# US 8,785,316 B2 · Methods for forming semiconductor materials by atomic layer deposition using halide precursors > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,785,316 B2 - Document ID: US8785316B2 - Status: Granted - Kind: B2 - Application number: 13/933,855 - Filed: 2013-07-02 - Published: 2013-11-07 - Granted: 2014-07-22 - Earliest claimed: 2010-09-30 - Assignees: Soitec - Applicants: Soitec - Inventors: Christiaan J. Werkhoven - Web page: https://patentgrep.com/patent/US8785316B2 ## CPC - H10P 14/24: using chemical vapour deposition [CVD] - C23C 16/301: {AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi} - C23C 16/4488: {by in situ generation of reactive gas by chemical or electrochemical reaction} - C23C 16/45551: {for relative movement of the substrate and the gas injectors or half-reaction reactor compartments} - C23C 16/545: {for coating elongated substrates} - H10P 14/3414: {being group IIIA-VIA materials} - H10P 14/3416: {Nitrides} - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 - 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 Methods of depositing a III-V semiconductor material on a substrate include sequentially introducing a gaseous precursor of a group III element and a gaseous precursor of a group V element to the substrate by altering spatial positioning of the substrate with respect to a plurality of gas columns. For example, the substrate may be moved relative to a plurality of substantially aligned gas columns, each disposing a different precursor. Thermalizing gas injectors for generating the precursors may include an inlet, a thermalizing conduit, a liquid container configured to hold a liquid reagent therein, and an outlet. Deposition systems for forming one or more III-V semiconductor materials on a surface of the substrate may include one or more such thermalizing gas injectors configured to direct the precursor to the substrate via the plurality of gas columns. ## Claims ### Claim 1 A method of depositing a semiconductor material, comprising: sequentially exposing a surface of a substrate to a group III element precursor and a group V element precursor in at least one atomic layer deposition (ALD) growth cycle and forming a first III-nitride semiconductor material over the surface of the substrate; and exposing a surface of the first III-nitride semiconductor material to one or more metal halide precursors and a group V element precursor and forming a gallium nitride semiconductor material over the first III-nitride semiconductor material. ### Claim 2 (depends on 1) The method of claim 1, wherein forming the first III-nitride semiconductor material over the surface of the substrate comprises forming aluminum nitride over the surface of the substrate. ### Claim 3 (depends on 2) The method of claim 2, wherein forming aluminum nitride over the surface of the substrate comprises forming a layer of aluminum nitride directly on the surface of the substrate. ### Claim 4 (depends on 3) The method of claim 3, further comprising selecting the substrate to comprise a sapphire substrate. ### Claim 5 (depends on 4) The method of claim 4, wherein forming the gallium nitride semiconductor material over the first III-nitride semiconductor material comprises forming at least one of GaN, InGaN, AlGaN, and InAlGaN over the first III-nitride semiconductor material. ### Claim 6 (depends on 5) The method of claim 5, wherein forming the gallium nitride semiconductor material over the first III-nitride semiconductor material comprises forming a layer of GaN directly on the layer of aluminum nitride. ### Claim 7 (depends on 6) The method of claim 6, wherein forming the layer of GaN further comprises thermally decomposing a source gas comprising GaCl3 to form a metal halide precursor comprising GaCl. ### Claim 8 (depends on 5) The method of claim 5, wherein forming at least one of GaN, InGaN, AlGaN, and InAlGaN further comprises thermally decomposing one or more source gases selected from the group consisting of GaCl3, InCl3, and AlCl3 and forming one or more metal halide precursors selected from the group consisting of GaCl, InCl, and AlCl. ### Claim 9 (depends on 4) The method of claim 4, further comprising forming the one or more metal halide precursors by thermally decomposing one or more source gases, the one or more source gases selected from the group consisting of GaCl3, InCl3, and AlCl3. ### Claim 10 (depends on 1) The method of claim 1, further comprising forming at least a portion of the one or more metal halide precursors by reacting a chlorinated species with liquid gallium. ### Claim 11 (depends on 10) The method of claim 10, wherein the one or more metal halide precursors comprises GaCl. ### Claim 12 (depends on 10) The method of claim 10, wherein the chlorinated species comprises one or more of hydrogen chloride and chlorine. ### Claim 13 (depends on 1) The method of claim 1, further comprising forming the one or more metal halide precursors by decomposing at least one of GaCl3, InCl3, and AlCl3 and forming at least one of GaCl, InCl, and AlCl. ### Claim 14 (depends on 1) The method of claim 1, further comprising exposing the substrate to a purge gas to remove at least one of excess group III element precursor and excess group V element precursor from the surface of the substrate. ### Claim 15 (depends on 1) The method of claim 1, further comprising doping the gallium nitride semiconductor material by mixing a dopant gas with the one or more metal halide precursors. ### Claim 16 (depends on 1) The method of claim 1, further comprising forming one or more active layers on or over the gallium nitride semiconductor material. ### Claim 17 (depends on 1) The method of claim 1, further comprising forming one or more device structures on or over the gallium nitride semiconductor material. ### Claim 18 (depends on 17) The method of claim 17, wherein the one or more device structures comprises one or more light-emitting diodes.