# US 10,865,470 B2 · Metal oxide film, semiconductor device, and display device > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,865,470 B2 - Document ID: US10865470B2 - Status: Granted - Kind: B2 - Application number: 16/068,719 - Filed: 2016-05-19 - Published: 2019-01-24 - Granted: 2020-12-15 - Earliest claimed: 2016-01-18 - Assignees: Semiconductor Energy Laboratory Co., Ltd. - Applicants: Semiconductor Energy Laboratory Co., Ltd. - Inventors: Shunpei Yamazaki; Junichi Koezuka; Kenichi Okazaki; Masashi Tsubuku - Web page: https://patentgrep.com/patent/US10865470B2 ## CPC - C23C 14/08: Oxides (C23C14/10 takes precedence) - C23C 14/34: Sputtering - C23C 14/3414: {Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy} - C30B 23/00: Single-crystal growth by condensing evaporated or sublimed materials - C30B 23/02: Epitaxial-layer growth - C30B 29/22: Complex oxides - H10D 30/6755: {Oxide semiconductors, e.g. zinc oxide, copper aluminium oxide or cadmium stannate} - H10D 30/6757: {characterised by the structure of the channel, e.g. transverse or longitudinal shape or doping profile (TFTs having channel structures for preventing kink or snapback effects H10D30/6708; TFTs having lightly-doped source or drain extensions H10D30/6715)} - H10D 62/405: {Orientations of crystalline planes} - H10D 86/423: {comprising semiconductor materials not belonging to the Group IV, e.g. InGaZnO} - H10D 86/60: wherein the TFTs are in active matrices - H10D 87/00: Integrated devices comprising both bulk components and either SOI or SOS components on the same substrate - 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) - C30B: SINGLE-CRYSTAL GROWTH (by using ultra-high pressure, e.g. for the formation of diamonds, B01J3/06); UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL (zone-refining of metals or alloys C22B); PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE (casting of metals, casting of other substances by the same processes or devices B22D; working of plastics B29; modifying the physical structure of metals or alloys C21D, C22F); SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE (for producing semiconductor devices or parts thereof H10); APPARATUS THEREFOR - H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES ## Abstract A metal oxide film containing a crystal part is provided. Alternatively, a metal oxide film with highly stable physical properties is provided. Alternatively, a metal oxide film with improved electrical characteristics is provided. Alternatively, a metal oxide film with which field-effect mobility can be increased is provided. A metal oxide film including In, M (M is Al, Ga, Y, or Sn), and Zn includes a first crystal part and a second crystal part; the first crystal part has c-axis alignment; the second crystal part has no c-axis alignment; and the existing proportion of the second crystal part is higher than the existing proportion of the first crystal part. ## Claims ### Claim 1 A metal oxide film comprising In, M (M is Al, Ga, Y, or Sn), and Zn, wherein: the metal oxide film comprises a first crystal part and a second crystal part; the first crystal part has c-axis alignment; the second crystal part has no c-axis alignment; and an existing proportion of the second crystal part is higher than an existing proportion of the first crystal part. ### Claim 2 A metal oxide film comprising In, M (M is Al, Ga, Y, or Sn), and Zn, wherein: the metal oxide film comprises a first crystal part and a second crystal part; the first crystal part has c-axis alignment; the second crystal part has no c-axis alignment; in the case where an electron diffraction pattern of the metal oxide film is observed by performing electron diffraction measurement on a cross section, the electron diffraction pattern comprises: a first region comprising a diffraction spot derived from the first crystal part; and a second region comprising a diffraction spot derived from the second crystal part; and an integrated intensity of luminance in the first region is higher than an integrated intensity of luminance in the second region. ### Claim 3 (depends on 2) The metal oxide film according to claim 2, wherein the integrated intensity of luminance in the first region is more than one time and less than or equal to 40 times the integrated intensity of luminance in the second region. ### Claim 4 (depends on 2) The metal oxide film according to claim 2, the integrated intensity of luminance in the first region is more than one time and less than or equal to 10 times the integrated intensity of luminance in the second region. ### Claim 5 (depends on 2) The metal oxide film according to claim 2, wherein the integrated intensity of luminance in the first region is more than one time and less than or equal to three times the integrated intensity of luminance in the second region. ### Claim 6 (depends on 2) The metal oxide film according to claim 2, wherein the metal oxide film comprises a region where a peak value of a density of shallow defect states is less than 5×1012 cm−2eV−1. ### Claim 7 (depends on 2) The metal oxide film according to claim 2, wherein: an atomic ratio of the In to the M and the Zn in the metal oxide film is in a neighborhood of In:M:Zn=4:2:3; and in the case where a ratio of the number of atoms of the In to a total number of atoms of the In, M, and Zn is 4, a ratio of the number of atoms of the M is greater than or equal to 1.5 and less than or equal to 2.5 and a ratio of the number of atoms of the Zn is greater than or equal to 2 and less than or equal to 4. ### Claim 8 (depends on 2) A semiconductor device comprising a semiconductor film, a gate insulating film, and a gate electrode, wherein the semiconductor film comprises the metal oxide film according to claim 2. ### Claim 9 (depends on 2) A display device comprising the metal oxide film according to claim 2. ### Claim 10 A metal oxide film, wherein a first crystal part and a second crystal part are mixed in the metal oxide film, wherein the first crystal part has c-axis alignment in a direction perpendicular to a surface of the metal oxide film, wherein the second crystal part has no c-axis alignment in a direction perpendicular to a surface of the metal oxide film, wherein a third region and a fourth region are mixed in the metal oxide film, wherein the third region includes In, element M, Zn, and O, wherein the fourth region includes In, element M, Zn, and O, wherein element M in the third region and element M in the fourth region are Al, Ga, Y, or Sn, wherein atomic ratio of In to element M in the third region is higher than atomic ratio of In to element M in the fourth region wherein, in the case where an electron diffraction pattern of the metal oxide film is observed by performing electron diffraction measurement on a cross section, the electron diffraction pattern includes a first region including a diffraction spot derived from the first crystal part and a second region including a diffraction spot derived from the second crystal part, and wherein the integrated intensity of the luminance in the first region is more than one time and less than or equal to 40 times the integrated intensity of the luminance in the second region. ### Claim 11 (depends on 10) The metal oxide film according to claim 10, wherein, in the case where an electron diffraction pattern of the metal oxide film is observed by performing electron diffraction measurement on a cross section, the electron diffraction pattern includes a first region including a diffraction spot derived from the first crystal part and a second region including a diffraction spot derived from the second crystal part, and wherein the integrated intensity of the luminance in the first region is more than one time and less than or equal to 10 times the integrated intensity of the luminance in the second region. ### Claim 12 (depends on 10) The metal oxide film according to claim 10, wherein, in the case where an electron diffraction pattern of the metal oxide film is observed by performing electron diffraction measurement on a cross section, the electron diffraction pattern includes a first region including a diffraction spot derived from the first crystal part and a second region including a diffraction spot derived from the second crystal part, and wherein the integrated intensity of the luminance in the first region is more than one time and less than or equal to 3 times the integrated intensity of the luminance in the second region. ### Claim 13 (depends on 10) The metal oxide film according to claim 10, wherein a ring-like pattern is observed in an electron diffraction pattern of the metal oxide film under a condition where a diameter of an electron beam is greater than or equal to 25 nmΦ and less than or equal to 100 nmΦ. ### Claim 14 (depends on 10) The metal oxide film according to claim 10, wherein a plurality of spots distributed in a circumferential direction is observed in an electron diffraction pattern of the metal oxide film under a condition where a diameter of an electron beam is greater than or equal to 1 nmΦ and less than or equal to 10 nmΦ. ### Claim 15 (depends on 10) A semiconductor device comprising a semiconductor film, a gate insulating film, and a gate electrode, wherein the semiconductor film includes the metal oxide film according to claim 10. ### Claim 16 A metal oxide film, wherein a first crystal part and a second crystal part are mixed in the metal oxide film, wherein the first crystal part has c-axis alignment in a direction perpendicular to a surface of the metal oxide film, wherein the second crystal part has no c-axis alignment in a direction perpendicular to a surface of the metal oxide film, wherein existing proportion of the second crystal part is higher than existing proportion of the first crystal part, wherein, in the case where an electron diffraction pattern of the metal oxide film is observed by performing electron diffraction measurement on a cross section, the electron diffraction pattern includes a first region including a diffraction spot derived from the first crystal part and a second region including a diffraction spot derived from the second crystal part, wherein a third region and a fourth region are mixed in the metal oxide film, wherein the third region includes In, element M, Zn, and O, wherein the fourth region includes In, element M, Zn, and O, wherein element M in the third region and element M in the fourth region are Al, Ga, Y, or Sn, wherein atomic ratio of In to element M in the third region is higher than atomic ratio of In to element M in the fourth region. ### Claim 17 (depends on 16) The metal oxide film according to claim 16, wherein the integrated intensity of the luminance in the first region is more than one time and less than or equal to 40 times the integrated intensity of the luminance in the second region. ### Claim 18 (depends on 16) The metal oxide film according to claim 16, wherein the integrated intensity of the luminance in the first region is more than one time and less than or equal to 10 times the integrated intensity of the luminance in the second region. ### Claim 19 (depends on 16) The metal oxide film according to claim 16, wherein the integrated intensity of the luminance in the first region is more than one time and less than or equal to 3 times the integrated intensity of the luminance in the second region. ### Claim 20 (depends on 16) The metal oxide film according to claim 16, wherein a ring-like pattern is observed in an electron diffraction pattern of the metal oxide film under a condition where a diameter of an electron beam is greater than or equal to 25 nmΦ and less than or equal to 100 nmΦ. ### Claim 21 (depends on 16) The metal oxide film according to claim 16, wherein a plurality of spots distributed in a circumferential direction is observed in an electron diffraction pattern of the metal oxide film under a condition where a diameter of an electron beam is greater than or equal to 1 nmΦ and less than or equal to 10 nmΦ. ### Claim 22 (depends on 16) A semiconductor device comprising a semiconductor film, a gate insulating film, and a gate electrode, wherein the semiconductor film includes the metal oxide film according to claim 16. ### Claim 23 A metal oxide film, wherein a first crystal part and a second crystal part are mixed in the metal oxide film, wherein the first crystal part has c-axis alignment in a direction perpendicular to a surface of the metal oxide film, wherein the second crystal part has no c-axis alignment in a direction perpendicular to a surface of the metal oxide film, wherein existing proportion of the second crystal part is higher than existing proportion of the first crystal part, wherein, in the case where an electron diffraction pattern of the metal oxide film is observed by performing electron diffraction measurement on a cross section, the electron diffraction pattern includes a first region including a diffraction spot derived from the first crystal part and a second region including a diffraction spot derived from the second crystal part, and integrated intensity of luminance in the first region is higher than integrated intensity of luminance in the second region, wherein a third region and a fourth region are mixed in the metal oxide film, wherein the third region includes In, element M, Zn, and O, wherein the fourth region includes In, element M, Zn, and O, wherein element M in the third region and element M in the fourth region are Al, Ga, Y, or Sn, wherein atomic ratio of In to element M in the third region is higher than atomic ratio of In to element M in the fourth region. ### Claim 24 (depends on 23) The metal oxide film according to claim 23, wherein the integrated intensity of the luminance in the first region is more than one time and less than or equal to 40 times the integrated intensity of the luminance in the second region. ### Claim 25 (depends on 23) The metal oxide film according to claim 23, wherein the integrated intensity of the luminance in the first region is more than one time and less than or equal to 10 times the integrated intensity of the luminance in the second region. ### Claim 26 (depends on 23) The metal oxide film according to claim 23, wherein the integrated intensity of the luminance in the first region is more than one time and less than or equal to 3 times the integrated intensity of the luminance in the second region. ### Claim 27 (depends on 23) The metal oxide film according to claim 23, wherein a ring-like pattern is observed in an electron diffraction pattern of the metal oxide film under a condition where a diameter of an electron beam is greater than or equal to 25 nmΦ and less than or equal to 100 nmΦ. ### Claim 28 (depends on 23) The metal oxide film according to claim 23, wherein a plurality of spots distributed in a circumferential direction is observed in an electron diffraction pattern of the metal oxide film under a condition where a diameter of an electron beam is greater than or equal to 1 nmΦ and less than or equal to 10 nmΦ. ### Claim 29 (depends on 23) A semiconductor device comprising a semiconductor film, a gate insulating film, and a gate electrode, wherein the semiconductor film includes the metal oxide film according to claim 23.