JPH03227576A - Manufacture of thin film solar cell - Google Patents
Manufacture of thin film solar cellInfo
- Publication number
- JPH03227576A JPH03227576A JP2020459A JP2045990A JPH03227576A JP H03227576 A JPH03227576 A JP H03227576A JP 2020459 A JP2020459 A JP 2020459A JP 2045990 A JP2045990 A JP 2045990A JP H03227576 A JPH03227576 A JP H03227576A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- oxide semiconductor
- semiconductor layer
- substrate
- solar cell
- 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
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000000758 substrate Substances 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 60
- 239000002245 particle Substances 0.000 claims abstract description 48
- 239000004065 semiconductor Substances 0.000 claims abstract description 46
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 238000007650 screen-printing Methods 0.000 claims description 8
- 238000010574 gas phase reaction Methods 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims description 2
- 238000009832 plasma treatment Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 4
- 239000004020 conductor Substances 0.000 abstract description 2
- 238000010248 power generation Methods 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 76
- 239000010408 film Substances 0.000 description 58
- 239000007789 gas Substances 0.000 description 51
- 235000014692 zinc oxide Nutrition 0.000 description 38
- 239000011787 zinc oxide Substances 0.000 description 38
- 239000000843 powder Substances 0.000 description 36
- 238000004544 sputter deposition Methods 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 7
- 229910021417 amorphous silicon Inorganic materials 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- -1 for example Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold 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
- 239000011810 insulating material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
【発明の詳細な説明】
［産業上の利用分野Ｊ
本発明は、主として太陽電池、光センサーなどの機能性
デバイスに用いられる機能性堆積膜の作製方法に関し、
特に、光透過性が良く、電気伝導性が良好な酸化物半導
体膜を有する薄膜太陽電池を作製する作製方法に関する
。[Detailed Description of the Invention] [Industrial Field of Application J] The present invention relates to a method for producing a functional deposited film mainly used for functional devices such as solar cells and optical sensors.
In particular, the present invention relates to a manufacturing method for manufacturing a thin film solar cell having an oxide semiconductor film with good optical transparency and good electrical conductivity.
［従来の技術］
太陽光を電気エネルギーに変換する光電変換素子である
太陽電池は、将来、石油エネルギーに代わる手段として
注目されている。[Background Art] Solar cells, which are photoelectric conversion elements that convert sunlight into electrical energy, are attracting attention as a future alternative to petroleum energy.
太陽電池の実用化を進めるに当たって解決すべき問題点
としては、現在おもに実用化されているシリコン半導体
は単結晶であるため大面積化が困難であり、ボンディン
グして用いなければならないことや、単結晶であるがた
めに高価であり、単位発電量に対する製造コストが石油
エネルギーに比べて割高になってしまう等がある。この
ような事情から低コスト化及び大面積化が重要な技術的
課題であり、様々な検討がなされている。とりわけ非晶
質半導体を光起電力発生層に用いた薄膜太陽電池は、車
結晶太陽電池に比して安価でしかも大面積にわたって均
一な特性が得られることで有望視されている。このよう
な薄膜太陽電池の材料としては、非晶質シリコン、非晶
質シリコンゲルマニュウム、非晶質炭化珪素などのテト
ラヘドラル系の非晶質半導体や、ＣｄＳ、 Ｃｕ２Ｓな
どのＩＩ−■族やＧａＡｓ、 ＧａＡｌＡｓなどのｍ−
ｖ族の化合物半導体が用いられる。Problems that need to be solved in order to advance the practical application of solar cells include the fact that silicon semiconductors, which are currently in practical use, are single-crystalline and therefore difficult to increase in area, and must be used by bonding; Because it is a crystal, it is expensive, and the manufacturing cost per unit power generation is relatively high compared to petroleum energy. Under these circumstances, reducing costs and increasing area are important technical issues, and various studies are being conducted. In particular, thin-film solar cells using amorphous semiconductors in the photovoltaic generation layer are seen as promising because they are cheaper than crystalline solar cells and can provide uniform characteristics over a large area. Materials for such thin-film solar cells include tetrahedral amorphous semiconductors such as amorphous silicon, amorphous silicon germanium, and amorphous silicon carbide, group II-III semiconductors such as CdS and Cu2S, GaAs, m- such as GaAlAs
A V group compound semiconductor is used.
素子構造としては、ｐｉｎ型、ＭＩＳ型、ペテロ接合型
などが知られているが、最も実用的に作製されている構
成は、ｐｉｎ型であり、より具体的には、例えば、第１
の電極となる金属基板上にｎ層、ｉ層、ｐ層の順番かま
たはｐ層、ｉ層、ｎ層の順に光起電力発生層を形成した
後、第２の電極を設ける構成が取られる。基板がガラス
等の絶縁性である場合には、基板上に適当な第１の電極
な形成した後、ｎ層、ｉＮ、ｐ層の順番かまたはｐ層、
ｉＭ、ｎ層の順に光起電力発生層を形成し、さらに、第
２の電極を設ければよい。この素子構造に於て金属基板
または、絶縁性基板上の第１の電極と光起電力発生層と
の間に酸化物半導体を積層することにより光電変換効率
が良くなり、ピンホールなどの欠陥による電圧の降下を
防ぎ、信頼性の高い薄膜太陽電池が得られることが知ら
れている。Device structures such as pin type, MIS type, and Peter junction type are known, but the most practically fabricated configuration is the pin type.More specifically, for example, the first
After forming the photovoltaic generation layer in the order of n layer, i layer, p layer or p layer, i layer, n layer on the metal substrate which will serve as the electrode, the second electrode is provided. . If the substrate is an insulating material such as glass, after forming a suitable first electrode on the substrate, the n-layer, iN, and p-layer are formed in this order, or the p-layer,
The photovoltaic generation layer may be formed in the order of the iM layer and the n layer, and then a second electrode may be provided. In this device structure, by stacking an oxide semiconductor between the first electrode on a metal substrate or an insulating substrate and the photovoltaic generation layer, the photoelectric conversion efficiency is improved, and defects such as pinholes can be avoided. It is known that a highly reliable thin film solar cell can be obtained by preventing voltage drop.
この酸化物半導体の機能は、光起電力発生層で吸収しき
れなかった光を基板表面まで透過させて、基板表面で反
射させた後、この反射光を光起電力発生層でもう一度吸
収させることにより光電変換効率を上昇させる機能と、
光起電力発生層にピンホールが生じた場合に起こる電流
のリークを防止するバリヤー層の機能を持っている。バ
リヤー層としての機能を果たすためには、高い抵抗を持
つことが望ましいが、光電変換によって発生した電流に
対しては、直列抵抗成分となるため適度な電気伝導性を
併せ持つことが必要である。また、第１の電極が非晶質
半導体層に直接接している場合には良く知られているよ
うに界面において第１の電極材料の金属が非晶質材料ヘ
マイグレーションしその結果太陽電池の特性が低下する
が、前記酸化物半導体層を第１の電極と非晶質半導体層
の間に形成することにより前記のような好ましくない現
象を防ぐはたらきもしている。The function of this oxide semiconductor is to transmit the light that cannot be absorbed by the photovoltaic generation layer to the substrate surface, reflect it on the substrate surface, and then absorb this reflected light once again in the photovoltaic generation layer. The function of increasing photoelectric conversion efficiency by
It functions as a barrier layer to prevent current leakage that occurs when pinholes occur in the photovoltaic generation layer. In order to function as a barrier layer, it is desirable to have high resistance, but since it becomes a series resistance component for the current generated by photoelectric conversion, it is also necessary to have appropriate electrical conductivity. Furthermore, when the first electrode is in direct contact with an amorphous semiconductor layer, as is well known, the metal of the first electrode material migrates into the amorphous material at the interface, resulting in the characteristics of the solar cell. However, forming the oxide semiconductor layer between the first electrode and the amorphous semiconductor layer serves to prevent such undesirable phenomena.
以上に説明したように前記酸化物半導体膜は。As explained above, the oxide semiconductor film is.
光に対する透過性が十分にあり、適度の電気伝導性を有
することが要求されており、具体的には、禁制帯幅Ｅｇ
が３ｅＶ以上で抵抗率ρが１０−４Ωｃｍ程度であるこ
とが望ましい、このような特性を有する材料としては、
酸化スズ釦０．やインジュウムとスズの酸化物の合金で
ある ＩＴＯや酸化亜鉛ＺｎＯが好適なものである。と
りわけ、ＺｎＯは、適度な電気伝導性を有し、安価であ
り、光透過性も良好であるため至適な材料として研究が
進められている。It is required to have sufficient transparency to light and appropriate electrical conductivity, specifically, the forbidden band width Eg
It is desirable that the resistivity ρ is 3 eV or more and the resistivity ρ is about 10-4 Ωcm. Materials with such characteristics include:
Tin oxide button 0. ITO, which is an alloy of oxides of indium and tin, and zinc oxide, ZnO, are suitable. In particular, ZnO has appropriate electrical conductivity, is inexpensive, and has good light transmittance, so research is progressing as an optimal material.
このＺｎＯを形成するための具体的な手段としては、Ｚ
ｎＯの粉末を焼成して得たターゲットを用いて、希ガス
中で平行平板型２極スパツタリング法により作製するの
が一般的である。またＺｎをターゲットとして１０−’
Ｔｏｒｒ程度の分圧の０２ガスとＡｒガスの混合ガス中
で反応性スパッタリングする方法もしばしば用いられる
。更に別の公知の方法は、酸素雰囲気で抵抗加熱法や、
エレクトロンビーム法などによりＺｎを気化させて基板
上に堆積させる、反応性蒸着法も用いられる。As a specific means for forming this ZnO, ZnO
It is generally produced by a parallel plate bipolar sputtering method in a rare gas using a target obtained by firing nO powder. In addition, 10-'
A method of reactive sputtering in a mixed gas of O2 gas and Ar gas at a partial pressure of about Torr is also often used. Still other known methods include resistance heating in an oxygen atmosphere;
A reactive vapor deposition method is also used in which Zn is vaporized and deposited on the substrate using an electron beam method or the like.
［発明が解決しようとする課題］
しかしながら、上記従来例では、基板温度により酸化物
半導体膜の特性は大きく変化するため、広い面積にわた
って基板温度を均一に保つ技術が必要であり、従って、
大面積にわたって均一な特性の薄膜を得るのは困難であ
った。また、これらの成膜方法は本質的に高真空の成膜
室を必要とするため生産装置としては高額となり管理項
目も多く、又成膜速度も遅い、更に、これらの方法は、
バッチ式の成膜方法であり、薄膜太陽電池に求められて
いる大面積化、低コスト化の実現のための方法である、
長尺のシート状基板に連続的に成膜を行なうためには不
向きであり低コスト化、大面積化の障害ともなっている
。[Problems to be Solved by the Invention] However, in the conventional example described above, the characteristics of the oxide semiconductor film vary greatly depending on the substrate temperature, so a technique for keeping the substrate temperature uniform over a wide area is required.
It has been difficult to obtain thin films with uniform properties over a large area. Furthermore, these film-forming methods essentially require a high-vacuum film-forming chamber, making them expensive as production equipment, requiring many management items, and slowing the film-forming speed.
It is a batch-type film formation method, and is a method for realizing the large area and low cost required for thin-film solar cells.
It is not suitable for continuously forming a film on a long sheet-like substrate, and is an obstacle to reducing costs and increasing the area.
このような問題を解決する手段として真空装置を用いず
に成膜する方法が考案されている。このような方法とし
ては、塗布法や、スプレー法等がある。具体的には、例
えば、スプレー法であれば、Ｚｎの塩化物を適当な有機
溶媒に溶かし酸素雰囲気で、加熱した基板に噴霧する方
法が考案されている。しかしこれらの方法に於いても、
温度管理は重要な項目であり、大面積にわたって作製す
るには、基板の温度分布を極力少なくしなければならな
い。また、このような作製法は、本来１μｍ以上の厚み
の膜を形成するには適するが、薄膜太陽電池に於て必要
な光透過性、電気伝導性を達成するのに好適な、１μｍ
未満の厚みの膜を精度良く均一に作製するには適さない
方法である。As a means to solve such problems, a method of forming a film without using a vacuum apparatus has been devised. Such methods include a coating method, a spray method, and the like. Specifically, for example, in the case of a spray method, a method has been devised in which Zn chloride is dissolved in a suitable organic solvent and sprayed onto a heated substrate in an oxygen atmosphere. However, even in these methods,
Temperature control is an important item, and in order to manufacture over a large area, the temperature distribution on the substrate must be minimized. In addition, although such a production method is originally suitable for forming a film with a thickness of 1 μm or more, it is preferable to form a film with a thickness of 1 μm or more, which is suitable for achieving the optical transparency and electrical conductivity necessary for thin-film solar cells.
This method is not suitable for producing uniformly and accurately films with a thickness of less than 100 mL.
本発明は上記従来の成膜方法に起因する酸化物半導体膜
の膜特性における問題点を解決する成膜法により優れた
薄膜太陽電池を作製する方法を提供するものである。The present invention provides a method for producing an excellent thin-film solar cell using a film-forming method that solves the problems in film characteristics of oxide semiconductor films caused by the conventional film-forming methods.
［課題を解決するための手段］
本発明は、基板上に、少なくとも、酸化物半導体層、光
起電力発生層、透明導電層及び金属電極をこの順に積層
することにより薄膜太陽電池を作製する方法であって、
酸化物半導体層を構成する原料粒子として平均粒径１０
００Å以下の金属酸化物粒子を用い、塗布法により前記
酸化物半導体層を形成することを特徴とする薄膜太陽電
池作製方法であり、本発明によれば、大面積にわたって
光電変換効率が高く電流のリークの少ない安定した特性
の薄膜太陽電池を得ることができる。[Means for Solving the Problems] The present invention provides a method for manufacturing a thin film solar cell by laminating at least an oxide semiconductor layer, a photovoltaic generation layer, a transparent conductive layer, and a metal electrode in this order on a substrate. And,
The average particle size of the raw material particles constituting the oxide semiconductor layer is 10.
A thin film solar cell manufacturing method is characterized in that the oxide semiconductor layer is formed by a coating method using metal oxide particles with a size of 00 Å or less, and according to the present invention, the photoelectric conversion efficiency is high over a large area, and the current flow is high. A thin film solar cell with stable characteristics and less leakage can be obtained.
本発明の特徴は、特定の平均粒径とした金属酸化物粒子
を用いて塗布法により酸化物半導体層を形成することで
あり、本発明で用いることのできる前記粒子としては、
ＺｎＯ，Ｓｎｏｗ、 Ｌ＊、Ｏｓ、 ＩＴＯ等が挙げら
れるが、薄膜太陽電池に該酸化物半導体層を用いる場合
は、その光透過性及び電気伝導性等からＺｎＯが好まし
い。A feature of the present invention is that an oxide semiconductor layer is formed by a coating method using metal oxide particles having a specific average particle size, and the particles that can be used in the present invention include:
Examples include ZnO, Snow, L*, Os, ITO, etc., but when the oxide semiconductor layer is used in a thin film solar cell, ZnO is preferable due to its light transmittance and electrical conductivity.
以下ＺｎＯ薄膜を用いる薄膜太陽電池に対して本発明を
実施した場合について、図面を参照して説明するが、本
発明は、以下の具体的説明によって発明の内容が限定さ
れるものではない。Hereinafter, a case in which the present invention is implemented for a thin film solar cell using a ZnO thin film will be described with reference to the drawings, but the content of the present invention is not limited to the following specific description.
第１図は、本発明の薄膜太陽電池作製法を適用するには
好適な薄膜太陽電池の構成を表わす模式図である。すな
わち、基板１０１上に酸化物半導体層１０２、光起電力
発生層１０３〜１０５、透明導電層１０６、金属電極１
０７から成っており、該光起電力発生層はｎｆｆｌ１０
３．１層１０４及び１層１０５より構成されている。も
ちろん、前記光起電力発生層の素子構造は必要により変
えてもよい。FIG. 1 is a schematic diagram showing the configuration of a thin film solar cell suitable for applying the thin film solar cell manufacturing method of the present invention. That is, an oxide semiconductor layer 102, photovoltaic generation layers 103 to 105, a transparent conductive layer 106, and a metal electrode 1 are formed on a substrate 101.
07, and the photovoltaic generation layer consists of nffl10
3. It is composed of a first layer 104 and a first layer 105. Of course, the element structure of the photovoltaic generation layer may be changed as necessary.
１０１は、基板であり、金属の場合は、例えば、ステン
レス、アルミニウムなどの工業的に安定して供給され、
安価で加工し易い材質が好ましい、また、工業的規模で
連続生産する場合は、前記金属基板は、シート状に形成
された長尺基板であって、ロール状に巻き取ることがで
き、充分に柔軟であることが望ましく、このため基板の
厚みとしては、１００μ−からＩＩＩＩｆｆｌくらいが
好適である。また、絶縁性基板としては、耐熱性、加工
性の点からガラスやセラミックスが好適に用いられ、こ
の場合は、公知の方法により表面に適当な電極を形成し
て用いらればよい、基板表面は、薄膜太陽電池の光吸収
層に於て吸収しきれない、主に、５００〜８００ｎｍ程
度の長波長の光を効率よく反射する機能を果たしていて
、そのため、表面処理は重要な工程であり、所望に応じ
て平滑な面にしたり、粗面にしたりして、必要に応じて
機械的な研磨や電解研磨等の処理をして用いる。101 is a substrate, and in the case of metal, for example, stainless steel, aluminum, etc., which are industrially stably supplied,
It is preferable to use a material that is inexpensive and easy to process, and in the case of continuous production on an industrial scale, the metal substrate is a long substrate formed in the form of a sheet, which can be wound up into a roll, and is sufficiently It is desirable that the substrate be flexible, and therefore the thickness of the substrate is preferably about 100 μ- to IIIffl. Glass or ceramics are preferably used as the insulating substrate from the viewpoint of heat resistance and workability. In this case, suitable electrodes may be formed on the surface by a known method. , it functions to efficiently reflect mainly long-wavelength light of about 500 to 800 nm that cannot be fully absorbed by the light absorption layer of a thin-film solar cell. Therefore, surface treatment is an important process and can achieve desired results. Depending on the situation, the surface is made smooth or rough, and if necessary, it is processed by mechanical polishing, electrolytic polishing, etc. before use.
１０２は、酸化物半導体層であるＺｎＯの層であり本発
明に係る薄膜形成の方法により好適に形成されるもので
、該方法は、後で詳しく述べる。Reference numeral 102 denotes a ZnO layer which is an oxide semiconductor layer, and is suitably formed by the thin film forming method according to the present invention, which will be described in detail later.
１０３、１０４．１０５は光起電力発生層であり、非晶
質シリコン、非晶質シリコンゲルマニュウム、非晶質炭
化珪素などのテトラヘドラル系の非晶質半導体が用いら
れる。さらに詳しく素子構造について一例を挙げて説明
すると、１０３はｎ型の導電性を持つ非晶質半導体層で
あり、ＳｉＨ４ガスとドーピング材用のＰＨ３ガスとを
プラズマで分解して作製する、１０４は光吸収を行ない
、光によって励起されたキャリアを発生させる非晶質半
導体層であり通常５ｉ）１４ガスをプラズマで分解して
作製する。Reference numerals 103, 104, and 105 are photovoltaic generation layers, and a tetrahedral amorphous semiconductor such as amorphous silicon, amorphous silicon germanium, and amorphous silicon carbide is used. To explain the element structure in more detail by giving an example, 103 is an amorphous semiconductor layer with n-type conductivity, which is produced by decomposing SiH4 gas and PH3 gas as a doping material with plasma. It is an amorphous semiconductor layer that absorbs light and generates carriers excited by the light, and is usually produced by decomposing 5i)14 gas with plasma.
１０５はｐ型の導電性を持つ非晶質半導体層であり、一
般的には５ｔ）Ｉ４ガスとドーピング材用のＢａＨａガ
スとをプラズマで分解して作製する。Reference numeral 105 denotes an amorphous semiconductor layer having p-type conductivity, which is generally produced by decomposing 5t) I4 gas and BaHa gas as a doping material using plasma.
１０６は光を透過させ、かつ導電性を有する透明導電膜
であり、一般的には、 ＩＴＯや５ｎＯｘをターゲット
としてスパッタリングで作製される。１０７は金属電極
であり、一般的には、ＣｒとＡｇの積層構造が用いられ
抵抗加熱法や、エレクトロンビーム法を用いて作製され
る。また該金属電極１０７は光の透過性を妨げないよう
に極力面積を少なくするように設計されるのが望ましく
、通常グリッド状に形成される。106 is a transparent conductive film that transmits light and has electrical conductivity, and is generally produced by sputtering using ITO or 5nOx as a target. Reference numeral 107 denotes a metal electrode, which generally has a laminated structure of Cr and Ag and is manufactured using a resistance heating method or an electron beam method. Further, the metal electrode 107 is desirably designed to have an area as small as possible so as not to impede light transmission, and is usually formed in a grid shape.
各層の層厚は一般に、酸化物半導体層１０２゜０．１〜
２μｎ＋ ％ ｎｌｌ ０３．．５０〜５００人、１Ｎ
１０４，１０００〜８００．０人、９層１０５．５０〜
３００人、透明導電層１０６，５００〜８００人程度で
よい変
形に、本発明に係る１０２のＺｎＯ膜の作製方法につい
て詳しく述べる１本発明ではＺｎＯ膜は連続生産に適す
る方法として塗布法を用いる。塗布法としては、スクリ
ーン印刷法、ロールコータ−法、ドクターブレード法な
どの通常知られた方法が適用できる。The thickness of each layer is generally 102°0.1 to 102° for the oxide semiconductor layer.
2μn+% nll 03. ．． 50-500 people, 1N
104,1000~800.0 people, 9th layer 105.50~
In the present invention, a coating method is used for the ZnO film as a method suitable for continuous production. As a coating method, commonly known methods such as a screen printing method, a roll coater method, and a doctor blade method can be applied.
以下にスクリーン印刷法を用いて作成する場合について
説明する。従来から、厚膜技術によって導電体膜、誘電
体膜、絶縁体膜を作製することは一般的に行なわれてい
る。厚膜技術は、一般にスクリーン印刷法と呼ばれ、目
的とする膜の原料となる物質の粉体を適当な溶媒に溶か
しスクリーン印刷により基板上に印刷し、その後適当な
温度で焼成し膜を形成する技術である。従ってＺｎＯの
膜を作製するには、原料となる７口０の粉体なスクリー
ン印刷すればよい。The case of creating using the screen printing method will be explained below. Conventionally, it has been common practice to produce conductor films, dielectric films, and insulator films using thick film technology. Thick film technology is generally called the screen printing method, and involves dissolving the powder of the substance that will be the raw material for the desired film in an appropriate solvent, printing it on the substrate using screen printing, and then baking it at an appropriate temperature to form the film. It is a technology that Therefore, in order to produce a ZnO film, it is sufficient to screen print a 7-hole powder as a raw material.
ＺｎＯの粉体は、亜鉛華と呼ばれ、従来から工業的に安
定して供給されており応用用途も多く実用化が行なわれ
ている。しかしながら通常商業的に人手可能なＺｎＯの
粉体は、その粒径が比較的太きなものであり、粒度分布
が広く均一な粒径の粉体が入手しにくいため、目的とす
る好適な厚さのＺｎ０１４に成膜することは困難であり
、不必要に厚い膜となってしまったり気孔が含まれる不
均一な膜となったりして所望の光の透過性や、電気伝導
性が得られない。このために従来、上記塗布法は薄膜形
成技術としては用いられず、又検討されていなかった０
本発明者らは塗布法のもつ上記問題点を解決するため鋭
意研究の結果、特定の粒子を用いることで、塗布法を薄
膜形成に用い、均一性、高速性、連続生産性を達成する
ことができることを見い出した。ZnO powder is called zinc white, has been stably supplied industrially, and has been put into practical use in many applications. However, commercially available ZnO powder has a relatively large particle size, and it is difficult to obtain powder with a wide and uniform particle size distribution, so it is difficult to obtain the desired thickness. It is difficult to form a film on Zn014, resulting in an unnecessarily thick film or an uneven film containing pores, making it difficult to obtain the desired light transparency and electrical conductivity. do not have. For this reason, the coating method described above has not been used or studied as a thin film forming technique in the past.
The present inventors have conducted intensive research to solve the above-mentioned problems with the coating method, and have found that by using specific particles, the coating method can be used to form a thin film, achieving uniformity, high speed, and continuous productivity. I discovered that it can be done.
以下、ＺｎＯ粉体の平均粒径と、薄膜太陽電池の特性と
の関係について１例をあげ説明する。尚粉末作製方法、
具体的塗布方法等は上記関係の実体に影響を及ぼすもの
ではない。Hereinafter, one example will be given and explained about the relationship between the average particle size of ZnO powder and the characteristics of a thin film solar cell. Furthermore, powder preparation method,
The specific application method etc. do not affect the substance of the above relationship.
ＺｎＯ粉体は、一般的にはＺｎを加熱蒸発させて酸素と
反応させる気相酸化法を用いることで作成できる。また
、液相においても重合法を用いることで作成可能であり
これらの公知の技術を用いることで所望の粒径の粉体が
得られる。しかしながらこれらの方法においては比較的
細かい粒径、例えば１０００オングストローム以下の粒
径の粉体を得るのは困難であり、また、粒度分布も広く
制御性が悪い。本発明に於て好適なＺｎＯ粉体の粒径を
求めるためにはより小粒径で粒度分布の小さい粉体が必
要であるため、以下に説明する方法でＺｎＯ粉体な作成
するとよい。ZnO powder can generally be created by using a gas phase oxidation method in which Zn is heated and evaporated and reacted with oxygen. In addition, it can also be produced in a liquid phase by using a polymerization method, and by using these known techniques, a powder with a desired particle size can be obtained. However, in these methods, it is difficult to obtain powder with a relatively fine particle size, for example, 1000 angstroms or less, and the particle size distribution is also wide and poorly controllable. In order to find a suitable particle size of ZnO powder in the present invention, a powder with a smaller particle size and narrow particle size distribution is required, so it is preferable to prepare the ZnO powder by the method described below.
第２図はＺｎＯ粉体作製装置である０図に於て、２０１
はマイクロ波発振器、２０２はマイクロ波を伝送するた
めの導波管、２０３はマイクロ波の入射パワー及び反射
パワーを測定するためのパワーモニター、２０４は整合
回路、２０５はマイクロ波投入窓、２０６は空洞共振器
、２０７は直径８１１ＩＩＩの穴が開孔率４０％となる
ように開いているパンチングメタルである。２０８はチ
ャンバー、２０９は排気ポンプ、２１０は圧力コントロ
ール装置、２１１は原料ガスバブリング装置、２１２は
酸素ボンベ、２１３は原料ガスバブリング用のＮ２ガス
ボンベ、２１４および２１５はそれぞれ原料ガスおよび
酸素ガスのマスフローコントローラーを示す、２１６は
原料ガス導入管、２１７は酸素ガス導入管をそれぞれ示
す。Figure 2 shows the ZnO powder production apparatus in Figure 0, 201
202 is a microwave oscillator, 202 is a waveguide for transmitting microwaves, 203 is a power monitor for measuring the incident power and reflected power of microwaves, 204 is a matching circuit, 205 is a microwave input window, 206 is a The cavity resonator 207 is a punched metal with holes having a diameter of 811III having an open area ratio of 40%. 208 is a chamber, 209 is an exhaust pump, 210 is a pressure control device, 211 is a source gas bubbling device, 212 is an oxygen cylinder, 213 is an N2 gas cylinder for source gas bubbling, and 214 and 215 are mass flow controllers for source gas and oxygen gas, respectively. 216 represents a raw material gas introduction pipe, and 217 represents an oxygen gas introduction pipe.
まず、排気ポンプ２０９を運転してチャンバー２０８内
を１０−’Ｔｏｒｒ以下の真空度に保つ６次に、原料ガ
スのバブリング装置２１１内にガスボンベ２１３に充填
されているキャリアーガスのＮ２ガスを導入する。原料
ガスはキャリアーガスに所定の蒸気圧で含有され、マス
フローコントローラー２１４にてｌＯ〜５０ ｓｅｃｍ
の流量に調整し空洞共振器２０６内に導入する。同様に
酸素ガスは、マスフローコントローラー２１５を介して
ｌＯ〜５０ ｓｃｃｍの流量で空洞共振器２０６に導入
した。First, the exhaust pump 209 is operated to keep the chamber 208 at a vacuum level of 10-'Torr or less.Next, N2 gas, which is a carrier gas filled in the gas cylinder 213, is introduced into the source gas bubbling device 211. . The raw material gas is contained in a carrier gas at a predetermined vapor pressure, and the mass flow controller 214 controls the flow rate from lO to 50 sec.
is introduced into the cavity resonator 206. Similarly, oxygen gas was introduced into cavity resonator 206 via mass flow controller 215 at a flow rate of IO to 50 sccm.
圧力コントローラー２１０によりチャンバー２０８内の
圧力を５〜ｌ ＯＯｍＴｏｒｒに調整する。A pressure controller 210 adjusts the pressure within the chamber 208 to 5-100 mTorr.
圧力が安定したところで、マイクロ波発振器２０１の電
源を入れて、５０〜２００Ｗのパワーのマイクロ波を発
生させる。パワーモニター２０３に示される反射パワー
を極力少なくなるように、整合回路２０４を調整する。When the pressure becomes stable, the microwave oscillator 201 is turned on to generate microwaves with a power of 50 to 200 W. The matching circuit 204 is adjusted so that the reflected power shown on the power monitor 203 is minimized.
空洞共振器２０６にプラズマが発生し、気相反応により
生成した粉体が、パンチングメタル２０７を介してチャ
ンバー２０８に引き出され、粉体が堆積する。反応の所
要時間はｌＯ〜１００分程度でよい。ＺｎＯの粉体の粒
径は作成条件により制御することが可能であり、マイク
ロ波投入パワー、チャンバー内圧、ガス流量を選ぶこと
により所望の粒径の粉体が得られる。すなわち内圧を上
げるかあるいはＰｗを下げると、粒径はより小さくなり
内圧を下げるかあるいはＰｗを上げるとより大きくなる
。Plasma is generated in the cavity resonator 206, and powder generated by a gas phase reaction is drawn into the chamber 208 via the punching metal 207, where the powder is deposited. The time required for the reaction may be about 10 to 100 minutes. The particle size of the ZnO powder can be controlled by the production conditions, and powder with a desired particle size can be obtained by selecting the microwave input power, chamber internal pressure, and gas flow rate. That is, if the internal pressure is increased or Pw is decreased, the particle size becomes smaller, and if the internal pressure is decreased or Pw is increased, the particle size becomes larger.
このようにして得たＺｎＯの粉体粒径は電子顕微鏡にて
観察し測定することができる０次に例として、作製条件
を様々に変えて平均粒径、２０．５０゜１００２００、
５００．１０００．２０００オングストロームの粉体を
作製し、これらを用いて得られた膜特性の一例について
説明する。ここで、平均粒径とは、光学顕微鏡や走査電
顕などによる観察において求められるものである。The particle size of the ZnO powder thus obtained can be observed and measured using an electron microscope.As an example, the average particle size is 20.50°, 100200°, 20.50°, 100200°,
Powders of 500, 1,000, and 2,000 angstroms were prepared, and an example of film characteristics obtained using these powders will be described. Here, the average particle size is determined by observation using an optical microscope, a scanning electron microscope, or the like.
それぞれについてＺｎＯ粉体通常１０〜１００ｇ程度、
本例では５０ｇに対しバインダーとして、ニトロセルロ
ースＩｇと溶剤としてカルピトールアセテートｌｏｇと
を加えて充分に混練しペーストを作製する。混線手段は
公知のものでよい。For each, ZnO powder is usually about 10 to 100 g,
In this example, nitrocellulose Ig as a binder and carpitol acetate log as a solvent are added to 50 g and sufficiently kneaded to prepare a paste. The crosstalk means may be of any known type.
その後コーニング社製＃７０５９ガラス基板上に、４０
０メツシユのスクリーンを用いて印刷を行ない電気炉で
、４５０℃に加熱焼成を行う。スクリーンのメツシュは
通常１００〜３００メツシユ程度でよい、焼成温度は、
バインダー及び溶剤として用いられる有機物が完全に気
化し、なおかつＺｎＯ粉体が焼結可能な温度であり基板
が充分耐えられる温度であり、通常５００〜８００℃程
度でよい。１例として、この時どの粉体な用いたサンプ
ルも成膜後の膜厚は５０００オングストロームになるよ
うにし、得られたサンプルを可視分光器を用いて可視領
域の光に対する透過性を測定した粒径の変化に対する光
の透過率を測定した。この結果の１例を第３図に示す、
第３図に結果を示したようにＺｎＯの粒径が１０００オ
ングストローム以下になると波長７００ｎａ＋の長波長
の光に対する透過率は低下しさらに２００オングストロ
ーム以下では透過率がさらに下がり、５０オングストロ
ーム以下では著しく透過率が低下することがわかる。Then, 40
Printing is carried out using a 0 mesh screen and then heated and fired at 450°C in an electric furnace. The mesh size of the screen is usually about 100 to 300 meshes, and the firing temperature is
The temperature is such that the organic substances used as the binder and solvent are completely vaporized, the ZnO powder can be sintered, and the substrate can withstand the temperature sufficiently, and the temperature is usually about 500 to 800°C. As an example, any powder sample used at this time was made to have a film thickness of 5000 angstroms after being formed, and the obtained sample was used as a particle whose transmittance to light in the visible region was measured using a visible spectrometer. The light transmittance with respect to the change in diameter was measured. An example of this result is shown in Figure 3.
As shown in Figure 3, when the particle size of ZnO is less than 1000 angstroms, the transmittance for long wavelength light of 700 na+ decreases, and when the particle size is less than 200 angstroms, the transmittance decreases further, and when the particle size is less than 50 angstroms, the transmittance decreases significantly. It can be seen that the rate decreases.
次に以下のようにして薄膜太陽電池を作製し評価を行な
った１例を示す、第１図に示す構成の薄膜太陽電池を公
知技術に従って作成した。まず、厚み５００μｍのステ
ンレススチール基板ｌｏｔを１０ｃｍＸ １０ｃｍの寸
法に切断して表面をアルミナの研磨剤を用いて研磨し表
面粗さＲａを５００オングストロームとした０次に、前
記の方法により得られた平均粒径２０オングストローム
のＺｎＯ粉体を原料にして作製したペーストを前記基板
上にスクリーン印刷法により印刷した。その後電気炉に
て４５０℃の温度で３時間加熱し、Ｚｎ０層１０２を形
成した０次にこの基板を第５図に示す構成を有する成膜
装置の成膜室５０１内の基板ホルダー５０２上に設置し
た。排気ポンプ５０６で成膜室５０１内を到達真空度１
０−’Ｔｏｒｒまで真空排気した。その後基板ホルダー
５０２を基板ヒーター５２２によって、２５０℃に加熱
した。ガスボン’Ｃ５１１に充填されているＳｉＨ４ガ
スをマスフローコントローラー５１５によって２ ｓｃ
ｃｍの流量に制御し、ガスボンベ５１３に充填されてい
る、■２ガスで１％に希釈されたＰＨ，ガスをマスフロ
ーコントローラー５１７によって２ ｓｅｃｍの流量に
制御してガス導入管５】９を介して成膜室５０】内に導
入した。Next, a thin-film solar cell having the configuration shown in FIG. 1, which is an example of a thin-film solar cell fabricated and evaluated as follows, was fabricated according to a known technique. First, a stainless steel substrate lot with a thickness of 500 μm was cut into a size of 10 cm x 10 cm, and the surface was polished using an alumina polishing agent to obtain a surface roughness Ra of 500 angstroms. Next, the average obtained by the above method was A paste prepared using ZnO powder with a particle size of 20 angstroms as a raw material was printed on the substrate by screen printing. Thereafter, the substrate was heated at a temperature of 450° C. for 3 hours in an electric furnace to form a Zn0 layer 102. Next, this substrate was placed on a substrate holder 502 in a film forming chamber 501 of a film forming apparatus having the configuration shown in FIG. installed. The exhaust pump 506 reaches a vacuum level of 1 in the film forming chamber 501.
The vacuum was evacuated to 0-'Torr. Thereafter, the substrate holder 502 was heated to 250° C. by the substrate heater 522. The SiH4 gas filled in the gas cylinder 'C511 is pumped by the mass flow controller 515 for 2 sc.
The PH gas diluted to 1% with 2 gases, which is filled in the gas cylinder 513, is controlled at a flow rate of 2 secm by the mass flow controller 517 and passed through the gas inlet pipe 5]9. was introduced into the film forming chamber 50].
その後内圧を０．７Ｔｏｒｒに保ち、ガスの流れと内圧
が安定した後、不図示のマツチング回路によって反射パ
ワーを極力少なくしてＲＦ電源５０８によりパワーを２
Ｗ投入した。この状態で３分間の成膜を行ない０層１０
３を形成した。その後放電を止めガスの供給も止めて成
膜室５０１内を真空度１０−’Ｔｏｒｒまで真空排気し
た。基板を不図示の搬送手段を用いて基板ホルダー５０
３に移動した。After that, the internal pressure is maintained at 0.7 Torr, and after the gas flow and internal pressure are stabilized, the reflected power is minimized by a matching circuit (not shown), and the power is increased to 2 by the RF power source 508.
I put in a W. In this state, film formation was performed for 3 minutes to form a layer of 0 and 10 layers.
3 was formed. Thereafter, the discharge was stopped, the gas supply was also stopped, and the inside of the film forming chamber 501 was evacuated to a vacuum degree of 10-' Torr. The substrate is transferred to the substrate holder 50 using a transport means (not shown).
Moved to 3.
基板ヒーター５２３によって、基板温度を２５０℃とし
た後、ガスボンベ５１１に充填されている５ｊＨ４ガス
をマスフローコントローラー５１５によって３５ｃｃｖ
ａの流量に制御し、ガスボンベ５１２に充填されている
Ｈ３ガスをマスフローコントローラー５１６によって３
０ ｓｅｃｍの流量に制御してガス導入管５２０を介し
て成膜室５０２内に導入した。その後内圧を０．４Ｔｏ
ｒｒに保ち、ガスの流れと内圧が安定した後、不図示の
マツチング回路によって反射パワーを極力少なくしてＲ
Ｆ電源５０９によりパワーを５Ｗ投入した。この状態で
６０分間の成膜を行ないｉ Ｊｉｉ ｌ ０４を形成し
た。After the substrate temperature is set to 250° C. by the substrate heater 523, the 5jH4 gas filled in the gas cylinder 511 is heated to 35 ccv by the mass flow controller 515.
The H3 gas filled in the gas cylinder 512 is controlled to a flow rate of 3 by the mass flow controller 516.
The gas was introduced into the film forming chamber 502 through the gas introduction pipe 520 while controlling the flow rate to be 0 seconds. After that, increase the internal pressure to 0.4To
rr, and after the gas flow and internal pressure are stabilized, a matching circuit (not shown) is used to reduce the reflected power as much as possible.
Power was applied at 5W using the F power supply 509. In this state, film formation was performed for 60 minutes to form iJiiI04.
その後放電を止めガスの供給も止めて成膜室５０３内を
真空度１０−’Ｔｏｒｒまで真空排気した。基板を不図
示の搬送手段を用いて基板ホルダー５０４に移動した。Thereafter, the discharge was stopped, the gas supply was also stopped, and the inside of the film forming chamber 503 was evacuated to a vacuum level of 10-' Torr. The substrate was moved to the substrate holder 504 using a transport means (not shown).
前述と同様にして基板ホルダー５０４を基板ヒーター５
２４によって、２５０℃に加熱した。ガスボンベ５１１
に充填されているＳｉＨ４ガスをマスフローコントロー
ラー５１５によって２ ｓｅｃｍの流量に制御し、ガス
ボンベ５１４に充填されているＨ２ガスで２％に希釈さ
れたＢＪａガスをマスフローコントローラー５１８によ
って３ ｓｅｃｍの流量に制御してガス導入管５２１を
介して成膜室５０１内に導入した。その後内圧を０．５
Ｔｏｒｒに保ち、ガスの流れと内圧が安定した後、不図
示のマツチング回路によって反射パワーを極力少なくし
てＲＦ電源５１０によりパワーを５ｗ投入した。この状
態で１分間の成膜を行ない９層１０５を形成した。The substrate holder 504 is attached to the substrate heater 5 in the same manner as described above.
24 to 250°C. gas cylinder 511
The SiH4 gas filled in the gas cylinder 514 is controlled at a flow rate of 2 sec by a mass flow controller 515, and the BJa gas diluted to 2% with H2 gas filled in a gas cylinder 514 is controlled at a flow rate of 3 sec by a mass flow controller 518. The gas was introduced into the film forming chamber 501 via the gas introduction pipe 521. Then reduce the internal pressure to 0.5
Torr was maintained, and after the gas flow and internal pressure were stabilized, a matching circuit (not shown) was used to reduce the reflected power as much as possible, and 5 W of power was applied from the RF power source 510. In this state, film formation was performed for 1 minute to form nine layers 105.
その後放電を止めガスの供給も止めて成膜室５０１内を
真空度１０−’Ｔｏｒｒまで真空排気した。基板を室温
になるまで放置したのち成膜室５０１から取り出した０
次に不図示のスパッタリング装置内に基板をセットし、
中心間の距離が１ｃｍで格子状に配置される有効面積が
１ ｃｍ”の円形のサブセルを形成するためのマスクを
９層１０５の上に設置した後、スパッタリング装置内を
真空度１Ｏ−７Ｔｏｒｒまで真空排気した。その後スパ
ッタリング装置内を２ Ｘ １０−’ｔＴｏｒｒとなる
ようにＡｒガスを流しＩＴＯのターゲットを５０Ｗのパ
ワーでＤＣスパッタリングを行ないＩＴＯの透明導電層
１０Ｅ１作製した。Thereafter, the discharge was stopped, the gas supply was also stopped, and the inside of the film forming chamber 501 was evacuated to a vacuum degree of 10-' Torr. After the substrate was left to reach room temperature, it was taken out from the film forming chamber 501.
Next, set the substrate in a sputtering device (not shown),
After installing a mask on the nine layers 105 to form circular subcells with a center-to-center distance of 1 cm and an effective area of 1 cm" arranged in a lattice pattern, the inside of the sputtering apparatus was heated to a vacuum level of 10-7 Torr. The sputtering apparatus was evacuated. Ar gas was then flowed through the sputtering apparatus at a pressure of 2.times.10-'tTorr, and an ITO target was subjected to DC sputtering with a power of 50 W to produce a transparent conductive layer 10E1 of ITO.
さらに不図示のＥＢの蒸着装置を用い前記基板上にＣｒ
５００オングストロームとＡｇ１０００オングストロー
ムとの積層したグリッド状電極１０７を設けた。Further, using an EB vapor deposition apparatus (not shown), Cr was deposited on the substrate.
A laminated grid-like electrode 107 of 500 angstroms and 1000 angstroms of Ag was provided.
以上のようにして作製した薄膜太陽電池の透明導電層１
０６側を受光面にしテＡＭ−１光（１００ｍＷ／ｃｍ”
ｌを照射しながら金属基板ｌｏｔと金属電極１０７の間
に電圧を印可し一〇、 ５Ｖｏｌｔから＋１．０Ｖｏｌ
ｔの範囲で掃引して電圧電流特性を測定した。Transparent conductive layer 1 of thin film solar cell produced as above
AM-1 light (100mW/cm") with the 06 side as the light receiving surface.
Apply a voltage between the metal substrate lot and the metal electrode 107 while irradiating the voltage 10, from 5 Volt to +1.0 Vol.
The voltage-current characteristics were measured by sweeping over a range of t.
印可電圧Ｏ近傍における電圧電流曲線の傾きから並列抵
抗を算出した。この並列抵抗はリーク電流に対する抵抗
を示すものであり並列抵抗値は＋０３Ω／ａｍ”以上あ
ることが望ましい。次に、上記と同様にしてＺｎＯの粉
体の平均粒径を、５０゜１００、２００．５００．１０
００．２０００オングストロームと変えて作製したペー
ストを使って薄膜太陽電池を作製し各々のサンプル並列
抵抗値を前記した方法と同様にして評価した。この結果
の１例を第４図に示す。図により粒径が５０オングスト
ロ一ム以上になると並列抵抗値（シイント抵抗値）が小
さくなり、ＺｎＯ層の電流リークに対するバリヤー性が
不十分となることがわかる。さらに２００オングストロ
ーム以上になるとシャント抵抗は小さくなり、１０００
オングストロームより大きくなるとシャント抵抗は著し
く小さくなることがわかる。The parallel resistance was calculated from the slope of the voltage-current curve near the applied voltage O. This parallel resistance indicates the resistance to leakage current, and it is desirable that the parallel resistance value is +03Ω/am or more.Next, in the same way as above, the average particle size of the ZnO powder was .500.10
Thin film solar cells were manufactured using pastes prepared with a thickness of 0.00.2000 angstroms, and the parallel resistance values of each sample were evaluated in the same manner as described above. An example of this result is shown in FIG. The figure shows that when the grain size is 50 angstroms or more, the parallel resistance value (shint resistance value) becomes small, and the barrier property of the ZnO layer against current leakage becomes insufficient. Furthermore, when the thickness exceeds 200 angstroms, the shunt resistance becomes smaller, and
It can be seen that the shunt resistance becomes significantly smaller when the diameter becomes larger than angstrom.
第３図と第４図に示した例からも判るように、スクリー
ン印刷に用いるためのＺｎＯの粉体の平均粒径は、５０
オングストロームからｔｏｏｏオングストロームまでが
好適であり、より好適には２００から５００オングスト
ロームが望ましい。As can be seen from the examples shown in Figures 3 and 4, the average particle size of ZnO powder used for screen printing is 50
A range of angstroms to too angstroms is preferred, and a range of 200 to 500 angstroms is more preferred.
尚、上述ｎ層、ｉ層、ｐ層、透明導電層、金属電極等の
作製手段は公知技術に基づいて行なうことができ、前記
、記載の工程に限定されるものではない。The means for producing the above-mentioned n-layer, i-layer, p-layer, transparent conductive layer, metal electrode, etc. can be performed based on known techniques, and are not limited to the steps described above.
［実施例］
以下に本発明による薄膜太陽電池の作製方法について実
施例を用いて具体的に説明を行なうが、本発、明は、以
下の実施例によって発明の内容が、限定されるものでは
ない。[Example] The method for producing a thin film solar cell according to the present invention will be specifically explained below using Examples, but the content of the present invention is not limited to the following Examples. do not have.
実施例１
長尺のシート状基板に、第１図に示した層構成と同様の
薄膜太陽電池を前項に述べた方法、条件とほぼ同様にし
て以下のようにして作製した。Example 1 A thin film solar cell having the same layer structure as shown in FIG. 1 was fabricated on a long sheet-like substrate using the method and conditions described in the previous section as follows.
厚み２００μｍ、幅３０ｃｍ、長さ１００ｍのステンレ
ス基板ｌｏｔ上に前述の方法で得られた平均粒径３００
μｍのＺｎＯ粉体な原料にして作製したペーストをドク
ターブレード法でコーティングし、その後トンネル炉内
で４００℃で加熱焼成して酸化物半導体層１０２を形成
した１層厚はｎｍであった。The average particle size of 300 particles obtained by the above method was placed on a stainless steel substrate lot with a thickness of 200 μm, a width of 30 cm, and a length of 100 m.
The oxide semiconductor layer 102 was formed by coating a paste prepared using μm-sized ZnO powder raw material by a doctor blade method and then heating and baking it in a tunnel furnace at 400° C. The thickness of one layer was nm.
次に第７図に示した連続生産用成膜装置の成膜炉７０１
内に基板７０５をロール状に巻いて設置し、ｎ層形成用
電極７０２．１層形成用電極７０３．９層形成用電極７
０４の中を連続的に搬送しながら、ｎ１ｉ１０３．１層
１０４．９層１０５、の順番で成膜を行ない成膜終了後
の基板７０６もロール状に巻き取った。各層厚はそれぞ
れ１００．３０００．１００人であった。Next, a film forming furnace 701 of a continuous production film forming apparatus shown in FIG.
A substrate 705 is wound into a roll and installed inside, and an electrode for forming an n layer 702, an electrode for forming a first layer 703, an electrode for forming a ninth layer 7
While continuously conveying the substrate 706 through the substrate 04, film formation was performed in the order of n1i103.1 layer 104.9 layer 105, and the substrate 706 after the film formation was also wound up into a roll. The thickness of each layer was 100.3000.100 people.
成膜終了後成膜室から基板を取り出し１０ｃｍ角に切断
した。次に前述した方法と同様に不図示のスパッタリン
グ装置内に基板をセットし、中心間の距離が１ｃｍで格
子状に配置される有効面積が１ ｃｍ”の円形のサブセ
ルを形成するためのマスクをｐｌｉ１０５の上に設置し
た後、ＩＴＯのターゲットでＤＣスパッタリングを行な
いＩＴＯの透明導電層１０６、層厚７００人を作製した
。さらに不図示のＥＢＢ着装置によりＣｒとＡｇとの積
層した電極１０７を設けた。以上のようにして作製した
薄膜太陽電池の透明導電層１０６側を受光面にしてＡＭ
−１光（１００ｍＷ／ｃｍ”）を照射して各サブセルの
電流電圧特性を測定したところ光電変換効率は７．２±
１．５％であった。また並列抵抗値を算出したところ２
．５±０．２ＸｌＯ”０７ｃｍ”であった。After the film formation was completed, the substrate was taken out from the film formation chamber and cut into 10 cm square pieces. Next, in the same way as in the method described above, the substrate was set in a sputtering device (not shown), and a mask was applied to form circular subcells with an effective area of 1 cm'' arranged in a grid pattern with a distance of 1 cm between centers. After installing it on the pli 105, DC sputtering was performed using an ITO target to produce an ITO transparent conductive layer 106 with a layer thickness of 700.Furthermore, an electrode 107 made of a layer of Cr and Ag was provided using an EBB deposition device (not shown). AM
-1 light (100mW/cm") and measured the current-voltage characteristics of each subcell, the photoelectric conversion efficiency was 7.2±
It was 1.5%. Also, when I calculated the parallel resistance value, it was 2
．． It was 5±0.2XlO"07cm".
この結果本発明の方法により、光電変換能力が良く、電
流のリークも少ない良好な特性の薄膜太陽電池が作製で
きることがわかった。As a result, it was found that by the method of the present invention, a thin film solar cell with good photoelectric conversion ability and good characteristics with little current leakage could be produced.
実施例２
次に第６図に示す層構成の薄膜太陽電池を以下のように
して作製した。厚み５００μｍ、幅１０ｃｍ、長さｌｏ
ｃｍの寸法のステンレス基板６０１に不図示のＤＣスパ
ッタリング装置によりＡｇ層６０２を１０００オングス
トローム堆積した。該Ａｇ層６０２は光の反射を効率的
に行なうための反射層の機能を有している。この土に実
施例１と同様に粒径３００オングストロームのＺｎＯ粉
体を原料にして作製したペーストによって酸化物半導体
層６０３を形成（５０００人）した後、１層６０４．１
層６０５．９層６０６の順番で作製した。Example 2 Next, a thin film solar cell having the layer structure shown in FIG. 6 was produced as follows. Thickness 500μm, width 10cm, length lo
An Ag layer 602 having a thickness of 1000 angstroms was deposited on a stainless steel substrate 601 having a size of cm by a DC sputtering device (not shown). The Ag layer 602 has the function of a reflective layer for efficiently reflecting light. On this soil, an oxide semiconductor layer 603 was formed (by 5000 people) using a paste made from ZnO powder with a particle size of 300 angstroms as a raw material in the same manner as in Example 1, and then one layer 604.1
Layers 605.9 and 606 were fabricated in this order.
次に実施例１と同様ので不図示のスパッタリング装置内
に基板セットし、中心間の距離が１ｃｍで格子状に配置
される有効面積が１ ｃｍ”の円形のサブセルを形成す
るためのマスクを９層６０６の上に設置した後、ＩＴＯ
のターゲットでＤＣスパッタリングを行ないＩＴＯの透
明導電層６０７を作製した。さらに不図示のＥＢ蒸蒸製
装置よりＣ「とＡｇとの積層した電極６０８を設けた。Next, the substrate was set in a sputtering apparatus (not shown) similar to that in Example 1, and a mask was applied to form circular subcells with an effective area of 1 cm" arranged in a grid pattern with a distance of 1 cm between centers. After being placed on top of layer 606, the ITO
A transparent conductive layer 607 of ITO was fabricated by performing DC sputtering using the target. Furthermore, an electrode 608 made of a layer of C and Ag was provided using an EB evaporation device (not shown).
以上のようにして作製した薄膜太陽電池の透明導電層６
０７側を受光面にしてＡＭ−１光（ｌθＯｍＷ／ｃｍ”
）を照射して各サブセルの電流電圧特性を測定したとこ
ろ光電変換効率は８．４±１．２％であった。また並列
抵抗を算出したところ３．１±０．４×１０”０７ｃｍ
２であった。Transparent conductive layer 6 of thin film solar cell produced as above
AM-1 light (lθOmW/cm”
) and measured the current-voltage characteristics of each subcell, the photoelectric conversion efficiency was 8.4±1.2%. Also, the parallel resistance was calculated as 3.1±0.4×10”07cm
It was 2.
この結果本発明の方法により、光電変換能力に優れ、電
流のリークも少ない良好な特性の薄膜太陽電池が作製で
きることがわかった。As a result, it was found that by the method of the present invention, a thin film solar cell with excellent photoelectric conversion ability and good characteristics with little current leakage could be produced.
実施例３
次に第８図に示す層構成の薄膜太陽電池を以下のように
して作製した。厚み８００μｍ、幅１０ Ｃ１１１％長
さ１０ｃｍのコーニング社製＃７０５９ガラス基板８０
１上に不図示のＥＢ蒸着装置を用い、Ｃ「とＡｇとの積
層したグリッド電極８０２を設けた。その後、粒径３０
０人のＺｎＯ粉体を原料にして作製したペースト Ｚｎ
Ｏをスクリーン印刷法で印刷して電気炉で４００℃にて
加熱焼成し酸化物半導体層８０３ （１０００人厚）金
形成した。Example 3 Next, a thin film solar cell having the layer structure shown in FIG. 8 was produced as follows. Corning #7059 glass substrate 80 with thickness 800μm, width 10C111% and length 10cm
1, a grid electrode 802 in which C and Ag were laminated was provided using an EB evaporation device (not shown).
Zn paste made from 0 people's ZnO powder as raw material
O was printed using a screen printing method and fired at 400° C. in an electric furnace to form an oxide semiconductor layer 803 (1000 layers thick) of gold.
次に第５図に示した成膜類を用いて実施例１と同様に、
１層８０４．１層８０５．９層８０６、の順番で作製し
た０次に実施例１と同様にで不図示のスパッタリング装
置内に基板セットし、中心間の距離が１ｃａ＋で格子状
に配置される有効面積がｌ ｃａｂ”の円形のサブセル
を形成するためのマスクを９層８０６の上に設置した後
、ＩＴＯのターゲットでＤＣスパッタリングを行ないＩ
ＴＯの透明導電層８０７を作製した。さらに不図示のＥ
Ｂ蒸着装置によりＣｒとＡｇとの積層した電極８０８を
設けた。Next, in the same manner as in Example 1 using the film forming method shown in FIG.
1 layer 804, 1 layer 805, and 9 layers 806 were fabricated in the following order: Next, the substrates were set in a sputtering apparatus (not shown) in the same manner as in Example 1, and the substrates were arranged in a grid pattern with a center-to-center distance of 1 ca+. After placing a mask on the 9-layer 806 to form a circular subcell with an effective area of l cab'', DC sputtering is performed using an ITO target.
A transparent conductive layer 807 of TO was produced. Furthermore, E (not shown)
A laminated electrode 808 of Cr and Ag was provided using a B evaporation device.
以上のようにして作製した薄膜太陽電池の透明導電層８
０７側を受光面にして＾Ｍ−１光（１００ｍＷ／ｃｍ、
）を照射して各サブセルの電流電圧特性を測定したとこ
ろ光電変換効率は７．５±１．６％であった。また並列
抵抗を算出したところ１．３±ｏ、８×１０３Ω／ｃｍ
”であった。Transparent conductive layer 8 of the thin film solar cell produced as above
^M-1 light (100mW/cm,
) and measured the current-voltage characteristics of each subcell, the photoelectric conversion efficiency was 7.5±1.6%. Also, the parallel resistance was calculated as 1.3±o, 8×103Ω/cm
"Met.
この結果本発明の方法により、光電変換能力に優れ、電
流のリークも少ない良好な特性の薄膜太陽電池が作製で
きることがわかった。As a result, it was found that by the method of the present invention, a thin film solar cell with excellent photoelectric conversion ability and good characteristics with little current leakage could be produced.
比較例１
次に、従来例として、第１図に示す層構成の薄膜太陽電
池を以下のようにして作製した。厚み８００μｍ、幅１
０ｃｍ、長さ１０ｃｍのステンレス製基板上に、ＺｎＯ
をターゲットとして不図示のＤＣスパッタリング装置に
よりＺｎＯ膜（５０００人厚）金形製した。さらに、実
施例１と同様な方法及び条件でｎ層１０３、ｉ ＮＩ
Ｏ４，９層１０５、の順番で成膜を行ない成膜終了後、
成膜室から基板を取り出し、実施例１と同様に不図示の
スパッタリング装置内に基板をセットし、中心間の距離
が１ｃｍで格子状に配置される有効面積がｌｃｎ＋１の
円形のサブセルを形成するためのマスクをｐ！１０５の
上に設置した後、ＩＴＤのターゲットでＤＣスパッタリ
ングを行ないＩＴＯの透明導電層ｌＯ６を作製した。さ
らに不図示のＥＢ蒸着装置によりＣ「とＡｇとの積層し
た電極１０７を設けた。Comparative Example 1 Next, as a conventional example, a thin film solar cell having the layer structure shown in FIG. 1 was manufactured as follows. Thickness 800μm, width 1
ZnO was deposited on a stainless steel substrate with a diameter of 0 cm and a length of 10 cm.
A ZnO film (5000 mm thick) was molded using a DC sputtering device (not shown) using the target as a target. Furthermore, the n layer 103, i NI
Films are formed in the order of O4 and 9 layers 105, and after the film formation is completed,
The substrate is taken out from the film forming chamber, and as in Example 1, the substrate is set in a sputtering device (not shown) to form circular subcells with an effective area of lcn+1 arranged in a grid pattern with a center-to-center distance of 1 cm. P for the mask! 105, DC sputtering was performed using an ITD target to produce an ITO transparent conductive layer lO6. Furthermore, an electrode 107 in which C' and Ag were laminated was provided using an EB evaporation apparatus (not shown).
以上のようにして作製した薄膜太陽電池の透明導電層１
０６側を受光面にしてＡＭ−１光（１００ｍＷ／ｃｍ”
）を照射して各サブセルの電流電圧特性を測定したとこ
ろ光電変換効率は７．１±１．４％であった。また並列
抵抗を算出したところ３．５±０．６×１０３Ω／Ｃが
であった。Transparent conductive layer 1 of thin film solar cell produced as above
AM-1 light (100mW/cm") with the 06 side as the light receiving surface.
) and measured the current-voltage characteristics of each subcell, the photoelectric conversion efficiency was 7.1±1.4%. Further, when the parallel resistance was calculated, it was 3.5±0.6×10 3 Ω/C.
この結果本発明の方法を用いて、実施例１から３で作製
した薄膜太陽電池はバッチ式である本比較例（従来例）
と比較して遜色ないことがわかり、本発明の方法によっ
て大面積にわたって安定した、均一な特性の薄膜太陽電
池が連続的に作製できることがわかった。As a result, using the method of the present invention, the thin film solar cells produced in Examples 1 to 3 are of the batch type in this comparative example (conventional example).
It was found that thin film solar cells with stable and uniform characteristics can be continuously produced over a large area by the method of the present invention.
［発明の効果〕
以上に説明したように、基板上に酸化物半導体層、光起
電力発生層、透明導電層及び金属電極の順番で形成され
る薄膜太陽電池に於て、前記酸化物半導体層の作製方法
が、塗布法であり、さらに該塗布法に用いる塗布材の原
料が、ＺｎＯの粉体であって、又該ＺｎＯの粉体が、５
０オングストロ一ム以上１０００オングストローム以下
でありより好適には、２００オングストロ一ム以上５０
０オングストローム以下とすることにより、大面積にわ
たって安定した特性の酸化物半導体層が得られ、該酸化
物半導体薄膜を用いて作製された薄膜太陽電池は、光電
変換効率が高く電流のリークの少ない安定した特性とな
る。[Effects of the Invention] As explained above, in a thin film solar cell in which an oxide semiconductor layer, a photovoltaic generation layer, a transparent conductive layer, and a metal electrode are formed on a substrate in this order, the oxide semiconductor layer The manufacturing method is a coating method, and the raw material of the coating material used in the coating method is ZnO powder, and the ZnO powder is
0 angstrom or more and 1000 angstrom or less, more preferably 200 angstrom or more and 50 angstrom
By setting the thickness to 0 angstrom or less, an oxide semiconductor layer with stable characteristics over a large area can be obtained, and a thin film solar cell produced using the oxide semiconductor thin film has a stable structure with high photoelectric conversion efficiency and low current leakage. It has the following characteristics.
又、本発明に係る酸化物半導体膜を均一に、かつ高速で
連続的に作製する方法は、太陽電池に限らず、光センサ
−、表示素子等における透明導電膜等の機能性堆積膜の
作製に好適に適用することのできる実用上非常に有用な
ものである。Furthermore, the method for manufacturing an oxide semiconductor film uniformly and continuously at high speed according to the present invention is applicable not only to solar cells but also to the manufacturing of functional deposited films such as transparent conductive films in optical sensors, display elements, etc. It is practically very useful and can be suitably applied to.
第１図は、本発明を実施するに好適な薄膜太陽電池の素
子構成を表わす構成図、第２図は、本発明のＺｎＯ膜を
作製するための原料となるＺｎＯの粉体な作製するため
のマイクロ波プラズマ反応装置の１例を示す構成図、第
３図は本発明で使用されるＺｎＯ粉体の粒径と該粉体を
用いて作製したＺｎＯ膜の光透過性との関係の１例を表
わす図、第４図は本発明で使用されるＺｎＯ粉体の粒径
と該粉体を用いて作製した薄膜太陽電池の並列抵抗（シ
ャント抵抗）との関係の１例を表わす図、第５図は薄膜
太陽電池の起電力発生層を連続で作製するための成膜装
置の構成図、第６図は実施例２で得られた本発明の薄膜
太陽電池作製方法を適用するに好適な第２の素子構成の
薄膜太陽電池の模式図、第７図は、第６図の薄膜太陽電
池の光起電力発生層を連続で作製するのに好適な成膜装
置の構成図、第８図は実施例３で得られた本発明の薄膜
太陽電池作製方法を適用するのに好適な第３の素子構成
の薄膜太陽電池の模式図を示す。
１０１・・・基板 １０２・・・酸化物半導体層１
０３・・・０層 １０４・・・１層１０５・・・ｐ
Ｈ１０６・・・透明導電層１０７・・・金属を極
２０１・・・マイクロ波発振器
２０２・・・導波管
２０３・・・パワーモニター
２０４・・・整合器 ２０５−・・マイクロ波投入窓
２０６・・・空洞共振器
２０７・・・開孔板 ２０８・・・成膜室２０９・・
・排気ポンプ
２１０・・・圧力コントローラー
２１１・・・原料ガスバブリング装置
２１２・・・酸素ガスボンベ
２１３．２１４・・・マスフローコントローラー２１５
、２１６・・・ガス供給管
５０１・・・成膜室
５０２、５０３．５０４・・・電極
５０５・・・圧力コントローラー
５０６・・・排気ポンプ
５０８、５０９．５１０・・・高周波電源５１１、５１
２．５１３．５１４・・・ガスボンベ５１５．５１６，
５１７，５１８−・・マスフローコントローラー５１９
、５２０．５２１・・・ガス供給バイブロ０１・・・基
板 ６０２・・・Ａｇ層６０３・・・酸化物半導体
層
６０４・・・０層 ６０５・・・１層６０６・・・
９層 ６０７・・・透明導電層６０８・・・金属電
極
７０１・・・成膜室
７０２、７０３．７０４・・・電極
７０５、７０６・・・基板
７０７、７０８．７０９・・・基板ヒーター８０１・・
・ガラス基板
８０２・・・金属電極
８０３・・・酸化物半導体層
８０４・・・０層 ８０５・・・１層８０６・・・
９層 ８０７・・・透明導電層８０８・・・金属電
極FIG. 1 is a block diagram showing the element configuration of a thin film solar cell suitable for carrying out the present invention, and FIG. 2 is a diagram showing the structure of a ZnO powder used as a raw material for producing the ZnO film of the present invention. FIG. 3 is a block diagram showing an example of a microwave plasma reactor according to the present invention, and FIG. FIG. 4 is a diagram showing an example of the relationship between the particle size of the ZnO powder used in the present invention and the parallel resistance (shunt resistance) of a thin film solar cell manufactured using the powder, Fig. 5 is a block diagram of a film forming apparatus for continuously producing the electromotive force generating layer of a thin film solar cell, and Fig. 6 is a diagram suitable for applying the method for producing a thin film solar cell of the present invention obtained in Example 2. FIG. 7 is a schematic diagram of a thin film solar cell having the second element configuration, and FIG. The figure shows a schematic diagram of a thin film solar cell obtained in Example 3 and having a third element configuration suitable for applying the thin film solar cell manufacturing method of the present invention. 101...Substrate 102...Oxide semiconductor layer 1
03...0 layer 104...1 layer 105...p
H106...Transparent conductive layer 107...Metal pole 201...Microwave oscillator 202...Waveguide 203...Power monitor 204...Matching device 205-...Microwave input window 206... ...Cavity resonator 207...Perforated plate 208...Deposition chamber 209...
- Exhaust pump 210...Pressure controller 211...Raw material gas bubbling device 212...Oxygen gas cylinder 213.214...Mass flow controller 215
, 216... Gas supply pipe 501... Film forming chamber 502, 503.504... Electrode 505... Pressure controller 506... Exhaust pump 508, 509.510... High frequency power source 511, 51
2.513.514...Gas cylinder 515.516,
517,518--Mass flow controller 519
, 520.521...Gas supply vibro 01...Substrate 602...Ag layer 603...Oxide semiconductor layer 604...0 layer 605...1 layer 606...
9 layers 607...Transparent conductive layer 608...Metal electrode 701...Film forming chamber 702, 703.704...Electrode 705, 706...Substrate 707, 708.709...Substrate heater 801.・
-Glass substrate 802...Metal electrode 803...Oxide semiconductor layer 804...0 layer 805...1 layer 806...
9 layers 807...Transparent conductive layer 808...Metal electrode
Claims (6)
力発生層、透明導電層及び金属電極をこの順に積層する
ことにより薄膜太陽電池を作製する方法であって、 酸化物半導体層を構成する原料粒子として平均粒径１０
００Å以下の金属酸化物粒子を用い、塗布法により前記
酸化物半導体層を形成することを特徴とする薄膜太陽電
池作製方法。(1) A method for manufacturing a thin film solar cell by laminating at least an oxide semiconductor layer, a photovoltaic generation layer, a transparent conductive layer, and a metal electrode in this order on a substrate, the oxide semiconductor layer comprising: The average particle size of the raw material particles is 10
A method for producing a thin film solar cell, characterized in that the oxide semiconductor layer is formed by a coating method using metal oxide particles of 00 Å or less.
に記載の方法。(2) Claim 1, wherein the metal oxide particles are ZnO particles.
The method described in.
の範囲である請求項２に記載の方法。(3) The average particle diameter of the ZnO particles is 50 Å to 1000 Å
3. The method of claim 2, wherein:
請求項３に記載の方法。(4) The method according to claim 3, wherein the average particle size is in the range of 200 Å to 500 Å.
記載の方法。(5) The method according to claim 1, wherein the coating method is a screen printing method.
る気相反応により得られたものである請求項２に記載の
方法。(6) The method according to claim 2, wherein the ZnO particles are obtained by a gas phase reaction using microwave plasma treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020459A JP2726323B2 (en) | 1990-02-01 | 1990-02-01 | Thin-film solar cell fabrication method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020459A JP2726323B2 (en) | 1990-02-01 | 1990-02-01 | Thin-film solar cell fabrication method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03227576A true JPH03227576A (en) | 1991-10-08 |
| JP2726323B2 JP2726323B2 (en) | 1998-03-11 |
Family
ID=12027664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020459A Expired - Fee Related JP2726323B2 (en) | 1990-02-01 | 1990-02-01 | Thin-film solar cell fabrication method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2726323B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5149820A (en) * | 1987-03-11 | 1992-09-22 | Norsk Hydro A.S. | Deuterated compounds |
| WO2009035112A1 (en) * | 2007-09-12 | 2009-03-19 | Mitsubishi Materials Corporation | Composite membrane for super straight solar cell, process for producing the composite membrane for super straight solar cell, composite membrane for substraight solar cell, and process for producing the composite membrane for substraight solar cell |
| JP2016066826A (en) * | 2010-07-09 | 2016-04-28 | 鷹羽産業株式会社 | Panel, method of manufacturing panel, solar cell module, printing device, and printing method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5857756A (en) * | 1981-10-01 | 1983-04-06 | Agency Of Ind Science & Technol | Amorphous silicon solar battery |
| JPS61216489A (en) * | 1985-03-22 | 1986-09-26 | Agency Of Ind Science & Technol | Thin film solar battery |
| JPS6465270A (en) * | 1987-09-04 | 1989-03-10 | Matsushita Electric Ind Co Ltd | Production of sintered zinc oxide film |
-
1990
- 1990-02-01 JP JP2020459A patent/JP2726323B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5857756A (en) * | 1981-10-01 | 1983-04-06 | Agency Of Ind Science & Technol | Amorphous silicon solar battery |
| JPS61216489A (en) * | 1985-03-22 | 1986-09-26 | Agency Of Ind Science & Technol | Thin film solar battery |
| JPS6465270A (en) * | 1987-09-04 | 1989-03-10 | Matsushita Electric Ind Co Ltd | Production of sintered zinc oxide film |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5149820A (en) * | 1987-03-11 | 1992-09-22 | Norsk Hydro A.S. | Deuterated compounds |
| WO2009035112A1 (en) * | 2007-09-12 | 2009-03-19 | Mitsubishi Materials Corporation | Composite membrane for super straight solar cell, process for producing the composite membrane for super straight solar cell, composite membrane for substraight solar cell, and process for producing the composite membrane for substraight solar cell |
| US8921688B2 (en) | 2007-09-12 | 2014-12-30 | Mitsubishi Materials Corporation | Composite film for superstrate solar cell having conductive film and electroconductive reflective film formed by applying composition containing metal nanoparticles and comprising air pores of preset diameter in contact surface |
| JP2016066826A (en) * | 2010-07-09 | 2016-04-28 | 鷹羽産業株式会社 | Panel, method of manufacturing panel, solar cell module, printing device, and printing method |
| US9559241B2 (en) | 2010-07-09 | 2017-01-31 | Takanoha Trading Co., Ltd. | Panel, method for producing panel, solar cell module, printing apparatus, and printing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2726323B2 (en) | 1998-03-11 |
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