JP4170454B2 - Article and manufacturing method thereof having a transparent conductive oxide thin film - Google Patents

Article and manufacturing method thereof having a transparent conductive oxide thin film Download PDF

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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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substrate
electrode
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general formula
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JP2000044236A (en
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裕道 太田
博司 川副
清 森田
秀雄 細野
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Hoya株式会社
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L29/00Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof; Multistep manufacturing processes therefor
    • H01L29/66Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76Unipolar devices, e.g. field effect transistors
    • H01L29/772Field effect transistors
    • H01L29/78Field effect transistors with field effect produced by an insulated gate
    • H01L29/786Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/7869Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
    • H01L29/78693Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate the semiconducting oxide being amorphous
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L29/00Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof; Multistep manufacturing processes therefor
    • H01L29/66Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/66007Multistep manufacturing processes
    • H01L29/66969Multistep manufacturing processes of devices having semiconductor bodies not comprising group 14 or group 13/15 materials

Description

【0001】 [0001]
【発明の属する技術分野】 BACKGROUND OF THE INVENTION
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。 The present invention has a high conductivity and visible, in particular has a blue light transmissive, and to articles and a manufacturing method thereof having a transparent conductive film comprising an amorphous oxide is easily produced. さらに本発明は、本発明の物品からなる電極に関する。 The invention further relates to an electrode made of an article of the present invention.
【0002】 [0002]
【従来の技術】 BACKGROUND OF THE INVENTION
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。 Light transmission type liquid crystal panel display is thin, widely used in various electric products as a lightweight display device. 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。 In particular, the introduction of the OA equipment such as a personal computer or a word processor is an active, notebook personal computers and the order of the current diagonal about 10 inches, there is an increasing more and more demand as a display for a desktop PC in a space-saving, further large area , the number of pixels, improvements in the direction of higher definition has been added.
【0003】 [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。 In the liquid crystal light transmission is essential transparent electrode, the transparent electrode material is mainly ITO is used. ITOは紫外域のほぼ全域で透明であり、電気抵抗率を1×10 −4 Ωcm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。 ITO is transparent in almost the entire ultraviolet region, since the electrical resistivity can be reduced to about 1 × 10 -4 Ωcm, it was suitable as a transparent electrode material of a liquid crystal infantis play like. 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。 In recent years, it has come to an amorphous phase of ITO, so-called amorphous ITO is used in response to demand for high resolution. 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。 Amorphous ITO because good patterning as compared to the crystalline ITO, because cut cleanly thin electrode pattern. 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。 The electrical resistivity increases as compared with the crystalline ITO, because of sufficient resistance for the pixel electrode of the TFT type mainstream of liquid crystal infantis play. 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。 Further, there is a tendency that the plastic substrate is used for the weight of the Sevilla play, are considered to be preferred capable amorphous ITO room temperature film formation. 結晶性ITOの成膜には200℃以上の温度を要するからである。 The formation of crystalline ITO because require temperatures above 200 ° C..
【0004】 [0004]
【発明が解決しようとする課題】 [Problems that the Invention is to Solve
アモルファスITOはその成分の90%以上がIn 2 O 3からなる。 Amorphous ITO is 90% or more of its components consists of In 2 O 3. このため、近年の液晶ディスプレイの普及に伴ってIn 2 O 3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。 Therefore, the price of In 2 O 3 with the spread of the liquid crystal display in recent years has soared up to about 2-fold, which is a factor of increasing the material cost. また、In 2 O 3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。 Further, an In 2 O 3 is a rare metal, it is expected to be depleted and to continue after about 30 years mining. このような理由から、In 2 O 3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。 For this reason, a low content of an In 2 O 3, the raw material cost is low, is becoming necessary resources environmental load is low material.
【0005】 [0005]
そこで本発明の目的は、資源環境負荷の高いIn O 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。 It is an object of the present invention, the content of high In 2 O 3 of resources environmental load can be kept low, can be easily produced at a temperature around room temperature, low resistance and optical absorption edge is in the ultraviolet region excellent novel transparent conductive material and a manufacturing method thereof in the blue permeability, furthermore, is to provide an electrode using such a transparent conductive material.
【0006】 [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。 The present inventors have found that zinc - a indium-based oxide, an oxide containing a predetermined amount of aluminum or gallium, can be easily produced at a temperature around room temperature, low resistance and optical absorption edge ultraviolet region to there, the present invention has been completed by finding that excellent blue permeability.
【0007】 [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。 Incidentally, JP-A-7-235219, zinc - indium-based transparent conductive film made of oxide is provided conductive transparent substrate is disclosed. 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。 The transparent conductive film is made of amorphous oxide containing indium (In) and zinc (Zn) as main cation elements, atomic ratio In / (In + Zn) is within the range of 0.8 to 0.9 . 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。 Further, this oxide, as a third element, which contains aluminum, gallium, antimony or germanium, and the content thereof, the atomic ratio in order to suppress the decrease in conductivity (total third element) / (In + Zn + total it is described that the third element) of 0.2 or less.
【0008】 [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。 In this publication, description of the absorption edge of the transparent conductive film made of the oxide is not, the optical properties have not been revealed only a light transmittance. 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。 That is, the transparent conductive film, is not clear if having any light transmittance spectrum, a low resistance, there optical absorption edge in the ultraviolet region, are either superior to blue permeability is unknown.
【0009】 [0009]
【課題を解決するための手段】 In order to solve the problems]
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Zn x M y In z O (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。 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 characterized by having a membrane. 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Zn x M y In z O (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。 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 selected from aluminum and gallium in the range ratio x / y is from 0.2 to 2, the ratio z / y is represented by some) in the range of 0.4 to 1.4, and those injected with cationic and having a film containing a certain amorphous oxide.
【0010】 [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。 The invention further relates to an electrode made of an article of the present invention.
【0011】 [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Zn x M y In z O (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。 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 selected from aluminum and gallium in the range ratio x / y is from 0.2 to 2, the oxide as a target for the ratio z / y is represented by some) 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 and features.
【0012】 [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Zn x M y In z O (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。 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 selected from aluminum and gallium in the range ratio x / y is from 0.2 to 2, the oxide as a target for the ratio z / y is represented by some) 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 wherein the implanting positive ions into the oxide film.
【0013】 [0013]
【発明の実施の態様】 [Aspect of the implementation of the invention]
本発明の第1の態様の物品 The article of the first aspect of the present invention
一般式Zn x M y In z O (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。 In the general formula Zn x M y In z O ( x + 3y / 2 + 3z / 2), M may be the sole one of aluminum and gallium, M may coexist aluminum and gallium. 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。 If aluminum and gallium coexist are no particular restrictions on the ratio of aluminum and gallium. 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。 However, there is a tendency that the crystallization temperature and the ratio of aluminum is increased becomes high. 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。 Crystallization temperature and the ratio of gallium is increased tends to be low.
【0014】 [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。 Ratio (x / y) is 0.2 or more, in the range of 2 or less, x / y is a raw material cost increases is less than 0.2. 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。 x / y is chemically unstable in air becomes too large Zn component exceeds 12. 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。 The preferred ratio (x / y) is in the range of 1 to 10, more preferably from 4 to 10. 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In 23が不足し、電気伝導性が低下する。 Ratio (z / y) is 0.4 or more, in the range of 1.4 or less, z / y is insufficient In 2 O 3 is less than 0.4, the electrical conductivity decreases. z/yが1.4を超えるとGa 23成分が不足して青色領域の透明性が低下する。 z / y is insufficient Ga 2 O 3 component exceeds 1.4 decreases the transparency of the blue region. 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。 The preferred ratio (z / y) is in the range of 0.6 to 1.4, more preferably in the range of 0.8 to 1.2.
【0015】 [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。 In yet an article of the present invention, it ratio x / (x + y + z) is 0.5 or more, lower the raw materials cost, from the viewpoint of reducing the environmental load. 比率x/(x+y+z)は、好ましくは0.6〜0.9の範囲である。 Ratio x / (x + y + z) is preferably in the range from 0.6 to 0.9.
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。 Further in the membrane with the article of the present invention, the oxide, the degree virtually total amount to be amorphous, but preferred in view of transmittance and conductivity, which does not impair the transmittance and conductivity, crystalline It can also contain oxides of quality.
【0016】 [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。 Conductive oxide of the present invention, the amount of carrier electrons in the conduction band becomes good when in a predetermined range. そのようなキャリア電子の量は、1×10 18 /cm 3 〜1×10 22 /cm 3の範囲である。 The amount of such carrier electrons is in the range of 1 × 10 18 / cm 3 ~1 × 10 22 / cm 3. また、好ましいキャリア電子の量は、1×10 19 /cm 3 〜5×10 21 /cm 3の範囲である。 Further, the preferred amount of carrier electrons is in the range of 1 × 10 19 / cm 3 ~5 × 10 21 / cm 3.
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。 The amount of carrier electrons, for example, can be measured by Fandeapau method electric conductivity measuring apparatus.
【0017】 [0017]
本発明の第2の態様の物品 The article of the second aspect of the present invention
本発明の第2の態様の物品において、一般式Zn x M y In z O (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。 The article 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, M, the ratio (x / y) and the ratio (z / for y), wherein it is the same as the article of the first aspect of the present invention. 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。 About the ratio x / (x + y + z) and amorphous features, the it is the same as the conductive oxide article of the first aspect of the present invention.
【0018】 [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。 Moreover, the article of the second aspect of the present invention, the oxide represented by the above general formula is obtained by implanting positive ions.
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。 In the article of the second aspect of the present invention, in addition to the introduction of oxygen vacancies can be carrier electrons are injected into the conduction band by injecting cations, to express the conductivity.
【0019】 [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Zn x M y In z O (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。 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 without destroying the crystal structure is not particularly limited as long as it can be dissolved. 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。 However, there is a tendency for better ionic radius smaller ions are likely to solid solution in the crystal lattice, as the ionic radius increases, there is a tendency to easily destroy the crystal structure.
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。 The cations as described above, e.g., 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 , mention may be made of Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, and Bi.
【0020】 [0020]
本発明の電極 Electrode of the present invention
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。 The electrode of the present invention includes an article of the first or second aspect of the present invention. 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。 Thickness of the conductive layer made of an oxide film in the electrode of the present invention, the optical properties required for the electrode can be appropriately determined in consideration of the conductivity and applications, and the like. 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。 For example, in the case of the liquid crystal panel electrodes, the lower limit is about 30 nm, the upper limit is about 1 [mu] m. 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。 However, depending on the type of elements contained in the oxide, also having some absorption in the visible region, in which case the relatively thin film is preferable. 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。 Also, for those it has little or no absorption in the visible region, by increasing the thickness, it is possible to obtain a higher conductivity.
【0021】 [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。 The transparent substrate corresponding to the substrate in the article of the present invention, mention may be made of a transparent substrate such as glass or resin. 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。 That can be used regardless of the glassy, ​​polymeric, etc., any transparent material as the substrate. 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。 The substrate forms are also planar substrate, sheet, corresponding to all forms films. ガラス基板は、液晶ディスプレイなどに多く用いられる。 Glass substrates are used such as in many liquid crystal displays. 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。 As the glass substrate, there is a soda glass and low alkali glass, and is generally widely used soda glass. 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。 However, low-alkali glass is superior, such as a color display and high-quality display. 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。 High transparency in the visible region, it is preferable to use a plane of glass excellent.
【0022】 [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。 As the resin substrate, for example, polyester substrates, PMMA substrate, and the like. 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。 Resin substrate, as compared with a glass substrate, it is lightweight, thinner, flexible there many utilizing the like that a high degree of freedom in shape and applications have been studied. 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。 For example, electrophotographic film, a liquid crystal display, an optical memory, a transparent tab Rent switches, antistatic films, solar reflective films, and the like face the heat generating film. 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。 The liquid crystal display, high transparency in the visible region, in addition to excellent planarity, processability, impact resistance, durability, it is preferable to use in consideration of adaptability to the assembly process.
【0023】 [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。 The electrode of the present invention may be provided on the base layer provided on the transparent substrate. 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。 As the base layer, a color filter, TFT layer, EL light-emitting layer, a metal layer, the semiconductor layer and the insulating layer and the like. また、下地層は2種以上を併設することもできる。 In addition, the base layer can also be features of two or more thereof.
【0024】 [0024]
本発明の電極は、種々の用途に利用することができる。 The electrode of the present invention can be utilized in a variety of applications. 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。 For example, a liquid crystal display, can be suitably used as an electrode such as an EL display and a solar cell.
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。 TFT type liquid crystal displays, there are various types such as STN-type or MIM type, an electric field is added to the liquid crystal sandwiched between the transparent electrode in each case, the principle of display by controlling the alignment direction of the liquid crystal It is used. 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。 The electrode of the present invention can be used as the transparent electrode.
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。 For example, the structure of the TFT type color LCD display, a backlight, a first polarizer, TFT substrate, a liquid crystal, consisting of a color filter substrate and six parts of the second polarizer. 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。 It is necessary to form a transparent electrode on the TFT substrate and the color filter substrate in order to control the alignment direction of liquid crystal, but transparent electrode also formed on the color filter substrate also on the TFT substrate by the above described method of the present invention can do. 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。 The transparent electrode of the present invention is most suitable as a transparent electrode provided on the TFT substrate or a color filter on a substrate since and conductivity even higher high transparency.
【0025】 [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。 Further, the transparent electrode of the present invention can also be used as an electrode for an EL display. 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。 Distributed in the EL display, there are such Rumosen structure type and double insulation structure type has a transparent electrode in each case a basic structure sandwiching the EL light-emitting layer between the back electrode, the electrode of the present invention , it is optimal as a transparent electrode described above.
【0026】 [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。 The electrode of the present invention, because of high transparency and conductivity, is excellent as an electrode for solar cells. 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。 Solar cells, pn junction, Schottky barrier type, heterozygous, but is classified into heterozygous face junction type or pin-type, sandwich the semiconductor or insulator between the transparent electrode in each case the back electrode having the basic structure. 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。 Solar cells, by utilizing the photovoltaic effect of semiconductor interface, because it is the element that converts light energy into electricity, it is necessary to guide the light to the semiconductor interface over as wide as possible spectral range, transparency of the transparent electrode must not high. 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。 Further, the transparent electrode of a solar cell because it has a function of deriving the terminal to collect photogenerated carriers generated in the semiconductor interface, in order to as much as possible effectively collect photogenerated carriers be high conductivity of the transparent electrode not not. 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。 The transparent electrode of the present invention, 450 nm containing more short-wavelength light, is excellent as an electrode for a solar cell because of its high electrical conductivity on the light over a wide spectral range of the entire visible region can be guided to the semiconductor surface.
【0027】 [0027]
本発明の製造方法 The production method of the present invention
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。 First and second production process of the present invention, respectively, is a method of making an article of the first and second aspects of the present invention. 本発明の第1の製造方法では、一般式Zn x M y In z O (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。 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, the ratio z / y is used as a target an oxide represented by any) in the range of 0.4 to 1.4. 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Zn x M y In z O (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。 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 at least one of an element, in the range ratio x / y is from 0.2 to 2, an oxide the ratio z / y is represented by some) in the range of 0.4 to 1.4 as the target.
【0028】 [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。 In the production method of the present invention, the composition of the thin film to be formed, it is hardly varied by the density of the target. 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。 However, considering the damage of a target by laser pulse irradiation, an oxide is used as a target, the relative density of preferably 40% or more, more preferably 70% or more. 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。 As the target for example, it may be used a sintered body.
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。 Further, the composition of the thin film to be formed is displaced from the target decreases, since it is 5% at most, the target composition, may be the same as the desired thin film composition. 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。 However, if necessary, it is possible to change the target composition.
【0029】 [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。 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】 [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。 In the production method of the present invention, the substrate temperature in the range of 300 ° C. from room temperature, and at 1 × 10 -2 [Pa] ~10 oxygen atmosphere or oxygen radical atmosphere at a pressure range of [Pa], sputtering or laser ablation by law, an oxide film.
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。 Also in the sputtering method and laser ablation method, in a range of from the substrate temperature in the range of 300 ° C. from room temperature and pressure (oxygen partial pressure) to 1 × 10 -2 [Pa] ~10 [Pa], amorphous it is possible to form the oxide film quality. 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。 The substrate temperature is preferably in the range of from 0 to 150 ° C., and the pressure is preferably in the range of 0.01 [Pa] ~1 [Pa].
【0031】 [0031]
スパッタリング法は、常法により行うことができる。 Sputtering method, it can be carried out by a conventional method.
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。 Further, in the laser ablation method, control of the oxygen partial pressure in the film forming apparatus can be carried out by introducing oxygen molecules from the appropriate leak valve or the like in the system, in particular, it was placed in the laser ablation apparatus be carried out by radical gun are suitable from firstlings viewpoint and easy to control the amount of oxygen contained in the film. 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。 Here, the radical gun is a device to be introduced into the vacuum system to generate radical species gas such as oxygen by rf plasma.
【0032】 [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。 The laser used in the laser ablation method of the production method of the present invention, any wavelength in the infrared region from ultraviolet region, i.e. 0.19~11Myuemu, desirably is capable of 0.19~0.3Myuemu, of either a continuous wave or pulsed mode it can be adopted. レーザー照射時のレーザー強度は、0.0001〜1000J/ cm 2・パルス、望ましくは0.1〜100J/cm 2・パルスである。 Laser intensity at the time of laser irradiation, 0.0001~1000J / cm 2 · pulse, and desirably 0.1~100J / cm 2 · pulse.
【0033】 [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。 In the production method of the second aspect, implanting positive ions into the oxide film formed by the above method. 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。 Carrier electrons are injected into the conduction band by injecting cations can be expressed conductivity. 陽イオン注入されるイオンは前述の通りである。 Cations implanted ions are as defined above.
【0034】 [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。 In the production method of the present invention, e.g., In as a target: Ga: Zn = 1: 1 : When using a sintered body, it is possible to easily obtain a thin film of 6.2 × 10 -3 [Ωcm]. 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。 In this case, the main cause of high conductivity mobility despite amorphous material is due to be shown more than 10 and a high value.
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 InGaO 3 (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。 Also, homologous IGZO InGaO 3 with increased Zn component as a target (ZnO) m: When using the (m 2 or more integer) of the sintered body, having 4 3 × 10 -3 resistivity [[Omega] cm]. thin film can be easily obtained. 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。 The reason for this is the carrier concentration to indicate exponential increasing tendency, due to the mobility hardly changes.
【0035】 [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。 Furthermore if one wants to lower the resistance of, by increasing the carrier density by using a gas reduction method or ion implantation method at a low temperature (desirably 300 ° C. or less) after the film formation, it is possible to improve the conductivity. 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。 Furthermore by utilizing the substitutional doping effect of varying the composition of the target, it may increase the carrier density.
【0036】 [0036]
【発明の効果】 【Effect of the invention】
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。 Since the articles of the present invention, since less In 2 O 3 content in the material low material cost, low environmental impact, and has a visible light transmittance of 85% or more, and absorption short wavelength is 385nm , it is possible to reduce the resistance by increasing the thickness in the color screen in black-and-white screen.
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。 Further, since the crystallization temperature of the material constituting the film is as high as 400 ° C. or higher, the normal temperature range, to maintain a stable amorphous nature, there is an advantage that variations in the resistivity no. 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。 It has excellent environmental resistance because a stable oxide, can be used as a transparent electrode for solar cells to be used in the field.
【0037】 [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。 Moreover, since the expression conductivity without reducing and annealing operations in deposition at about room temperature, production efficiency is high, it is possible to reduce the device also simple pre production costs.
【0038】 [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。 In particular, the article of the present invention has both a visible light-transmissive including excellent electrical conductivity and blue region, because of its potential as a useful transparent electrodes, be used as an electrode for displays and solar cells can. 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。 Further, since the film formation temperature may be about room temperature, a high production efficiency. さらに、材料の結晶化温度は高く、耐環境性にも優れる。 Furthermore, the crystallization temperature of the material is high, excellent in environmental resistance.
【0039】 [0039]
【実施例】 【Example】
本実施例の条件は以下のとおりである。 Conditions of this embodiment are as follows.
【0040】 [0040]
1.ターゲットの作成 1. Create a target
In 2 O 3 、Ga 2 O 3 、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。 The powders of In 2 O 3, Ga 2 O 3, ZnO, ratio of containing metal was weighed so that each becomes one. 秤量した粉末を、遊星ボールミル装置で湿式混合。 The weighed powder, wet mixing by a planetary ball mill. 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。 After 5 hours, calcined at 1000 ℃, it was disintegrated in a planetary ball mill again. 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。 After molding the powder into a disk form having a diameter of 20mm in a uniaxial pressure multiplied by CIP. 大気下、1550℃で2時間焼成して焼結体を得た。 The atmosphere, to obtain a by baking for 2 hours at 1550 ° C. sintered body. XRDによりInGaZnO 4で表される酸化物が生成していることを確認した。 It was confirmed that the oxide represented by InGaZnO 4 is generated by XRD.
【0041】 [0041]
ホモロガスInGaO 3 (ZnO) mの場合は、In 2 O 3 、Ga 2 O 3 、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。 Homologous InGaO 3 (ZnO) when m is, In 2 O 3, Ga 2 O 3, the respective powders of ZnO, the ratio of containing metal is 1: 1: m weighed so that (m is an integer of 2 or more) did. 秤量した粉末を、遊星ボールミル装置で湿式混合。 The weighed powder, wet mixing by a planetary ball mill. 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。 After 5 hours, calcined at 1000 ℃, it was disintegrated in a planetary ball mill again. 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。 After molding the powder into a disk form having a diameter of 20mm in a uniaxial pressure multiplied by CIP. 大気下、1550℃で2時間焼成して焼結体を得た。 The atmosphere, to obtain a by baking for 2 hours at 1550 ° C. sintered body. XRDによりそれぞれのm値に対応したInGaO 3 (ZnO) mで表される酸化物が生成していることを確認した。 Oxide represented by InGaO 3 (ZnO) m corresponding to each of the m value was confirmed that generated by XRD.
【0042】 [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。 2. showing a film forming method using a laser ablation method as in Example below deposition.
実施例1 Example 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。 Among sintered body created above, In: Ga: Zn = 1: 1: 1 of polishing the surface of the sintered body, and fixed to the Inconel holder with metal In. 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/cm 2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。 This was fixed in Japan vacuum Corp. laser ablation apparatus, the energy density of the Lambda Physic Inc. KrF excimer laser light 4J / cm 2 on a surface which is rotating, irradiating a pulse interval 5 Hz, vertical plumes It was. チャンバー中の雰囲気はO 2ガスを15 - 25CCM流し、全圧を0.8− 1.0[Pa]とした。 The atmosphere in the chamber the O 2 gas 15 - 25CCM flow, was a total pressure 0.8- 1.0 [Pa]. 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。 The quartz glass substrate having a thickness of 0.5mm was placed at 10mm angle 30mm directly from the target, by exposure to 30 minutes in the plume while rotating so that the film thickness becomes uniform, to obtain a thin film of approximately 300 nm. 組成比は蛍光X線法により得た。 The composition ratio was obtained by the fluorescent X-ray method. 膜が均一な非晶質であることはXRDより確認した(図1)。 Film that was confirmed from the XRD is a homogeneous amorphous (Figure 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。 Absorption edge was obtained from calculating the optical constants from transmission and reflection spectra of the sample. 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。 Electrical characteristics were determined by Hall effect measurement by Fandeapau method.
【0043】 [0043]
【表1】 [Table 1]
【0044】 [0044]
実施例2 Example 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。 By using an acrylic substrate having a thickness of 1.0mm at 10mm angle deposition substrate under the same conditions as in Example 1 to obtain an amorphous thin film of IGZO.
【0045】 [0045]
【表2】 [Table 2]
【0046】 [0046]
実施例3 Example 3
実施例1と同様にチャンバー雰囲気をO 2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。 Similarly chamber atmosphere as in Example 1 O 2 gas 5-20 flowed [CCM], to generate oxygen radicals by applying RF power 50W using a radical gun was a total pressure 0.2- 0.4 and [Pa].
【0047】 [0047]
【表3】 [Table 3]
【0048】 [0048]
実施例4 Example 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。 Among sintered body created above, In: Ga: Zn = 1: 1: polishing a surface of the sintered body 4, fixed to the Inconel holder with metal In. 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/cm 2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。 This was fixed in Japan vacuum Corp. laser ablation apparatus, the energy density of the Lambda Physic Inc. KrF excimer laser light 4J / cm 2 on a surface which is rotating, irradiating a pulse interval 5 Hz, vertical plumes It was. チャンバー中の雰囲気はO 2ガスを15 - 25CCM流し、全圧を0.8− 1.0[Pa]とした。 The atmosphere in the chamber the O 2 gas 15 - 25CCM flow, was a total pressure 0.8- 1.0 [Pa]. 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。 The quartz glass substrate having a thickness of 0.5mm was placed at 10mm angle 30mm directly from the target, by exposure to 30 minutes in the plume while rotating so that the film thickness becomes uniform, to obtain a thin film of approximately 300 nm. 組成比は蛍光X線法により得た。 The composition ratio was obtained by the fluorescent X-ray method. 膜が均一な非晶質であることはXRDより確認した。 Film that was confirmed from the XRD is a homogeneous amorphous. 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。 Absorption edge was obtained from calculating the optical constants from transmission and reflection spectra of the sample. 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。 Electrical characteristics were determined by Hall effect measurement by Fandeapau method.
【0049】 [0049]
【表4】 [Table 4]

【図面の簡単な説明】 BRIEF DESCRIPTION OF THE DRAWINGS
【図1】 InGaZnO 4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。 [1] The XRD to confirm that the oxide represented by InGaZnO 4 has generated results.

Claims (13)

  1. 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Zn x M y In z O (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.
  2. 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Zn x M y In z O (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 ranged ratio x / y is from 0.2 to 2, the ratio z / y is represented by some) in the range of 0.4 to 1.4, and the film containing an amorphous oxide is obtained by injecting a cation article characterized in that it has.
  3. キャリア電子の量が1×10 18 〜1×10 22 /cm 3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.
  4. 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。 Ratio x / (x + y + z) is article according to any one of claims 1 to 3 is 0.5 or more.
  5. 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 substrate is a polymeric substrate, polymeric flexible substrate or a glass substrate An article according to any one of claims 1 to 4.
  6. 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.
  7. 請求項1〜6のいずれか1項に記載の物品からなる電極。 Electrode consisting article according to any one of claims 1-6.
  8. 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 of claim 7 having an underlying layer between the substrate and the film.
  9. 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。 Underlayer filter layer, TFT layer, EL layer semiconductor layer and one or more layers and is according to claim 8, wherein the electrode is selected from the group consisting of an insulating layer.
  10. 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。 Liquid crystal displays, electrode according to any one of claims 8-9 for use in EL displays or solar cells.
  11. 請求項1に記載の物品の製造方法であって、一般式Zn x M y In z O (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.
  12. 請求項2に記載の物品の製造方法であって、一般式Zn x M y In z O (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 how to with.
  13. 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。 Performing heat treatment and / or reduction treatment at a temperature in the range of 10 to 300 ° C. after the film formation method according to claim 11 or 12.
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