# US 11,309,181 B2 · Sputtering apparatus, sputtering target, and method for forming semiconductor film with the sputtering apparatus > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,309,181 B2 - Document ID: US11309181B2 - Status: Granted - Kind: B2 - Application number: 15/609,148 - Filed: 2017-05-31 - Published: 2017-12-07 - Granted: 2022-04-19 - Earliest claimed: 2016-06-06 - Assignees: Semiconductor Energy Laboratory Co., Ltd. - Applicants: Semiconductor Energy Laboratory Co., Ltd. - Inventors: Masahiro Watanabe; Takuya Handa; Yasuharu Hosaka; Kenichi Okazaki; Shunpei Yamazaki - Web page: https://patentgrep.com/patent/US11309181B2 ## CPC - H10P 14/22: using physical deposition, e.g. vacuum deposition or sputtering - C23C 14/086: {of zinc, germanium, cadmium, indium, tin, thallium or bismuth} - C23C 14/3407: {Cathode assembly for sputtering apparatus, e.g. Target} - C23C 14/3457: {using other particles than noble gas ions (C23C14/0036, C23C14/46 take precedence)} - C23C 14/54: Controlling or regulating the coating process - C23C 14/564: {Means for minimising impurities in the coating chamber such as dust, moisture, residual gases} - C23C 14/566: {using a load-lock chamber} - H01J 37/3426: {Material} - H10D 30/6723: {having light shields} - H10D 30/6734: {having gate electrodes arranged on both top and bottom sides of the channel, e.g. dual-gate TFTs} - H10D 30/6755: {Oxide semiconductors, e.g. zinc oxide, copper aluminium oxide or cadmium stannate} - H10D 99/00: Subject matter not provided for in other groups of this subclass - H10P 14/3434: {being oxide semiconductor materials (Group IIB-VIA semiconductor materials H10P14/3424)} - H10P 72/0402: {Apparatus for fluid treatment (H10P72/0441, H10P72/0448 take precedence)} - H10P 72/0462: {characterised by the construction of the processing chambers, e.g. modular processing chambers} - H10P 72/0464: {characterised by the construction of the transfer chamber} - H10P 72/0466: {characterised by the construction of the load-lock chamber} - H10P 72/0468: {comprising a chamber adapted to a particular process} - H10P 72/7618: {characterised by a movable susceptor, stage or support, others than those only rotating on their own vertical axis, e.g. susceptors on a rotating carrousel} - G02F 1/1303: {Apparatus specially adapted to the manufacture of LCDs} - G02F 1/134309: {characterised by their geometrical arrangement} - G02F 1/1368: in which the switching element is a three-electrode device {(G02F1/136277 takes precedence)} - H10K 59/1213: {the pixel elements being TFTs} - 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) - H01J: ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS (spark-gaps H01T; electric arc lamps H05B31/00; particle accelerators H05H) - H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES - G02F: OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS - H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES ## Abstract To provide a sputtering apparatus capable of forming a semiconductor film in which impurities such as hydrogen or water are reduced. The sputtering apparatus is capable of forming a semiconductor film and includes a deposition chamber, a gas supply device connected to the deposition chamber, a gas refining device connected to the gas supply device, a vacuum pump for evacuating the deposition chamber, a target disposed in the deposition chamber, and a cathode disposed to face the target. The gas supply device is configured to supply at least one of an argon gas, an oxygen gas, and a nitrogen gas. The partial pressure of hydrogen molecules is lower than or equal to 0.01 Pa and the partial pressure of water molecules is lower than or equal to 0.0001 Pa in the deposition chamber. ## Claims ### Claim 1 A method for forming an oxide semiconductor film, comprising: setting a sputtering target and a substrate in a deposition chamber; introducing a deposition gas into the deposition chamber; and applying voltage to the sputtering target so as to form the oxide semiconductor film over the substrate, wherein the sputtering target comprises indium, gallium, and zinc, wherein the sputtering target comprises a first region and a second region, wherein an atomic proportion of gallium of the first region is higher than an atomic proportion of gallium of the whole sputtering target, wherein an atomic proportion of indium of the second region is higher than an atomic proportion of indium of the whole sputtering target, wherein the first region has a spherical shape, and wherein a proportion of the oxygen gas in the deposition gas is higher than 30% and lower than or equal to 100%. ### Claim 2 (depends on 1) The method for forming an oxide semiconductor film according to claim 1, wherein the first region is between a surface of the sputtering target and the second region. ### Claim 3 (depends on 1) The method for forming an oxide semiconductor film according to claim 1, wherein one or both of the first region and the second region comprises a cluster. ### Claim 4 (depends on 1) The method for forming an oxide semiconductor film according to claim 1, wherein setting the sputtering target and the substrate, introducing the deposition gas, and applying voltage to the sputtering target are performed at a temperature without intentional heating. ### Claim 5 (depends on 1) The method for forming an oxide semiconductor film according to claim 1, further comprising introducing nitrogen molecules to the deposition chamber after introducing the deposition gas and before applying voltage to the sputtering target. ### Claim 6 A method for forming an oxide semiconductor film, comprising: setting a sputtering target and a substrate in a deposition chamber; introducing a deposition gas into the deposition chamber; and applying voltage to the sputtering target so as to form the oxide semiconductor film over the substrate, wherein the sputtering target comprises indium, gallium, and zinc, wherein the sputtering target comprises a first region and a second region, wherein the first region is a region where gallium is segregated and is a Ga-rich region, wherein the second region is a region where indium is segregated and is an In-rich region, wherein the first region has a spherical shape, and wherein a proportion of the oxygen gas in the deposition gas is higher than 30% and lower than or equal to 100%. ### Claim 7 (depends on 6) The method for forming an oxide semiconductor film according to claim 6, wherein the first region is between a surface of the sputtering target and the second region. ### Claim 8 (depends on 6) The method for forming an oxide semiconductor film according to claim 6, wherein one or both of the first region and the second region comprises a cluster. ### Claim 9 (depends on 6) The method for forming an oxide semiconductor film according to claim 6, wherein setting the sputtering target and the substrate, introducing the deposition gas, and applying voltage to the sputtering target are performed at a temperature without intentional heating. ### Claim 10 (depends on 6) The method for forming an oxide semiconductor film according to claim 6, further comprising introducing nitrogen molecules to the deposition chamber after introducing the deposition gas and before applying voltage to the sputtering target. ### Claim 11 A method for forming an oxide semiconductor film, comprising: setting a sputtering target and a substrate in a deposition chamber; introducing a deposition gas into the deposition chamber; and applying voltage to the sputtering target so as to form the oxide semiconductor film over the substrate, wherein the sputtering target comprises indium, gallium, and zinc, wherein the sputtering target comprises a first region and a second region, wherein an atomic proportion of gallium of the first region is higher than an atomic proportion of gallium of the whole sputtering target, wherein an atomic proportion of indium of the second region is higher than an atomic proportion of indium of the whole sputtering target, wherein the first region has a spherical shape, and wherein a proportion of the oxygen gas in the deposition gas is higher than or equal to 0% and lower than or equal to 30%. ### Claim 12 (depends on 11) The method for forming an oxide semiconductor film according to claim 11, wherein the first region is between a surface of the sputtering target and the second region. ### Claim 13 (depends on 11) The method for forming an oxide semiconductor film according to claim 11, wherein one or both of the first region and the second region comprises a cluster. ### Claim 14 (depends on 11) The method for forming an oxide semiconductor film according to claim 11, wherein setting the sputtering target and the substrate, introducing the deposition gas, and applying voltage to the sputtering target are performed at a temperature without intentional heating. ### Claim 15 (depends on 11) The method for forming an oxide semiconductor film according to claim 11, further comprising introducing nitrogen molecules to the deposition chamber after introducing the deposition gas and before applying voltage to the sputtering target. ### Claim 16 A method for forming an oxide semiconductor film, comprising: setting a sputtering target and a substrate in a deposition chamber; introducing a deposition gas into the deposition chamber; and applying voltage to the sputtering target so as to form the oxide semiconductor film over the substrate, wherein the sputtering target comprises indium, gallium, and zinc, wherein the sputtering target comprises a first region and a second region, wherein the first region is a region where gallium is segregated and is a Ga-rich region, wherein the second region is a region where indium is segregated and is an In-rich region, wherein the first region has a spherical shape, and wherein a proportion of the oxygen gas in the deposition gas is higher than or equal to 0% and lower than or equal to 30%. ### Claim 17 (depends on 16) The method for forming an oxide semiconductor film according to claim 16, wherein the first region is between a surface of the sputtering target and the second region. ### Claim 18 (depends on 16) The method for forming an oxide semiconductor film according to claim 16, wherein one or both of the first region and the second region comprises a cluster. ### Claim 19 (depends on 16) The method for forming an oxide semiconductor film according to claim 16, wherein setting the sputtering target and the substrate, introducing the deposition gas, and applying voltage to the sputtering target are performed at a temperature without intentional heating. ### Claim 20 (depends on 16) The method for forming an oxide semiconductor film according to claim 16, further comprising introducing nitrogen molecules to the deposition chamber after introducing the deposition gas and before applying voltage to the sputtering target.