# US 11,993,842 B2 · Selective deposition of metal oxide by pulsed chemical vapor deposition > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,993,842 B2 - Document ID: US11993842B2 - Status: Granted - Kind: B2 - Application number: 18/072,392 - Filed: 2022-11-30 - Published: 2023-04-20 - Granted: 2024-05-28 - Earliest claimed: 2020-04-08 - Assignees: Applied Materials, Inc.; The Regents of the University of California - Applicants: Applied Materials, Inc.; The Regents of the University of California - Inventors: Keith Tatseun Wong; Srinivas D. Nemani; Andrew C. Kummel; James Huang; Yunil Cho - Web page: https://patentgrep.com/patent/US11993842B2 ## CPC - C23C 16/405: {of refractory metals or yttrium} - C23C 16/04: Coating on selected surface areas, e.g. using masks - C23C 16/45523: {Pulsed gas flow or change of composition over time} - C23C 28/04: only coatings of inorganic non-metallic material - C23C 28/042: {including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides} - C23C 28/40: {Coatings including alternating layers following a pattern, a periodic or defined repetition} - C23C 28/42: {characterized by the composition of the alternating layers} - H10P 14/61: using masks - H10P 14/6336: {in the presence of a plasma [PECVD]} - H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD} - H10P 14/662: {Laminate layers, e.g. stacks of alternating high-k metal oxides (adhesion layers or buffer layers H10P14/6508, H10P14/6548)} - H10P 14/668: {the materials being characterised by the deposition precursor materials} - H10P 14/69391: {the material containing aluminium, e.g. Al2O3} - H10P 14/69392: {the material containing hafnium, e.g. HfO2} - H10P 14/69394: {the material containing titanium, e.g. TiO2} - H10P 14/69395: {the material containing zirconium, e.g. ZrO2} - 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) - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 ## Abstract Embodiments described and discussed herein provide methods for selectively depositing a metal oxides on a substrate. In one or more embodiments, methods for forming a metal oxide material includes positioning a substrate within a processing chamber, where the substrate has passivated and non-passivated surfaces, exposing the substrate to a first metal alkoxide precursor to selectively deposit a first metal oxide layer on or over the non-passivated surface, and exposing the substrate to a second metal alkoxide precursor to selectively deposit a second metal oxide layer on the first metal oxide layer. The method also includes sequentially repeating exposing the substrate to the first and second metal alkoxide precursors to produce a laminate film containing alternating layers of the first and second metal oxide layers. Each of the first and second metal alkoxide precursors contains a different metal selected from titanium, zirconium, hafnium, aluminum, or lanthanum. ## Claims ### Claim 1 A method of forming a metal oxide material, comprising: positioning a substrate within a processing chamber, wherein the substrate comprises a passivated surface and a non-passivated surface, and wherein the non-passivated surface is terminated with hydride groups, hydroxide groups, or a combination thereof; exposing the substrate to a first metal alkoxide precursor to produce a first metal oxide layer on or over the non-passivated surface while the passivated surface remains at least substantially free of the first metal oxide layer, wherein the first metal alkoxide precursor is thermally decomposed to produce the first metal oxide layer; exposing the substrate to a second metal alkoxide precursor to produce a second metal oxide layer on the first metal oxide layer while the passivated surface remains at least substantially free of the second metal oxide layer, wherein the second metal alkoxide precursor is thermally decomposed to produce the second metal oxide layer, and wherein the first metal alkoxide precursor and the second metal alkoxide precursor have different metals; and sequentially repeating exposing the substrate to the first metal alkoxide precursor and the second metal alkoxide precursor to produce a laminate film comprising alternating layers of the first and second metal oxide layers, wherein the laminate film comprises about 5 pairs to about 200 pairs of the first and second metal oxide layers. ### Claim 2 (depends on 1) The method of claim 1, wherein the laminate film is amorphous. ### Claim 3 (depends on 1) The method of claim 1, wherein the substrate is maintained at a temperature of about 150° C. to about 450° C. when producing the first metal oxide layer and/or the second metal oxide layer. ### Claim 4 (depends on 1) The method of claim 1, wherein: each of the first metal oxide layer and the second metal oxide layer independently has a thickness of about 0.1 nm to about 5 nm; and the laminate film has a thickness of about 5 nm to about 50 nm. ### Claim 5 (depends on 1) The method of claim 1, wherein the laminate film comprises about 10 pairs to about 50 pairs of the first and second metal oxide layers. ### Claim 6 (depends on 1) The method of claim 1, wherein: the first metal oxide layer is produced during a first pulsed-chemical vapor deposition process; the substrate is sequentially exposed to the first metal alkoxide precursor and a first purge gas during the first pulsed-chemical vapor deposition process; and the substrate is exposed to the first metal alkoxide precursor for a period of about 0.1 seconds to about 10 seconds and exposed to the first purge gas for a period of about 1 second to about 120 seconds. ### Claim 7 (depends on 1) The method of claim 1, wherein: the second metal oxide layer is produced during a second pulsed-chemical vapor deposition process; the substrate is sequentially exposed to the second metal alkoxide precursor and a second purge gas during the second pulsed-chemical vapor deposition process; and the substrate is exposed to the second metal alkoxide precursor for a period of about 0.1 seconds to about 10 seconds and exposed to the second purge gas for a period of about 1 second to about 120 seconds. ### Claim 8 (depends on 1) The method of claim 1, wherein each of the first metal alkoxide precursor and the second metal alkoxide precursor independently comprises a metal selected from the group consisting of titanium, zirconium, hafnium, aluminum, and lanthanum. ### Claim 9 (depends on 1) The method of claim 1, wherein each of the first metal alkoxide precursor and the second metal alkoxide precursor independently comprises a metal propoxide compound or a metal butoxide compound. ### Claim 10 (depends on 1) The method of claim 1, wherein each of the first metal alkoxide precursor and the second metal alkoxide precursor independently comprises titanium (IV) n-propoxide, titanium (IV) iso-propoxide, titanium (IV) n-butoxide, titanium (IV) tert-butoxide, hafnium (IV) n-propoxide, hafnium (IV) iso-propoxide, hafnium (IV) n-butoxide, hafnium (IV) Cert-butoxide, zirconium (IV) n-propoxide, zirconium (IV) iso-propoxide, zirconium (IV) n-butoxide, zirconium (IV) tert-butoxide, aluminum (III) n-propoxide, aluminum (III) iso-propoxide, aluminum (III) n-butoxide, aluminum (III) Cert-butoxide, lanthanum (III) n-propoxide, lanthanum (III) iso-propoxide, lanthanum (III) n-butoxide, lanthanum (III) tert-butoxide, isomers thereof, or any combination thereof. ### Claim 11 (depends on 1) The method of claim 1, wherein the first metal oxide layer comprises titanium oxide and the second metal oxide layer comprises hafnium oxide. ### Claim 12 (depends on 1) The method of claim 1, wherein: the first metal oxide layer comprises a first metal and the second metal oxide layer comprises a second metal; and the laminate film has an atomic ratio of the first metal to the second metal of about 5:1 to about 15:1. ### Claim 13 (depends on 1) The method of claim 1, wherein the passivated surface is terminated with one or more alkyl groups. ### Claim 14 (depends on 1) The method of claim 1, wherein at least the first metal alkoxide precursor or the second metal alkoxide precursor is thermally decomposed by β-hydride elimination process. ### Claim 15 (depends on 1) The method of claim 1, wherein at least the first metal alkoxide precursor or the second metal alkoxide precursor is thermally decomposed while in the absence of a co-reactant. ### Claim 16 A method of forming a metal oxide material, comprising: positioning a substrate within a processing chamber, wherein the substrate comprises a passivated surface and a non-passivated surface, and wherein the non-passivated surface is terminated with hydride groups, hydroxide groups, or a combination thereof; and depositing a laminate film selectively on the non-passivated surface while the passivated surface remains at least substantially free of the laminate film, wherein: the laminate film comprises two or more pairs of alternating layers of a first metal oxide layer and a second metal oxide layer; each of the first metal oxide layer and the second metal oxide layer independently has a thickness of about 0.05 nm to about 10 nm; a first metal alkoxide precursor is thermally decomposed to produce the first metal oxide layer during a first pulsed-chemical vapor deposition process; a second metal alkoxide precursor is thermally decomposed to produce the second metal oxide layer during a second pulsed-chemical vapor deposition process; the first metal alkoxide precursor and the second metal alkoxide precursor have different metals; the substrate is maintained at a first temperature during the first pulsed-chemical vapor deposition process and at a second temperature during the second pulsed-chemical vapor deposition process; and each of the first temperature and the second temperature is independently at about 150° C. to about 450° C. ### Claim 17 (depends on 16) The method of claim 16, wherein each of the first metal alkoxide precursor and the second metal alkoxide precursor independently comprises a metal selected from the group consisting of titanium, zirconium, hafnium, aluminum, and lanthanum. ### Claim 18 (depends on 17) The method of claim 17, wherein each of the first temperature and the second temperature is independently at about 200° C. to about 350° C. ### Claim 19 (depends on 16) The method of claim 16, wherein: each of the first metal oxide layer and the second metal oxide layer independently has a thickness of about 0.1 nm to about 5 nm; and the laminate film comprises about 10 pairs to about 50 pairs of the first and second metal oxide layers. ### Claim 20 A method of forming a metal oxide material, comprising: positioning a substrate within a processing chamber, wherein the substrate comprises a passivated surface and a non-passivated surface, and wherein the non-passivated surface is terminated with hydride groups, hydroxide groups, or a combination thereof; exposing the substrate to a first metal alkoxide precursor to produce a first metal oxide layer on or over the non-passivated surface while the passivated surface remains at least substantially free of the first metal oxide layer, wherein the first metal alkoxide precursor is thermally decomposed to produce the first metal oxide layer while the substrate is maintained at a first temperature of about 150° C. to about 350° C.; exposing the substrate to a second metal alkoxide precursor to produce a second metal oxide layer on the first metal oxide layer while the passivated surface remains at least substantially free of the second metal oxide layer, wherein the second metal alkoxide precursor is thermally decomposed to produce the second metal oxide layer while the substrate is maintained at a second temperature of about 150° C. to about 350° C.; and sequentially repeating exposing the substrate to the first metal alkoxide precursor and the second metal alkoxide precursor to produce a laminate film comprising alternating layers of the first and second metal oxide layers, wherein the laminate film is amorphous, and wherein the laminate film comprises about 10 pairs to about 100 pairs of the first and second metal oxide layers, wherein: each of the first metal oxide layer and the second metal oxide layer independently has a thickness of about 0.05 nm to about 10 nm; and the first metal oxide layer and the second metal oxide layer contain different metal oxides.