7. The composition of claim 5, wherein the composition is a gas or vapor and further comprises a carrier gas such as Helium, Argon or Nitrogen.

8. The composition of claim 7, further comprising a co-reactant suitable for use with the chemical to perform a vapor phase deposition in which the co-reactant participates in the vapor phase deposition process to yield a desired deposition structure or composition.

9. The composition of claim 8, wherein the co-reactant is selected from the group consisting of O2, O3, H2O, H2O2, NO, N2O, NO2, TMPO, oxygen radicals thereof, and mixtures thereof.

10. A method of forming a V or Nb or Ta containing deposit, the method comprising a step of introducing into a reactor, having a substrate therein, a vapor of the chemical of any one of claims 1-4; and a step of forming a V or Nb or Ta containing deposit, from the vapor of the chemical of any one of claims 1-4, on the substrate.2021P00136 11. The method of claim 10, wherein the chemical is provided as the composition of any one of claims 5-9.

12. The method of claim 10, further comprising a step of introducing a co-reactant into the reactor.

13. The method of claim 12, wherein the co-reactant is selected from the group consisting of O2, O3, H2O, H2O2, NO, N2O, NO2, TMPO, oxygen radicals thereof, and mixtures thereof.

14. The method of any one of claims 10-13, wherein M in the chemical of any one of claims 1-4, is Nb and the deposit formed on the substrate is a Niobium-containing deposit.

15. The method of any one of claims 10-14, wherein the deposit is at least partially formed by an Atomic Layer Deposition process.

16. The method of any one of claims 10-15, wherein the substrate is a cathode active material powder.

17. The method of claim 16, wherein the substrate is a cathode material comprising a cathode active material powder, a conductive carbon and a binder material, deposited onto a current collector foil.

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