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JP4170454B2 - Article having transparent conductive oxide thin film and method for producing the same - Google Patents

Article having transparent conductive oxide thin film and method for producing the same Download PDF

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Publication number
JP4170454B2
JP4170454B2 JP20894898A JP20894898A JP4170454B2 JP 4170454 B2 JP4170454 B2 JP 4170454B2 JP 20894898 A JP20894898 A JP 20894898A JP 20894898 A JP20894898 A JP 20894898A JP 4170454 B2 JP4170454 B2 JP 4170454B2
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range
ratio
substrate
article
film
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JP2000044236A (en
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清 森田
裕道 太田
秀雄 細野
博司 川副
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Hoya Corp
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Hoya Corp
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10DINORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00Field-effect transistors [FET]
    • H10D30/60Insulated-gate field-effect transistors [IGFET]
    • H10D30/67Thin-film transistors [TFT]
    • H10D30/674Thin-film transistors [TFT] characterised by the active materials
    • H10D30/6755Oxide semiconductors, e.g. zinc oxide, copper aluminium oxide or cadmium stannate
    • H10D30/6756Amorphous oxide semiconductors
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10DINORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D64/00Electrodes of devices having potential barriers
    • H10D64/60Electrodes characterised by their materials
    • H10D64/62Electrodes ohmically coupled to a semiconductor
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10DINORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D99/00Subject matter not provided for in other groups of this subclass

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  • Liquid Crystal (AREA)
  • Non-Insulated Conductors (AREA)
  • Manufacturing Of Electric Cables (AREA)

Description

【0001】
【発明の属する技術分野】
本発明は、高い導電性と可視、特に青色光透過性を有し、かつ作製が容易である非晶質性酸化物を含む透明導電体膜を有する物品およびその製造方法に関する。さらに本発明は、本発明の物品からなる電極に関する。
【0002】
【従来の技術】
光透過型液晶パネルディスプレイは薄型、軽量の表示装置として各種の電気製品に幅広く用いられている。特にパーソナルコンピュータやワードプロセッサ等のOA機器への導入は活発であり、現在対角約10インチ程度のノート型パソコンや、省スペースのデスクトップパソコン用のディスプレイとして益々需要が高まっており、更に大面積化、多画素化、高精細化の方向で改良が加えられている。
【0003】
光透過型の液晶では透明電極が不可欠であり、透明電極材料としては主にITOが使用されている。ITOは紫外域のほぼ全域で透明であり、電気抵抗率を1×10−4Ωcm程度まで低減できるので、液晶ティスプレイ等の透明電極材料として好適であった。近年は、高精細化の要求に応えてITOのアモルファス相、いわゆるアモルファスITOが使用されるようになってきている。アモルファスITOは結晶性のITOに比べてパターニング性が良好なため、細い電極パターンをきれいに切れるからである。電気抵抗率は結晶性ITOに比べて増大してしまうが、液晶ティスプレイの主流を占めるTFT型の画素電極用には十分な抵抗値であるからである。また、ティスプレイを軽量化するためにプラスチック基板が用いられる傾向にあり、室温成膜の可能なアモルファスITOが好適と考えられる。結晶性ITOの成膜には200℃以上の温度を要するからである。
【0004】
【発明が解決しようとする課題】
アモルファスITOはその成分の90%以上がIn2O3からなる。このため、近年の液晶ディスプレイの普及に伴ってIn2O3の価格が2倍程度まで高騰して、原料コストを大きくする要因となっている。また、In2O3は希少金属であって、あと30年程度採掘を継続すると枯渇すると予測されている。このような理由から、In2O3の含有量が低く、原料コストが低く、資源環境負荷が低い材料が必要になりつつある。
【0005】
そこで本発明の目的は、資源環境負荷の高いInOの含有量を低く抑えることができ、室温付近の温度で容易に作製することができ、低抵抗かつ光学吸収端が紫外域にあり、青色透過性に優れた新規な透明導電体材料及びその製造方法、さらには、そのような透明導電体材料を用いた電極を提供することにある。
【0006】
本発明者らは、亜鉛-インジウム系酸化物であって、所定量のアルミニウム又はガリウムを含む酸化物が、室温付近の温度で容易に作製することができ、低抵抗かつ光学吸収端が紫外域にあり、青色透過性に優れていることを見いだして本発明を完成した。
【0007】
尚、特開平7-235219号公報には、亜鉛-インジウム系酸化物からなる透明導電膜が設けられた導電性透明基材が開示されている。この透明導電膜は、主要カチオン元素としてインジウム(In)および亜鉛(Zn)を含有する非晶質酸化物からなり、原子比In/(In+Zn)が0.8〜0.9の範囲内である。さらに、この酸化物は、第3元素として、アルミニウム、ガリウム、アンチモンまたはゲルマニウムを含有すること、及びその含有量は、導電性の低下を抑制するため原子比(全第3元素)/(In+Zn+全第3元素)が0.2以下であることが記載されている。
【0008】
この公報には、上記酸化物からなる透明導電膜の吸収端についての記述は無く、光学特性については光線透過率のみしか明らかにされていない。即ち、上記透明導電膜が、どのような光線透過率スペクトルを有するかは明らかでなく、低抵抗であり、光学吸収端が紫外域にあり、さらに青色透過性に優れているかは不明である。
【0009】
【課題を解決するための手段】
本発明の物品の第1の態様は、基材の少なくとも一方の表面の少なくとも一部に、一般式ZnxMyInzO(x+3y/2+3z/2)(式中、Mはアルミニウム及びガリウムのうち少なくとも一つの元素であり、比率x/yが0.2〜2の範囲であり、比率z/yが0.4〜1.4の範囲にある)で表される非晶質酸化物を含有する膜を有することを特徴とする。本発明の物品の第2の態様は、基材の少なくとも一方の表面の少なくとも一部に、一般式ZnxMyInzO(x+3y/2+3z/2)(式中、Mはアルミニウム及びガリウムのうち少なくとも一つの元素であり、比率x/yが0.2〜2の範囲であり、比率z/yが0.4〜1.4の範囲にある)で表され、かつ陽イオンを注入したものである非晶質酸化物を含有する膜を有することを特徴とする。
【0010】
さらに本発明は、上記本発明の物品からなる電極に関する。
【0011】
本発明の第1の製造方法は、上記本発明の第1の態様の物品の製造方法であって、一般式ZnxMyInzO(x+3y/2+3z/2)(式中、Mはアルミニウム及びガリウムのうち少なくとも一つの元素であり、比率x/yが0.2〜2の範囲であり、比率z/yが0.4〜1.4の範囲にある)で表される酸化物をターゲットとし、基板温度を室温から300℃の範囲とし、かつ圧力を1×10-2[Pa]〜10[Pa]の範囲として、スパッタリング法またはレーザーアブレーション法により、酸化物膜を形成することを特徴とする。
【0012】
本発明の第2の製造方法は、上記本発明の第2の態様の物品の製造方法であって、一般式ZnxMyInzO(x+3y/2+3z/2)(式中、Mはアルミニウム及びガリウムのうち少なくとも一つの元素であり、比率x/yが0.2〜2の範囲であり、比率z/yが0.4〜1.4の範囲にある)で表される酸化物をターゲットとし、基板温度を室温から300℃の範囲とし、かつ圧力を1×10-2[Pa]〜10[Pa]の範囲として、スパッタリング法またはレーザーアブレーション法により、酸化物膜を形成し、次いで前記酸化物膜に陽イオンを注入することを特徴とする。
【0013】
【発明の実施の態様】
本発明の第1の態様の物品
一般式ZnxMyInzO(x+3y/2+3z/2)中、Mはアルミニウム及びガリウムのいずれか単独であってもよいし、Mはアルミニウム及びガリウムが共存してもよい。アルミニウム及びガリウムが共存する場合、アルミニウムとガリウムの比率には特に制限はない。但し、アルミニウムの比率が増えると結晶化温度が高くなる傾向がある。ガリウムの比率が増えると結晶化温度が低くなる傾向がある。
【0014】
比率(x/y)は0.2以上、2以下の範囲であり、x/yが0.2未満では原料コストが高くなる。x/yが12を超えるとZn成分が大きくなりすぎて大気中で化学的に不安定になる。好ましい比率(x/y)は1〜10の範囲であり、より好ましくは4〜10の範囲である。比率(z/y)は0.4以上、1.4以下の範囲であり、z/yが0.4未満ではIn23が不足し、電気伝導性が低下する。z/yが1.4を超えるとGa23成分が不足して青色領域の透明性が低下する。好ましい比率(z/y)は0.6以上1.4以下の範囲であり、より好ましくは0.8以上1.2以下の範囲である。
【0015】
さらに本発明の物品において、比率x/(x+y+z)が0.5以上であることが、原料コストを下げ、環境負荷を低減するという観点から好ましい。比率x/(x+y+z)は、好ましくは0.6〜0.9の範囲である。
さらに本発明の物品が有する膜において、上記酸化物は、実質的全量が非晶質であることが、透過率及び導電性の点で好ましいが、透過率及び導電性を損なわない程度に、結晶質の酸化物を含有することもできる。
【0016】
本発明の酸化物の導電性は、伝導帯におけるキャリア電子の量が所定の範囲にあるときに良好となる。そのようなキャリア電子の量は、1×1018/cm3〜1×1022/cm3の範囲である。また、好ましいキャリア電子の量は、1×1019/cm3〜5×1021/cm3の範囲である。
尚、キャリア電子の量は、例えば、ファンデアパウ法電気伝導率測定装置により測定することができる。
【0017】
本発明の第2の態様の物品
本発明の第2の態様の物品において、一般式ZnxMyInzO(x+3y/2+3z/2)の式中、Zn、M、比率(x/y)及び比率(z/y)については、前記本発明の第1の態様の物品と同様である。比率x/(x+y+z)及び非晶質であることについても、前記本発明の第1の態様の物品の導電性酸化物と同様である。
【0018】
さらに、本発明の第2の態様の物品は、上記一般式で表される酸化物に、陽イオンを注入したものである。
本発明の第2の態様の物品では、酸素欠損を導入すること以外に、陽イオンを注入することによりキャリア電子が伝導帯に注入されて、導電性を発現させることができる。
【0019】
本発明の第2の態様の物品が有する導電性酸化物に注入される陽イオンは、一般式ZnxMyInzO(x+3y/2+3z/2)で表される酸化物の結晶構造を破壊することなく、固溶できるものであれば特に制限はない。但し、イオン半径の小さいイオンの方が結晶格子中に固溶しやすい傾向があり、イオン半径が大きくなる程、結晶構造を破壊し易くなる傾向がある。
上記のような陽イオンとしては、例えば、H、Li、Be、B、C、Na、Mg、Al、Si、K、Ca、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Ge、Y、Zr、Nb、Mo、Tc、Ru、Rh、Pd、Ag、Cd、In、Sn、Sb、Cs、Ba、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Hf、Ta、W、Re、Os、Ir、Pt、Au、Hg、Tl、Pb、Biを挙げることができる。
【0020】
本発明の電極
本発明の電極は、上記本発明の第1または第2の態様の物品を含むものである。本発明の電極における酸化物膜からなる導電層の膜厚は、電極に要求される光学的特性、伝導性及び用途等を考慮して適宜決定できる。例えば、液晶パネル用電極の場合には、下限は約30nmであり、上限は約1μmである。但し、酸化物に含まれる元素の種類によっては、可視領域に一部吸収を有するものもあり、その場合には、比較的薄い膜が好ましい。また、可視領域にほとんどまたはまったく吸収を有さないものについては、膜厚を厚くすることで、より高い伝導性を得ることができる。
【0021】
本発明の物品における基材に相当する透明基板としては、ガラスや樹脂などの透明な基体を挙げることができる。即ち、ガラス質・高分子性等にかかわらず、あらゆる透明材料を基板として利用することができる。また基板形態も平面基板、シート、フィルム等あらゆる形態に対応する。ガラス基板は、液晶ディスプレイなどに多く用いられる。ガラス基板には、ソーダ系ガラスと低アルカリガラスがあり、一般的にはソーダ系ガラスが広く用いられている。但し、カラーディスプレイや高品質ディスプレイなどには低アルカリガラスが優れている。可視領域における透明性が高く、平面性の優れたガラスを用いることが好ましい。
【0022】
樹脂基板としては、例えば、ポリエステル基板、PMMA基板等が挙げられる。樹脂基板は、ガラス基板に比べて、軽量であること、薄いこと、可撓性があって形の自由度が高いことなどを生かした多くの用途が検討されている。例えば、電子写真用フィルム、液晶ディスプレイ、光メモリ、透明タブレントスイッチ、帯電防止フィルム、熱線反射フィルム、面発熱フィルムなどである。液晶ディスプレイには、可視領域における透明性が高いこと、平面性に優れることの他に、加工性、耐衝撃性、耐久性、組立プロセスへの適合性などを考慮して用いることが好ましい。
【0023】
また、本発明の電極は、前記透明基板上に設けた下地層上に設けることもできる。下地層としては、カラーフィルター、TFT層、EL発光層、金属層、半導体層及び絶縁体層などを挙げることができる。また、下地層は2種以上を併設することもできる。
【0024】
本発明の電極は、種々の用途に利用することができる。例えば、液晶ディスプレイ、ELディスプレイ及び太陽電池等の電極として好適に用いることができる。
液晶ディスプレイにはTFT型、STN型やMIM型など種々の型があるが、いずれの場合にも透明電極にはさまれた液晶に電場を加え、液晶の配向方向を制御して表示する原理を用いている。本発明の電極は、上記透明電極として用いることができる。
例えば、TFT型のカラー液晶ディスプレイの構造は、バックライト、第一の偏光板、TFT基板、液晶、カラーフィルター基板及び第二の偏光板の6つの部分からなる。液晶の配向方向を制御するためにTFT基板上とカラーフィルター基板上に透明電極を形成する必要があるが、本発明の透明電極は上述の方法によりTFT基板上にもカラーフィルター基板上にも形成することができる。本発明の透明電極は、透明性が高くかつ導電性も高いのでTFT基板上またはカラーフィルター基板上に設ける透明電極として最適である。
【0025】
また、本発明の透明電極は、ELディスプレイ用電極として用いることもできる。ELディスプレイには分散型、ルモセン構造型や二重絶縁構造型などがあるが、いずれの場合にも透明電極と背面電極の間にEL発光層を挟み込む基本構造を有し、本発明の電極は、上記の透明電極として最適である。
【0026】
本発明の電極は、透明性及び導電性が高いことから、太陽電池用電極としても優れている。太陽電池は、pn接合型、ショットキーバリア型、ヘテロ接合型、ヘテロフェイス接合型やpin型などに分類されるが、いずれの場合にも透明電極と背面電極の間に半導体や絶縁体を挟み込む基本構造を有する。太陽電池は、半導体界面の光起電力効果を利用して、光エネルギーを電気に変換する素子であるので、なるべく広いスペクトル範囲にわたって光を半導体界面に導くことが必要であり、透明電極の透明性は高くなくてはならない。また、太陽電池の透明電極は半導体界面に生成した光生成キャリアを収集して端子に導き出す機能を持つので、光生成キャリアをなるべく有効に収集するためには透明電極の導電性が高くなくてはならない。本発明の透明電極は、450nmより短波長の光を含む、可視領域全域の広いスペクトル範囲にわたって光を半導体界面に導くことができる上に導電性が高いので太陽電池用の電極として優れている。
【0027】
本発明の製造方法
本発明の第1及び第2の製造方法は、それぞれ、上記本発明の第1及び第2の態様の物品の製造方法である。本発明の第1の製造方法では、一般式ZnxMyInzO(x+3y/2+3z/2)(式中、Mはアルミニウム及びガリウムのうち少なくとも一つの元素であり、比率x/yが0.2〜2の範囲であり、比率z/yが0.4〜1.4の範囲にある)で表される酸化物をターゲットとして用いる。本発明の第2の製造方法では、第1の製造方法と同様に、一般式ZnxMyInzO(x+3y/2+3z/2)(式中、Mはアルミニウム及びガリウムのうち少なくとも一つの元素であり、比率x/yが0.2〜2の範囲であり、比率z/yが0.4〜1.4の範囲にある)で表される酸化物をターゲットとして用いる。
【0028】
本発明の製造方法では、形成される薄膜の組成が、ターゲットの密度により変化することは殆どない。但し、レーザーパルス照射によるターゲットのダメージを考慮すると、ターゲットとして用いる酸化物は、相対密度が好ましくは40%以上であり、さらに好ましくは70%以上である。ターゲットとしては例えば、焼結体を用いることができる。
また、形成される薄膜の組成はターゲットとのずれは少なく、多くても5%であることから、ターゲット組成は、所望の薄膜組成と同一とすることができる。但し、必要により、ターゲット組成を変更することはできる。
【0029】
ターゲットは、例えば、x/y>1の範囲では、Znの酸化物との混晶焼結体、あるいはZnの酸化物を整数倍だけ含んだ、ホモロガスの焼結体を用いることができる。
【0030】
本発明の製造方法では、基板温度を室温から300℃の範囲とし、かつ1×10-2[Pa]〜10[Pa]の圧力範囲の酸素雰囲気あるいは酸素ラジカル雰囲気中で、スパッタリング法またはレーザーアブレーション法により、酸化物膜を形成する。
スパッタリング法及びレーザーアブレーション法においても、基板温度を室温から300℃の範囲とし、かつ圧力(酸素分圧)を1×10-2[Pa]〜10[Pa]の範囲とすることで、非晶質の酸化物膜を形成することができる。基板温度は、好ましくは0〜150℃の範囲であり、かつ圧力は、好ましくは0.01[Pa]〜1[Pa]の範囲である。
【0031】
スパッタリング法は、常法により行うことができる。
また、レーザーアブレーション法では、薄膜形成装置内の酸素分圧の制御は、酸素分子を適当なリークバルブ等から系内に導入することにより行うことができるが、特に、レーザーアブレーション装置内に設置したラジカル銃により行うことが、膜中に含まれる酸素量を制御しやすいとうい観点から適当である。尚、ラジカル銃とはrfプラズマにより酸素等のガスのラジカル種を発生させ真空系内に導入する装置である。
【0032】
本発明の製造方法のレーザーアブレーション法に用いるレーザーとしては、紫外域から赤外域のいずれの波長、すなわち0.19〜11μm 、望ましくは0.19〜0.3μm が可能であり、連続発振又はパルス発振のいずれの方式を採用することができる。レーザー照射時のレーザー強度は、0.0001〜1000J/ cm2・パルス、望ましくは0.1〜100J/cm2・パルスである。
【0033】
第2の態様の製造方法においては、上記方法により形成した酸化物膜に陽イオンを注入する。陽イオンを注入することによりキャリア電子が伝導帯に注入されて、導電性を発現させることができる。陽イオン注入されるイオンは前述の通りである。
【0034】
本発明の製造方法においては、例えば、ターゲットとしてIn:Ga:Zn=1:1:1の焼結体を用いた場合、6.2×10-3[Ωcm]の薄膜を容易に得ることができる。この場合、高導電性の主因は非晶質物質にも関わらず移動度が10以上と高い値を示すことによる。
また、ターゲットとしてZn成分を増加させたホモロガスIGZO InGaO3(ZnO)m(m:2以上の整数)の焼結体を用いた場合、4. 3×10-3[Ωcm]の抵抗率を有する薄膜を容易に得ることができる。この理由はキャリア濃度が指数関数的増大傾向を示すのに対し、移動度がほとんど変化しないことに起因する。
【0035】
更に低抵抗化を望む場合は、成膜後に低温(300℃以下が望ましい)でガス還元法あるいはイオン注入法を用いることでキャリア密度を上げることにより、導電性を向上させることができる。更にターゲットの組成を変える置換ドーピング効果を利用して、キャリア密度を向上してもよい。
【0036】
【発明の効果】
本発明の物品は、材料中のIn含有量が少ないので材料コストが低く、環境負荷が小さく、かつ可視光透過率が85%以上であり、かつ吸収短波長が385nmであることから、白黒画面でもカラー画面でも膜厚を厚くすることで低抵抗化を図ることが可能である。
また、膜を構成する材料の結晶化温度が400℃以上と高いため、通常の使用温度範囲では、安定な非晶質性を維持し、抵抗率の変動がないという利点がある。安定な酸化物であることから耐環境性に優れており、野外で使用する太陽電池用の透明電極として利用できる。
【0037】
また、室温程度の温度での成膜で還元・アニール操作なしに導電性を発現するので、生産効率も高く、装置も簡便で済み生産コストを低減することができる。
【0038】
特に、本発明の物品は、優れた電気伝導性と青色領域を含む可視光透過性を兼ね備えており、有用な透明電極としてのポテンシャルを持つことから、ディスプレイや太陽電池用の電極として利用することができる。また、成膜温度を室温付近とすることができるので、生産効率が高い。さらに、材料の結晶化温度は高く、耐環境性にも優れる。
【0039】
【実施例】
本実施例の条件は以下のとおりである。

Figure 0004170454
【0040】
1.ターゲットの作成
In2O3、Ga2O3、ZnOの各粉末を、含有金属の比率がそれぞれ1になるように秤量した。秤量した粉末を、遊星ボールミル装置で湿式混合。1000℃で5時間仮焼した後、再び遊星ボールミルで解砕処理した。この粉体を一軸加圧で直径20mmの円板状に成形の後CIPをかけた。大気下、1550℃で2時間焼成して焼結体を得た。XRDによりInGaZnO4で表される酸化物が生成していることを確認した。
【0041】
ホモロガスInGaO3(ZnO)mの場合は、In2O3、Ga2O3、ZnOの各粉末を、含有金属の比率が1:1:m(mは2以上の整数) となるように秤量した。秤量した粉末を、遊星ボールミル装置で湿式混合。1000℃で5時間仮焼した後、再び遊星ボールミルで解砕処理した。この粉体を一軸加圧で直径20mmの円板状に成形の後CIPをかけた。大気下、1550℃で2時間焼成して焼結体を得た。XRDによりそれぞれのm値に対応したInGaO3(ZnO)mで表される酸化物が生成していることを確認した。
【0042】
2.成膜
以下に実施例としてレーザーアブレーション法を用いる成膜法を示す。
実施例1
上で作成した焼結体のうち、In:Ga:Zn=1:1:1の焼結体の表面を研磨し、金属Inでインコネル製のホルダーに固定した。これを日本真空(株)製レーザーアブレーション装置に固定し、自転させている表面上にラムダフィジック社製KrFエキシマレーザー光を4J/cm2のエネルギー密度、パルス間隔5Hzで照射し、プルームをたてた。チャンバー中の雰囲気はO2ガスを15 - 25CCM流し、全圧を0.8− 1.0[Pa]とした。ターゲットから30mm直上に10mm角で厚さ0.5mmの石英ガラス基板を設置し、膜厚が均等となるように自転させながら30分プルーム中に曝すことにより、約300nmの薄膜を得た。組成比は蛍光X線法により得た。膜が均一な非晶質であることはXRDより確認した(図1)。吸収端は試料の透過及び反射スペクトルから光学定数を計算することから求めた。電気特性はファンデアパウ法によるHall効果測定より求めた。
【0043】
【表1】
Figure 0004170454
【0044】
実施例2
実施例1と同条件で成膜基板に10mm角で厚さ1.0mmのアクリル基板を用いることにより、IGZOの非晶質薄膜を得た。
【0045】
【表2】
Figure 0004170454
【0046】
実施例3
実施例1と同様にチャンバー雰囲気をO2ガス5-20[CCM]流し、ラジカルガンを用いてRF電力50Wかけることにより酸素ラジカルを発生させ、全圧を0.2− 0.4[Pa]とした。
【0047】
【表3】
Figure 0004170454
【0048】
実施例4
上で作成した焼結体のうち、In:Ga:Zn=1:1:4の焼結体の表面を研磨し、金属Inでインコネル製のホルダーに固定した。これを日本真空(株)製レーザーアブレーション装置に固定し、自転させている表面上にラムダフィジック社製KrFエキシマレーザー光を4J/cm2のエネルギー密度、パルス間隔5Hzで照射し、プルームをたてた。チャンバー中の雰囲気はO2ガスを15 - 25CCM流し、全圧を0.8− 1.0[Pa]とした。ターゲットから 30mm直上に10mm角で厚さ0.5mmの石英ガラス基板を設置し、膜厚が均等となるように自転させながら30分プルーム中に曝すことにより、約300nmの薄膜を得た。組成比は蛍光X線法により得た。膜が均一な非晶質であることはXRDより確認した。吸収端は試料の透過及び反射スペクトルから光学定数を計算することから求めた。電気特性はファンデアパウ法によるHall効果測定より求めた。
【0049】
【表4】
Figure 0004170454

【図面の簡単な説明】
【図1】 InGaZnO4で表される酸化物が生成していることを確認するXRDの結果。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an article having a transparent conductor film containing an amorphous oxide having high conductivity and visible, particularly blue light transmittance, and easy to produce, and a method for producing the same. The present invention further relates to an electrode comprising the article of the present invention.
[0002]
[Prior art]
Light transmissive liquid crystal panel displays are widely used in various electrical products as thin and light display devices. In particular, it is actively introduced to office automation equipment such as personal computers and word processors. Currently, the demand for laptop computers with a diagonal of about 10 inches and displays for space-saving desktop computers is increasing, and the area is further increased. Improvements have been made in the direction of increasing the number of pixels and increasing the definition.
[0003]
A transparent electrode is indispensable for a light-transmissive liquid crystal, and ITO is mainly used as a transparent electrode material. ITO is transparent over almost the entire ultraviolet region, and its electrical resistivity can be reduced to about 1 × 10 −4 Ωcm. Therefore, ITO is suitable as a transparent electrode material for liquid crystal displays and the like. In recent years, in response to the demand for higher definition, an amorphous phase of ITO, so-called amorphous ITO, has been used. This is because amorphous ITO has better patterning properties than crystalline ITO, so that a thin electrode pattern can be cut cleanly. This is because the electrical resistivity increases as compared with crystalline ITO, but is a sufficient resistance value for a TFT type pixel electrode that occupies the mainstream of liquid crystal displays. In addition, plastic substrates tend to be used to reduce the weight of the display, and amorphous ITO that can be formed at room temperature is considered preferable. This is because a film of crystalline ITO requires a temperature of 200 ° C. or higher.
[0004]
[Problems to be solved by the invention]
Amorphous ITO consists of In 2 O 3 in 90% or more of its components. For this reason, with the recent spread of liquid crystal displays, the price of In 2 O 3 has soared to about twice, which is a factor in increasing raw material costs . In 2 O 3 is a rare metal and is expected to be depleted if mining continues for another 30 years. For these reasons, there is a need for materials with low In 2 O 3 content, low raw material costs, and low resource environmental impact.
[0005]
Therefore, the object of the present invention is to reduce the content of In 2 O 3 which has a high environmental burden on the environment, and can be easily manufactured at a temperature near room temperature, and has a low resistance and an optical absorption edge in the ultraviolet region. Another object of the present invention is to provide a novel transparent conductor material excellent in blue transmittance and a method for producing the same, and an electrode using such a transparent conductor material.
[0006]
The inventors of the present invention can easily produce a zinc-indium oxide containing a predetermined amount of aluminum or gallium at a temperature near room temperature, and has a low resistance and an optical absorption edge in the ultraviolet region. Thus, the present invention was completed by finding that it has excellent blue transmittance.
[0007]
JP-A-7-235219 discloses a conductive transparent substrate provided with a transparent conductive film made of a zinc-indium oxide. This transparent conductive film is made of an amorphous oxide containing indium (In) and zinc (Zn) as main cation elements, and has an atomic ratio In / (In + Zn) in the range of 0.8 to 0.9. . Further, this oxide contains aluminum, gallium, antimony or germanium as the third element, and the content thereof is atomic ratio (all third elements) / (In + Zn + total) in order to suppress the decrease in conductivity. The third element) is 0.2 or less.
[0008]
In this publication, there is no description about the absorption edge of the transparent conductive film made of the oxide, and only the light transmittance is clarified as to the optical characteristics. That is, it is not clear what light transmittance spectrum the transparent conductive film has, and it is unclear whether it has low resistance, the optical absorption edge is in the ultraviolet region, and is excellent in blue transmittance.
[0009]
[Means for Solving the Problems]
A first aspect of the article of the present invention, at least a portion of at least one surface of a substrate, the general formula Zn x M y In z O ( x + 3y / 2 + 3z / 2) ( in the formula, M at least one element selected from aluminum and gallium in the range ratio x / y is from 0.2 to 2, containing an amorphous oxide ratio z / y is represented by some) in the range of 0.4 to 1.4 It has a film. A second aspect of the article of the present invention, at least a portion of at least one surface of a substrate, the general formula Zn x M y In z O ( x + 3y / 2 + 3z / 2) ( in the formula, M At least one element of aluminum and gallium, in which the ratio x / y is in the range of 0.2 to 2 and the ratio z / y is in the range of 0.4 to 1.4) and is injected with cations It has a film containing a certain amorphous oxide.
[0010]
Furthermore, this invention relates to the electrode which consists of an article | item of the said invention.
[0011]
The first production method of the present invention is a method of manufacturing an article of the first aspect of the present invention, the general formula Zn x M y In z O ( x + 3y / 2 + 3z / 2) ( in the formula , M is at least one element of aluminum and gallium, the ratio x / y is in the range of 0.2 to 2 , and the ratio z / y is in the range of 0.4 to 1.4) , a substrate temperature of range of the range of 300 ° C. from room temperature, and the pressure 1 × 10 -2 [Pa] ~10 [Pa], Ri by the sputtering or laser ablation method, to form an acid fluoride film Features.
[0012]
The second production method of the present invention is a method of manufacturing an article of the second aspect of the present invention, the general formula Zn x M y In z O ( x + 3y / 2 + 3z / 2) ( in the formula , M is at least one element of aluminum and gallium, the ratio x / y is in the range of 0.2 to 2 , and the ratio z / y is in the range of 0.4 to 1.4) the substrate temperature in the range of 300 ° C. from room temperature, and a range of pressure 1 × 10 -2 [Pa] ~10 [Pa], Ri by the sputtering or laser ablation method, the oxides film formed, then A cation is implanted into the oxide film.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
In the article <br/> formula of the first aspect Zn x M y In z O of the present invention (x + 3y / 2 + 3z / 2), M may be the sole one of aluminum and gallium , M may coexist with aluminum and gallium. When aluminum and gallium coexist, the ratio of aluminum to gallium is not particularly limited. However, as the aluminum ratio increases, the crystallization temperature tends to increase. As the gallium ratio increases, the crystallization temperature tends to decrease.
[0014]
The ratio (x / y) is in the range of 0.2 or more and 2 or less. If x / y is less than 0.2, the raw material cost increases. When x / y exceeds 12, the Zn component becomes too large and becomes chemically unstable in the atmosphere. A preferred ratio (x / y) is in the range of 1 to 10, more preferably in the range of 4 to 10. The ratio (z / y) is in the range of 0.4 or more and 1.4 or less. When z / y is less than 0.4, In 2 O 3 is insufficient and the electrical conductivity is lowered. When z / y exceeds 1.4, the Ga 2 O 3 component is insufficient and the transparency of the blue region is lowered. A preferred ratio (z / y) is in the range of 0.6 to 1.4, and more preferably in the range of 0.8 to 1.2.
[0015]
Furthermore, in the article of the present invention, the ratio x / (x + y + z) is preferably 0.5 or more from the viewpoint of reducing raw material costs and reducing environmental burden. The ratio x / (x + y + z) is preferably in the range of 0.6 to 0.9.
Further, in the film of the article of the present invention, it is preferable that the oxide is substantially amorphous in terms of transmittance and conductivity. However, the oxide is crystalline to the extent that the transmittance and conductivity are not impaired. Quality oxides can also be included.
[0016]
The conductivity of the oxide of the present invention is good when the amount of carrier electrons in the conduction band is within a predetermined range. The amount of such carrier electrons is in the range of 1 × 10 18 / cm 3 to 1 × 10 22 / cm 3 . A preferable amount of carrier electrons is in the range of 1 × 10 19 / cm 3 to 5 × 10 21 / cm 3 .
The amount of carrier electrons can be measured by, for example, a van der Pauw electric conductivity measuring device.
[0017]
The article of the second aspect of the article <br/> present invention of the second aspect of the present invention, the general formula Zn x M y In z wherein the O (x + 3y / 2 + 3z / 2), Zn, About M, a ratio (x / y), and a ratio (z / y), it is the same as that of the article | item of the said 1st aspect of this invention. The ratio x / (x + y + z) and the amorphous state are the same as the conductive oxide of the article of the first aspect of the present invention.
[0018]
Furthermore, the article of the second aspect of the present invention is obtained by injecting a cation into the oxide represented by the above general formula.
In the article according to the second aspect of the present invention, in addition to introducing oxygen vacancies, carrier electrons can be injected into the conduction band by injecting cations, and conductivity can be expressed.
[0019]
Cations article of the second aspect is injected into the conductive oxide having the present invention, of the general formula Zn x M y In z O ( x + 3y / 2 + 3z / 2) oxide represented by There is no particular limitation as long as it can be dissolved without destroying the crystal structure. However, ions having a small ion radius tend to be dissolved in the crystal lattice, and the larger the ion radius, the easier it is to destroy the crystal structure.
Examples of such cations include H, Li, Be, B, C, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, and Cu. Zn, Ga, Ge, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi.
[0020]
Electrode of the Present Invention The electrode of the present invention includes the article of the first or second aspect of the present invention. The film thickness of the conductive layer made of the oxide film in the electrode of the present invention can be appropriately determined in consideration of the optical characteristics, conductivity, application, and the like required for the electrode. For example, in the case of a liquid crystal panel electrode, the lower limit is about 30 nm and the upper limit is about 1 μm. However, depending on the type of element contained in the oxide, there are some that have partial absorption in the visible region. In that case, a relatively thin film is preferable. For those that have little or no absorption in the visible region, higher conductivity can be obtained by increasing the film thickness.
[0021]
Examples of the transparent substrate corresponding to the base material in the article of the present invention include a transparent substrate such as glass and resin. In other words, any transparent material can be used as the substrate regardless of glassy or high polymer. Also, the substrate form corresponds to all forms such as a flat substrate, a sheet, and a film. Glass substrates are often used for liquid crystal displays and the like. Glass substrates include soda-based glass and low alkali glass, and soda-based glass is generally widely used. However, low alkali glass is excellent for color displays and high-quality displays. It is preferable to use a glass having high transparency in the visible region and excellent flatness.
[0022]
Examples of the resin substrate include a polyester substrate and a PMMA substrate. Resin substrates are being studied for many uses that take advantage of their light weight, thinness, flexibility, and high degree of freedom of shape as compared to glass substrates. For example, an electrophotographic film, a liquid crystal display, an optical memory, a transparent tabular switch, an antistatic film, a heat ray reflective film, and a surface heating film. In addition to high transparency in the visible region and excellent flatness, the liquid crystal display is preferably used in consideration of processability, impact resistance, durability, suitability for assembly processes, and the like.
[0023]
Moreover, the electrode of this invention can also be provided on the base layer provided on the said transparent substrate. Examples of the underlayer include a color filter, a TFT layer, an EL light emitting layer, a metal layer, a semiconductor layer, and an insulator layer. Two or more underlayers can be provided side by side.
[0024]
The electrode of the present invention can be used for various applications. For example, it can be suitably used as an electrode for liquid crystal displays, EL displays, solar cells and the like.
There are various types of liquid crystal displays such as TFT type, STN type and MIM type. In either case, the principle of displaying by controlling the alignment direction of the liquid crystal by applying an electric field to the liquid crystal sandwiched between transparent electrodes. Used. The electrode of the present invention can be used as the transparent electrode.
For example, the structure of a TFT-type color liquid crystal display is composed of six parts: a backlight, a first polarizing plate, a TFT substrate, a liquid crystal, a color filter substrate, and a second polarizing plate. In order to control the alignment direction of the liquid crystal, it is necessary to form transparent electrodes on the TFT substrate and the color filter substrate, but the transparent electrode of the present invention is formed on the TFT substrate and the color filter substrate by the above method. can do. The transparent electrode of the present invention is optimal as a transparent electrode provided on a TFT substrate or a color filter substrate because of its high transparency and high conductivity.
[0025]
The transparent electrode of the present invention can also be used as an EL display electrode. The EL display includes a dispersion type, a lumocene structure type, and a double insulation structure type. In any case, the EL display has a basic structure in which an EL light emitting layer is sandwiched between a transparent electrode and a back electrode. It is most suitable as the transparent electrode.
[0026]
The electrode of the present invention is excellent as a solar cell electrode because of its high transparency and conductivity. Solar cells are classified into pn junction type, Schottky barrier type, heterojunction type, heteroface junction type, pin type, etc. In any case, a semiconductor or an insulator is sandwiched between a transparent electrode and a back electrode. Has a basic structure. Solar cells are devices that convert light energy into electricity using the photovoltaic effect at the semiconductor interface, so it is necessary to guide light to the semiconductor interface over as wide a spectral range as possible. Must be expensive. In addition, since the transparent electrode of the solar cell has the function of collecting the photogenerated carriers generated at the semiconductor interface and leading them to the terminal, the conductivity of the transparent electrode must be high in order to collect the photogenerated carriers as effectively as possible. Don't be. The transparent electrode of the present invention is excellent as an electrode for a solar cell because it can guide light to a semiconductor interface over a wide spectral range of the entire visible region including light having a wavelength shorter than 450 nm and has high conductivity.
[0027]
Manufacturing method of the present invention The first and second manufacturing methods of the present invention are the manufacturing methods of the articles of the first and second aspects of the present invention, respectively. In the first manufacturing method of the present invention, in the general formula Zn x M y In z O ( x + 3y / 2 + 3z / 2) ( wherein, M is at least one element selected from aluminum and gallium, the ratio x / Y is in the range of 0.2 to 2 and the ratio z / y is in the range of 0.4 to 1.4). In the second manufacturing method of the present invention, as in the first manufacturing method, the general formula Zn x M y In z O ( x + 3y / 2 + 3z / 2) ( wherein, M is one of aluminum and gallium An oxide represented by at least one element and having a ratio x / y in the range of 0.2 to 2 and a ratio z / y in the range of 0.4 to 1.4 is used as a target.
[0028]
In the manufacturing method of the present invention, the composition of the thin film to be formed hardly changes depending on the density of the target. However, considering the damage of the target due to laser pulse irradiation, the oxide used as the target preferably has a relative density of 40% or more, and more preferably 70% or more. As the target, for example, a sintered body can be used.
Further, since the composition of the thin film to be formed is little shifted from the target and is at most 5%, the target composition can be the same as the desired thin film composition. However, the target composition can be changed as necessary.
[0029]
The target, for example, in the range of x / y> 1, containing a mixed crystal sintered body of an oxide of Zn, or an oxide of Zn integer number, it is possible to use a sintered body of homologous.
[0030]
In the production method of the present invention, the sputtering method or laser ablation is performed in an oxygen atmosphere or an oxygen radical atmosphere in which the substrate temperature is in the range of room temperature to 300 ° C. and in the pressure range of 1 × 10 −2 [Pa] to 10 [Pa]. An oxide film is formed by the method.
Even in sputtering and laser ablation methods, the substrate temperature is in the range of room temperature to 300 ° C and the pressure (oxygen partial pressure) is in the range of 1 × 10 -2 [Pa] to 10 [Pa]. A quality oxide film can be formed. The substrate temperature is preferably in the range of 0 to 150 ° C., and the pressure is preferably in the range of 0.01 [Pa] to 1 [Pa].
[0031]
The sputtering method can be performed by a conventional method.
In the laser ablation method, the oxygen partial pressure in the thin film forming apparatus can be controlled by introducing oxygen molecules into the system from an appropriate leak valve or the like. Performing with a radical gun is appropriate from the viewpoint of easily controlling the amount of oxygen contained in the film. The radical gun is a device that generates radical species of gas such as oxygen by rf plasma and introduces it into the vacuum system.
[0032]
The laser used in the laser ablation method of the production method of the present invention can be any wavelength from the ultraviolet region to the infrared region, that is, 0.19 to 11 μm, preferably 0.19 to 0.3 μm, and can be either continuous oscillation or pulse oscillation. Can be adopted. Laser intensity at the time of laser irradiation, 0.0001~1000J / cm 2 · pulse, and desirably 0.1~100J / cm 2 · pulse.
[0033]
In the manufacturing method of the second aspect, cations are implanted into the oxide film formed by the above method. By injecting cations, carrier electrons are injected into the conduction band, and conductivity can be developed. The ions to be positively implanted are as described above.
[0034]
In the production method of the present invention, for example, when a sintered body of In: Ga: Zn = 1: 1: 1 is used as a target, a thin film of 6.2 × 10 −3 [Ωcm] can be easily obtained. In this case, the main cause of high conductivity is that the mobility is as high as 10 or more despite the amorphous material.
Further, when a sintered body of homologous IGZO InGaO 3 (ZnO) m (m: integer of 2 or more) with an increased Zn component is used as a target, it has a resistivity of 4.3 × 10 −3 [Ωcm]. A thin film can be obtained easily. The reason for this is that the carrier concentration shows an exponential increasing tendency while the mobility hardly changes.
[0035]
If further reduction in resistance is desired, the conductivity can be improved by increasing the carrier density by using a gas reduction method or ion implantation method at a low temperature (300 ° C. or lower is desirable) after film formation. Furthermore, the carrier density may be improved by utilizing a substitution doping effect that changes the composition of the target.
[0036]
【The invention's effect】
Since the article of the present invention has a low In 2 O 3 content in the material, the material cost is low, the environmental load is small, the visible light transmittance is 85% or more, and the absorption short wavelength is 385 nm. It is possible to reduce the resistance by increasing the film thickness for both monochrome and color screens.
In addition, since the crystallization temperature of the material constituting the film is as high as 400 ° C. or higher, there is an advantage that stable amorphousness is maintained and there is no change in resistivity in a normal use temperature range. Since it is a stable oxide, it has excellent environmental resistance and can be used as a transparent electrode for solar cells used outdoors.
[0037]
In addition, since film formation at a temperature of about room temperature exhibits conductivity without a reduction / annealing operation, the production efficiency is high, the apparatus is simple, and the production cost can be reduced.
[0038]
In particular, the article of the present invention has excellent electrical conductivity and visible light transmittance including a blue region, and has potential as a useful transparent electrode, so that it can be used as an electrode for a display or a solar cell. Can do. In addition, since the film formation temperature can be set near room temperature, the production efficiency is high. Furthermore, the material has a high crystallization temperature and is excellent in environmental resistance.
[0039]
【Example】
The conditions of this example are as follows.
Figure 0004170454
[0040]
1. Create target
Each powder of In 2 O 3 , Ga 2 O 3 , and ZnO was weighed so that the ratio of the contained metal was 1 respectively. Weighed powder is wet mixed with a planetary ball mill. After calcining at 1000 ° C for 5 hours, it was crushed again with a planetary ball mill. This powder was formed into a disk shape having a diameter of 20 mm by uniaxial pressing, and then CIP was applied. The sintered body was obtained by firing at 1550 ° C. for 2 hours in the air. It was confirmed by XRD that an oxide represented by InGaZnO 4 was formed.
[0041]
In the case of homologous InGaO 3 (ZnO) m , each powder of In 2 O 3 , Ga 2 O 3 , and ZnO is weighed so that the ratio of contained metal is 1: 1: m (m is an integer of 2 or more). did. Weighed powder is wet mixed with a planetary ball mill. After calcining at 1000 ° C for 5 hours, it was crushed again with a planetary ball mill. This powder was formed into a disk shape having a diameter of 20 mm by uniaxial pressing, and then CIP was applied. The sintered body was obtained by firing at 1550 ° C. for 2 hours in the air. It was confirmed by XRD that an oxide represented by InGaO 3 (ZnO) m corresponding to each m value was generated.
[0042]
2. Deposition The film formation method using the laser ablation method is shown as an example below.
Example 1
Among the sintered bodies produced above, the surface of the sintered body with In: Ga: Zn = 1: 1: 1 was polished and fixed to a holder made of Inconel with metal In. This is fixed to a laser ablation device manufactured by Nippon Vacuum Co., Ltd., and a lambda physics KrF excimer laser beam is irradiated at an energy density of 4 J / cm 2 and a pulse interval of 5 Hz on the surface being rotated. It was. The atmosphere in the chamber was 15-25 CCM of O 2 gas, and the total pressure was 0.8-1.0 [Pa]. A quartz glass substrate of 10 mm square and 0.5 mm thickness was placed 30 mm directly above the target and exposed to the plume for 30 minutes while rotating so that the film thickness was uniform, thereby obtaining a thin film of about 300 nm. The composition ratio was obtained by fluorescent X-ray method. It was confirmed by XRD that the film was uniform amorphous (FIG. 1). The absorption edge was determined by calculating the optical constant from the transmission and reflection spectra of the sample. Electrical characteristics were obtained by Hall effect measurement by van der Pau method.
[0043]
[Table 1]
Figure 0004170454
[0044]
Example 2
An IGZO amorphous thin film was obtained by using an acrylic substrate having a thickness of 10 mm and a thickness of 1.0 mm as the film formation substrate under the same conditions as in Example 1.
[0045]
[Table 2]
Figure 0004170454
[0046]
Example 3
As in Example 1, O 2 gas 5-20 [CCM] was flowed in the chamber atmosphere, and oxygen radicals were generated by applying an RF power of 50 W using a radical gun, so that the total pressure was 0.2-0.4 [Pa].
[0047]
[Table 3]
Figure 0004170454
[0048]
Example 4
Of the sintered bodies produced above, the surface of the sintered body of In: Ga: Zn = 1: 1: 4 was polished and fixed to a holder made of Inconel with metal In. This is fixed to a laser ablation device manufactured by Nippon Vacuum Co., Ltd., and a lambda physics KrF excimer laser beam is irradiated at an energy density of 4 J / cm 2 and a pulse interval of 5 Hz on the surface being rotated. It was. The atmosphere in the chamber was 15-25 CCM of O 2 gas, and the total pressure was 0.8-1.0 [Pa]. A quartz glass substrate of 10 mm square and 0.5 mm thickness was placed 30 mm above the target, and exposed to the plume for 30 minutes while rotating so that the film thickness was uniform, thereby obtaining a thin film of about 300 nm. The composition ratio was obtained by fluorescent X-ray method. XRD confirmed that the film was uniform and amorphous. The absorption edge was determined by calculating the optical constant from the transmission and reflection spectra of the sample. Electrical characteristics were obtained by Hall effect measurement by van der Pau method.
[0049]
[Table 4]
Figure 0004170454

[Brief description of the drawings]
FIG. 1 shows an XRD result for confirming that an oxide represented by InGaZnO 4 is formed.

Claims (13)

基材の少なくとも一方の表面の少なくとも一部に、一般式ZnxMyInzO(x+3y/2+3z/2)(式中、Mはアルミニウム及びガリウムのうち少なくとも一つの元素であり、比率x/yが0.2〜2の範囲であり、比率z/yが0.4〜1.4の範囲にある)で表される非晶質酸化物を含有する膜を有することを特徴とする物品。At least a portion of at least one surface of a substrate, the general formula Zn x M y In z O ( x + 3y / 2 + 3z / 2) ( wherein, M is at least one element of aluminum and gallium ranged ratio x / y is from 0.2 to 2, article ratio z / y is characterized by having a film containing an amorphous oxide represented by any) in the range of 0.4 to 1.4. 基材の少なくとも一方の表面の少なくとも一部に、一般式ZnxMyInzO(x+3y/2+3z/2)(式中、Mはアルミニウム及びガリウムのうち少なくとも一つの元素であり、比率x/yが0.2〜2の範囲であり、比率z/yが0.4〜1.4の範囲にある)で表され、かつ陽イオンを注入したものである非晶質酸化物を含有する膜を有することを特徴とする物品。At least a portion of at least one surface of a substrate, the general formula Zn x M y In z O ( x + 3y / 2 + 3z / 2) ( wherein, M is at least one element of aluminum and gallium And the ratio x / y is in the range of 0.2 to 2 , and the ratio z / y is in the range of 0.4 to 1.4), and a film containing an amorphous oxide in which cations are implanted Article characterized by having. キャリア電子の量が1×1018〜1×1022/cm3の範囲になるように、酸素欠損量d及び陽イオンの注入量を選んだ請求項2記載の物品。Such that the amount of carrier electrons is in the range of 1 × 10 18 ~1 × 10 22 / cm 3, article of claim 2, wherein the selected amount of injected oxygen deficiency d and cations. 比率x/(x+y+z)が0.5以上である請求項1〜3のいずれか1項に記載の物品。 The article according to any one of claims 1 to 3, wherein the ratio x / (x + y + z) is 0.5 or more. 基材が高分子性基板、高分子性可撓性基板またはガラス基板である、請求項1〜4のいずれか一項に記載の物品。 The article according to any one of claims 1 to 4, wherein the substrate is a polymer substrate, a polymer flexible substrate, or a glass substrate. 基材がフィルムまたはシートの透明高分子からなる、請求項5に記載の物品。Substrate made of a film-like or sheet-like transparent polymer article according to claim 5. 請求項1〜6のいずれか1項に記載の物品からなる電極。 The electrode which consists of an article | item of any one of Claims 1-6. 基材と膜との間に下地層を有する請求項7に記載の電極。 The electrode according to claim 7, further comprising an underlayer between the substrate and the film. 下地層がフィルター層、TFT層、EL層半導体層及び絶縁層から成る群から選ばれる1または2以上の層である請求項8記載の電極。 9. The electrode according to claim 8, wherein the underlayer is one or more layers selected from the group consisting of a filter layer, a TFT layer, an EL layer semiconductor layer, and an insulating layer. 液晶ディスプレイ、ELディスプレイまたは太陽電池に用いられる請求項8〜9のいずれか1項に記載の電極。 The electrode according to any one of claims 8 to 9, which is used for a liquid crystal display, an EL display or a solar cell. 請求項1に記載の物品の製造方法であって、一般式ZnxMyInzO(x+3y/2+3z/2)(式中、Mはアルミニウム及びガリウムのうち少なくとも一つの元素であり、比率x/yが0.2〜2の範囲であり、比率z/yが0.4〜1.4の範囲にある)で表される酸化物をターゲットとし、基板温度を室温から300℃の範囲とし、かつ圧力を1×10-2[Pa]〜10[Pa]の範囲として、スパッタリング法またはレーザーアブレーション法により、酸化物膜を形成することを特徴とする方法。A method of making an article according to claim 1, the general formula Zn x M y In z O ( x + 3y / 2 + 3z / 2) ( wherein, M represents at least one element of aluminum and gallium There is a range ratio x / y is from 0.2 to 2, the oxide ratio z / y is represented by some) in the range of 0.4 to 1.4 as a target, the range of the substrate temperature from room temperature to 300 ° C., and wherein a range of 1 × 10 -2 pressure [Pa] ~10 [Pa], Ri by the sputtering or laser ablation method, to form an acid fluoride film. 請求項2に記載の物品の製造方法であって、一般式ZnxMyInzO(x+3y/2+3z/2)(式中、Mはアルミニウム及びガリウムのうち少なくとも一つの元素であり、比率x/yが0.2〜2の範囲であり、比率z/yが0.4〜1.4の範囲にある)で表される酸化物をターゲットとし、基板温度を室温から300℃の範囲とし、かつ圧力を1×10-2[Pa]〜10[Pa]の範囲として、スパッタリング法またはレーザーアブレーション法により、酸化物膜を形成し、次いで前記酸化物膜に陽イオンを注入することを特徴とする方法。A method of making an article according to claim 2, general formula Zn x M y In z O ( x + 3y / 2 + 3z / 2) ( wherein, M represents at least one element of aluminum and gallium There is a range ratio x / y is from 0.2 to 2, the oxide ratio z / y is represented by some) in the range of 0.4 to 1.4 as a target, the range of the substrate temperature from room temperature to 300 ° C., and wherein a range of 1 × 10 -2 pressure [Pa] ~10 [Pa], Ri by the sputtering or laser ablation method, oxides film is formed and then the implanting positive ions into the oxide film And how to. 成膜後に10〜300℃の範囲の温度で熱処理及び/または還元処理を行う、請求項11または12に記載の製造方法。The manufacturing method according to claim 11 or 12 , wherein heat treatment and / or reduction treatment is performed at a temperature in the range of 10 to 300 ° C after film formation.
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