JP6146773B2 - Oxide sintered body and manufacturing method thereof - Google Patents
Oxide sintered body and manufacturing method thereof Download PDFInfo
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- JP6146773B2 JP6146773B2 JP2013242686A JP2013242686A JP6146773B2 JP 6146773 B2 JP6146773 B2 JP 6146773B2 JP 2013242686 A JP2013242686 A JP 2013242686A JP 2013242686 A JP2013242686 A JP 2013242686A JP 6146773 B2 JP6146773 B2 JP 6146773B2
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- 238000004519 manufacturing process Methods 0.000 title claims description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 56
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 238000005245 sintering Methods 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 description 47
- 239000000843 powder Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 19
- 229910003437 indium oxide Inorganic materials 0.000 description 18
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 18
- 239000002994 raw material Substances 0.000 description 17
- 238000004544 sputter deposition Methods 0.000 description 16
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 239000010408 film Substances 0.000 description 14
- 229910052738 indium Inorganic materials 0.000 description 14
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 13
- 229910052726 zirconium Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005477 sputtering target Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- 230000002159 abnormal effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 229910006404 SnO 2 Inorganic materials 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- NQBRDZOHGALQCB-UHFFFAOYSA-N oxoindium Chemical compound [O].[In] NQBRDZOHGALQCB-UHFFFAOYSA-N 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011324 bead Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000002706 hydrostatic effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- MMTGNODXMIZDKS-UHFFFAOYSA-N [O].[Zr].[In] Chemical compound [O].[Zr].[In] MMTGNODXMIZDKS-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- ZEWMZYKTKNUFEF-UHFFFAOYSA-N indium;oxozinc Chemical compound [In].[Zn]=O ZEWMZYKTKNUFEF-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
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Description
本発明は酸化インジウム系酸化物焼結体及びその製造方法に関する。 The present invention relates to an indium oxide-based oxide sintered body and a method for producing the same.
酸化インジウムを成分とする酸化物焼結体には各種のものが有るが、その中でもインジウム−スズ−酸素からなるＩＴＯ(Indium tin oxide)は、液晶表示装置等の各種のフラットパネルディスプレイ装置に最も広く使用されている透明導電体である。 There are various oxide sintered bodies containing indium oxide as a component. Among them, ITO (Indium tin oxide) composed of indium-tin-oxygen is the most suitable for various flat panel display devices such as liquid crystal display devices. It is a widely used transparent conductor.
透明導電体の用途は、フラットパネルディスプレイ以外にも各種有るが、その中でも、近年は太陽電池の光入射面側の窓層電極材料としての需要が高まってきている。ＩＴＯを太陽電池の窓層電極材料に使用すると、ＩＴＯは低抵抗率である利点の反面、キャリア濃度が高いために、波長１２００ｎｍ付近以上の長波長領域における透過率が劣り、太陽光の長波長領域を有効に利用できないので、太陽電池の変換効率が悪くなってしまう問題がある。 There are various uses of the transparent conductor other than the flat panel display. Among them, in recent years, the demand for the window layer electrode material on the light incident surface side of the solar cell is increasing. When ITO is used as a window layer electrode material for solar cells, while ITO has the advantage of low resistivity, the carrier concentration is high, resulting in poor transmittance in the long wavelength region of wavelength near 1200 nm or longer, and the long wavelength of sunlight. Since the area cannot be used effectively, there is a problem that the conversion efficiency of the solar cell deteriorates.
そこで、最近はＩＴＯに代わる太陽電池窓層の材料として、インジウム−酸素(Ｉｎ2Ｏ3、Indium oxide)に水素を添加したもの（非特許文献１）、インジウム−ジルコニウム−酸素(Ｉｎ2Ｏ3：Ｚｒ)からなるもの（非特許文献２）等が提案されている。これらの材料は、抵抗率はＩＴＯとほぼ同等であるが、電子移動度が高いために、キャリア濃度を低く抑えることができるので、長波長領域における透過率の低下を抑制することができる利点を有している。 Therefore, recently, as a material for a solar cell window layer replacing ITO, indium-oxygen (In 2 O 3 , Indium oxide) in which hydrogen is added (Non-patent Document 1), indium-zirconium-oxygen (In 2 O 3). : Zr) (Non-Patent Document 2) and the like have been proposed. These materials have almost the same resistivity as that of ITO, but since the electron mobility is high, the carrier concentration can be kept low, so that the reduction in transmittance in the long wavelength region can be suppressed. Have.
しかしながら、これらの先行技術文献には材料の光学的、電気的特性に関する記載はあるものの、産業上の使用にあたっては、大面積に均一に成膜することができるスパッタリング法での製造方法が適切であり、そのためにはこれらの材料の焼結体が、スパッタリングターゲットとして必要な特性を有することが重要であるが、ターゲット特性に関しては一切記載がない。 However, although these prior art documents describe the optical and electrical properties of materials, a manufacturing method using a sputtering method that can form a film uniformly over a large area is appropriate for industrial use. For this purpose, it is important that the sintered body of these materials has characteristics necessary as a sputtering target, but there is no description regarding target characteristics.
スパッタリングターゲットとして必要な特性には各種のものが有るが、その中でも焼結体の密度は重要である。密度が低いとスパッタ成膜当初は、特に問題が無い場合であっても、スパッタを長時間し続けていくと、ターゲット表面に黒色の突起物であるノジュールが生成されるようになり、ノジュール部分は高抵抗であるために、その部分を起点として、異常放電が起こり、スパッタを継続できなくなったり、作製された膜にパーティクルが付着したりして良好な膜を得ることができなくなったりする。 There are various properties required as a sputtering target, and among these, the density of the sintered body is important. If the density is low, even when there is no particular problem at the beginning of sputter deposition, if the sputtering is continued for a long time, nodules that are black projections are generated on the target surface, and nodule parts Because of the high resistance, abnormal discharge occurs from that portion, and sputtering cannot be continued, or particles adhere to the produced film and a good film cannot be obtained.
ＩＴＯの高密度化については、これまで色々な報告があり（特許文献１）、高密度化がなされてきているが、上記のインジウム−酸素からなるターゲット及びインジウム−ジルコニウム−酸素からなるターゲットについては、高密度の焼結体が得られていないのが現状である。 Regarding the densification of ITO, there have been various reports so far (Patent Document 1), and the densification has been made. Regarding the above-mentioned target composed of indium-oxygen and the target composed of indium-zirconium-oxygen. At present, a high-density sintered body has not been obtained.
また、近年酸化インジウムを成分とする酸化物焼結体の中で、インジウム−ガリウム−亜鉛−酸素(Ｉｎ2Ｏ3−ＺｎＯ−Ｇａ2Ｏ3：ＩＧＺＯ)が、透明半導体用材料として注目を集めている（非特許文献３）。
この材料はアモルファスシリコンより移動度が高いという他に、室温での成膜が可能であり、非晶質であることから表面平坦性に優れる等の利点を有している。この材料はターゲットのスパッタ成膜によって薄膜を得ることができるので、ターゲットの密度が高いことが重要であるが、これまで高密度のターゲットを得ることはできなかった。
In recent years, indium-gallium-zinc-oxygen (In 2 O 3 —ZnO—Ga 2 O 3 : IGZO) attracts attention as a transparent semiconductor material among oxide sintered bodies containing indium oxide as a component. (Non-patent Document 3).
In addition to having a higher mobility than amorphous silicon, this material has advantages such as being capable of film formation at room temperature and being excellent in surface flatness because it is amorphous. Since this material can obtain a thin film by sputtering deposition of a target, it is important that the target has a high density, but until now it has not been possible to obtain a high-density target.
本発明に関連する従来技術としては、ＩＴＯに銅等を添加するもの（特許文献１）、インジウム−亜鉛−酸素(Ｉｎ2Ｏ3−ＺｎＯ：ＩＺＯ）にスズを添加するもの（特許文献１）、ＩＧＺＯ（インジウム−ガリウム−亜鉛−酸素）にスズを添加するもの（特許文献３、４）、酸化インジウム含有水酸化物中に錫が含有されたもの（特許文献５）等が知られているが、これらに開示されている発明と本発明との差異については後述する。 Prior arts related to the present invention include adding copper or the like to ITO (Patent Document 1), adding tin to indium-zinc-oxygen (In 2 O 3 —ZnO: IZO) (Patent Document 1). , IGZO (indium-gallium-zinc-oxygen) added with tin (Patent Documents 3 and 4), indium oxide-containing hydroxide containing tin (Patent Document 5), etc. However, the difference between the invention disclosed therein and the present invention will be described later.
本発明は、酸化インジウムを成分とする高密度酸化物焼結体及びその製造方法を提供することを目的とする。 An object of this invention is to provide the high-density oxide sintered compact which uses indium oxide as a component, and its manufacturing method.
本発明者らは鋭意研究した結果、酸化インジウムを成分とする酸化物焼結体にスズを適切濃度添加することで、酸化粒焼結体の密度を高くすることができることを見出し、本発明を完成させた。
本発明によれば、以下の酸化物焼結体及びこれらの製造方法が提供できる。
As a result of diligent research, the present inventors have found that the density of an oxide grain sintered body can be increased by adding an appropriate concentration of tin to an oxide sintered body containing indium oxide as a component. Completed.
According to the present invention, the following oxide sintered bodies and methods for producing them can be provided.
１．添加元素としてスズを含有するＩｎ2Ｏ3焼結体であって、スズの原子数の、焼結体中の全金属元素の原子数の総和に対する比率が０．０１〜０．２％であり、相対密度が９８％以上であることを特徴とするＩｎ2Ｏ3焼結体、
２．上記添加元素に加えて、ジルコニウムを含有するＩｎ2Ｏ3焼結体であって、ジルコニウムの原子数の、焼結体中の全金属元素の原子数の総和に対する比率が０．５〜８％であり、相対密度が９８％以上であることを特徴とする上記１に記載のＩｎ2Ｏ3焼結体、
３．添加元素としてスズを含有するＩｎ2Ｏ3−ＺｎＯ−Ｇａ2Ｏ3焼結体であって、スズの原子数の、焼結体中の全金属元素の原子数の総和に対する比率が０．０１〜０．２％であり、相対密度が９８％以上であることを特徴とするＩｎ2Ｏ3−ＺｎＯ−Ｇａ2Ｏ3焼結体、
４．上記焼結体をＩｎxＧａyＺｎzＯaと表した時に、０．２≦ｘ／（ｘ＋ｙ）≦０．８、０．１≦ｚ／（ｘ＋ｙ＋ｚ）≦０．５、ａ＝（３／２）ｘ＋（３／２）ｙ＋ｚの範囲にあることを特徴とする上記３に記載のＩｎ2Ｏ3−ＺｎＯ−Ｇａ2Ｏ3焼結体
５．上記焼結体を、酸素雰囲気中、焼結温度１４００〜１５００℃で焼結して製造することを特徴とする上記１〜５のいずれか一に記載の焼結体の製造方法。
1. In 2 O 3 sintered body containing tin as an additive element, the ratio of the number of tin atoms to the total number of atoms of all the metal elements in the sintered body is 0.01 to 0.2% In 2 O 3 sintered body characterized by having a relative density of 98% or more,
2. In 2 O 3 sintered body containing zirconium in addition to the additive elements, the ratio of the number of zirconium atoms to the total number of atoms of all metal elements in the sintered body is 0.5 to 8% The In 2 O 3 sintered body according to 1 above, wherein the relative density is 98% or more,
3. In 2 O 3 —ZnO—Ga 2 O 3 sintered body containing tin as an additive element, the ratio of the number of atoms of tin to the total number of atoms of all metal elements in the sintered body is 0.01 In 2 O 3 —ZnO—Ga 2 O 3 sintered body, characterized in that it has a relative density of not less than 0.2% and a relative density of 98% or more,
4). When the sintered body is expressed as In x Ga y Zn z O a , 0.2 ≦ x / (x + y) ≦ 0.8, 0.1 ≦ z / (x + y + z) ≦ 0.5, a = (3 / 2) In 2 O 3 —ZnO—Ga 2 O 3 sintered body according to 3 above, which is in the range of x + (3/2) y + z. 6. The method for producing a sintered body according to any one of 1 to 5, wherein the sintered body is produced by sintering at a sintering temperature of 1400 to 1500 ° C. in an oxygen atmosphere.
本発明によれば、高密度の酸化物焼結体が提供できるので、これらの焼結体をスパッタリングターゲットとして使用した際に、長時間のスパッタ後においても、ターゲット表面のノジュールの発生を抑制することができ、スパッタ時の異常放電や膜へのパーティクル発生等の防止効果があるという優れた効果を有する。 According to the present invention, since a high-density oxide sintered body can be provided, when these sintered bodies are used as a sputtering target, generation of nodules on the target surface is suppressed even after long-time sputtering. It has an excellent effect that it has an effect of preventing abnormal discharge during sputtering and generation of particles on the film.
酸化物焼結体中における添加元素の含有量は、添加元素の原子数の、焼結体中の全金属元素の原子数の総和に対する比率で規定する。
例えば、インジウム−酸素からなる酸化物焼結体にスズを添加した場合には、焼結体中に含まれる全金属元素はインジウムとスズになるので、インジウムの原子数をＩｎ、スズの原子数をＳｎで表すと、｛Ｓｎ／（Ｉｎ＋Ｓｎ）×１００｝が、スズの原子数の、焼結体中の全金属元素の原子数の総和に対する比率となる。
同様に、インジウム−酸素からなる酸化物焼結体にスズに加えてジルコニウムを添加した場合には、焼結体中に含まれる全金属元素はインジウムとスズとジルコニウムになるので、インジウムの原子数をＩｎ、スズの原子数をＳｎ、ジルコニウムの原子数をＺｒで表すと、｛Ｚｒ／（Ｉｎ＋Ｓｎ＋Ｚｒ）×１００｝が、ジルコニウムの原子数の、焼結体中の全金属元素の原子数の総和に対する比率となる。
また、インンジウム−ガリウム−亜鉛−酸素からなる酸化物焼結体にスズを添加した場合には、焼結体中に含まれる全金属元素はインジウム、ガリウム、亜鉛、スズになるので、インジウムの原子数をＩｎ、ガリウムの原子数をＧａ、亜鉛の原子数をＺｎ、スズの原子数をＳｎで表すと、[Ｓｎ／(Ｉｎ＋Ｇａ＋Ｚｎ＋Ｓｎ)×１００]が、スズの原子数の、焼結体中の全金属元素の原子数の総和に対する比率となる。
The content of the additive element in the oxide sintered body is defined by the ratio of the number of atoms of the additive element to the total number of atoms of all the metal elements in the sintered body.
For example, when tin is added to an oxide sintered body made of indium-oxygen, all metal elements contained in the sintered body are indium and tin, so that the number of indium atoms is In, the number of tin atoms Is represented by Sn, {Sn / (In + Sn) × 100} is the ratio of the number of tin atoms to the total number of atoms of all metal elements in the sintered body.
Similarly, when adding zirconium in addition to tin to an oxide sintered body made of indium-oxygen, all metal elements contained in the sintered body are indium, tin, and zirconium. In, Sn represents the number of tin atoms, and Zr represents the number of zirconium atoms, {Zr / (In + Sn + Zr) × 100} is the sum of the number of atoms of zirconium and the total number of atoms of all metal elements in the sintered body. It becomes the ratio to.
In addition, when tin is added to an oxide sintered body made of indium-gallium-zinc-oxygen, all metal elements contained in the sintered body are indium, gallium, zinc, and tin. When the number is In, the number of gallium atoms is Ga, the number of zinc atoms is Zn, and the number of tin atoms is Sn, [Sn / (In + Ga + Zn + Sn) × 100] is the number of tin atoms in the sintered body. This is the ratio of the total number of atoms of all metal elements.
本発明の酸化物焼結体において、焼結体中におけるスズの原子数の比率は０．０１〜０．２％であることが望ましい。スズの比率が０．０１％未満では、焼結体密度向上効果が小さくなるからである。一方、スズの比率が０．２％を超えると、焼結体密度向上効果が飽和するだけでなく、添加されたスズが電気的なドーパントの役割をしていることから、Ｉｎ2Ｏ3焼結体やＩｎ2Ｏ3：Ｚｒ焼結体への添加の場合には、スズから供給される電子が多くなり、キャリア濃度の増加によって長波長領域の透過率が低減することになる。また、ＩＧＺＯへの添加の場合にも、キャリア濃度の増加によって、半導体的特性が導電体的特性となり、作製されたトランジスタのｏｎ／ｏｆｆ比を悪化させることがある。
さらに、このような特性をより良好なものとするためには、スズの比率は、好ましくは０．０５〜０．２％、更に好ましくは０．０８〜０．２％とする。
In the oxide sintered body of the present invention, the ratio of the number of tin atoms in the sintered body is desirably 0.01 to 0.2%. This is because if the tin ratio is less than 0.01%, the effect of improving the density of the sintered body is reduced. On the other hand, when the ratio of tin exceeds 0.2%, not only the density of the sintered improving effect is saturated, since the tin is added is the role of electrical dopant, an In 2 O 3 sintered In the case of addition to a sintered body or an In 2 O 3 : Zr sintered body, more electrons are supplied from tin, and the transmittance in the long wavelength region is reduced by increasing the carrier concentration. In addition, in the case of addition to IGZO, an increase in the carrier concentration may make the semiconductor characteristics become conductive characteristics and deteriorate the on / off ratio of the manufactured transistor.
Furthermore, in order to make such characteristics better, the ratio of tin is preferably 0.05 to 0.2%, and more preferably 0.08 to 0.2%.
本発明の酸化物焼結体において、焼結体中におけるジルコニウムの比率は０．５〜８％であることが好ましい。ジルコニウムの比率が０．５％未満では、ジルコニウムから放出される電子数が少なく、導電性が良くならないからである。一方、ジルコニウムの比率が８％を超えると、ジルコニウムからの放出電子が飽和して、ジルコニウムが中性不純物散乱要因として働くようになり、電子移動度を低下させて、導電性を低下させてしまうからである。 In the oxide sintered body of the present invention, the ratio of zirconium in the sintered body is preferably 0.5 to 8%. This is because when the zirconium ratio is less than 0.5%, the number of electrons emitted from zirconium is small, and the conductivity is not improved. On the other hand, if the proportion of zirconium exceeds 8%, the electrons emitted from the zirconium are saturated and the zirconium acts as a neutral impurity scattering factor, lowering the electron mobility and lowering the conductivity. Because.
ＩＧＺＯの組成範囲は、ＩｎxＧａyＺｎzＯaとした時、０．２≦ｘ／（ｘ＋ｙ）≦０．８、０．１≦ｚ／（ｘ＋ｙ＋ｚ）≦０．５、ａ＝（３／２）ｘ＋（３／２）ｙ＋ｚであることが好ましい。インジウムの比率がこの範囲より高いと、スパッタ膜のキャリア濃度が増加して素子特性であるｏｎ／ｏｆｆ比が悪くなる。一方、インジウムの比率がこの範囲より低いと、スパッタ膜の移動度が低下し、素子特性を悪くする。
なお、酸素の原子数比を上式のようにａ＝（３／２）ｘ＋（３／２）ｙ＋ｚと規定しているが、実際は、酸素欠損のためこれより若干小さいものとなる。しかし、その厳密な定量化は困難であるため、本願発明ではこのような規定としているが、これは通常の製造方法で製造された通常含む程度の酸素欠陥を有する場合も包含することは言うまでもない。
The composition range of IGZO is 0.2 ≦ x / (x + y) ≦ 0.8, 0.1 ≦ z / (x + y + z) ≦ 0.5, a = (3 when In x Ga y Zn z O a is used. / 2) x + (3/2) y + z. When the ratio of indium is higher than this range, the carrier concentration of the sputtered film increases and the on / off ratio, which is a device characteristic, is deteriorated. On the other hand, when the ratio of indium is lower than this range, the mobility of the sputtered film is lowered and the device characteristics are deteriorated.
In addition, although the atomic ratio of oxygen is defined as a = (3/2) x + (3/2) y + z as in the above equation, it is actually slightly smaller than this due to oxygen deficiency. However, since strict quantification is difficult, the present invention defines such a provision, but it is needless to say that this also includes a case where oxygen defects that are normally included in the manufacturing method are included. .
亜鉛の比率がこの範囲より高いと、膜の安定性や耐湿性が劣化する。一方、亜鉛の比率がこの範囲より低いと、スパッタ膜の非晶質性が悪くなり、結晶化してしまって素子特性が劣化する。 When the ratio of zinc is higher than this range, the stability and moisture resistance of the film deteriorate. On the other hand, if the ratio of zinc is lower than this range, the amorphousness of the sputtered film is deteriorated and crystallized to deteriorate device characteristics.
酸化インジウムを主成分等とする酸化物焼結体に微量金属元素を添加する技術に関してはいくつかの報告があるが、本発明との技術的相違について以下に説明する。 There are several reports regarding the technique of adding trace metal elements to an oxide sintered body containing indium oxide as a main component, but the technical differences from the present invention will be described below.
特許文献１には、ＩＴＯに亜鉛等の金属元素を添加することで、高密度のＩＴＯ焼結体が得られることが示されている。しかしながら、この技術はあくまで、酸化インジウムと酸化スズの重量比が約９０：１０と、スズが酸化物焼結体中に構成要素元素と言える程度まで高濃度に添加されているＩＴＯについての焼結密度の向上に関する技術であり、本発明は、これとは異なり、ＩＴＯの様にスズが構成元素として含有されていないＩｎ2Ｏ3やＩｎ2Ｏ3：ＺｒやＩＧＺＯの高密度化のために、スズを微量に添加する点で、明らかに異なる発明である。 Patent Document 1 shows that a high-density ITO sintered body can be obtained by adding a metal element such as zinc to ITO. However, this technique is only about 90:10 in weight ratio of indium oxide and tin oxide, and sintering of ITO in which tin is added at a high concentration to the extent that it can be said that it is a constituent element in the oxide sintered body. In contrast to this, the present invention is a technique for improving the density. In order to increase the density of In 2 O 3 or In 2 O 3 : Zr or IGZO that does not contain tin as a constituent element like ITO. The invention is clearly different in that a small amount of tin is added.
特許文献２には、ＩＺＯに微量のスズを添加することで、ＩＺＯスパッタリングターゲットのバルク抵抗を低下させる技術が示されている。しかしながら、この技術はスズを電気的ドーパントとして作用させる効果を利用したものであり、実施例の試料Ｎｏ．１０１〜Ｎｏ．１０３の結果からは、確かにスズの添加濃度が増加するにつれて、バルク抵抗が低下していくことが示されているが、焼結体の密度に関しては、逆にスズの添加濃度が増加するにつれて小さくなっている。 Patent Document 2 discloses a technique for reducing the bulk resistance of an IZO sputtering target by adding a small amount of tin to IZO. However, this technique utilizes the effect of allowing tin to act as an electrical dopant. 101-No. The results of No. 103 show that the bulk resistance decreases as the tin concentration increases, but as regards the density of the sintered body, conversely as the tin concentration increases. It is getting smaller.
つまり、ＩＺＯに関しては、スズ添加は焼結体の密度向上には逆効果であることが示されているのであって、単に酸化インジウムを主成分等とする酸化物焼結体にスズを添加すれば、焼結体密度向上効果が得られるのではなく、酸化インジウムのみならず、他の構成元素の種類や濃度によっては、スズ添加の効果は色々であり、本発明において、初めてある特定の酸化インジウムを主成分等とする酸化物焼結体にスズを添加することで、酸化物焼結体の密度向上効果が得られることが見出されたのであり、またその様な効果が得られることは、先行技術から示唆されることはなく、逆に単にスズを添加するのみでは、焼結体密度を低下させることが有ることが示されているため、着想の阻害要因となっていたのである。 In other words, regarding IZO, tin addition has been shown to have an adverse effect on improving the density of the sintered body, and simply adding tin to an oxide sintered body mainly composed of indium oxide. For example, the effect of improving the density of the sintered body is not obtained, but depending on the type and concentration of not only indium oxide but also other constituent elements, there are various effects of tin addition. It has been found that by adding tin to an oxide sintered body containing indium as a main component, an effect of improving the density of the oxide sintered body can be obtained, and such an effect can be obtained. Is not suggested by the prior art, and conversely, simply adding tin has been shown to reduce the density of the sintered body, which was a hindrance to the idea. .
特許文献３には、ＩＧＺＯにスズ等の正四価以上の金属を所定濃度添加することで、スパッタリングターゲットのバルク抵抗が低減できる技術が示されている。
しかしながら、この技術もスズの電気的ドーパント効果を利用したものである。実施例１及び比較例１には焼結体密度がそれぞれ６．１２ｇ／ｃｍ3、５．９８ｇ／ｃｍ3であったことが記載されているが、その他の実施例や比較例では、焼結体密度についての記載が全くないので、スズ添加によって焼結体密度が本当に増加するのかどうかについては全く不明である。
Patent Document 3 discloses a technique that can reduce the bulk resistance of a sputtering target by adding a predetermined concentration of a positive tetravalent or higher metal such as tin to IGZO.
However, this technique also uses the electric dopant effect of tin. Example 1 and sintered densities respectively in Comparative Examples 1 6.12 g / cm 3, although it is described that was 5.98 g / cm 3, in other embodiments and comparative examples, sintering Since there is no description about the body density, it is completely unknown whether or not the sintered body density really increases by adding tin.
更に、上記の焼結体密度はＩｎＧａＺｎＯ4の理論結密度は６．３７９ｇ／ｃｍ3であることから、相対密度としては、それぞれ９５．９％、９３．７％とスパッタリングターゲットとしてはさほど高密度とはいえないものである。
これは、後述するようにこの技術でのターゲット作製プロセス条件が、本発明のプロセス条件とは異なっているためであり、本発明のプロセス条件及びスズの適切添加濃度によって、焼結体の相対密度が９８％以上と非常に高密度のＩＧＺＯ焼結体が、初めて得られるようになったのである。
Furthermore, since the above sintered body density is 6.379 g / cm 3 for InGaZnO 4 , the relative density is 95.9% and 93.7%, respectively, which are very high as a sputtering target. It cannot be said.
This is because the target production process conditions in this technique are different from the process conditions of the present invention as will be described later, and the relative density of the sintered body depends on the process conditions of the present invention and the appropriate concentration of tin. The IGZO sintered body having a very high density of 98% or more can be obtained for the first time.
特許文献４には、特許文献３と同様に、ＩＧＺＯにスズ等の正四価以上の金属を所定濃度添加することで、スパッタリングターゲットのバルク抵抗が低減できる技術が示されている。
しかしながら、この技術もスズの電気的ドーパント効果を利用したものである。実施例１及び比較例１には焼結体密度がそれぞれ６．０６ｇ／ｃｍ3、５．８５ｇ／ｃｍ3であったことが記載されているが、その他の実施例や比較例では、焼結体密度についての記載が全くないので、スズ添加によって焼結体密度が本当に増加するのかどうかについては全く不明である。
Patent Document 4 discloses a technique in which, as in Patent Document 3, a bulk resistance of a sputtering target can be reduced by adding a predetermined concentration of a positive tetravalent or higher metal such as tin to IGZO.
However, this technique also uses the electric dopant effect of tin. Example 1 and sintered densities respectively in Comparative Examples 1 6.06 g / cm 3, although it is described that was 5.85 g / cm 3, in other embodiments and comparative examples, sintering Since there is no description about the body density, it is completely unknown whether or not the sintered body density really increases by adding tin.
特許文献５には、インジウム含有水酸化物中の錫濃度を５０質量ｐｐｍ以下とすることが示されている。しかしながら、この技術はインジウム含有水溶液中に、鉛や錫などの金属が不純物として含まれている場合に、これらの不純物金属を析出させ、残渣として回収することにより、インジウム含有水酸化物における錫の残留量を少なくするというもので、焼結体密度の向上を図るために積極的にスズを添加するというものではない。 Patent Document 5 shows that the tin concentration in the indium-containing hydroxide is 50 mass ppm or less. However, in this technique, when a metal such as lead or tin is contained as an impurity in the indium-containing aqueous solution, these impurity metals are precipitated and recovered as a residue, whereby the tin in the indium-containing hydroxide is recovered. This is to reduce the residual amount, and not to add tin positively in order to improve the density of the sintered body.
本発明の酸化物焼結体は、各種原料粉の混合、粉砕、焼結等のプロセスによって作製することができる。例えば、ＩＧＺＯ焼結体の場合は、以下の様にして作製できる。
原料粉としては、酸化インジウム（Ｉｎ2Ｏ3）、酸化ガリウム（Ｇａ2Ｏ3）、酸化亜鉛（ＺｎＯ）、及び酸化スズ（ＳｎＯ2）であって、比表面積が約１０ｍ2／ｇ程度のものを使用するのが好ましい。比表面積が小さいと、粒径が大きいということであり、焼結体の密度が充分に高くならない。
また、一般的には比表面積が大きい方が、焼結体密度は高くなる傾向はあるが、これ以上更に大きくすることのみでは、焼結性の向上効果は飽和するとともに、原料粉自体の価格も高くなり、経済的ではない。
The oxide sintered body of the present invention can be produced by a process such as mixing, pulverization, and sintering of various raw material powders. For example, in the case of an IGZO sintered body, it can be produced as follows.
The raw material powder is indium oxide (In 2 O 3 ), gallium oxide (Ga 2 O 3 ), zinc oxide (ZnO), and tin oxide (SnO 2 ), and the specific surface area is about 10 m 2 / g. It is preferable to use one. When the specific surface area is small, the particle size is large, and the density of the sintered body is not sufficiently high.
In general, the larger the specific surface area, the higher the density of the sintered body tends to be. However, the effect of improving the sinterability is saturated only by further increasing the density, and the price of the raw material powder itself. It is also expensive and not economical.
原料粉間の比表面積の差は、必ずしも同じである必要はなく、逆に、多少の差が有る方が焼結体密度増加の効果がある場合もある。比表面積が同じ方が効率的な混合等に有利である場合もあるが、仮焼を実施する場合は、比表面積に差がある程度あったほうが、より良く仮焼が進む場合もあり、比表面積差が５ｍ2／ｇ程度までは何ら問題がない。 The difference in specific surface area between the raw material powders is not necessarily the same, and conversely, if there is a slight difference, the sintered body density may be increased. In some cases, the same specific surface area may be advantageous for efficient mixing, but when calcining, there is a case where the calcining proceeds better if there is a difference in specific surface area. There is no problem until the difference is about 5 m 2 / g.
原料粉を所望の組成比となるように秤量後、混合を行う。混合が不充分であると、製造したターゲット中に各成分が偏析して、高抵抗率領域と低抵抗率領域が存在することになり、スパッタ成膜時に高抵抗率領域での帯電等によるアーキングなどの異常放電の原因となってしまうので、充分な混合が必要である。 The raw material powder is weighed so as to have a desired composition ratio, and then mixed. Insufficient mixing causes each component to segregate in the manufactured target, resulting in a high resistivity region and a low resistivity region, and arcing due to charging in the high resistivity region during sputtering deposition. Therefore, sufficient mixing is necessary.
そのためには例えば、スーパーミキサーで、大気中、回転数２０００〜４０００ｒｐｍ、回転時間３〜５分混合する。原料紛は酸化物であるために雰囲気ガスは、特に原料の酸化を防止する必要がないので、アルゴン等の高価なガスを使用する必要は無く、大気でかまわない。混合方法としては他にボールミルによる長時間混合等の方法でも良く、その他の方法でも原料の均一混合という趣旨を実現できる方法であればかまわない。 For this purpose, for example, in a supermixer, the number of rotations is 2000 to 4000 rpm and the rotation time is 3 to 5 minutes. Since the raw material powder is an oxide, the atmospheric gas does not need to prevent the oxidation of the raw material in particular. Therefore, it is not necessary to use an expensive gas such as argon, and the atmospheric gas may be used. The mixing method may be a method such as long-time mixing using a ball mill, or any other method as long as it can achieve the purpose of uniform mixing of raw materials.
次に、混合粉を電気炉にて、大気雰囲気中で、９００〜１１００℃の温度範囲で、４〜６時間程度保持することで、混合粉の仮焼を行う。仮焼は高温で揮発し易い酸化亜鉛を酸化ガリウムと反応させて、揮発し難いスピネル等に変化させて、焼結体密度を向上させる効果がある。
但し、焼結条件を含めたターゲット製造プロセス条件の適正化によっては必ずしも、仮焼を行わなくても、高密度焼結体を得ることができる場合もあるので、仮焼の工程は必須ではない。
Next, the mixed powder is calcined in an electric furnace in an air atmosphere at a temperature range of 900 to 1100 ° C. for about 4 to 6 hours. Calcination has the effect of improving the density of the sintered body by reacting zinc oxide, which is easily volatilized at high temperature, with gallium oxide and changing it to spinel or the like which is difficult to volatilize.
However, depending on the optimization of the target manufacturing process conditions including the sintering conditions, a high-density sintered body may be obtained without necessarily performing the calcination, so the calcination step is not essential. .
次に、微粉砕を行う。これは原料紛の各組成のターゲット中での均一分散化するためである。充分に微粉砕が行われないと、粒径の大きい原料粉が存在することになり、場所により組成むらが生じてしまい、スパッタ成膜時の異常放電の原因となる。仮焼粉をアトライターにジルコニアビーズと共に投入し、回転数２００〜４００ｒｐｍ、回転時間２〜４時間微粉砕を行う。
微粉砕は原料紛の粒径が、平均粒径（Ｄ５０）１μｍ以下、好ましくは０．６μｍ以下となるまで行うことが望ましい。
Next, pulverization is performed. This is because the raw material powder is uniformly dispersed in the target of each composition. If fine pulverization is not performed sufficiently, raw material powder having a large particle size will be present, resulting in uneven composition depending on the location, causing abnormal discharge during sputter deposition. The calcined powder is put into an attritor together with zirconia beads and finely pulverized at a rotation speed of 200 to 400 rpm and a rotation time of 2 to 4 hours.
The fine pulverization is desirably performed until the particle size of the raw material powder becomes 1 μm or less, preferably 0.6 μm or less, of the average particle size (D50).
次に、造粒を行う。これは、原料紛の流動性を良くして、プレス成型時の充填状況を充分良好なものにするためである。微粉砕した原料を固形分４０〜６０％のスラリーとなるように水分量を調整して造粒を行う。この際、入口温度は１８０〜２２０℃、出口温度は１１０〜１３０℃に設定する。 Next, granulation is performed. This is to improve the flowability of the raw material powder and to make the filling state at the time of press molding sufficiently good. Granulation is performed by adjusting the amount of moisture so that the finely pulverized raw material becomes a slurry having a solid content of 40 to 60%. At this time, the inlet temperature is set to 180 to 220 ° C, and the outlet temperature is set to 110 to 130 ° C.
次に、プレス成型を行う。造粒粉を４００〜８００ｋｇｆ／ｃｍ2の面圧、１〜３分保持の条件でプレス成形する。面圧力４００ｋｇｆ／ｃｍ2未満であると、充分な密度の成形体を得ることができず、面圧力８００ｋｇｆ／ｃｍ2超にする必要も無く、無駄なコストやエネルギーを要するので生産上好ましくない。 Next, press molding is performed. The granulated powder is press-molded under a condition of a surface pressure of 400 to 800 kgf / cm 2 and a hold of 1 to 3 minutes. If the surface pressure is less than 400 kgf / cm 2 , a molded body having a sufficient density cannot be obtained, and it is not necessary to increase the surface pressure to over 800 kgf / cm 2 , and wasteful cost and energy are required, which is not preferable in production.
次に、静水圧加圧装置（ＣＩＰ）で１７００〜１９００ｋｇｆ／ｃｍ2の面圧、１〜３分保持の条件で成形する。そして、電気炉にて酸素雰囲気中、昇温速度０．５〜２．０℃／ｍｉｎで７００〜９００℃まで昇温後、４〜６時間保持、その後、昇温速度０．５〜５．０℃／ｍｉｎで１４００〜１５００℃まで昇温後、１０〜３０時間保持、その後、炉冷または降温速度２．０〜５．０℃／ｍｉｎで降温する。この場合、焼結温度が１４００℃より低いと、焼結体が高密度とならないが、一方、１５００℃を超えると、酸化亜鉛の揮発等が起こり、焼結密度の低下や組成ずれが生じてしまう。また、炉ヒーター寿命が低下してしまうというコスト的問題もある。 Next, it shape | molds on the conditions of a surface pressure of 1700-1900kgf / cm < 2 >, and hold | maintaining for 1 to 3 minutes with a hydrostatic pressure pressurization apparatus (CIP). And it heats up to 700-900 degreeC by the temperature rising rate of 0.5-2.0 degreeC / min in oxygen atmosphere with an electric furnace, Then, it hold | maintains for 4-6 hours, Then, temperature rising speed of 0.5-5. After raising the temperature to 1400-1500 ° C. at 0 ° C./min, the temperature is maintained for 10-30 hours, and then the temperature is lowered at a furnace cooling rate or a cooling rate of 2.0-5.0 ° C./min. In this case, if the sintering temperature is lower than 1400 ° C., the sintered body does not become high density. On the other hand, if it exceeds 1500 ° C., volatilization of zinc oxide occurs, resulting in a decrease in sintering density and composition shift. End up. There is also a cost problem that the life of the furnace heater is reduced.
焼結温度における保持時間が１０時間より短いと、原料紛間の反応が充分進まず、焼結体の密度が充分高くならなかったり、焼結体が反ってしまったりする。焼結時間が３０時間を越えても、不必要なエネルギーと時間を要する無駄が生じて生産上好ましくない。
昇温速度が０．５℃／分より小さいと、所定温度になるまでに不必要に時間を要してしまい、昇温速度が５．０℃／分より大きいと、炉内の温度分布が均一に上昇せずに、むらが生じたり、焼結体が割れてしまったりする。この様にして得られた焼結体は、高密度が達成可能となる。
If the holding time at the sintering temperature is shorter than 10 hours, the reaction between the raw material powders does not proceed sufficiently, and the density of the sintered body does not increase sufficiently, or the sintered body warps. Even if the sintering time exceeds 30 hours, unnecessary energy and time is required, which is not preferable for production.
If the rate of temperature increase is less than 0.5 ° C / min, it takes time to reach the predetermined temperature. If the rate of temperature increase is greater than 5.0 ° C / min, the temperature distribution in the furnace will be Even if it does not rise uniformly, unevenness occurs or the sintered body breaks. The sintered body obtained in this way can achieve high density.
参考例１〜８及び比較例１〜４は酸化インジウムにスズの比率を色々に変化させた場合である。これらの結果をまとめて表１に示す。なお、表１には代表的な特性を評価として掲載する。 Reference Examples 1 to 8 and Comparative Examples 1 to 4 are cases where the ratio of tin to indium oxide was variously changed. These results are summarized in Table 1. Table 1 shows typical characteristics as evaluation.
まず、平均粒径約２．０μｍのIｎ2Ｏ3粉とＳｎＯ2粉とを、表１に示すような各所定割合を秤量後、スーパーミキサー３０００ｒｐｍで３分間充分に混合させた後、ジルコニアビーズで３時間微粉砕する。造粒後、６００ｋｇｆ／ｃｍ2の面圧で２分間プレス、静水圧加圧装置（ＣＩＰ）で１８００ｋｇｆ／ｃｍ2の面圧で２分間保持して成形する。電気炉にて、酸素雰囲気中１４５０℃で２０時間焼結することで、酸化物焼結体を得る。焼結体の密度はアルキメデス法で、焼結体のバルク抵抗は四端子法でそれぞれ測定した。 First, the In 2 O 3 powder and SnO 2 powder having an average particle size of about 2.0 μm were weighed in predetermined proportions as shown in Table 1, and then sufficiently mixed for 3 minutes at a super mixer 3000 rpm, and then zirconia beads. For 3 hours. After granulation, molding and held 2 min 2 min pressed at a surface pressure of 600 kgf / cm 2, in hydrostatic pressure device (CIP) at a surface pressure of 1800kgf / cm 2. Sintering is performed in an electric furnace at 1450 ° C. for 20 hours in an oxygen atmosphere to obtain an oxide sintered body. The density of the sintered body was measured by the Archimedes method, and the bulk resistance of the sintered body was measured by the four-terminal method.
焼結体を直径６インチ厚さ６ｍｍに加工したものをスパッタリングターゲットとして、インジウムメタルを介して、銅製のバッキングプレートに貼り付け、アルゴンガスを０．５Ｐａの圧力として、ＤＣ５００Ｗのスパッタパワーで、２０ｋＷｈスパッタ後のターゲット表面のノジュール数を数えた。
また、スパッタ中に異常放電が認められた場合は、表１の異常放電の欄に「あり」、認められなかった場合は、「なし」と記載した。
これらの結果をまとめて、表１に示す。なお、インジウムの比率は、全金属元素の総和（１００％）からインジウムを除く各金属元素の総和を除いた比率である。
A sintered body processed to a diameter of 6 inches and a thickness of 6 mm was used as a sputtering target, and was attached to a copper backing plate via indium metal. The number of nodules on the target surface after sputtering was counted.
Moreover, when abnormal discharge was recognized during sputtering, it was described as “Yes” in the column of abnormal discharge in Table 1, and when it was not recognized, “No”.
These results are summarized in Table 1. The indium ratio is a ratio obtained by removing the sum of all metal elements excluding indium from the sum of all metal elements (100%).
参考例９〜１６及び比較例５〜８は酸化インジウムと所定量のジルコニウムに対して、スズの比率を色々に変化させた場合である。ジルコニウムの比率は、２％に固定した。 Reference Examples 9 to 16 and Comparative Examples 5 to 8 are cases in which the ratio of tin is changed variously with respect to indium oxide and a predetermined amount of zirconium. The zirconium ratio was fixed at 2%.
まず、平均粒径約２．０μｍのIｎ2Ｏ3粉とＺｒＯ2粉とＳｎＯ2粉とを表１に示すような各所定割合を秤量後、実施例１と同様条件でスパッタリングターゲットを作製し、長時間スパッタ後も行い、ターゲットの諸特性を評価した。
これらの結果をまとめて、表１に示す。
First, after weighing each predetermined ratio as shown in Table 1 of In 2 O 3 powder, ZrO 2 powder and SnO 2 powder having an average particle diameter of about 2.0 μm, a sputtering target was prepared under the same conditions as in Example 1. Also, after sputtering for a long time, various characteristics of the target were evaluated.
These results are summarized in Table 1.
実施例１７〜１８、参考例１９、実施例２０〜２４及び比較例９〜１２は、ＩＧＺＯの組成Ｉｎ：Ｇａ：Ｚｎ＝１：１：１に対して、スズの比率を色々に変化させた場合である。実施例２５〜２６、参考例２７、実施例２８〜３２及び比較例１３〜１８は、ＩＧＺＯの組成Ｉｎ：Ｇａ：Ｚｎ＝２：２：１に対して、スズの比率を色々に変化させた場合、及び焼結温度を変化させた場合である。
まず、平均粒径が約１．６〜４．６μｍの酸化インジウム（Ｉｎ２Ｏ３）、酸化ガリウム（Ｇａ２Ｏ３）、酸化亜鉛（ＺｎＯ）、酸化スズ（ＳｎＯ２）の各原料粉末を所定の各金属元素の組成比となるように秤量し、スーパーミキサーで、大気中、回転数３０００ｒｐｍ、回転時間４分混合した。
In Examples 17 to 18, Reference Example 19, Examples 20 to 24, and Comparative Examples 9 to 12, the ratio of tin was variously changed with respect to the composition In: Ga: Zn = 1: 1: 1 of IGZO. Is the case. In Examples 25 to 26, Reference Example 27, Examples 28 to 32, and Comparative Examples 13 to 18, the tin ratio was variously changed with respect to the composition In: Ga: Zn = 2: 2: 1 of IGZO. And the case where the sintering temperature is changed.
First, each raw material powder of indium oxide (In 2 O 3 ), gallium oxide (Ga 2 O 3 ), zinc oxide (ZnO), and tin oxide (SnO 2 ) having an average particle diameter of about 1.6 to 4.6 μm is prepared. It weighed so that it might become a composition ratio of each predetermined metal element, and it mixed in air | atmosphere in the air | atmosphere at the rotation speed of 3000 rpm, and rotation time 4 minutes.
この混合粉を電気炉にて、大気雰囲気中で、１０００℃で、５時間程度保持することで仮焼した。仮焼粉をアトライターにジルコニアビーズと共に投入し、回転数３００ｒｐｍ、回転時間３時間微粉砕を行った。微粉砕後の原料紛の平均粒径（Ｄ５０）は０．５９μｍとなった。 The mixed powder was calcined in an electric furnace in an air atmosphere at 1000 ° C. for about 5 hours. The calcined powder was put into an attritor together with zirconia beads, and finely pulverized with a rotation speed of 300 rpm and a rotation time of 3 hours. The average particle diameter (D50) of the finely pulverized raw material powder was 0.59 μm.
微粉砕した原料粉を固形分５０％のスラリーとなるように水分量を調整し、入口温度を２００℃、出口温度を１２０℃に設定し、造粒を行った。造粒粉を４００ｋｇｆ／ｃｍ2の面圧、１分保持の条件でプレス成形した後、静水圧加圧装置（ＣＩＰ）で１８００ｋｇｆ／ｃｍ2の面圧で、１分保持の条件で成形した。 The amount of water was adjusted so that the finely pulverized raw material powder became a slurry having a solid content of 50%, and the inlet temperature was set to 200 ° C. and the outlet temperature was set to 120 ° C. to perform granulation. The granulated powder of 400 kgf / cm 2 surface pressure, after press-molded under the conditions of 1 minute hold at a surface pressure of 1800kgf / cm 2 at hydrostatic pressure device (CIP), was molded under the conditions of 1 minute hold.
次に、電気炉にて酸素雰囲気中、昇温速度１．０℃／ｍｉｎで８００℃まで昇温後、５時間保持、その後、昇温速度１．０℃／ｍｉｎで１４５０℃まで昇温後、２０時間保持、その後、炉冷で降温した。 Next, after raising the temperature to 800 ° C. at a heating rate of 1.0 ° C./min in an oxygen atmosphere in an electric furnace, holding for 5 hours, then raising the temperature to 1450 ° C. at a heating rate of 1.0 ° C./min , Held for 20 hours, and then cooled by furnace cooling.
焼結体の密度、バルク抵抗測定後、スパッタリングターゲットに加工して、長時間スパッタ後のノジュール数を評価した。これらの結果をまとめて、表１に示す。
この表１に示すように、本願発明の実施例については、いずれも相対密度が高く、９８％以上を達成していることが分かる。この結果、本願発明の実施例は、いずれもスパッタリング時のノジュールの発生量が少なく、また異常放電も発生しない。またバルク抵抗値も適切な範囲を維持しているのが確認できる。
これに対して、本願発明から逸脱する比較例については、相対密度が低くなり、ノジュールの発生量が多く、場合によっては異常放電が発生するという問題を生じた。スズの比率が本願発明から逸脱する比較例については、長波長領域の透過率が低減し、また、所望の半導体特性が得られないという問題を生じた。
以上の実施例及び比較例から、本願発明の焼結体は優れた特性を有することが分かる。
After measuring the density and bulk resistance of the sintered body, it was processed into a sputtering target, and the number of nodules after long-time sputtering was evaluated. These results are summarized in Table 1.
As shown in Table 1, it can be seen that the examples of the present invention all have a high relative density and achieve 98% or more. As a result, in all of the embodiments of the present invention, the amount of nodules generated during sputtering is small, and abnormal discharge does not occur. It can also be confirmed that the bulk resistance value is maintained within an appropriate range.
On the other hand, the comparative example deviating from the present invention has a problem in that the relative density is low, the amount of nodules is large, and abnormal discharge occurs in some cases. About the comparative example from which the ratio of tin deviates from this invention, the transmittance | permeability of a long wavelength region reduced and the problem that a desired semiconductor characteristic was not acquired was produced.
From the above Examples and Comparative Examples, it can be seen that the sintered body of the present invention has excellent characteristics.
本発明の酸化インジウム焼結体は高密度であることから、スパッタリングターゲットとして使用した場合に、その表面にノジュールが発生することを抑制し、スパッタリング時の異常放電を防止することができる。また、本発明の酸化インジウム焼結体はバルク抵抗率が低いので、スパッタリングによって形成される膜の抵抗率を低くすることができ、透明導電膜形成用として有用である。
さらに、本発明の酸化インジウム透明導電膜は可視光領域及び赤外線領域において透過率が高く、また、電子移動度が高く膜の抵抗率が低いので、太陽電池用透明導電膜として極めて有用である。
Since the indium oxide sintered body of the present invention has a high density, when used as a sputtering target, generation of nodules on its surface can be suppressed, and abnormal discharge during sputtering can be prevented. In addition, since the indium oxide sintered body of the present invention has a low bulk resistivity, the resistivity of a film formed by sputtering can be lowered, which is useful for forming a transparent conductive film.
Furthermore, since the indium oxide transparent conductive film of the present invention has high transmittance in the visible light region and infrared region, and has high electron mobility and low film resistivity, it is extremely useful as a transparent conductive film for solar cells.
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