# US 9,518,075 B2 · Group 5 cyclopentadienyl transition metal-containing precursors for deposition of group 5 transition metal-containing films > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,518,075 B2 - Document ID: US9518075B2 - Status: Granted - Kind: B2 - Application number: 14/106,241 - Filed: 2013-12-13 - Published: 2014-04-17 - Granted: 2016-12-13 - Earliest claimed: 2013-12-13 - Assignees: L'Air Liquide, Societe Anonyme pour l'Etude et l'Exploitation des Procedes Georges Claude - Applicants: L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude - Inventors: Clément Lansalot-Matras; Wontae Noh - Web page: https://patentgrep.com/patent/US9518075B2 ## CPC - C07F 17/00: Metallocenes - C07F 9/00: Compounds containing elements of Groups 5 or 15 of the Periodic Table - C23C 16/18: from metallo-organic compounds - C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22) - C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04) ## Abstract Transition metal-containing precursors are disclosed. Also disclosed are methods of synthesizing and using the disclosed precursors to deposit transition metal-containing films on one or more substrates via a vapor deposition process. ## Claims ### Claim 1 A transition metal-containing precursor having the formula: Formula 1), wherein M is selected from the group consisting of V and Ta and each of R1, R2, R3, R4, and R5 is independently selected from the group consisting of H; a C1-C5 linear, branched, or cyclic alkyl group; a C1-C5 linear, branched, or cyclic alkylsilyl group; a C1-C5 linear, branched, or cyclic alkylamino group; and a C1-C5 linear, branched, or cyclic fluoroalkyl group. ### Claim 2 (depends on 1) The transition metal-containing precursor of claim 1, wherein R2 and R3 are the same. ### Claim 3 (depends on 1) The transition metal-containing precursor of claim 1, wherein the transition metal-containing precursor is selected from the group consisting of: tert-butylimidocyclopentadienylmono(diethylamido)mono(iso-propylalkoxo)Vanadium(V); tert-butylimidocyclopentadienylmono(diethylamido)mono(tert-butylalkoxo)Vanadium(V); tert-butylimidocyclopentadienylmono(dimethylamido)mono(iso-propylalkoxo)Vanadium(V); tert-butylimidocyclopentadienylmono(dimethylamido)mono(tert-butylalkoxo)Vanadium(V); tert-butylimidomethylcyclopentadienylmono(diethylamido)mono(iso-propylalkoxo)Vanadium(V); tert-butylimidomethylcyclopentadienylmono(diethylamido)mono(tert-butylalkoxo)Vanadium(V); tert-butylimidomethylcyclopentadienylmono(dimethylamido)mono(iso-propylalkoxo)Vanadium(V); tert-butylimidomethylcyclopentadienylmono(dimethylamido)mono(tert-butylalkoxo)Vanadium(V); tert-amylimidocyclopentadienylmono(diethylamido)mono(iso-propylalkoxo)Vanadium(V); tert-amylimidocyclopentadienylmono(diethylamido)mono(tert-butylalkoxo)Vanadium(V); tert-amylimidocyclopentadienylmono(dimethylamido)mono(iso-propylalkoxo)Vanadium(V); tert-amylimidocyclopentadienylmono(dimethylamido)mono(tert-butylalkoxo)Vanadium(V); tert-butylimidocyclopentadienylmono(diethylamido)mono(iso-propylalkoxo)Tantalum(V); tert-butylimidocyclopentadienylmono(diethylamido)mono(tert-butylalkoxo)Tantalum(V); tert-butylimidocyclopentadienylmono(dimethylamido)mono(iso-propylalkoxo)Tantalum(V); tert-butylimidocyclopentadienylmono(dimethylamido)mono(tert-butylalkoxo)Tantalum(V); tert-butylimidomethylcyclopentadienylmono(diethylamido)mono(iso-propylalkoxo)Tantalum(V); tert-butylimidomethylcyclopentadienylmono(diethylamido)mono(tert-butylalkoxo)Tantalum(V); tert-butylimidomethylcyclopentadienylmono(dimethylamido)mono(iso-propylalkoxo)Tantalum(V); tert-butylimidomethylcyclopentadienylmono(dimethylamido)mono(tert-butylalkoxo)Tantalum(V); tert-amylimidocyclopentadienylmono(diethylamido)mono(iso-propylalkoxo)Tantalum(V); and tert-amylimidocyclopentadienylmono(diethylamido)mono(tert-butylalkoxo)Tantalum(V). ### Claim 4 (depends on 2) The transition metal-containing precursor of claim 2, wherein the transition metal-containing precursor is tert-butylimidocyclopentadienyl mono(dimethylamino)mono(tert-butylalkoxo)Tantalum(V). ### Claim 5 A process for the deposition of a transition metal-containing film on a substrate, comprising: introducing at least one transition metal-containing precursor into a reactor having at least one substrate disposed therein, the at least one transition metal-containing precursor having the following formula: wherein M is selected from the group consisting of V, and Ta and each of R1, R2, R3, R4, and R5 is independently selected from H; a C1-C5 linear, branched, or cyclic alkyl group; a C1-C5 linear, branched, or cyclic alkylsilyl group; a C1-C5 linear, branched, or cyclic alkylamino group; and a C1-C5 linear, branched, or cyclic fluoroalkyl group; and depositing at least part of the at least one transition metal-containing precursor onto the at least one substrate to form the transition metal-containing film using a vapor deposition method. ### Claim 6 (depends on 5) The process of claim 5, further comprising introducing at least one reactant into the reactor. ### Claim 7 (depends on 6) The process of claim 6, wherein the reactant is selected from the group consisting of H2, H2CO N2H4, NH3, SiH4, Si2H6, Si3H8, SiH2Me2, SiH2Et2, N(SiH3)3, hydrogen radicals thereof; and mixtures thereof. ### Claim 8 (depends on 6) The process of claim 6, wherein the reactant is selected from the group consisting of: O2, O3, H2O, H2O2 NO, N2O, NO2, oxygen radicals thereof; and mixtures thereof. ### Claim 9 (depends on 6) The process of claim 6, wherein the transition metal-containing precursor and the reactant are introduced into the reactor sequentially. ### Claim 10 (depends on 5) The process of claim 5, wherein the vapor deposition method is chemical vapor deposition. ### Claim 11 (depends on 6) The process of claim 6, wherein the transition metal-containing precursor and the reactant are introduced into the reactor sequentially. ### Claim 12 (depends on 5) The process of claim 5, wherein the vapor deposition method is atomic layer deposition. ### Claim 13 (depends on 5) The process of claim 5, wherein the transition metal-containing precursor is selected from the group consisting of: tert-butylimidocyclopentadienylmono(diethylamido)mono(iso-propylalkoxo)Vanadium(V); tert-butylimidocyclopentadienylmono(diethylamido)mono(tert-butylalkoxo)Vanadium(V); tert-butylimidocyclopentadienylmono(dimethylamido)mono(iso-propylalkoxo)Vanadium(V); tert-butylimidocyclopentadienylmono(dimethylamido)mono(tert-butylalkoxo)Vanadium(V); tert-butylimidomethylcyclopentadienylmono(diethylamido)mono(iso-propylalkoxo)Vanadium(V); tert-butylimidomethylcyclopentadienylmono(diethylamido)mono(tert-butylalkoxo)Vanadium(V); tert-butylimidomethylcyclopentadienylmono(dimethylamido)mono(iso-propylalkoxo)Vanadium(V); tert-butylimidomethylcyclopentadienylmono(dimethylamido)mono(tert-butylalkoxo)Vanadium(V); tert-amylimidocyclopentadienylmono(diethylamido)mono(iso-propylalkoxo)Vanadium(V); tert-amylimidocyclopentadienylmono(diethylamido)mono(tert-butylalkoxo)Vanadium(V); tert-amylimidocyclopentadienylmono(dimethylamido)mono(iso-propylalkoxo)Vanadium(V); tert-amylimidocyclopentadienylmono(dimethylamido)mono(tert-butylalkoxo)Vanadium(V); tert-butylimidocyclopentadienylmono(diethylamido)mono(iso-propylalkoxo)Tantalum(V); tert-butylimidocyclopentadienylmono(diethylamido)mono(tert-butylalkoxo)Tantalum(V); tert-butylimidocyclopentadienylmono(dimethylamido)mono(iso-propylalkoxo)Tantalum(V); tert-butylimidocyclopentadienylmono(dimethylamido)mono(tert-butylalkoxo)Tantalum(V); tert-butylimidomethylcyclopentadienylmono(diethylamido)mono(iso-propylalkoxo)Tantalum(V); tert-butylimidomethylcyclopentadienylmono(diethylamido)mono(tert-butylalkoxo)Tantalum(V); tert-butylimidomethylcyclopentadienylmono(dimethylamido)mono(iso-propylalkoxo)Tantalum(V); tert-butylimidomethylcyclopentadienylmono(dimethylamido)mono(tert-butylalkoxo)Tantalum(V); tert-amylimidocyclopentadienylmono(diethylamido)mono(iso-propylalkoxo)Tantalum(V); and tert-amylimidocyclopentadienylmono(diethylamido)mono(tert-butylalkoxo)Tantalum(V). ### Claim 14 (depends on 13) The process of claim 13, wherein the transition metal-containing precursor is tert-butylimidocyclopentadienylmono(dimethylamido)mono(tert-butylalkoxo)Niobium(V) or tert-butylimidocyclopentadienylmono(dimethylamido)mono(tert-butylalkoxo)Tantalum(V). ### Claim 15 A transition metal-containing precursor having the formula: Formula 1), wherein M is Nb and each of R1, R2, R3, R4, and R5 is independently selected from the group consisting of H; a C1-C5 linear, branched, or cyclic alkyl group; a C1-C5 linear, branched, or cyclic alkylsilyl group; a C1-C5 linear, branched, or cyclic alkylamino group; and a C1-C5 linear, branched, or cyclic fluoroalkyl group, provided that R2 and R3 are the same. ### Claim 16 (depends on 15) The transition metal-containing precursor of claim 15, wherein the transition metal-containing precursor is selected from the group consisting of: tert-butylimidocyclopentadienylmono(diethylamido)mono(iso-propylalkoxo)Niobium(V); tert-butylimidocyclopentadienylmono(diethylamido)mono(tert-butylalkoxo)Niobium(V); tert-butylimidocyclopentadienylmono(dimethylamido)mono(iso-propylalkoxo)Niobium(V); tert-butylimidocyclopentadienylmono(dimethylamido)mono(tert-butylalkoxo)Niobium(V); tert-butylimidomethylcyclopentadienylmono(diethylamido)mono(iso-propylalkoxo)Niobium(V); tert-butylimidomethylcyclopentadienylmono(diethylamido)mono(tert-butylalkoxo)Niobium(V); tert-butylimidomethylcyclopentadienylmono(dimethylamido)mono(iso-propylalkoxo)Niobium(V); tert-butylimidomethylcyclopentadienylmono(dimethylamido)mono(tert-butylalkoxo)Niobium(V); tert-amylimidocyclopentadienylmono(diethylamido)mono(iso-propylalkoxo)Niobium(V); and tert-amylimidocyclopentadienylmono(diethylamido)mono(tert-butylalkoxo)Niobium(V). ### Claim 17 (depends on 15) The transition metal-containing precursor of claim 15, wherein the transition metal-containing precursor is tert-butylimidocyclopentadienylmono(dimethylamino)mono(tert-butylalkoxo)Niobium(V). ### Claim 18 A process for the deposition of a transition metal-containing film on a substrate, comprising: introducing at least one transition metal-containing precursor into a reactor having at least one substrate disposed therein, the at least one transition metal-containing precursor having the following formula: wherein M is Nb and each of R1, R2, R3, R4, and R5 is independently selected from H; a C1-C5 linear, branched, or cyclic alkyl group; a C1-C5 linear, branched, or cyclic alkylsilyl group; a C1-C5 linear, branched, or cyclic alkylamino group; and a C1-C5 linear, branched, or cyclic fluoroalkyl group, provided that R2 and R3 are the same; and depositing at least part of the at least one transition metal-containing precursor onto the at least one substrate to form the transition metal-containing film using a vapor deposition method. ### Claim 19 (depends on 5) The process of claim 5, further comprising introducing at least one reactant into the reactor. ### Claim 20 (depends on 18) The transition metal-containing precursor of claim 18, wherein the transition metal-containing precursor is selected from the group consisting of: tert-butylimidocyclopentadienylmono(diethylamido)mono(iso-propylalkoxo)Niobium(V); tert-butylimidocyclopentadienylmono(diethylamido)mono(tert-butylalkoxo)Niobium(V); tert-butylimidocyclopentadienylmono(dimethylamido)mono(iso-propylalkoxo)Niobium(V); tert-butylimidocyclopentadienylmono(dimethylamido)mono(tert-butylalkoxo)Niobium(V); tert-butylimidomethylcyclopentadienylmono(diethylamido)mono(iso-propylalkoxo)Niobium(V); tert-butylimidomethylcyclopentadienylmono(diethylamido)mono(tert-butylalkoxo)Niobium(V); tert-butylimidomethylcyclopentadienylmono(dimethylamido)mono(iso-propylalkoxo)Niobium(V); tert-butylimidomethylcyclopentadienylmono(dimethylamido)mono(tert-butylalkoxo)Niobium(V); tert-amylimidocyclopentadienylmono(diethylamido)mono(iso-propylalkoxo)Niobium(V); and tert-amylimidocyclopentadienylmono(diethylamido)mono(tert-butylalkoxo)Niobium(V).