# US 10,770,310 B2 · Semiconductor device > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,770,310 B2 - Document ID: US10770310B2 - Status: Granted - Kind: B2 - Application number: 16/524,733 - Filed: 2019-07-29 - Published: 2019-11-21 - Granted: 2020-09-08 - Earliest claimed: 2013-10-10 - Assignees: Semiconductor Energy Laboratory Co., Ltd. - Applicants: Semiconductor Energy Laboratory Co., Ltd. - Inventors: Shunpei Yamazaki; Yasuharu Hosaka; Toshimitsu Obonai; Junichi Koezuka; Yukinori Shima; Masahiko Hayakawa; Takashi Hamochi; Suzunosuke Hiraishi - Web page: https://patentgrep.com/patent/US10770310B2 ## CPC - H10P 95/90: Thermal treatments, e.g. annealing or sintering - H10D 30/6704: {having supplementary regions or layers in the thin films or in the insulated bulk substrates for controlling properties of the device} - H10D 30/6755: {Oxide semiconductors, e.g. zinc oxide, copper aluminium oxide or cadmium stannate} - H10D 62/80: characterised by the materials - H10D 62/875: {being semiconductor metal oxide, e.g. InGaZnO (Group II-VI materials H10D62/86; Group I-VI materials H10D62/871; Pb compounds or alloys H10D62/874)} - H10D 64/011: {of electrodes ohmically coupled to a semiconductor} - H10P 14/2914: {Oxides} - H10P 14/68: Organic materials, e.g. photoresists - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 - H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES ## Abstract To suppress a change in electrical characteristics and to improve reliability in a semiconductor device using a transistor including an oxide semiconductor. The semiconductor device includes a gate electrode over an insulating surface, an oxide semiconductor film overlapping with the gate electrode, a gate insulating film which is between the gate electrode and the oxide semiconductor film and is in contact with a surface of the oxide semiconductor film, a protective film in contact with an opposite surface of the surface of the oxide semiconductor film, and a pair of electrodes in contact with the oxide semiconductor film. In the gate insulating film or the protective film, the amount of gas having a mass-to-charge ratio m/z of 17 released by heat treatment is greater than the amount of nitrogen oxide released by heat treatment. ## Claims ### Claim 1 A semiconductor device comprising: an oxide semiconductor layer and a first electrode overlapping with each other; an insulating layer between the first electrode and the oxide semiconductor layer, the insulating layer being in contact with the oxide semiconductor layer; and a pair of second electrodes in electrical contact with the oxide semiconductor layer, wherein the insulating layer includes silicon, oxygen, and nitrogen oxide, wherein the insulating layer includes a portion whose spin density measured by electron spin resonance spectroscopy is greater than or equal to 1×1017 spins/cm3 and less than 1×1018 spins/cm3, wherein an electron spin resonance spectrum of the portion has a first signal that appears at a g-factor in a range greater than or equal to 2.037 and less than or equal to 2.039, a second signal that appears at a g-factor in a range greater than or equal to 2.001 and less than or equal to 2.003, and a third signal that appears at a g-factor in a range greater than or equal to 1.964 and less than or equal to 1.966, and wherein the first signal, the second signal, and the third signal are attributed to the nitrogen oxide. ### Claim 2 (depends on 1) The semiconductor device according to claim 1, wherein the insulating layer includes a region where an amount of gas having a mass-to-charge ratio m/z of 17 released by heat treatment is greater than an amount of nitrogen oxide released by the heat treatment. ### Claim 3 (depends on 2) The semiconductor device according to claim 2, wherein at least one of an amount of gas having a mass-to-charge ratio m/z of 30 released by the heat treatment and an amount of gas having a mass-to-charge ratio m/z of 46 released by the heat treatment is less than or equal to a detection limit in the region, and wherein the amount of the gas having the mass-to-charge ratio m/z of 17 released by the heat treatment is greater than or equal to 1×1018 molecules/cm3 and less than or equal to 5×1019 molecules/cm3 in the region. ### Claim 4 (depends on 3) The semiconductor device according to claim 3, wherein the gas having the mass-to-charge ratio m/z of 30 comprises nitrogen monoxide, wherein the gas having the mass-to-charge ratio m/z of 46 comprises nitrogen dioxide, and wherein the gas having the mass-to-charge ratio m/z of 17 comprises ammonia. ### Claim 5 (depends on 1) The semiconductor device according to claim 1, wherein a split width of the first signal and the second signal and a split width of the second signal and the third signal measured by electron spin resonance spectroscopy using an X-band are each 5 mT. ### Claim 6 (depends on 1) The semiconductor device according to claim 1, wherein the nitrogen oxide includes at least one of nitrogen monoxide and nitrogen dioxide. ### Claim 7 (depends on 1) The semiconductor device according to claim 1, wherein the first electrode is over an insulating surface, and wherein the oxide semiconductor layer, and the insulating layer are between the insulating surface and the first electrode. ### Claim 8 (depends on 1) The semiconductor device according to claim 1, wherein the first electrode is over an insulating surface, and wherein the first electrode and the insulating layer are between the insulating surface and the oxide semiconductor layer. ### Claim 9 (depends on 1) The semiconductor device according to claim 1, wherein the insulating layer is in direct contact with the oxide semiconductor layer. ### Claim 10 (depends on 2) The semiconductor device according to claim 2, wherein the region includes a first number of ammonia molecules and a second number of nitrogen oxide molecules so that the amount of the gas having the mass-to-charge ratio m/z of 17 released by the heat treatment is greater than the amount of nitrogen oxide released by the heat treatment. ### Claim 11 A semiconductor device comprising: an oxide semiconductor layer and a first electrode overlapping with each other; a first insulating layer between the first electrode and the oxide semiconductor layer, the first insulating layer being in contact with a first surface of the oxide semiconductor layer; a second insulating layer in contact with a second surface of the oxide semiconductor layer, the second surface being on a side opposite to the first surface; and a pair of second electrodes in electrical contact with the oxide semiconductor layer, wherein the second insulating layer includes silicon, oxygen, and nitrogen oxide, wherein the second insulating layer includes a portion whose spin density measured by electron spin resonance spectroscopy is greater than or equal to 1×1017 spins/cm3 and less than 1×1018 spins/cm3, wherein an electron spin resonance spectrum of the portion has a first signal that appears at a g-factor in a range greater than or equal to 2.037 and less than or equal to 2.039, a second signal that appears at a g-factor in a range greater than or equal to 2.001 and less than or equal to 2.003, and a third signal that appears at a g-factor in a range greater than or equal to 1.964 and less than or equal to 1.966, and wherein the first signal, the second signal, and the third signal are attributed to the nitrogen oxide. ### Claim 12 (depends on 11) The semiconductor device according to claim 11, wherein the second insulating layer includes a region where an amount of gas having a mass-to-charge ratio m/z of 17 released by heat treatment is greater than an amount of nitrogen oxide released by the heat treatment. ### Claim 13 (depends on 12) The semiconductor device according to claim 12, wherein at least one of an amount of gas having a mass-to-charge ratio m/z of 30 released by the heat treatment and an amount of gas having a mass-to-charge ratio m/z of 46 released by the heat treatment is less than or equal to a detection limit in the region, and wherein the amount of the gas having the mass-to-charge ratio m/z of 17 released by the heat treatment is greater than or equal to 1×1018 molecules/cm3 and less than or equal to 5×1019 molecules/cm3 in the region. ### Claim 14 (depends on 13) The semiconductor device according to claim 13, wherein the gas having the mass-to-charge ratio m/z of 30 comprises nitrogen monoxide, wherein the gas having the mass-to-charge ratio m/z of 46 comprises nitrogen dioxide, and wherein the gas having the mass-to-charge ratio m/z of 17 comprises ammonia. ### Claim 15 (depends on 11) The semiconductor device according to claim 11, wherein a split width of the first signal and the second signal and a split width of the second signal and the third signal measured by electron spin resonance spectroscopy using an X-band are each 5 mT. ### Claim 16 (depends on 11) The semiconductor device according to claim 11, wherein the nitrogen oxide includes at least one of nitrogen monoxide and nitrogen dioxide. ### Claim 17 (depends on 11) The semiconductor device according to claim 11, wherein the first electrode is over an insulating surface, and wherein the second insulating layer, the oxide semiconductor layer, and the first insulating layer are between the insulating surface and the first electrode. ### Claim 18 (depends on 11) The semiconductor device according to claim 11, wherein the first electrode is over an insulating surface, and wherein the first electrode and the first insulating layer are between the insulating surface and the oxide semiconductor layer. ### Claim 19 (depends on 11) The semiconductor device according to claim 11, wherein the first insulating layer is in direct contact with the first surface of the oxide semiconductor layer, and wherein the second insulating layer is in direct contact with the second surface of the oxide semiconductor layer. ### Claim 20 (depends on 12) The semiconductor device according to claim 12, wherein the region includes a first number of ammonia molecules and a second number of nitrogen monoxide molecules so that the amount of the gas having the mass-to-charge ratio m/z of 17 released by the heat treatment is greater than the amount of the gas having the mass-to-charge ratio m/z of 30 released by the heat treatment.