JP3527944B2 - Method for producing CuAlO2 thin film by chemical process - Google Patents
Method for producing CuAlO2 thin film by chemical processInfo
- Publication number
- JP3527944B2 JP3527944B2 JP2000301840A JP2000301840A JP3527944B2 JP 3527944 B2 JP3527944 B2 JP 3527944B2 JP 2000301840 A JP2000301840 A JP 2000301840A JP 2000301840 A JP2000301840 A JP 2000301840A JP 3527944 B2 JP3527944 B2 JP 3527944B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- solution
- coated
- copper acetate
- producing
- 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 - Lifetime
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Classifications
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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
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 1. Field of the Invention The present invention relates to a method for producing a thin film containing CuAlO 2 as a main component, and more specifically to a CuAlO 2 thin film which is transparent (wide band gap) and exhibits p-type conductivity. The present invention relates to a manufacturing method by 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, n-type transparent conductive thin films such as ITO are used as transparent electrodes for flat panel displays and solar cells. On the other hand, p-type transparent conductive thin films are 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 the appearance of new optoelectronic devices such as transparent transistors 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。Thin film formation by a chemical process represented by the sol-gel method is lower in cost and superior in composition homogeneity than thin film formation by a dry process in a vacuum container. Up to now, there has been an example in which a CuAlO 2 thin film showing a p-type high conductivity is prepared by a laser ablation method (Kawazoe 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 these circumstances, the present inventors, in view of the above-mentioned prior art, established a method for producing a CuAlO 2 thin film by a chemical process with high yield and low cost. As a result of earnest research, a precursor solution was prepared using a starting solution prepared by adding an aluminum alkoxide solution to a solution of copper acetate monohydrate or an anhydrous specific alcohol, and this was prepared on a substrate. The inventors have found that the intended purpose can be achieved by coating and firing, and have completed the present invention.
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 until now. Another object of the present invention is to provide a method for efficiently producing a transparent (wide bandgap) CuAlO 2 thin film exhibiting p-type conductivity by a chemical process at a high yield and a low cost. 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水塩あるいは無水酢酸銅をアルコール類
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Ｃｕ 2+ とＡｌ 3+ とからの合計金属イオン濃度が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。
（２）酢酸銅１水塩あるいは無水酢酸銅をエタノール及
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。The present invention for solving the above-mentioned problems is constituted by the following technical means. (1) After the copper acetate monohydrate or anhydrous copper acetate was dissolved in an alcohol, adding aluminum alkoxide solution containing 0.8 to 1.5 moles of aluminum to prepare a starting solution to copper, the following The solution was refluxed and then distilled to obtain a total metal ion concentration of Cu 2+ and Al 3+ of 0.
A precursor solution of 5 to 1.5 M / L is prepared, and further, this solution is dip-coated or spin-coated to be deposited on a substrate and dried, and then baked in a nitrogen or argon atmosphere to form CuAlO. A method for producing a CuAlO 2 thin film, which comprises producing a thin film containing 2 as a main component. (2) the dissolving of copper acetate monohydrate or anhydrous copper acetate in ethanol and 2-methoxyethanol (1) The method according. (3) The method according to (1) above, wherein the steps of depositing and drying are repeated to stack films having an appropriate thickness, and then firing. (4) The method according to (1) above, wherein the solution is dip-coated or spin-coated and deposited on the substrate. (5) The method according to (1) above, which comprises firing at 700 to 900 ° C.
【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。BEST MODE FOR CARRYING OUT THE INVENTION 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 a wide band gap and p-type conductivity by a chemical process. The method for producing a thin film according to the present invention is carried out by dissolving copper acetate (monohydrate or anhydrous) in alcohols, preferably ethanol and 2-methoxyethanol, and then 0.8 to 1.5 times that of copper. An aluminum alkoxide solution containing moles of aluminum is added to make a starting solution. Then, after refluxing this solution,
Distilled to give metal ion concentration (Cu 2+ + Al 3+ ) of 0.5-
After forming a precursor solution of 1.5 M / L, further dip-coating or spin-coating this solution to deposit it on the substrate, and then drying, repeating the operation of laminating a film having an appropriate thickness, Firing is performed in a nitrogen or argon atmosphere to form 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 the starting material for the copper component. This is dissolved in alcohols, preferably ethanol and 2-methoxyethanol, and in this case, the concentration of ethanol is preferably 0.05 to 0.2 M / L, and more preferably to copper acetate. 10- to 30-fold equivalent of 2-methoxyethanol is added. Next, to this solution, an aluminum alkoxide containing 0.5 to 1.5 times, and preferably an equimolar amount of aluminum with respect to copper, for example, aluminum butoxide, aluminum isopropoxide solution is added, and a starting solution To prepare.
【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, this solution was stirred and refluxed at about 80 ° C. for 1 to 3 hours, and then the metal ion concentration (Cu 2+ + A
l 3+ ) is 0.5 to 1.5 M / L, preferably 0.8 M / L
A precursor solution is prepared by distilling until L or more. In this case, if necessary, for the purpose of adjusting the Al / Cu ratio or increasing the conductivity, a dopant element (for example, Be, Mg, Ca, etc. substituting the Al site) is dissolved in the precursor solution according to the desired concentration. Can be crowded. The solution is then coated on the 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 substrate is not limited to these, and any substrate that can withstand a temperature of about 800 ° C. can be similarly used, and the type of substrate is not particularly limited. Not a thing. As the coating method, dip coating, spin coating and the like are preferably exemplified. Above coating-
A drying operation is performed once or more, and if necessary, an appropriate number of times is repeated to deposit a film having an appropriate thickness, followed by firing in an inert atmosphere such as nitrogen or argon. The firing conditions are preferably 700 to 900 ° C. C below 700 ° C
Since the amount of uAlO 2 produced is small, it does not exhibit high conductivity, and at 900 ° C. or higher, there is a risk of devitrification of the transparent substrate or reaction between the substrate and the film, so firing at around 800 ° C. is more preferable. .
【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 showing resistivity of 0 Ω · cm or less and 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 the thin film production by the dry process, and
The yield is close to 100%, which is a very low-cost process. (3) Dissolving a dopant element added for the purpose of adjusting the Al / Cu ratio or increasing the conductivity (for example, Be, Mg, Ca, etc. substituting the Al site) in the precursor solution according to the desired concentration. By incorporating it, it is possible to relatively easily prepare a homogeneous thin film having a desired chemical composition.
【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。EXAMPLES Next, the present invention will be specifically described based on examples, but the present invention is not limited to the examples. Example (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, 1.0 mol / l Al-tri-sec-butoxide solution 15-2
2.5 ml was added to make a starting solution. Next, this 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. for 10 minutes in the atmosphere. After repeating this operation 10 times, in a nitrogen stream at 700 to 900 ° C.
Firing was performed for a time to form a thin film containing CuAlO 2 as a main component.
【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 the resistivity (4-probe method) of the sample (film thickness: about 1 micron) baked at each temperature. The resistivity decreased as the Al / Cu atomic ratio approached 1.0. At 700 ° C. or lower, the amount of CuAlO 2 produced was small, and the film did not exhibit high conductivity. Also, 90
At 0 ° C or higher, pores increase with the 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 silica glass. Therefore, at a low temperature that does not affect the resistivity, preferably,
It is desirable to bake 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 above in detail, according to the present invention, CuAl which is transparent (wide band gap) and exhibits p-type conductivity is used.
The present invention relates to a method for producing an O 2 thin film by a chemical process, and according to the present invention, 1) a method for producing a CuAlO 2 thin film by a chemical process, which has been difficult so far, can be realized, and 2) a CuAlO produced by the present invention. 2
The thin film exhibits high conductivity as a p-type oxide conductor,
3) Therefore, according to the present invention, C which is transparent and exhibits p-type conductivity
It is possible to provide a uAlO 2 thin film at a lower cost, 4) a dopant element added for the purpose of adjusting the Al / Cu ratio or increasing the conductivity (eg, Be, Mg, Ca replacing Al sites). And the like) are dissolved in the precursor solution according to the desired concentration, and it is possible to relatively easily prepare a homogeneous thin film having a desired chemical composition, which is a particular 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.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C01G 1/00 - 7/00 H01B 13/00 503 H01L 21/205 H01L 31/04 ＣＡ（ＳＴＮ)─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields investigated (Int.Cl. 7 , DB name) C01G 1/00-7/00 H01B 13/00 503 H01L 21/205 H01L 31/04 CA (STN)
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Ｃｕ 2+ とＡｌ 3+ とからの合計金属イオン濃
度が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ＣｕＡｌＯ
2 を主成分とする薄膜を作製することを特徴とするＣｕ
ＡｌＯ2薄膜の製造方法。The method according to claim 1] copper acetate monohydrate or anhydrous copper acetate was dissolved in an alcohol, aluminum alkoxide solution was added to prepare a starting solution containing 0.8 to 1.5 moles of aluminum to copper Next, after refluxing this solution, it was distilled to prepare a precursor solution having a total metal ion concentration of 0.5 to 1.5 M / L from Cu 2+ and Al 3+, and further preparing this solution. Is dip-coated or spin-coated to be deposited on the substrate, dried, and then baked in a nitrogen or argon atmosphere to form CuAlO.
Cu characterized by producing a thin film containing 2 as a main component
Method for manufacturing AlO 2 thin film.
ノール及び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. A copper acetate monohydrate or anhydrous copper acetate is dissolved in ethanol and 2-methoxyethanol.
The method described.
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 and deposited on the substrate.
載の方法。5. The method according to claim 1, which is fired at 700 to 900 ° C.
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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 |
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| 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 |
| DE10323625B3 (en) * | 2003-05-21 | 2005-01-05 | Hahn-Meitner-Institut Berlin Gmbh | Process for the preparation of transparent p-type CuAIO2 and its use |
| 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 |
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