Group 5 transition metal-containing precursors and their use in the semiconductor manufacturing

Abstract

The invention relates to a Metal-containing film forming composition comprising a precursor having the formula M(=NR1)L3, in which M = V or Nb or Ta; R1 is H or C1- C10 alkyl group; and L is substituted or unsubstituted diketones, aminoketones, alkoxyalcohols, alkoxyalkanes, alkanediols, alkanolamines, aminoaldehydes, diimines, dienes.

Description

[0001]2021P00168 GROUP 5 TRANSITION METAL-CONTAINING PRECURSORS AND THEIR USE IN THE SEMICONDUCTOR MANUFACTURING Cross Reference to Related Applications This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 526,740, 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 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. 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, VNx wherein x is approximately one) have been extensively utilized in various fields of technology. Traditionally these nitrides have been applied as hard and decorative 2021P00168 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 are 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 example, 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 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]. NbCl5 for 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 NbCl5 and 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 NbCl5 also 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)4 and 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 2021P00168 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)3 or 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=C1-12 alkyl, C5-12 cycloalkyl, 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 compound with group 5 metal monocyclopentadienyl complexes to form NbCp(NH(CH2)2-NH2)CI3 and 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 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, 2021P00168 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: Fig. 1. is a ThermoGravimetric Analysis (TGA) graph demonstrating the percentage of weight with increasing temperature of Nb(=NtBu)(mmp)3; Fig. 2. is a ThermoGravimetric Analysis (TGA) graph demonstrating the percentage of weight with increasing temperature of Nb(=NtBu)(tmhd)3. Detailed Description of the 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(=NR1)L3 wherein: M = V or Nb or Ta; R1= independently H or a C1-C10alkyl group; and L = substituted or unsubstituted diketones, aminoketones, alkoxyalcohols, alkoxyalkanes, alkanediols, alkanolamines, aminoaldehydes, diimines, dienes. According to other particular embodiments, the invention concerns chemicals (and metal-containing film forming compositions comprising the chemical) of formulae: 2021P00168 Formula 1: wherein X1is independently O or NR14or CR15R16; X2is independently OR17or NR18R19; X3is independently O or NR20or CR21R22; X4is independently OR23or NR24R25; X5is independently O or NR26or CR27R28; X6is independently OR29or NR30R31; each R1to R31is independently H or C1-C10alkyl group or fluoroalkyl group. Formula 2: wherein X1is independently O or NR8or CR9R10; X2is independently O or NR11or CR12R13; X3is independently O or NR14or CR15R16; X4is independently O or NR17or CR18R19; X5is independently O or NR20or CR21R22; X6is independently O or NR23or CR24R25; each R1to R25is independently H or C1-C10 alkyl 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 2021P00168 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 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. 2021P00168 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)(mmp)3 To a solution of Nb(=NtBu)(NEt2)3(2g, 5.26mmol) in 30mL of Toluene at -78oC, was added dropwise a solution of 1-Methoxy-2-methyl-2-propanol (1.72g, 16.56mmol). After stirring the mixture at room temperature for 12h, the solvent was removed under vacuum to give colorless oil. The material was then purified by distillation up to 110oC at 25mTorr to give 1.8g (72.3%) of colorless oil. The material was characterized by NMR1H (δ, ppm, C6D6): 3.36 (s, 9H), 3.30 (s, 6H), 1.42 (s, 9H), 1.41 (s, 18H). 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 at 200mL / min. These results are shown in Fig 1, which is a TGA graph illustrating the percentage of weight upon temperature increase. Example 2: Synthesis of Nb(=NtBu)(tmhd)3 To a solution of Nb(=NtBu)(NEt2)3(2g, 5.26mmol) in 30mL of Toluene at -78oC, was added dropwise a solution of 2,2,6,6-Tetramethyl-3,5-heptanedione (3.05g, 16.56mmol). 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 1.5g (40%) of yellow solid. The material was characterized by NMR1H (δ, ppm, C6D6): 6.03 (s, 2H), 5.83 (s, 1H), 1.47 (s, 9H), 1.33(m, 36H), 1.23 (s, 9H), 1.01(s, 9H). The purified product left a 0.8% residual mass during open-cup TGA analysis measured at a temperature rising rate of 10oC / min in an atmosphere which flows nitrogen at 200mL / min. These results are shown in Fig 2, which is a TGA graph illustrating the percentage of weight upon temperature increase. Industrial Applicability The present invention is at least industrially applicable to producing Niobium Oxide (Nb2O5) in semiconductor applications. 2021P00168 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, 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. 2021P00168 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 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.

Claims

2021P00168 CLAIMS:

1. A chemical having the formula M(=NR1)L3, wherein: M = V or Nb or Ta; R1= H or a C1-C10 alkyl group; and L = substituted or unsubstituted diketones, aminoketones, alkoxyalcohols, alkoxyalkanes, alkanediols, alkanolamines, aminoaldehydes, diimines, dienes.

2. The chemical of claim 1, wherein the chemical is selected from the group consisting of:wherein X1is independently O or NR14or CR15R16; X2is independently OR17or NR18R19; X3is independently O or NR20or CR21R22; X4is independently OR23or NR24R25; X5is independently O or NR26or CR27R28; X6is independently OR29or NR30R31; each R1to R31is independently H or C1-C10 alkyl group or fluoroalkyl group; and, wherein X1is independently O or NR8or CR9R10; X2is independently O or NR11or CR12R13; X3is independently O or NR14or CR15R16; X4is independently O or NR17or2021P00168 CR18R19; X5is independently O or NR20or CR21R22; X6is independently O or NR23or CR24R25; each R1to R25is independently H or C1-C10alkyl group or fluoroalkyl group.

3. A composition comprising the chemical of any one of claims 1-2.

4. The composition of claim 3, further comprising a solvent such as toluene.

5. The composition of claim 3, wherein the composition is a gas or vapor and further comprises a carrier gas such as Helium, Argon or Nitrogen.

6. The composition of claim 5, 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.

7. The composition of claim 6, 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.

8. 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 or 2; 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 or 2, on the substrate.

9. The method of claim 8, wherein the chemical is provided as the composition of any one of claims 3-7.

10. The method of claim 8, further comprising a step of introducing a co-reactant into the reactor.

11. The method of claim 10, wherein the co-reactant is selected from the group2021P00168 consisting of O2, O3, H2O, H2O2, NO, N2O, NO2, TMPO, oxygen radicals thereof, and mixtures thereof.

12. The method of any one of claims 8-11, wherein M in the chemical of any one of claims 1 or 2, is Nb and the deposit formed on the substrate is a Niobium- containing deposit.

13. The method of any one of claims 8-12, wherein the deposit is at least partially formed by an Atomic Layer Deposition process.

14. The method of any one of claims 8-13, wherein the substrate is a cathode active material powder.

15. The method of claim 14, 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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