JP3628566B2 - Sputtering target and manufacturing method thereof - Google Patents
Sputtering target and manufacturing method thereof Download PDFInfo
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- JP3628566B2 JP3628566B2 JP31823099A JP31823099A JP3628566B2 JP 3628566 B2 JP3628566 B2 JP 3628566B2 JP 31823099 A JP31823099 A JP 31823099A JP 31823099 A JP31823099 A JP 31823099A JP 3628566 B2 JP3628566 B2 JP 3628566B2
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- 238000005477 sputtering target Methods 0.000 title claims description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 32
- NJWNEWQMQCGRDO-UHFFFAOYSA-N indium zinc Chemical compound [Zn].[In] NJWNEWQMQCGRDO-UHFFFAOYSA-N 0.000 claims description 29
- 239000013078 crystal Substances 0.000 claims description 28
- 239000011701 zinc Substances 0.000 claims description 22
- 238000005452 bending Methods 0.000 claims description 16
- 239000011787 zinc oxide Substances 0.000 claims description 15
- 230000003746 surface roughness Effects 0.000 claims description 14
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 13
- 238000004453 electron probe microanalysis Methods 0.000 claims description 12
- 229910003437 indium oxide Inorganic materials 0.000 claims description 11
- 229910052738 indium Inorganic materials 0.000 claims description 10
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 238000000462 isostatic pressing Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 19
- 238000005498 polishing Methods 0.000 description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 7
- 239000013077 target material Substances 0.000 description 7
- 238000000227 grinding Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- 238000004451 qualitative analysis Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000005211 surface analysis Methods 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000001513 hot isostatic pressing Methods 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- -1 for example Chemical compound 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Conductive Materials (AREA)
Description
【０００１】
【発明の属する技術分野】
この発明は、結晶組織が微細であり、焼結体密度が高く、抗折強度が大きいインジウム及び亜鉛酸化物を主成分とする透明導電膜形成に好適なＩＺＯスパッタリングターゲット及びその製造方法に関する。
【０００２】
【従来の技術】
いくつかの金属複合酸化物からなる透明導電膜は、高導電性と可視光透過性を有しているので、液晶表示装置、薄膜エレクトロルミネッセンス表示装置、放射線検出装置、端末機器の透明タブレット、窓ガラスの結露防止用発熱膜、帯電防止膜あるいは太陽光集熱器用選択透過膜、タッチパネルの電極などの多岐に亘る用途に使用されている。
このような金属複合酸化物からなる透明導電膜の中で最も普及しているものはＩＴＯと呼ばれている酸化インジウム−酸化錫からなる透明導電膜である。
この他に、酸化錫にアンチモン（ＡＴＯ）を添加したものあるいは酸化亜鉛にアルミニウム（ＡＺＯ）を添加したものなどが知られている。これらは、膜特性や製造コストなどそれぞれ異なるので、その用途に応じて適宜使用されている
【０００３】
この中で、ＩＴＯ膜よりもエッチング速度が大きいインジウム及び亜鉛の複合酸化物（以下、特に言及しない限り「ＩＺＯ」という。）を主成分とする透明導電膜を用いる提案がなされている（特許第２６９５６０５号公報参照）。
この時の成膜時に使用したＩＺＯターゲットは、熱間静水圧プレス法により製造されたものである（上記特許公報実施例４〜１２参照）。ところが、この方法で製造された従来のＩＺＯスパッタリングターゲットは焼結密度が十分高いとはいえず、結晶粒径も不均一であった。又、得られたターゲットはバルク抵抗が十分低いとはいえず、ＤＣスパッタリング用として必ずしも最適なスパッタリングターゲットではなかった。
さらに熱間静水圧プレス法による焼結ターゲットの機械的強度が低いために、スパッタリング中又はターゲットの取り扱い中に欠けや割れが発生するという問題があった。
【０００４】
【発明が解決しようとする課題】
以上の点に鑑み、本発明はインジウム及び亜鉛の酸化物を主成分とするＩＺＯ透明導電膜の持つ特性を失うことなく改良を図ることを目的とし、ターゲット密度の向上を図り、結晶粒径を均一微細化し、機械的特性の改善を行い、スパッタリングの放電を安定化させるとともに、透明導電膜を安定かつ再現性よく得ることのできるＩＺＯスパッタリングターゲット及びその製造方法を提供する。
【０００５】
【課題を解決するための手段】
本発明は、１）酸化インジウム結晶中にＺｎが固溶した又は未固溶のＩｎリッチ相と酸化亜鉛結晶中にＩｎが固溶した又は未固溶のＺｎリッチ相の２相の組織を備えていることを特徴とするインジウム−亜鉛系酸化物からなるスパッタリングターゲット、２）ＥＰＭＡにて観察したＺｎ原子の凝集体の平均径が１０μｍ以下であることを特徴とする上記１記載のインジウム−亜鉛系酸化物からなるスパッタリングターゲット、３）ＥＰＭＡにて観察したＺｎ原子の凝集体の平均径が５μｍ以下であることを特徴とする上記１記載のインジウム−亜鉛系酸化物からなるスパッタリングターゲット、４）焼結体密度が６．５ｇ／ｃｍ３以上であることを特徴とする上記１〜３のそれぞれに記載のインジウム−亜鉛系酸化物からなるスパッタリングターゲット、５）平均結晶粒径が３μｍ以下であることを特徴とする上記１〜４のそれぞれに記載のインジウム−亜鉛系酸化物からなるスパッタリングターゲット、６）平均結晶粒径が２μｍ以下であることを特徴とする上記１〜５のそれぞれに記載のインジウム−亜鉛系酸化物からなるスパッタリングターゲット、７）表面粗さがＲａで２μｍ以下、平均抗折強度が６８ＭＰａ以上であることを特徴とする上記１〜６のそれぞれに記載のインジウム−亜鉛系酸化物からなるスパッタリングターゲット、８）表面粗さがＲａで０．５μｍ以下、平均抗折強度が７８ＭＰａ以上であることを特徴とする上記１〜６のそれぞれに記載のインジウム−亜鉛系酸化物からなるスパッタリングターゲット、９）インジウム−亜鉛系酸化物焼結体中の不純物であるＦｅ、Ａｌ、Ｓｉ、Ｎｉ、Ｔｉ、Ｃｕが各々１０ｐｐｍ（ｗｔ）以下であることを特徴とする上記１〜８のそれぞれに記載のインジウム−亜鉛系酸化物からなるスパッタリングターゲット、１０）酸化インジウムと酸化亜鉛とを微粉砕後、混合造粒し、これをコールドプレス及び又は静水圧冷間圧縮により成型した後、酸素雰囲気又は大気中で１３００〜１５００°Ｃに加熱焼結することを特徴とする、酸化インジウム結晶中にＺｎが固溶した又は未固溶のＩｎリッチ相と酸化亜鉛結晶中にＩｎが固溶した又は未固溶のＺｎリッチ相の２相の組織を備えているインジウム−亜鉛系酸化物からなるスパッタリングターゲットの製造方法、１１）ＥＰＭＡにて観察したＺｎ原子の凝集体の径が１０μｍ以下であることを特徴とする上記１０記載のインジウム−亜鉛系酸化物からなるスパッタリングターゲットの製造方法、１２）焼結体密度が６．５ｇ／ｃｍ３以上であることを特徴とする上記１０又は１１記載のインジウム−亜鉛系酸化物からなるスパッタリングターゲットの製造方法、１３）平均結晶粒径が３μｍ以下であることを特徴とする上記１０〜１２のそれぞれに記載のインジウム−亜鉛系酸化物からなるスパッタリングターゲットの製造方法、１４）平均結晶粒径が２μｍ以下であることを特徴とする上記１０〜１２のそれぞれに記載のインジウム−亜鉛系酸化物からなるスパッタリングターゲットの製造方法、１５）表面粗さがＲａで２μｍ以下、平均抗折強度が６８ＭＰａ以上であることを特徴とする上記１０〜１４のそれぞれに記載のインジウム−亜鉛系酸化物からなるスパッタリングターゲットの製造方法、１６）表面粗さがＲａで０．５μｍ以下、平均抗折強度が７８ＭＰａ以上であることを特徴とする上記１０〜１５のそれぞれに記載のインジウム−亜鉛系酸化物からなるスパッタリングターゲットの製造方法、１７）インジウム−亜鉛系酸化物焼結体中の不純物であるＦｅ、Ａｌ、Ｓｉ、Ｎｉ、Ｔｉ、Ｃｕが各々１０ｐｐｍ（ｗｔ）以下であることを特徴とする上記１０〜１６のそれぞれに記載のインジウム−亜鉛系酸化物からなるスパッタリングターゲットの製造方法、に関する。
【０００６】
【発明の実施の形態】
インジウム及び亜鉛の酸化物を主成分とするスパッタリングターゲットの製造に際しては、例えば平均粒径が２μｍの酸化インジウム粉と同粒径の酸化亜鉛粉を重量比でほぼ９０：１０となるように秤量し、成形用バインダーを加えて均一に混合する。
次に、この混合粉を金型に充填し、コールドプレス及び又はＣＩＰで加圧成形した後、大気中又は酸素雰囲気中、１３００〜１５００°Ｃの温度で焼結する。
ＩＺＯスパッタリングターゲット焼結体の結晶粒径は３μｍ以下、好ましくは２μｍ以下、より好ましくは１μｍ以下にする。また、必要に応じて焼結体の密度を６．５ｇ／ｃｍ３以上（相対密度９２．９％以上）に、さらにＩＺＯ中の不純物Ｆｅ、Ａｌ、Ｓｉ、Ｎｉ、Ｔｉ、Ｃｕを各々１０ｐｐｍ（ｗｔ）以下となるように調整する。
これにより得られたＩＺＯスパッタリングターゲットは、酸化インジウム結晶中にＺｎが固溶した又は未固溶のＩｎリッチ相と酸化亜鉛結晶中にＩｎが固溶した又は未固溶のＺｎリッチ相の２相の組織を備えており、ＥＰＭＡにて観察したＺｎ原子の平均凝集体の径が１０μｍ以下であることは、本発明の著しい特徴である。
このようにして得たＩＺＯスパッタリングターゲット焼結体を平面研削盤で研削して表面粗さＲａ２μｍ以下のＩＺＯターゲット素材とすることにより、抗折強度の平均値が６８ＭＰａ以上となる。又Ｒａ０．５μｍ以下にすることにより、抗折強度の平均値が７８ＭＰａ以上となる。
ここで、さらにＩＺＯスパッタリングターゲットのスパッタ面に鏡面加工を施して、平均表面粗さＲａが０．２μｍ以下としてもよい。
この鏡面加工（研磨）は機械的な研磨、化学研磨、メカノケミカル研磨（機械的な研磨と化学研磨の併用）等の、すでに知られている研磨技術を用いることができる。
【０００７】
例えば、固定砥粒ポリッシャー（ポリッシュ液：水）でポリッシングしたり、又は遊離砥粒ラップ（研磨材：ＳｉＣペースト等）にてラッピング後、研磨材をダイヤモンドペーストに換えてラッピングすることによって得ることができる。このような研磨方法には特に制限はなく、良好な平均表面粗さＲａが達せられれば、他の研磨方法を採用してもよい。得られたＩＺＯスパッタリングターゲットをバッキングプレートへボンディングする。
【０００８】
次に、エアーブローあるいは流水洗浄などの清浄処理を行なう。エアーブローで異物を除去する際には、ノズルの向い側から集塵機で吸気を行なうとより有効に除去できる。しかし、以上のエアーブローや流水洗浄では限界があるので、さらに超音波洗浄等を行なってもよい。この超音波洗浄は周波数２５〜３００ＫＨｚの間で多重発振させて行なう方法が有効である。例えば周波数２５〜３００ＫＨｚの間で、２５ＫＨｚ刻みに１２種類の周波数を多重発振させて超音波洗浄を行なうのが良い。
【０００９】
このようにして形成された透明導電膜形成用ＩＺＯスパッタリングターゲットのバルク抵抗値を１０ｍΩ・ｃｍ以下にすることができる。このようにＩＺＯの従来の特性を変えずにＩＺＯスパッタリングターゲットのバルク抵抗値を下げることができる。特に微量添加物を制御（Ｓｎを１００〜２０００ｐｐｍ添加）することにより、１〜５ｍΩ・ｃｍの範囲にコントロールも可能である（特願平１１−１２８１２２参照）。
また、本発明のターゲットは密度が高く、結晶粒径がより均一微細化した組織を持ち、かつ機械的強度が高いという特徴を有する。これによって、透明導電膜を安定かつ再現性よく得ることのできるターゲットが得られる。
【００１０】
【実施例および比較例】
続いて、本発明を実施例により比較例と対比しながら説明する。
ＩＺＯスパッタリングターゲットの製造に際しては、まず平均粒径が２μｍの酸化インジウム粉と同粒度の酸化亜鉛粉を約９０：１０の割合に秤量し、均一に微粉砕混合後、成形用バインダーを加えて造粒した。
次に、この原料混合粉を金型へ均一に充填しコールドプレス機にて加圧成形した。このようにして得た成形体を焼結炉により１３８０°Ｃで５時間焼結した。昇温中は酸素雰囲気、その他は大気中（雰囲気）、昇温速度４°Ｃ／ｍｉｎ、降温速度１０°Ｃ／ｍｉｎで実施した。
さらに、このようにして得られた焼結体の表面を平面研削盤で研削し、側辺をダイヤモンドカッターで切断して、ＩＺＯターゲット素材とした。
このＩＺＯターゲット素材は、酸化インジウム−１０．７ｗｔ％酸化亜鉛であり、密度は６．８７ｇ／ｃｍ３（理論密度は７．００ｇ／ｃｍ３）であった。又バルク抵抗は３．２ｍΩｃｍであった。又Ｆｅ、Ａｌ、Ｓｉ、Ｔｉ、Ｎｉ、Ｃｕの不純物量は１０ｐｐｍ以下であった。
【００１１】
次に、このＩＺＯターゲット素材の組織の観察とＥＰＭＡによるターゲット表面の定性分析をおこなった。この結果、平均結晶粒径は１．３６μｍであった。ＥＰＭＡによる定性分析の結果を、図１、図２及び図３に示す。図１はインジウム原子の面分析結果、図２は亜鉛原子の面分析結果、そして図３は酸素原子の面分析結果である。
図１、図２及び図３に示す通り、面内に一様に凝集した亜鉛原子が点在していることが分かる。また、亜鉛原子の平均凝集径は５μｍ以下であった。さらに、空孔は結晶粒径よりも小さく、全体的に均一に分散している。
【００１２】
次に、ポリッシングを行い、本発明の実施例としてＲａ０．４μｍにした板（実施例１）と長手方向に平面研削を行いＲａ１．２μｍにした板（実施例２）とを作成し、また比較例として長手方向に平面研削を行いＲａ２．２μｍにした板とを作成した。
そして、これらを三点曲げ試験を行い、強度を測定した。その結果を図４及び図５に示す。図４はメジアン・ランク法による曲げ強度に対する累積破壊確率、図５は単一モードによるワイブルプロットを示す。
また、図５より破壊確率のばらつきを示すワイブル係数（ｍ値）を求めこれを表１に示す。なお、ワイブル係数は線形回帰直線を求めることによりｍ値を得た。ワイブル係数が大きいほど、非破壊応力の最大値にバラツキが見られなくなることを意味しているが、表１より、従来品より実施例品の方がバラツキが少なく、安定した材料であることが確認できる。
図４より、Ｒａが２．０μｍ以上となると、抗折強度が低くなることが分かる。一般的に、平面研削後の表面粗さは結晶粒径に対応する。粒径が不均一な場合には、Ｒａはより大きくなり、その分抗折強度が低下する。従来の組織は不均一であったので、これに該当する。
上記の対比から明らかなように、本発明の結晶粒径は微細かつ表面粗さの小さなターゲットにより、従来品を上回る品質のターゲットを得ることが可能となった。
【００１３】
【表１】
【発明の効果】
本発明の透明導電膜形成用ＩＺＯスパッタリングターゲットは、インジウム及び亜鉛酸化物を主成分とする（ＩＺＯ）透明導電膜の持つ特性を本質的に失うことなく、実質的にバルク抵抗を効果的に低下させることができる。そして、このようにして形成された透明導電膜形成用ＩＺＯスパッタリングターゲットのバルク抵抗値を１０ｍΩ・ｃｍ以下の範囲にコントロールすることができる。
また、本発明のターゲットは密度が高く、結晶粒径がより均一微細化した組織を持ち、かつ抗折強度が高いという特徴を有する。これによって、スパッタリングの放電を安定化させることができ、透明導電膜を安定かつ再現性よく得ることのできるターゲットが得ることができるという優れた特徴を有している。
【図面の簡単な説明】
【図１】本発明のＩＺＯターゲット素材表面のＥＰＭＡによるインジウムの定性分析結果を示す図である。
【図２】本発明のＩＺＯターゲット素材表面のＥＰＭＡによる亜鉛の定性分析結果を示す図である。
【図３】本発明のＩＺＯターゲット素材表面のＥＰＭＡによる酸素の定性分析結果を示す図である。
【図４】本発明のＩＺＯターゲットの曲げ強度に対する累積破壊確率を示す図である。
【図５】本発明のＩＺＯターゲットの同ワイブルプロットを示す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an IZO sputtering target suitable for forming a transparent conductive film mainly composed of indium and zinc oxide having a fine crystal structure, a high sintered body density, and a high bending strength, and a method for producing the same.
[0002]
[Prior art]
Transparent conductive films made of some metal composite oxides have high conductivity and visible light transmission, so liquid crystal display devices, thin film electroluminescence display devices, radiation detection devices, transparent tablets for terminals, windows It is used in a wide variety of applications such as a heat generation film for preventing condensation of glass, an antistatic film or a selective transmission film for solar collectors, and electrodes for touch panels.
Among the transparent conductive films made of such metal composite oxides, the most widespread is a transparent conductive film made of indium oxide-tin oxide called ITO.
In addition to this, there are known tin oxide added with antimony (ATO) or zinc oxide added with aluminum (AZO). Since these have different film properties and manufacturing costs, they are used as appropriate according to their use.
Among them, a proposal has been made to use a transparent conductive film whose main component is a complex oxide of indium and zinc (hereinafter referred to as “IZO” unless otherwise specified), which has a higher etching rate than the ITO film (Patent No. 1). 2695605).
The IZO target used at the time of film formation at this time was manufactured by a hot isostatic pressing method (see Patent Publication Examples 4 to 12). However, the conventional IZO sputtering target manufactured by this method cannot be said to have a sufficiently high sintered density, and the crystal grain size is not uniform. Moreover, it cannot be said that the obtained target has a sufficiently low bulk resistance, and is not necessarily an optimum sputtering target for DC sputtering.
Further, since the mechanical strength of the sintered target by the hot isostatic pressing method is low, there is a problem that chipping or cracking occurs during sputtering or handling of the target.
[0004]
[Problems to be solved by the invention]
In view of the above points, the present invention aims to improve without losing the characteristics of the IZO transparent conductive film mainly composed of oxides of indium and zinc, to improve the target density, and to reduce the crystal grain size. Provided are an IZO sputtering target and a method for producing the same, which can be uniformly refined, improve mechanical characteristics, stabilize sputtering discharge, and obtain a transparent conductive film stably and with good reproducibility.
[0005]
[Means for Solving the Problems]
The present invention comprises 1) a two-phase structure of an In-rich phase in which Zn is solid-dissolved or insoluble in an indium oxide crystal and a Zn-rich phase in which In is solid-dissolved or insoluble in a zinc oxide crystal. 2. A sputtering target comprising an indium-zinc-based oxide, characterized in that 2) the average diameter of aggregates of Zn atoms observed by EPMA is 10 μm or less; 2. Sputtering target made of an indium-zinc based oxide according to 1 above, wherein the average diameter of aggregates of Zn atoms observed by EPMA is 5 μm or less, 4) indium according to each of the 1 to 3 sintered density is equal to or is 6.5 g / cm 3 or more - sputtering consisting zinc oxide 5) Sputtering target comprising the indium-zinc oxide according to each of the above 1 to 4, wherein the average crystal grain size is 3 μm or less, 6) The average crystal grain size is 2 μm or less. (7) A sputtering target comprising the indium-zinc-based oxide according to any one of (1) to (5) above, 7) The surface roughness is 2 μm or less in Ra, and the average bending strength is 68 MPa or more. 1 to 6, wherein the sputtering target is made of an indium-zinc based oxide, 8) The surface roughness Ra is 0.5 μm or less, and the average bending strength is 78 MPa or more. 9) Sputtering targets made of indium-zinc-based oxides described in the above, 9) Impurities in the indium-zinc-based oxide sintered body Each of Fe, Al, Si, Ni, Ti, and Cu is 10 ppm (wt) or less, and the sputtering target made of an indium-zinc-based oxide according to each of 1 to 8 above, 10) indium oxide After being finely pulverized and zinc oxide, they are mixed and granulated, molded by cold pressing and / or isostatic pressing, and then heated and sintered at 1300-1500 ° C in an oxygen atmosphere or air. Indium having a two-phase structure of an In-rich phase in which Zn is dissolved or not dissolved in an indium oxide crystal and a Zn-rich phase in which In is dissolved or not dissolved in a
[0006]
DETAILED DESCRIPTION OF THE INVENTION
In manufacturing a sputtering target mainly composed of oxides of indium and zinc, for example, indium oxide powder having an average particle diameter of 2 μm and zinc oxide powder having the same particle diameter are weighed so that the weight ratio is approximately 90:10. Add a molding binder and mix uniformly.
Next, the mixed powder is filled in a mold, pressed with a cold press and / or CIP, and then sintered in the air or in an oxygen atmosphere at a temperature of 1300 to 1500 ° C.
The crystal grain size of the IZO sputtering target sintered body is 3 μm or less, preferably 2 μm or less, more preferably 1 μm or less. If necessary, the density of the sintered body is set to 6.5 g / cm 3 or more (relative density 92.9% or more), and impurities Fe, Al, Si, Ni, Ti, and Cu in IZO are each 10 ppm ( wt) or less.
The IZO sputtering target thus obtained has two phases: an In-rich phase in which Zn is solid-dissolved or not dissolved in the indium oxide crystal and a Zn-rich phase in which In is solid-solved or insoluble in the zinc oxide crystal. It is a remarkable feature of the present invention that the average aggregate diameter of Zn atoms observed by EPMA is 10 μm or less.
By grinding the IZO sputtering target sintered body thus obtained with a surface grinder to obtain an IZO target material having a surface roughness Ra of 2 μm or less, the average value of the bending strength becomes 68 MPa or more. Moreover, by setting Ra to 0.5 μm or less, the average value of the bending strength becomes 78 MPa or more.
Here, the sputtering surface of the IZO sputtering target may be further mirror-finished so that the average surface roughness Ra is 0.2 μm or less.
For this mirror finishing (polishing), a known polishing technique such as mechanical polishing, chemical polishing, mechanochemical polishing (a combination of mechanical polishing and chemical polishing) can be used.
[0007]
For example, it can be obtained by polishing with a fixed abrasive polisher (polishing liquid: water) or lapping with a loose abrasive lapping (abrasive: SiC paste, etc.) and then wrapping the abrasive with diamond paste. it can. There is no restriction | limiting in particular in such a grinding | polishing method, As long as favorable average surface roughness Ra is achieved, you may employ | adopt another grinding | polishing method. The obtained IZO sputtering target is bonded to a backing plate.
[0008]
Next, a cleaning process such as air blow or running water cleaning is performed. When removing foreign matter by air blow, it is possible to remove the foreign matter more effectively by suctioning with a dust collector from the opposite side of the nozzle. However, since there are limits to the above air blow and running water cleaning, ultrasonic cleaning or the like may be further performed. This ultrasonic cleaning is effective by performing multiple oscillations at a frequency of 25 to 300 KHz. For example, it is preferable to perform ultrasonic cleaning by multiplying twelve types of frequencies at 25 KHz intervals between frequencies of 25 to 300 KHz.
[0009]
The bulk resistance value of the transparent conductive film forming IZO sputtering target thus formed can be made 10 mΩ · cm or less. Thus, the bulk resistance value of the IZO sputtering target can be lowered without changing the conventional characteristics of IZO. In particular, by controlling a trace amount additive (addition of Sn of 100 to 2000 ppm), it is possible to control within a range of 1 to 5 mΩ · cm (see Japanese Patent Application No. 11-128122).
In addition, the target of the present invention is characterized by a high density, a structure in which the crystal grain size is more uniform and refined, and a high mechanical strength. Thereby, a target capable of stably and reproducibly obtaining the transparent conductive film is obtained.
[0010]
Examples and Comparative Examples
Subsequently, the present invention will be described with reference to comparative examples by way of examples.
When manufacturing an IZO sputtering target, first, indium oxide powder having an average particle size of 2 μm and zinc oxide powder having the same particle size are weighed in a ratio of about 90:10, and after uniformly pulverizing and mixing, a molding binder is added to prepare the IZO sputtering target. Grained.
Next, this raw material mixed powder was uniformly filled into a mold and pressure-molded with a cold press machine. The molded body thus obtained was sintered at 1380 ° C. for 5 hours in a sintering furnace. During the temperature increase, an oxygen atmosphere was used, and the others were performed in the air (atmosphere) at a temperature increase rate of 4 ° C / min and a temperature decrease rate of 10 ° C / min.
Furthermore, the surface of the sintered body thus obtained was ground with a surface grinder, and the sides were cut with a diamond cutter to obtain an IZO target material.
This IZO target material was indium oxide-10.7 wt% zinc oxide, and the density was 6.87 g / cm 3 (theoretical density was 7.00 g / cm 3 ). The bulk resistance was 3.2 mΩcm. The amount of impurities of Fe, Al, Si, Ti, Ni, and Cu was 10 ppm or less.
[0011]
Next, the structure of this IZO target material was observed and the target surface was qualitatively analyzed by EPMA. As a result, the average crystal grain size was 1.36 μm. The results of qualitative analysis by EPMA are shown in FIG. 1, FIG. 2 and FIG. 1 is a surface analysis result of indium atoms, FIG. 2 is a surface analysis result of zinc atoms, and FIG. 3 is a surface analysis result of oxygen atoms.
As shown in FIGS. 1, 2 and 3, it can be seen that uniformly agglomerated zinc atoms are scattered in the plane. The average agglomerated diameter of zinc atoms was 5 μm or less. Furthermore, the vacancies are smaller than the crystal grain size and are uniformly dispersed as a whole.
[0012]
Next, polishing was performed to prepare a plate (Example 1) having Ra of 0.4 μm as an example of the present invention and a plate (Example 2) having surface grinding in the longitudinal direction to be Ra 1.2 μm. As an example, a plate having a surface roughness of 2.2 μm by surface grinding in the longitudinal direction was prepared.
These were subjected to a three-point bending test to measure the strength. The results are shown in FIGS. FIG. 4 shows the cumulative failure probability with respect to the bending strength according to the median rank method, and FIG. 5 shows a Weibull plot with a single mode.
Further, the Weibull coefficient (m value) indicating the variation of the fracture probability is obtained from FIG. The Weibull coefficient was obtained by calculating a linear regression line. This means that the larger the Weibull coefficient, the less the variation in the maximum value of the non-destructive stress. However, from Table 1, the example product has less variation than the conventional product, and is a stable material. I can confirm.
FIG. 4 shows that the bending strength decreases when Ra is 2.0 μm or more. Generally, the surface roughness after surface grinding corresponds to the crystal grain size. When the particle size is not uniform, Ra becomes larger, and the bending strength is lowered accordingly. This is the case because the conventional structure is uneven.
As is clear from the above comparison, it is possible to obtain a target having a quality exceeding that of the conventional product by using a target having a fine crystal grain size and a small surface roughness.
[0013]
[Table 1]
【The invention's effect】
The IZO sputtering target for forming a transparent conductive film of the present invention effectively reduces bulk resistance without substantially losing the properties of an indium and zinc oxide-based (IZO) transparent conductive film. Can be made. And the bulk resistance value of the IZO sputtering target for transparent conductive film formation formed in this way can be controlled in the range of 10 mΩ · cm or less.
In addition, the target of the present invention is characterized by a high density, a structure with a finer crystal grain size, and a high bending strength. Accordingly, the sputtering discharge can be stabilized, and an excellent feature is obtained in that a target capable of stably and reproducibly obtaining the transparent conductive film can be obtained.
[Brief description of the drawings]
FIG. 1 is a diagram showing the results of qualitative analysis of indium by EPMA on the surface of an IZO target material of the present invention.
FIG. 2 is a diagram showing the results of qualitative analysis of zinc by EPMA on the surface of an IZO target material of the present invention.
FIG. 3 is a diagram showing the results of qualitative analysis of oxygen by EPMA on the surface of the IZO target material of the present invention.
FIG. 4 is a diagram showing a cumulative failure probability with respect to bending strength of an IZO target of the present invention.
FIG. 5 is a diagram showing the same Weibull plot of the IZO target of the present invention.
Claims (15)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31823099A JP3628566B2 (en) | 1999-11-09 | 1999-11-09 | Sputtering target and manufacturing method thereof |
| PCT/JP2000/005172 WO2001034869A1 (en) | 1999-11-09 | 2000-08-02 | Sputtering target and method for preparation thereof |
| KR10-2001-7008548A KR100413958B1 (en) | 1999-11-09 | 2000-08-02 | Sputtering target and method for preparation thereof |
| TW089126329A TWI225521B (en) | 1999-11-09 | 2000-12-08 | Sputtering target and method of manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31823099A JP3628566B2 (en) | 1999-11-09 | 1999-11-09 | Sputtering target and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001131736A JP2001131736A (en) | 2001-05-15 |
| JP3628566B2 true JP3628566B2 (en) | 2005-03-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31823099A Expired - Lifetime JP3628566B2 (en) | 1999-11-09 | 1999-11-09 | Sputtering target and manufacturing method thereof |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP3628566B2 (en) |
| KR (1) | KR100413958B1 (en) |
| TW (1) | TWI225521B (en) |
| WO (1) | WO2001034869A1 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4843883B2 (en) * | 2001-08-17 | 2011-12-21 | 東ソー株式会社 | Sputtering target |
| JP4611198B2 (en) * | 2003-03-04 | 2011-01-12 | Ｊｘ日鉱日石金属株式会社 | Sputtering target for forming amorphous protective film for optical information recording medium, amorphous protective film for optical information recording medium, and manufacturing method thereof |
| JP4826066B2 (en) * | 2004-04-27 | 2011-11-30 | 住友金属鉱山株式会社 | Amorphous transparent conductive thin film and method for producing the same, and sputtering target for obtaining the amorphous transparent conductive thin film and method for producing the same |
| JP5156181B2 (en) * | 2005-06-30 | 2013-03-06 | 出光興産株式会社 | Method for producing indium oxide / zinc oxide sintered body |
| KR101317080B1 (en) * | 2005-07-01 | 2013-10-11 | 이데미쓰 고산 가부시키가이샤 | Process for producing izo sputtering target |
| KR101241524B1 (en) | 2005-09-01 | 2013-03-11 | 이데미쓰 고산 가부시키가이샤 | Sputtering target, transparent conductive film and transparent electrode |
| EP2471972B1 (en) | 2006-12-13 | 2014-01-29 | Idemitsu Kosan Co., Ltd. | Sputtering target |
| JP5237557B2 (en) * | 2007-01-05 | 2013-07-17 | 出光興産株式会社 | Sputtering target and manufacturing method thereof |
| JP4859726B2 (en) * | 2007-03-29 | 2012-01-25 | 三井金属鉱業株式会社 | SnO2-based sputtering target and sputtered film |
| JP5096250B2 (en) * | 2008-07-18 | 2012-12-12 | 出光興産株式会社 | Oxide sintered body manufacturing method, oxide sintered body, sputtering target, oxide thin film, thin film transistor manufacturing method, and semiconductor device |
| US20100108503A1 (en) * | 2008-10-31 | 2010-05-06 | Applied Quantum Technology, Llc | Chalcogenide alloy sputter targets for photovoltaic applications and methods of manufacturing the same |
| KR20140011945A (en) * | 2012-07-19 | 2014-01-29 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Sputtering target, method for using the same, and method for forming oxide film |
| JP6278229B2 (en) * | 2012-08-10 | 2018-02-14 | 三菱マテリアル株式会社 | Sputtering target for forming transparent oxide film and method for producing the same |
| JP5902333B1 (en) * | 2015-02-27 | 2016-04-13 | Ｊｘ金属株式会社 | Sputtering target and manufacturing method thereof |
| JP6125689B1 (en) | 2016-03-31 | 2017-05-10 | Ｊｘ金属株式会社 | Indium oxide-zinc oxide (IZO) sputtering target |
| JP6453990B2 (en) * | 2017-12-21 | 2019-01-16 | Ｊｘ金属株式会社 | Sintered body, sputtering target and manufacturing method thereof |
| CN115572167A (en) * | 2022-10-18 | 2023-01-06 | 长沙壹纳光电材料有限公司 | IWZO target material and preparation method and application thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05214523A (en) * | 1992-02-05 | 1993-08-24 | Toshiba Corp | Sputtering target and its manufacture |
| US5417816A (en) * | 1992-12-09 | 1995-05-23 | Nikko Kyodo, Ltd. | Process for preparation of indium oxide-tin oxide powder |
| WO1997001853A1 (en) * | 1995-06-28 | 1997-01-16 | Idemitsu Kosan Co., Ltd. | Transparent conductive laminate and touch panel made by using the same |
| JP4081840B2 (en) * | 1997-02-28 | 2008-04-30 | 東ソー株式会社 | Manufacturing method of sputtering target |
| JPH11302835A (en) * | 1998-04-21 | 1999-11-02 | Sumitomo Metal Mining Co Ltd | Method for producing ZnO-based sintered body |
| JPH11302074A (en) * | 1998-04-22 | 1999-11-02 | Central Glass Co Ltd | Production of compound oxide sintered body |
-
1999
- 1999-11-09 JP JP31823099A patent/JP3628566B2/en not_active Expired - Lifetime
-
2000
- 2000-08-02 WO PCT/JP2000/005172 patent/WO2001034869A1/en not_active Ceased
- 2000-08-02 KR KR10-2001-7008548A patent/KR100413958B1/en not_active Expired - Lifetime
- 2000-12-08 TW TW089126329A patent/TWI225521B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR20010093248A (en) | 2001-10-27 |
| JP2001131736A (en) | 2001-05-15 |
| KR100413958B1 (en) | 2004-01-07 |
| TWI225521B (en) | 2004-12-21 |
| WO2001034869A1 (en) | 2001-05-17 |
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