JP2002114515A - METHOD FOR PRODUCING THIN CuAlO2 FILM BY CHEMICAL PROCESS - Google Patents
METHOD FOR PRODUCING THIN CuAlO2 FILM BY CHEMICAL PROCESSInfo
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- JP2002114515A JP2002114515A JP2000301840A JP2000301840A JP2002114515A JP 2002114515 A JP2002114515 A JP 2002114515A JP 2000301840 A JP2000301840 A JP 2000301840A JP 2000301840 A JP2000301840 A JP 2000301840A JP 2002114515 A JP2002114515 A JP 2002114515A
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- thin film
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- cualo2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ＣｕＡｌＯ2 を主
成分とする薄膜を製造する方法に関するものであり、更
に詳しくは、透明（ワイドバンドギャップ）でｐ型の導
電性を示すＣｕＡｌＯ2 薄膜のケミカルプロセスによる
製造方法に関するものである。BACKGROUND OF THE INVENTION The present invention relates to a method for producing a film on the basis of CuAlO 2, more particularly, transparent illustrates a p-type conductivity in (wide band gap) CuAlO 2 thin film The present invention relates to a manufacturing method using a chemical process.
【０００２】[0002]
【従来の技術】現在、ＩＴＯ等のｎ型の透明導電性薄膜
は、フラットパネルディスプレーや太陽電池等の透明電
極として応用されている。それに対して、ｐ型の透明導
電性薄膜は殆ど見あたらない。仮に、高導電性を持つｐ
型の透明導電性薄膜が開発されれば、透明なｐ−ｎ接合
体が作製可能となり、透明トランジスタ等の新しいオプ
トエレクトロニクスデバイスの出現が期待できる。2. Description of the Related Art At present, an n-type transparent conductive thin film such as ITO is applied as a transparent electrode for flat panel displays and solar cells. In contrast, a p-type transparent conductive thin film is hardly found. Assuming that p has high conductivity
If a transparent conductive thin film of the type is developed, a transparent pn junction can be produced, and a new optoelectronic device such as a transparent transistor can be expected.
【０００３】ゾル−ゲル法に代表されるケミカルプロセ
スによる薄膜作製は、真空容器内でのドライプロセスに
よる薄膜作製に比べ、低コストであり、組成均質性に優
れている。これまで、レーザーアブレーション法でｐ型
の高導電性を示すＣｕＡｌＯ2 薄膜が作製された例はあ
るが（川副ら，Ｎａｔｕｒｅ，３８９（１９９７）ｐ．
９４１）、ケミカルプロセスによりＣｕＡｌＯ2 薄膜が
作製されたという報告は見あたらない。[0003] Thin film production by a chemical process represented by the sol-gel method is lower in cost and excellent in composition uniformity than thin film production by a dry process in a vacuum vessel. Until now, there has been an example in which a Cu-AlO 2 thin film exhibiting high conductivity of p-type has been produced by a laser ablation method (Kawasoe et al., Nature, 389 (1997) p.
941), there is no report that a CuAlO 2 thin film was produced by a chemical process.
【０００４】[0004]
【発明が解決しようとする課題】このような状況の中
で、本発明者らは、上記従来技術に鑑みて、ケミカルプ
ロセスにより高収率かつ低コストでＣｕＡｌＯ2 薄膜を
作製する方法を確立することを目標として鋭意研究を積
み重ねた結果、酢酸銅１水塩あるいは無水の特定のアル
コール類の溶液にアルミニウムアルコキシド溶液を加え
た出発溶液を用いて、前駆体溶液を調製し、これを基板
上にコーティングして焼成することにより所期の目的を
達成し得ることを見出し、本発明を完成するに至った。
本発明の目的は、これまで極めて困難であったケミカル
プロセスによるＣｕＡｌＯ2 薄膜の作製法を提供するこ
とである。また、本発明は、透明（ワイドバンドギャッ
プ）でｐ型の導電性を示すＣｕＡｌＯ2 薄膜を化学的プ
ロセスで効率よく、高収率かつ低コストで作製する方法
を提供することを目的とするものである。Under such circumstances, the present inventors have established a method for producing a CuAlO 2 thin film at a high yield and at low cost by a chemical process in view of the above prior art. As a result of intensive research aiming at this, a precursor solution was prepared using a starting solution obtained by adding an aluminum alkoxide solution to a solution of copper acetate monohydrate or anhydrous specific alcohols, and this was prepared on a substrate. It has been found that the desired object can be achieved by coating and firing, and the present invention has been completed.
An object of the present invention is to provide a method for producing a CuAlO 2 thin film by a chemical process, which has been extremely difficult to date. Another object of the present invention is to provide a method for efficiently producing a CuAlO 2 thin film exhibiting p-type conductivity with transparency (wide band gap) by a chemical process at high yield and at low cost. It is.
【０００５】[0005]
【課題を解決するための手段】上記課題を解決するため
の本発明は、以下の技術的手段により構成される。 （１）酢酸銅（１水塩あるいは無水）をアルコール類に
溶解した後、銅に対して０．８〜１．５倍モルのアルミ
ニウムを含むアルミニウムアルコキシド溶液を加えて出
発溶液を作製し、次に、この溶液を還流した後、蒸留し
て金属イオン濃度（Ｃｕ2+＋Ａｌ3+）が０．５〜１．５
Ｍ／Ｌの前駆体溶液を作製し、更に、この溶液をディッ
プコーティングあるいはスピンコーティングして基板上
に堆積させ、乾燥する操作をした後、窒素又はアルゴン
雰囲気で焼成を行ってＣｕＡｌＯ2 を主成分とする薄膜
を作製することを特徴とするＣｕＡｌＯ2 薄膜の製造方
法。 （２）酢酸銅（１水塩あるいは無水）をエタノール及び
２−メトキシエタノールに溶解する前記（１）記載の方
法。 （３）堆積させ、乾燥する操作を繰り返して適当な厚み
を持った膜を積層した後、焼成する前記（１）記載の方
法。 （４）溶液をディップコーティング、又はスピンコーテ
ィングして基板上に堆積する前記（１）記載の方法。 （５）７００〜９００℃で焼成する前記（１）記載の方
法。[MEANS FOR SOLVING THE PROBLEMS]
The present invention is constituted by the following technical means. (1) Convert copper acetate (monohydrate or anhydrous) into alcohol
After melting, 0.8-1.5 times mole of aluminum
Add aluminum alkoxide solution containing
The solution is then refluxed and then distilled.
Metal ion concentration (Cu2++ Al3+) Is 0.5 to 1.5
A precursor solution of M / L was prepared, and this solution was further
Pre-coated or spin-coated on the substrate
After drying and drying, nitrogen or argon
Firing in an atmosphere to obtain CuAlOTwo Thin film mainly composed of
CuAlO characterized by producingTwo How to make thin films
Law. (2) Copper acetate (monohydrate or anhydrous) is converted to ethanol and
The method according to the above (1), which is dissolved in 2-methoxyethanol.
Law. (3) An appropriate thickness by repeating the operation of depositing and drying
After laminating a film having
Law. (4) Dip coating the solution or spin coating
The method according to the above (1), wherein the substrate is deposited on a substrate. (5) The method described in (1) above, which is fired at 700 to 900 ° C.
Law.
【０００６】[0006]
【発明の実施の形態】次に、本発明について更に詳細に
説明する。本発明は、ワイドバンドギャップでｐ型導電
性を示すＣｕＡｌＯ2 薄膜をケミカルプロセスにより作
製する方法に関するものである。本発明に係わる薄膜の
製造方法は、酢酸銅（１水塩あるいは無水）をアルコー
ル類、好適には、エタノール及び２−メトキシエタノー
ルに溶解した後、銅に対して０．８〜１．５倍モルのア
ルミニウムを含むアルミニウムアルコキシド溶液を加え
て出発溶液を作製する。次に、この溶液を還流した後、
蒸留して金属イオン濃度（Ｃｕ2+＋Ａｌ3+）が０．５〜
１．５Ｍ／Ｌの前駆体溶液とし、更に、この溶液をディ
ップコーティングあるいはスピンコーティングして基板
上に堆積させ、次に乾燥するという操作を繰り返して適
当な厚みを持った膜を積層した後、窒素又はアルゴン雰
囲気で焼成を行ってＣｕＡｌＯ2 を主成分とする薄膜を
作製する。Next, the present invention will be described in more detail. The present invention relates to a method for producing a CuAlO 2 thin film having p-type conductivity with a wide band gap by a chemical process. In the method for producing a thin film according to the present invention, copper acetate (monohydrate or anhydrous) is dissolved in alcohols, preferably ethanol and 2-methoxyethanol, and then 0.8 to 1.5 times the amount of copper. An aluminum alkoxide solution containing moles of aluminum is added to make a starting solution. Next, after refluxing the solution,
After distillation, the metal ion concentration (Cu 2+ + Al 3+ ) is 0.5 to
After forming a precursor solution of 1.5 M / L, and further dip coating or spin coating this solution to deposit on the substrate, and then repeating drying, a film having an appropriate thickness is laminated. Firing is performed in a nitrogen or argon atmosphere to produce a thin film containing CuAlO 2 as a main component.
【０００７】本発明において、銅成分の出発原料として
は、酢酸銅１水塩（Ｃｕ（ＣＨ3 ＣＯＯ）2 Ｈ2 Ｏ）あ
るいは無水酢酸銅（Ｃｕ（ＣＨ3 ＣＯＯ）2 ）が使用さ
れる。これをアルコール類、好適には、エタノール及び
２−メトキシエタノールに溶解するが、この場合、好適
には、エタノールの濃度は、０．０５〜０．２Ｍ／Ｌが
好ましく、更に、酢酸銅に対して１０〜３０倍当量程度
の２−メトキシエタノールを加える。次に、この溶液中
に、銅に対して０．５〜１．５倍モル、好ましくは等モ
ルのアルミニウムを含むアルミニウムアルコキシド、例
えば、アルミニウムブトキサイド、アルミニウムイソプ
ロポキシド溶液を加えて出発溶液を調製する。In the present invention, copper acetate monohydrate (Cu (CH 3 COO) 2 H 2 O) or anhydrous copper acetate (Cu (CH 3 COO) 2 ) is used as a starting material for the copper component. This is dissolved in alcohols, preferably ethanol and 2-methoxyethanol. In this case, preferably, the concentration of ethanol is preferably 0.05 to 0.2 M / L. And add about 10 to 30 equivalents of 2-methoxyethanol. Next, an aluminum alkoxide containing aluminum in an amount of 0.5 to 1.5 times, preferably equimolar to copper, aluminum, for example, aluminum butoxide, aluminum isopropoxide solution is added to this solution, and a starting solution is added. Is prepared.
【０００８】次に、この溶液を攪拌しながら、８０℃前
後で１〜３ｈ還流した後、金属イオン濃度（Ｃｕ2+＋Ａ
ｌ3+）が０．５〜１．５Ｍ／Ｌ、好ましくは０．８Ｍ／
Ｌ以上になるまで蒸留して前駆体溶液を調製する。この
場合、必要により、Ａｌ／Ｃｕ比の調整、あるいは導電
率を高める目的でドーパント元素（例えば、Ａｌサイト
を置換するＢｅ、Ｍｇ、Ｃａ等）を前駆体溶液中に目的
の濃度に合わせて溶かし込むことができる。次いで、こ
の溶液を基板上にコーティングし、乾燥する。この場
合、基板としては、例えば、好適には、シリカガラス、
アルミナ、ジルコニア、ムライト等の基板が例示される
が、これらに限らず、８００℃程度の温度に耐え得る基
板であれば同様に使用することが可能であり、基板の種
類は、特に限定されるものではない。また、コーティン
グ方法としては、好適には、ディップコーティング、ス
ピンコーティング等が例示される。上記コーティング−
乾燥の操作を１回以上、必要により、適宜の回数の操作
を繰り返して適当な厚みを持った膜を堆積させた後、窒
素、アルゴン等の不活性雰囲気で焼成する。焼成条件
は、７００〜９００℃が好ましい。７００℃以下ではＣ
ｕＡｌＯ2 の生成量が少なく、高い導電性を示さず、ま
た、９００℃以上では、透明基板の失透、あるいは基板
と膜との反応のおそれがあるため、８００℃付近での焼
成がより好ましい。Next, the solution is refluxed for 1 to 3 hours at about 80 ° C. while stirring, and then the metal ion concentration (Cu 2+ + A
l3 + ) is 0.5 to 1.5 M / L, preferably 0.8 M / L.
Distill until L or more to prepare the precursor solution. In this case, if necessary, a dopant element (for example, Be, Mg, Ca, etc. which replaces an Al site) is dissolved in the precursor solution in accordance with a target concentration for the purpose of adjusting the Al / Cu ratio or increasing the conductivity. Can be included. The solution is then coated on a substrate and dried. In this case, as the substrate, for example, preferably, silica glass,
Substrates such as alumina, zirconia, and mullite are exemplified, but the present invention is not limited thereto, and any substrate that can withstand a temperature of about 800 ° C. can be used in the same manner, and the type of substrate is particularly limited. Not something. Further, as the coating method, preferably, dip coating, spin coating, or the like is exemplified. The above coating
The film is dried one or more times, and if necessary, repeated an appropriate number of times to deposit a film having an appropriate thickness, and then fired in an inert atmosphere such as nitrogen or argon. The firing conditions are preferably from 700 to 900C. C below 700 ° C
Since the production amount of uAlO 2 is small and does not show high conductivity, and at 900 ° C. or higher, there is a possibility of devitrification of the transparent substrate or a reaction between the substrate and the film. .
【０００９】本発明の方法は、特に、以下のような利点
を有する。 （１）本発明により、ｐ型の酸化物導電体として、２５
０Ω・ｃｍ以下の抵抗率と高透過率（図１）を示すＣｕ
ＡｌＯ2 薄膜が得られる。 （２）本発明の方法は、ドライプロセスによる薄膜作製
のように、高価な真空装置や原料を必要とせず、また、
収率も１００％に近く、非常に低コストなプロセスであ
る。 （３）Ａｌ／Ｃｕ比の調整、あるいは導電率を高める目
的で添加されるドーパント元素（例えば、Ａｌサイトを
置換するＢｅ、Ｍｇ、Ｃａ等）を前駆体溶液中に目的の
濃度に合わせて溶かし込むことにより、目的の化学組成
を持った均質な薄膜を比較的容易に作製することが可能
である。The method of the present invention has the following advantages. (1) According to the present invention, as a p-type oxide conductor, 25
Cu exhibiting a resistivity of 0 Ω · cm or less and a high transmittance (FIG. 1)
An AlO 2 thin film is obtained. (2) The method of the present invention does not require expensive vacuum equipment and raw materials, unlike a thin film produced by a dry process.
The yield is close to 100%, which is a very low-cost process. (3) Dissolve a dopant element (for example, Be, Mg, Ca, etc. that replaces an Al site) added to adjust the Al / Cu ratio or increase the electrical conductivity in the precursor solution according to the target concentration. By doing so, a homogeneous thin film having a desired chemical composition can be relatively easily produced.
【００１０】[0010]
【実施例】次に、実施例に基づいて本発明を具体的に説
明するが、本発明は、当該実施例によって何ら限定され
るものではない。 実施例 （１）ＣｕＡｌＯ2 薄膜の作製方法 ０．０１５モルの酢酸銅１水塩（Ｃｕ（ＣＨ3 ＣＯＯ）
2 Ｈ2 Ｏ）を０．２ｌのエタノール及び０．６モルの２
−メトキシエタノールに溶解した後、１．０モル／ｌの
Ａｌ−ｔｒｉ−ｓｅｃ−ｂｕｔｏｘｉｄｅ溶液１５〜２
２．５ｍｌを加えて出発溶液を作製した。次に、この溶
液を１．５時間還流した後、約１．５時間蒸留して金属
イオン濃度（Ｃｕ2+＋Ａｌ3+）が０．８Ｍ／Ｌの前駆体
溶液を調製した。更に、この溶液をシリカガラス基板上
にディップコーティング（８ｃｍ／ｍｉｎ）した後、大
気中４００℃で１０分間乾燥した。この操作を１０回繰
り返した後、窒素気流中において７００〜９００℃で１
時間焼成を行ってＣｕＡｌＯ2 を主成分とする薄膜を作
製した。Next, the present invention will be specifically described based on examples, but the present invention is not limited to the examples. EXAMPLES (1) Method for producing CuAlO 2 thin film 0.015 mol of copper acetate monohydrate (Cu (CH 3 COO))
2 H 2 O) in 0.2 l of ethanol and 0.6 mol of 2
After dissolving in methoxyethanol, a 1.0 mol / l Al-tri-sec-butoxide solution 15 to 2
2.5 ml was added to make a starting solution. Next, the solution was refluxed for 1.5 hours, and then distilled for about 1.5 hours to prepare a precursor solution having a metal ion concentration (Cu 2+ + Al 3+ ) of 0.8 M / L. Further, this solution was dip-coated (8 cm / min) on a silica glass substrate, and then dried at 400 ° C. in the atmosphere for 10 minutes. After repeating this operation 10 times, the temperature is reduced to 1 to 700-900 ° C. in a nitrogen stream.
By firing for a time, a thin film containing CuAlO 2 as a main component was prepared.
【００１１】（２）ＣｕＡｌＯ2 薄膜の特性 各温度で焼成した試料（膜厚約１ミクロン）の構成結晶
相（粉末Ｘ線回折法）及び抵抗率（４探針法）を表１に
示す。Ａｌ／Ｃｕ原子比が１．０に近いほど抵抗率が低
下した。また、７００℃以下ではＣｕＡｌＯ2 の生成量
が少なく、膜は高い導電性を示さなかった。また、９０
０℃以上では、粒子の粗大化に伴う気孔の増大により、
僅かに抵抗率が増大した。更に、図１に示すように同薄
膜は高い透過率を示した（Ａｌ／Ｃｕ比＝１．０）。焼
成温度の上昇に伴って透過率が低下しているのは、シリ
カガラスの結晶化による基板ガラスの白濁による。従っ
て、抵抗率に影響がでない程度に低温で、好ましくは、
８００℃前後で焼成することが望ましい。(2) Characteristics of CuAlO 2 thin film Table 1 shows the constituent crystal phases (powder X-ray diffraction method) and resistivity (four-point probe method) of the sample (thickness: about 1 μm) fired at each temperature. The resistivity decreased as the Al / Cu atomic ratio was closer to 1.0. At 700 ° C. or lower, the amount of generated CuAlO 2 was small, and the film did not show high conductivity. Also, 90
At 0 ° C. or higher, pores increase due to coarsening of particles,
The resistivity increased slightly. Further, as shown in FIG. 1, the thin film showed high transmittance (Al / Cu ratio = 1.0). The decrease in the transmittance with the increase in the firing temperature is due to the cloudiness of the substrate glass due to the crystallization of the silica glass. Therefore, at a temperature as low as not affecting the resistivity, preferably,
It is desirable to fire at around 800 ° C.
【００１２】[0012]
【表１】 [Table 1]
【００１３】[0013]
【発明の効果】以上詳述したように、本発明は、透明
（ワイドバンドギャップ）でｐ型導電性を示すＣｕＡｌ
Ｏ2 薄膜をケミカルプロセスにより作製する方法に係る
ものであり、本発明により、１）これまで困難であった
ケミカルプロセスによるＣｕＡｌＯ2 薄膜の作製方法を
実現できる、２）本発明により作製されるＣｕＡｌＯ2
薄膜は、ｐ型の酸化物導電体として高い導電性を示す、
３）従って、本発明により、透明でｐ型導電性を示すＣ
ｕＡｌＯ2 薄膜をより低コストで提供することが可能と
なる、４）Ａｌ／Ｃｕ比の調整、あるいは導電率を高め
る目的で添加されるドーパント元素（例えば、Ａｌサイ
トを置換するＢｅ、Ｍｇ、Ｃａ等）を前駆体溶液中に目
的の濃度に合わせて溶かし込むことにより、目的の化学
組成を持った均質な薄膜を比較的容易に作製することが
可能となる、という格別の効果が得られる。As described in detail above, the present invention provides a transparent (wide band gap) CuAl which exhibits p-type conductivity.
The present invention relates to a method of producing an O 2 thin film by a chemical process. According to the present invention, 1) a method of producing a CuAlO 2 thin film by a chemical process, which has been difficult until now, can be realized. 2) CuAlO produced by the present invention. Two
The thin film shows high conductivity as a p-type oxide conductor,
3) Therefore, according to the present invention, C is transparent and exhibits p-type conductivity.
It is possible to provide a uAlO 2 thin film at lower cost. 4) A dopant element added for the purpose of adjusting the Al / Cu ratio or increasing the conductivity (for example, Be, Mg, Ca for replacing the Al site) ) Is dissolved in the precursor solution in accordance with the desired concentration, whereby a uniform thin film having the desired chemical composition can be relatively easily produced, thereby obtaining a special effect.
【図１】各温度で焼成した試料の波長と透過率の関係を
示す。FIG. 1 shows the relationship between the wavelength and the transmittance of a sample fired at each temperature.
Claims (5)
コール類に溶解した後、銅に対して０．８〜１．５倍モ
ルのアルミニウムを含むアルミニウムアルコキシド溶液
を加えて出発溶液を作製し、次に、この溶液を還流した
後、蒸留して金属イオン濃度（Ｃｕ2+＋Ａｌ3+）が０．
５〜１．５Ｍ／Ｌの前駆体溶液を作製し、更に、この溶
液をディップコーティングあるいはスピンコーティング
して基板上に堆積させ、乾燥する操作をした後、窒素又
はアルゴン雰囲気で焼成を行ってＣｕＡｌＯ2 を主成分
とする薄膜を作製することを特徴とするＣｕＡｌＯ2 薄
膜の製造方法。1. A starting solution is prepared by dissolving copper acetate (monohydrate or anhydrous) in alcohols and then adding an aluminum alkoxide solution containing 0.8 to 1.5 times mol of aluminum to copper. Then, the solution was refluxed and distilled to obtain a metal ion concentration (Cu 2+ + Al 3+ ) of 0.1.
After preparing a precursor solution of 5 to 1.5 M / L, dip-coating or spin-coating this solution to deposit it on a substrate, and drying it, calcination is performed in a nitrogen or argon atmosphere to obtain CuAlO. 2. A method for producing a CuAlO 2 thin film, comprising producing a thin film containing 2 as a main component.
ール及び２−メトキシエタノールに溶解する請求項１記
載の方法。2. The method according to claim 1, wherein copper acetate (monohydrate or anhydrous) is dissolved in ethanol and 2-methoxyethanol.
当な厚みを持った膜を積層した後、焼成する請求項１記
載の方法。3. The method according to claim 1, wherein the steps of depositing and drying are repeated to form a film having an appropriate thickness, and then firing.
ンコーティングして基板上に堆積する請求項１記載の方
法。4. The method according to claim 1, wherein the solution is dip-coated or spin-coated to deposit on the substrate.
載の方法。5. The method according to claim 1, wherein the calcination is performed at 700 to 900 ° C.
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|---|---|---|---|
| JP2000301840A JP3527944B2 (en) | 2000-10-02 | 2000-10-02 | Method for producing CuAlO2 thin film by chemical process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000301840A JP3527944B2 (en) | 2000-10-02 | 2000-10-02 | Method for producing CuAlO2 thin film by chemical process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002114515A true JP2002114515A (en) | 2002-04-16 |
| JP3527944B2 JP3527944B2 (en) | 2004-05-17 |
Family
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|---|---|---|---|
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| Country | Link |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003324206A (en) * | 2002-04-30 | 2003-11-14 | National Institute Of Advanced Industrial & Technology | Photovoltaic cell for converting ultraviolet radiation to electric power, and method of manufacturing the same |
| JP2004311845A (en) * | 2003-04-09 | 2004-11-04 | National Institute Of Advanced Industrial & Technology | Visible-ray transmitting structure having power generating function |
| WO2004106593A3 (en) * | 2003-05-21 | 2005-02-17 | Hahn Meitner Inst Berlin Gmbh | METHOD FOR PRODUCING TRANSPARENT P-CONDUCTIVE CuAlO2 |
| CN100494064C (en) * | 2006-07-19 | 2009-06-03 | 中国科学院合肥物质科学研究院 | Method of manufacturing alumine acid cuprous polycrystalline material with delafossite structure and manufacturing material thereof |
| KR101316237B1 (en) * | 2011-12-06 | 2013-10-08 | 연세대학교 산학협력단 | Manufacturing Method of Solution-processed semiconductor buffer layer And solar cells using it |
-
2000
- 2000-10-02 JP JP2000301840A patent/JP3527944B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003324206A (en) * | 2002-04-30 | 2003-11-14 | National Institute Of Advanced Industrial & Technology | Photovoltaic cell for converting ultraviolet radiation to electric power, and method of manufacturing the same |
| JP2004311845A (en) * | 2003-04-09 | 2004-11-04 | National Institute Of Advanced Industrial & Technology | Visible-ray transmitting structure having power generating function |
| WO2004106593A3 (en) * | 2003-05-21 | 2005-02-17 | Hahn Meitner Inst Berlin Gmbh | METHOD FOR PRODUCING TRANSPARENT P-CONDUCTIVE CuAlO2 |
| CN100494064C (en) * | 2006-07-19 | 2009-06-03 | 中国科学院合肥物质科学研究院 | Method of manufacturing alumine acid cuprous polycrystalline material with delafossite structure and manufacturing material thereof |
| KR101316237B1 (en) * | 2011-12-06 | 2013-10-08 | 연세대학교 산학협력단 | Manufacturing Method of Solution-processed semiconductor buffer layer And solar cells using it |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3527944B2 (en) | 2004-05-17 |
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