JP5532093B2 - ZnO vapor deposition material and method of forming ZnO film using the same - Google Patents
ZnO vapor deposition material and method of forming ZnO film using the same Download PDFInfo
- Publication number
- JP5532093B2 JP5532093B2 JP2012199491A JP2012199491A JP5532093B2 JP 5532093 B2 JP5532093 B2 JP 5532093B2 JP 2012199491 A JP2012199491 A JP 2012199491A JP 2012199491 A JP2012199491 A JP 2012199491A JP 5532093 B2 JP5532093 B2 JP 5532093B2
- Authority
- JP
- Japan
- Prior art keywords
- zno
- film
- vapor deposition
- mass
- deposition material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 title claims description 59
- 238000007740 vapor deposition Methods 0.000 title claims description 57
- 238000000034 method Methods 0.000 title claims description 21
- 239000008188 pellet Substances 0.000 claims description 18
- 229910052684 Cerium Inorganic materials 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 7
- 238000004544 sputter deposition Methods 0.000 claims description 5
- 238000005566 electron beam evaporation Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000007733 ion plating Methods 0.000 claims description 3
- 239000013077 target material Substances 0.000 claims description 3
- 238000001771 vacuum deposition Methods 0.000 claims description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 218
- 239000011787 zinc oxide Substances 0.000 description 109
- 239000010408 film Substances 0.000 description 74
- 239000000843 powder Substances 0.000 description 44
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 238000005477 sputtering target Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000003826 uniaxial pressing Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Description
本発明は、例えば太陽電池などに用いられる透明導電膜や、液晶表示装置、エレクトロルミネッセンス表示装置、タッチパネル装置の透明圧電センサーの透明電極、また表示装置を構成するアクティブマトリクス駆動装置、帯電防止導電膜コーティング、ガスセンサー、電磁遮蔽パネル、圧電デバイス、光電変換装置、発光装置、薄膜型二次電池などに用いられる膜を成膜するために用いられるＺｎＯ蒸着材及びこれを用いたＺｎＯ膜の形成方法に関するものである。 The present invention relates to a transparent conductive film used for, for example, a solar cell, a liquid crystal display device, an electroluminescence display device, a transparent electrode of a transparent piezoelectric sensor of a touch panel device, an active matrix driving device constituting the display device, and an antistatic conductive film ZnO vapor deposition material used for forming a film used for coating, gas sensor, electromagnetic shielding panel, piezoelectric device, photoelectric conversion device, light emitting device, thin film type secondary battery, and the like, and method of forming ZnO film using the same It is about.
近年、太陽電池などの光電変換装置などを製造する場合には、透明導電膜が不可欠である。従来の透明導電膜としては、ＩＴＯ膜（錫をドープしたインジウム酸化物膜）が知られている。ＩＴＯ膜は、透明性に優れ、低抵抗であるという利点を有する。 In recent years, a transparent conductive film is indispensable when manufacturing photoelectric conversion devices such as solar cells. An ITO film (indium oxide film doped with tin) is known as a conventional transparent conductive film. The ITO film has the advantages of excellent transparency and low resistance.
一方、太陽電池や液晶表示装置等にあっては、その低コスト化が求められている。しかし、インジウムが高価なことから、ＩＴＯ膜を透明導電膜として用いると、その太陽電池も必然的に高価なものになってしまう難点があった。また、太陽電池などを製造する場合などには、透明導電膜上にアモルファスシリコンをプラズマＣＶＤ法により成膜することになるが、その際に、透明導電膜がＩＴＯ膜であると、プラズマＣＶＤ時の水素プラズマにより、ＩＴＯ膜が劣化するという問題点もあった。 On the other hand, cost reduction is required for solar cells, liquid crystal display devices, and the like. However, since indium is expensive, when an ITO film is used as a transparent conductive film, the solar cell inevitably becomes expensive. In addition, when manufacturing solar cells or the like, amorphous silicon is deposited on the transparent conductive film by plasma CVD. At that time, if the transparent conductive film is an ITO film, There was also a problem that the ITO film deteriorated by the hydrogen plasma.
これらの点を解消するために、一層安価に作製することのできるＡｌ、Ｂ、Ｓｉなどの導電活性元素をドープした酸化亜鉛系膜を太陽電池等の透明導電膜として使用することが提案され、この酸化亜鉛系膜をスパッタリングにより形成するための酸化亜鉛系スパッタリング用ターゲットが提案されている（例えば、特許文献１参照。）。この酸化亜鉛系スパッタリング用ターゲットによると、上記導電活性元素を亜鉛に対して所定量含有させることにより極めて低抵抗な酸化亜鉛系焼結体が得られ、この焼結体は、原料粉末が微細で高分散性を有するほど焼結密度が向上し導電性が向上するとされている。 In order to eliminate these points, it has been proposed to use a zinc oxide-based film doped with a conductive active element such as Al, B, and Si that can be produced at a lower cost as a transparent conductive film such as a solar cell, A zinc oxide-based sputtering target for forming this zinc oxide-based film by sputtering has been proposed (for example, see Patent Document 1). According to this zinc oxide-based sputtering target, an extremely low resistance zinc oxide-based sintered body can be obtained by containing a predetermined amount of the conductive active element with respect to zinc. It is said that the higher the dispersibility, the higher the sintered density and the higher the conductivity.
しかし、上記従来の酸化亜鉛系スパッタリング用ターゲットを用いて高速成膜するために高電圧をかけながらスパッタリングを行うと、異常放電が発生しやすく、放電状態が不安定でターゲットが不均一に消耗し、得られた膜に組成ずれが生じて低抵抗の膜を得ることが困難となる不具合があった。一方、投入電力を小さくして電圧を低くすると成膜速度が遅くなり、酸化亜鉛系膜の成膜効率は大幅に低下する不具合があった。
本発明の目的は、ＩＴＯ膜に迫る高い導電率の膜を高速成膜することのできるＺｎＯ蒸着材及びこれを用いたＺｎＯ膜の形成方法を提供することにある。
However, if sputtering is performed while applying a high voltage to form a high-speed film using the conventional zinc oxide sputtering target, abnormal discharge is likely to occur, the discharge state is unstable, and the target is consumed unevenly. However, there was a problem that it was difficult to obtain a low-resistance film due to composition deviation in the obtained film. On the other hand, when the input power is reduced and the voltage is lowered, the film formation rate is reduced, and the film formation efficiency of the zinc oxide film is greatly reduced.
An object of the present invention is to provide a ZnO vapor deposition material capable of forming a film having a high conductivity approaching that of an ITO film at high speed, and a method for forming a ZnO film using the same .
請求項１に係る発明は、透明導電膜を成膜するために用いられるＺｎＯ蒸着材である。
その特徴ある構成は、ＺｎＯを主成分とした多結晶体のペレットからなり、ペレットがＣｅとＡｌの双方の元素を含み、Ｃｅの含有割合が３質量％以上１４．９質量％以下、Ａｌの含有割合が１質量％以上１０質量％以下の範囲内であり、Ｃｅ／Ａｌの含有割合の比率が質量比で１．４９〜３の範囲内であるところにある。
請求項１に係る発明では、ＺｎＯを主成分としたペレットに、ＣｅとＡｌの２元素が上記含有割合で含むので、このＺｎＯ蒸着材を用いると、ＩＴＯ膜に迫る高い導電性を有するＺｎＯ膜を成膜できる。
The invention according to claim 1 is a ZnO vapor deposition material used for forming a transparent conductive film.
Its characteristic configuration consists pellet of a polycrystalline body composed mainly of ZnO, pellets comprising an element of both Ce and Al, the content of C e is 3 mass% or more 14.9 wt% or less, Al content of Ri der within the following 10 mass% 1 mass% or more, the ratio of the content of Ce / Al is in the range der Rutokoro of 1.49 to 3 mass ratio.
In the invention according to claim 1, since two elements of Ce and Al are contained in the above-described content ratio in a pellet mainly composed of ZnO, when this ZnO vapor deposition material is used, a ZnO film having high conductivity approaching that of an ITO film. Can be formed.
請求項２に係る発明は、ＣｅとＡｌの合計の含有割合が４質量％以上２４．９質量％以下の範囲内であるＺｎＯ蒸着材である。
請求項２に係る発明では、ＺｎＯ蒸着材中のＣｅとＡｌの合計の含有割合が４質量％以上２４．９質量％以下の範囲内であることにより、導電特性及び分光特性において優れた効果が得られる。
The invention according to claim 2 is a ZnO vapor deposition material in which the total content of Ce and Al is in the range of 4 mass% or more and 24.9 mass% or less.
In the invention which concerns on Claim 2, when the total content rate of Ce and Al in a ZnO vapor deposition material exists in the range of 4 mass% or more and 24.9 mass% or less, the effect excellent in the electroconductive characteristic and the spectral characteristic is shown. can get.
請求項３に係る発明は、請求項１又は２に記載のＺｎＯ蒸着材をターゲット材とする真空成膜法によりＺｎＯ膜を形成する方法である。
請求項３に係る発明では、上記請求項１又は２に記載のＺｎＯ蒸着材を用いてＺｎＯ膜を成膜するため、このＺｎＯ膜は、ＩＴＯ膜に迫る高い導電性が得られる。
The invention according to claim 3 is a method of forming a by Ri Z nO film vacuum deposition the ZnO deposition material as a target material according to claim 1 or 2.
In the invention according to claim 3 , since the ZnO film is formed by using the ZnO vapor deposition material according to claim 1 or 2 , the ZnO film has high conductivity approaching that of the ITO film.
請求項４に係る発明は、請求項３に係る発明であって、真空成膜法が電子ビーム蒸着法、イオンプレーティング法、スパッタリング法又はプラズマ蒸着法であるＺｎＯ膜の形成方法である。 The invention according to claim 4 is the invention according to claim 3, a vacuum deposition method is electron beam evaporation method, an ion plating method, a method of forming a ZnO film is a sputtering method or a plasma deposition method.
以上述べたように、本発明の透明導電膜を成膜するために用いられるＺｎＯ蒸着材によれば、ＺｎＯを主成分とした多結晶体のペレットからなり、ペレットがＣｅとＡｌの双方の元素を含み、Ｃｅの含有割合が３質量％以上１４．９質量％以下、Ａｌの含有割合が１質量％以上１０質量％以下の範囲内であり、Ｃｅ／Ａｌの含有割合の比率が質量比で１．４９〜３の範囲内であるので、このＺｎＯ蒸着材を用いると、ＩＴＯ膜に迫る高い導電性を有するＺｎＯ膜を成膜できる。本発明のＺｎＯ蒸着材は、添加元素としてＣｅとＡｌの双方を含むため、イオン半径がＺｎより大きいＣｅにより歪んだ結晶を、イオン半径の小さいＡｌを添加して回復整合させることにより、透過率の高いＺｎＯ膜が成膜でき、更に、緻密性に優れた膜を得られることにより、耐久性が高いＺｎＯ膜が成膜できる。
また、本発明に係るＺｎＯ膜の形成方法では、本発明に係るＺｎＯ蒸着材を用いてＺｎＯ膜を成膜するため、高い導電率、高い透過率が得られ、更に、膜の耐久性が向上する。
As described above, according to the ZnO vapor deposition material used for forming the transparent conductive film of the present invention, it consists of a polycrystalline pellet mainly composed of ZnO, and the pellet is an element of both Ce and Al. The Ce content ratio is 3 mass% or more and 14.9 mass% or less, the Al content ratio is 1 mass% or more and 10 mass% or less, and the ratio of the Ce / Al content ratio is the mass ratio. in range der Runode of 1.49 to 3, the use of this ZnO deposition material, can be a ZnO film having a high conductivity approaching the ITO film. Since the ZnO vapor deposition material of the present invention contains both Ce and Al as additive elements, a crystal distorted by Ce having an ion radius larger than Zn is recovered and matched by adding Al having a small ion radius, thereby obtaining a transmittance. A high-durability ZnO film can be formed, and a highly durable ZnO film can be formed by obtaining a film with excellent denseness.
Further, in the method for forming a ZnO film according to the present invention, since the ZnO film is formed using the ZnO vapor deposition material according to the present invention, high conductivity and high transmittance can be obtained, and the durability of the film is further improved. To do.
次に本発明を実施するための最良の形態を説明する。
本発明者は、ＺｎＯ蒸着材及びこの蒸着材を用いて成膜されたＺｎＯ膜中の添加物種及びその含有量における導電性への影響を詳細に調査したところ、ＺｎＯのペレット中に添加元素として含まれるＣｅとＡｌの２元素のそれぞれの含有割合が大きく影響していることが確認された。ＺｎＯのペレット中において、このＣｅとＡｌの２元素の含有割合が増加するほど概して導電性は良好となるが、更に増加すると逆に劣化することから、製品への適用を考えた場合、これら２元素の最適な含有割合の範囲が存在することが判った。
Next, the best mode for carrying out the present invention will be described.
The present inventor has investigated in detail the effect of conductivity on the ZnO vapor deposition material and the additive species in the ZnO film formed using this vapor deposition material and its content. As an additive element in the ZnO pellet, It was confirmed that the content ratios of the two elements, Ce and Al, were greatly affected. In the ZnO pellet, the conductivity generally becomes better as the content ratio of the two elements of Ce and Al increases. However, when the content is further increased, the conductivity deteriorates. It has been found that there is an optimum content range for the elements.
本発明に係るＺｎＯ蒸着材は、ＺｎＯを主成分とし、ＣｅとＡｌの双方の元素を含有する。添加元素としてＣｅとＡｌの２種類の元素を含むため、導電に寄与する過電子を大量に発現させ維持することにより、高い導電率を有するＺｎＯ膜を成膜できる。本発明に係るＺｎＯ蒸着材中のＣｅは３質量％以上１４．９質量％以下の範囲内とする。Ｃｅが下限値である３質量％未満になると導電性が著しく低下し、上限値である１４．９質量％を越えると、透過率が著しく低下するからである。また、Ａｌは１質量％以上１０質量％以下の範囲内とする。Ａｌが下限値である１質量％未満になると、導電性が著しく低下し、上限値である１０質量％を越えると、蒸着時の組成ずれを生じさせるからである。このうち、Ｃｅ元素は３〜６質量％の範囲内が好ましく、Ａｌは１〜３質量％の範囲内であることが好ましい。なお、緻密な結晶構造を維持するために、Ｃｅの含有割合はＡｌの含有割合よりも高くする。一方、Ｃｅの含有割合がＡｌの含有割合よりも低くなると、導電性及び透過率が悪化する。また、ＣｅとＡｌの合計の含有割合は４質量％以上２４．９質量％以下の範囲内であることが好ましい。これらの添加元素は、ＺｎＯ蒸着材中に微量に含まれる場合には、ＺｎＯマトリックスの粒界や粒内に粒状の析出物として存在するのではなく、ＺｎＯ蒸着材中に均一に分散している。また、ＺｎＯ蒸着材中では、ＣｅはＣｅＯ2又はＣｅ2Ｏ3のような酸化物として存在し、ＡｌはＡｌ2Ｏ3として存在すると考えられる。 The ZnO vapor deposition material according to the present invention contains ZnO as a main component and contains both elements of Ce and Al. Since two kinds of elements, Ce and Al, are included as additive elements, a ZnO film having high conductivity can be formed by expressing and maintaining a large amount of overelectrons that contribute to conduction. Ce in the ZnO vapor deposition material according to the present invention is in the range of 3 mass% or more and 14.9 mass% or less. This is because when Ce is less than the lower limit of 3 % by mass, the conductivity is remarkably lowered, and when it exceeds 14.9% by mass of the upper limit, the transmittance is remarkably lowered. Moreover, Al shall be in the range of 1 to 10 mass%. This is because when the Al content is less than the lower limit of 1 % by mass, the conductivity is remarkably lowered, and when the Al content exceeds the upper limit of 10% by mass, a composition shift occurs during vapor deposition. Among these, the Ce element is preferably in the range of 3 to 6% by mass, and Al is preferably in the range of 1 to 3% by mass. In order to maintain a dense crystal structure, the Ce content is set higher than the Al content. On the other hand, when the Ce content ratio is lower than the Al content ratio, conductivity and transmittance deteriorate. The total content of Ce and Al is preferably in the range of 4 % by mass or more and 24.9% by mass or less. When these additive elements are contained in a trace amount in the ZnO vapor deposition material, they do not exist as granular precipitates in the grain boundaries and grains of the ZnO matrix, but are uniformly dispersed in the ZnO vapor deposition material. . In the ZnO vapor deposition material, Ce is present as an oxide such as CeO 2 or Ce 2 O 3 , and Al is considered to be present as Al 2 O 3 .
本発明に係るＺｎＯ蒸着材は、ＺｎＯを主成分としたペレットからなる。このペレットは直径が５〜５０ｍｍであって、厚さが２〜３０ｍｍであることが好ましい。このペレットの直径を５〜５０ｍｍとするのは安定かつ高速な成膜の実施のためであり、その直径が５ｍｍ未満ではスプラッシュ等が発生する不具合があり、５０ｍｍを越えるとハース（蒸着材溜）への充填率が低下することに起因する蒸着における膜の不均一及び成膜速度の低下をもたらす不具合がある。また、その厚さを２〜３０ｍｍとするのは安定かつ高速な成膜の実施のためであり、その厚さが２ｍｍ未満ではスプラッシュ等が発生する不具合があり、３０ｍｍを越えるとハース（蒸着材溜）への充填率が低下することに起因する蒸着における膜の不均一及び成膜速度の低下をもたらす不具合がある。また、このＺｎＯのペレットは、多結晶体である。 The ZnO vapor deposition material which concerns on this invention consists of a pellet which has ZnO as a main component. This pellet is preferably 5 to 50 mm in diameter and 2 to 30 mm in thickness. The diameter of the pellet is set to 5 to 50 mm for the purpose of stable and high-speed film formation. If the diameter is less than 5 mm, there is a problem that splash or the like occurs. If the diameter exceeds 50 mm, the hearth (deposition material reservoir) There is a defect that causes non-uniformity of the film in vapor deposition and a decrease in the film formation rate due to a decrease in filling rate. Further, the thickness is set to 2 to 30 mm for the purpose of stable and high-speed film formation. If the thickness is less than 2 mm, there is a problem that splash or the like occurs. There is a defect that causes non-uniformity of the film in vapor deposition and a decrease in the film formation rate due to a decrease in the filling rate into the reservoir. In addition, the pellets of the ZnO is, Ru polycrystalline der.
このように構成された本発明のＺｎＯ蒸着材では、３価又は４価の希土類元素であるＣｅを添加元素として含むため、２価であるＺｎに対して過剰のキャリア電子を発生させることにより、高い導電率を確保できる。また、希土類はＺｎＯ蒸着材に添加した場合、蒸着時の組成ずれを起こしにくい材料であり、膜で所望の組成比率を維持することができる。また、導電の機構としては、キャリア電子の強制投入以外に酸素欠損によるものがある。通常蒸着法では酸素ガスを導入するが、一般的には膜組成において酸素が不足状態となる。透明導電膜形成において酸素欠損を生成させ抵抗を下げる手法が採られるけれども、希土類元素を添加する場合、蒸発性能に優れるため制御しやすいといった特徴がある。本発明では、この特徴に加え、Ａｌを添加元素として含むことで、ＩＴＯに迫る高い導電率を得ることができるものである。 In the ZnO vapor deposition material of the present invention configured as described above, since trivalent or tetravalent rare earth element Ce is added as an additive element, by generating excess carrier electrons with respect to divalent Zn, High conductivity can be secured. Moreover, when rare earth is added to the ZnO vapor deposition material, it is a material that hardly causes a composition shift during vapor deposition, and a desired composition ratio can be maintained in the film. In addition to the forced injection of carrier electrons, the conduction mechanism includes oxygen vacancies. In general vapor deposition, oxygen gas is introduced, but in general, oxygen is insufficient in the film composition. Although a method of generating oxygen vacancies and reducing the resistance is employed in forming the transparent conductive film, when a rare earth element is added, there is a feature that it is easy to control because of its excellent evaporation performance. In the present invention, in addition to this feature, by including Al as an additive element, a high conductivity approaching that of ITO can be obtained.
次に、ＺｎＯ蒸着材の製造方法を、焼結法により作製する場合を代表して説明する。
先ず、高純度ＺｎＯ粉末と、ＺｎＯ蒸着材中のＣｅの含有割合が３質量％以上１４．９質量％以下の範囲となる量のＣｅＯ2粉末と、ＺｎＯ蒸着材中のＡｌの含有割合が１質量％以上１０質量％以下の範囲となる量のＡｌ2Ｏ3粉末と、バインダと、有機溶媒とを混合して、濃度が３０〜７５質量％、好ましくは４０〜６５質量％のスラリーを調製する。高純度ＺｎＯ粉末は、純度が９８％以上であることが好ましく、９８．４％以上であることが更に好ましい。ＺｎＯ粉末の純度が９８％以上であれば、不純物の影響による導電率の低下を抑えることができるからである。スラリーの濃度を３０〜７５質量％に限定したのは、７５質量％を越えると上記スラリーが非水系であるため、安定した混合造粒が難しく、３０質量％未満では均一な組織を有する緻密なＺｎＯ焼結体が得られ難いからである。ＺｎＯ粉末の平均粒径は０．１〜５．０μｍの範囲内にあることが好ましい。０．１μｍ未満では、粉末が細かすぎて凝集するため、粉末のハンドリングが悪くなり、高濃度スラリーを調製し難い傾向があり、５．０μｍを越えると、微細構造の制御が難しく、緻密なペレットが得られ難い傾向があるからである。
Next, the manufacturing method of a ZnO vapor deposition material is demonstrated on behalf of the case where it produces by a sintering method.
First, a high-purity ZnO powder, and CeO 2 powder in an amount content of Ce in the ZnO deposition material is in the range of 3 mass% or more 14.9% by mass or less, the content of Al in ZnO deposition material 1 An Al 2 O 3 powder in an amount ranging from 10% by mass to 10% by mass, a binder, and an organic solvent are mixed to prepare a slurry having a concentration of 30 to 75% by mass, preferably 40 to 65% by mass. To do. The high purity ZnO powder preferably has a purity of 98% or more, more preferably 98.4% or more. This is because if the purity of the ZnO powder is 98% or more, a decrease in conductivity due to the influence of impurities can be suppressed. The concentration of the slurry is limited to 30 to 75% by mass. If the slurry exceeds 75% by mass, the slurry is non-aqueous, so that stable mixed granulation is difficult. This is because it is difficult to obtain a ZnO sintered body. The average particle size of the ZnO powder is preferably in the range of 0.1 to 5.0 μm. If it is less than 0.1 μm, the powder is too fine and agglomerates, so that the handling of the powder tends to be poor, and it tends to be difficult to prepare a high-concentration slurry. This is because it tends to be difficult to obtain.
ＣｅＯ2粉末はＣｅ存在量の偏在の防止とＺｎＯマトリックスとの反応性及びＣｅ化合物の純度を考慮した場合、１次粒子径がナノスケールの酸化セリウム粒子を添加することが好ましい。Ａｌ2Ｏ3粉末は平均粒径が０．０１〜１μｍの範囲内のものを使用することが好ましい。０．０１〜１μｍの範囲内のものを使用すれば、ＣｅＯ2粉末を均一に分散するのに好適であるからである。このうち、０．０５〜０．５μｍの範囲のものが特に好ましい。 In consideration of prevention of uneven distribution of Ce abundance, reactivity with the ZnO matrix and purity of the Ce compound, CeO 2 powder is preferably added with cerium oxide particles having a primary particle size of nanoscale. It is preferable to use an Al 2 O 3 powder having an average particle size in the range of 0.01 to 1 μm. This is because the use of a material in the range of 0.01 to 1 μm is suitable for uniformly dispersing CeO 2 powder. Among these, the thing of the range of 0.05-0.5 micrometer is especially preferable.
バインダとしてはポリエチレングリコールやポリビニールブチラール等を、有機溶媒としてはエタノールやプロパノール等を用いることが好ましい。バインダは０．２〜５．０質量％添加することが好ましい。 It is preferable to use polyethylene glycol or polyvinyl butyral as the binder, and ethanol or propanol as the organic solvent. The binder is preferably added in an amount of 0.2 to 5.0% by mass.
また高純度粉末とバインダと有機溶媒との湿式混合、特に高純度粉末と分散媒である有機溶媒との湿式混合は、湿式ボールミル又は撹拌ミルにより行われる。湿式ボールミルでは、ＺｒＯ2製ボールを用いる場合には、直径５〜１０ｍｍの多数のＺｒＯ2製ボールを用いて８〜２４時間、好ましくは２０〜２４時間湿式混合される。ＺｒＯ2製ボールの直径を５〜１０ｍｍと限定したのは、５ｍｍ未満では混合が不十分となることからであり、１０ｍｍを越えると不純物が増える不具合があるからである。また混合時間が最長２４時間と長いのは、長時間連続混合しても不純物の発生が少ないからである。 The wet mixing of the high purity powder, the binder, and the organic solvent, particularly the wet mixing of the high purity powder and the organic solvent that is the dispersion medium is performed by a wet ball mill or a stirring mill. In the wet ball mill, when ZrO 2 balls are used, wet mixing is performed for 8 to 24 hours, preferably 20 to 24 hours, using a large number of ZrO 2 balls having a diameter of 5 to 10 mm. The reason why the diameter of the ZrO 2 balls is limited to 5 to 10 mm is that mixing is insufficient when the diameter is less than 5 mm, and there is a problem that impurities increase when the diameter exceeds 10 mm. The reason why the mixing time is as long as 24 hours is that the generation of impurities is small even if the mixing is continued for a long time.
次に、上記スラリーを噴霧乾燥して平均粒径が５０〜２５０μｍ、好ましくは５０〜２００μｍの混合造粒粉末を得る。この造粒粉末を所定の型に入れて所定の圧力で成形する。上記噴霧乾燥はスプレードライヤを用いて行われることが好ましく、所定の型は一軸プレス装置又は冷間静水圧成形装置（ＣＩＰ（Cold Isostatic Press）成形装置）が用いられる。一軸プレス装置では、造粒粉末を７５０〜２０００ｋｇ／ｃｍ2（７３５．５〜１９６１．３ＭＰａ）、好ましくは１０００〜１５００ｋｇ／ｃｍ2（９８０．７〜１４７１．０ＭＰａ）の圧力で一軸加圧成形し、ＣＩＰ成形装置では、造粒粉末を１０００〜３０００ｋｇ／ｃｍ2（９８０．７〜２９４２．０ＭＰａ）、好ましくは１５００〜２０００ｋｇ／ｃｍ2（１４７１．０〜１９６１．３ＭＰａ）の圧力でＣＩＰ成形する。圧力を上記範囲に限定したのは、成形体の密度を高めるとともに焼結後の変形を防止し、後加工を不要にするためである。 Next, the slurry is spray-dried to obtain a mixed granulated powder having an average particle size of 50 to 250 μm, preferably 50 to 200 μm. This granulated powder is put into a predetermined mold and molded at a predetermined pressure. The spray drying is preferably performed using a spray dryer, and the predetermined die is a uniaxial press device or a cold isostatic press (CIP (Cold Isostatic Press) molding device). In uniaxial pressing apparatus, granulated powder 750~2000kg / cm 2 (735.5~1961.3MPa), preferably uniaxial pressing at a pressure of 1000~1500kg / cm 2 (980.7~1471.0MPa) In the CIP molding apparatus, the granulated powder is CIP molded at a pressure of 1000 to 3000 kg / cm 2 (980.7 to 2942.0 MPa), preferably 1500 to 2000 kg / cm 2 (1471.0 to 1961.3 MPa). The reason why the pressure is limited to the above range is to increase the density of the molded body, prevent deformation after sintering, and eliminate the need for post-processing.
更に、成形体を所定の温度で焼結する。焼結は大気、不活性ガス、真空又は還元ガス雰囲気中で１０００℃以上、好ましくは１２００〜１４００℃の温度で１〜１０時間、好ましくは２〜５時間行う。これにより所望のＺｎＯを主成分とするペレットが得られる。ペレットの相対密度は９０％以上であることが好ましく、９５％以上であることが更に好ましい。相対密度が９０％以上であれば、成膜時のスプラッシュを低減できるからである。上記焼結は大気圧下で行うが、ホットプレス（ＨＰ）焼結や熱間静水圧プレス（ＨＩＰ、Hot Isostatic Press）焼結のように加圧焼結を行う場合には、不活性ガス、真空又は還元ガス雰囲気中で１０００℃以上の温度で１〜５時間行うことが好ましい。 Further, the molded body is sintered at a predetermined temperature. Sintering is carried out at a temperature of 1000 ° C. or higher, preferably 1200 to 1400 ° C. for 1 to 10 hours, preferably 2 to 5 hours in the atmosphere, inert gas, vacuum or reducing gas atmosphere. Thereby, the pellet which has desired ZnO as a main component is obtained. The relative density of the pellets is preferably 90% or more, and more preferably 95% or more. This is because if the relative density is 90% or more, splash during film formation can be reduced. The above sintering is performed under atmospheric pressure, but when performing pressure sintering such as hot pressing (HP) sintering or hot isostatic pressing (HIP) sintering, an inert gas, It is preferable to carry out at a temperature of 1000 ° C. or higher for 1 to 5 hours in a vacuum or a reducing gas atmosphere.
次いで、得られたペレットの多結晶ＺｎＯ蒸着材をターゲット材として、真空成膜法により基板表面にＺｎＯ膜を形成する。本発明のＺｎＯ蒸着材を用いて成膜するのに適する真空成膜法としては、電子ビーム蒸着法、イオンプレーティング法、スパッタリング法及びプラズマ蒸着法が挙げられる。これらの本発明の成膜方法により成膜されるＺｎＯ膜は、本発明のＺｎＯ蒸着材を使用しているため、ＩＴＯに迫るような、比抵抗が３〜５×１０-4Ω・ｃｍの高い導電率、可視光透過率が９０％以上の高い透過率が得られる。更に、イオン半径がＺｎより大きいＣｅにより歪んだ結晶を、イオン半径の小さいＡｌを添加して回復整合させることにより、膜の耐久性も向上する。 Next, a ZnO film is formed on the substrate surface by a vacuum film-forming method using the obtained polycrystalline ZnO vapor deposition material in pellets as a target material. Examples of the vacuum film formation method suitable for forming a film using the ZnO vapor deposition material of the present invention include an electron beam vapor deposition method, an ion plating method, a sputtering method, and a plasma vapor deposition method. Z nO film that will be deposited by the deposition method of these present invention, due to the use of ZnO deposition material of the present invention, such as approaching ITO, the resistivity is 3~5 × 10 -4 Ω · cm High conductivity and visible light transmittance of 90% or higher. Furthermore, the durability of the film is improved by adding and crystallizing the crystal distorted by Ce having an ionic radius larger than Zn by adding Al having a small ionic radius.
なお、本発明で使用されるＺｎＯ粉末、Ａｌ2Ｏ3粉末及び混合造粒粉末の平均粒径の値はレーザー回折法により算出又は測定される値である。 The value of the average particle diameter of ZnO powder, Al 2 O 3 powder and mixing the granulated powder used in the present invention is a value calculated or measured by a laser diffraction method.
次に本発明の実施例を比較例とともに詳しく説明する。（なお、以下の記載の「実施例１」は「参考例」である。）
Next, examples of the present invention will be described in detail together with comparative examples. ("Example 1" described below is a "reference example".)
得られたＺｎＯ蒸着材は、相対密度が９５％であり、また以下の表１に示すように、Ｃｅ濃度が０．２質量％、Ａｌ濃度が０．１質量％である多結晶ＺｎＯのペレットであった。またペレットの直径及び厚さはそれぞれ５ｍｍ及び１．６ｍｍであった。 The obtained ZnO vapor deposition material has a relative density of 95% and, as shown in Table 1 below, a polycrystalline ZnO pellet having a Ce concentration of 0.2% by mass and an Al concentration of 0.1% by mass. Met. The diameter and thickness of the pellets were 5 mm and 1.6 mm, respectively.
次に、ガラス基板（無アルカリガラス）上に、上記ＺｎＯ蒸着材を用いて電子ビーム蒸着法により、膜厚２００ｎｍのＺｎＯ膜を成膜した。具体的には、直径５０ｍｍ、深さ２５ｍｍの電子ビーム蒸着装置のハースに仕込まれた上記ＺｎＯ蒸着材に、到達真空度２．６６×１０-4Ｐａ、酸素分圧１．３３×１０-2の雰囲気において、加速電圧１０ｋＶ、ビームスキャンエリア約４０ｍｍφの電子ビームを照射、加熱することにより行った。 Next, a 200 nm-thick ZnO film was formed on a glass substrate (non-alkali glass) by the electron beam evaporation method using the ZnO evaporation material. Specifically, the ultimate vacuum degree is 2.66 × 10 −4 Pa and the partial pressure of oxygen is 1.33 × 10 −2 on the ZnO vapor deposition material charged in the hearth of the electron beam vapor deposition apparatus having a diameter of 50 mm and a depth of 25 mm. In this atmosphere, an electron beam having an acceleration voltage of 10 kV and a beam scan area of about 40 mmφ was irradiated and heated.
＜実施例２＞
ＺｎＯ粉末を９４４．２ｇ、ＣｅＯ2粉末を３６．９ｇ、Ａｌ2Ｏ3粉末を１８．９ｇとしたこと以外は、実施例１と同様に、ＺｎＯ蒸着材を作製し、ガラス基板上にＺｎＯ膜を成膜した。なお、得られたＺｎＯ蒸着材は、相対密度が９５％であり、また以下の表１に示すように、Ｃｅ濃度が３質量％、Ａｌ濃度が１質量％であった。
<Example 2>
A ZnO vapor deposition material was prepared in the same manner as in Example 1 except that 944.2 g of ZnO powder, 36.9 g of CeO 2 powder, and 18.9 g of Al 2 O 3 powder were used, and a ZnO film was formed on the glass substrate. Was deposited. The obtained ZnO vapor deposition material had a relative density of 95%, and as shown in Table 1 below, the Ce concentration was 3% by mass and the Al concentration was 1% by mass.
＜実施例３＞
ＺｎＯ粉末を８６９．６１ｇ、ＣｅＯ2粉末を７３．７０ｇ、Ａｌ2Ｏ3粉末を５６．６９ｇとしたこと以外は、実施例１と同様に、ＺｎＯ蒸着材を作製し、ガラス基板上にＺｎＯ膜を成膜した。なお、得られたＺｎＯ蒸着材は、相対密度が９５％であり、また以下の表１に示すように、Ｃｅ濃度が６質量％、Ａｌ濃度が３質量％であった。
<Example 3>
A ZnO vapor deposition material was prepared in the same manner as in Example 1 except that 869.61 g of ZnO powder, 73.70 g of CeO 2 powder and 56.69 g of Al 2 O 3 powder were used, and a ZnO film was formed on the glass substrate. Was deposited. In addition, the obtained ZnO vapor deposition material had a relative density of 95%, and as shown in Table 1 below, the Ce concentration was 6% by mass and the Al concentration was 3% by mass.
＜実施例４＞
ＺｎＯ粉末を６２８．０５ｇ、ＣｅＯ2粉末を１８３．００ｇ、Ａｌ2Ｏ3粉末を１８８．９５ｇとしたこと以外は、実施例１と同様に、ＺｎＯ蒸着材を作製し、ガラス基板上にＺｎＯ膜を成膜した。なお、得られたＺｎＯ蒸着材は、相対密度が９５％であり、また以下の表１に示すように、Ｃｅ濃度が１４．９質量％、Ａｌ濃度が１０質量％であった。
<Example 4>
A ZnO vapor deposition material was prepared in the same manner as in Example 1 except that the ZnO powder was 628.05 g, the CeO 2 powder was 183.00 g, and the Al 2 O 3 powder was 188.95 g, and a ZnO film was formed on the glass substrate. Was deposited. In addition, the obtained ZnO vapor deposition material had a relative density of 95%, and as shown in Table 1 below, the Ce concentration was 14.9% by mass and the Al concentration was 10% by mass.
＜比較例１＞
ＺｎＯ粉末を９９９．５６ｇ、ＣｅＯ2粉末を０．２５ｇ、Ａｌ2Ｏ3粉末を０．１９ｇとしたこと以外は、実施例１と同様に、ＺｎＯ蒸着材を作製し、ガラス基板上にＺｎＯ膜を成膜した。なお、得られたＺｎＯ蒸着材は、相対密度が９５％であり、また以下の表１に示すように、Ｃｅ濃度が０．０２質量％、Ａｌ濃度が０．０１質量％であった。
<Comparative Example 1>
A ZnO vapor deposition material was prepared in the same manner as in Example 1 except that the ZnO powder was 999.56 g, the CeO 2 powder was 0.25 g, and the Al 2 O 3 powder was 0.19 g, and a ZnO film was formed on the glass substrate. Was deposited. In addition, the obtained ZnO vapor deposition material had a relative density of 95%, and as shown in Table 1 below, the Ce concentration was 0.02 mass% and the Al concentration was 0.01 mass%.
＜比較例２＞
ＺｎＯ粉末を７５４．３ｇ、ＣｅＯ2粉末を２４５．７ｇとし、Ａｌ2Ｏ3粉末は添加しなかったこと以外は、実施例１と同様に、ＺｎＯ蒸着材を作製し、ガラス基板上にＺｎＯ膜を成膜した。なお、得られたＺｎＯ蒸着材は、相対密度が９５％であり、また以下の表１に示すように、Ｃｅ濃度が２０質量％であった。即ち、得られたＺｎＯ蒸着材はＡｌを含まない。
<Comparative example 2>
A ZnO vapor deposition material was prepared in the same manner as in Example 1 except that the ZnO powder was 754.3 g, the CeO 2 powder was 245.7 g, and the Al 2 O 3 powder was not added, and a ZnO film was formed on the glass substrate. Was deposited. In addition, the obtained ZnO vapor deposition material had a relative density of 95% and, as shown in Table 1 below, the Ce concentration was 20% by mass. That is, the obtained ZnO vapor deposition material does not contain Al.
＜比較例３＞
ＺｎＯ粉末を４７０．８７ｇ、ＣｅＯ2粉末を２４５．７０ｇ、Ａｌ2Ｏ3粉末を２８３．４３ｇとしたこと以外は、実施例１と同様に、ＺｎＯ蒸着材を作製し、ガラス基板上にＺｎＯ膜を成膜した。なお、得られたＺｎＯ蒸着材は、相対密度が９５％であり、また以下の表１に示すように、Ｃｅ濃度が２０質量％、Ａｌ濃度が１５質量％であった。
<Comparative Example 3>
A ZnO vapor deposition material was prepared in the same manner as in Example 1 except that the ZnO powder was 470.87 g, the CeO 2 powder was 245.70 g, and the Al 2 O 3 powder was 283.43 g, and a ZnO film was formed on the glass substrate. Was deposited. The obtained ZnO vapor deposition material had a relative density of 95%, and as shown in Table 1 below, the Ce concentration was 20 mass% and the Al concentration was 15 mass%.
＜比較例４＞
ＺｎＯ粉末を７１６．５７ｇ、Ａｌ2Ｏ3粉末を２８３．４３ｇとし、ＣｅＯ2粉末は添加しなかったこと以外は、実施例１と同様に、ＺｎＯ蒸着材を作製し、ガラス基板上にＺｎＯ膜を成膜した。なお、得られたＺｎＯ蒸着材は、相対密度が９５％であり、また以下の表１に示すように、Ａｌ濃度が１５質量％であった。即ち、得られたＺｎＯ蒸着材は、Ｃｅを含まない。
<Comparative Example 4>
A ZnO vapor deposition material was prepared in the same manner as in Example 1 except that the ZnO powder was 716.57 g, the Al 2 O 3 powder was 283.43 g, and the CeO 2 powder was not added, and a ZnO film was formed on the glass substrate. Was deposited. The obtained ZnO vapor deposition material had a relative density of 95% and an Al concentration of 15% by mass as shown in Table 1 below. That is, the obtained ZnO vapor deposition material does not contain Ce.
＜比較例５＞
ＺｎＯ粉末を１０００ｇとし、Ａｌ2Ｏ3粉末及びＣｅＯ2粉末を添加しなかったこと以外は、実施例１と同様に、ＺｎＯ蒸着材を作製し、ガラス基板上にＺｎＯ膜を成膜した。なお、得られたＺｎＯ蒸着材は、相対密度が９５％であり、Ｃｅ及びＡｌを含まないＺｎＯ蒸着材であった。
<Comparative Example 5>
A ZnO vapor deposition material was prepared and a ZnO film was formed on a glass substrate in the same manner as in Example 1 except that the ZnO powder was 1000 g and the Al 2 O 3 powder and CeO 2 powder were not added. In addition, the obtained ZnO vapor deposition material was a ZnO vapor deposition material which has a relative density of 95% and does not contain Ce and Al.
＜比較試験及び評価＞
実施例１〜４及び比較例１〜５で成膜したＺｎＯ膜について、比抵抗及び透過率を測定した。その結果を以下の表１に示す。比抵抗は測定器（三菱化学株式会社 商品名：ロレスタ ＨＰ型、ＭＣＰ−Ｔ４１０、プローブ：直列１．５ｍｍピッチ）を用い、雰囲気が２５℃において定電流印加による４端子４探針法により測定した。また透過率は分光光度計（株式会社日立製作所製 Ｕ−４０００）を用い、可視光波長域（３８０〜７８０ｍｍ）について、成膜後の基板を測定光に対して垂直に設置して測定した。
<Comparison test and evaluation>
Specific resistance and transmittance were measured for the ZnO films formed in Examples 1 to 4 and Comparative Examples 1 to 5. The results are shown in Table 1 below. The specific resistance was measured by a four-terminal four-probe method by applying a constant current at 25 ° C. using a measuring instrument (Mitsubishi Chemical Corporation, trade name: Loresta HP type, MCP-T410, probe: series 1.5 mm pitch). . The transmittance was measured using a spectrophotometer (U-4000, manufactured by Hitachi, Ltd.) in the visible light wavelength range (380 to 780 mm) by placing the substrate after film formation perpendicular to the measurement light.
表１から明らかなように、実施例１〜４と比較例１〜５を比較すると、実施例１〜４のＺｎＯ膜が有する比抵抗はいずれも比較例１〜５よりも低い結果となった。また透過率については、実施例２〜４のＺｎＯ膜が、比較例１及び５よりも若干低かったものの、比較例２〜４と比較すれば、十分に高い透過率が得られたと言える。このことから、本発明のＺｎＯ蒸着材が効果的であることが確認された。 As is clear from Table 1, when Examples 1-4 and Comparative Examples 1-5 were compared, the specific resistances of the ZnO films of Examples 1-4 were lower than those of Comparative Examples 1-5. . Moreover, about the transmittance | permeability, although the ZnO film | membrane of Examples 2-4 was a little lower than Comparative Examples 1 and 5, when compared with Comparative Examples 2-4, it can be said that sufficiently high transmittance was obtained. From this, it was confirmed that the ZnO vapor deposition material of the present invention is effective.
Claims (4)
ＺｎＯを主成分とした多結晶体のペレットからなり、
前記ペレットがＣｅとＡｌの双方の元素を含み、
前記Ｃｅの含有割合が３質量％以上１４．９質量％以下、前記Ａｌの含有割合が１質量％以上１０質量％以下の範囲内であり、
Ｃｅ／Ａｌの含有割合の比率が質量比で１．４９〜３の範囲内である
ことを特徴とするＺｎＯ蒸着材。 In a ZnO vapor deposition material used for forming a transparent conductive film,
It consists of a polycrystalline pellet mainly composed of ZnO,
The pellet contains both elements of Ce and Al;
14.9 wt% content of 3 mass% or more of the previous SL Ce below, Ri range der ratio following 10 mass% 1 mass% or more content of the Al,
The ZnO vapor deposition material characterized by the ratio of the Ce / Al content ratio being in the range of 1.49 to 3 by mass ratio .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012199491A JP5532093B2 (en) | 2007-03-09 | 2012-09-11 | ZnO vapor deposition material and method of forming ZnO film using the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007059898 | 2007-03-09 | ||
| JP2007059898 | 2007-03-09 | ||
| JP2012199491A JP5532093B2 (en) | 2007-03-09 | 2012-09-11 | ZnO vapor deposition material and method of forming ZnO film using the same |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008048898A Division JP5169313B2 (en) | 2007-03-09 | 2008-02-29 | Method for producing ZnO vapor deposition material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2012237072A JP2012237072A (en) | 2012-12-06 |
| JP5532093B2 true JP5532093B2 (en) | 2014-06-25 |
Family
ID=39979348
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008048898A Expired - Fee Related JP5169313B2 (en) | 2007-03-09 | 2008-02-29 | Method for producing ZnO vapor deposition material |
| JP2012199491A Expired - Fee Related JP5532093B2 (en) | 2007-03-09 | 2012-09-11 | ZnO vapor deposition material and method of forming ZnO film using the same |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008048898A Expired - Fee Related JP5169313B2 (en) | 2007-03-09 | 2008-02-29 | Method for producing ZnO vapor deposition material |
Country Status (1)
| Country | Link |
|---|---|
| JP (2) | JP5169313B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5418747B2 (en) * | 2007-09-27 | 2014-02-19 | 三菱マテリアル株式会社 | ZnO vapor deposition material, method for producing the same, and method for forming the ZnO film |
| KR101342721B1 (en) | 2007-09-27 | 2013-12-18 | 미쓰비시 마테리알 가부시키가이샤 | ZnO VAPOR DEPOSITION MATERIAL, PROCESS FOR PRODUCING THE SAME, AND ZnO FILM |
| JP5299662B2 (en) * | 2007-10-26 | 2013-09-25 | 三菱マテリアル株式会社 | Transparent conductive film and sputtering target for forming the transparent conductive film |
| JP2015113512A (en) * | 2013-12-13 | 2015-06-22 | 三菱マテリアル株式会社 | Oxide sputtering target |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2805813B2 (en) * | 1988-08-09 | 1998-09-30 | 東ソー株式会社 | Sputtering target and method for manufacturing the same |
| JP3301755B2 (en) * | 1990-08-22 | 2002-07-15 | 東ソー株式会社 | Sputtering target and manufacturing method thereof |
| JPH04219359A (en) * | 1990-12-19 | 1992-08-10 | Tosoh Corp | Electrically conductive zinc oxide sintered compact |
| JP3128861B2 (en) * | 1991-06-06 | 2001-01-29 | 東ソー株式会社 | Sputtering target and method for manufacturing the same |
| JP2000040429A (en) * | 1998-07-24 | 2000-02-08 | Sumitomo Metal Mining Co Ltd | Manufacturing of zinc oxide transparent conductive film |
| JP4577924B2 (en) * | 1999-06-29 | 2010-11-10 | 三井金属鉱業株式会社 | Method for producing sputtering target containing zinc oxide |
| JP3826755B2 (en) * | 2001-09-28 | 2006-09-27 | 株式会社村田製作所 | ZnO film, method for producing the same, and light emitting device |
| JP2005219982A (en) * | 2004-02-06 | 2005-08-18 | Mitsubishi Heavy Ind Ltd | Translucent conductive material |
-
2008
- 2008-02-29 JP JP2008048898A patent/JP5169313B2/en not_active Expired - Fee Related
-
2012
- 2012-09-11 JP JP2012199491A patent/JP5532093B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2012237072A (en) | 2012-12-06 |
| JP2008255475A (en) | 2008-10-23 |
| JP5169313B2 (en) | 2013-03-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5109418B2 (en) | ZnO vapor deposition material, method for producing the same, and method for forming ZnO film | |
| JP2008088544A5 (en) | ||
| JP5082928B2 (en) | ZnO vapor deposition material, method for producing the same, and ZnO film formed thereby | |
| JP5082927B2 (en) | Method for producing ZnO vapor deposition material | |
| JP5411945B2 (en) | Indium oxide-based sintered body and indium oxide-based transparent conductive film | |
| JP5532093B2 (en) | ZnO vapor deposition material and method of forming ZnO film using the same | |
| JP4962355B2 (en) | ZnO vapor deposition material and ZnO film formed thereby | |
| JP5018553B2 (en) | ZnO vapor deposition material, method for producing the same, and ZnO film formed thereby | |
| JP5418752B2 (en) | ZnO vapor deposition material, method for producing the same, and method for forming the ZnO film | |
| JP4962356B2 (en) | ZnO vapor deposition material and ZnO film formed thereby | |
| JP5499453B2 (en) | ZnO vapor deposition material, method for producing the same, and method for forming the ZnO film | |
| JP5381725B2 (en) | Method for producing ZnO vapor deposition material | |
| JP5381724B2 (en) | Method for producing ZnO vapor deposition material | |
| JP5568946B2 (en) | Method for producing ZnO vapor deposition material | |
| JP5402520B2 (en) | Method for producing ZnO vapor deposition material | |
| JP5018552B2 (en) | ZnO vapor deposition material, method for producing the same, and ZnO film formed thereby | |
| JP5428872B2 (en) | Method for producing ZnO vapor deposition material | |
| JP5428873B2 (en) | Method for producing ZnO vapor deposition material | |
| JP5562000B2 (en) | Oxide sintered body and manufacturing method thereof | |
| JP5428871B2 (en) | Method for producing ZnO vapor deposition material | |
| JP5428870B2 (en) | Method for producing ZnO vapor deposition material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120911 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140121 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140304 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140325 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140407 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5532093 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |