JPH03112850A - Sintered oxide, its production and use thereof - Google Patents
Sintered oxide, its production and use thereofInfo
- Publication number
- JPH03112850A JPH03112850A JP1250518A JP25051889A JPH03112850A JP H03112850 A JPH03112850 A JP H03112850A JP 1250518 A JP1250518 A JP 1250518A JP 25051889 A JP25051889 A JP 25051889A JP H03112850 A JPH03112850 A JP H03112850A
- Authority
- JP
- Japan
- Prior art keywords
- tin oxide
- indium
- sintered body
- sintered
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 69
- 229910003437 indium oxide Inorganic materials 0.000 claims abstract description 39
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000006104 solid solution Substances 0.000 claims abstract description 21
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims description 14
- 238000005477 sputtering target Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 5
- 239000011163 secondary particle Substances 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 4
- 230000002159 abnormal effect Effects 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 3
- 239000007790 solid phase Substances 0.000 abstract 2
- 239000007787 solid Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- -1 0.5 Pa Substances 0.000 description 7
- 239000012300 argon atmosphere Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000001755 magnetron sputter deposition Methods 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 239000011362 coarse particle Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 229910000846 In alloy Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
[産業上の利用分野]
本発明は、透明導電膜製造の際の原料として用いられる
インジウム−錫酸化物(ITOと略称する)焼結体に関
する。更に詳しくは、スパッタリング法によってITO
透明導電膜を形成するのに好適なITO焼結体に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a sintered body of indium-tin oxide (abbreviated as ITO) used as a raw material in producing a transparent conductive film. More specifically, ITO is produced by sputtering method.
The present invention relates to an ITO sintered body suitable for forming a transparent conductive film.
[従来の技術]
近年、太陽電池、デイスプレー機器の透明電極や、帯電
防止用の導7ヒ性コーティング物として透明導電性薄膜
の需要が高まっている。このような透明導電性薄膜は、
スパッタリング法、CVD法、イオンブレーティング法
等により形成されているが、特に工業的にはインジウム
と錫の合金をスパッタリングする方法と、ITO焼結体
をスパッタリングする方法が主流であり、現在ではその
操作性の簡便さからITO焼結体をスパッタリングする
方法が最も一般的となっている。[Prior Art] In recent years, there has been an increasing demand for transparent conductive thin films as transparent electrodes for solar cells and display devices, and as conductive coatings for antistatic purposes. Such a transparent conductive thin film is
It is formed by sputtering method, CVD method, ion blating method, etc., but in particular industrially, methods of sputtering an alloy of indium and tin and methods of sputtering an ITO sintered body are mainstream; The most common method is to sputter an ITO sintered body because of its ease of operation.
従来ITO焼結体スパッタリングターゲットは酸化イン
ジウムと酸化錫を均一に混合したものの焼結体が用いら
れており、このものは酸化インジウムに酸化錫が比較的
均一に分散したものであり、混合添加した酸化錫の25
%以上は酸化インジウム中に固溶した状態で構成されて
いる。Conventionally, the ITO sintered sputtering target uses a sintered body of a uniform mixture of indium oxide and tin oxide.This is a mixture of indium oxide and tin oxide dispersed relatively uniformly. 25 of tin oxide
% or more is composed of solid solution in indium oxide.
しかしこのような従来のITO焼結体スパッタリングタ
ーゲットを用いてスパッタリングして得た膜の比抵抗は
高々0.2mΩ・C11までであり、近時、工業的な方
法で、より低抵抗な透明導電膜が得られるITOスパッ
タリングターゲットが要望されている。However, the specific resistance of films sputtered using such conventional ITO sintered body sputtering targets is at most 0.2 mΩ・C11. There is a need for an ITO sputtering target that provides a film.
[問題点を解決する手段]
本発明者等は酸化錫をドープした酸化インジウムのスパ
ッタリング成膜特性に関して鋭意検討を重ねた結果、ス
パッタリングターゲットを構成する酸化インジウム中へ
の酸化錫の固溶が進行するほど、これを用いて得られる
透明導電膜の抵抗が上昇する傾向のあること、従って酸
化錫の酸化インジウムへの固溶をある程度までに抑制し
たもの、あるいは酸化インジウム焼結体中に酸化錫焼結
体を埋め込むなどして、酸化錫が酸化インジウム中に固
溶していない状態のターゲットとしたものを用いること
により、従来のターゲットを用いた場合よりも10%以
上抵抗の低い透明導電膜が得られることを見出だし本発
明を完成した。[Means for Solving the Problem] As a result of intensive studies on the sputtering film formation characteristics of indium oxide doped with tin oxide, the inventors of the present invention found that solid solution of tin oxide progresses in the indium oxide constituting the sputtering target. However, the resistance of the transparent conductive film obtained using this material tends to increase. By using a target in which tin oxide is not solidly dissolved in indium oxide, such as by embedding a sintered body, we can create a transparent conductive film with a resistance that is 10% or more lower than when using a conventional target. The present invention was completed based on the discovery that the following can be obtained.
即ち本発明は、酸化インジウム粉末と平均二次粒径が5
μm以上の酸化錫粉末との混合物を1450℃未満の温
度で焼結することを特徴とするインジウム−錫酸化物焼
結体の製造法に関するものであり、更に、酸化インジウ
ム中の酸化錫の25%未満が固溶した酸化錫であり、か
つ見掛けの焼結密度が5.5g/ c+s3以上である
インジウム−錫酸化物焼結体及びこれを用いたスパッタ
リングターゲットに関するものである。That is, the present invention uses indium oxide powder and an average secondary particle size of 5.
The present invention relates to a method for producing an indium-tin oxide sintered body, characterized by sintering a mixture with tin oxide powder of μm or more at a temperature of less than 1450° C. The present invention relates to an indium-tin oxide sintered body in which less than % of the indium-tin oxide sintered body is solid-dissolved tin oxide and has an apparent sintered density of 5.5 g/c+s3 or more, and a sputtering target using the same.
ITO焼結体において酸化インジウム格子中に拡散固溶
した酸化錫は、焼結体において既にドーパント状態とな
っており、過剰の価電子を自由電子として放出している
と考えられる。そのような酸化錫はスパッタリングされ
た膜中では過剰の価電子を有しておらず、ドーパントと
しては不活性であると考えられる。It is thought that the tin oxide diffused and solid-solved in the indium oxide lattice in the ITO sintered body is already in a dopant state in the sintered body, and releases excess valence electrons as free electrons. Such tin oxide does not have excess valence electrons in the sputtered film and is considered inactive as a dopant.
一方焼結体中でSnO□粒子の状態で存在し、酸化イン
ジウム格子中に拡散固溶していない酸化錫は、焼結体中
ではドーパントとして働いておらず、4価の価電子を十
分に保有しいる。このような酸化錫はスパッタリングに
よって成膜された後に初めて酸化インジウム格子に拡散
固溶し、膜中で初めて過剰価電子を自由電子として放出
するため、膜中において活性なドーパントとして働くも
のと考えられる。On the other hand, tin oxide, which exists in the form of SnO□ particles in the sintered body and is not diffused and dissolved in the indium oxide lattice, does not function as a dopant in the sintered body and does not fully absorb the tetravalent valence electrons. I have it. This type of tin oxide diffuses into the indium oxide lattice as a solid solution only after it is formed by sputtering, and releases excess valence electrons as free electrons for the first time in the film, so it is thought to act as an active dopant in the film. .
本発明での酸化錫の固溶許容範囲は25%未満であるが
、特に20%未満であることが好ましい。The allowable solid solution range of tin oxide in the present invention is less than 25%, and particularly preferably less than 20%.
ITO焼結体中の酸化錫の固溶率は、焼結体を濃塩酸に
溶解することによって確認できる。酸化錫は一般に濃塩
酸に溶解しないが、酸化インジウム中に固溶拡散した酸
化錫は濃塩酸に容易に溶解する。このように溶解した酸
化錫と酸化インジウムの比を化学分析することにより酸
化錫の固溶率は確認できる。The solid solution rate of tin oxide in the ITO sintered body can be confirmed by dissolving the sintered body in concentrated hydrochloric acid. Tin oxide generally does not dissolve in concentrated hydrochloric acid, but tin oxide diffused as a solid solution in indium oxide easily dissolves in concentrated hydrochloric acid. The solid solution rate of tin oxide can be confirmed by chemically analyzing the ratio of tin oxide and indium oxide dissolved in this manner.
上記した方法によれば従来のITO焼結体における酸化
インジウム中への酸化錫の固溶率は30%以上であるこ
とが判る。According to the method described above, it is found that the solid solution rate of tin oxide in indium oxide in the conventional ITO sintered body is 30% or more.
ITO焼結体における、酸化錫の含有量は、5〜15重
量%、特に7〜12重量%の範囲が適当である。The content of tin oxide in the ITO sintered body is suitably in the range of 5 to 15% by weight, particularly 7 to 12% by weight.
この酸化錫が少なすぎると、得られる膜の電子密度が小
さく低抵抗の膜が得られない。一方酸化錫が多すぎても
電子密度は飽和し、酸化錫による散乱による電子移動度
が低下し、やはり低抵抗な膜は得られない。If the amount of tin oxide is too small, the resulting film will have a low electron density and will not have a low resistance. On the other hand, if the amount of tin oxide is too large, the electron density will be saturated and the electron mobility will decrease due to scattering by tin oxide, so that a film with low resistance will still not be obtained.
ITO焼結体中で固溶した不活性な酸化錫を相対的に減
少させる意味で、全体の酸化錫添加量を増加し本来の酸
化錫の持つ作用を補足することが考えられるが、不活性
な酸化錫の散乱による電子移動度の低下のために、この
ような焼結体を用いても低抵抗膜は得られない。In order to relatively reduce the amount of inert tin oxide dissolved in the ITO sintered body, it is possible to increase the total amount of tin oxide added to supplement the original effect of tin oxide. Even if such a sintered body is used, a low-resistance film cannot be obtained because of a decrease in electron mobility due to the scattering of tin oxide.
このような酸化錫の固溶を抑制した本発明のITO焼結
体の調製は、平均二次粒径5μm以上、特にlOμ■以
上の酸化錫を用いることで可能である。The preparation of the ITO sintered body of the present invention in which such solid solution of tin oxide is suppressed is possible by using tin oxide having an average secondary particle size of 5 μm or more, particularly 10 μm or more.
ここで用いる酸化錫の一次粒径に関しては特に制限はな
いが、なるべく表面積の小さい粗粒子が好ましい。この
ような粗粒酸化錫は表面積が小さいために焼結時に酸化
錫の酸化インジウム中への拡散が抑制され、本発明の効
果が得られる。There is no particular restriction on the primary particle size of the tin oxide used here, but coarse particles with as small a surface area as possible are preferred. Since such coarse-grained tin oxide has a small surface area, diffusion of tin oxide into indium oxide during sintering is suppressed, and the effects of the present invention can be obtained.
このような粗粒の酸化錫を得るには、従来の酸化錫粉末
を1000℃以上で熱処理する方法、又は粗粒の得られ
易いシュウ酸塩熱分解法等によって調製することができ
る。In order to obtain such coarse particles of tin oxide, it can be prepared by a conventional method of heat treating tin oxide powder at 1000° C. or higher, or by an oxalate pyrolysis method that easily produces coarse particles.
本発明のITO焼結体を調製するのに用いる酸化インジ
ウムの粒径は特に制限はないが、焼結体は高密度である
ことが好ましいために、焼結により高い焼結密度の得ら
れる1μm未満の微細で高分散な粉末を用いることが好
ましい。There is no particular restriction on the particle size of the indium oxide used to prepare the ITO sintered body of the present invention, but since the sintered body preferably has a high density, it is possible to obtain a high sintered density by sintering. It is preferable to use a fine and highly dispersed powder of less than
本発明のITO焼結体の焼結密度は5.5g/ cm’
(理論密度の約80%)以上、概ね6.3g/ c+a
3(理論密度の約90%)以上である。このような高密
度な焼結体はスパッタリングによるターゲットの表面還
元が抑制され、より低抵抗で安定な透明導電膜が得られ
る。The sintered density of the ITO sintered body of the present invention is 5.5 g/cm'
(approximately 80% of theoretical density) or more, approximately 6.3g/c+a
3 (approximately 90% of the theoretical density) or more. Such a high-density sintered body suppresses surface reduction of the target due to sputtering, and a stable transparent conductive film with lower resistance can be obtained.
従来酸化錫は酸化インジウムに対して不純物として働き
、ITOの焼結を疎外していたが、本発明においては酸
化インジウムに酸化錫の固溶を抑制するために酸化イン
ジウムの焼結が容易に進行し、高い焼結密度が容易に達
成される。Conventionally, tin oxide acted as an impurity for indium oxide, making it difficult to sinter ITO, but in the present invention, sintering of indium oxide progresses easily in order to suppress the solid solution of tin oxide in indium oxide. However, high sintered density is easily achieved.
本発明のITO焼結体は通常の方法で予備成型したもの
をのは、1450℃未満、特に1350℃〜1430℃
の範囲の焼結温度で焼結する。この温度が1350℃未
満では本発明における高い焼結密度が得られ難く、一方
1450℃以上の高温では、酸化錫の昇華の際に、酸化
錫の酸化インジウム格子への拡散が進行し、本発明で目
的とする酸化錫の拡散固溶抑制は困難となる。又焼結時
間は2〜10時間である。The ITO sintered body of the present invention is preformed by a conventional method at a temperature below 1450°C, particularly between 1350°C and 1430°C.
Sinter at a sintering temperature in the range of . If this temperature is less than 1,350°C, it is difficult to obtain the high sintered density of the present invention, while at a high temperature of 1,450°C or higher, the diffusion of tin oxide into the indium oxide lattice progresses during sublimation of tin oxide, and the present invention Therefore, it becomes difficult to suppress the diffusion and solid solution of tin oxide, which is the objective. Also, the sintering time is 2 to 10 hours.
ITO焼結体において酸化錫の拡散固溶を抑制すること
により、焼結体抵抗が上昇し、直流スパッタリングにこ
れを用いる際に支障をきたすことが懸念される。しかし
酸化インジウムは、高密度体はそれ自身で0,1Ω・c
m程度の導電性を有しており、ITO焼結体中の酸化錫
の固溶率を25%未満に抑制したものでも十分に導電性
を有し、直流スパッタリングでの使用に支障はない。By suppressing the diffusion and solid solution of tin oxide in the ITO sintered body, there is a concern that the resistance of the sintered body increases, which may cause problems when using this for DC sputtering. However, indium oxide has a high density of 0.1Ω・c by itself.
The ITO sintered body has sufficient conductivity even when the solid solution rate of tin oxide in the ITO sintered body is suppressed to less than 25%, and there is no problem in using it in DC sputtering.
一方絶縁体を用いてもスパッタリングが可能な高周波ス
パッタリング法では、酸化インジウム単独の高密度焼結
体に酸化錫の焼結体チップを埋め込むなどして、酸化錫
の固溶が全くないターゲットの使用が効果的である。こ
のような方法でスパッタリングする場合は、酸化インジ
ウムと酸化錫の表面積を95=5から85:15となる
ように調整したものを用いることにより制御された膜組
成を得ることができる。ただしマグネトロンスパッタリ
ング法のように、ターゲット表面のスパッタリング率に
差がある場合は、得られる膜中における酸化インジウム
/酸化錫比が9278〜88712程度になるようにさ
らに適当な、調整が必要である。On the other hand, in the high-frequency sputtering method, which allows sputtering even when using an insulator, a target with no solid solution of tin oxide is used, such as by embedding a sintered chip of tin oxide in a high-density sintered body of indium oxide alone. is effective. In the case of sputtering using such a method, a controlled film composition can be obtained by using a material in which the surface areas of indium oxide and tin oxide are adjusted from 95=5 to 85:15. However, when there is a difference in the sputtering rate on the target surface as in magnetron sputtering, further appropriate adjustment is required so that the indium oxide/tin oxide ratio in the resulting film is about 9278 to 88712.
上記方法で用いる酸化インジウム単独の高密度焼結体は
通常の方法、例えば0.1〜数μmの粒径の酸化インジ
ウム粉末を、前述したITOの場合と同様の焼結温度で
焼結して得る。The high-density sintered body of indium oxide alone used in the above method is produced by a normal method, for example, by sintering indium oxide powder with a particle size of 0.1 to several μm at the same sintering temperature as in the case of ITO described above. obtain.
[本発明の効果]
本発明のITO焼結体をスバタリングターゲットとして
用いることにより従来よりも低抵抗な透明導電膜、すな
わち0..2mΩ・effi未満の低抵抗膜の形成が可
能となった。−又操作時の異常放電等の問題もなく、均
一な膜が得られる。[Effects of the present invention] By using the ITO sintered body of the present invention as a sputtering target, a transparent conductive film with lower resistance than before, that is, 0. .. It became possible to form a low resistance film of less than 2 mΩ·effi. -Also, there are no problems such as abnormal discharge during operation, and a uniform film can be obtained.
[実施例]
以下実施例に基づき本発明を説明するが、本発明は実施
例になんら限定されるものではない。[Examples] The present invention will be described below based on Examples, but the present invention is not limited to the Examples in any way.
実施例1
市販の酸化錫粉末を1300℃で熱処理することにより
粒成長させ、平均粒径約lOμmの粗粒酸化錫粉末を調
製した。Example 1 A commercially available tin oxide powder was heat-treated at 1300° C. to grow grains, thereby preparing coarse-grained tin oxide powder having an average grain size of about 10 μm.
このような酸化錫を平均粒径0.2μmの酸化インジウ
ムとmW比で90:10となるように混合し、1400
℃で5時間焼結した。得られたITO焼結体の焼結密度
は8.0g/ cm3で、濃塩酸溶解による酸化錫の固
溶率は15%であった。Such tin oxide was mixed with indium oxide with an average particle size of 0.2 μm at a mW ratio of 90:10, and
Sintered at ℃ for 5 hours. The sintered density of the obtained ITO sintered body was 8.0 g/cm3, and the solid solution rate of tin oxide by dissolving in concentrated hydrochloric acid was 15%.
この焼結体をスパッタリングターゲットとして用い、D
Cマグネトロンスパッタリング法によって透明導電膜を
形成した。スパッタリング条件は、投入電力4v/Cr
a2、アルゴン雰囲気、0.5 Pa、基板温度250
℃である。Using this sintered body as a sputtering target,
A transparent conductive film was formed by C magnetron sputtering method. The sputtering conditions are input power 4v/Cr
a2, argon atmosphere, 0.5 Pa, substrate temperature 250
It is ℃.
得られた透明導電膜は550 nmにおける光透過率は
85%以上で、比抵抗は0.17rRΩ・cmであった
。The obtained transparent conductive film had a light transmittance of 85% or more at 550 nm and a specific resistance of 0.17 rRΩ·cm.
実施例2
塩化錫水溶液に化学量論量のシュウ酸アンモニウムを添
加しシュウ酸錫を沈殿させ、当該シュウ酸錫を800℃
で熱分解することによって、サイコロ状に形状の整った
平均粒径10μIの酸化錫粉末を調製した。Example 2 A stoichiometric amount of ammonium oxalate was added to an aqueous tin chloride solution to precipitate tin oxalate, and the tin oxalate was heated at 800°C.
By thermally decomposing the powder, a dice-shaped tin oxide powder having an average particle size of 10 μI was prepared.
この酸化錫を平均粒径0.2μmの微細な酸化インジウ
ムと重量比で90:10となるように混合し、1400
℃で5時間焼結した。得られたITO焼結体の焼結密度
は6.2g/ c+++3で、濃塩酸溶解による酸化錫
の固溶率の分析値は14%であった。This tin oxide was mixed with fine indium oxide with an average particle size of 0.2 μm in a weight ratio of 90:10,
Sintered at ℃ for 5 hours. The sintered density of the obtained ITO sintered body was 6.2 g/c++3, and the analysis value of the solid solution rate of tin oxide by dissolving in concentrated hydrochloric acid was 14%.
この焼結体をスパッタリングターゲットとして用い、D
Cマグネトロンスパッタリング法によって透明導電膜を
形成した。スパッタリング条件は、投入電力4vlC1
12、アルゴン雰囲気、0.5 Pa、基板温度250
℃である。Using this sintered body as a sputtering target,
A transparent conductive film was formed by C magnetron sputtering method. The sputtering conditions are input power 4vlC1
12. Argon atmosphere, 0.5 Pa, substrate temperature 250
It is ℃.
得られた透明導電膜は550 nmにおける光透過率は
85%以上で、比抵抗はO,1BIIΩ・cmであった
。The obtained transparent conductive film had a light transmittance of 85% or more at 550 nm and a specific resistance of O.1BIIΩ·cm.
実施例3
平均粒径0.2μ■の酸化インジウムを1400℃で5
時間焼結し、焼結密度6.5g/ cg3の高密度焼結
体を調製した。この焼結体に直径5mmの孔をあけ、そ
こに酸化錫の焼結体チップを埋め込み、酸化インジウム
と酸化錫のターゲット表面の面積比が90:10となる
ようにした。Example 3 Indium oxide with an average particle size of 0.2 μ
A high-density sintered body with a sintered density of 6.5 g/cg3 was prepared by sintering for a time. A hole with a diameter of 5 mm was made in this sintered body, and a sintered body chip of tin oxide was embedded in the hole so that the area ratio of the target surfaces of indium oxide and tin oxide was 90:10.
この焼結体をスパッタリングターゲットとして用い、R
Fスパッタリング法によって透明導電膜を形成した。ス
パッタリング条件は、投入電力4w/cm2、アルゴン
雰囲気、0.5 Pa、基板温度250℃である。Using this sintered body as a sputtering target, R
A transparent conductive film was formed by F sputtering method. The sputtering conditions were an input power of 4 W/cm2, an argon atmosphere, 0.5 Pa, and a substrate temperature of 250°C.
得られた透明導電膜は550 nmにおける光透過率ば
85%以上で、比抵抗は0.15 mΩ・elllであ
った。The obtained transparent conductive film had a light transmittance of 85% or more at 550 nm and a specific resistance of 0.15 mΩ·ell.
比較例1
市販の平均粒径1μmの酸化錫を平均粒径0.2μ0の
微細な酸化インジウムと重量比で90:10となるよう
に混合し、1400℃で5時間焼結した。得られたIT
O焼結体の焼結密度は5.4g/ cm3で、濃塩酸溶
解による酸化錫の固溶率の分析値は32%であった。Comparative Example 1 Commercially available tin oxide having an average particle size of 1 μm was mixed with fine indium oxide having an average particle size of 0.2 μm in a weight ratio of 90:10, and sintered at 1400° C. for 5 hours. Obtained IT
The sintered density of the O sintered body was 5.4 g/cm3, and the analysis value of the solid solution rate of tin oxide by dissolving in concentrated hydrochloric acid was 32%.
この焼結体をスパッタリングターゲットとして用い、D
Cマグネトロンスパッタリング法によって透明導電膜を
形成した。スパッタリング条件は、投入電力4v/cf
l12、アルゴン雰囲気、0.5 Pa、基板温度25
0℃である。Using this sintered body as a sputtering target,
A transparent conductive film was formed by C magnetron sputtering method. Sputtering conditions are input power 4v/cf
l12, argon atmosphere, 0.5 Pa, substrate temperature 25
It is 0°C.
スパッタリング条件は、投入電力4w/Cl112、ア
ルゴン雰囲気、0.5 Pa、基板温度250℃である
。The sputtering conditions were an input power of 4 w/Cl112, an argon atmosphere, 0.5 Pa, and a substrate temperature of 250°C.
得られた透明導電膜は550na+における光透過率は
85%以上であったが、比抵抗は0.23mΩ・cra
であった。The obtained transparent conductive film had a light transmittance of 85% or more at 550 na+, but a specific resistance of 0.23 mΩ・cra.
Met.
比較例2
市販の平均粒径1μmの酸化錫を平均粒径0,2μmの
微細な酸化インジウムと重量比で90:10となるよう
に混合し、1500℃の高温で5時間焼結した。得られ
たITO焼結体の焼結密度は6.0g/ ca+3で濃
塩酸溶解による酸化錫の固溶率の分析値は100%であ
った。Comparative Example 2 Commercially available tin oxide having an average particle size of 1 μm was mixed with fine indium oxide having an average particle size of 0.2 μm in a weight ratio of 90:10, and sintered at a high temperature of 1500° C. for 5 hours. The sintered density of the obtained ITO sintered body was 6.0 g/ca+3, and the analysis value of the solid solution rate of tin oxide by dissolving in concentrated hydrochloric acid was 100%.
この焼結体をスパッタリングターゲットとして用い、D
Cマグネトロンスパッタリング法によって透明導電膜を
形成した。スパッタリング条件は、投入電力4v/cr
a2、アルゴン雰囲気、0.5 Pa、基板温度250
℃である。Using this sintered body as a sputtering target,
A transparent conductive film was formed by C magnetron sputtering method. Sputtering conditions are input power 4v/cr
a2, argon atmosphere, 0.5 Pa, substrate temperature 250
It is ℃.
得られた透明導電膜は55On11における光透過率は
85%以上であったが、比抵抗は0.851!lΩ・C
rl1と高抵抗であった。The obtained transparent conductive film had a light transmittance of 85% or more at 55On11, but a specific resistance of 0.851! lΩ・C
It had a high resistance of rl1.
比較例3
塩化錫と塩化インジウム水溶液からインジウムと錫の水
酸化物を共沈させ、当該共沈物を800℃で加熱し共沈
ITO粉末を調製した。当該共沈ITO粉末の酸化イン
ジウムと酸化錫の比は90:10となるように調製した
。Comparative Example 3 Indium and tin hydroxide were coprecipitated from an aqueous solution of tin chloride and indium chloride, and the coprecipitate was heated at 800° C. to prepare a coprecipitated ITO powder. The coprecipitated ITO powder was prepared so that the ratio of indium oxide to tin oxide was 90:10.
この共沈ITO粉末を1400℃で5時間焼結し、5゜
4g/ C13の焼結体を得た。この焼結体の濃塩酸溶
解による酸化錫固溶率分析値は85%であった。This co-precipitated ITO powder was sintered at 1400°C for 5 hours to obtain a sintered body weighing 5°4g/C13. The tin oxide solid solution rate analysis value of this sintered body by dissolving it in concentrated hydrochloric acid was 85%.
この焼結体をスパッタリングターゲットとして用い、D
Cマグネトロンスパッタリング法によって透明導電膜を
形成した。スパッタリング条件は、投入電力4vlcI
52、アルゴン雰囲気、0.5 Pa、基板温度250
℃である。Using this sintered body as a sputtering target,
A transparent conductive film was formed by C magnetron sputtering method. The sputtering conditions are input power 4vlcI.
52, Argon atmosphere, 0.5 Pa, substrate temperature 250
It is ℃.
得られた透明導電膜は550 r+mにおける光透過率
は85%以上であったが、比抵抗は0.45mΩ・el
ll3と高抵抗であった。The obtained transparent conductive film had a light transmittance of 85% or more at 550 r+m, but a specific resistance of 0.45 mΩ・el.
It had a high resistance of ll3.
Claims (1)
た酸化錫であり、かつ見掛けの焼結密度が5.5g/c
m^3以上であるインジウム−錫酸化物焼結体。 [2]酸化インジウム粉末と平均二次粒径が5μm以上
の酸化錫粉末との混合物を1450℃未満の温度で焼結
することを特徴とするインジウム−錫酸化物焼結体の製
造法。 [3]酸化インジウム中の酸化錫の25%未満が固溶し
た酸化錫であり、かつ見掛けの焼結密度が5.5g/c
m^3以上であるインジウム−錫酸化物焼結体からなる
スパッタリングターゲット。 [4]見掛けの焼結密度が5.5g/cm^3以上の酸
化インジウム焼結体中に酸化錫焼結体を埋め込んだイン
ジウム−錫酸化物焼結体スパッタリングターゲット。[Claims] [1] Less than 25% of the tin oxide in indium oxide is solid solution tin oxide, and the apparent sintered density is 5.5 g/c
An indium-tin oxide sintered body having a particle diameter of m^3 or more. [2] A method for producing an indium-tin oxide sintered body, which comprises sintering a mixture of indium oxide powder and tin oxide powder having an average secondary particle size of 5 μm or more at a temperature below 1450°C. [3] Less than 25% of the tin oxide in indium oxide is solid-dissolved tin oxide, and the apparent sintered density is 5.5 g/c
A sputtering target made of an indium-tin oxide sintered body having a diameter of m^3 or more. [4] An indium-tin oxide sintered body sputtering target in which a tin oxide sintered body is embedded in an indium oxide sintered body having an apparent sintered density of 5.5 g/cm^3 or more.
Priority Applications (1)
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Applications Claiming Priority (1)
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---|---|---|---|
JP1250518A JP2756598B2 (en) | 1989-09-28 | 1989-09-28 | Oxide sintered body, its production method and use |
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ID=17209086
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003008658A1 (en) * | 2001-07-18 | 2003-01-30 | Nikko Materials Company, Limited | Ito sintered body sputtering target for forming high-resistance film and its manufacturing method |
JP2006069882A (en) * | 2004-08-05 | 2006-03-16 | Mitsubishi Materials Corp | Fine tin oxide powder, and its production method and application |
-
1989
- 1989-09-28 JP JP1250518A patent/JP2756598B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003008658A1 (en) * | 2001-07-18 | 2003-01-30 | Nikko Materials Company, Limited | Ito sintered body sputtering target for forming high-resistance film and its manufacturing method |
JP2006069882A (en) * | 2004-08-05 | 2006-03-16 | Mitsubishi Materials Corp | Fine tin oxide powder, and its production method and application |
Also Published As
Publication number | Publication date |
---|---|
JP2756598B2 (en) | 1998-05-25 |
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