JP5081959B2 - Oxide sintered body and oxide semiconductor thin film - Google Patents
Oxide sintered body and oxide semiconductor thin film Download PDFInfo
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- JP5081959B2 JP5081959B2 JP2010194455A JP2010194455A JP5081959B2 JP 5081959 B2 JP5081959 B2 JP 5081959B2 JP 2010194455 A JP2010194455 A JP 2010194455A JP 2010194455 A JP2010194455 A JP 2010194455A JP 5081959 B2 JP5081959 B2 JP 5081959B2
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- oxide
- sintered body
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- oxide semiconductor
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- 239000010409 thin film Substances 0.000 title claims abstract description 27
- 239000004065 semiconductor Substances 0.000 title claims abstract description 24
- 239000011701 zinc Substances 0.000 claims abstract description 56
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052738 indium Inorganic materials 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 18
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000010408 film Substances 0.000 abstract description 38
- 239000000203 mixture Substances 0.000 abstract description 23
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052733 gallium Inorganic materials 0.000 abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 abstract description 5
- 229910052719 titanium Inorganic materials 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract 2
- 238000004544 sputter deposition Methods 0.000 description 32
- 239000007789 gas Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- 239000011135 tin Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000005477 sputtering target Methods 0.000 description 10
- 230000002159 abnormal effect Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000009616 inductively coupled plasma Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000011812 mixed powder Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 238000000227 grinding Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910007604 Zn—Sn—O Inorganic materials 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 231100000989 no adverse effect Toxicity 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000024121 nodulation Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
Description
本発明は表示装置中の薄膜トランジスタや透明電極の作製に有用な酸化物焼結体及び透明酸化物半導体薄膜に関する。 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.
透明酸化物半導体は液晶表示装置、プラズマ表示装置及び有機ＥＬ表示装置などの表示装置中の薄膜トランジスタの活性層のほか、太陽電池及びタッチパネル等の透明電極として利用されている。従来、透明酸化物半導体としてはＩｎ−Ｇａ−Ｚｎ−Ｏ系（以降、「ＩＧＺＯ系」と記載）が知られており（非特許文献１参照）、更に、特性改善を意図して錫（Ｓｎ）を添加した系についての報告もある（特許文献１及び２参照）。しかし、これらの系の必須構成要素であるガリウム（Ｇａ）は希少元素であり、価格も高い等の理由から、産業上、大量に使用するには大きな制約があった。 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. Conventionally, an In—Ga—Zn—O-based (hereinafter referred to as “IGZO-based”) is known as a transparent oxide semiconductor (see Non-Patent Document 1). Further, tin (Sn) is intended to improve characteristics. There is also a report about the system which added (refer patent document 1 and 2). However, 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.
Ｇａを使用しない透明酸化物半導体としては、Ｉｎ−Ｚｎ−Ｓｎ−Ｏ系（特許文献３参照）についての報告がある。特許文献３では、インジウム、錫、亜鉛及び酸素を含有し、インジウムの原子の数（＝［Ｉｎ］）と錫の原子の数（＝［Ｓｎ］）と亜鉛の原子の数（＝［Ｚｎ］）の合計に対する前記［Ｓｎ］の原子比が、０．１を超え０．２未満のときは下記原子比１を満たし、０．２以上０．３未満のときは下記原子比２を満たすことが記載されている。
原子比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
原子比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
As a transparent oxide semiconductor not using Ga, there is a report on an In—Zn—Sn—O system (see Patent Document 3). In Patent Document 3, indium, tin, zinc and oxygen are contained, the number of indium atoms (= [In]), the number of tin atoms (= [Sn]), and the number of zinc atoms (= [Zn]). When 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
しかしながら、特許文献３に記載のＩｎ−Ｚｎ−Ｓｎ−Ｏ系では、バルク抵抗が高いためにスパッタ時に異常放電を発生し易いという問題が残されている。 However, the In—Zn—Sn—O system described in Patent Document 3 has a problem in that abnormal discharge is likely to occur during sputtering due to high bulk resistance.
そこで、本発明は、希少資源であり、高価なガリウム（Ｇａ）を含有せず、バルク抵抗を小さくすることの出来る酸化物焼結体を提供することを課題とする。また、本発明は当該酸化物焼結体と同一組成をもつ酸化物半導体薄膜を提供することを別の課題とする。 Therefore, an object of the present invention is to provide an oxide sintered body which 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.
本発明者は、希少かつ高価な元素であるガリウム（Ｇａ）の代替元素として、ガリウムと同じ３価の金属元素であるアルミニウム（Ａｌ）、４価の金属元素であるチタン（Ｔｉ）が有望であることを見出し、これらの元素の原子比や焼結体や膜の製造条件等について、鋭意検討をして本発明を完成させた。 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. As a result, they have intensively studied the atomic ratio of these elements, the production conditions of the sintered body and the film, and the like, thereby completing the present invention.
本発明は一側面において、インジウム（Ｉｎ）と、亜鉛（Ｚｎ）と、金属元素Ｘ（但し、ＸはＡｌ及びＴｉから選択される１種以上の元素を表す。）と、酸素（Ｏ）とからなる酸化物焼結体であって、インジウム（Ｉｎ）、亜鉛（Ｚｎ）、及び金属元素Ｘの原子数比がそれぞれ、０．２≦Ｉｎ／（Ｉｎ＋Ｚｎ＋Ｘ）≦０．８、０．１≦Ｚｎ／（Ｉｎ＋Ｚｎ＋Ｘ）≦０．５、及び０．１≦Ｘ／（Ｉｎ＋Ｚｎ＋Ｘ）≦０．５を満たす酸化物焼結体である。 In one aspect of the present invention, 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.
本発明に係る酸化物焼結体は一実施形態において、相対密度が９８％以上である。 In one embodiment, the oxide sintered body according to the present invention has a relative density of 98% or more.
本発明に係る酸化物焼結体は別の一実施形態において、バルク抵抗が３ｍΩｃｍ以下である。 In another embodiment, the oxide sintered body according to the present invention has a bulk resistance of 3 mΩcm or less.
本発明は別の一側面において、インジウム（Ｉｎ）と、亜鉛（Ｚｎ）と、金属元素Ｘ（但し、ＸはＡｌ及びＴｉから選択される１種以上の元素を表す。）と、酸素（Ｏ）とからなる酸化物半導体薄膜であって、インジウム（Ｉｎ）、亜鉛（Ｚｎ）、金属元素Ｘの原子数比が、０．２≦Ｉｎ／（Ｉｎ＋Ｚｎ＋Ｘ）≦０．８、０．１≦Ｚｎ／（Ｉｎ＋Ｚｎ＋Ｘ）≦０．５、０．１≦Ｘ／（Ｉｎ＋Ｚｎ＋Ｘ）≦０．５を満たす酸化物半導体薄膜である。 In another aspect of the present invention, 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.
本発明に係る酸化物半導体薄膜は一実施形態において、非晶質である。 In one embodiment, the oxide semiconductor thin film according to the present invention is amorphous.
本発明に係る酸化物半導体薄膜は別の一実施形態において、キャリア濃度が１０16〜１０18ｃｍ-3である。 In another embodiment, the oxide semiconductor thin film according to the present invention has a carrier concentration of 10 16 to 10 18 cm −3 .
本発明に係る酸化物半導体薄膜は更に別の一実施形態において、移動度が１ｃｍ2／Ｖｓ以上である。 In still another embodiment, the oxide semiconductor thin film according to the present invention has a mobility of 1 cm 2 / Vs or more.
本発明は更に別の一側面において、上記酸化物半導体薄膜を活性層として備えた薄膜トランジスタである。 In yet another aspect, the present invention is a thin film transistor including the oxide semiconductor thin film as an active layer.
本発明は更に別の一側面において、上記薄膜トランジスタを備えたアクティブマトリックス駆動表示パネルである。 In still another aspect, the present invention provides an active matrix drive display panel including the thin film transistor.
本発明によればガリウム（Ｇａ）を含有せず、バルク抵抗を小さくすることの出来る酸化物焼結体を提供することができる。本酸化物焼結体はスパッタリングターゲットとして有用である。本ターゲットを用いてスパッタ成膜することにより、透明酸化物半導体膜を作製することができる。 According to the present invention, it is possible to provide an oxide sintered body that does not contain gallium (Ga) and can reduce bulk resistance. This oxide sintered body is useful as a sputtering target. A transparent oxide semiconductor film can be formed by sputtering using this target.
（酸化物焼結体の組成）
本発明に係る酸化物焼結体は、インジウム（Ｉｎ）、亜鉛（Ｚｎ）、金属元素Ｘ（但し、ＸはＡｌ及びＴｉから選択される１種以上の元素を表す。）、並びに酸素（Ｏ）を構成元素とする。但し、通常入手可能な原料の精製工程上、不可避的に含まれてくる元素や、酸化物焼結体製造プロセス上不可避的に混入する不純物元素を、不可避的に含まれる濃度程度、例えば各元素１０ｐｐｍ程度まで含むものは本発明に係る焼結体に包含される。
(Composition of oxide sinter)
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. However, 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.
インジウム、亜鉛及び金属元素Ｘの合計原子数に対するインジウムの原子数の比［Ｉｎ］／（［Ｉｎ］＋［Ｚｎ］＋［Ｘ］）は０．２〜０．８であることが望ましい。［Ｉｎ］／（［Ｉｎ］＋［Ｚｎ］＋［Ｘ］）が０．２未満であると、ターゲット作製時の相対密度が小さくなり、バルク抵抗が高くなって、スパッタ時の異常放電が発生し易くなってしまう。逆に、［Ｉｎ］／（［Ｉｎ］＋［Ｚｎ］＋［Ｘ］）が０．８を超えると、その組成のターゲットをスパッタして得られる膜のキャリア濃度が高くなりすぎてしまい、トランジスタのチャネル層としてはオンオフ比が小さくなってしまう。［Ｉｎ］／（［Ｉｎ］＋［Ｚｎ］＋［Ｘ］）は、より望ましくは０．２５〜０．６の範囲であり、更に望ましくは０．３〜０．５の範囲である。ここで、［Ｉｎ］はインジウムの原子数、［Ｚｎ］は亜鉛の原子数、［Ｘ］は金属元素Ｘの原子数をそれぞれ表す。 The ratio [In] / ([In] + [Zn] + [X]) of the number of atoms of indium 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. Here, [In] represents the number of atoms of indium, [Zn] represents the number of atoms of zinc, and [X] represents the number of atoms of the metal element X.
インジウム、亜鉛及び金属元素Ｘの合計原子数に対する亜鉛の原子数の比［Ｚｎ］／（［Ｉｎ］＋［Ｚｎ］＋［Ｘ］）は０．１〜０．５であることが望ましい。［Ｚｎ］／（［Ｉｎ］＋［Ｚｎ］＋［Ｘ］）が０．１未満であると、膜のキャリア濃度が大きくなりすぎてしまう。逆に、［Ｚｎ］／（［Ｉｎ］＋［Ｚｎ］＋［Ｘ］）０．５を超えると、膜のキャリア濃度が小さくなりすぎてしまう。ターゲット作製時の相対密度が小さくなってしまう。［Ｚｎ］／（［Ｉｎ］＋［Ｚｎ］＋［Ｘ］）は、より望ましくは０．１５〜０．４の範囲であり、更に望ましくは０．２〜０．３５の範囲である。 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.
インジウム、亜鉛及び金属元素Ｘの合計原子数に対する金属元素Ｘの合計の原子数の比［Ｘ］／（［Ｉｎ］＋［Ｚｎ］＋［Ｘ］）は０．１〜０．５であることが望ましい。［Ｘ］／（［Ｉｎ］＋［Ｚｎ］＋［Ｘ］）が０．１未満であると、その組成のターゲットをスパッタして得られる膜のキャリア濃度が高くなりすぎてしまい、トランジスタのチャネル層としてはオンオフ比が小さくなってしまう。逆に、［Ｘ］／（［Ｉｎ］＋［Ｚｎ］＋［Ｘ］）が０．５を超えると、膜のキャリア濃度が小さくなりすぎてしまい、ターゲット作製時の相対密度が小さくなり、バルク抵抗が高くなって、スパッタ時の異常放電が発生し易くなってしまう。［Ｘ］／（［Ｉｎ］＋［Ｚｎ］＋［Ｘ］）は、より望ましくは０．１５〜０．４の範囲であり、更に望ましくは０．２〜０．３５の範囲である。 The ratio [X] / ([In] + [Zn] + [X]) of the total number of atoms of metal element X to the total number of atoms of indium, zinc and 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. On the other hand, when [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.
（酸化物焼結体の相対密度）
酸化物焼結体の相対密度は、スパッタ時の表面のノジュール発生と相関があり、酸化物焼結体が低密度であると、その酸化物焼結体をターゲットに加工してスパッタ成膜する際に、スパッタの成膜の経過に従って、表面にインジウムの低級酸化物である、突起状のノジュールと呼ばれる高抵抗部分が発生してきて、その後のスパッタ時に異常放電の起点となり易い。本発明では、酸化物焼結体の相対密度を９８％以上とすることができ、この程度の高密度であれば、スパッタ時のノジュールによる悪影響は殆どない。相対密度は好ましくは９９％以上であり、より好ましくは９９．５％以上である。
なお、酸化物焼結体の相対密度は、酸化物焼結体を所定の形状に加工した後の重量と外形寸法より算出した密度を、その酸化物焼結体の理論密度で除することで求めることができる。
(Relative density of sintered oxide)
The relative density of the sintered oxide is correlated with nodule formation of surface during sputtering, the oxide sintered body is a low density, by processing the oxide sintered body target sputtering In this case, a high resistance portion called a protruding nodule, which is a lower oxide of indium, is generated on the surface with the progress of sputtering film formation, and is likely to be a starting point of abnormal discharge during subsequent sputtering. In the present invention, 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.
（酸化物焼結体のバルク抵抗）
酸化物焼結体のバルク抵抗は、スパッタ時の異常放電の発生のし易さと相関があり、バルク抵抗が高いとスパッタ時に異常放電が発生し易い。本発明では、組成の適正範囲や製造条件の適正化によってバルク抵抗を３ｍΩｃｍ以下とすることができ、この程度の低バルク抵抗であれば、スパッタ時の異常放電発生への悪影響は殆どない。バルク抵抗は好ましくは２．７ｍΩｃｍ以下であり、より好ましくは２．５ｍΩｃｍ以下である。
なお、バルク抵抗は四探針法により抵抗率計を使用して測定することができる。
(Bulk resistance of sintered oxide)
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. In the present invention, the bulk resistance can be reduced to 3 mΩcm or less by optimizing the appropriate range of composition and 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 mΩcm or less, more preferably 2.5 mΩcm or less.
Bulk resistance can be measured using a resistivity meter by the four-probe method.
（酸化物焼結体の製造方法）
本発明に係る各種組成の酸化物焼結体は、例えば、原料である酸化インジウム、酸化亜鉛等の各原料粉体の配合比や原料粉体の粒径、粉砕時間、焼結温度、焼結時間、焼結雰囲気ガス種類等の条件を調整することにより得ることができる。
(Method for manufacturing oxide sintered body)
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, pulverization time, sintering temperature, sintering It can be obtained by adjusting conditions such as time and kind of sintering atmosphere gas.
原料粉は平均粒径１〜２μｍであることが望ましい。平均粒径が２μｍを超えると、焼結体の密度が向上し難くなるため、その原料粉単独又は混合粉として湿式微粉砕等を行って、平均粒径を約１μｍ程度に小さくすると良い。湿式混合粉砕前に焼結性の向上を目的として、仮焼することも有効である。一方、１μｍ未満の原料は入手し難く、また、あまり小さいと粒子間の凝集が起き易くなって扱い難くなるので、焼結前の混合粉の平均粒径は１〜２μｍが好ましい。ここで、原料粉の平均粒径はレーザ回折式粒度分布測定装置によって測定した体積分布におけるメディアン径を指す。なお、本発明の均等と解釈できる範囲で、所定の原料粉の外に焼結体特性に悪影響を及ぼさず、焼結性を向上させる等の効果を有する他の成分を添加しても良い。粉砕後の原料混合粉をスプレードライヤー等で造粒して流動性や成形性を高めた後に成型するのが好ましい。成型は通常の加圧成形や冷間静水圧加圧等の方法を採用することができる。 The raw material powder preferably has an average particle size of 1 to 2 μm. When the average particle diameter exceeds 2 μm, 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 μm. For the purpose of improving the sinterability before wet mixing and pulverization, it is also effective to calcine. On the other hand, raw materials of less than 1 μm are difficult to obtain, and if it is too small, aggregation between particles tends to occur and handling becomes difficult, so the average particle size of the mixed powder before sintering is preferably 1 to 2 μm. Here, 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 apparatus. In addition, within the range which can be interpreted as equivalent to this invention, you may add the other component which has the effect of improving a sinterability etc. without having a bad influence on a sintered compact characteristic besides a predetermined raw material powder | flour. It is preferable to mold the pulverized raw material mixed powder after granulating it with a spray dryer or the like to improve fluidity and moldability. For molding, a method such as normal pressure molding or cold isostatic pressing can be employed.
その後、成形物を焼結して焼結体を得る。焼結は、１４００〜１６００℃で２〜２０時間焼結することが好ましい。これにより、相対密度を９８％以上とすることができる。焼結温度が１４００℃未満では、密度が向上し難く、逆に、焼結温度が１６００℃を超えると、構成成分元素の揮発等により、焼結体の組成が変化したり、揮発による空隙発生による密度低下の原因となったりする。焼結時の雰囲気ガスには、大気を用いることができ、焼結体への酸素欠損量を増加させて、バルク抵抗を小さくすることができる。但し、焼結体の組成によっては、雰囲気ガスを酸素としても充分高密度の焼結体を得ることもできる。 Thereafter, the molded product is sintered to obtain a sintered body. The 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 the constituent elements, and 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.
（スパッタ成膜）
上記の様にして得られた酸化物焼結体は、研削や研磨等の加工を施すことによりスパッタリング用ターゲットとすることができ、これを使用して成膜することにより、当該ターゲットと同一組成をもつ酸化物膜を形成することができる。加工の際は、平面研削等の方法で表面を研削することによって、表面粗さ（Ｒａ）を５μｍ以下とすることが望ましい。表面粗さを小さくすることによって、異常放電の原因となるノジュール発生の起点を減少させることができる。
(Sputter deposition)
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 μm 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.
スパッタリング用ターゲットは、銅製等のバッキングプレートに貼り付けて、スパッタ装置内に設置して、適切な真空度、雰囲気ガス、スパッタパワー等の適切条件でスパッタすることで、ターゲットとほぼ同組成の膜を得ることができる。 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.
スパッタ法の場合、成膜前のチャンバー内到達真空度を、２×１０-4Ｐａ以下とするのが望ましい。圧力が高すぎると、残留雰囲気ガス中の不純物の影響によって、得られた膜の移動度が低下する可能性がある。 In the case of sputtering, it is desirable that 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.
スパッタガスとして、アルゴン及び酸素の混合ガスを使用することができる。混合ガス中の酸素濃度を調整する方法としては、例えば、アルゴン１００％のガスボンベと、アルゴン中の酸素が２％のガスボンベを用いて、それぞれのガスボンベからチャンバーへの供給流量をマスフローで適宜設定することで行うことができる。ここで、混合ガス中の酸素濃度とは、酸素分圧／（酸素分圧＋アルゴン分圧）を意味するものであり、酸素の流量を酸素とアルゴンの流量の合計で除したものとも等しい。酸素濃度は所望のキャリア濃度に応じて適宜変更すればよいが、典型的には１〜３％とすることができ、より典型的には１〜２％とすることができる。 As the sputtering gas, a mixed gas of argon and oxygen can be used. As a method for adjusting the oxygen concentration in the mixed gas, for example, 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. Can be done. Here, 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 can typically be 1 to 3%, more typically 1 to 2%.
スパッタガスの全圧は０．３〜０．８Ｐａ程度とする。全圧がこれより低いと、プラズマ放電が立ち難くなり、立ったとしてもプラズマが不安定となってしまう。また、全圧がこれより高いと、成膜速度が遅くなり、生産性に悪影響を及ぼす等の不都合が生じる。 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.
スパッタパワーは、ターゲットサイズが６インチの場合、２００〜１２００Ｗ程度で成膜する。スパッタパワーが小さすぎると、成膜速度が小さく、生産性に劣るし、逆に、大き過ぎると、ターゲットの割れ等の問題が生ずる。２００〜１２００Ｗは、スパッタパワー密度に換算すると、１．１Ｗ／ｃｍ2〜６．６Ｗ／ｃｍ2であり、３．２〜４．５Ｗ／ｃｍ2とすることが望ましい。ここで、スパッタパワー密度とは、スパッタパワーをスパッタリングターゲットの面積で除したものであり、同じスパッタパワーでもスパッタリングターゲットサイズによって、スパッタリングターゲットが実際に受けるパワーが異なり、成膜速度が異なることから、スパッタリングターゲットに印加するパワーを統一的に表現するための指標である。 The sputtering power is about 200 to 1200 W when the target size is 6 inches. 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 to 1200 W is 1.1 W / cm 2 to 6.6 W / cm 2 in terms of sputtering power density, and is desirably 3.2 to 4.5 W / cm 2 . Here, 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.
酸化物焼結体から膜を得る方法としては、真空蒸着法、イオンプレーティング法、ＰＬＤ（パルスレーザーディポジション）法等も用いることもできるが、産業上利用し易いのは、大面積、高速成膜、放電安定性等の要件を満たすＤＣマグネトロンスパッタ法である。 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.
スパッタ成膜時には、基板を加熱する必要がない。基板を加熱せずとも、比較的高移動度を得ることができるためであり、また、昇温のための時間やエネルギーを掛ける必要がない。基板を加熱することなくスパッタ成膜すると、得られる膜は非晶質となる。但し、基板を加熱することで、室温成膜後のアニールと同様の効果を得ることも期待できるので、基板加熱で成膜しても良い。 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. When sputter deposition is performed without heating the substrate, the resulting film becomes amorphous. However, 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.
（酸化物膜のキャリア濃度）
酸化物膜のキャリア濃度は、その膜をトランジスタのチャネル層に使用した際に、トランジスタの各種特性と相関がある。キャリア濃度が高すぎると、トランジスタのオフ時にも、微少漏れ電流が発生してしまい、オンオフ比が低下してしまう。一方、キャリア濃度が低すぎると、トランジスタを流れる電流が小さくなってしまう。本発明では、組成の適正範囲等によって、酸化物膜のキャリア濃度を１０16〜１０18ｃｍ-3とすることができ、この範囲であれば、特性が良好なトランジスタを作製することができる。
(Carrier concentration of oxide film)
The carrier concentration of the 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. In the present invention, 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.
（酸化物膜の移動度）
移動度はトランジスタの特性の中でも、最も重要な特性の一つであり、酸化物半導体がトランジスタのチャネル層として使用される競合材料であるアモルファスシリコンの移動度である１ｃｍ2／Ｖｓ以上であることが望ましい。移動度は基本的には、高ければ高いほど良い。本発明に係る酸化物膜は組成の適正範囲等によって、１ｃｍ2／Ｖｓ以上の移動度を有することができ、好ましくは３ｃｍ2／Ｖｓ以上の移動度を有することができ、より好ましくは５ｃｍ2／Ｖｓ以上の移動度を有することができる。これによって、アモルファスシリコンより優れた特性となって、産業上の応用可能性がより高まる。
(Mobility of oxide film)
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.
本発明に係る酸化物半導体薄膜は例えば薄膜トランジスタの活性層として使用することができる。また、上記製造方法を使用して得られた薄膜トランジスタをアクティブ素子として使用し、アクティブマトリックス駆動表示パネルに利用することができる。 The oxide semiconductor thin film according to the present invention can be used, for example, as an active layer of a thin film transistor. In addition, 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.
以下に本発明の実施例を比較例と共に示すが、これらの実施例は本発明及びその利点をよりよく理解するために提供するものであり、発明が限定されることを意図するものではない。従って、本発明は、本発明の技術思想の範囲内で、実施例以外の態様あるいは変形を全て包含するものである。 Examples of the present invention will be described below together with comparative examples, but these examples are provided for better understanding of the present invention and its advantages, and are not intended to limit the invention. Accordingly, the present invention encompasses all aspects or modifications other than the examples within the scope of the technical idea of the present invention.
下記の実施例及び比較例において、焼結体及び膜の物性は以下の方法によって測定した。
（ア）焼結体の相対密度
重量及び外形寸法の測定結果と、構成元素からの理論密度とにより求めた。
（イ）焼結体のバルク抵抗
四探針法（ＪＩＳ Ｋ７１９４）により、ＮＰＳ（エヌピイエス）社製型式Σ−５＋装置を用いて求めた。
（ウ）焼結体及び膜の組成
ＳＩＩナノテクノロジー社製型式ＳＰＳ３０００を用いてＩＣＰ（高周波誘導結合プラズマ）分析法によって求めた。
（エ）膜厚
段差計（Ｖｅｅｃｏ社製、型式Ｄｅｋｔａｋ８ ＳＴＹＬＵＳ ＰＲＯＦＩＬＥＲ）を用いて求めた。
（オ）膜のキャリア濃度及び移動度
成膜したガラス基板を約１０ｍｍ角に切り出し、四隅にインジウム電極をつけて、ホール測定装置（東陽テクニカ社製、型式Ｒｅｓｉｔｅｓｔ８２００）にセットして測定した。
（カ）膜の結晶又は非晶質構造
リガク社製ＲＩＮＴ−１１００Ｘ線回折装置を用いて結晶性を判定した。バックグランドレベル以上の有意なピークが認められない場合、非晶質と判断した。
（キ）粉体の平均粒径
島津製作所製ＳＡＬＤ−３１００で平均粒径を測定した。
In the following Examples and Comparative Examples, 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-point probe method (JIS K7194) using a model Σ-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).
(E) Carrier concentration and mobility of the film The formed glass substrate was cut into about 10 mm square, indium electrodes were attached to the four corners, and the measurement was performed by setting in a Hall measuring device (manufactured by Toyo Technica, Model Reset 8200).
(F) Crystal or amorphous structure of film Crystallinity was determined using a RINT-1100 X-ray diffractometer manufactured by Rigaku Corporation. When no significant peak above the background level was observed, it was judged as amorphous.
(G) Average particle size of powder The average particle size was measured with SALD-3100 manufactured by Shimadzu Corporation.
＜実施例１＞
酸化インジウム粉（平均粒径１．０μｍ）、酸化亜鉛粉（平均粒径１．０μｍ）、及び酸化アルミニウム粉（平均粒径１．０μｍ）、を金属元素の原子数比（Ｉｎ：Ｚｎ：Ａｌ）が０．４：０．３：０．３となる様に秤量し、湿式混合粉砕した。粉砕後の混合粉の平均粒径０．８μｍであった。この混合粉を、スプレードライヤーで造粒後、金型に充填し、加圧成形した後、大気雰囲気中１４５０℃の高温で１０時間焼結した。得られた焼結体を直径６インチ、厚さ６ｍｍの円盤状に加工し、平面研削してスパッタリングターゲットとした。当該ターゲットについて、重量と外形寸法との測定結果と理論密度から相対密度を算出したところ９９．８％であった。また、四探針法により測定した焼結体のバルク抵抗は２．１ｍΩｃｍだった。ＩＣＰ（高周波誘導結合プラズマ）分析法による焼結体組成分析の結果、Ｉｎ：Ｚｎ：Ａｌ＝０．４：０．３：０．３（原子比）であった。
<Example 1>
Indium oxide powder (average particle size: 1.0 μm), zinc oxide powder (average particle size: 1.0 μm), and aluminum oxide powder (average particle size: 1.0 μm), 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 μm. 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 obtained sintered body was processed into a disk shape having a diameter of 6 inches and a thickness of 6 mm, and was subjected to surface grinding to obtain a sputtering target. With respect to the target, the relative density was calculated from the measurement results of the weight and the external dimensions and the theoretical density, and found to be 99.8%. Moreover, the bulk resistance of the sintered compact measured by the four probe method was 2.1 mΩcm. It was In: Zn: Al = 0.4: 0.3: 0.3 (atomic ratio) as a result of the sintered body composition analysis by ICP (high frequency inductively coupled plasma) analysis.
上記で作製したスパッタリングターゲットを銅製のバッキングプレートにインジウムをロウ材として使用して貼り付けて、ＤＣマグネトロンスパッタ装置（ＡＮＥＬＶＡ製ＳＰＬ−５００スパッタ装置）に設置した。ガラス基板はコーニング１７３７を用いて、スパッタ条件を、基板温度：２５℃、到達圧力：１．２×１０-4Ｐａ、雰囲気ガス：Ａｒ９９％、酸素１％、スパッタ圧力（全圧）：０．５Ｐａ、投入電力５００Ｗとして、膜厚が約１００ｎｍの薄膜を作製した。酸化物半導体薄膜の成膜時には、異常放電は認められなかった。 The sputtering target produced above was affixed to a copper backing plate using indium as a brazing material, and installed in a DC magnetron sputtering apparatus (AELVA 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.
得られた膜のホール測定を行ったところ、キャリア濃度５．０×１０17ｃｍ-3、移動度５．１ｃｍ2／Ｖｓを得た。ＩＣＰ（高周波誘導結合プラズマ）分析法による膜組成分析の結果、Ｉｎ：Ｚｎ：Ａｌ＝０．４：０．３：０．３（原子比）であった。Ｘ線回折による測定の結果、当該膜は非晶質であった。 When hole measurement was performed on the obtained film, a carrier concentration of 5.0 × 10 17 cm −3 and a mobility of 5.1 cm 2 / Vs were obtained. As a result of film composition analysis by ICP (high frequency inductively coupled plasma) analysis, it was In: Zn: Al = 0.4: 0.3: 0.3 (atomic ratio). As a result of measurement by X-ray diffraction, the film was amorphous.
＜実施例２〜実施例９＞
原料粉の組成比を表１に記載のそれぞれの値となる様にした以外は、実施例１と同様にして、酸化物焼結体及び酸化物半導体薄膜を得た。それぞれの相対密度、バルク抵抗、キャリア濃度、移動度は、表１に記載の通りであった。また、焼結体及び膜の組成はそれぞれ原料粉の組成比と同一であった。
<Example 2 to Example 9>
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.
＜比較例１〜比較例１３＞
原料粉の組成比を表１に記載のそれぞれの値となる様にした以外は、実施例１と同様にして、酸化物焼結体及び酸化物半導体薄膜を得た。それぞれの相対密度、バルク抵抗、キャリア濃度、移動度は、表１に記載の通りであった。また、焼結体及び膜の組成はそれぞれ原料粉の組成比と同一であった。
<Comparative Examples 1 to 13>
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.
表１に記載の結果から分かるように、本発明の実施例に係る酸化物焼結体は相対密度が高く、バルク抵抗が小さい。また、本発明に係る酸化物焼結体をスパッタリングターゲットとして成膜した場合、適切なキャリア濃度及び高い移動度をもつ酸化物半導体薄膜が得られる。 As can be seen from the results shown in Table 1, the oxide sintered bodies according to the examples of the present invention have a high relative density and a low bulk resistance. In addition, when the oxide sintered body according to the present invention is formed as a sputtering target, an oxide semiconductor thin film having an appropriate carrier concentration and high mobility can be obtained.
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| JP2009253204A (en) * | 2008-04-10 | 2009-10-29 | Idemitsu Kosan Co Ltd | Field-effect transistor using oxide semiconductor, and its manufacturing method |
| JP5218032B2 (en) * | 2008-12-25 | 2013-06-26 | 東ソー株式会社 | Method for producing sintered body for transparent conductive film |
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| WO2012029455A1 (en) | 2012-03-08 |
| JP2012054335A (en) | 2012-03-15 |
| TWI405863B (en) | 2013-08-21 |
| KR101331293B1 (en) | 2013-11-20 |
| KR20130041365A (en) | 2013-04-24 |
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