WO2012029455A1 - Oxyde fritté et film mince semi-conducteur en oxyde - Google Patents

Oxyde fritté et film mince semi-conducteur en oxyde Download PDF

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WO2012029455A1
WO2012029455A1 PCT/JP2011/067133 JP2011067133W WO2012029455A1 WO 2012029455 A1 WO2012029455 A1 WO 2012029455A1 JP 2011067133 W JP2011067133 W JP 2011067133W WO 2012029455 A1 WO2012029455 A1 WO 2012029455A1
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oxide
thin film
sintered body
oxide semiconductor
semiconductor thin
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PCT/JP2011/067133
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English (en)
Japanese (ja)
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英生 高見
幸三 長田
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Jx日鉱日石金属株式会社
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Priority to KR1020137007631A priority Critical patent/KR101331293B1/ko
Publication of WO2012029455A1 publication Critical patent/WO2012029455A1/fr

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    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
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Definitions

  • the present invention relates to an oxide sintered body and a transparent oxide semiconductor thin film useful for the production of a thin film transistor and a transparent electrode in a display device.
  • Transparent oxide semiconductors are used as active electrodes of thin film transistors in display devices such as liquid crystal display devices, plasma display devices and organic EL display devices, as well as transparent electrodes such as solar cells and touch panels.
  • display devices such as liquid crystal display devices, plasma display devices and organic EL display devices, as well as transparent electrodes such as solar cells and touch panels.
  • IGZO-based an In—Ga—Zn—O-based
  • tin (Sn) is intended to improve characteristics.
  • gallium (Ga) which is an essential component of these systems, is a rare element and has a large limitation in terms of industrial use because of its high price.
  • Patent Document 3 As a transparent oxide semiconductor not using Ga, there is a report on an In—Zn—Sn—O system (see Patent Document 3).
  • the atomic ratio of [Sn] with respect to the sum of) exceeds 0.1 and less than 0.2, the following atomic ratio 1 is satisfied, and when it is 0.2 or more and less than 0.3, the following atomic ratio 2 is satisfied. Is described.
  • Atomic ratio 1 0.1 ⁇ [In] / ([In] + [Sn] + [Zn]) ⁇ 0.5 0.1 ⁇ [Sn] / ([In] + [Sn] + [Zn]) ⁇ 0.2 0.3 ⁇ [Zn] / ([In] + [Sn] + [Zn]) ⁇ 0.8 Atomic ratio 2 0.01 ⁇ [In] / ([In] + [Sn] + [Zn]) ⁇ 0.3 0.2 ⁇ [Sn] / ([In] + [Sn] + [Zn]) ⁇ 0.3 0.4 ⁇ [Zn] / ([In] + [Sn] + [Zn]) ⁇ 0.8
  • Patent Document 3 has a problem that abnormal discharge is likely to occur during sputtering because of high bulk resistance.
  • an object of the present invention is to provide an oxide sintered body that is a scarce resource and does not contain expensive gallium (Ga) and can reduce bulk resistance.
  • Another object of the present invention is to provide an oxide semiconductor thin film having the same composition as the oxide sintered body.
  • the present inventor is promising as an alternative element for gallium (Ga), which is a rare and expensive element, aluminum (Al), which is the same trivalent metal element as gallium, and titanium (Ti), which is the tetravalent metal element.
  • Ga gallium
  • Al aluminum
  • Ti titanium
  • indium (In), zinc (Zn), a metal element X (where X represents one or more elements selected from Al and Ti), oxygen (O),
  • An oxide sintered body comprising: in atomic ratios of indium (In), zinc (Zn), and metal element X are 0.2 ⁇ In / (In + Zn + X) ⁇ 0.8 and 0.1 ⁇ , respectively.
  • the oxide sintered body satisfies Zn / (In + Zn + X) ⁇ 0.5 and 0.1 ⁇ X / (In + Zn + X) ⁇ 0.5.
  • the oxide sintered body according to the present invention has a relative density of 98% or more.
  • the oxide sintered body according to the present invention has a bulk resistance of 3 m ⁇ cm or less.
  • indium (In), zinc (Zn), a metal element X (where X represents one or more elements selected from Al and Ti), oxygen (O
  • the atomic ratio of indium (In), zinc (Zn), and metal element X is 0.2 ⁇ In / (In + Zn + X) ⁇ 0.8, 0.1 ⁇ Zn. /(In+Zn+X) ⁇ 0.5 and 0.1 ⁇ X / (In + Zn + X) ⁇ 0.5.
  • the oxide semiconductor thin film according to the present invention is amorphous.
  • the oxide semiconductor thin film according to the present invention has a carrier concentration of 10 16 to 10 18 cm ⁇ 3 .
  • the oxide semiconductor thin film according to the present invention has a mobility of 1 cm 2 / Vs or more.
  • the present invention is a thin film transistor including the oxide semiconductor thin film as an active layer.
  • the present invention is an active matrix drive display panel including the thin film transistor.
  • an oxide sintered body that does not contain gallium (Ga) and can reduce bulk resistance can be provided.
  • This oxide sintered body is useful as a sputtering target.
  • a transparent oxide semiconductor film can be formed by sputtering using this target.
  • the oxide sintered body according to the present invention includes indium (In), zinc (Zn), metal element X (where X represents one or more elements selected from Al and Ti), and oxygen (O ) As a constituent element.
  • indium (In) zinc (Zn)
  • zinc (Zn) zinc (Zn)
  • metal element X where X represents one or more elements selected from Al and Ti
  • oxygen (O ) oxygen
  • elements that are inevitably included in the purification process of raw materials that are usually available, and impurity elements that are inevitably mixed in the oxide sintered body manufacturing process are inevitably contained at a concentration, for example, each element. What contains about 10 ppm is included in the sintered compact which concerns on this invention.
  • the ratio [In] / ([In] + [Zn] + [X]) of the number of indium atoms to the total number of atoms of indium, zinc and metal element X is preferably 0.2 to 0.8. If [In] / ([In] + [Zn] + [X]) is less than 0.2, the relative density during target fabrication becomes small, the bulk resistance becomes high, and abnormal discharge occurs during sputtering. It becomes easy to do. On the other hand, when [In] / ([In] + [Zn] + [X]) exceeds 0.8, the carrier concentration of the film obtained by sputtering the target having the composition becomes too high, and the transistor As a channel layer, the on / off ratio becomes small.
  • [In] / ([In] + [Zn] + [X]) is more preferably in the range of 0.25 to 0.6, and still more preferably in the range of 0.3 to 0.5.
  • [In] represents the number of atoms of indium
  • [Zn] represents the number of atoms of zinc
  • [X] represents the number of atoms of the metal element X.
  • the ratio of the number of zinc atoms to the total number of atoms of indium, zinc and metal element X [Zn] / ([In] + [Zn] + [X]) is preferably 0.1 to 0.5. If [Zn] / ([In] + [Zn] + [X]) is less than 0.1, the carrier concentration of the film becomes too high. On the other hand, when [Zn] / ([In] + [Zn] + [X]) 0.5 is exceeded, the carrier concentration of the film becomes too small. The relative density at the time of target preparation will become small. [Zn] / ([In] + [Zn] + [X]) is more preferably in the range of 0.15 to 0.4, and still more preferably in the range of 0.2 to 0.35.
  • the ratio [X] / ([In] + [Zn] + [X]) of the total number of atoms of the metal element X to the total number of atoms of indium, zinc and the metal element X is 0.1 to 0.5. Is desirable. When [X] / ([In] + [Zn] + [X]) is less than 0.1, the carrier concentration of the film obtained by sputtering the target having the composition becomes too high, and the channel of the transistor As a layer, the on / off ratio becomes small.
  • [X] / ([In] + [Zn] + [X]) exceeds 0.5, the carrier concentration of the film becomes too small, the relative density at the time of target fabrication becomes small, and the bulk Resistance becomes high, and abnormal discharge at the time of sputtering tends to occur.
  • [X] / ([In] + [Zn] + [X]) is more preferably in the range of 0.15 to 0.4, and still more preferably in the range of 0.2 to 0.35.
  • the relative density of the oxide sintered body correlates with the generation of joules on the surface during sputtering. If the oxide sintered body has a low density, the oxide sintered body is processed into a target to form a sputter film. At the same time, a high-resistance portion called a protruding nodule, which is a lower oxide of indium, is generated on the surface as the film formation of the sputter occurs, and it tends to be the starting point of abnormal discharge during subsequent sputtering.
  • the relative density of the oxide sintered body can be set to 98% or more. If the density is at this level, there is almost no adverse effect due to nodules during sputtering.
  • the relative density is preferably 99% or more, more preferably 99.5% or more.
  • the relative density of the oxide sintered body is obtained by dividing the density calculated from the weight and outer dimensions after processing the oxide sintered body into a predetermined shape by the theoretical density of the oxide sintered body. Can be sought.
  • the bulk resistance of the oxide sintered body has a correlation with the ease of occurrence of abnormal discharge during sputtering, and when the bulk resistance is high, abnormal discharge is likely to occur during sputtering.
  • the bulk resistance can be reduced to 3 m ⁇ cm or less by optimizing the appropriate range of the composition and the manufacturing conditions. With such a low bulk resistance, there is almost no adverse effect on the occurrence of abnormal discharge during sputtering.
  • the bulk resistance is preferably 2.7 m ⁇ cm or less, more preferably 2.5 m ⁇ cm or less. Bulk resistance can be measured using a resistivity meter by the four-probe method.
  • the oxide sintered body of various compositions according to the present invention includes, for example, the mixing ratio of each raw material powder such as indium oxide and zinc oxide as raw materials, the particle size of the raw material powder, the pulverization time, the sintering temperature, and the sintering. It can be obtained by adjusting conditions such as time and kind of sintering atmosphere gas.
  • the raw material powder preferably has an average particle size of 1 to 2 ⁇ m.
  • the average particle diameter exceeds 2 ⁇ m, the density of the sintered body is difficult to improve. Therefore, wet pulverization or the like is performed as the raw material powder alone or as a mixed powder, and the average particle diameter is preferably reduced to about 1 ⁇ m.
  • wet pulverization or the like is performed as the raw material powder alone or as a mixed powder, and the average particle diameter is preferably reduced to about 1 ⁇ m.
  • it is also effective to perform calcination.
  • raw materials having a particle size of less than 1 ⁇ m are difficult to obtain, and if the particle size is too small, agglomeration between particles tends to occur and handling becomes difficult.
  • the average particle diameter of the raw material powder refers to the median diameter in the volume distribution measured by a laser diffraction particle size distribution measuring device.
  • the molded product is sintered to obtain a sintered body.
  • Sintering is preferably performed at 1400 to 1600 ° C. for 2 to 20 hours. Thereby, a relative density can be 98% or more. If the sintering temperature is less than 1400 ° C., the density is difficult to improve. Conversely, if the sintering temperature exceeds 1600 ° C., the composition of the sintered body changes due to volatilization of constituent elements, or voids are generated due to volatilization. May cause a decrease in density. Air can be used as the atmosphere gas during sintering, and the amount of oxygen vacancies in the sintered body can be increased to reduce the bulk resistance. However, depending on the composition of the sintered body, a sufficiently high density sintered body can be obtained even if the atmospheric gas is oxygen.
  • the oxide sintered body obtained as described above can be used as a sputtering target by performing processing such as grinding and polishing, and by using this film, the same composition as that of the target can be obtained. It is possible to form an oxide film having At the time of processing, it is desirable that the surface roughness (Ra) be 5 ⁇ m or less by grinding the surface by a method such as surface grinding. By reducing the surface roughness, the starting point of nodule generation that causes abnormal discharge can be reduced.
  • the sputtering target is affixed to a backing plate made of copper or the like, placed in a sputtering apparatus, and sputtered under appropriate conditions such as an appropriate degree of vacuum, atmospheric gas, and sputtering power, so that the film has almost the same composition as the target. Can be obtained.
  • the degree of vacuum reached in the chamber before film formation is 2 ⁇ 10 ⁇ 4 Pa or less. If the pressure is too high, the mobility of the obtained film may decrease due to the influence of impurities in the residual atmospheric gas.
  • a mixed gas of argon and oxygen can be used as the sputtering gas.
  • a gas cylinder with 100% argon and a gas cylinder with 2% oxygen in argon are used, and the supply flow rate from each gas cylinder to the chamber is appropriately set by mass flow.
  • the oxygen concentration in the mixed gas means oxygen partial pressure / (oxygen partial pressure + argon partial pressure), and is equal to the oxygen flow rate divided by the sum of oxygen and argon flow rates.
  • the oxygen concentration may be appropriately changed according to the desired carrier concentration, but it can typically be 1 to 3%, more typically 1 to 2%.
  • the total pressure of the sputtering gas is about 0.3 to 0.8 Pa. If the total pressure is lower than this, the plasma discharge is difficult to stand up, and even if it stands, the plasma becomes unstable. On the other hand, if the total pressure is higher than this, the film formation rate becomes slow, which causes inconveniences such as adversely affecting productivity.
  • the film is formed with a sputtering power of about 200 to 1200 W. If the sputtering power is too low, the film forming speed is low and the productivity is poor. Conversely, if the sputtering power is too high, problems such as cracking of the target occur. 200 ⁇ 1200 W when converted to a sputtering power density is 1.1W / cm 2 ⁇ 6.6W / cm 2, it is desirable that the 3.2 ⁇ 4.5W / cm 2.
  • the sputtering power density is a value obtained by dividing the sputtering power by the area of the sputtering target, and even with the same sputtering power, the power actually received by the sputtering target varies depending on the sputtering target size, and the film formation speed differs. It is an index for uniformly expressing the power applied to the sputtering target.
  • a vacuum deposition method As a method for obtaining a film from an oxide sintered body, a vacuum deposition method, an ion plating method, a PLD (pulse laser deposition) method, or the like can be used.
  • This is a DC magnetron sputtering method that satisfies requirements such as film formation and discharge stability.
  • the substrate there is no need to heat the substrate during sputter deposition. This is because a relatively high mobility can be obtained without heating the substrate, and it is not necessary to spend time and energy for raising the temperature.
  • the resulting film becomes amorphous.
  • the film since the same effect as annealing after film formation at room temperature can be expected by heating the substrate, the film may be formed by heating the substrate.
  • carrier concentration of oxide film correlates with various characteristics of the transistor when the film is used for the channel layer of the transistor. If the carrier concentration is too high, a minute leakage current is generated even when the transistor is turned off, and the on / off ratio is lowered. On the other hand, if the carrier concentration is too low, the current flowing through the transistor becomes small.
  • the carrier concentration of the oxide film can be set to 10 16 to 10 18 cm ⁇ 3 depending on an appropriate range of the composition and the like, and a transistor with favorable characteristics can be manufactured within this range.
  • the mobility is one of the most important characteristics of the transistor, and the oxide semiconductor has a mobility of 1 cm 2 / Vs or more which is the mobility of amorphous silicon which is a competitive material used as a channel layer of the transistor. Is desirable. Basically, the higher the mobility, the better.
  • the oxide film according to the present invention can have a mobility of 1 cm 2 / Vs or more, preferably a mobility of 3 cm 2 / Vs or more, more preferably 5 cm 2 depending on an appropriate range of the composition. It can have a mobility of / Vs or higher. Thereby, it becomes a characteristic superior to amorphous silicon, and industrial applicability is further increased.
  • the oxide semiconductor thin film according to the present invention can be used, for example, as an active layer of a thin film transistor.
  • the thin film transistor obtained by using the above manufacturing method can be used as an active element and used for an active matrix drive display panel.
  • the physical properties of the sintered bodies and films were measured by the following methods.
  • A Relative density of sintered body It was determined from the measurement results of weight and outer dimensions and the theoretical density from the constituent elements.
  • B Bulk resistance of sintered body The bulk resistance was determined by a four probe method (JIS K7194) using a model ⁇ -5 + apparatus manufactured by NPS.
  • C Composition of sintered body and film It was determined by an ICP (high frequency inductively coupled plasma) analysis method using a model SPS3000 manufactured by SII Nanotechnology.
  • D Film thickness It was determined using a step meter (Veeco, Model Dektak8 STYLUS PROFILER).
  • Example 1 Indium oxide powder (average particle size: 1.0 ⁇ m), zinc oxide powder (average particle size: 1.0 ⁇ m), and aluminum oxide powder (average particle size: 1.0 ⁇ m), the atomic ratio of metal elements (In: Zn: Al ) was 0.4: 0.3: 0.3, and wet mixed and pulverized.
  • the average particle size of the mixed powder after pulverization was 0.8 ⁇ m. This mixed powder was granulated with a spray dryer, filled into a mold, pressed, and then sintered at 1450 ° C. for 10 hours in an air atmosphere.
  • the sputtering target prepared above was attached to a copper backing plate using indium as a brazing material, and was installed in a DC magnetron sputtering apparatus (APLVA SPL-500 sputtering apparatus).
  • the glass substrate uses Corning 1737, and the sputtering conditions are as follows: substrate temperature: 25 ° C., ultimate pressure: 1.2 ⁇ 10 ⁇ 4 Pa, atmospheric gas: Ar 99%, oxygen 1%, sputtering pressure (total pressure): 0.
  • a thin film having a thickness of about 100 nm was prepared at 5 Pa and input power of 500 W. No abnormal discharge was observed during the formation of the oxide semiconductor thin film.
  • Example 2 to Example 6 An oxide sintered body and an oxide semiconductor thin film were obtained in the same manner as in Example 1 except that the composition ratio of the raw material powder was set to the respective values shown in Table 1. The relative density, bulk resistance, carrier concentration, and mobility of each were as shown in Table 1. The composition of the sintered body and the film was the same as the composition ratio of the raw material powder.
  • the oxide sintered bodies according to the examples of the present invention have a high relative density and a low bulk resistance.
  • an oxide semiconductor thin film having an appropriate carrier concentration and high mobility can be obtained.

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Abstract

La présente invention concerne un oxyde fritté ne contenant pas de gallium (Ga), élément onéreux et présentant une faible résistance volumique, ainsi qu'un film mince semi-conducteur en oxyde présentant la même composition chimique que ledit oxyde fritté. L'oxyde fritté selon l'invention comprend de l'indium (In), du zinc (Zn), un élément métallique (X) (où X représente au moins un élément parmi Al et Ti) et de l'oxygène (O), le rapport du nombre d'atomes d'indium (In), de zinc (Zn) et de l'élément métallique (X) remplissant les conditions suivantes : 0,2 ≤ In/(In + Zn + X) ≤ 0,8, 0,1 ≤ Zn/(In + Zn + X) ≤ 0,5 et 0,1 ≤ X/(In + Zn + X) ≤ 0,5. L'invention concerne également un film mince semi-conducteur en oxyde présentant la même composition chimique que l'oxyde fritté.
PCT/JP2011/067133 2010-08-31 2011-07-27 Oxyde fritté et film mince semi-conducteur en oxyde WO2012029455A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5968462B2 (ja) * 2013-10-24 2016-08-10 Ｊｘ金属株式会社 酸化物焼結体、酸化物スパッタリングターゲット及び高屈折率の導電性酸化物薄膜並びに酸化物焼結体の製造方法
CN108352410A (zh) * 2015-11-25 2018-07-31 株式会社爱发科 薄膜晶体管、氧化物半导体膜以及溅射靶材

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012091126A1 (fr) * 2010-12-28 2012-07-05 株式会社神戸製鋼所 Oxyde pour couche de semi-conducteur de transistor à film mince, cible de pulvérisation et transistor à film mince
JP5929911B2 (ja) * 2011-06-15 2016-06-08 住友電気工業株式会社 導電性酸化物およびその製造方法ならびに酸化物半導体膜
CN102779758B (zh) * 2012-07-24 2015-07-29 复旦大学 一种以铟锌铝氧化物为沟道层的薄膜晶体管的制备方法
JP6052967B2 (ja) * 2012-08-31 2016-12-27 出光興産株式会社 スパッタリングターゲット
TWI591197B (zh) * 2012-11-08 2017-07-11 Idemitsu Kosan Co Sputtering target

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08245220A (ja) * 1994-06-10 1996-09-24 Hoya Corp 導電性酸化物およびそれを用いた電極
JPH09152940A (ja) * 1995-11-30 1997-06-10 Idemitsu Kosan Co Ltd タッチパネル
JPH1045496A (ja) * 1996-07-31 1998-02-17 Hoya Corp 導電性酸化物薄膜、この薄膜を有する物品及びその製造方法
WO2009081885A1 (fr) * 2007-12-25 2009-07-02 Idemitsu Kosan Co., Ltd. Transistor à effet de champ à oxyde semi-conducteur et son procédé de fabrication
JP2009231613A (ja) * 2008-03-24 2009-10-08 Fujifilm Corp 薄膜電界効果型トランジスタおよび表示装置
JP2009253204A (ja) * 2008-04-10 2009-10-29 Idemitsu Kosan Co Ltd 酸化物半導体を用いた電界効果型トランジスタ及びその製造方法
JP2010150093A (ja) * 2008-12-25 2010-07-08 Tosoh Corp 透明導電膜用焼結体の製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100295042A1 (en) * 2008-01-23 2010-11-25 Idemitsu Kosan Co., Ltd. Field-effect transistor, method for manufacturing field-effect transistor, display device using field-effect transistor, and semiconductor device

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08245220A (ja) * 1994-06-10 1996-09-24 Hoya Corp 導電性酸化物およびそれを用いた電極
JPH09152940A (ja) * 1995-11-30 1997-06-10 Idemitsu Kosan Co Ltd タッチパネル
JPH1045496A (ja) * 1996-07-31 1998-02-17 Hoya Corp 導電性酸化物薄膜、この薄膜を有する物品及びその製造方法
WO2009081885A1 (fr) * 2007-12-25 2009-07-02 Idemitsu Kosan Co., Ltd. Transistor à effet de champ à oxyde semi-conducteur et son procédé de fabrication
JP2009231613A (ja) * 2008-03-24 2009-10-08 Fujifilm Corp 薄膜電界効果型トランジスタおよび表示装置
JP2009253204A (ja) * 2008-04-10 2009-10-29 Idemitsu Kosan Co Ltd 酸化物半導体を用いた電界効果型トランジスタ及びその製造方法
JP2010150093A (ja) * 2008-12-25 2010-07-08 Tosoh Corp 透明導電膜用焼結体の製造方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5968462B2 (ja) * 2013-10-24 2016-08-10 Ｊｘ金属株式会社 酸化物焼結体、酸化物スパッタリングターゲット及び高屈折率の導電性酸化物薄膜並びに酸化物焼結体の製造方法
JPWO2015059938A1 (ja) * 2013-10-24 2017-03-09 Ｊｘ金属株式会社 酸化物焼結体、酸化物スパッタリングターゲット及び高屈折率の導電性酸化物薄膜並びに酸化物焼結体の製造方法
CN108352410A (zh) * 2015-11-25 2018-07-31 株式会社爱发科 薄膜晶体管、氧化物半导体膜以及溅射靶材
CN108352410B (zh) * 2015-11-25 2021-06-29 株式会社爱发科 薄膜晶体管、氧化物半导体膜以及溅射靶材
US11049976B2 (en) 2015-11-25 2021-06-29 Ulvac, Inc. Thin-film transistor, oxide semiconductor film, and sputtering target

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