JPH08330614A - Thin film solar cell and manufacture thereof - Google Patents

Thin film solar cell and manufacture thereof

Info

Publication number
JPH08330614A
JPH08330614A JP15276295A JP15276295A JPH08330614A JP H08330614 A JPH08330614 A JP H08330614A JP 15276295 A JP15276295 A JP 15276295A JP 15276295 A JP15276295 A JP 15276295A JP H08330614 A JPH08330614 A JP H08330614A
Authority
JP
Grant status
Application
Patent type
Prior art keywords
thin film
semiconductor thin
compound semiconductor
zinc
sulfur
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.)
Granted
Application number
JP15276295A
Other languages
Japanese (ja)
Other versions
JP3249342B2 (en )
Inventor
Tetsuo Arai
Katsumi Kushiya
哲郎 新居
勝巳 櫛屋
Original Assignee
Showa Shell Sekiyu Kk
昭和シェル石油株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date

Links

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/54Material technologies
    • Y02E10/541CuInSe2 material PV cells

Abstract

PURPOSE: To obtain a thin film solar cell having high conversion efficiency, without using harmful materials.
CONSTITUTION: A thin film solar cell 1 has a structure comprising a metal back electrode 3, first p-type multi-element compd. semiconductor thin film 4 forming a photoabsorptive layer on the electrode layer 3, second n-type transparent and conductive metal oxide semiconductor thin film 6 forming a window layer, and third transparent high-resistance S-contained Zn mixed crystal compd. semiconductor thin film 5 laid at the interface between the films 4 and 5. The first semiconductor thin film 4 is grown on the layer 3, third semiconductor thin film 5 is chemically grown from a soln. on the film 4, and second semiconductor thin film 6 is grown on the film 5 to produce the cell 1.
COPYRIGHT: (C)1996,JPO

Description

【発明の詳細な説明】 DETAILED DESCRIPTION OF THE INVENTION

【0001】 [0001]

【産業上の利用分野】本発明は、多元化合物半導体薄膜を光吸収層として使用したヘテロ接合薄膜太陽電池、特に光吸収層としてCu-III-VI 2族カルコパイライト半導体、例えば二セレン化銅インジウム (CIS)、ニセレン化銅インジウム・ガリウム(CIGS)あるいはニセレン・イオウ化銅インジウム・ガリウム (CIGSS)のようなp形半導体の光吸収層とpnヘテロ接合を有する薄膜太陽電池を製造する方法に関する。 The present invention relates to a heterojunction thin-film solar cell using multinary compound semiconductor thin film as a light absorbing layer, in particular Cu-III-VI 2 Group chalcopyrite semiconductor as a light absorbing layer, for example, copper indium diselenide (CIS), a method for producing a thin-film solar cell having a p-type semiconductor of the light absorbing layer and the pn heterojunction as Niseren copper indium gallium (CIGS) or Niseren-sulfur copper indium gallium (CIGSS).

【0002】 [0002]

【従来の技術】前記タイプの薄膜太陽電池は広範囲に実用化可能であるとみなされ、米国特許第 4335226号明細書(Michelsen 他による、1982年6月15日発行)に記載され、かつ高い変換効率の薄膜太陽電池を提供するために CISからなる光吸収層上に硫化カドミウム (CdS)層を成長することを開示している。 Thin-film solar cell of the prior art, wherein the type is considered to be widely commercialized possible (by Michelsen et issued Jun. 15, 1982) U.S. Pat. No. 4,335,226 is described in, and high conversion the light-absorbing layer made of CIS to provide a thin film solar cell efficiency discloses the growth of cadmium sulfide (CdS) layer.

【0003】このような高い変換効率の薄膜太陽電池を開発することを目的とした多くの刊行分献の中でも、米国特許第 4611091号明細書(Choudray 他による、1986 [0003] Among the many publications fraction Document aimed at developing thin-film solar cell having such a high conversion efficiency, according to U.S. Patent No. 4,611,091 Pat (Choudray other, 1986
年9月9日発行)及び米国特許第 5045409号明細書(Eb September 9 year issue) and US Pat. No. 5045409 (Eb
erspacher 他による、1991年9月3日発行)は重要である。 By erspacher other, issued Sep. 3, 1991) it is important.

【0004】米国特許第 5045409号明細書は CISの薄膜光吸収層のセレン化の改良方法を、また、米国特許第 4 [0004] U.S. Pat. No. 5,045,409 is an improved method of selenization of the CIS thin film light absorbing layer, also U.S. Patent No. 4
611091号明細書は、CIS 薄膜光吸収層上に溶液から化学的に成長したCdS 薄膜上に、有機金属化学的気相成長法 611091 Pat are chemically grown on CdS thin film from solution CIS thin-film light absorbing layer, a metal organic chemical vapor deposition
(MOCVD法) により作製した酸化亜鉛のような、透明で導電性を有する広い禁制帯幅のn形半導体薄膜を成長させることにより CdS層の厚さを大幅に減少させる製造方法を開示している。 Discloses a method to significantly reduce the thickness of the CdS layer by such as zinc oxide prepared, growing a n-type semiconductor thin film of a wide band gap having a transparent conductive by (MOCVD method) .

【0005】前記2つの特許明細書は、大面積薄膜太陽電池モジュールの製造方法において極めて重要と理解されているセレン化水素及びCdS等のような毒性の高い構成材料の使用量を最小限に抑えるかまたは排除するために有用な製造方法を開示している。 [0005] The two patents, to minimize the use of highly toxic constituent material, such as hydrogen selenide and CdS are understood to be very important in the manufacturing method of large-area thin-film solar cell module disclosing the manufacturing method for or eliminated.

【0006】米国特許第4611091 号明細書に記載された溶液から化学的にCdS薄膜を成長する作製方法はそれ以外の作製方法によるCdSよりもCIS薄膜光吸収層と高品質なヘテロ接合を形成し、かつシャント抵抗を高める効果を有するが、このような改良点はCIS薄膜光吸収層の溶液中への侵漬により形成されるヘテロ接合界面、特に薄膜光吸収層表面のエッチングあるいは選択的なクリーニング効果も含まれるとみなしている。 [0006] forming a by solution chemical manufacturing method of growing a CdS thin film quality heterojunction CIS thin-film light absorbing layer than CdS by other manufacturing method of the described in U.S. Patent No. 4,611,091 Pat and it has the effect of increasing the shunt resistor, etching or selective cleaning of such improvements heterojunction interface formed by the immersed into a solution of CIS thin-film light absorbing layer, especially thin light absorbing layer surface is regarded as the effect is also included.

【0007】 [0007]

【発明が解決しようとする課題】ここ数年来、薄膜太陽電池からカドミウムのような毒性のある材料を原則的に排除しようとする試みが積極的に提案され実施されている。 THE INVENTION Problems to be Solved] In recent years, an attempt to from a thin film solar cell trying to eliminate material that is toxic, such as cadmium principle is implemented been proposed actively. しかしながら、カドミウム等の毒性のある材料を含まないことと高品質なヘテロ接合を形成することで高い変換効率の薄膜太陽電池を作製する試みは成功していなかった。 However, attempts to produce a thin-film solar cell that is high conversion efficiency to form high-quality heterojunction and it does not contain material that is toxic cadmium was not successful. 例えば、水酸化アンモニウムに酢酸亜鉛を溶解した溶液から成長した亜鉛化合物層は製膜後の大気中でのアニールを実施しても水酸化亜鉛を30モル%程度まで多量に含んだ酸化亜鉛薄膜であり、CdS と同程度の良好な薄膜層は得られなかった。 For example, a zinc compound layer grown from a solution of zinc acetate ammonium hydroxide in large amounts inclusive zinc oxide thin film of zinc hydroxide be carried out annealing in air after film up to about 30 mole% There, good film layers comparable to CdS was not obtained. 本発明の課題は、前記構造を有するがカドミウムを含まない高い変換効率のヘテロ接合を有する薄膜太陽電池およびその製造方法を提供することである。 An object of the present invention has the structure to provide a thin film solar cell and a manufacturing method thereof heterojunction high conversion efficiency which does not contain cadmium.

【0008】本発明のもう一つの課題は、大容量で経済性に優れ、良好な再現性で大量生産に適用可能で、かつ使用化学薬品の濃度や必要量が少ない、前記薄膜太陽電池およびその製造方法を提供することである。 [0008] Another object of the present invention is excellent in economical efficiency in mass, applicable to mass production with good reproducibility, and the concentration and the required amount of used chemicals is small, the thin film solar cell and its it is to provide a manufacturing method.

【0009】本発明のもう一つの課題は、高い開放電圧 [0009] Another object of the present invention, high open-circuit voltage
(V OC ) を有する薄膜太陽電池を提供することである。 It is to provide a thin film solar cell having a (V OC).

【0010】 [0010]

【課題を解決するための手段】上記の課題は、本発明における、金属裏面電極層と、当該裏面電極層上のp形の導電形を有し、かつ光吸収層として供される第1の多元化合物半導体薄膜、特にCu−III −VI 2族カルコパイライト構造の半導体薄膜と、前記第1の多元化合物半導体薄膜上の第1の導電形と反対の導電形を有し窓層として供される第2の禁制帯幅が広くかつ透明で導電性を有する金属酸化物半導体薄膜と、前記第1の多元化合物半導体薄膜と第2の金属酸化物半導体薄膜との間の界面に、 SUMMARY OF THE INVENTION The above problem is, in the present invention, a metallic back electrode layer has a conductivity type of p-type on the back electrode layer, and first to serve as a light absorbing layer multinary compound semiconductor thin film, in particular provided as a window layer comprises a semiconductor thin film, the opposite conductivity type as the first conductivity type of said first multi-compound on the semiconductor thin film of Cu-III -VI 2 chalcopyrite structure a semiconductor thin film metal oxide having a second band gap is wide, transparent conductive, the interface between the first multinary compound semiconductor thin film and a second metal oxide semiconductor thin film,
溶液から化学的に成長した透明で高抵抗を有するイオウ含有亜鉛混晶化合物半導体薄膜からなることを特徴とする薄膜太陽電池により、解決できる。 The thin-film solar cell, comprising the chemical and grown transparent sulfur-containing zinc mixed crystal compound semiconductor thin film having a high resistance from the solution, can be solved.

【0011】より詳細には、前記薄膜太陽電池は、窓層として供される第2の半導体薄膜が酸化亜鉛からなり、 [0011] More specifically, the thin film solar cell, the second semiconductor thin film to be provided as a window layer is made of zinc oxide,
p形の導電形を有し、かつ光吸収層として供される第1 It has a conductivity type of p-type, and first to serve as a light absorbing layer
の多元化合物半導体薄膜が、CIS 、CIGSあるいはCIGSS Multinary compound semiconductor thin film, CIS, CIGS or CIGSS
カルコパイライト構造の半導体薄膜からなり、かつ溶液から化学的に成長した透明で高抵抗なイオウ含有亜鉛混晶化合物半導体薄膜を前記第1と第2の半導体薄膜の界面に有する構造からなる。 It consists semiconductor thin film having a chalcopyrite structure, and consists chemically grown transparent high resistance sulfur-containing zinc mixed crystal compound semiconductor thin film said first structure having the interface of the second semiconductor thin film from solution.

【0012】より詳細には、前記薄膜太陽電池は、光吸収層として供される第1の半導体薄膜と窓層として供される第2の半導体薄膜の界面に、溶液から化学的に成長される透明で高抵抗なイオウ含有亜鉛混晶化合物半導体薄膜が、硫酸亜鉛、塩化亜鉛及び酢酸亜鉛、有利には酢酸亜鉛を適当な錯形成剤、例えば水酸化アンモニウムに溶解して作製した溶液中で亜鉛アンモニウム錯塩を形成させ、その溶液中にイオウ含有塩、例えば、チオリア、 [0012] More specifically, the thin film solar cell, the interface of the second semiconductor thin film serves as a first semiconductor thin film and the window layer to serve as a light absorbing layer, it is chemically grown from the solution high resistance sulfur-containing zinc mixed crystal compound semiconductor thin film is transparent, zinc sulfate, zinc chloride and zinc acetate, preferably in a suitable complexing agent zinc acetate, for example, zinc in a solution prepared by dissolving ammonium hydroxide to form an ammonium complex salt, a sulfur-containing salt in the solution, for example, Chioria,
チオアセトアミド、トリエタノールアミン、チオウレタン、トリエチルアミン及びチオセミカルバジド、有利にはチオリアを溶解し、光吸収層として供される第1の半導体薄膜を前記溶液と接触させて、第1の半導体薄膜上に当該溶液からイオウ含有亜鉛混晶化合物半導体薄膜を成長させ、かつ成長したイオウ含有亜鉛混晶化合物半導体薄膜を大気中で数分〜数十分間アニールすることで乾燥し、かつ膜中の水酸化亜鉛を酸化亜鉛に転化すると同時にイオウによる第1の半導体薄膜表面の改質を促進する工程により作製されたイオウ含有亜鉛混晶化合物半導体薄膜を有する構造からなる。 Thioacetamide, triethanolamine, thiourethane, triethylamine and thiosemicarbazide advantageously dissolve the Chioria and the first semiconductor thin film to serve as a light-absorbing layer in contact with said solution, the first semiconductor thin film the solution grown sulfur-containing zinc mixed crystal compound semiconductor thin film from, and sulfur-containing zinc mixed crystal compound semiconductor thin film grown dried by annealing several minutes to several tens minutes in the atmosphere, and hydroxide in the film zinc made from a structure having a sulfur-containing zinc mixed crystal compound semiconductor thin film made by the process of promoting the modification of the first semiconductor thin film surface due to sulfur and at the same time converted into zinc oxide. イオウ含有亜鉛混晶化合物半導体薄膜はアニール工程の前に、窒素ガスを表面に吹き付けることで乾燥させることができる。 Sulfur-containing zinc mixed crystal compound semiconductor thin film before the annealing step, the nitrogen gas can be dried by blowing on the surface.

【0013】より詳細には、前記イオウ含有亜鉛混晶化合物半導体薄膜の作製に有利な溶液は、2.5 M水酸化アンモニウム中に溶解した0.025 M亜鉛塩及び0.375 Mチオリアからなる。 [0013] More particularly, advantageous solution for the production of the sulfur-containing zinc mixed crystal compound semiconductor thin film is comprised of 0.025 M zinc salt and 0.375 M Chioria was dissolved in 2.5 M ammonium hydroxide. 亜鉛塩が、有利には酢酸亜鉛である。 Zinc salts, preferably zinc acetate.
有利な溶液温度は80℃であり、浸漬時間は3分間及びアニール温度は設定温度で200 ℃であり、アニール時間は Advantageous solution temperature was 80 ° C., soaking time is 200 ° C. for 3 minutes and the annealing temperature is the set temperature, annealing time
15分間である。 Is 15 minutes. 50%までの酢酸亜鉛またはチオリア濃度の低下は、イオウ含有亜鉛混晶化合物半導体薄膜作製に許容される浸漬時間内であるが、再現性が幾分か劣り、 Reduction of zinc acetate or Chioria concentration of up to 50 percent, but is within the immersion time allowed for the sulfur-containing zinc mixed crystal compound semiconductor thin film produced, reproducibility is inferior somewhat,
かつ生産性からは短時間の方が望ましい。 And from productivity is desirable direction of a short period of time. 2 Mまでのチオリア濃度の増加も許容されるが、より低い濃度、有利には0.35M〜1.1 Mの範囲では同程度の変換効率が得られるが、より低い濃度の方が化学薬品使用量の削減から好ましい。 Although an increase in Chioria concentrations up 2 M acceptable lower concentrations, preferably conversion efficiency comparable to obtain a range of 0.35M~1.1 M, but lower concentrations it is chemical usage preferable from the reduction.

【0014】より詳細には、前記イオウ含有亜鉛混晶化合物半導体薄膜の作製に有利な浸漬時間は1〜5分間であり、この時間内で良好な変換効率を有する薄膜太陽電池が得られる。 [0014] More particularly, the sulfur-containing zinc mixed crystal compound semiconductor thin film advantageous immersion time for the preparation of 1-5 minutes, thin-film solar cell with good conversion efficiency in this time is obtained. 特に、高い開放電圧(V OC )を有する薄膜太陽電池を作製するためには浸漬時間3分間が好ましい。 In particular, in order to produce a thin film solar cell having a high open voltage (V OC) preferably immersion time 3 minutes.

【0015】より詳細には、良好な変換効率を有する薄膜太陽電池を作製するためには、設定温度で150 〜250 [0015] More specifically, in order to produce a thin film solar cell with good conversion efficiency, 150-250 at a set temperature
℃の範囲のアニールが必要である。 Annealing range ℃ are required. 有利には設定温度で Advantageously at a set temperature
200℃であり、時間は15分間である。 Was 200 ° C., the time is 15 minutes.

【0016】より詳細には、光吸収層として供される第1の半導体薄膜と窓層として供される第2の半導体薄膜の界面に、溶液から化学的に成長される透明で高抵抗な半導体薄膜がZn、O 、S 及びOHから構成されることは、 [0016] More specifically, the interface of the second semiconductor thin film serves as a first semiconductor thin film and the window layer to serve as a light absorbing layer, transparent and highly resistive semiconductors are chemically grown from solution the thin film is Zn, O, is composed of S and OH is
X PS(X-ray PhotoelectronSpectroscopy、X 線による光電子分光法)により裏付けられた。 X PS (X-ray PhotoelectronSpectroscopy, photoelectron spectroscopy by X-ray) was confirmed by.

【0017】高抵抗のイオウ含有混晶化合物半導体は、 [0017] The sulfur-containing mixed crystal compound semiconductor of high resistance,
n形の導電形を有するSn(O,OH,S) x 、Cd(O,OH,S) x 、CdZ Sn having n-type conductivity type (O, OH, S) x , Cd (O, OH, S) x, CdZ
n(O,OH, S) X 、ZnSn(O,OH,S) x 、Zn(O,OH,S) x 、In(O, n (O, OH, S) X, ZnSn (O, OH, S) x, Zn (O, OH, S) x, In (O,
OH,S) x 、 Ga(O,OH,S) x 、InGa(O,OH,S) xを含むことができる。 OH, S) x, it may include Ga (O, OH, S) x, InGa (O, OH, S) x.

【0018】 [0018]

【作用】溶液から化学的に、透明で高抵抗なイオウ含有亜鉛混晶化合物半導体薄膜を、p形の導電形を有するCu [Action] solution from chemically, a high resistance sulfur-containing zinc mixed crystal compound semiconductor thin film is transparent, Cu having a conductivity type of p-type
−III −VI 2族カルコパイライト構造の光吸収層として供される半導体薄膜上に安定に成長することで高い変換効率の薄膜太陽電池が作製され、従来の硫化カドミウムをその構成材料として含むCu−III −VI 2族カルコパイライト構造の光吸収層を有する薄膜太陽電池のカドミウムの毒性という問題を解決し、かつ簡単な装置構成と安価な作製法で、安全性に問題のない大面積太陽電池モジュールの製造を可能にする。 -III -VI 2 Group chalcopyrite thin film solar cell can be high conversion efficiency stably grown on the semiconductor thin film to serve as a light absorbing layer of the light structure is fabricated, including the conventional cadmium sulfide as a constituent material Cu- solves the problem cadmium toxicity of the thin-film solar cell having a light absorbing layer of the III -VI 2 chalcopyrite structure, and simple in apparatus construction and inexpensive fabrication method, large-area solar cell module having no safety problems to allow for the production. また、溶液からの化学的成長であるが、カドミウムのような毒性のある材料を含んだ廃液が生成せず、結果的に廃液処理コストの削減から製造コストの引下げに寄与し、薄膜太陽電池自体のコスト引下げが可能となる。 Although chemically grown from solution, without generating waste liquid containing a material which is toxic, such as cadmium, eventually contributes to reduction of manufacturing cost reduction of liquid waste treatment cost, thin-film solar cell itself the possible cost reductions of.

【0019】 [0019]

【実施例】以下、本発明の実施例を図面に基づいて説明する。 BRIEF DESCRIPTION OF THE PREFERRED embodiment of the present invention with reference to the drawings.

【0020】図1に本発明の薄膜太陽電池の構造例を示す。 [0020] showing a structural example of a thin-film solar cell of the present invention in FIG. 薄膜太陽電池1は1〜3mm厚さを有するガラス基板2上に形成される。 Thin-film solar cell 1 is formed on the glass substrate 2 having a 1~3mm thickness. 裏面電極3は、前記ガラス基板2上に作製される1〜2ミクロンの厚さのモリブデンあるいはチタン等の金属である。 The back electrode 3 is a metal such as molybdenum or titanium having a thickness of 1 to 2 microns, which is fabricated on the glass substrate 2. 光吸収層として供される第1 The is subjected as a light absorbing layer 1
の半導体薄膜4は、p形の導電形を有するCu−III −VI Of the semiconductor thin film 4, Cu-III -VI having conductivity type p-type
2族カルコパイライト構造の厚さ1〜3ミクロンの薄膜、例えば、CIS 、CIGSあるいはCIGSS 等の多元化合物半導体薄膜である。 Thickness 1-3 micron film of 2 chalcopyrite structure, e.g., CIS, a multinary compound semiconductor thin film such as CIGS or CIGSS. この薄膜上に、以下に記載するような溶液から化学的に成長させた高抵抗のイオウ含有亜鉛混晶化合物半導体薄膜5が形成される。 This on the thin film, is chemically grown in the high resistance sulfur-containing zinc mixed crystal compound semiconductor thin film 5 from a solution as described is formed below. その上に、窓層として供されるn形の導電形を有する禁制帯幅が広くかつ透明で導電性を有する厚さ0.5 〜3ミクロンの酸化亜鉛からなる第2の金属酸化物半導体薄膜6が形成される。 Thereon, a second metal oxide semiconductor thin film 6 made of zinc oxide having a thickness of 0.5-3 microns band gap has a wide and transparent conductive having n-type conductivity type that is provided as a window layer It is formed. 更に、上部電極あるいはスクライブライン7が、n Further, the upper electrode or the scribe line 7, n
形酸化亜鉛からなる第2の金属酸化物半導体薄膜6の露出表面に作製される。 It is produced on the second exposed surface of the metal oxide semiconductor thin film 6 consisting of shape of zinc oxide.

【0021】本発明の薄膜太陽電池1は、光吸収層として供される第1の半導体薄膜4と窓層として供される第2の半導体薄膜6の界面に、酢酸亜鉛を液温80℃の水酸化アンモニウムに溶解して亜鉛アンモニウム錯塩を形成させ、その溶液中にイオウ含有塩であるチオリアを溶解し、光吸収層として供される第1の半導体薄膜4を前記溶液と3分間接触させて、第1の半導体薄膜4上に当該溶液からイオウ含有亜鉛混晶化合物半導体薄膜5を化学的に成長させ、かつ成長したイオウ含有亜鉛混晶化合物半導体薄膜5を大気中で設定温度200 ℃で15分間アニールすることで乾燥し、かつ膜中の水酸化亜鉛を酸化亜鉛に転化すると同時にイオウによる第1の半導体薄膜4 The thin-film solar cell 1 of the present invention, the interface of the second semiconductor thin film 6 which serves as a first semiconductor thin film 4 and the window layer to serve as a light absorbing layer, the zinc acetate solution temperature 80 ° C. to form a zinc ammonium complex salt was dissolved in ammonium hydroxide, it was dissolved Chioria a sulfur-containing salt in the solution, and the first semiconductor thin film 4 to serve as a light absorbing layer contacting the solution for 3 minutes , sulfur-containing zinc mixed crystal compound semiconductor thin film 5 from the solution on the first semiconductor thin film 4 chemically grown, and a sulfur-containing zinc mixed crystal compound semiconductor thin film 5 grown at a set temperature 200 ° C. in air 15 minutes and dried by annealing, and the by sulfur at the same time the zinc hydroxide in the film converted to zinc oxide first semiconductor thin film 4
表面の改質を促進する工程により作製されたイオウ含有亜鉛混晶化合物半導体薄膜5を有する構造からなることを特徴とする。 Characterized by comprising the structure with a sulfur-containing zinc mixed crystal compound semiconductor thin film 5 made by a process that promotes the modification of the surface.

【0022】図2に、チオリア濃度を変化させて作製したイオウ含有亜鉛混晶化合物半導体薄膜を有するCIS 薄膜太陽電池の開放電圧V OC及び曲線因子FFの変化特性を示す。 [0022] FIG. 2 shows the change characteristics of the open-circuit voltage V OC and fill factor FF of CIS thin-film solar cell having a sulfur-containing zinc mixed crystal compound semiconductor thin film prepared by changing the Chioria concentration. 図2に示す前記特性より、有利なチオリア濃度は、化学薬品使用量の削減から好ましい低い濃度である From the characteristics shown in FIG. 2, an advantageous Chioria concentration is the preferred low concentration of reducing chemical usage
0.3〜0.4 M、特に 0.375Mで高い開放電圧V OCを、0. 0.3~0.4 M, a high open-circuit voltage V OC, particularly in 0.375M, 0.
4 Mで高い曲線因子FFを夫々示した。 A high fill factor FF with 4 M shown respectively. この時の他の薬品濃度は、2.5 M水酸化アンモニウム、0.025 M酢酸亜鉛であった。 Other chemical concentration at this time, 2.5 M ammonium hydroxide, was 0.025 M zinc acetate.

【0023】図3に、イオウ含有亜鉛混晶化合物半導体薄膜を有する CIS薄膜太陽電池のアニール温度に対する曲線因子FFの変化特性を示す。 [0023] FIG. 3 shows a change characteristic of the fill factor FF for annealing temperatures of CIS thin-film solar cell having a sulfur-containing zinc mixed crystal compound semiconductor thin film. 図3に示す前記特性より、良好な変換効率を有する薄膜太陽電池を作製するためには、設定温度で 150〜250 ℃の範囲のアニール、有利には設定温度で 200℃が必要であることがわかる。 From the characteristics shown in FIG. 3, in order to produce a thin film solar cell with good conversion efficiency, the annealing in the range of 150 to 250 ° C. at a set temperature, it advantageously requires a 200 ° C. at a set temperature Recognize. アニール時間はいずれも15分間である。 Both annealing time is 15 minutes.

【0024】図4に、図1に示す本発明の界面層(バッファー層)がイオウ含有亜鉛混晶化合物半導体薄膜からなる CIS薄膜太陽電池の電圧V[V] の変化に対する電流密度J[mA/cm 2 ]の変化特性を、前記 CIS薄膜太陽電池と同様の構造で界面層(バッファー層)が薄膜CdS 層からなる CIS薄膜太陽電池のそれと比較して示す。 [0024] FIG. 4, the current density J [mA with respect to a change in the interface layer voltage of the CIS thin film solar cell (buffer layer) is made of sulfur-containing zinc mixed crystal compound semiconductor thin film V [V] of the present invention shown in FIG. 1 / the change characteristics of cm 2], in comparison with that of the CIS thin film solar cell interfacial layer in the same structure as the CIS thin film solar cell (buffer layer) is made of a thin-film CdS layer. なお、前記特性の測定条件および結果は、以下のとおりである。 The measurement conditions and the results of the properties are as follows.
有効発電面積 0.95 cm 2 、エアマスAM1.5 、照射強度100mW/cm 2で、Zn混晶化合物界面層(a) においては、開放電圧V OC =0.480[V]、短絡電流密度J SC =37.8 Effective power generation area of 0.95 cm 2, air mass AM 1.5, at an irradiation intensity of 100 mW / cm 2, in the Zn mixed crystal compound interfacial layer (a), the open circuit voltage V OC = 0.480 [V], a short circuit current density J SC = 37.8
[mA/cm 2 ]、曲線因子FF=0.67、変換効率E ff =12.1 [mA / cm 2], fill factor FF = 0.67, the conversion efficiency E ff = 12.1
[%] であり、CdS界面層(b) においては、開放電圧V A [%], in the CdS interface layer (b), the open circuit voltage V
OC =0.458[V]、短絡電流密度J SC =36.2[mA/cm 2 ]、曲線因子FF=0.68、変換効率E ff =11.26[%]である。 OC = 0.458 [V], a short circuit current density J SC = 36.2 [mA / cm 2], fill factor FF = 0.68, the conversion efficiency E ff = 11.26 [%]. 前記特性から明らかなように、イオウ含有亜鉛混晶化合物半導体薄膜を有するCIS薄膜太陽電池の方が高い開放電圧V OCを示している。 As apparent from the characteristics, towards the CIS thin film solar cell having a sulfur-containing zinc mixed crystal compound semiconductor thin film shows higher open circuit voltage V OC. その結果、イオウ含有亜鉛混晶化合物半導体薄膜を使用することでCdS と同程度あるいはそれ以上の性能を有する CIS薄膜太陽電池が作製できることが示された。 As a result, it was shown that CIS thin-film solar cells with CdS and equal to or higher performance by using a sulfur-containing zinc mixed crystal compound semiconductor thin film can be produced.

【0025】 [0025]

【発明の効果】以上の記載のように本発明によれば、従来からの硫化カドミウムをその構成材料として含むCu-I According to the present invention as described above, according to the present invention, Cu-I containing cadmium sulfide from the conventional as a constituent material
II-VI 2族カルコパイライト構造の光吸収層を有する薄膜太陽電池のカドミウムの毒性に関係した課題が解決でき、かつ安全性に問題のない大面積太陽電池モジュールの製造を可能にし、また、溶液からの化学的成長であるが、カドミウムのような毒性のある材料を含んだ廃液が生成せず、結果的に廃液処理コストの削減から製造コストの引き下げに寄与し、薄膜太陽電池自体のコスト引き下げが可能となる高抵抗なイオウ含有亜鉛混晶化合物半導体薄膜を有する、高い変換効率の薄膜太陽電池を作製することが可能である。 Problems related to the toxicity of cadmium thin film solar cell having a light absorbing layer of II-VI 2 Group chalcopyrite structure can be resolved, and enables the production of no problem large area solar cell module in safety, also, the solution is a chemical growing from, without generating waste liquid containing a material which is toxic, such as cadmium, eventually contributes to reduction of manufacturing cost reduction of the waste liquid treatment costs, the cost reduction of the thin-film solar cell itself having high resistance sulfur-containing zinc mixed crystal compound semiconductor thin film is possible, it is possible to produce a thin film solar cell having a high conversion efficiency.

【図面の簡単な説明】 BRIEF DESCRIPTION OF THE DRAWINGS

【図1】本発明の実施例の薄膜太陽電池の構造を示す断面図である。 1 is a cross-sectional view showing a structure of a thin film solar cell of the embodiment of the present invention.

【図2】イオウ含有亜鉛混晶化合物半導体薄膜を有する [Figure 2] a sulfur-containing zinc mixed crystal compound semiconductor thin film
CIS薄膜太陽電池のチオリヤ濃度の変化に対する開放電圧V OC及び曲線因子FFの変化の特性を示す図である。 Is a diagram showing characteristics of change of the open circuit voltage V OC and fill factor FF to changes in Chioriya concentration of CIS thin-film solar cell.

【図3】イオウ含有亜鉛混晶化合物半導体薄膜を有する Having 3] sulfur-containing zinc mixed crystal compound semiconductor thin film
CIS薄膜太陽電池特性の曲線因子FFに及ぼすアニールの効果を示す図である。 It shows the effect of annealing on the fill factor FF of CIS thin-film solar cell characteristics.

【図4】図1に図示の界面層がイオウ含有亜鉛混晶化合物半導体薄膜からなる CIS薄膜太陽電池の電流電圧特性を、前記 CIS薄膜太陽電池と同じ構造で界面層が薄膜Cd [4] the interface layer illustrated in FIG. 1 is a current-voltage characteristic of the CIS thin film solar cell comprising a sulfur-containing zinc mixed crystal compound semiconductor thin film, interfacial layer in the same structure as the CIS thin film solar cell is thin Cd
S 層からなる CIS薄膜太陽電池のそれと比較して示した図である。 It is a diagram showing, in comparison with that of the CIS thin film solar cell consisting of S layer.

【符号の説明】 DESCRIPTION OF SYMBOLS

1 薄膜太陽電池 2 基板(ガラス) 3 裏面電極(金属) 4 p形の第1の半導体薄膜(光吸収層) 5 イオウ含有亜鉛混晶化合物からなる第3の半導体薄膜(界面層) 6 n形の第2の半導体薄膜(窓層) 7 上部電極あるいはスクライブライン 1 thin-film solar cells 2 substrate (glass) 3 back electrode (metal) 4 first semiconductor thin film (light absorbing layer) of p-type 5 third semiconductor thin film made of sulfur-containing zinc mixed crystal compound (interfacial layer) 6 n-type a second semiconductor thin film (window layer) 7 upper electrode or scribe line

Claims (18)

    【特許請求の範囲】 [The claims]
  1. 【請求項1】 金属裏面電極層と、当該裏面電極層上に設けられp形またはn形の導電形を有する第1の多元化合物半導体薄膜と、前記第1の多元化合物半導体薄膜上の第1の導電形と反対の導電形を有し禁制帯幅が広くかつ透明で導電性を有する第2の金属酸化物半導体薄膜と、前記第1の多元化合物半導体薄膜と第2の金属酸化物半導体薄膜の間の界面に設けられ透明で高抵抗を有する混晶化合物半導体薄膜を有する構造からなることを特徴とする薄膜太陽電池。 1. A metal back electrode layer, a first first and multinary compound semiconductor thin film, said first multinary compound on the semiconductor thin film having a p-type or n-type conductivity type provided in the back electrode layer conductivity type as the band gap have opposite conductivity type is wide and transparent second metal oxide having conductivity and the semiconductor thin film, said first multinary compound semiconductor thin film and a second metal oxide semiconductor thin film thin-film solar cell, comprising the structure with a transparent mixed crystal compound semiconductor thin film having a high resistance is provided at the interface between.
  2. 【請求項2】 第1の導電形と反対の導電形を有し透明で導電性を有する第2の金属酸化物半導体薄膜が、窓層として供され、酸化亜鉛からなることを特徴とする請求項1記載の薄膜太陽電池。 2. A second metal oxide semiconductor thin film having a first conductivity type and a transparent have opposite conductivity type conductivity, is provided as a window layer, characterized by comprising zinc oxide claimed thin-film solar cell of claim 1, wherein.
  3. 【請求項3】 第1の多元化合物半導体薄膜と第2の金属酸化物半導体薄膜の間の界面に設けられ透明で高抵抗を有する混晶化合物半導体薄膜が、溶液から化学的に成長したものからなることを特徴とする請求項1記載の薄膜太陽電池。 3. A mixed crystal compound semiconductor thin film having first and multinary compound semiconductor thin film surface transparent high resistance provided between a second metal oxide semiconductor thin film, from those chemically grown from the solution thin-film solar cell according to claim 1, characterized in that.
  4. 【請求項4】 第1の多元化合物半導体薄膜と第2の金属酸化物半導体薄膜の間の界面に設けられ透明で高抵抗を有する混晶化合物半導体薄膜が、酸素、イオウ及び水酸基を含んだ亜鉛混晶化合物からなることを特徴とする請求項1または3記載の薄膜太陽電池。 4. A mixed crystal compound semiconductor thin film having first and multinary compound semiconductor thin film surface transparent high resistance provided between a second metal oxide semiconductor thin film, a zinc containing oxygen, sulfur and hydroxyl claim 1 or 3 thin-film solar cell according to characterized in that it consists of a mixed crystal compound.
  5. 【請求項5】 第1の多元化合物半導体薄膜が、光吸収層として供され、ニセレン化銅インジウム及びI −III 5. The first multinary compound semiconductor thin film, is provided as a light absorbing layer, Niseren copper indium and I -III
    −VI 2族カルコパイライト化合物半導体の1つからなることを特徴とする請求項1記載の薄膜太陽電池。 Thin-film solar cell according to claim 1, characterized in that from one of -VI 2 Group chalcopyrite semiconductor.
  6. 【請求項6】 第1の多元化合物半導体薄膜が、ニセレン・イオウ化銅インジウム・ガリウムからなることを特徴とする請求項1記載の薄膜太陽電池。 6. The first multinary compound semiconductor thin film, thin film solar cell according to claim 1, comprising the Niseren-sulfur copper indium gallium.
  7. 【請求項7】 ヘテロ接合薄膜太陽電池を製造する方法において、金属裏面電極層上にp形の導電形を有する第1の多元化合物半導体薄膜を作成し、前記第1の多元化合物半導体薄膜上に透明で高抵抗を有する混晶化合物半導体薄膜を溶液から化学的に成長させ、その上に前記第1の多元化合物半導体薄膜の第1の導電形と反対の導電形を有し禁制帯幅が広くかつ透明で導電性を有する第2 7. A method of manufacturing a heterojunction thin-film solar cell, to create a first multinary compound semiconductor thin film having a conductivity type of p-type on a metal back electrode layer, the first multinary compound semiconductor thin film clear is chemically growing a mixed crystal compound semiconductor thin film from a solution having a high resistance, the forbidden band width has a conductivity type opposite to the first conductivity type of said first multinary compound semiconductor thin film thereon is wide and second with a transparent conductive
    の金属酸化物半導体薄膜を成長させることを特徴とするヘテロ接合薄膜太陽電池の製造方法。 Heterojunction thin-film solar method for producing a battery, characterized in that growing a metal oxide semiconductor thin film.
  8. 【請求項8】 前記第1の多元化合物半導体薄膜と第2 Wherein said first multinary compound semiconductor thin film and the second
    の金属酸化物半導体薄膜の間の界面に設けられ透明で高抵抗を有する混晶化合物半導体薄膜が、亜鉛塩及びイオウ含有塩を適当な錯形成剤と混合して亜鉛塩及びイオウ含有塩を溶解させた溶液中に亜鉛アンモニア錯塩を形成させ、第1の多元化合物半導体薄膜を前記溶液中で接触させて、当該溶液から酸素、イオウ及び水酸基を含んだ混晶化合物半導体薄膜を第1の多元化合物半導体薄膜上に成長させることを特徴とする請求項7記載の製造方法。 Dissolving a transparent provided on the interface mixed crystal compound semiconductor thin film having a high resistance, a mixture of zinc salts and sulfur-containing salt with a suitable complexing agent zinc salt and a sulfur-containing salt between the metal oxide semiconductor thin film to form a zinc ammonia complex salt in the solution was the first multinary compound semiconductor thin film in contact with said solution, oxygen from the solution, the mixed crystal compound semiconductor thin film containing a sulfur and a hydroxyl group first multinary compound the method of claim 7 wherein the grown on the semiconductor thin film.
  9. 【請求項9】 亜鉛塩及びイオウ含有塩を適当な錯形成剤と混合して亜鉛塩及びイオウ含有塩を溶解させた溶液中に亜鉛アンモニア錯塩を形成させ、第1の多元化合物半導体薄膜を前記溶液中で接触させて、当該溶液から酸素、イオウ及び水酸基を含んだ混晶化合物半導体薄膜を第1の多元化合物半導体薄膜上に成長させ、その後混晶化合物半導体薄膜を成長させた第1の多元化合物半導体薄膜を大気中でアニールして亜鉛混晶化合物中の水酸化物の一部を酸化物に、あるいは第1の多元化合物半導体薄膜と亜鉛混晶化合物間のアニオン種の相互拡散を通して第1の多元化合物半導体薄膜表面の改質を行なうことにより、透明で高抵抗の酸素、イオウ及び水酸基を含んだ亜鉛混晶化合物を作製することを特徴とする請求項7 9. to form a zinc salt and a solution of zinc ammonium complex salts in dissolving the zinc salt and a sulfur-containing salt in a mixture of sulfur-containing salt with a suitable complexing agent, wherein the first multinary compound semiconductor thin film in contact in solution, first multiple of the oxygen from the solution, sulfur and mixed crystal compound semiconductor thin film containing a hydroxyl grown first multinary compound semiconductor thin film is grown thereafter mixed crystal compound semiconductor thin film compound semiconductor thin film on a part of the oxide of the hydroxide in the zinc mixed crystal compound is annealed in the atmosphere, or the first through the anionic species of the mutual diffusion between the first multinary compound semiconductor thin film and a zinc mixed crystal compound claims by performing the modification of the multi-compound semiconductor thin film surface, characterized by preparing a transparent highly resistive oxygen, zinc mixed crystal compound containing sulfur and hydroxyl 7
    記載の製造方法。 The method according.
  10. 【請求項10】 禁制帯幅が広くかつ透明で導電性を有する第2の金属酸化物半導体薄膜が、窓層として供され、n形酸化亜鉛であることを特徴とする請求項7、8 10. The second metal oxide semiconductor thin film having a band gap wide and transparent conductive, is provided as a window layer, claim, characterized in that an n-type zinc oxide 7,8
    または9記載の製造方法。 Or 9 The method according.
  11. 【請求項11】 第1の多元化合物半導体薄膜が、光吸収層として供され、二セレン化銅インジニム、二セレン化銅インジニム・ガリウムあるいは二セレン・イオウ化銅インジニム・ガリウムからなることを特徴とする請求項7、8または9記載の製造方法。 11. The first multinary compound semiconductor thin film, is provided as a light absorbing layer, and characterized in that it consists diselenide copper Injinimu, diselenide copper Injinimu gallium or diselenide-sulfur copper Injinimu gallium the method according to claim 7, 8 or 9, wherein for.
  12. 【請求項12】 亜鉛塩が、硫酸亜鉛、塩化亜鉛及び酢酸亜鉛の1つであることを特徴とする請求項8または9 12. zinc salt is zinc sulfate, claim 8, characterized in that one of the zinc chloride and zinc acetate or 9
    記載の製造方法。 The method according.
  13. 【請求項13】 イオウ含有塩が、チオアセトアミド、 13. The sulfur-containing salt, thioacetamide,
    チオリア、チオセミカルバジド、チオウレタン、ジエチルアミン、トリエタノールアミンの1つであることを特徴とする請求項8または9記載の製造方法。 Chioria, thiosemicarbazide, thiourethane, diethylamine The method according to claim 8 or 9, wherein the is one of triethanolamine.
  14. 【請求項14】 亜鉛塩及びイオウ含有塩と混合される錯形成剤が、水酸化アンモニウムからなることを特徴とする請求項8または9記載の製造方法。 14. complexing agent is mixed with a zinc salt and a sulfur-containing salt is The process according to claim 8 or 9, wherein in that it consists of ammonium hydroxide.
  15. 【請求項15】 亜鉛塩が、酢酸亜鉛であり、イオウ含有塩がチオリアからなることを特徴とする請求項8または9記載の製造方法。 15. zinc salt is a zinc acetate, The process according to claim 8, wherein the sulfur-containing salt consists Chioria.
  16. 【請求項16】 溶液が 0.1M〜4M水酸化アンモニウム中に溶解した0.01M〜1M亜鉛塩及び 0.1M〜1Mチオリアからなることを特徴とする請求項7、8または9 16. A method according to claim solution is characterized in that it consists 0.01M~1M zinc salts and 0.1M~1M Chioria dissolved in 0.1M~4M ammonium hydroxide 7, 8 or 9
    記載の製造方法。 The method according.
  17. 【請求項17】 溶液が1M〜3M水酸化アンモニウム中に溶解した0.01M〜0.05M亜鉛塩及び0.1 M〜 0.5M 17. 0.01M~0.05M solution dissolved in 1M~3M ammonium hydroxide zinc salt and 0.1 M to 0.5M
    チオリアからなることを特徴とする請求項7、8または9記載の製造方法。 The method according to claim 7, 8 or 9, wherein in that it consists Chioria.
  18. 【請求項18】 溶液がほぼ 2.5M水酸化アンモニウム中に溶解した 0.025M亜鉛塩及び 0.375Mチオリアからなることを特徴とする請求項7、8または9記載の製造方法。 18. The method of claim 7, 8 or 9 wherein the solution is characterized in that it consists substantially 2.5M 0.025 M zinc salt was dissolved in ammonium hydroxide and 0.375M Chioria.
JP15276295A 1995-05-29 1995-05-29 Heterojunction thin-film solar cell and a manufacturing method thereof Expired - Lifetime JP3249342B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP15276295A JP3249342B2 (en) 1995-05-29 1995-05-29 Heterojunction thin-film solar cell and a manufacturing method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP15276295A JP3249342B2 (en) 1995-05-29 1995-05-29 Heterojunction thin-film solar cell and a manufacturing method thereof

Publications (2)

Publication Number Publication Date
JPH08330614A true true JPH08330614A (en) 1996-12-13
JP3249342B2 JP3249342B2 (en) 2002-01-21

Family

ID=15547601

Family Applications (1)

Application Number Title Priority Date Filing Date
JP15276295A Expired - Lifetime JP3249342B2 (en) 1995-05-29 1995-05-29 Heterojunction thin-film solar cell and a manufacturing method thereof

Country Status (1)

Country Link
JP (1) JP3249342B2 (en)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6259016B1 (en) 1999-03-05 2001-07-10 Matsushita Electric Industrial Co., Ltd. Solar cell
JP2002343987A (en) * 2001-05-15 2002-11-29 Showa Shell Sekiyu Kk Manufacturing method for heterojunction thin film solar battery
US6534704B2 (en) 2000-10-18 2003-03-18 Matsushita Electric Industrial Co., Ltd. Solar cell
WO2003081684A1 (en) 2002-03-26 2003-10-02 Honda Giken Kogyo Kabushiki Kaisha Compound thin-film solar cell and process for producing the same
WO2003105241A1 (en) * 2002-06-07 2003-12-18 本田技研工業株式会社 Method for manufacturing compound thin-film solar cell
DE102006039331A1 (en) * 2006-08-15 2008-02-28 Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg Photovoltaic-thin layer structure for solar cells and/or photovoltaic module, comprises photoelectric active absorber layer, transparent front contact layer and multi-layer buffer layer placed between absorber layer and front contact layer
WO2008120306A1 (en) * 2007-03-28 2008-10-09 Showa Shell Sekiyu K.K. Method for manufacturing cis based thin film solar cell device
WO2009069582A1 (en) * 2007-11-30 2009-06-04 Showa Shell Sekiyu K.K. Laminated structure for cis-family solar cell, and integrated structure and manufacturing method for cis-family thin-film solar cell
JP2009259938A (en) * 2008-04-15 2009-11-05 Honda Motor Co Ltd Method of manufacturing chalcopyrite thin film solar cell, and apparatus therefor
JP2010073021A (en) * 2008-09-19 2010-04-02 Nissha Printing Co Ltd Coordinate input device
JP2010073022A (en) * 2008-09-19 2010-04-02 Nissha Printing Co Ltd Coordinate input device
JP2010129659A (en) * 2008-11-26 2010-06-10 Kyocera Corp Method of manufacturing compound semiconductor thin film, and method of manufacturing thin-film solar cell
JP2010129658A (en) * 2008-11-26 2010-06-10 Kyocera Corp Method of manufacturing compound semiconductor thin film, and method of manufacturing thin-film solar cell
JP2011187732A (en) * 2010-03-09 2011-09-22 Institute Of National Colleges Of Technology Japan Sulfide thin film device and method of manufacturing the same
US8093096B2 (en) 2005-05-27 2012-01-10 Showa Shell Sekiyu K.K. Method of successive high-resistance buffer layer/window layer (transparent conductive film) formation for CIS based thin-film solar cell and apparatus for successive film formation for practicing the method of successive film formation
JP2012028650A (en) * 2010-07-26 2012-02-09 Institute Of National Colleges Of Technology Japan Photoelectric element and manufacturing method thereof
WO2012147427A1 (en) 2011-04-25 2012-11-01 京セラ株式会社 Photovoltaic converter
WO2013111443A1 (en) 2012-01-27 2013-08-01 京セラ株式会社 Photoelectric conversion device
KR20160108451A (en) 2014-05-22 2016-09-19 도시바 미쓰비시덴키 산교시스템 가부시키가이샤 Buffer layer film-forming method and buffer layer

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004040546B3 (en) 2004-08-18 2006-05-18 Hahn-Meitner-Institut Berlin Gmbh A process for applying a zinc sulfide buffer layer on a semiconductor substrate by chemical bath deposition, and in particular, the absorber layer of a chalcopyrite thin film solar cell
JP5003698B2 (en) 2009-02-18 2012-08-15 Tdk株式会社 Method for manufacturing a solar cell, and solar cell
JP5517696B2 (en) * 2010-03-29 2014-06-11 京セラ株式会社 Process for producing a photovoltaic device and a photoelectric conversion device
JP5495891B2 (en) * 2010-03-29 2014-05-21 京セラ株式会社 Method of manufacturing a photoelectric conversion device

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6259016B1 (en) 1999-03-05 2001-07-10 Matsushita Electric Industrial Co., Ltd. Solar cell
US6534704B2 (en) 2000-10-18 2003-03-18 Matsushita Electric Industrial Co., Ltd. Solar cell
JP2002343987A (en) * 2001-05-15 2002-11-29 Showa Shell Sekiyu Kk Manufacturing method for heterojunction thin film solar battery
EP2216824A2 (en) 2002-03-26 2010-08-11 Honda Giken Kogyo Kabushiki Kaisha Compound thin-film solar cell and process for producing the same
WO2003081684A1 (en) 2002-03-26 2003-10-02 Honda Giken Kogyo Kabushiki Kaisha Compound thin-film solar cell and process for producing the same
US7939745B2 (en) 2002-03-26 2011-05-10 Honda Giken Kogyo Kabushiki Kaisha Compound thin-film solar cell and process for producing the same
US7141449B2 (en) 2002-06-07 2006-11-28 Honda Giken Kogyo Kabushiki Kaisha Method of fabricating a compound semiconductor thin-layer solar cell
WO2003105241A1 (en) * 2002-06-07 2003-12-18 本田技研工業株式会社 Method for manufacturing compound thin-film solar cell
US8093096B2 (en) 2005-05-27 2012-01-10 Showa Shell Sekiyu K.K. Method of successive high-resistance buffer layer/window layer (transparent conductive film) formation for CIS based thin-film solar cell and apparatus for successive film formation for practicing the method of successive film formation
DE102006039331B9 (en) * 2006-08-15 2012-02-23 Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg Photovoltaic thin-film structure and manufacturing method
DE102006039331A1 (en) * 2006-08-15 2008-02-28 Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg Photovoltaic-thin layer structure for solar cells and/or photovoltaic module, comprises photoelectric active absorber layer, transparent front contact layer and multi-layer buffer layer placed between absorber layer and front contact layer
DE102006039331B4 (en) * 2006-08-15 2011-07-28 Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg, 70565 Photovoltaic thin-film structure and manufacturing method
DE102006039331C5 (en) * 2006-08-15 2013-08-22 Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg Photovoltaic thin-film structure and manufacturing method
WO2008120306A1 (en) * 2007-03-28 2008-10-09 Showa Shell Sekiyu K.K. Method for manufacturing cis based thin film solar cell device
US7977139B2 (en) 2007-03-28 2011-07-12 Showa Shell Sekiyu K.K. Method for manufacturing CIS based thin film solar cell device
JP5180188B2 (en) * 2007-03-28 2013-04-10 昭和シェル石油株式会社 Method for producing Cis-based thin-film solar cell device
WO2009069582A1 (en) * 2007-11-30 2009-06-04 Showa Shell Sekiyu K.K. Laminated structure for cis-family solar cell, and integrated structure and manufacturing method for cis-family thin-film solar cell
US8691619B2 (en) 2007-11-30 2014-04-08 Showa Shell Sekiyu, K.K. Laminated structure for CIS based solar cell, and integrated structure and manufacturing method for CIS based thin-film solar cell
JP2009259938A (en) * 2008-04-15 2009-11-05 Honda Motor Co Ltd Method of manufacturing chalcopyrite thin film solar cell, and apparatus therefor
JP2010073021A (en) * 2008-09-19 2010-04-02 Nissha Printing Co Ltd Coordinate input device
JP2010073022A (en) * 2008-09-19 2010-04-02 Nissha Printing Co Ltd Coordinate input device
JP2010129658A (en) * 2008-11-26 2010-06-10 Kyocera Corp Method of manufacturing compound semiconductor thin film, and method of manufacturing thin-film solar cell
JP2010129659A (en) * 2008-11-26 2010-06-10 Kyocera Corp Method of manufacturing compound semiconductor thin film, and method of manufacturing thin-film solar cell
JP2011187732A (en) * 2010-03-09 2011-09-22 Institute Of National Colleges Of Technology Japan Sulfide thin film device and method of manufacturing the same
JP2012028650A (en) * 2010-07-26 2012-02-09 Institute Of National Colleges Of Technology Japan Photoelectric element and manufacturing method thereof
US9935219B2 (en) 2011-04-25 2018-04-03 Kyocera Corporation Photoelectric conversion device
WO2012147427A1 (en) 2011-04-25 2012-11-01 京セラ株式会社 Photovoltaic converter
US9484476B2 (en) 2011-04-25 2016-11-01 Kyocera Corporation Photoelectric conversion device
EP3142155A1 (en) 2012-01-27 2017-03-15 Kyocera Corporation Photoelectric conversion device
WO2013111443A1 (en) 2012-01-27 2013-08-01 京セラ株式会社 Photoelectric conversion device
KR20160108451A (en) 2014-05-22 2016-09-19 도시바 미쓰비시덴키 산교시스템 가부시키가이샤 Buffer layer film-forming method and buffer layer

Also Published As

Publication number Publication date Type
JP3249342B2 (en) 2002-01-21 grant

Similar Documents

Publication Publication Date Title
Lincot et al. Chalcopyrite thin film solar cells by electrodeposition
BASOL ELECTRODEPOSITED CdTe AND HgCďTe SOLAR CELLS
Fulop et al. High‐efficiency electrodeposited cadmium telluride solar cells
Hariskos et al. A novel cadmium free buffer layer for Cu (In, Ga) Se2 based solar cells
Kumar et al. Physics and chemistry of CdTe/CdS thin film heterojunction photovoltaic devices: fundamental and critical aspects
US6307148B1 (en) Compound semiconductor solar cell and production method thereof
US5871630A (en) Preparation of copper-indium-gallium-diselenide precursor films by electrodeposition for fabricating high efficiency solar cells
US4915745A (en) Thin film solar cell and method of making
Nakada et al. 18% efficiency Cd-free Cu (In, Ga) Se2 thin-film solar cells fabricated using chemical bath deposition (CBD)-ZnS buffer layers
US8217261B2 (en) Thin film sodium species barrier method and structure for cigs based thin film photovoltaic cell
US4642140A (en) Process for producing chalcogenide semiconductors
US4581108A (en) Process of forming a compound semiconductive material
US20070289624A1 (en) Cis Compound Semiconductor Thin-Film Solar Cell and Method of Forming Light Absorption Layer of the Solar Cell
US5125984A (en) Induced junction chalcopyrite solar cell
US7297868B2 (en) Preparation of CIGS-based solar cells using a buffered electrodeposition bath
US5028274A (en) Group I-III-VI2 semiconductor films for solar cell application
US20050028861A1 (en) Light absorbing layer producing method
Nakada et al. High-efficiency Cu (In, Ga) Se2 thin-film solar cells with a CBD-ZnS buffer layer
US7141449B2 (en) Method of fabricating a compound semiconductor thin-layer solar cell
US5948176A (en) Cadmium-free junction fabrication process for CuInSe2 thin film solar cells
Chu et al. Recent progress in thin‐film cadmium telluride solar cells
US5112410A (en) Cadmium zinc sulfide by solution growth
US7960204B2 (en) Method and structure for adhesion of absorber material for thin film photovoltaic cell
US6048442A (en) Method for producing thin-film solar cell and equipment for producing the same
US4612411A (en) Thin film solar cell with ZnO window layer

Legal Events

Date Code Title Description
R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

S531 Written request for registration of change of domicile

Free format text: JAPANESE INTERMEDIATE CODE: R313531

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20081109

Year of fee payment: 7

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20091109

Year of fee payment: 8

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20101109

Year of fee payment: 9

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20101109

Year of fee payment: 9

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20111109

Year of fee payment: 10

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20111109

Year of fee payment: 10

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20121109

Year of fee payment: 11

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20131109

Year of fee payment: 12

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

EXPY Cancellation because of completion of term