JP5735190B1 - Oxide sintered body, sputtering target, and oxide thin film - Google Patents
Oxide sintered body, sputtering target, and oxide thin film Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims description 36
- 238000005477 sputtering target Methods 0.000 title claims description 26
- 239000010936 titanium Substances 0.000 claims abstract description 61
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 22
- 239000011701 zinc Substances 0.000 claims abstract description 21
- 229910052738 indium Inorganic materials 0.000 claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 20
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 19
- 229910052718 tin Inorganic materials 0.000 claims abstract description 18
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 8
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims abstract description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 18
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 18
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 17
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 16
- 230000008033 biological extinction Effects 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 abstract description 42
- 239000000126 substance Substances 0.000 abstract description 16
- 238000002834 transmittance Methods 0.000 abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 abstract 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract 2
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 abstract 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 87
- 239000010408 film Substances 0.000 description 52
- 230000003287 optical effect Effects 0.000 description 38
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 36
- 239000003513 alkali Substances 0.000 description 25
- 230000015572 biosynthetic process Effects 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- 239000011787 zinc oxide Substances 0.000 description 19
- 238000005530 etching Methods 0.000 description 16
- 239000000523 sample Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 239000011812 mixed powder Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 238000003754 machining Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000001771 impaired effect Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000470 constituent Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002310 reflectometry Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000001552 radio frequency sputter deposition Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007496 glass forming Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 101000892301 Phomopsis amygdali Geranylgeranyl diphosphate synthase Proteins 0.000 description 1
- JODIJOMWCAXJJX-UHFFFAOYSA-N [O-2].[Al+3].[O-2].[Zn+2] Chemical compound [O-2].[Al+3].[O-2].[Zn+2] JODIJOMWCAXJJX-UHFFFAOYSA-N 0.000 description 1
- AZWHFTKIBIQKCA-UHFFFAOYSA-N [Sn+2]=O.[O-2].[In+3] Chemical compound [Sn+2]=O.[O-2].[In+3] AZWHFTKIBIQKCA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- -1 and 0.5 Pa Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- OYQCBJZGELKKPM-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O-2].[Zn+2].[O-2].[In+3] OYQCBJZGELKKPM-UHFFFAOYSA-N 0.000 description 1
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- Ceramic Engineering (AREA)
- Physical Vapour Deposition (AREA)
- Compositions Of Oxide Ceramics (AREA)
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Abstract
亜鉛（Ｚｎ）、インジウム（Ｉｎ）、チタン（Ｔｉ）、錫（Ｓｎ）、ガリウム（Ｇａ）、ゲルマニウム（Ｇｅ）、及び、酸素（Ｏ）からなり、Ｚｎ含有量がＺｎＯ換算で４０〜８０ｍｏｌ％、Ｉｎ含有量がＩｎ２Ｏ３換算で３〜２５ｍｏｌ％、Ｔｉ含有量がＴｉＯ２換算で２〜１５ｍｏｌ％、Ｓｎ含有量がＳｎＯ２換算で５〜３５ｍｏｌ％、Ｇａ含有量がＧａ２Ｏ３換算で０．５〜１０ｍｏｌ％、Ｇｅ含有量がＧｅＯ２換算で０．５〜１０ｍｏｌ％であることを特徴とする酸化物焼結体。本発明によれば、バルク抵抗率が低くＤＣスパッタリングが可能であり、所望の屈折率や透過率、さらには優れた化学的特性を備えた透明導電膜を形成することができる。【選択図】なしIt consists of zinc (Zn), indium (In), titanium (Ti), tin (Sn), gallium (Ga), germanium (Ge), and oxygen (O), and the Zn content is 40-80 mol% in terms of ZnO. The In content is 3 to 25 mol% in terms of In2O3, the Ti content is 2 to 15 mol% in terms of TiO2, the Sn content is 5 to 35 mol% in terms of SnO2, and the Ga content is 0.5 to 10 mol% in terms of Ga2O3. An oxide sintered body characterized in that the Ge content is 0.5 to 10 mol% in terms of GeO2. According to the present invention, it is possible to form a transparent conductive film having a low bulk resistivity and capable of DC sputtering, and having a desired refractive index and transmittance, as well as excellent chemical characteristics. [Selection figure] None
Description
本発明は、酸化物焼結体、スパッタリングターゲット及び酸化物薄膜に関し、特には、ＤＣスパッタリングが可能な酸化物スパッタリングターゲット及び所望の特性を備えた薄膜に関する。 The present invention relates to an oxide sintered body, a sputtering target, and an oxide thin film, and more particularly, to an oxide sputtering target capable of DC sputtering and a thin film having desired characteristics.
有機ＥＬ、液晶ディスプレイやタッチパネル等の各種光デバイスにおいて可視光を利用する場合、使用する材料は透明である必要があり、特に可視光領域の全域において、高い透過率をもつことが望まれる。また、各種光デバイスでは、構成される膜材料や基板との界面での屈折率差による光損失が生じることがある。このような、高透過率や光損失低減、反射防止のために光学調整層（膜）を導入するという方法がある。 When using visible light in various optical devices such as an organic EL, a liquid crystal display, and a touch panel, the material to be used needs to be transparent, and it is desired to have a high transmittance particularly in the entire visible light region. Also, in various optical devices, light loss may occur due to a difference in refractive index at the interface with the film material or substrate that is configured. There is a method of introducing an optical adjustment layer (film) for such high transmittance, light loss reduction, and antireflection.
光学調整層に必要とされる特性として、従来は、屈折率や消衰係数（高透過率）が主であったが、近年では、更なる高性能化のために、屈折率や消衰係数（高透過率）以外にも、導電性やエッチング性（エッチング可能）、耐水性、アモルファス膜といった、複数の特性の共存が求められている。このような複数の特性を共存させるためには、単体の酸化物膜では難しく、複数の酸化物を混合させた複合酸化物膜が必要である。特に、三元系以上の酸化物を混合させた複合酸化物膜が有効である。 Conventionally, the refractive index and extinction coefficient (high transmittance) were the main characteristics required for the optical adjustment layer. However, in recent years, the refractive index and extinction coefficient have been improved for further performance enhancement. In addition to (high transmittance), coexistence of a plurality of characteristics such as conductivity, etching property (etchable), water resistance, and amorphous film is required. In order to make such a plurality of characteristics coexist, it is difficult to use a single oxide film, and a complex oxide film in which a plurality of oxides are mixed is necessary. In particular, a composite oxide film in which an oxide of a ternary system or higher is mixed is effective.
一般に、透明で導電性のある材料としては、ＩＴＯ（酸化インジウム−酸化錫）、ＩＺＯ（酸化インジウム−酸化亜鉛）、ＧＺＯ（酸化ガリウム−酸化亜鉛）、ＡＺＯ（酸化アルミニウム−酸化亜鉛）などが知られている（特許文献１〜３）。しかし、これらの材料は短波長域に吸収をもっていたり、結晶化しやすかったりと、上述した複数の特性を十分に制御することができないといった問題がある。 In general, ITO (indium oxide-tin oxide), IZO (indium oxide-zinc oxide), GZO (gallium oxide-zinc oxide), AZO (aluminum oxide-zinc oxide), etc. are known as transparent and conductive materials. (Patent Documents 1 to 3). However, these materials have a problem that the above-mentioned plurality of characteristics cannot be sufficiently controlled, such as absorption in a short wavelength region and easy crystallization.
特許文献４には、ＩＺＯにさらに別の元素を添加することで、膜の移動度やキャリア密度を向上させることが記載されている。また、特許文献５には、ビックスバイト構造とスピネル構造を含むＩＧＺＯ（酸化インジウム−酸化ガリウム−酸化亜鉛）は抵抗率が低く、成膜安定性に優れていることが開示されている。しかし、いずれも主として導電性向上を企図するものであり、上述した複数の特性を同時に制御するものではない。 Patent Document 4 describes that the mobility and carrier density of a film are improved by adding another element to IZO. Further, Patent Document 5 discloses that IGZO (indium oxide-gallium oxide-zinc oxide) including a bixbite structure and a spinel structure has low resistivity and excellent film formation stability. However, all of them are mainly intended to improve conductivity and do not simultaneously control the above-described plurality of characteristics.
また、特許文献６には、製造方法を工夫することで、緻密なＡＺＯやＧＺＯを製造する技術が開示されており、特許文献７は、本発明者によるものであるが、良好な透過率と導電率を備えた透明導電膜を得るための酸化物焼結体が開示されている。しかし、いずれの技術においても、複数の特性を同時に調整することが困難という問題があった。
なお、以上の技術はいずれも透明導電膜（電極）として使用されるものであって、電極に隣接配置して、光学特性等を制御するための膜（光学調整膜、保護膜等）とは、用途も異なるものである。
Further, Patent Document 6 discloses a technique for manufacturing dense AZO and GZO by devising a manufacturing method, and Patent Document 7 is by the present inventor. An oxide sintered body for obtaining a transparent conductive film having electrical conductivity is disclosed. However, any of the techniques has a problem that it is difficult to adjust a plurality of characteristics at the same time.
All of the above techniques are used as transparent conductive films (electrodes), and the films (optical adjustment films, protective films, etc.) that are disposed adjacent to the electrodes to control optical characteristics and the like The uses are also different.
また、本発明者は、先に、亜鉛（Ｚｎ）、インジウム（Ｉｎ）、チタン（Ｔｉ）、ガリウム（Ｇａ）、ゲルマニウム（Ｇｅ）、酸素（Ｏ）からなるスパッタリングターゲット、及びそのターゲットから作製した薄膜に関する発明を行った（特許文献８）。その薄膜は所望の光学特性や導電性や、良好なエッチング性や耐候性（高温高湿耐性）を示したが、フォトリソグラフィによるパターニング時に用いるアルカリ溶液に溶けやすい（耐アルカリ性が低い）という問題があった。これに対して、構成元素の比率を調整すると、他の特性が損なわれ、耐アルカリ性とその他複数の特性を同時に制御することが困難という問題があった。 In addition, the present inventor previously prepared a sputtering target made of zinc (Zn), indium (In), titanium (Ti), gallium (Ga), germanium (Ge), and oxygen (O), and the target. Invented a thin film (Patent Document 8). The thin film showed the desired optical properties, electrical conductivity, good etching properties and weather resistance (high temperature and high humidity resistance), but it was easily dissolved in the alkaline solution used for patterning by photolithography (low alkali resistance). there were. On the other hand, when the ratio of the constituent elements is adjusted, other characteristics are impaired, and there is a problem that it is difficult to simultaneously control alkali resistance and other characteristics.
本発明は、所望の光学特性と電気的特性、さらには良好な化学的特性を備えた導電性酸化物薄膜を得ることが可能な焼結体を提供することを課題とする。この薄膜は、透過率が高く、且つ、所望の屈折率を有し、さらに、良好な導電性とエッチング性、耐アルカリ性等を有しており、有機ＥＬ、液晶ディスプレイ、タッチパネルなどの光デバイス用の薄膜、特に光学調整用薄膜として有用である。また、本発明は、バルク抵抗率が低く、ＤＣスパッタが可能なスパッタリングターゲットを提供することを課題とする。本発明は、光デバイスの特性向上、生産コストの低減化、成膜特性を大幅に改善することを目的とする。 An object of the present invention is to provide a sintered body capable of obtaining a conductive oxide thin film having desired optical characteristics, electrical characteristics, and good chemical characteristics. This thin film has a high transmittance and a desired refractive index, and also has good conductivity, etching property, alkali resistance, etc., for optical devices such as organic EL, liquid crystal display and touch panel. It is useful as a thin film, particularly as an optical adjustment thin film. Another object of the present invention is to provide a sputtering target having a low bulk resistivity and capable of DC sputtering. An object of the present invention is to improve the characteristics of optical devices, reduce production costs, and significantly improve film formation characteristics.
上記の課題を解決するために、本発明者は鋭意研究を行った結果、下記に提示する材料系を採用することで、所望の光学特性と電気的特性と、さらには優れた化学的特性を備えた薄膜を得ることが可能となり、さらにはＤＣスパッタによる安定的な成膜が可能であり、該薄膜を使用する光デバイスの特性改善、生産性向上が可能であるとの知見を得た。 In order to solve the above-mentioned problems, the present inventor has conducted intensive research, and as a result, by adopting the material system shown below, desired optical characteristics and electrical characteristics as well as excellent chemical characteristics can be obtained. It was possible to obtain the thin film provided, and furthermore, stable film formation by DC sputtering was possible, and it was found that the characteristics of the optical device using the thin film can be improved and the productivity can be improved.
本発明者はこの知見に基づき、下記の発明を提供する。
１）亜鉛（Ｚｎ）、インジウム（Ｉｎ）、チタン（Ｔｉ）、錫（Ｓｎ）、ガリウム（Ｇａ）、ゲルマニウム（Ｇｅ）、及び、酸素（Ｏ）からなり、Ｚｎ含有量がＺｎＯ換算で４０〜８０ｍｏｌ％、Ｉｎ含有量がＩｎ２Ｏ３換算で３〜２５ｍｏｌ％、Ｔｉ含有量がＴｉＯ２換算で２〜１５ｍｏｌ％、Ｓｎ含有量がＳｎＯ２換算で５〜３５ｍｏｌ％、Ｇａ含有量がＧａ２Ｏ３換算で０．５〜１０ｍｏｌ％、Ｇｅ含有量がＧｅＯ２換算で０．５〜１０ｍｏｌ％であることを特徴とする酸化物焼結体。
２）Ｔｉに対するＩｎの含有量が原子数比で３．０≦Ｉｎ／Ｔｉ≦５．０、Ｇｅに対するＧａの含有量が原子数比で１．２≦Ｇａ／Ｇｅ≦３．０、ＩｎとＴｉとＳｎとＧａとＧｅに対するＺｎの含有量が原子数比で０．５≦Ｚｎ／（Ｉｎ＋Ｔｉ＋Ｓｎ＋Ｇａ＋Ｇｅ）≦３．０、ＧａとＧｅに対するＳｎとＩｎとＴｉの含有量が原子数比で１．０≦（Ｓｎ＋Ｉｎ＋Ｔｉ）／（Ｇａ＋Ｇｅ）の関係式を満たすことを特徴とする上記１）記載の酸化物焼結体。
３）相対密度が９０％以上であることを特徴とする上記１）又は２）記載の酸化物焼結体。
４）バルク抵抗が１０Ω・ｃｍ以下であることを特徴とする上記１）〜３）のいずれか一に記載の酸化物焼結体。
５）上記１）〜４）のいずれか一に記載される酸化物焼結体を用いることを特徴とするスパッタリングターゲット。
６）亜鉛（Ｚｎ）、インジウム（Ｉｎ）、チタン（Ｔｉ）、錫（Ｓｎ）、ガリウム（Ｇａ）、ゲルマニウム（Ｇｅ）、及び、酸素（Ｏ）からなり、Ｚｎ含有量がＺｎＯ換算で４０〜８０ｍｏｌ％、Ｉｎ含有量がＩｎ２Ｏ３換算で３〜２５ｍｏｌ％、Ｔｉ含有量がＴｉＯ２換算で２〜１５ｍｏｌ％、Ｓｎ含有量がＳｎＯ２換算で５〜３５ｍｏｌ％、Ｇａ含有量がＧａ２Ｏ３換算で０．５〜１０ｍｏｌ％、Ｇｅ含有量がＧｅＯ２換算で０．５〜１０ｍｏｌ％であることを特徴とする薄膜。
７）Ｔｉに対するＩｎの含有量が原子数比で３．０≦Ｉｎ／Ｔｉ≦５．０、Ｇｅに対するＧａの含有量が原子数比で１．２≦Ｇａ／Ｇｅ≦３．０、ＩｎとＴｉとＳｎとＧａとＧｅに対するＺｎの含有量が原子数比で０．５≦Ｚｎ／（Ｉｎ＋Ｔｉ＋Ｓｎ＋Ｇａ＋Ｇｅ）≦３．０、ＧａとＧｅに対するＳｎとＩｎとＴｉの含有量が原子数比で１．０≦（Ｓｎ＋Ｉｎ＋Ｔｉ）／（Ｇａ＋Ｇｅ）の関係式を満たすことを特徴とする上記６）記載の薄膜。
８）波長５５０ｎｍにおける屈折率が１．９５〜２．１０であることを特徴とする上記６）又は７）記載の薄膜。
９）波長４０５ｎｍにおける消衰係数が０．０５以下であることを特徴とする上記６）〜８）のいずれか一に記載の薄膜。
１０）体積抵抗率が１ｋΩ・ｃｍ以下であることを特徴とする上記６）〜９）のいずれか一に記載の薄膜。
Based on this finding, the present inventor provides the following invention.
1) It consists of zinc (Zn), indium (In), titanium (Ti), tin (Sn), gallium (Ga), germanium (Ge), and oxygen (O), and the Zn content is 40 to 40 in terms of ZnO. 80 mol%, In content is 3 to 25 mol% in terms of In 2 O 3 , Ti content is 2 to 15 mol% in terms of TiO 2 , Sn content is 5 to 35 mol% in terms of SnO 2 , and Ga content is Ga 2 An oxide sintered body characterized by 0.5 to 10 mol% in terms of O 3 and a Ge content of 0.5 to 10 mol% in terms of GeO 2 .
2) The content of In with respect to Ti is 3.0 ≦ In / Ti ≦ 5.0 by atomic ratio, the content of Ga with respect to Ge is 1.2 ≦ Ga / Ge ≦ 3.0 by atomic ratio, and In Zn content with respect to Ti, Sn, Ga and Ge is 0.5 ≦ Zn / (In + Ti + Sn + Ga + Ge) ≦ 3.0 in terms of atomic ratio, and Sn, In and Ti contents with respect to Ga and Ge are 1. The oxide sintered body according to 1) above, which satisfies a relational expression of 0 ≦ (Sn + In + Ti) / (Ga + Ge).
3) The oxide sintered body according to 1) or 2) above, wherein the relative density is 90% or more.
4) The oxide sintered body according to any one of 1) to 3) above, wherein the bulk resistance is 10 Ω · cm or less.
5) A sputtering target using the oxide sintered body described in any one of 1) to 4) above.
6) It consists of zinc (Zn), indium (In), titanium (Ti), tin (Sn), gallium (Ga), germanium (Ge), and oxygen (O), and the Zn content is 40 to 40 in terms of ZnO. 80 mol%, In content is 3 to 25 mol% in terms of In 2 O 3 , Ti content is 2 to 15 mol% in terms of TiO 2 , Sn content is 5 to 35 mol% in terms of SnO 2 , and Ga content is Ga 2 A thin film characterized in that it is 0.5 to 10 mol% in terms of O 3 and the Ge content is 0.5 to 10 mol% in terms of GeO 2 .
7) The content of In with respect to Ti is 3.0 ≦ In / Ti ≦ 5.0 by atomic ratio, the content of Ga with respect to Ge is 1.2 ≦ Ga / Ge ≦ 3.0 by atomic ratio, and In Zn content with respect to Ti, Sn, Ga and Ge is 0.5 ≦ Zn / (In + Ti + Sn + Ga + Ge) ≦ 3.0 in terms of atomic ratio, and Sn, In and Ti contents with respect to Ga and Ge are 1. The thin film as described in 6) above, which satisfies a relational expression of 0 ≦ (Sn + In + Ti) / (Ga + Ge).
8) The thin film according to 6) or 7) above, wherein the refractive index at a wavelength of 550 nm is 1.95 to 2.10.
9) The thin film as described in any one of 6) to 8) above, wherein an extinction coefficient at a wavelength of 405 nm is 0.05 or less.
10) Volume resistivity is 1 kohm * cm or less, The thin film as described in any one of said 6) -9) characterized by the above-mentioned.
本発明によれば、上記に示す材料系を採用することにより、抵抗率と屈折率とを調整することが可能となり、良好な光学特性と導電性を確保することができると共に、良好な化学的特性（エッチング特性、耐候性、耐アルカリ性が共存）を確保することできる。また、本発明は、ＤＣスパッタによる安定的な成膜が可能であり、これより、生産性向上が可能となる。 According to the present invention, by adopting the material system shown above, it becomes possible to adjust the resistivity and the refractive index, it is possible to ensure good optical properties and conductivity, and good chemical properties. Characteristics (etching characteristics, weather resistance, alkali resistance coexist) can be ensured. In addition, according to the present invention, stable film formation by DC sputtering is possible, and thus productivity can be improved.
本発明は、亜鉛（Ｚｎ）、インジウム（Ｉｎ）、チタン（Ｔｉ）、錫（Ｓｎ）、ガリウム（Ｇａ）、ゲルマニウム（Ｇｅ）、及び、酸素（Ｏ）からなり、Ｚｎ含有量がＺｎＯ換算で４０〜８０ｍｏｌ％、Ｉｎ含有量がＩｎ２Ｏ３換算で３〜２５ｍｏｌ％、Ｔｉ含有量がＴｉＯ２換算で２〜１５ｍｏｌ％、Ｓｎ含有量がＳｎＯ２換算で５〜３５ｍｏｌ％、
Ｇａ含有量がＧａ２Ｏ３換算で０．５〜１０ｍｏｌ％、Ｇｅ含有量がＧｅＯ２換算で０．５〜１０ｍｏｌ％であることを特徴とする。このような組成からなる酸化物焼結体スパッタリングターゲットを用いることにより、所望の光学特性（屈折率、透過率）及び電気的特性、さらに、良好な化学的特性（エッチング性、耐候性、耐アルカリ性）が共存する導電性酸化物薄膜を形成することができる。特に、Ｓｎの添加により、他の特性を損なうことなく、耐アルカリ性を向上させることができる。
The present invention comprises zinc (Zn), indium (In), titanium (Ti), tin (Sn), gallium (Ga), germanium (Ge), and oxygen (O), and the Zn content is converted to ZnO. 40~80mol%, 3~25mol% of in content is in 2 O 3 in terms of, 5~35mol% Ti content 2～15Mol% in terms of TiO 2, Sn content is calculated as SnO 2,
0.5 to 10 mol% Ga content is terms of Ga 2 O 3, Ge content is characterized by a 0.5 to 10 mol% with GeO 2 terms. By using an oxide sintered sputtering target having such a composition, desired optical properties (refractive index, transmittance) and electrical properties, as well as good chemical properties (etching properties, weather resistance, alkali resistance) ) Can coexist and a conductive oxide thin film can be formed. In particular, the addition of Sn can improve the alkali resistance without impairing other characteristics.
本発明は、亜鉛（Ｚｎ）、インジウム（Ｉｎ）、チタン（Ｔｉ）、錫（Ｓｎ）、ガリウム（Ｇａ）、ゲルマニウム（Ｇｅ）、及び、酸素（Ｏ）を構成元素とするが、該材料中には、不可避的不純物も含まれる。また、焼結体中の各金属は、その一部又は全てが複合酸化物として存在している。本発明では、焼結体中の各金属の含有量を酸化物換算で規定しているが、これは、原料の配合を酸化物で調整しているためであり、その範囲と技術的意義を説明するのに都合が良いからである。なお、通常の分析装置においては、酸化物ではなく、各金属元素の含有量（重量％）が特定可能である。したがって、ターゲットの各組成を特定するには、各金属元素の含有量を、各酸化物を想定して換算した量（ｍｏｌ％）で特定すればよい。 In the present invention, zinc (Zn), indium (In), titanium (Ti), tin (Sn), gallium (Ga), germanium (Ge), and oxygen (O) are constituent elements. Includes unavoidable impurities. In addition, some or all of each metal in the sintered body exists as a composite oxide. In the present invention, the content of each metal in the sintered body is specified in terms of oxide, but this is because the composition of the raw material is adjusted with the oxide, the range and technical significance Because it is convenient to explain. In a normal analyzer, the content (% by weight) of each metal element can be specified instead of the oxide. Therefore, in order to specify each composition of a target, what is necessary is just to specify content of each metal element by the quantity (mol%) converted considering each oxide.
本発明において、Ｚｎ含有量は、ＺｎＯ換算で４０〜８０ｍｏｌ％とする。この範囲を超えると、所望の光学特性や電気的特性が得られないため好ましくない。特に、Ｚｎ含有量がＺｎＯ換算で４０ｍｏｌ％未満であると、薄膜の抵抗が高くなり導電膜としての機能を損なうため好ましくない。一方、８０ｍｏｌ％超であると、屈折率などの光学特性の制御が困難になり、さらにエッチング性や耐水性、耐アルカリ性が低下するため好ましくない。 In the present invention, the Zn content is 40 to 80 mol% in terms of ZnO. Exceeding this range is not preferable because desired optical characteristics and electrical characteristics cannot be obtained. In particular, if the Zn content is less than 40 mol% in terms of ZnO, the resistance of the thin film is increased and the function as the conductive film is impaired, which is not preferable. On the other hand, if it exceeds 80 mol%, it is difficult to control optical properties such as refractive index, and etching resistance, water resistance, and alkali resistance are further deteriorated.
本発明において、Ｉｎ含有量は、Ｉｎ２Ｏ３換算で３〜２５ｍｏｌ％とする。この範囲を超えると所望の光学的、電気的特性が得られないため好ましくない。特に、Ｉｎ含有量が３ｍｏｌ％未満であると、導電性付与のための添加の効果が得られず（すなわち、高抵抗となるため好ましくない）、一方、２５ｍｏｌ％を超えると可視光の短波長領域における光の吸収が大きくなるため好ましくない。また、Ｉｎは３価の金属元素であるが、他の同価数金属（例えば、ＡｌやＢなど）への置き換えは、薄膜の抵抗率が上昇したり、耐水性を低下させたりするため好ましくない。 In the present invention, the In content is 3 to 25 mol% in terms of In 2 O 3 . Exceeding this range is not preferable because desired optical and electrical characteristics cannot be obtained. In particular, if the In content is less than 3 mol%, the effect of addition for imparting conductivity cannot be obtained (that is, it is not preferable because of high resistance), whereas if it exceeds 25 mol%, the short wavelength of visible light This is not preferable because light absorption in the region increases. Although In is a trivalent metal element, replacement with another equivalent metal (for example, Al or B) is preferable because the resistivity of the thin film increases or the water resistance decreases. Absent.
本発明において、Ｔｉ含有量は、ＴｉＯ２換算で２〜１５ｍｏｌ％とする。この範囲を超えると所望の光学的、電気的特性が得られないため好ましくない。特に、Ｔｉ含有量が２ｍｏｌ％未満であると、光学調整のための添加の効果が得られず、一方、１５ｍｏｌ％超であると薄膜の抵抗が高くなり導電膜としての機能を損なうため好ましくない。また、Ｔｉ酸化物は高屈折率材として知られているが、他の同様の効能を備えた金属（例えば、Ｂｉ、Ｆｅ、Ｃｏなど）への置き換えは、可視光短波長域での吸収が生じてしまうため好ましくない。 In the present invention, Ti content is to 2～15Mol% in terms of TiO 2. Exceeding this range is not preferable because desired optical and electrical characteristics cannot be obtained. In particular, if the Ti content is less than 2 mol%, the effect of addition for optical adjustment cannot be obtained, whereas if it exceeds 15 mol%, the resistance of the thin film increases and the function as the conductive film is impaired, which is not preferable. . Ti oxide is known as a high refractive index material, but replacement with other metals having the same effect (for example, Bi, Fe, Co, etc.) can absorb in the visible light short wavelength region. Since it will occur, it is not preferable.
本発明において、Ｓｎ含有量は、ＳｎＯ２換算で５〜３５ｍｏｌ％とする。この範囲を超えると所望の化学的特性（特に、耐アルカリ性）が得られないため好ましくない。特に、Ｓｎ含有量が５ｍｏｌ％未満であると、耐アルカリ性が低下し（アルカリに溶けてしまう）、一方、３５ｍｏｌ％を越えると、他の特性（特に、エッチング性：エッチングのし易さ）が低下するため好ましくない。また、Ｓｎ酸化物以外に、耐アルカリ性を有する酸化物としては、Ｔｉ酸化物、Ｉｎ酸化物、Ｚｒ酸化物があるが、Ｔｉ酸化物、Ｉｎ酸化物は元々構成成分であり、耐アルカリ性向上のために添加量を増やすと他特性との共存が困難となるため好ましくない。Ｚｒ酸化物への置き換えについては、薄膜の抵抗率が上昇するために好ましくない。 In the present invention, Sn content is the 5～35Mol% in terms of SnO 2. Exceeding this range is not preferred because desired chemical properties (particularly alkali resistance) cannot be obtained. In particular, when the Sn content is less than 5 mol%, the alkali resistance is lowered (dissolves in alkali), while when it exceeds 35 mol%, other characteristics (especially, etching property: ease of etching) are obtained. Since it falls, it is not preferable. In addition to Sn oxides, oxides having alkali resistance include Ti oxides, In oxides, and Zr oxides. Ti oxides and In oxides are originally constituents, and improve alkali resistance. Therefore, it is not preferable to increase the amount of addition because coexistence with other characteristics becomes difficult. The replacement with Zr oxide is not preferable because the resistivity of the thin film increases.
本発明において、Ｇａ含有量は、Ｇａ２Ｏ３換算で０．５〜１０ｍｏｌ％とする。この範囲を超えると所望の光学的や電気的特性が得られないため好ましくない。特にＧａ含有量が０．５ｍｏｌ％未満であると、光学調整や導電性付与のための添加の効果が得られず、一方、１０ｍｏｌ％を超えると、焼結体や膜の抵抗が高くなるため好ましくない。また、Ｇａは３価の金属元素であるが、他の同価数金属（例えば、ＡｌやＢなど）への置き換えは、抵抗が上昇したり、耐水性を低下させたりするため好ましくない。 In the present invention, Ga content shall be 0.5 to 10 mol% in terms of Ga 2 O 3. Exceeding this range is not preferable because desired optical and electrical characteristics cannot be obtained. In particular, when the Ga content is less than 0.5 mol%, the effect of addition for optical adjustment and conductivity imparting cannot be obtained, while when it exceeds 10 mol%, the resistance of the sintered body and the film increases. It is not preferable. Ga is a trivalent metal element, but replacement with another equivalent metal (for example, Al or B) is not preferable because resistance increases and water resistance decreases.
本発明において、Ｇｅ含有量は、ＧｅＯ２換算で０．５〜１０ｍｏｌ％とする。この範囲を超えると所望の光学的、電気的特性が得られないため好ましくない。特にＧｅ含有量が０．５ｍｏｌ％未満であると、光学調整のための添加の効果が得られず、一方、１０ｍｏｌ％を超えると、焼結体や膜の抵抗が高くなるため好ましくない。また、Ｇｅは低屈折率且つガラス形成酸化物を構成する金属元素であるが、他のガラス形成酸化物を構成する金属（例えば、ＳｉやＢなど）への置き換えは、抵抗が上昇したり、耐水性を低下させたりするため好ましくない。 In the present invention, Ge content shall be 0.5 to 10 mol% with GeO 2 terms. Exceeding this range is not preferable because desired optical and electrical characteristics cannot be obtained. In particular, if the Ge content is less than 0.5 mol%, the effect of addition for optical adjustment cannot be obtained, while if it exceeds 10 mol%, the resistance of the sintered body or film increases, which is not preferable. Further, Ge is a metal element that constitutes a glass-forming oxide with a low refractive index, but replacement with a metal that constitutes another glass-forming oxide (for example, Si or B) increases the resistance, It is not preferable because water resistance is lowered.
本発明において、Ｔｉに対するＩｎの含有量を原子数比で３．０≦Ｉｎ／Ｔｉ≦５．０、且つ、Ｇｅに対するＧａの含有量を原子数比で１．２≦Ｇａ／Ｇｅ≦３．０、の関係式を満たすようにするのが好ましい。この範囲を超えると、所望の光学特性と電気的特性の両立が困難となる。さらに、ＩｎとＴｉとＳｎとＧａとＧｅに対するＺｎの含有量を原子数比で０．５≦Ｚｎ／（Ｉｎ＋Ｔｉ＋Ｓｎ＋Ｇａ＋Ｇｅ）≦３．０の関係式を満たすようにするのが好ましい。この範囲を超えると、所望の光学特性と電気的特性、良好な化学的特性の共存が困難となるとともに、３．０を超えると、Ｉｎ、Ｔｉ、Ｓｎ、Ｇａ、Ｇｅの添加効果が低下し、耐候性（高温高湿耐性）、エッチング性、耐アルカリ性を損なうことがある。また、０．５未満では、所望の導電性が得られず、導電膜としての機能を損なうことがある。さらに、ＧａとＧｅに対するＳｎとＩｎとＴｉの含有量が原子数比で１．０≦（Ｓｎ＋Ｉｎ＋Ｔｉ）／（Ｇａ＋Ｇｅ）の関係式を満たすようにするのが好ましい。この範囲を超えると、耐アルカリ性が低下するため好ましくない。 In the present invention, the content of In with respect to Ti is 3.0 ≦ In / Ti ≦ 5.0 by atomic ratio, and the content of Ga with respect to Ge is 1.2 ≦ Ga / Ge ≦ 3. It is preferable to satisfy the relational expression of 0. Beyond this range, it becomes difficult to achieve both desired optical characteristics and electrical characteristics. Furthermore, it is preferable that the Zn content with respect to In, Ti, Sn, Ga, and Ge satisfies the relational expression of 0.5 ≦ Zn / (In + Ti + Sn + Ga + Ge) ≦ 3.0 in terms of the atomic ratio. Beyond this range, coexistence of desired optical characteristics, electrical characteristics, and good chemical characteristics becomes difficult. When exceeding 3.0, the effect of adding In, Ti, Sn, Ga, and Ge decreases. , Weather resistance (high temperature and high humidity resistance), etching property, alkali resistance may be impaired. If it is less than 0.5, desired conductivity cannot be obtained, and the function as a conductive film may be impaired. Furthermore, it is preferable that the contents of Sn, In, and Ti with respect to Ga and Ge satisfy the relational expression 1.0 ≦ (Sn + In + Ti) / (Ga + Ge) in terms of the atomic ratio. Exceeding this range is not preferable because alkali resistance decreases.
本発明の焼結体は、スパッタリングターゲットとして使用する場合、相対密度９０％以上とすることが好ましい。密度の向上は、スパッタ膜の均一性を高め、またスパッタ時のパーティクルの発生を抑制することができるという効果を有する。相対密度９０％以上は、後述する本発明の焼結体の製造方法により、実現することができる。
また、本発明の焼結体は、スパッタリングターゲットとして使用する場合、バルク抵抗１０Ω・ｃｍ以下とすることが好ましい。バルク抵抗の低下により、ＤＣスパッタによる成膜が可能となる。ＤＣスパッタはＲＦスパッタに比べて、成膜速度が速く、スパッタリング効率が優れており、スループットを向上できる。
When the sintered body of the present invention is used as a sputtering target, the relative density is preferably 90% or more. The improvement in density has the effect of improving the uniformity of the sputtered film and suppressing the generation of particles during sputtering. The relative density of 90% or more can be realized by the method for producing a sintered body of the present invention described later.
Moreover, when using the sintered compact of this invention as a sputtering target, it is preferable to set it as bulk resistance 10 ohm * cm or less. Due to the decrease in bulk resistance, film formation by DC sputtering becomes possible. Compared with RF sputtering, DC sputtering is faster in film formation, has better sputtering efficiency, and can improve throughput.
本発明の薄膜は、上述した焼結体スパッタリングターゲットを用いて成膜することができる。得られる薄膜は、スパッタリングターゲット（焼結体）の成分組成と実質的に同一になることが確認される。ところで、一般に反射防止や光損失低減のために、特定の屈折率を持つ材料が必要とされるが、必要な屈折率はデバイス構造（光学調整膜の周辺層の屈折率）によって異なる。本発明では、薄膜の波長５５０ｎｍにおける屈折率ｎを１．９５≦ｎ≦２．１０の範囲に制御することが可能となる。また、光学調整膜自体、高透過率（低消衰係数）であることが好ましく、本発明では、波長４０５ｎｍにおける消衰係数が０．０５以下と可視光の短波長域において吸収の少ない膜を得ることができる。さらに、光学調整層は、隣接する電極層の補助のため適度な導電性が必要とされることがあり、本発明では、薄膜の体積抵抗率を１ｋΩ・ｃｍ以下に制御することが可能となる。さらに、本発明の薄膜は、良好なエッチング特性、優れた耐候性（高温高湿耐性）及び耐アルカリ性を備えることを特徴とする。 The thin film of this invention can be formed into a film using the sintered compact sputtering target mentioned above. It is confirmed that the obtained thin film becomes substantially the same as the component composition of the sputtering target (sintered body). By the way, in general, a material having a specific refractive index is required for preventing reflection and reducing optical loss. The required refractive index varies depending on the device structure (the refractive index of the peripheral layer of the optical adjustment film). In the present invention, the refractive index n of the thin film at a wavelength of 550 nm can be controlled in the range of 1.95 ≦ n ≦ 2.10. In addition, the optical adjustment film itself preferably has a high transmittance (low extinction coefficient). In the present invention, an extinction coefficient at a wavelength of 405 nm is 0.05 or less, and a film with little absorption in a short wavelength region of visible light is used. Can be obtained. Furthermore, the optical adjustment layer may require appropriate conductivity to assist the adjacent electrode layer, and in the present invention, the volume resistivity of the thin film can be controlled to 1 kΩ · cm or less. . Furthermore, the thin film of the present invention is characterized by having good etching characteristics, excellent weather resistance (high temperature and high humidity resistance) and alkali resistance.
本発明の焼結体は、各構成金属の酸化物粉末からなる原料粉末を秤量、混合した後、この混合粉末を不活性ガス雰囲気又は真空雰囲気の下、加圧焼結（ホットプレス）するか、又は、原料粉末をプレス成形した後、この成形体を常圧焼結することによって、製造することができる。このとき、焼結温度は、９００℃以上１５００℃以下とすることが好ましい。９００℃未満とすると高密度の焼結体が得られず、一方、１５００℃超とすると、材料の蒸発による組成ズレや密度の低下が生じるため、好ましくない。また、プレス圧力は、１５０〜５００ｋｇｆ／ｃｍ２とするのが好ましい。
さらに密度を向上させるためには、原料粉末を秤量、混合した後、この混合粉末を仮焼（合成）し、その後、これを微粉砕したものを焼結用粉末として用いることが有効である。このように予め合成と微粉砕を行うことで均一微細な原料粉末を得ることができ、緻密な焼結体を作製することができる。微粉砕後の粒径については、平均粒径５μｍ以下、好ましくは、平均粒径２μｍ以下とする。また、仮焼温度は、好ましくは８００℃以上１２００℃以下とする。このような範囲とすることで、焼結性が良好となり、さらなる高密度化が可能となる。
The sintered body of the present invention is obtained by weighing and mixing raw material powders composed of oxide powders of constituent metals, and then subjecting the mixed powder to pressure sintering (hot pressing) in an inert gas atmosphere or a vacuum atmosphere. Alternatively, after the raw material powder is press-molded, the compact can be produced by normal-pressure sintering. At this time, the sintering temperature is preferably 900 ° C. or higher and 1500 ° C. or lower. When the temperature is lower than 900 ° C., a high-density sintered body cannot be obtained. On the other hand, when the temperature is higher than 1500 ° C., composition deviation and density decrease due to evaporation of the material are not preferable. Moreover, it is preferable that a press pressure shall be 150-500 kgf / cm < 2 >.
In order to further improve the density, it is effective to weigh and mix the raw material powders, then calcine (synthesize) the mixed powders, and then use the finely pulverized powders as sintering powders. Thus, by carrying out synthesis and pulverization in advance, a uniform fine raw material powder can be obtained, and a dense sintered body can be produced. The particle size after pulverization is set to an average particle size of 5 μm or less, preferably 2 μm or less. The calcining temperature is preferably 800 ° C. or higher and 1200 ° C. or lower. By setting it as such a range, sinterability becomes favorable and further densification becomes possible.
以下、実施例および比較例に基づいて説明する。なお、本実施例はあくまで一例であり、この例によって何ら制限されるものではない。すなわち、本発明は特許請求の範囲によってのみ制限されるものであり、本発明に含まれる実施例以外の種々の変形を包含するものである。 Hereinafter, description will be made based on Examples and Comparative Examples. In addition, a present Example is an example to the last, and is not restrict | limited at all by this example. In other words, the present invention is limited only by the scope of the claims, and includes various modifications other than the examples included in the present invention.
実施例、比較例における評価方法等は、以下の通りである。
（成分組成について）
装置：ＳＩＩ社製ＳＰＳ３５００ＤＤ
方法：ＩＣＰ-ＯＥＳ（高周波誘導結合プラズマ発光分析法）
（密度測定について）
寸法測定（ノギス）、重量測定
（相対密度について）
下記、理論密度を用いて算出する。
相対密度（％）＝寸法密度／理論密度×１００
理論密度は、各金属元素の酸化物換算配合比から計算する。
ＺｎのＺｎＯ換算重量をａ（ｗｔ％）、ＩｎのＩｎ２Ｏ３換算重量をｂ（ｗｔ％）、
ＴｉのＴｉＯ２換算重量をｃ（ｗｔ％）、ＳｎのＳｎＯ２換算重量をｄ（ｗｔ％）、
ＧａのＧａ２Ｏ３換算重量をｅ（ｗｔ％）、ＧｅのＧｅＯ２換算重量をｆ（ｗｔ％）としたとき、
理論密度＝１００／（ａ／５．６１＋ｂ／７．１８＋ｃ／４．２６＋ｄ／７．００＋ｅ／５．９５＋ｆ／４．７０）
また、各金属元素の酸化物換算密度は下記値を使用。
ＺｎＯ：５．６１ｇ／ｃｍ３、Ｉｎ２Ｏ３：７．１８ｇ／ｃｍ３、
ＴｉＯ２：４．２６ｇ／ｃｍ３、ＳｎＯ２：７．００ｇ／ｃｍ３、
Ｇａ２Ｏ３：５．９５ｇ／ｃｍ３、ＧｅＯ２：４．７０ｇ／ｃｍ３
（バルク抵抗、体積抵抗率について）
装置：ＮＰＳ社製 抵抗率測定器 Σ−５＋
方法：直流４探針法
（成膜方法、条件について）
装置：ＡＮＥＬＶＡ ＳＰＬ−５００
基板：φ４ｉｎｃｈ
基板温度：室温
（屈折率、消衰係数について）
装置：ＳＨＩＭＡＤＺＵ社製 分光光度計 ＵＶ−２４５０
測定サンプル：
膜厚５００ｎｍ以上のガラス基板上成膜サンプル、及び、未成膜ガラス基板
測定データ：
（成膜サンプル）：薄膜面からの反射率及び透過率及び基板面からの反射率（いずれも裏面反射あり）
（ガラス基板）：裏面反射あり反射率及び透過率、裏面反射なし反射率
計算方法：測定データから以下の資料に基づき算出（小檜山光信著、光学薄膜の基礎理論、株式会社オプトロニクス社、（２００６）、１２６−１３１）
（エッチング性、高温高湿耐性、耐アルカリ性について）
エッチング性試験：各種酸によりエッチング可能なものを〇、エッチングできな
い若しくは溶解し過ぎるものを×、と判断する。
高温高湿耐性（耐候性）試験：温度８０℃、湿度８０％条件下にて４８時間保管後、
光学定数及び抵抗測定を実施し、高温高湿試験前後において、特性差が１０％未満の場合には〇、１０％以上の場合には×、と判断する。
耐アルカリ性試験：成膜サンプルをアルカリ性溶液（３ｗｔ％ＫＯＨ水溶液：ｐＨ１３程度、３５℃）に５分間浸した前後において、光学定数及び抵抗測定を実施し、特性差が１０％未満の場合には〇、１０％以上の場合には×と判断する。
Evaluation methods and the like in Examples and Comparative Examples are as follows.
(About component composition)
Device: SPS3500DD manufactured by SII
Method: ICP-OES (High Frequency Inductively Coupled Plasma Atomic Emission Analysis)
(About density measurement)
Dimension measurement (caliper), weight measurement (relative density)
Calculated using the theoretical density below.
Relative density (%) = Dimensional density / Theoretical density × 100
The theoretical density is calculated from the oxide conversion ratio of each metal element.
The terms of ZnO by weight a (wt%) of Zn, the In 2 O 3 reduced weight of In b (wt%),
The terms of TiO 2 by weight of Ti c (wt%), the terms of SnO 2 weight Sn d (wt%),
When the Ga 2 O 3 equivalent weight of Ga is e (wt%) and the Ge GeO 2 equivalent weight is f (wt%),
Theoretical density = 100 / (a / 5.61 + b / 7.18 + c / 4.26 + d / 7.00 + e / 5.95 + f / 4.70)
In addition, the oxide conversion density of each metal element uses the following values.
ZnO: 5.61 g / cm 3 , In 2 O 3 : 7.18 g / cm 3 ,
TiO 2 : 4.26 g / cm 3 , SnO 2 : 7.00 g / cm 3,
Ga 2 O 3: 5.95g / cm 3, GeO 2: 4.70g / cm 3
(About bulk resistance and volume resistivity)
Apparatus: Resistivity measuring instrument Σ-5 + manufactured by NPS
Method: DC 4 probe method (deposition method and conditions)
Equipment: ANELVA SPL-500
Substrate: φ4inch
Substrate temperature: room temperature (refractive index, extinction coefficient)
Apparatus: Spectrophotometer UV-2450 manufactured by SHIMADZU
Measurement sample:
Film formation sample on glass substrate having a film thickness of 500 nm or more and non-film formation glass substrate Measurement data:
(Film formation sample): Reflectivity and transmittance from the thin film surface and reflectivity from the substrate surface (both have back surface reflection)
(Glass substrate): Reflectivity and transmittance with back reflection, Reflectivity without back reflection Calculation method: Calculated based on the following materials from measurement data (Mitsunobu Koyama, Basic theory of optical thin film, Optronics Inc., (2006) 126-131)
(Etching, high temperature and high humidity resistance, alkali resistance)
Etchability test: Yes, what can be etched with various acids can not be etched
If it is too much or dissolves, it is judged as x.
High-temperature and high-humidity resistance (weather resistance) test: after storage for 48 hours at a temperature of 80 ° C. and a humidity of 80%,
Optical constants and resistance measurements are performed, and before and after the high-temperature and high-humidity test, it is judged as “Yes” when the characteristic difference is less than 10% and “X” when it is 10% or more.
Alkali resistance test: Optical constants and resistance measurements were performed before and after immersing a film-forming sample in an alkaline solution (3 wt% KOH aqueous solution: about pH 13 and 35 ° C.) for 5 minutes. When it is 10% or more, it is judged as x.
（実施例１）
ＺｎＯ粉、Ｉｎ２Ｏ３粉、ＴｉＯ２粉、ＳｎＯ２粉、Ｇａ２Ｏ３粉、ＧｅＯ２粉を準備し、これらの粉末を表１に記載される配合比に調合し、これを混合した。次に、この混合粉末を大気中、温度１０５０℃で仮焼した後、湿式微粉砕（ＺｒＯ２ビーズ使用）にて平均粒径２μｍ以下に粉砕し、乾燥後、目開き１５０μｍの篩で篩別を行った。その後、この微粉砕粉をＡｒ雰囲気中、温度１１００℃、圧力２５０ｋｇｆ／ｃｍ２の条件でホットプレス焼結した。その後、この焼結体を機械加工でスパッタリングターゲット形状に仕上げた。得られたターゲットのバルク抵抗率と相対密度を測定した結果、表１に示す通り、相対密度は９９．３％に達し、バルク抵抗は０．１０Ω・ｃｍとなり、安定したＤＣスパッタが可能であった。また、スパッタリングターゲットの成分組成を分析した結果、原料粉末の配合比と同等になることを確認した。
Example 1
ZnO powder, In 2 O 3 powder, TiO 2 powder, SnO 2 powder, Ga 2 O 3 powder, and GeO 2 powder were prepared, and these powders were prepared to the mixing ratios described in Table 1 and mixed. . Next, this mixed powder is calcined in the atmosphere at a temperature of 1050 ° C., then pulverized to a mean particle size of 2 μm or less by wet pulverization (using ZrO 2 beads), dried, and sieved with a sieve having an opening of 150 μm. Went. Thereafter, this finely pulverized powder was hot-press sintered in an Ar atmosphere at a temperature of 1100 ° C. and a pressure of 250 kgf / cm 2 . Thereafter, this sintered body was finished into a sputtering target shape by machining. As a result of measuring the bulk resistivity and relative density of the obtained target, as shown in Table 1, the relative density reached 99.3%, the bulk resistance became 0.10 Ω · cm, and stable DC sputtering was possible. It was. Moreover, as a result of analyzing the component composition of a sputtering target, it confirmed that it became equivalent to the compounding ratio of raw material powder.
上記仕上げ加工したターゲットを使用して、スパッタリングを行った。スパッタ条件は、ＤＣスパッタ、スパッタパワー５００Ｗ、酸素を０．８ｖｏｌ％含有するＡｒガス圧０．５Ｐａとし、膜厚５０００〜７０００Åに成膜した。成膜サンプルの、屈折率（波長５５０ｎｍ）、消衰係数（波長４０５ｎｍ）、体積抵抗率、を測定した。表１に示す通り、スパッタにより形成した薄膜は、屈折率が２．００、消衰係数が０．０１未満、体積抵抗率が１×１０３Ω・ｃｍ以下と、所望の光学特性と導電性が得られた。またエッチング性、高温高湿耐性（耐候性）、耐アルカリ性の化学的特性は、いずれも良好であった。 Sputtering was performed using the above-finished target. The sputtering conditions were DC sputtering, sputtering power of 500 W, Ar gas pressure of 0.5 Pa containing 0.8 vol%, and a film thickness of 5000 to 7000 mm. The refractive index (wavelength 550 nm), extinction coefficient (wavelength 405 nm), and volume resistivity of the film formation sample were measured. As shown in Table 1, the thin film formed by sputtering has a refractive index of 2.00, an extinction coefficient of less than 0.01, a volume resistivity of 1 × 10 3 Ω · cm or less, and desired optical characteristics and conductivity. was gotten. Further, the chemical properties of etching property, high temperature and high humidity resistance (weather resistance), and alkali resistance were all good.
（実施例２〜１１）
実施例２〜１１について、ＺｎＯ粉、Ｉｎ２Ｏ３粉、ＴｉＯ２粉、ＳｎＯ２粉、Ｇａ２Ｏ３粉、ＧｅＯ２粉を準備し、これらの粉末を表１に記載される配合比に調合し、これを混合した。次に、この混合粉末を実施例１と同様に仮焼、粉砕、乾燥、篩分けを行った後、微粉砕粉を実施例１と同様の条件でホットプレス焼結した。その後、この焼結体を機械加工でスパッタリングターゲット形状に仕上げた。得られたターゲットのバルク抵抗と相対密度を測定した結果、表１に示す通り、相対密度は、いずれも９０％以上であり、バルク抵抗は、いずれも１０Ω・ｃｍ以下と、安定したＤＣスパッタが可能であった。
(Examples 2 to 11)
For example 2 to 11, ZnO powder, an In 2 O 3 powder, TiO 2 powder, SnO 2 powder, Ga 2 O 3 powder, to prepare a GeO 2 powder, these powders compounding ratio described in Table 1 Prepared and mixed. Next, the mixed powder was calcined, pulverized, dried and sieved in the same manner as in Example 1, and then the finely pulverized powder was hot-press sintered under the same conditions as in Example 1. Thereafter, this sintered body was finished into a sputtering target shape by machining. As a result of measuring the bulk resistance and relative density of the obtained target, as shown in Table 1, the relative density was 90% or more, and the bulk resistance was 10 Ω · cm or less. It was possible.
次に、仕上げ加工したターゲットを使用して、スパッタリングを行った。スパッタ条件は、実施例１と同様とした。成膜サンプルの、屈折率（波長５５０ｎｍ）、消衰係数（波長４０５ｎｍ）、体積抵抗率、を測定した結果、表１に示す通り、スパッタにより形成した薄膜は、屈折率がいずれも１．９５〜２．１０、消衰係数が０．０５以下、体積抵抗率が１×１０３Ω・ｃｍ以下と、所望の光学特性と導電性が得られた。また、エッチング性、高温高湿耐性（耐候性）、耐アルカリ性の化学的特性は、いずれも良好であった。 Next, sputtering was performed using the finished target. The sputtering conditions were the same as in Example 1. As a result of measuring the refractive index (wavelength 550 nm), extinction coefficient (wavelength 405 nm), and volume resistivity of the film formation sample, as shown in Table 1, the thin films formed by sputtering have a refractive index of 1.95. The desired optical characteristics and conductivity were obtained, which were ˜2.10, the extinction coefficient was 0.05 or less, and the volume resistivity was 1 × 10 3 Ω · cm or less. Further, the chemical properties of etching property, high temperature and high humidity resistance (weather resistance), and alkali resistance were all good.
（比較例１）
比較例１は、Ｓｎを含有しない例である。
ＺｎＯ粉、Ｉｎ２Ｏ３粉、ＴｉＯ２粉、Ｇａ２Ｏ３粉、ＧｅＯ２粉を準備し、これらの粉末を表１に記載される配合比に調合し、これを混合した。次に、この混合粉末を実施例１と同様に仮焼、粉砕、乾燥、篩分けを行った後、この微粉砕粉を実施例１と同様の条件でホットプレス焼結した。その後、この焼結体を機械加工でスパッタリングターゲット形状に仕上げた。次に、仕上げ加工したターゲットを使用して、スパッタリングを行った。スパッタ条件は、実施例１と同様とした。成膜サンプルの、化学的特性などについて確認した結果、表１に示すとおり、耐アルカリ性が劣る結果となった。
(Comparative Example 1)
Comparative Example 1 is an example not containing Sn.
ZnO powder, In 2 O 3 powder, TiO 2 powder, Ga 2 O 3 powder, and GeO 2 powder were prepared, and these powders were prepared in a mixing ratio described in Table 1 and mixed. Next, this mixed powder was calcined, pulverized, dried and sieved in the same manner as in Example 1, and then this finely pulverized powder was hot-press sintered under the same conditions as in Example 1. Thereafter, this sintered body was finished into a sputtering target shape by machining. Next, sputtering was performed using the finished target. The sputtering conditions were the same as in Example 1. As a result of confirming the chemical characteristics of the film formation sample, as shown in Table 1, the alkali resistance was inferior.
（比較例２）
比較例２は、Ｓｎの含有量が本発明で規定する量より少ない例である。
ＺｎＯ粉、Ｉｎ２Ｏ３粉、ＴｉＯ２粉、ＳｎＯ２粉、Ｇａ２Ｏ３粉、ＧｅＯ２粉を準備し、これらの粉末を表１に記載される配合比に調合し、これを混合した。次に、この混合粉末を実施例１と同様に仮焼、粉砕、乾燥、篩分けを行った後、この微粉砕粉を実施例１と同様の条件でホットプレス焼結した。その後、この焼結体を機械加工でスパッタリングターゲット形状に仕上げた。次に、仕上げ加工したターゲットを使用して、スパッタリングを行った。スパッタ条件は、実施例１と同様とした。成膜サンプルの、化学的特性などについて確認した結果、表１に示す通り、耐アルカリ性が劣る結果となった。
(Comparative Example 2)
Comparative Example 2 is an example in which the Sn content is less than the amount specified in the present invention.
ZnO powder, In 2 O 3 powder, TiO 2 powder, SnO 2 powder, Ga 2 O 3 powder, and GeO 2 powder were prepared, and these powders were prepared to the mixing ratios described in Table 1 and mixed. . Next, this mixed powder was calcined, pulverized, dried and sieved in the same manner as in Example 1, and then this finely pulverized powder was hot-press sintered under the same conditions as in Example 1. Thereafter, this sintered body was finished into a sputtering target shape by machining. Next, sputtering was performed using the finished target. The sputtering conditions were the same as in Example 1. As a result of confirming the chemical characteristics of the film formation sample, as shown in Table 1, the alkali resistance was inferior.
（比較例３）
比較例３は、Ｓｎの含有量が本発明で規定する量より多い例である。
ＺｎＯ粉、Ｉｎ２Ｏ３粉、ＴｉＯ２粉、ＳｎＯ２粉、Ｇａ２Ｏ３粉、ＧｅＯ２粉を準備し、これらの粉末を表１に記載される配合比に調合し、これを混合した。次に、この混合粉末を実施例１と同様に仮焼、粉砕、乾燥、篩分けを行った後、この微粉砕粉を実施例１と同様の条件でホットプレス焼結した。その後、この焼結体を機械加工でスパッタリングターゲット形状に仕上げた。次に、仕上げ加工したターゲットを使用して、スパッタリングを行った。但し、得られたターゲットは、表１に示す通り、バルク抵抗が５００ｋΩ・ｃｍ超となり、ＤＣスパッタは困難であったため、ＲＦスパッタを行った。スパッタ条件は、スパッタパワー５００Ｗ、酸素を０．８ｖｏｌ％含有するＡｒガス圧０．５Ｐａとし、膜厚５０００〜７０００Åに成膜した。成膜サンプルの、化学的特性などについて確認した結果、表１に示す通り、膜が高抵抗となり、エッチング性が劣る結果となった。
(Comparative Example 3)
Comparative Example 3 is an example in which the Sn content is greater than the amount specified in the present invention.
ZnO powder, In 2 O 3 powder, TiO 2 powder, SnO 2 powder, Ga 2 O 3 powder, and GeO 2 powder were prepared, and these powders were prepared to the mixing ratios described in Table 1 and mixed. . Next, this mixed powder was calcined, pulverized, dried and sieved in the same manner as in Example 1, and then this finely pulverized powder was hot-press sintered under the same conditions as in Example 1. Thereafter, this sintered body was finished into a sputtering target shape by machining. Next, sputtering was performed using the finished target. However, as shown in Table 1, the obtained target had a bulk resistance of over 500 kΩ · cm, and DC sputtering was difficult, so RF sputtering was performed. The sputtering conditions were a sputtering power of 500 W, an Ar gas pressure containing 0.8 vol% of oxygen, and 0.5 Pa, and a film thickness of 5000 to 7000 mm was formed. As a result of confirming the chemical characteristics and the like of the film formation sample, as shown in Table 1, the film became high resistance and the etching property was inferior.
（比較例４）
比較例４は、Ｚｎの含有量が本発明で規定する量より多い例である。
ＺｎＯ粉、Ｉｎ２Ｏ３粉、ＴｉＯ２粉、ＳｎＯ２粉、Ｇａ２Ｏ３粉、ＧｅＯ２粉を準備し、これらの粉末を表１に記載される配合比に調合し、これを混合した。次に、この混合粉末を実施例１と同様に仮焼、粉砕、乾燥、篩分けを行った後、この微粉砕粉を実施例１と同様の条件でホットプレス焼結した。その後、この焼結体を機械加工でスパッタリングターゲット形状に仕上げた。次に、仕上げ加工したターゲットを使用して、スパッタリングを行った。スパッタ条件は、実施例１と同様とした。成膜サンプルの、化学的特性などについて確認した結果、表１に示す通り、エッチング性（溶け過ぎる）、耐候性、耐アルカリ性のいずれにおいても劣る結果となった。
(Comparative Example 4)
Comparative Example 4 is an example in which the Zn content is greater than the amount specified in the present invention.
ZnO powder, In 2 O 3 powder, TiO 2 powder, SnO 2 powder, Ga 2 O 3 powder, and GeO 2 powder were prepared, and these powders were prepared to the mixing ratios described in Table 1 and mixed. . Next, this mixed powder was calcined, pulverized, dried and sieved in the same manner as in Example 1, and then this finely pulverized powder was hot-press sintered under the same conditions as in Example 1. Thereafter, this sintered body was finished into a sputtering target shape by machining. Next, sputtering was performed using the finished target. The sputtering conditions were the same as in Example 1. As a result of confirming the chemical characteristics and the like of the film formation sample, as shown in Table 1, it was inferior in all of the etching property (too soluble), the weather resistance, and the alkali resistance.
（比較例５）
比較例５は、Ｇｅの含有量が本発明で規定する量より多い（Ｇａ／Ｇｅの比が小さい）例である。
ＺｎＯ粉、Ｉｎ２Ｏ３粉、ＴｉＯ２粉、ＳｎＯ２粉、Ｇａ２Ｏ３粉、ＧｅＯ２粉を準備し、これらの粉末を表１に記載される配合比に調合し、これを混合した。次に、この混合粉末を実施例１と同様に仮焼、粉砕、乾燥、篩分けを行った後、この微粉砕粉を実施例１と同様の条件でホットプレス焼結した。その後、この焼結体を機械加工でスパッタリングターゲット形状に仕上げた。次に、仕上げ加工したターゲットを使用して、スパッタリングを行った。但し、得られたターゲットは、表１に示す通りバルク抵抗が５００ｋΩ・ｃｍ超となり、ＤＣスパッタは困難であったため、ＲＦスパッタを行った。スパッタ条件は、比較例３と同様とした。成膜サンプルの、化学的特性などについて確認した結果、表１に示す通り、膜が高抵抗となり、耐アルカリ性が劣る結果となった。
(Comparative Example 5)
Comparative Example 5 is an example in which the Ge content is larger than the amount specified in the present invention (Ga / Ge ratio is small).
ZnO powder, In 2 O 3 powder, TiO 2 powder, SnO 2 powder, Ga 2 O 3 powder, and GeO 2 powder were prepared, and these powders were prepared to the mixing ratios described in Table 1 and mixed. . Next, this mixed powder was calcined, pulverized, dried and sieved in the same manner as in Example 1, and then this finely pulverized powder was hot-press sintered under the same conditions as in Example 1. Thereafter, this sintered body was finished into a sputtering target shape by machining. Next, sputtering was performed using the finished target. However, since the obtained target had a bulk resistance exceeding 500 kΩ · cm as shown in Table 1 and DC sputtering was difficult, RF sputtering was performed. The sputtering conditions were the same as in Comparative Example 3. As a result of confirming the chemical characteristics and the like of the film formation sample, as shown in Table 1, the film had high resistance and the alkali resistance was inferior.
（比較例６）
比較例６は、Ｉｎの含有量が本発明で規定する量より少ない（Ｉｎ／Ｔｉの比が小さい）例である。
ＺｎＯ粉、Ｉｎ２Ｏ３粉、ＴｉＯ２粉、ＳｎＯ２粉、Ｇａ２Ｏ３粉、ＧｅＯ２粉を準備し、これらの粉末を表１に記載される配合比に調合し、これを混合した。次に、この混合粉末を実施例１と同様に仮焼、粉砕、乾燥、篩分けを行った後、この微粉砕粉を実施例１と同様の条件でホットプレス焼結した。その後、この焼結体を機械加工でスパッタリングターゲット形状に仕上げた。次に、仕上げ加工したターゲットを使用して、スパッタリングを行った。スパッタ条件は、実施例１と同様とした。成膜サンプルの、化学的特性などについて確認した結果、表１に示す通り、膜が高抵抗となり、耐アルカリ性が劣る結果となった。
(Comparative Example 6)
Comparative Example 6 is an example in which the content of In is smaller than the amount specified in the present invention (the ratio of In / Ti is small).
ZnO powder, In 2 O 3 powder, TiO 2 powder, SnO 2 powder, Ga 2 O 3 powder, and GeO 2 powder were prepared, and these powders were prepared to the mixing ratios described in Table 1 and mixed. . Next, this mixed powder was calcined, pulverized, dried and sieved in the same manner as in Example 1, and then this finely pulverized powder was hot-press sintered under the same conditions as in Example 1. Thereafter, this sintered body was finished into a sputtering target shape by machining. Next, sputtering was performed using the finished target. The sputtering conditions were the same as in Example 1. As a result of confirming the chemical characteristics and the like of the film formation sample, as shown in Table 1, the film had high resistance and the alkali resistance was inferior.
（比較例７）
比較例７は、Ｉｎの含有量が本発明で規定する量よりも多い（Ｉｎ／Ｔｉの比が大きい）例である。
ＺｎＯ粉、Ｉｎ２Ｏ３粉、ＴｉＯ２粉、ＳｎＯ２粉、Ｇａ２Ｏ３粉、ＧｅＯ２粉を準備し、これらの粉末を表１に記載される配合比に調合し、これを混合した。次に、この混合粉末を実施例１と同様に仮焼、粉砕、乾燥、篩分けを行った後、この微粉砕粉を実施例１と同様の条件でホットプレス焼結した。その後、この焼結体を機械加工でスパッタリングターゲット形状に仕上げた。次に、仕上げ加工したターゲットを使用して、スパッタリングを行った。スパッタ条件は、実施例１と同様とした。成膜サンプルの、屈折率（波長５５０ｎｍ）、消衰係数（波長４０５ｎｍ）などについて測定した結果、表１に示す通り、消衰係数が０．０６と、所望の光学特性が得られなかった。
(Comparative Example 7)
Comparative Example 7 is an example in which the content of In is larger than the amount specified in the present invention (the ratio of In / Ti is large).
ZnO powder, In 2 O 3 powder, TiO 2 powder, SnO 2 powder, Ga 2 O 3 powder, and GeO 2 powder were prepared, and these powders were prepared to the mixing ratios described in Table 1 and mixed. . Next, this mixed powder was calcined, pulverized, dried and sieved in the same manner as in Example 1, and then this finely pulverized powder was hot-press sintered under the same conditions as in Example 1. Thereafter, this sintered body was finished into a sputtering target shape by machining. Next, sputtering was performed using the finished target. The sputtering conditions were the same as in Example 1. As a result of measuring the refractive index (wavelength 550 nm), extinction coefficient (wavelength 405 nm), etc. of the film formation sample, as shown in Table 1, the extinction coefficient was 0.06, and the desired optical characteristics were not obtained.
（比較例８）
比較例８は、Ｚｎの含有量が本発明で規定する量よりも少ない例である。
ＺｎＯ粉、Ｉｎ２Ｏ３粉、ＴｉＯ２粉、ＳｎＯ２粉、Ｇａ２Ｏ３粉、ＧｅＯ２粉を準備し、これらの粉末を表１に記載される配合比に調合し、これを混合した。次に、この混合粉末を実施例１と同様に仮焼、粉砕、乾燥、篩分けを行った後、この微粉砕粉を実施例１と同様の条件でホットプレス焼結した。その後、この焼結体を機械加工でスパッタリングターゲット形状に仕上げた。次に、仕上げ加工したターゲットを使用して、スパッタリングを行った。スパッタ条件は、実施例１と同様とした。成膜サンプルの、体積抵抗率、などを測定した結果、表１に示す通り、体積抵抗率が１×１０３Ω・ｃｍ超と、所望の導電性が得られなかった。
(Comparative Example 8)
Comparative Example 8 is an example in which the Zn content is less than the amount specified in the present invention.
ZnO powder, In 2 O 3 powder, TiO 2 powder, SnO 2 powder, Ga 2 O 3 powder, and GeO 2 powder were prepared, and these powders were prepared to the mixing ratios described in Table 1 and mixed. . Next, this mixed powder was calcined, pulverized, dried and sieved in the same manner as in Example 1, and then this finely pulverized powder was hot-press sintered under the same conditions as in Example 1. Thereafter, this sintered body was finished into a sputtering target shape by machining. Next, sputtering was performed using the finished target. The sputtering conditions were the same as in Example 1. As a result of measuring the volume resistivity and the like of the film formation sample, as shown in Table 1, the volume resistivity exceeded 1 × 10 3 Ω · cm, and the desired conductivity was not obtained.
本発明の焼結体は、スパッタリングターゲットとすることができ、スパッタリングターゲットを使用して形成された薄膜は、各種ディスプレイにおける透明導電膜や光ディスクの保護膜、光学調整用の膜として、透過率、屈折率、導電性、等において、極めて優れた特性を有するという効果がある。さらには、良エッチング性、耐候性（耐水性）、耐アルカリ性といった化学的特性を共存させることが出来るという効果がある。
また、本発明のスパッタリングターゲットは、バルク抵抗値が低く、相対密度が９０％以上と高密度であることから、安定したＤＣスパッタを可能とする。そして、このＤＣスパッタリングの特徴であるスパッタの制御性を容易にし、成膜速度を上げ、スパッタリング効率を向上させることができるという著しい効果がある。また、成膜の際にスパッタ時に発生するパーティクル（発塵）やノジュールを低減し、品質のばらつきが少なく量産性を向上させることができる。
The sintered body of the present invention can be used as a sputtering target, and the thin film formed using the sputtering target is used as a transparent conductive film in various displays, a protective film for optical disks, a film for optical adjustment, transmittance, There is an effect that it has extremely excellent characteristics in terms of refractive index, conductivity, and the like. Furthermore, there is an effect that chemical characteristics such as good etching property, weather resistance (water resistance), and alkali resistance can coexist.
Moreover, since the sputtering target of the present invention has a low bulk resistance value and a high relative density of 90% or more, stable DC sputtering is possible. And there is a remarkable effect that the controllability of sputtering, which is a feature of this DC sputtering, can be facilitated, the film forming speed can be increased, and the sputtering efficiency can be improved. In addition, particles (dust generation) and nodules generated during sputtering during film formation can be reduced, and quality variation can be reduced and mass productivity can be improved.
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| JP7425933B1 (en) | 2022-09-16 | 2024-01-31 | 株式会社アルバック | Sputtering target for forming an oxide semiconductor thin film, method for manufacturing a sputtering target for forming an oxide semiconductor thin film, oxide semiconductor thin film, thin film semiconductor device, and method for manufacturing the same |
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