JPH0731950B2 - Method for producing transparent conductive film - Google Patents
Method for producing transparent conductive filmInfo
- Publication number
- JPH0731950B2 JPH0731950B2 JP60262940A JP26294085A JPH0731950B2 JP H0731950 B2 JPH0731950 B2 JP H0731950B2 JP 60262940 A JP60262940 A JP 60262940A JP 26294085 A JP26294085 A JP 26294085A JP H0731950 B2 JPH0731950 B2 JP H0731950B2
- Authority
- JP
- Japan
- Prior art keywords
- conductive film
- transparent conductive
- film
- specific resistance
- target
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 36
- 239000011787 zinc oxide Substances 0.000 claims description 17
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 238000004544 sputter deposition Methods 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000010408 film Substances 0.000 description 39
- 239000000758 substrate Substances 0.000 description 25
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 15
- 239000007789 gas Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 229910006404 SnO 2 Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electromagnetism (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physical Vapour Deposition (AREA)
- Non-Insulated Conductors (AREA)
- Electroluminescent Light Sources (AREA)
- Manufacturing Of Electric Cables (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Description
【発明の詳細な説明】 技術分野 本発明は、透明導電膜の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a transparent conductive film.
従来の技術 透明導電膜は、大きな導電性と可視域での高透光性を兼
備したものであり、EL（エレクトロ・ルミネサンス）表
示素子、液晶表示素子などの表示パネルの透明電極や、
太陽電池、各種受光素子の電極膜などとして用いられて
いる。従来、透明導電膜としては、Auなどの金属薄膜や
SuO2,In2O3,CaO,ZnS,ZnOなどの薄膜が知られている。し
かし、これらの多くは電気伝導度が不十分であるばかり
か、機械的性質（硬さ、密着性）、化学的安定性の点か
ら欠点が多いため、現在では、In2O3,SnO2,ITO（Indium
in Oxide）が広く利用されている。2. Description of the Related Art A transparent conductive film has both large conductivity and high translucency in the visible range, and is used for transparent electrodes of display panels such as EL (electro luminescence) display elements and liquid crystal display elements.
It is used as an electrode film for solar cells and various light-receiving elements. Conventionally, as a transparent conductive film, a metal thin film such as Au or
Thin films such as SuO 2 , In 2 O 3 , CaO, ZnS, and ZnO are known. However, most of these have not only insufficient electric conductivity, but also many defects in terms of mechanical properties (hardness, adhesion) and chemical stability. Therefore, currently, In 2 O 3 , SnO 2 , ITO (Indium
in Oxide) is widely used.
しかしながら、In2O3,SnO2,ITOも、次のような欠点を有
しており、よりいっそうの改善がまたれていた。However, In 2 O 3 , SnO 2 , and ITO also have the following drawbacks, and further improvements have been made.
（１）熱的安定性が悪く、EL等のデバイスに用いた場
合、熱処理を受けると比抵抗が大きくなったり、InやSn
が発光層等に拡散して悪影響を及ぼす。(1) It has poor thermal stability, and when it is used in devices such as EL, it undergoes heat treatment to increase its specific resistance.
Are diffused into the light emitting layer and the like, and have an adverse effect.
（２）比抵抗を下げるために成膜時または成膜後に300
℃以上の熱処理が必要である。(2) 300 to reduce the specific resistance during or after film formation
Heat treatment at ℃ or above is required.
（３）材料が非常に高価である。(3) The material is very expensive.
酸化亜鉛（ZnO）は、In2O3やSnO2に比べて価格が非常に
安く、透明導電膜の工業的な材料としては好ましいもの
であった。しかし、ZnOは可視域における透光性が高い
ものの、電気伝導度が十分でなかった。Zinc oxide (ZnO) has a very low price compared to In 2 O 3 and SnO 2 , and was preferable as an industrial material for the transparent conductive film. However, although ZnO has high translucency in the visible region, its electrical conductivity was not sufficient.
発明の目的 本発明は、電気伝導度が高く耐熱性を有し、かつ、安価
な材料から形成可能な透明導電膜を製造することを目的
とする。OBJECT OF THE INVENTION It is an object of the present invention to produce a transparent conductive film which has a high electric conductivity and heat resistance and can be formed from an inexpensive material.
発明の構成 本発明の透明導電膜の製造方法は、酸化亜鉛を主成分と
し酸化アルミニウムを混合したターゲットを用い、スパ
ッタガス圧10-2Torr以下におけるDCマグネトロンスパッ
タリング法により、酸化亜鉛を主成分とし、アルミニウ
ムを含むＣ軸配向膜からなる透明導電膜を形成すること
を特徴とする。Structure of the invention, the method for producing a transparent conductive film of the present invention, using a target in which aluminum oxide is mixed with zinc oxide as a main component, by DC magnetron sputtering method at a sputtering gas pressure of 10 -2 Torr or less, zinc oxide as a main component. A transparent conductive film formed of a C-axis alignment film containing aluminum is formed.
以下、本発明についてさらに詳細に説明する。Hereinafter, the present invention will be described in more detail.
酸化亜鉛（ZnO）膜は、本来電気伝導度が大きく、ま
た、可視域での透過率も高いが、これに対してアルミニ
ウムを添加することにより比抵抗をさらに小さくできる
ことが判った。The zinc oxide (ZnO) film originally has high electric conductivity and high transmittance in the visible region, but it was found that the resistivity can be further reduced by adding aluminum.
また、この膜は熱的安定性もすぐれている。Further, this film also has excellent thermal stability.
第１図は、アルミニウムの添加量と比抵抗の関係を示す
グラフである。これはAl2O3粉体とZnO粉体とを混合し、
焼結したものをターゲット材として用い、基板温度300
℃、膜厚2000Åの条件でDCマグネトロンスパッタ法によ
り作成したものである。Al2O3の添加量により、比抵抗
が変化することが判る。透明導電膜におけるAl2O3量
は、（Al2O3）／（ZnO＋Al2O3）で0.5〜５重量％の範囲
が好ましく、より好ましくは1.0〜4.0重量％の範囲であ
る。なお、Al2O3を6wt％以上含むターゲットを用いた場
合は、ターゲット自体の抵抗が大きくなり、DC電源では
放電できなかつた。FIG. 1 is a graph showing the relationship between the added amount of aluminum and the specific resistance. This mixes Al 2 O 3 powder and ZnO powder,
Using the sintered material as the target material, the substrate temperature is 300
It was created by DC magnetron sputtering under the conditions of ℃ and film thickness 2000Å. It can be seen that the specific resistance changes depending on the amount of Al 2 O 3 added. The amount of Al 2 O 3 in the transparent conductive film is 0.5 to 5% by weight (Al 2 O 3) / ( ZnO + Al 2 O 3) is preferably, and more preferably from 1.0 to 4.0 wt%. When a target containing Al 2 O 3 in an amount of 6 wt% or more was used, the resistance of the target itself increased and it was impossible to discharge with a DC power supply.
第２図は透明導電膜のＣ軸配向性を示す特性値としての
（002）面のロッキングカーブの半値幅：Δθ50と、比
抵抗：ρとの関係を示すグラフである。透明導電膜のΔ
θ50が小さくなるほど、即ちＣ軸配向性が向上するほど
比抵抗が小さくなることが判る。よつて、透明導電膜と
してはΔθ50を8.0（deg）以下とすることが好ましく、
より好ましくは4.0（deg）以下である。FIG. 2 is a graph showing the relationship between the half value width: Δθ 50 of the rocking curve of the (002) plane as a characteristic value showing the C-axis orientation of the transparent conductive film and the specific resistance: ρ. Δ of transparent conductive film
It can be seen that the specific resistance decreases as θ 50 decreases, that is, as the C-axis orientation improves. Therefore, it is preferable that the transparent conductive film has Δθ 50 of 8.0 (deg) or less,
It is more preferably 4.0 (deg) or less.
Alを含むZnOの軸配向膜は、DCマグネトロンスパツタ法
により適宜の基板上に形成することができる。The ZnO axial alignment film containing Al can be formed on an appropriate substrate by the DC magnetron sputtering method.
次に、DCマグネトロンスパッタ法による本発明の製造方
法について評価する。Next, the manufacturing method of the present invention by the DC magnetron sputtering method will be evaluated.
第３図は、DCマグネトロンスパッタ装置の構成を示す概
略図である。真空槽11内には、スパッタ電極13が設けら
れ、その上にターゲット15が配設されている。ターゲッ
ト15の表面に対して平行となるように、ターゲット15と
対向して基板17が保持されている。排気系21により真空
槽11内を高真空、たとえば10-6〜10-7Torrまで排気した
のち、ガス導入バルブ23により、Ar、Ar＋O2などのスパ
ッタガスを例えば10-2〜10-3Torrの真空度となるまで導
入してスパッタ圧力を10-2Torrに設定する。ついで、ス
パッタ電源25により電極間に高電圧を印加すると、スパ
ッタ電極13の裏面に設けられている磁石（図示せず）に
よる磁界によってマグネトロン放電が起こり、ターゲッ
トがスパッタされて基板17の表面に透明導電膜が形成さ
れる。図中においては、電源25として直流電源が用いら
れるが、RFマグネトロンスパッタ法による場合はRF電源
を用いればよい。しかし、DCマグネトロンスパッタ法
は、スパッタ速度が早く、しかも基板表面に与える熱的
ダメージも少ない。図中、19は基板温度測定用の熱電対
を示す。ターゲットの組成は（Al2O3）／（Al2O3）／
（Al2O3＋ZnO）で0.5〜5.0重量％の範囲が好ましく、よ
り好ましくは1.0〜3.0重量％である。ターゲットはZnO
粉末とAl2O3粉末とを混合し、粉砕、圧縮成形後、900〜
1000℃程度で本焼結し、さらに高温で例えば1300℃程度
で熱処理して低抵抗化したものを用いる。FIG. 3 is a schematic diagram showing the configuration of a DC magnetron sputtering apparatus. A sputtering electrode 13 is provided in the vacuum chamber 11, and a target 15 is provided on the sputtering electrode 13. The substrate 17 is held facing the target 15 so as to be parallel to the surface of the target 15. After the inside of the vacuum chamber 11 is evacuated to a high vacuum, for example, 10 −6 to 10 −7 Torr by the exhaust system 21, the gas introduction valve 23 is used to supply sputter gas such as Ar and Ar + O 2 to 10 −2 to 10 −3 Torr. And the sputtering pressure is set to 10 -2 Torr. Then, when a high voltage is applied between the electrodes by the sputtering power source 25, a magnetron discharge is generated by a magnetic field generated by a magnet (not shown) provided on the back surface of the sputtering electrode 13, and the target is sputtered to be transparent on the surface of the substrate 17. A conductive film is formed. Although a DC power supply is used as the power supply 25 in the figure, an RF power supply may be used in the case of the RF magnetron sputtering method. However, the DC magnetron sputtering method has a high sputtering speed and has little thermal damage to the substrate surface. In the figure, 19 indicates a thermocouple for measuring the substrate temperature. The composition of the target is (Al 2 O 3 ) / (Al 2 O 3 ) /
The range of (Al 2 O 3 + ZnO) is preferably 0.5 to 5.0% by weight, more preferably 1.0 to 3.0% by weight. Target is ZnO
900 ~ after mixing powder and Al 2 O 3 powder, crushing and compression molding
What is used is one that has been main-sintered at about 1000 ° C. and further heat-treated at a high temperature, for example, at about 1300 ° C. to reduce the resistance.
第４図は、基板温度と比抵抗ρとの関係を示すグラフで
ある。基板温度が高くなると比抵抗が低下し、300℃で
２〜３×10-4（Ω・cm）と最小値をとるが、300℃を越
えるとρはまた多少大きくなる。これは、アルゴンガス
圧:0.5×10-2Torr、膜厚2000Åの条件でDCマグネトロン
スパッタ法により行った。このように、本発明の透明導
電膜は、比較的低温でも、小さな比抵抗を実現すること
が可能である。FIG. 4 is a graph showing the relationship between the substrate temperature and the specific resistance ρ. The resistivity decreases as the substrate temperature rises, reaching a minimum value of 2 to 3 x 10 -4 (Ω · cm) at 300 ° C, but ρ increases somewhat above 300 ° C. This was performed by a DC magnetron sputtering method under the conditions of argon gas pressure: 0.5 × 10 -2 Torr and film thickness 2000 Å. Thus, the transparent conductive film of the present invention can realize a small specific resistance even at a relatively low temperature.
第５図は、基板温度300℃、膜厚2000Åの条件で、マグ
ネトロンスパッタ法により透明導電膜を形成した場合
の、Arガス圧（ＰＡｒ）と比抵抗ρとの関係を示すグラ
フである。アルゴンガス圧が小さい方が、比抵抗が小さ
な導電膜が得られることが判る。Figure 5 is a substrate temperature of 300 ° C., under conditions of film thickness of 2000 Å, is a graph showing the case of forming the transparent conductive film by a magnetron sputtering method, the relationship between the specific resistance ρ and Ar gas pressure (P A r) . It can be seen that a conductive film having a smaller specific resistance can be obtained when the argon gas pressure is smaller.
第７図は基板温度が300℃、第６図は基板水冷（〜100
℃）での、ρ（比抵抗）、ｎ（キャリア密度）、μＨ
（ホール移動度）についてのAlドープZnO膜の膜厚依存
性を示すグラフである。基板温度300℃の方がρが小さ
く、n,μＨは大きい。また、膜厚依存性も改善される。In Fig. 7, the substrate temperature is 300 ℃, and in Fig. 6, the substrate is water-cooled (~ 100
Ρ (specific resistance), n (carrier density), μH
It is a graph which shows the film thickness dependence of Al-doped ZnO film about (hole mobility). When the substrate temperature is 300 ° C., ρ is smaller and n, μH is larger. Further, the film thickness dependency is also improved.
第９図は基板温度が300℃、第８図は基板水冷でのＸ線
回折パターンを示す図である。両者とも（002）、（00
4）面のピークしか認められず、Ｃ軸に配向した膜構造
であることが判る。さらに、基板温度300℃が回折強度
が20倍程大きく、より配向度が強いものであると考えら
れる。FIG. 9 is an X-ray diffraction pattern when the substrate temperature is 300 ° C. and when the substrate is water-cooled. Both (002), (00
4) Only the peak of the plane is recognized, which indicates that the film structure is oriented along the C axis. Furthermore, it is considered that the substrate temperature of 300 ° C. has a diffraction intensity about 20 times higher, and the degree of orientation is stronger.
また、DCマグネトロン法により得られたAlドープZnO膜
は、可視域で80％以上の透過率を示す。The Al-doped ZnO film obtained by the DC magnetron method shows a transmittance of 80% or more in the visible region.
発明の効果 本発明によれば、耐熱性を有し熱的に安定で、比抵抗が
小さな透明導電膜が得られる。また、100℃以下でも10
-3〜10-4Ω・cmのオーダーの低抵抗な透明導電膜が得ら
れ、成膜後の熱処理も必要ないため耐熱温度の低いプラ
スチツクフイルム上にも形成できる。本発明で使用され
るZnOおよびAl2O3は、In2O3やSnO2に比較して非常に安
価であるため、工業上極めて有利である。EFFECTS OF THE INVENTION According to the present invention, a transparent conductive film having heat resistance, thermal stability, and low specific resistance can be obtained. Also, even at 100 ° C or lower, 10
A transparent conductive film having a low resistance on the order of -3 to 10 -4 Ωcm can be obtained, and since heat treatment after film formation is not required, it can be formed on a plastic film having a low heat resistance temperature. ZnO and Al 2 O 3 used in the present invention are extremely inexpensive as compared with In 2 O 3 and SnO 2 , and are industrially extremely advantageous.
実施例１ ZnO粉末とAl2O3粉末とを、（Al2O3）／（Al2O3＋ZnO）
で2wt％となるように混合し、仮焼、粉砕、圧縮成形
後、900〜1000℃で本焼結したのち、さらに1300℃で熱
処理して低抵抗化してターゲットを作成した。Example 1 ZnO powder and Al 2 O 3 powder were mixed into (Al 2 O 3 ) / (Al 2 O 3 + ZnO)
Was mixed so as to be 2% by weight, calcined, crushed, compression-molded, then main-sintered at 900 to 1000 ℃, and further heat-treated at 1300 ℃ to reduce the resistance to prepare a target.
このターゲットを用いて第３図に示した装置により基板
温度300℃でDCマグネトロンスパッタし、7059ガラス
（コーニング社製）上に透明導電膜を形成した。Using this target, DC magnetron sputtering was performed at a substrate temperature of 300 ° C. by the apparatus shown in FIG. 3 to form a transparent conductive film on 7059 glass (made by Corning Incorporated).
得られた透明導電膜の特性は以下の各実施例と共に後記
第１表に示した。The characteristics of the obtained transparent conductive film are shown in Table 1 below together with the following examples.
実施例２ 水冷により基板温度を100℃以下に維持した以外は実施
例１と同様に行つた。Example 2 Example 1 was repeated except that the substrate temperature was kept at 100 ° C. or lower by water cooling.
実施例３ 基板としてポリエチレンテレフタレートフィルムを用
い、水冷により基板温度を100℃以下保った以外は、実
施例１と同様にして透明導電膜を作成した。Example 3 A transparent conductive film was prepared in the same manner as in Example 1 except that a polyethylene terephthalate film was used as the substrate and the substrate temperature was kept at 100 ° C. or lower by water cooling.
第１図は、ターゲットへのAl2O3の添加量と膜の比抵抗
ρとの関係を示すグラフである。 第２図は、Δθ50と比抵抗との関係を示すグラフであ
る。 第３図は、DCマグネトロンスパッタ装置の構成を示す概
略図である。 第４図は、基板温度と比抵抗ρとの関係を示すグラフで
ある。 第５図は、アルゴンガス圧と比抵抗ρとの関係を示すグ
ラフである。 第７図は基板温度が300℃、第６図は基板水冷（〜100
℃）での、ρ（比抵抗）、ｎ（キャリア密度）、μＨ
（ホール移動度）についてのAlドープZnO膜の膜厚依存
性を示すグラフである。 第９図は基板温が300℃、第８図は基板水冷でのＸ線回
折パターンを示すグラフである。 11……真空槽 13……スパッタ電極 15……ターゲット 17……基板FIG. 1 is a graph showing the relationship between the amount of Al 2 O 3 added to the target and the specific resistance ρ of the film. FIG. 2 is a graph showing the relationship between Δθ 50 and specific resistance. FIG. 3 is a schematic diagram showing the configuration of a DC magnetron sputtering apparatus. FIG. 4 is a graph showing the relationship between the substrate temperature and the specific resistance ρ. FIG. 5 is a graph showing the relationship between the argon gas pressure and the specific resistance ρ. In Fig. 7, the substrate temperature is 300 ℃, and in Fig. 6, the substrate is water-cooled (~ 100
Ρ (specific resistance), n (carrier density), μH
It is a graph which shows the film thickness dependence of Al-doped ZnO film about (hole mobility). FIG. 9 is a graph showing an X-ray diffraction pattern when the substrate temperature is 300 ° C. and when the substrate is water-cooled. 11 …… Vacuum chamber 13 …… Sputtering electrode 15 …… Target 17 …… Substrate
フロントページの続き (72)発明者 町田 元 東京都大田区中馬込１丁目３番６号 株式 会社リコー内 (72)発明者 和多田 篤行 東京都大田区中馬込１丁目３番６号 株式 会社リコー内 (72)発明者 中村 均 東京都大田区中馬込１丁目３番６号 株式 会社リコー内 (56)参考文献 特開 昭61−96609（ＪＰ，Ａ) 特開 昭61−214306（ＪＰ，Ａ)Front Page Continuation (72) Inventor Gen Machida 1-3-6 Nakamagome, Ota-ku, Tokyo In Ricoh Co., Ltd. (72) Inventor Atsuyuki Watada 1-3-6 Nakamagome, Ota-ku, Tokyo In Ricoh Co., Ltd. (72) Inventor Hitoshi Nakamura 1-3-6 Nakamagome, Ota-ku, Tokyo Within Ricoh Co., Ltd. (56) References JP-A-61-96609 (JP, A) JP-A-61-214306 (JP, A)
Claims (1)
混合したターゲットを用い、スパッタガス圧10-2Torr以
下におけるDCマグネトロンスパッタリング法により、酸
化亜鉛を主成分とし、アルミニウムを含むＣ軸配向膜か
らなる透明導電膜を形成することを特徴とする透明導電
膜の製造方法。1. A C-axis oriented film containing zinc oxide as a main component and containing aluminum by a DC magnetron sputtering method at a sputtering gas pressure of 10 -2 Torr or less using a target containing zinc oxide as a main component and mixed with aluminum oxide. A method for producing a transparent conductive film, comprising:
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60262940A JPH0731950B2 (en) | 1985-11-22 | 1985-11-22 | Method for producing transparent conductive film |
| DE19863639508 DE3639508A1 (en) | 1985-11-22 | 1986-11-20 | Transparent, electrically conducting film and method of fabricating it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60262940A JPH0731950B2 (en) | 1985-11-22 | 1985-11-22 | Method for producing transparent conductive film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62122011A JPS62122011A (en) | 1987-06-03 |
| JPH0731950B2 true JPH0731950B2 (en) | 1995-04-10 |
Family
ID=17382680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60262940A Expired - Fee Related JPH0731950B2 (en) | 1985-11-22 | 1985-11-22 | Method for producing transparent conductive film |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH0731950B2 (en) |
| DE (1) | DE3639508A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006200016A (en) * | 2005-01-21 | 2006-08-03 | Tosoh Corp | ZnO:Al TARGET, THIN FILM THEREOF, AND METHOD FOR MANUFACTURING THIN FILM |
| CN101548343A (en) * | 2007-09-05 | 2009-09-30 | 株式会社村田制作所 | Transparent conductive film and method for producing transparent conductive film |
| US10889888B2 (en) | 2011-06-08 | 2021-01-12 | Semiconductor Energy Laboratory Co., Ltd. | Sputtering target, method for manufacturing sputtering target, and method for forming thin film |
Families Citing this family (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4948529A (en) * | 1985-12-18 | 1990-08-14 | Andus Corporation | Stable high resistance transparent coating |
| US4710441A (en) * | 1985-12-18 | 1987-12-01 | Andus Corp. | Stable high resistance transparent coating |
| JPH01265495A (en) * | 1988-04-15 | 1989-10-23 | Gunze Ltd | Electroluminescent element |
| DE68919299T2 (en) * | 1988-08-09 | 1995-04-06 | Tosoh Corp | Zinc oxide sintered body and its manufacture. |
| JP2758660B2 (en) * | 1989-07-18 | 1998-05-28 | グンゼ株式会社 | Dispersion type electroluminescent device using zinc oxide as transparent electrode |
| JPH03164461A (en) * | 1989-08-10 | 1991-07-16 | Tosoh Corp | Sputtering target of sintered body of conductive zinc oxide and production thereof |
| JPH0688218A (en) * | 1990-11-15 | 1994-03-29 | Tosoh Corp | Sintered compact of zinc oxide system and its production and application |
| US5171411A (en) * | 1991-05-21 | 1992-12-15 | The Boc Group, Inc. | Rotating cylindrical magnetron structure with self supporting zinc alloy target |
| DE29711973U1 (en) * | 1997-07-08 | 1998-11-05 | Glas Platz Fa | Electrical device, electrical device or lighting device |
| DE10306925A1 (en) * | 2003-02-19 | 2004-09-02 | GfE Gesellschaft für Elektrometallurgie mbH | PVD coating material |
| US7867636B2 (en) | 2006-01-11 | 2011-01-11 | Murata Manufacturing Co., Ltd. | Transparent conductive film and method for manufacturing the same |
| JP4797712B2 (en) * | 2006-03-08 | 2011-10-19 | 東ソー株式会社 | ZnO-Al2O3-based sintered body, sputtering target, and method for producing transparent conductive film |
| TW200834610A (en) * | 2007-01-10 | 2008-08-16 | Nitto Denko Corp | Transparent conductive film and method for producing the same |
| WO2008105198A1 (en) * | 2007-02-26 | 2008-09-04 | Murata Manufacturing Co., Ltd. | Conductive film and method for production of conductive film |
| DE102007024986A1 (en) | 2007-05-28 | 2008-12-04 | Forschungszentrum Jülich GmbH | Temperature-stable TCO layer, method of manufacture and application |
| EP2028695A1 (en) * | 2007-07-12 | 2009-02-25 | Applied Materials, Inc. | Method for creating a transparent conductible oxide coating |
| JP4537434B2 (en) * | 2007-08-31 | 2010-09-01 | 株式会社日立製作所 | Zinc oxide thin film, transparent conductive film using the same, and display element |
| JP5352878B2 (en) * | 2008-03-31 | 2013-11-27 | 公立大学法人高知工科大学 | Display substrate, method for manufacturing the same, and display device |
| JP5432501B2 (en) * | 2008-05-13 | 2014-03-05 | 日東電工株式会社 | Transparent conductive film and method for producing the same |
| KR101146980B1 (en) * | 2009-02-17 | 2012-05-22 | 삼성모바일디스플레이주식회사 | Organic light emitting diode and manufacturing method thereof |
| JP5348394B2 (en) * | 2009-03-13 | 2013-11-20 | 三菱マテリアル株式会社 | (Zn, Al) O-based transparent electrode layer for solar cell and ZnO-Al2O3-based sputtering target used for forming the same |
| JP5348399B2 (en) * | 2009-03-31 | 2013-11-20 | 三菱マテリアル株式会社 | (Zn, Ga, Al) O-based transparent electrode layer for solar cell and ZnO-Ga2O3-Al-based sputtering target used for forming the same |
| JP5333144B2 (en) * | 2009-10-14 | 2013-11-06 | 住友金属鉱山株式会社 | Sintered body target for thin film manufacturing and its manufacturing method |
| JP5533448B2 (en) | 2010-08-30 | 2014-06-25 | 住友金属鉱山株式会社 | Transparent conductive film laminate and manufacturing method thereof, thin film solar cell and manufacturing method thereof |
| US9057126B2 (en) | 2011-11-29 | 2015-06-16 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing sputtering target and method for manufacturing semiconductor device |
| JP5809952B2 (en) * | 2011-12-12 | 2015-11-11 | 本田技研工業株式会社 | Manufacturing method of solar cell |
| JP2013144820A (en) * | 2012-01-13 | 2013-07-25 | Mitsubishi Materials Corp | Oxide sputtering target and protective film for optical recording medium |
| US9885108B2 (en) | 2012-08-07 | 2018-02-06 | Semiconductor Energy Laboratory Co., Ltd. | Method for forming sputtering target |
| EP2904128A1 (en) * | 2012-10-08 | 2015-08-12 | Corning Incorporated | Sputtered transparent conductive aluminum doped zinc oxide films |
| CN103046013A (en) * | 2012-12-30 | 2013-04-17 | 青海天誉汇新能源开发有限公司 | Method for preparing photovoltaic cell transparent oxide film with flexible substrate |
| JP6141777B2 (en) | 2013-02-28 | 2017-06-07 | 株式会社半導体エネルギー研究所 | Method for manufacturing semiconductor device |
| JP7378938B2 (en) * | 2019-02-22 | 2023-11-14 | 日東電工株式会社 | Light-transparent conductive film |
| JP7205313B2 (en) * | 2019-03-11 | 2023-01-17 | セイコーエプソン株式会社 | Cables and ultrasound equipment |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3766041A (en) * | 1970-09-29 | 1973-10-16 | Matsushita Electric Ind Co Ltd | Method of producing piezoelectric thin films by cathodic sputtering |
| JPS557554A (en) * | 1978-06-30 | 1980-01-19 | Murata Mfg Co Ltd | Dielectric thin film |
| JPS5516554A (en) * | 1978-07-21 | 1980-02-05 | Toko Inc | Manufacture of thin film of zinc oxide |
| JPS6196609A (en) * | 1984-10-15 | 1986-05-15 | 大阪特殊合金株式会社 | Transparent conductive film |
| JPS61214306A (en) * | 1985-03-18 | 1986-09-24 | 大阪特殊合金株式会社 | Method and apparatus for transparent conducting film |
-
1985
- 1985-11-22 JP JP60262940A patent/JPH0731950B2/en not_active Expired - Fee Related
-
1986
- 1986-11-20 DE DE19863639508 patent/DE3639508A1/en not_active Ceased
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006200016A (en) * | 2005-01-21 | 2006-08-03 | Tosoh Corp | ZnO:Al TARGET, THIN FILM THEREOF, AND METHOD FOR MANUFACTURING THIN FILM |
| CN101548343A (en) * | 2007-09-05 | 2009-09-30 | 株式会社村田制作所 | Transparent conductive film and method for producing transparent conductive film |
| US10889888B2 (en) | 2011-06-08 | 2021-01-12 | Semiconductor Energy Laboratory Co., Ltd. | Sputtering target, method for manufacturing sputtering target, and method for forming thin film |
| US11066739B2 (en) | 2011-06-08 | 2021-07-20 | Semiconductor Energy Laboratory Co., Ltd. | Sputtering target, method for manufacturing sputtering target, and method for forming thin film |
| US11959165B2 (en) | 2011-06-08 | 2024-04-16 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device comprising oxide semiconductor film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62122011A (en) | 1987-06-03 |
| DE3639508A1 (en) | 1987-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0731950B2 (en) | Method for producing transparent conductive film | |
| JP2000040429A (en) | Manufacturing of zinc oxide transparent conductive film | |
| JPH056766B2 (en) | ||
| JP3780932B2 (en) | Sintered target for producing transparent conductive thin film and method for producing the same | |
| JPH02232358A (en) | Production of transparent conductive film and apparatus for producing such film | |
| Igasaki et al. | Some properties of Al-doped ZnO transparent conducting films prepared by RF reactive sputtering | |
| JP2004006221A (en) | Transparent conductive thin film, manufacturing method thereof, sintering body target for manufacturing the same, organic electroluminescent element and its manufacturing process | |
| CN1600895A (en) | Method for preparing transparent conducting film made from multi-element oxides with antimony being doped into | |
| JPH06293956A (en) | Zinc oxide transparent conductive film, its formation and sputtering target used therefor | |
| JPH0344465A (en) | Production of sputtering target for electrically conductive transparent ito film | |
| JP2017193755A (en) | Method of manufacturing transparent conductive film, and transparent conductive film | |
| JP2000108244A (en) | Transparent conductive film, its manufacture, and base having transparent conductive film | |
| JPH0756131A (en) | Production of transparent conductive film | |
| JP2003027216A (en) | Method and apparatus for producing transparent electrically conductive film | |
| JP3355610B2 (en) | Method for increasing resistance of tin-doped indium oxide film | |
| JPH0765167B2 (en) | Sputtering target for ITO transparent conductive film | |
| JPH07224383A (en) | Method for making indium-tin oxide film high in resistance | |
| JP2004168636A (en) | Oxide sintered compact and sputtering target, and method for manufacturing oxide transparent electrode film | |
| JPH04341707A (en) | Transparent conductive film | |
| CN102465273A (en) | Multielement composite transparent conductive film and preparation method and application thereof | |
| JP2002256423A (en) | Sintered target for manufacturing transparent electroconductive film, and manufacturing method therefor | |
| JP2010215948A (en) | Method for manufacturing transparent conductive film | |
| CN102465272A (en) | Multielement composite transparent conductive film and preparation method and application thereof | |
| JPH07224374A (en) | Method for making tin doped indium oxide film high resistant | |
| TWI228544B (en) | Method for forming transparent conducting oxide film by arc ion plating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |