JPH0432268A - Continuous manufacture of large area solar cell substrate - Google Patents
Continuous manufacture of large area solar cell substrateInfo
- Publication number
- JPH0432268A JPH0432268A JP2140433A JP14043390A JPH0432268A JP H0432268 A JPH0432268 A JP H0432268A JP 2140433 A JP2140433 A JP 2140433A JP 14043390 A JP14043390 A JP 14043390A JP H0432268 A JPH0432268 A JP H0432268A
- Authority
- JP
- Japan
- Prior art keywords
- solar cell
- surface roughness
- strip member
- cell substrate
- semiconductor layer
- 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.)
- Pending
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 98
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 88
- 238000012545 processing Methods 0.000 claims abstract description 24
- 238000005259 measurement Methods 0.000 claims abstract description 12
- 230000003746 surface roughness Effects 0.000 abstract description 58
- 239000010409 thin film Substances 0.000 abstract description 27
- 238000004544 sputter deposition Methods 0.000 abstract description 20
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 238000005238 degreasing Methods 0.000 abstract 1
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 description 76
- 239000010408 film Substances 0.000 description 65
- 239000007789 gas Substances 0.000 description 54
- 229910052751 metal Inorganic materials 0.000 description 21
- 239000002184 metal Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 19
- 230000008569 process Effects 0.000 description 15
- 238000006073 displacement reaction Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000004804 winding Methods 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 229910021417 amorphous silicon Inorganic materials 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000010248 power generation Methods 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 238000007405 data analysis Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- -1 polyethylene terephthalate Polymers 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000004439 roughness measurement Methods 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000012777 electrically insulating material Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229920006015 heat resistant resin Polymers 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 229910052704 radon Inorganic materials 0.000 description 2
- 238000005546 reactive sputtering Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000009751 slip forming Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003079 width control Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910005542 GaSb Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910000673 Indium arsenide Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910007709 ZnTe Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000001017 electron-beam sputter deposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000003904 radioactive pollution Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 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
Landscapes
- Photovoltaic Devices (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の属する技術分野〕
本発明は、大面積の太陽電池基板を連続的に製造する方
法に関し、該太陽電池基板の表面粗さの均−性及び再限
性を簡単な方法で向上させることにより、該太陽電池基
板を用いて作製される太陽電池の量産化を低コストで実
現させ得るものである。Detailed Description of the Invention [Technical Field to which the Invention Pertains] The present invention relates to a method for continuously manufacturing large-area solar cell substrates, and to improving the uniformity and relimitation of the surface roughness of the solar cell substrates. By improving this by a simple method, mass production of solar cells made using the solar cell substrate can be realized at low cost.
太陽光を利用する太陽電池による発電方式は、放射能汚
染や地球温暖化等の問題を惹起することはなく、また、
太陽光は地球上至るところに降り注いでいるためエネル
ギー源の偏在が少なく、さらには、複雑な大型の設備を
必要とせず比較的高い発電効率が得られる等、今後の電
力需要の増大に対しても、環境破壊を引き起こすことな
く対応できるクリーンな発電方式として注目を集め、実
用化に向けて様々な研究開発がなされている。The power generation method using solar cells that uses sunlight does not cause problems such as radioactive pollution or global warming, and
Since sunlight shines all over the earth, energy sources are less unevenly distributed, and furthermore, relatively high power generation efficiency can be obtained without the need for large and complex equipment, making it possible to cope with future increases in electricity demand. It has also attracted attention as a clean power generation method that can be used without causing environmental destruction, and various research and development efforts are being carried out to put it into practical use.
太陽電池を用いる発電方式については、それを電力需要
を賄うものとして確立させるためには、使用する太陽電
池が、光電変換効率が充分に高く、特性安定性に優れた
ものであり、且つ大量生産し得るものであることが基本
的に要求される。In order to establish a power generation system using solar cells as a means of meeting electricity demand, it is necessary that the solar cells used have sufficiently high photoelectric conversion efficiency, excellent characteristic stability, and mass production. Basically, it is required that it be possible.
こうしたことから、容易に入手できるシラン等の気体状
の原料ガスを使用し、これをグロー放電分解して、ガラ
スや金属シート等の比較的安価な基板上にアモルファス
シリコン（以下、ａ−Ｓｉと記す）等の半導体薄膜を堆
積させることにより作製できる太陽電池が、量産性に冨
み、単結晶シリコン等を用いて作製される太陽電池に比
較して低コストで生産ができる可能性があるとして注目
され、その製造方法について各種の提案がなされている
。For this reason, we use easily available gaseous raw material gas such as silane, decompose it by glow discharge, and deposit amorphous silicon (hereinafter referred to as a-Si) on a relatively inexpensive substrate such as glass or metal sheet. Solar cells that can be fabricated by depositing semiconductor thin films such as those described above have the potential to be mass-producible and can be produced at lower costs than solar cells fabricated using single-crystal silicon, etc. It has attracted attention, and various proposals have been made regarding its manufacturing method.
太陽電池による発電方法の中で、太陽電池基板の果たす
役割は、単に製造工程及び実使用条件下での機械的強度
を太陽電池に与えるにとどまらず、以下に説明する理由
によって、太陽電池の発電効率の良否に対して大きな影
響を与え得るものである。In the power generation method using solar cells, the role played by the solar cell substrate is not only to provide mechanical strength to the solar cells during the manufacturing process and under actual usage conditions, but also to improve the power generation of the solar cells for the reasons explained below. This can have a large impact on efficiency.
光反射性基板を用いた太陽電池において、その光反射面
を凹凸のある粗面として形成し、とりわけ吸収係数の小
さい長波長光の光路長を増大せしめることによりその出
力電流を向上させることが可能である。この方法は、例
えば、ＵＳＰ４．１２６．１５０号公報（出願人ＲＣＡ
）第７カラム３行目〜８行目に示唆され、特開昭５６−
１５２２７６号公報（奇人）においても述べられている
。更に特開昭５９−１０４１８５号公報（エクソン・リ
サーチ・アンド・エンジニアリング・カンパニー）にお
いて、粗面化基板の光学的効果が詳述されている。In a solar cell using a light-reflective substrate, it is possible to improve the output current by forming the light-reflecting surface as a rough surface with unevenness and increasing the optical path length of long-wavelength light with a particularly small absorption coefficient. It is. This method is described, for example, in USP 4.126.150 (applicant RCA
) Suggested in column 7, lines 3 to 8, JP-A-1988-
It is also stated in Publication No. 152276 (Kyoujin). Further, in Japanese Patent Application Laid-Open No. 59-104185 (Exxon Research and Engineering Company), the optical effects of a roughened substrate are detailed.
この意味では、太陽電池基板の表面は粗面である方が入
射した光の効果的な利用という面で望ましい。反面、太
陽電池基板の粗面化率が大きくなりすぎると今度は該太
陽電池において短絡（シャント）が発生し易くなり、出
力電圧が低下する原因となる。すなわち、太陽電池基板
の表面粗さには最適値が存在し、その値よりも大きくて
も小さくても太陽電池の出力特性は低下してしまう。こ
のことから、太陽電池基板の表面に粗さを与える工程は
充分に管理されていなければならず、高い再現性を有す
ることが要求される。In this sense, it is desirable that the surface of the solar cell substrate be rough in terms of effective use of incident light. On the other hand, if the surface roughening rate of the solar cell substrate becomes too large, short circuits (shunts) are likely to occur in the solar cell, causing a decrease in output voltage. That is, there is an optimum value for the surface roughness of the solar cell substrate, and the output characteristics of the solar cell will deteriorate even if the surface roughness is larger or smaller than that value. For this reason, the process of imparting roughness to the surface of the solar cell substrate must be sufficiently controlled and required to have high reproducibility.
更に加えて、一般に製品としての太陽電池を構成する際
に、太陽電池の最小構成要素たる単位セルを直列又は並
列に接続し、モジュール化して所望の電流、電圧を得る
形式が採用されることが多く、各単位セル間の出力電圧
や出力電流にばらつきがあると、結果として得られる太
陽電池全体の出力特性が低下してしまう、このことから
、各単位セルの出力特性を左右する太陽電池基板の表面
粗さには高い均一性が要求されるのである。In addition, when constructing a solar cell as a product, a format is generally adopted in which unit cells, which are the minimum components of a solar cell, are connected in series or parallel to form a module to obtain the desired current and voltage. In many cases, if there are variations in the output voltage or output current between each unit cell, the output characteristics of the resulting solar cell as a whole will deteriorate.For this reason, the solar cell substrate, which affects the output characteristics of each unit cell, High uniformity of surface roughness is required.
すなわち、太陽電池量産性を高め、生産コストの大幅な
低減を達成せしめるためには、太陽電池基板の表面粗さ
を大面積に亘って均一に保ちながら、再現性良く製造す
るための技術が要求されるのである。In other words, in order to increase the mass productivity of solar cells and achieve a significant reduction in production costs, a technology is required to manufacture solar cell substrates with good reproducibility while maintaining uniform surface roughness over a large area. It will be done.
太陽電池の重要な構成要素たる半導体層は、いわゆるｐ
ｎ接合、ｐｉｎ接合等の半導体接合がなされている。そ
れたの半導体接合は、導電型の異なる半導体層を順次積
層したり、−導電型の半導体層中に異なる導電型のドー
パントをイオン打込み法等によって打込んだり、熱拡散
によって拡散させたりすることにより達成される。The semiconductor layer, which is an important component of solar cells, is a so-called p
Semiconductor junctions such as n-junctions and pin junctions are made. Such semiconductor junctions are created by sequentially stacking semiconductor layers of different conductivity types, implanting dopants of different conductivity types into semiconductor layers of -conductivity type by ion implantation, or diffusing them by thermal diffusion. This is achieved by
この点を、前述した注目されているａ−５ｉ等の薄膜半
導体を用いた太陽電池についてみると、その作製におい
ては、ホスフィン（ＰＨｓ ） 、ジボラン（Ｂｚ Ｈ
ｅ ）等のドーパントとなる元素を含む原料ガスを主原
料ガスであるシラン等に混合してグロー放電分解するこ
とにより所望の導電型を有する半導体膜が得られ、所望
の基板上にこれらの半導体膜を順次積層形成することに
よって容易に半導体接合が達成できることが知られてい
る。そしてこのことから、ａ−Ｓｉ系の太陽電池を作製
するについて、その各々の半導体層形成用の独立した成
膜室を設け、該成膜室にて各々の半導体層の形成を行う
方法が提案されている。Looking at this point with respect to solar cells using thin film semiconductors such as a-5i, which is attracting attention as mentioned above, in its production, phosphine (PHs), diborane (Bz H
A semiconductor film having a desired conductivity type can be obtained by mixing a raw material gas containing an element that will become a dopant such as e) with a main raw material gas such as silane and decomposing it by glow discharge, and deposit these semiconductors on a desired substrate. It is known that semiconductor junctions can be easily achieved by sequentially stacking films. Based on this, a method was proposed to create an a-Si solar cell by providing an independent film-forming chamber for forming each semiconductor layer and forming each semiconductor layer in the film-forming chamber. has been done.
因に米国特許第４．４００．４０９号特許明細書には、
ロール・ツー・ロール（Ｒｏｌｌ ｔ。Incidentally, the patent specification of U.S. Patent No. 4.400.409 states that
Roll to Roll (Roll t.
Ｒｏｌｌ）方式を採用した連続プラズマＣＶＤ装置が開
示されている。この装置によれば、複数のグロー放電領
域を設け、所望の幅の十分に長い可撓性の基板を、該基
板が前記各グロー放電領域を順次貫通する経路に沿って
配置し、前記各グロー放電領域において必要とされる導
電型の半導体層を堆積形成しつつ、前記基板をその長手
方向に連続的に搬送せしめることによって、半導体接合
を有する素子を連続形成することができるとされている
。なお、該明細書においては、各半導体層形成時に用い
るドーパントガスが他のグロー放電領域へ拡散、混入す
るのを防止するにはガスゲートが用いられている。具体
的には、前記各グロー放電領域同志を、スリット状の分
離通路によって相互に分離し、さらに該分離通路に例え
ばＡｒ、Ｈ２等の掃気用ガスの流れを形成させる手段が
採用されている。A continuous plasma CVD apparatus employing the Roll method has been disclosed. According to this device, a plurality of glow discharge regions are provided, a sufficiently long flexible substrate having a desired width is arranged along a path in which the substrate sequentially passes through each of the glow discharge regions, and each of the glow discharge regions is It is said that elements having semiconductor junctions can be continuously formed by continuously transporting the substrate in its longitudinal direction while depositing a semiconductor layer of the conductivity type required in the discharge region. In this specification, a gas gate is used to prevent the dopant gas used when forming each semiconductor layer from diffusing and mixing into other glow discharge regions. Specifically, a means is adopted in which the glow discharge regions are separated from each other by a slit-shaped separation passage, and a scavenging gas such as Ar or H2 is formed in the separation passage.
そこで、太陽電池の製造工程において、機能性堆積膜形
成工程の前工程として、前記帯状部材上に予め凹凸表面
を有する反射性導電層を形成した後、大気中に取り出す
ことなく連続して該機能性堆積膜を形成することが案出
され得る。この場合、太陽電池基板を製造した後、−旦
大気中に取り出して表面性の検査を行い、検査に合格し
たものを選んで、改めて前記機能性堆積膜形成用の真空
容器等に入れる場合以上に上記の問題が大きな影響を有
することとなる。すなわち、該太陽電池基板製造工程に
おける様々な要因によって該太陽電池基板の表面粗さの
程度が変動したとき、１０ット分の全工程が終るまでそ
れを検出できず、結果として製造コストの増大につなが
るという問題点があった。この欠点が、長尺の帯状部材
上に連続に太陽電池の作製を行う際に解決されねばなら
ない問題点として残されており、この問題点の早期解決
が望まれていた。Therefore, in the solar cell manufacturing process, a reflective conductive layer having an uneven surface is formed on the band-shaped member in advance as a pre-process of the functional deposited film forming process, and then the reflective conductive layer is continuously applied without being taken out into the atmosphere. It may be devised to form a chemically deposited film. In this case, after manufacturing the solar cell substrate, it is first taken out into the atmosphere and inspected for surface properties, and those that pass the inspection are selected and placed again into the vacuum container etc. for forming the functional deposited film. The above problems will have a major impact on That is, when the degree of surface roughness of the solar cell substrate changes due to various factors in the solar cell substrate manufacturing process, it cannot be detected until the entire process for 10 tons is completed, resulting in an increase in manufacturing costs. There was a problem in that it led to This drawback remains as a problem that must be solved when solar cells are continuously manufactured on a long strip-shaped member, and an early solution to this problem has been desired.
［発明の目的］
本発明は、上述のごとき従来の太陽電池基板製造方法に
おける問題を克服して、大面積に亘って均一、かつ再現
性良好な太陽電池基板を製造することにより高い光電変
換効率を有する大面積太陽電池の量産化を低コストで行
なうための方法を提供するものである。[Object of the Invention] The present invention overcomes the problems in the conventional solar cell substrate manufacturing method as described above, and achieves high photoelectric conversion efficiency by manufacturing a solar cell substrate that is uniform over a large area and has good reproducibility. The present invention provides a method for mass-producing large-area solar cells having the following characteristics at low cost.
また、大面積太陽電池基板の製造工程後、真空容器から
取り出して表面性の検査をするという工程を省くことに
より、大面積太陽電池基板の製造工程後、真空を破らず
に連続して大面積太陽電池の製造工程に安定的につなげ
ること、その結果として、稼動率、歩留まりの向上を図
り、安価で高効率の太陽電池を量産化することを目的と
する。In addition, by omitting the process of removing the large-area solar cell substrate from the vacuum container and inspecting its surface properties after the manufacturing process of the large-area solar cell substrate, it is possible to continue manufacturing large-area solar cell substrates without breaking the vacuum. The purpose is to stably connect to the solar cell manufacturing process, and as a result, improve operating rates and yields, and mass-produce inexpensive, high-efficiency solar cells.
［発明の構成１
本発明者らは、従来の太陽電池基板製造方法に存在した
上述の諸問題を解決し、前記本発明の目的を達成すべく
鋭意研究を重ねたところ、帯状部材を、その長手方向に
連続的に移動せしめながら、複数の太陽電池基板処理空
間を順次通過させ、該帯状部材の表面に複数工程の処理
を施し、大面積の太陽電池基板を連続的に製造する方法
において、前記帯状部材の移動方向に対して少なくとも
ひとつ以上の前記太陽電池基板処理空間の後の空間にお
いて、前記帯状部材表面の表面粗さをインプロセスで測
定し、その測定結果を用いて、少なくとも一種類以上の
前記太陽電池基板処理工程に対する制御パラメータをそ
の場で決定することにより、上記の諸問題を解決し、大
面積に亘って均一な、かつ再現性良好な太陽電池基板の
作製、及び、該太陽電池基板を用いて変換効率が高く、
かつ、特性の揃った太陽電池を低コストで量産化すると
いう本発明の目的が達成可能であるという知見を得た。[Structure 1 of the Invention The present inventors have conducted extensive research to solve the above-mentioned problems that existed in the conventional solar cell substrate manufacturing method and to achieve the object of the present invention. In a method for continuously manufacturing large-area solar cell substrates by sequentially passing through a plurality of solar cell substrate processing spaces while continuously moving in the longitudinal direction, and performing multiple steps of processing on the surface of the strip-shaped member, The surface roughness of the surface of the strip member is measured in-process in a space after at least one of the solar cell substrate processing spaces in the moving direction of the strip member, and at least one type of surface roughness is measured using the measurement results. By determining the control parameters for the above solar cell substrate processing process on the spot, the above problems can be solved, and a solar cell substrate that is uniform over a large area and with good reproducibility can be produced. High conversion efficiency using solar cell substrate,
In addition, it was found that the objective of the present invention, which is to mass-produce solar cells with uniform characteristics at low cost, can be achieved.
本発明は、上述の知見に基づき検討を重ねた結果完成に
至ったものであり、上述するところを骨子とする大面積
の太陽電池基板の連続製造方法を包含する。The present invention was completed as a result of repeated studies based on the above-mentioned findings, and includes a continuous manufacturing method for large-area solar cell substrates having the above-mentioned main points.
本発明の方法は、帯状部材を、その長手方向に連続的に
移動せしめながら、複数の太陽電池基板処理空間を順次
通過させ、該帯状部材の表面に複数工程の処理を施し、
大面積の太陽電池基板を連続的に製造する方法において
、前記帯状部材の移動方向に対して少なくともひとつ以
上の前記太陽電池基板処理空間の後の空間において、前
記帯状部材表面の表面粗さをインプロセスで測定し、そ
の測定結果を用いて、少なくとも一種類以上の前記太陽
電池基板処理工程に対する制御パラメータをその場で決
定しながら大面積太陽電池基板の連続製造を行なう方法
である。The method of the present invention involves sequentially passing a strip member through a plurality of solar cell substrate processing spaces while continuously moving the strip member in its longitudinal direction, and subjecting the surface of the strip member to multiple steps of processing,
In a method for continuously manufacturing large-area solar cell substrates, the surface roughness of the surface of the strip member is measured in a space after at least one solar cell substrate processing space in the moving direction of the strip member. In this method, large-area solar cell substrates are continuously manufactured while measuring in the process and using the measurement results to determine on the spot control parameters for at least one type of the solar cell substrate processing step.
以下、本発明者が本発明を完成させるにあたり行った実
験について説明する。Hereinafter, experiments conducted by the present inventor in completing the present invention will be explained.
（実験例）
後述する装置例１で示す装置を用いて、帯状部材を複数
の処理工程と表面粗さ測定手段を通過させることにより
、大面積太陽電池基板を形成した０本実験例では、表面
粗さ測定手段を機能させない、すなわち処理工程に対し
て制御をかけないという点を除いて、処理方法、条件及
び使用した装置等は後述の実施例１と同じにした。(Experimental example) In this experimental example, a large-area solar cell substrate was formed by passing a strip member through a plurality of processing steps and a surface roughness measuring means using an apparatus shown in apparatus example 1 described later. The processing method, conditions, equipment used, etc. were the same as in Example 1 described later, except that the roughness measuring means was not activated, that is, the processing process was not controlled.
このようにして製造された大面積太陽電池基板の表面粗
さにおけるむらを、中心線平均粗さ（Ｒａ）をパラメー
タとして全長に亘って測定したところ、最大２０％もの
むらがあることがわかった。また、この大面積太陽電池
基板を用いて作製した後述のａ−Ｓｉ太陽電池単位セル
の出力特性を測定したところ、短絡電流において最大１
５％、開放電圧において最大１０％のむらが確認された
。When the unevenness in surface roughness of the large-area solar cell substrate manufactured in this way was measured over the entire length using the center line average roughness (Ra) as a parameter, it was found that there was an unevenness of up to 20%. . In addition, when we measured the output characteristics of the a-Si solar cell unit cell, which will be described later, produced using this large-area solar cell substrate, we found that the short-circuit current was up to 1
5%, and a maximum of 10% unevenness in open circuit voltage was confirmed.
本実験の結果から明らかなように、処理工程に対して制
御をかけないで製造した大面積太陽電池基板は帯状部材
の長手方向においてその表面粗さにむらがかなりあり、
その結果として、得られた単位セルの出力特性が大きく
バラついたものになっていることがわかった。As is clear from the results of this experiment, large-area solar cell substrates manufactured without controlling the processing process have considerable unevenness in surface roughness in the longitudinal direction of the strip member.
As a result, it was found that the output characteristics of the obtained unit cells varied widely.
そこで後述の表面粗さ測定手段を機能させ、後述の反射
性導電膜を形成する際の、粗さにおける変動に対して補
正を施すために、後述のＤＣスパッタ法を用いた反射性
導電膜形成手段に対してフィードバックをかける実験を
行なった。フィードバックは、前記ＤＣスパッタ法を用
いた反射性導電膜形成時における前記帯状部材表面の温
度制御に対してかけた。Therefore, in order to make the surface roughness measuring means described later function and to correct for variations in roughness when forming the reflective conductive film described later, we formed a reflective conductive film using the DC sputtering method described later. We conducted an experiment in which feedback was applied to the means. Feedback was applied to the temperature control of the surface of the strip member during formation of the reflective conductive film using the DC sputtering method.
その結果フィードバックの係数がゼロ（フィードバック
をかけていない状態）から徐々に大きくなって行くに従
って反射性導電膜の長手方向における粗さのむらも減少
するが、フィードバックの係数を大きくしすぎると逆に
粗さのむらを大きくしてしまう結果となった。すなわち
、フィードバックのかけ方には最適なポイントが存在し
、装置ごとに適宜決定する必要がある。As a result, as the feedback coefficient gradually increases from zero (the state in which no feedback is applied), the unevenness of the roughness in the longitudinal direction of the reflective conductive film decreases, but if the feedback coefficient becomes too large, the roughness becomes uneven. This resulted in increased unevenness. That is, there is an optimal point in how to apply feedback, and it is necessary to determine it appropriately for each device.
以下に、本発明の大面積太陽電池基板の連続製造方法の
構成及び特徴点について、詳細を順に追って説明する。Below, the structure and features of the continuous manufacturing method for large-area solar cell substrates of the present invention will be explained in detail in order.
（帯状部材）
本発明の方法において好適に用いられる帯状部材の材質
としては、ａ−Ｓｉ膜等の機能性堆積形成時に必要とさ
れる温度において変形、歪が少なく、所望の強度を有し
、また、導電性を有するものであることが好ましく、具
体的にはステンレススチール、アルミニウム及びその合
金、鉄及びその合金、銅及びその合金等の金属の薄板及
びその複合体、及びそれらの表面に異種材質の金属薄膜
及び／または５ｉ０２．３１３ Ｎ４ 、Ａｌ□０３、
ＡＩＮ等の絶縁性薄膜をスパッタ法、蒸着法、鍍金法等
により表面コーティング処理を行なったもの。又、ポリ
イミド、ポリアミド、ポリエチレンテレフタレート、エ
ポキシ等の耐熱性樹脂製シート又はこれらとガラスファ
イバー、カーボンファイバー、ホウ素ファイバー、金属
繊維等との複合体の表面に金属単体または合金、及び透
明導電性酸化物（ＴＣＯ）等を鍍金、蒸着、スパッタ、
塗布等の方法で導電性処理を行なったものが挙げられる
。(Band-shaped member) The material of the band-shaped member suitably used in the method of the present invention is such that it has less deformation and distortion at the temperature required for forming a functional deposit such as an a-Si film, and has desired strength. In addition, it is preferable that the material has conductivity, and specifically, thin plates and composites of metals such as stainless steel, aluminum and its alloys, iron and its alloys, copper and its alloys, and materials with different types on their surfaces. Material thin metal film and/or 5i02.313 N4, Al□03,
Surface coating of an insulating thin film such as AIN using sputtering, vapor deposition, plating, etc. In addition, single metals or alloys, and transparent conductive oxides may be applied to the surface of heat-resistant resin sheets such as polyimide, polyamide, polyethylene terephthalate, and epoxy, or composites of these and glass fibers, carbon fibers, boron fibers, metal fibers, etc. (TCO), etc. by plating, vapor deposition, sputtering,
Examples include those that have been subjected to conductive treatment by a method such as coating.
また、前記帯状部材の厚さとしては、前記搬送手段によ
る搬送時に形成される湾曲形状が維持される強度を発揮
する範囲内であれば、コスト、収納スペース等を考慮し
て可能な限り薄い方が望ましい。具体的には、好ましく
は０．０１ｍｍ乃至５ｍｍ、より好ましくは０．０２ｍ
ｍ乃至２ｍｍ、最適には０．０５ｍｍ乃至１ｍｍである
ことが望ましいが、金属等の薄板を用いる場合、厚さを
比較的薄くしても所望の強度が得られやすい。Further, the thickness of the band-shaped member is determined to be as thin as possible in consideration of cost, storage space, etc., as long as it is within a range that exhibits strength that maintains the curved shape formed during transportation by the transportation means. is desirable. Specifically, preferably 0.01 mm to 5 mm, more preferably 0.02 m
It is desirable that the thickness be 0.05 mm to 2 mm, most preferably 0.05 mm to 1 mm, but when a thin plate of metal or the like is used, the desired strength can be easily obtained even if the thickness is relatively thin.
前記帯状部材の幅については、特に制限されることはな
く、機能性堆積膜形成手段、あるいはその容器等のサイ
ズによって決定される。The width of the band member is not particularly limited, and is determined by the size of the functional deposited film forming means or its container.
前記帯状部材の長さについては、特に制限されることは
なく、ロール状に巻き取られる程度の長さであっても良
く、長尺のものを溶接等によって更に長尺化したもので
あっても良い。The length of the band-shaped member is not particularly limited, and may be long enough to be wound into a roll, or a long one made longer by welding or the like. Also good.
前記帯状部材が金属等の電気導電性である場合には直接
電流取り出し用の電極としても良いし、合成樹脂等の電
気絶縁性である場合には堆積膜の形成される側の表面に
Ａ１、Ａｇ、Ｐｔ、Ａｕ、Ｎｉ、Ｔｉ、Ｍｏ、Ｗ％Ｆｅ
、Ｖ％Ｃｒ、Ｃｕ、ステンレス、真ちゅう、ニクロム、
５ｎ０２、Ｉ ｎ ｚ Ｏｓ Ｚ ｎ ０１ＳｎＯ
２Ｉｎｇ ０３（ＩＴＯ）等のいわゆる金属単体又は合
金、及び透明導電性酸化物（ＴＣＯ）を鍍金、蒸着、ス
パッタ等の方法であらかじめ表面処理を行なって電流取
り出し用の電極を形成しておくことが望ましい。If the band-shaped member is made of electrically conductive material such as metal, it may be used as an electrode for direct current extraction, or if it is made of electrically insulating material such as synthetic resin, A1, Ag, Pt, Au, Ni, Ti, Mo, W%Fe
, V%Cr, Cu, stainless steel, brass, nichrome,
5n02, I n z Os Z n 01SnO
2Ing 03 (ITO) and other so-called metals or alloys, and transparent conductive oxides (TCO) can be surface-treated in advance by plating, vapor deposition, sputtering, or other methods to form electrodes for current extraction. desirable.
前記帯状部材が金属等の非透光性のものである場合、長
波長光の基板表面上での反射率を向上させるための反射
性導電膜を該帯状部材上に形成することが前述のように
好ましい。該反射性導電膜の材質として好適に用いられ
るものとしてＡｇ、Ａ１、Ｃｒ等が挙げられる。When the strip-like member is made of a non-light-transmitting material such as metal, it is preferable to form a reflective conductive film on the strip-like member to improve the reflectance of long-wavelength light on the substrate surface, as described above. preferred. Suitable materials for the reflective conductive film include Ag, A1, Cr, and the like.
また、基板材質と機能性堆積膜との間での構成元素の相
互拡散を防止したり短絡防止用の緩衝層とする等の目的
で金属層等を反射性導電膜として、前記基板上の堆積膜
が形成される側に設けることが好ましい。該緩衝層の材
質として好適に用いられるものとして、Ｚｎｏが挙げら
れる。In addition, a metal layer or the like is deposited on the substrate as a reflective conductive film for the purpose of preventing mutual diffusion of constituent elements between the substrate material and the functional deposited film or as a buffer layer to prevent short circuits. It is preferable to provide it on the side where the film is formed. An example of a material suitably used for the buffer layer is Zno.
また、前記帯状部材が比較的透明であって、該帯状部材
の側から光入射を行う層構成の太陽電池とする場合には
前記透明導電性酸化物や金属薄膜等の導電性薄膜をあら
かじめ堆積形成しておくことが望ましい。In addition, in the case of a solar cell having a layered structure in which the strip member is relatively transparent and light enters from the side of the strip member, a conductive thin film such as the transparent conductive oxide or metal thin film is deposited in advance. It is desirable to form it.
太陽電池基板表面の凹凸形状は球状、円錐状、角錐状等
であって、中心線平均粗さ（Ｒａ）は好ましくは０．１
μｍ乃至１０μｍ、且つその最大高さ（Ｒ，、、）は好
ましくは０．０５μｍ乃至０．５μｍとすることにより
、該表面での可視光の反射が乱反射となり、該表面での
反射光の光路長の増大をもたらし、結果として太陽電池
の変換効率を向上させる。The uneven shape of the surface of the solar cell substrate is spherical, conical, pyramidal, etc., and the center line average roughness (Ra) is preferably 0.1.
μm to 10 μm, and the maximum height (R,,) is preferably 0.05 μm to 0.5 μm, so that the reflection of visible light on the surface becomes diffuse reflection, and the optical path of the reflected light on the surface This results in an increase in the length of the solar cell, resulting in an improvement in the conversion efficiency of the solar cell.
また、該太陽電池基板表面の凹凸形状は、前記反射性導
電膜、あるいは前記透明導電性酸化膜を形成する際の基
板温度等の条件を変えることにより制御が可能である。Moreover, the uneven shape of the surface of the solar cell substrate can be controlled by changing conditions such as the substrate temperature when forming the reflective conductive film or the transparent conductive oxide film.
一般に、前記凹凸表面構造形成時の基板温度が高ければ
高いほど該凹凸表面構造を構成する金属粒界が粗くなる
という事実が知られている。すなわち、前記表面粗さ測
定手段によって得られた測定結果に現われた表面粗さが
大きくなった場合には前記凹凸表面構造形成手段におけ
る基板温度を低くし、表面粗さが小さくなった場合には
基板温度を高くすれば、該凹凸表面構造の粗さの変動を
抑制することが可能である。It is generally known that the higher the substrate temperature during formation of the uneven surface structure, the coarser the metal grain boundaries forming the uneven surface structure. That is, when the surface roughness appearing in the measurement results obtained by the surface roughness measuring means becomes large, the substrate temperature in the uneven surface structure forming means is lowered, and when the surface roughness becomes small, the temperature of the substrate is lowered. By increasing the substrate temperature, it is possible to suppress variations in the roughness of the uneven surface structure.
（ガスゲート手段）
本発明の方法において、前記反射性導電膜形成手段、金
属酸化膜形成手段、機能性堆積膜形成手段等を格納する
容器を分離独立させ、且つ、前記帯状部材をそれらの中
を貫通させて連続的に搬送するにはガスゲート手段が好
適に用いられる。該ガスゲート手段の能力としては前記
各容器間に生じる圧力差によって、相互に使用している
堆積膜形成原料ガス等の雰囲気を拡散させない能力を有
することが必要である。従って、その基本概念は米国特
許第４．４３８．７２３号に開示されているガスゲート
手段を採用することができるが、更にその能力は改善さ
れる必要がある。具体的には、最大１０６倍程度の圧力
差に耐え得ることが必要であり、排気ポンプとしては排
気能力の大ぎい油拡散ポンプ、ターボ分子ポンプ、メカ
ニカルブースターポンプ等が好適に用いられる。また、
ガスゲートの断面形状としてはスリット状又はこれに類
似する形状であり、その全長及び用いる排気ポンプの排
気能力等と合わせて、一般のコンダクタンス計算式を用
いてそれらの寸法が計算、設計される。更に、分離能力
を高めるためにゲートガスを併用することが好ましく、
例えばＡｒ、Ｈｅ、Ｎｅ、Ｋｒ、Ｘｅ、Ｒｎ等の希ガス
又はＨ２等の堆積膜形成用希釈ガスが挙げられる。(Gas Gate Means) In the method of the present invention, containers storing the reflective conductive film forming means, the metal oxide film forming means, the functional deposited film forming means, etc. are separated and independent, and the strip-shaped member is inserted into them. Gas gate means is suitably used for continuous conveyance through the passage. The gas gate means must have the ability to prevent the atmosphere of the deposited film forming raw material gas used between the containers from diffusing due to the pressure difference generated between the containers. Therefore, although the basic concept can be adopted of the gas gating means disclosed in US Pat. No. 4,438,723, its capabilities need to be further improved. Specifically, it is necessary to be able to withstand a pressure difference of about 106 times at maximum, and as the exhaust pump, an oil diffusion pump, a turbo molecular pump, a mechanical booster pump, etc. having a large exhaust capacity are preferably used. Also,
The gas gate has a slit-like cross-sectional shape or a similar shape, and its dimensions are calculated and designed using a general conductance calculation formula, along with its overall length and the exhaust capacity of the exhaust pump used. Furthermore, it is preferable to use a gate gas in combination to increase the separation ability.
Examples include rare gases such as Ar, He, Ne, Kr, Xe, and Rn, and diluent gases for forming deposited films such as H2.
ゲートガス流量としてはガスゲート全体のコンダクタン
ス及び用いる排気ポンプの能力等によって適宜決定され
るが、概ね第２図（Ａ）、（Ｂ）に示したような圧力勾
配を形成するようにすれば良い。第２図（Ａ）において
、ガスゲートのほぼ中央部に圧力の最大となるポイント
があるため、ゲートガスはガスゲート中央部から両サイ
ドの真空容器側へ流れ、第２図（Ｂ）においてはガスケ
ートのほぼ中央部に圧力の最小となるポイントがあるた
め、両サイドの容器から流れ込む堆積膜形成用原料ガス
と共にケートガスもガスゲート中央部から排気される。The gate gas flow rate is appropriately determined depending on the conductance of the entire gas gate and the capacity of the exhaust pump used, but it is sufficient to form a pressure gradient as shown in FIGS. 2(A) and 2(B). In Figure 2 (A), there is a point where the pressure is maximum approximately at the center of the gas gate, so the gate gas flows from the center of the gas gate to the vacuum vessel side on both sides, and in Figure 2 (B), the point where the pressure is maximum is approximately at the center of the gas gate. Since there is a point at the center where the pressure is minimum, the cate gas is exhausted from the center of the gas gate along with the deposited film forming raw material gas flowing from the containers on both sides.
従って両者の場合において両サイドの容器間での相互の
ガス拡散を最小限に抑えることができる。実際には、質
量分析計を用いて拡散してくるガス量を測定したり、堆
積膜の組成分析を行うことによって最適条件を決定する
。Therefore, in both cases, mutual gas diffusion between the containers on both sides can be minimized. In practice, the optimal conditions are determined by measuring the amount of diffused gas using a mass spectrometer or by analyzing the composition of the deposited film.
（機能性堆積膜、機能性堆積膜形成手段）本発明の方法
によって製造される大面積太陽電池基板上に形成される
機能性堆積膜としては非晶質、結晶質を問わず、Ｓｉ、
Ｇｅ、Ｃ等いわゆる■族生導体薄膜、５ｉＧｅ、ＳｉＣ
，５ｉＳｎ等いわゆる■族合金半導体薄膜、ＧａＡｓ、
ＧａＰ、ＧａＳｂ、ＩｎＰ％ＩｎＡｓ等いわゆる■−Ｖ
族化合物半導体薄膜、及びＺｎ５ｅ、ＺｎＳ、ＺｎＴｅ
、ＣｄＳ、ＣｄＳｅ、ＣｄＴｅ等いわゆる■−■族化合
物半導体薄膜等が挙げられる。(Functional deposited film, functional deposited film forming means) The functional deposited film formed on the large-area solar cell substrate manufactured by the method of the present invention may be Si,
So-called group III bioconductor thin films such as Ge and C, 5iGe, SiC
, 5iSn and other so-called group III alloy semiconductor thin films, GaAs,
GaP, GaSb, InP%InAs, etc. so-called ■-V
group compound semiconductor thin film, and Zn5e, ZnS, ZnTe
, CdS, CdSe, CdTe, and other so-called ■-■ group compound semiconductor thin films.
これらの機能性堆積膜を形成する際に用いられる前記機
能性堆積膜形成用原料ガスとしては、上述した各種半導
体薄膜の構成元素の水素化物、ハロゲン化物、有機金属
化合物等で前記成膜室内へ好ましくは気体状態で導入で
きるものが選ばれ使用される。The functional deposited film forming raw material gases used in forming these functional deposited films include hydrides, halides, organometallic compounds, etc. of the constituent elements of the various semiconductor thin films mentioned above, which are introduced into the film forming chamber. Preferably, those that can be introduced in a gaseous state are selected and used.
勿論、これらの原料化合物は１種のみならず、２種以上
混合して使用することもできる。又、これらの原料化合
物はＨｅ、Ｎｅ、Ａｒ、Ｋｒ、Ｘ ｅ ％Ｒｎ等の希ガ
ス、及びＨＲ、ＨＦ、ＨＣＩ等の希釈ガスと混合して導
入されても良い。Of course, these raw material compounds can be used not only alone, but also in combination of two or more. Further, these raw material compounds may be introduced in a mixture with rare gases such as He, Ne, Ar, Kr, and X e %Rn, and diluent gases such as HR, HF, and HCI.
また、連続形成される前記半導体薄膜は価電子制御及び
禁制帯幅制御を行うことができる。具体的には価電子制
御剤又は禁制帯幅制御剤となる元素を含む原料化合物を
単独で、又は前記堆積膜形成用原料ガス又は前記希釈ガ
スに混合して前記成膜室内へ導入してやれば良い。Further, the continuously formed semiconductor thin film can perform valence electron control and forbidden band width control. Specifically, a raw material compound containing an element serving as a valence electron control agent or a forbidden band width control agent may be introduced into the film forming chamber alone or mixed with the deposited film forming raw material gas or the diluent gas. .
本発明の大面積太陽電池基板製造方法において、前記帯
状部材を太陽電池基板製造工程と機能性堆積膜形成工程
を連続して通過させることにより、太陽電池の量産性を
更に向上させることが可能である。この場合、前記ガス
ケート手段を介して本発明の大面積太陽電池基板製造手
段に連設され得る機能性堆積膜形成手段として、マイク
ロ波プラズマＣＶＤ法、ＲＦプラズマＣＶＤ法、スパッ
タリング法及び反応性スパッタリング法、イオンブレー
ティング法、光ＣＶＤ法、熱ＣＶＤ法、ＭＯＣＶＤ法、
ＭＢＥ法そしてＨＲ−ＣＶＤ法等、いわゆる機能性堆積
膜形成用に用いられる方法を実現するための手段を挙げ
ることができ、所望の太陽電池作製のため適宜手段を選
択し、前記ガスケート手段を用いて接続される。In the large-area solar cell substrate manufacturing method of the present invention, mass productivity of solar cells can be further improved by sequentially passing the strip member through the solar cell substrate manufacturing process and the functional deposited film forming process. be. In this case, the functional deposited film forming means that can be connected to the large-area solar cell substrate manufacturing means of the present invention via the gasket means include microwave plasma CVD method, RF plasma CVD method, sputtering method, and reactive sputtering method. , ion blating method, photo CVD method, thermal CVD method, MOCVD method,
Means for realizing a method used for forming a so-called functional deposited film, such as MBE method and HR-CVD method, can be mentioned, and an appropriate method can be selected for producing a desired solar cell, and the gasket method can be used. connected.
また、前記機能性堆積膜形成手段に引き続いて、透明導
電膜、集電電極としての各種金属及び／または各種酸化
物を形成する場合には電子ビーム蒸着法、抵抗加熱蒸着
法、スパッタリング法、及び反応性スパッタリング法等
の方法を実現するための手段を適宜選択し、前記ガスゲ
ート手段を介して接続され得る。Further, when forming a transparent conductive film, various metals and/or various oxides as current collecting electrodes following the functional deposited film forming means, electron beam evaporation method, resistance heating evaporation method, sputtering method, and A means for realizing a method such as a reactive sputtering method can be selected as appropriate and connected via the gas gate means.
（表面粗さの測定手段）
一般に、表面粗さの測定方法は、接触式と非接触式のふ
たつに分類される。前者の例としては、触針で被測定表
面を走査し渦電流による変位計を用いて粗さを評価する
引っかき式、検出部を突出さでた回転ドラムを被測定表
面上で回転させて１回転ごとの変位を読み取り統計をと
ることにより粗さの評価を行う多点測定式、接触電極と
被測定表面の間の電気容量の変化から表面粗さを評価す
る電気容量式等が挙げられる。また、後者の例としては
、光マイクロメータの原理を用いたレーザ変位計による
方法、被測定表面に対して斜めに照射したスリット光に
対する反射光の形状を観察する光切断法、被測定表面に
光を当てながら走査を行い、反射光の強度変化から表面
粗さを評価する反射光強度法、光の反射角度分布から表
面粗さを評価する散乱光分布による散乱光分布法、レー
ザ光によるスペックルの最大コントラストから表面粗さ
を評価するレーザ光によるスペックル法、被測定表面に
マイクロ波を照射し、反射したマイクロ波の強度から表
面粗さを評価するマイクロ波反射強度法が挙げられる。(Method for Measuring Surface Roughness) Generally, methods for measuring surface roughness are classified into two types: contact type and non-contact type. Examples of the former include the scratch type, which scans the surface to be measured with a stylus and evaluates the roughness using an eddy current displacement meter; Examples include a multi-point measurement method in which roughness is evaluated by reading the displacement for each rotation and taking statistics, and a capacitance method in which surface roughness is evaluated from changes in capacitance between a contact electrode and the surface to be measured. Examples of the latter include a method using a laser displacement meter that uses the principle of an optical micrometer, a light cutting method that observes the shape of reflected light from a slit beam that is irradiated obliquely to the surface to be measured, and a method that uses a laser displacement meter that uses the principle of an optical micrometer. Reflected light intensity method, which scans while shining light and evaluates surface roughness from changes in the intensity of reflected light; Scattered light distribution method, which uses scattered light distribution to evaluate surface roughness from light reflection angle distribution; and specs using laser light. The speckle method uses laser light to evaluate the surface roughness based on the maximum contrast of the surface, and the microwave reflection intensity method uses the intensity of the reflected microwaves to evaluate the surface roughness.
本発明において用いられ得る表面粗さの測定方法として
、測定に要する時間が短くて済みその場で表面粗さを検
査できるという点で、前記多点測定式、レーザ変位計に
よる方法、反射光強度法、散乱光分布法、レーザ光スペ
ックル法、マイクロ波反射強度法が好適に用いられる。Surface roughness measurement methods that can be used in the present invention include the multi-point measurement method, the method using a laser displacement meter, and the method using a reflected light intensity, since the time required for measurement is short and the surface roughness can be inspected on the spot. method, scattered light distribution method, laser light speckle method, and microwave reflection intensity method are preferably used.
なかでも、マイクロ波反射強度法は、表面粗さの測定精
度はそれほど高くないが、被測定表面の物理的、化学的
、機械的な特性を同時に評価することができ、大面積太
陽電池基板の表面抵抗率のばらつきも同時に検査できる
という利点を持っている。Among them, the microwave reflection intensity method does not have very high surface roughness measurement accuracy, but it can simultaneously evaluate the physical, chemical, and mechanical properties of the surface to be measured, and is useful for large-area solar cell substrates. It has the advantage that variations in surface resistivity can also be inspected at the same time.
（フィードバック手段）
前記表面粗さ測定手段によって測定された表面粗さのデ
ータは主に太陽電池の前記反射性導電層における凹凸表
面構造の制御、及び、前記短絡防止用の緩衝層の形成工
程における該緩衝層の層厚の制御に用いられる。(Feedback means) The surface roughness data measured by the surface roughness measuring means is mainly used to control the uneven surface structure in the reflective conductive layer of the solar cell and in the step of forming the buffer layer for preventing short circuits. It is used to control the layer thickness of the buffer layer.
測定データを見て適切な制御を行うというような操作は
手動によって行うことも可能であるが、例えば太陽電池
等を連続で大量に生産するような場合には、上記のよう
な操作を自動的に行う必要がある。その用途に対しては
、測定データの取り込み、各種機器の制御用インターフ
ェースを備え、所定のアルゴリズムに従ってデータ解析
及び外部機器の制御が可能がコンピュータが好適に用い
られる。Although it is possible to perform operations such as checking measurement data and performing appropriate controls manually, for example, in the case of continuous mass production of solar cells, etc., it is possible to perform the above operations automatically. need to be done. For this purpose, a computer is preferably used because it is equipped with an interface for importing measurement data and controlling various devices, and is capable of data analysis and control of external devices according to a predetermined algorithm.
〔装置例１
以下、図面を用いて本発明の方法に用いられ得る具体的
装置例を挙げて説明するが、本発明はこれらの装置例に
よって限定されるものではない。[Apparatus Example 1 Hereinafter, specific apparatus examples that can be used in the method of the present invention will be described with reference to the drawings, but the present invention is not limited to these apparatus examples.
（表面粗さ測定手段例１）
第３図に本発明に用いられる表面粗さ測定手段の一例と
して、反射光強度法を用いた場合の表面粗さの測定手段
の概念的模式図を示す。(Example 1 of Surface Roughness Measuring Means) FIG. 3 shows a conceptual diagram of a surface roughness measuring means using a reflected light intensity method as an example of the surface roughness measuring means used in the present invention.
３０１は帯状部材であり、支持・搬送用、ローラー３０
２．３０３によって支持・搬送される。301 is a belt-shaped member for supporting and conveying roller 30
2. Supported and transported by 303.
３０４は白色光照射及び反射光受光部分であり、前記帯
状部材に対して位置が保たれている。Reference numeral 304 denotes a white light irradiation and reflected light receiving portion, and its position is maintained with respect to the band-shaped member.
３０５は光ファイバーを束ねて成る光伝送路であり、光
反射率計側装置３０６と連結されている。３０７はデー
タ解析及び各種機器制御用コンピュータであり、インタ
ーフェース３０８及び３０９を介して前記光反射率計側
装置３０６及び各種機器（不図示）と各々接続されてい
る。305 is an optical transmission line formed by bundling optical fibers, and is connected to a light reflectance meter side device 306. Reference numeral 307 denotes a computer for data analysis and various equipment control, and is connected to the light reflectance meter side device 306 and various equipment (not shown) via interfaces 308 and 309, respectively.
（表面粗さ測定手段例２）
第４図に本発明に用いられる表面粗さ測定手段の一例と
して、多点測定式の方法を用いた場合の表面粗さ測定手
段の概念的模式図を示す。(Example 2 of Surface Roughness Measuring Means) FIG. 4 shows a conceptual diagram of a surface roughness measuring means when a multi-point measurement method is used as an example of the surface roughness measuring means used in the present invention. .
４０１は帯状部材であり、支持・搬送用ローラー４０２
．４０３によって支持・搬送される。401 is a band-shaped member, and a support/conveyance roller 402
．． It is supported and conveyed by 403.
４０４は表面粗さＪｌｌｌ周定探針を有するドラムであ
り、帯状部材４０１の表面に押し当てられ、滑ることな
く回転している。該ドラムには探針な緩やかに保持する
板バネ４０５、探針の変位を検出する変位検出器４０６
、該変位検出器の出力を伝送するためのスリップリング
４０７を有している。404 is a drum having a circumferential probe having a surface roughness of Jllll, which is pressed against the surface of the band member 401 and rotates without slipping. The drum includes a leaf spring 405 that gently holds the probe, and a displacement detector 406 that detects the displacement of the probe.
, has a slip ring 407 for transmitting the output of the displacement detector.
該変位検出器の出力は表面粗さ測定手段例１と同様に伝
送ケーブル４０８によってＡ／Ｄコンバータ４０９に送
られる。４１０はデータ解析及び各種機器制御用コンピ
ュータであり、インターフェース４１１及び４１２を介
してＡ／Ｄコンバータ４０９及び各種機器（不図示）と
各々接続されている。The output of the displacement detector is sent to an A/D converter 409 via a transmission cable 408, similar to the surface roughness measuring means example 1. 410 is a computer for data analysis and various equipment control, and is connected to the A/D converter 409 and various equipment (not shown) via interfaces 411 and 412, respectively.
（装置例１）
本発明の全体的装置例として、第１図に示したごとく、
前記帯状部材１０１の送り出し及び巻き取り用の真空容
器１０２及び１０３、前記反射性導電膜形成手段用真空
容器１２０、前記表面粗さ測定手段用真空容器１２１、
及び前記緩衝層形成手段用真空容器１２２をガスゲート
を介して接続した装置を挙げることができる。(Apparatus Example 1) As an example of the overall apparatus of the present invention, as shown in FIG.
Vacuum containers 102 and 103 for feeding and winding up the strip member 101, vacuum container 120 for the reflective conductive film forming means, vacuum container 121 for the surface roughness measuring means,
and an apparatus in which the vacuum container 122 for the buffer layer forming means is connected via a gas gate.
１０４は帯状部材の送り出し用ボビン、１０５は帯状部
材の巻き取り用ボビンであり、図中矢印方向に帯状部材
が搬送される。もちろんこれは逆転させて搬送すること
もできる。また、真空容器１０２．１０３中には帯状部
材の表面保護用に用いられる台紙の巻き取り、及び送り
込み手段を配設しても良い、前記台紙の材質としては、
耐熱性樹脂であるポリイミド系、テフロン系及びグラス
ウール等が好適に用いられる。１０６．１０７は張力調
整及び帯状部材の位置出しを兼ねた搬送用ローラである
。１３３．１３４は帯状部材の予備加熱又は冷却用に用
いられる温度調整機構である。１０８．１０９．１３１
．１３２は排気管であり、それぞれ不図示の排気ポンプ
に接続されている。１１０．１１１は圧力計、また、１
１２．１１３．１１４．１１５はゲートガス導入管、１
１６．１１７．１１８．１１９はゲートガス排気管であ
り、不図示の排気ポンプによりゲートガス及びスパッタ
ガス等の基板処理補助用ガスが排気される。１２３は前
記反射性導電膜形成用帯状部材温度コントローラ、１２
４は前記緩衝層形成用帯状部材温度コントローラであり
、各々の処理において帯状部材の温度をコントロールす
る。Reference numeral 104 denotes a bobbin for feeding out the strip-shaped member, and 105 denotes a bobbin for winding up the strip-shaped member, in which the strip-shaped member is conveyed in the direction of the arrow in the figure. Of course, this can also be carried in reverse. Further, in the vacuum container 102, 103, winding and feeding means for a mount used for protecting the surface of the band-shaped member may be disposed, and the material of the mount may be as follows:
Heat-resistant resins such as polyimide, Teflon, and glass wool are preferably used. 106 and 107 are conveyance rollers that also serve as tension adjustment and positioning of the strip member. 133 and 134 are temperature adjustment mechanisms used for preheating or cooling the strip member. 108.109.131
．． Reference numeral 132 indicates exhaust pipes, each of which is connected to an exhaust pump (not shown). 110.111 is a pressure gauge, and 1
12.113.114.115 is gate gas introduction pipe, 1
Reference numerals 16, 117, 118, and 119 are gate gas exhaust pipes, from which gate gas and substrate processing auxiliary gas such as sputtering gas are exhausted by an exhaust pump (not shown). 123 is the reflective conductive film forming strip member temperature controller;
Reference numeral 4 denotes the temperature controller for the band-shaped member for forming the buffer layer, which controls the temperature of the band-shaped member in each process.
１２７は前記反射性導電膜形成用ＤＣスパッタターゲッ
ト、１２８は前記緩衝屡形成用ＤＣスパッタターゲット
である。１２５．１２６は前記帯状部材の支持・搬送用
のローラーであり、１２９は前記反射光強度法による表
面粗さ測定手段における白色光照射及び反射光受光部分
であり、前記帯状部材に対して位置が保たれている。127 is the DC sputter target for forming the reflective conductive film, and 128 is the DC sputter target for forming the buffer layer. 125 and 126 are rollers for supporting and conveying the strip member, and 129 is a white light irradiation and reflected light receiving portion of the surface roughness measuring means using the reflected light intensity method, which is located at a position relative to the strip member. It is maintained.
１３０は光ファイバーを束ねて成る光伝送路であり、光
反射率計側装置（不図示）と連結されている。Reference numeral 130 denotes an optical transmission line formed by bundling optical fibers, and is connected to a light reflectance meter side device (not shown).
なお、第１図の装置構成を更に簡略化して第５図（Ａ）
のように表わすものとし、以下の装置例では該様式にし
たがって図示するものとする。第５（Ａ）図中で、５０
１．５０２は帯状部材の送りだし及び巻き取り手段を、
５０３はガスゲート手段を、５０４は前記の表面粗さ測
定手段を、５０５．５０６はＤＣスパッタ装置を各々表
わしている。In addition, the device configuration in FIG. 1 is further simplified as shown in FIG. 5 (A).
The following device examples will be illustrated in accordance with this format. In Figure 5(A), 50
1.502 refers to a means for feeding and winding a strip member,
503 represents a gas gate means, 504 represents the surface roughness measuring means, and 505 and 506 represent a DC sputtering device, respectively.
（装置例２）
本発明の方法を用いて大面積太陽電池基板を製造し、か
つ該大面積太陽電池基板上に太陽電池を連続して作製す
るための装置例の簡略化した模式図を第５図（Ｂ）に示
す。(Apparatus Example 2) A simplified schematic diagram of an apparatus example for producing a large-area solar cell substrate using the method of the present invention and continuously producing solar cells on the large-area solar cell substrate is shown in FIG. This is shown in Figure 5 (B).
５０１．５０２は帯状部材の送りだし及び巻き取り手段
を、５０３はガスゲート手段を、５０４は前記の表面粗
さ測定手段を、５０５．５０６はＤＣスパッタ装置を各
々表わしている。５０７．５０９は通常のＲＦグロー放
電ＣＶＤ法を用いた前記機能性堆積膜形成手段を、５０
８はマイクロ波ＣＶＤ法を用いた前記機能性堆積膜形成
手段を、５１０は抵抗加熱蒸着法を用いた前記透明導電
膜形成手段を、５１１は銀ペーストのスクリーン印刷法
を用いた前記集電電極形成手段を各々表わしている。Reference numerals 501 and 502 represent means for feeding and winding up the strip member, 503 represents a gas gate means, 504 represents the surface roughness measuring means, and 505 and 506 represent a DC sputtering device. 507.509 is a method for forming a functional deposited film using a normal RF glow discharge CVD method.
8 is the functional deposited film forming means using microwave CVD method, 510 is the transparent conductive film forming means using resistance heating vapor deposition method, and 511 is the current collecting electrode using silver paste screen printing method. Each represents a forming means.
本装置例によりて製造される大面積太陽電池の層構成と
して典型的な例を第６図（Ａ）に模式的に示す。A typical example of the layer structure of a large-area solar cell manufactured by this example of the apparatus is schematically shown in FIG. 6(A).
また、本発明の方法によって製造される大面積太陽電気
基板上に好適に製造される太陽電池の他の層構成の例を
第６図（Ｂ）乃至（Ｄ）に模式的に示す。Further, examples of other layer configurations of solar cells suitably manufactured on a large-area solar electric substrate manufactured by the method of the present invention are schematically shown in FIGS. 6(B) to 6(D).
第６図（Ａ）に示す例は、支持体６０１上に下部電極６
０２、ｎ型半導体層６０３、ｉ型半導体層６０４、ｐ型
半導体層６０５、透明電極６０６及び集電電極６０７を
この順に堆積形成した太陽電池６００である。なお、本
太陽電池では透明電極６０６の側より光の入射が行われ
ることを前提としている。In the example shown in FIG. 6(A), the lower electrode 6 is placed on the support 601.
02, a solar cell 600 in which an n-type semiconductor layer 603, an i-type semiconductor layer 604, a p-type semiconductor layer 605, a transparent electrode 606, and a current collecting electrode 607 are deposited in this order. Note that this solar cell is based on the assumption that light is incident from the transparent electrode 606 side.
第６図ＣＢ）に示す例は透光性の支持体６０１上に透明
電極６０６、ｐ型半導体層６０５、ｉ型半導体層６０４
、ｎ型半導体層６０３及び下部電極６０２をこの順に堆
積形成した太陽電池６００’である。本太陽電池では透
光性の支持体６０１の側より光の入射が行われることを
前提としている。In the example shown in FIG. 6 CB), a transparent electrode 606, a p-type semiconductor layer 605, an i-type semiconductor layer 604 are placed on a transparent support 601.
, a solar cell 600' in which an n-type semiconductor layer 603 and a lower electrode 602 are deposited in this order. This solar cell is based on the premise that light is incident from the transparent support 601 side.
第６図（Ｃ）に示す例は、バンドギャップ及び／又は層
厚の異なる２種の半導体層をｉ層として用いたｐｉｎ接
合型太陽電池６１１．６１２を２素子積層して構成され
たいわゆるタンデム型太陽電池６１３である。６０１は
支持体であり、下部電極６０２、ｎ型半導体層６０３、
ｉ型半導体層６０４、ｎ型半導体層６０５、ｎ型半導体
層６０８、ｉ型半導体層６０９、ｎ型半導体層６１０、
透明電極６０６及び集電電極６０７がこの順に積層形成
され、本太陽電池では透明電極６０６の側より光の入射
が行われることを前提としている。The example shown in FIG. 6(C) is a so-called tandem solar cell constructed by stacking two pin junction solar cells 611 and 612 using two types of semiconductor layers with different band gaps and/or layer thicknesses as the i-layer. It is a type solar cell 613. 601 is a support body, which includes a lower electrode 602, an n-type semiconductor layer 603,
i-type semiconductor layer 604, n-type semiconductor layer 605, n-type semiconductor layer 608, i-type semiconductor layer 609, n-type semiconductor layer 610,
It is assumed that a transparent electrode 606 and a current collecting electrode 607 are laminated in this order, and that light is incident from the transparent electrode 606 side in this solar cell.
第６図（Ｄ）に示す例は、バンドギャップ及び／又は層
厚の異なる３種の半導体層をｉ層として用いたｐｉｎ接
合型太陽電池６２０．６２１．６２３を３素子積層して
構成された、いわゆるトリプル型太陽電池６２４である
。６０１は支持体であり、下部電極６０２、ｎ型半導体
層６０３、ｉ型半導体層６０４、ｎ型半導体層６０５、
ｎ型半導体Ｎ６１４、ｉ型半導体層６１５、ｎ型半導体
層６１６、ｎ型半導体層６１７、ｉ型半導体層６１８、
ｎ型半導体層６１９、透明電極６０６及び集電電極６０
７がこの順に積層形成され、本太陽電池では透明電極６
０６の側より光の入射が行われることを前提としている
。The example shown in FIG. 6(D) is constructed by stacking three pin junction solar cells 620, 621, and 623 in which three types of semiconductor layers with different band gaps and/or layer thicknesses are used as the i-layer. This is a so-called triple solar cell 624. 601 is a support body, which includes a lower electrode 602, an n-type semiconductor layer 603, an i-type semiconductor layer 604, an n-type semiconductor layer 605,
n-type semiconductor N614, i-type semiconductor layer 615, n-type semiconductor layer 616, n-type semiconductor layer 617, i-type semiconductor layer 618,
N-type semiconductor layer 619, transparent electrode 606, and current collecting electrode 60
7 are laminated in this order, and in this solar cell, the transparent electrode 6
It is assumed that light is incident from the 06 side.
なお、いずれの太陽電池においてもｎ型半導体層とｐ型
半導体層とは目的に応じて各層の積層順を入れ変えて使
用することもできる。Note that in any solar cell, the n-type semiconductor layer and the p-type semiconductor layer can be used by changing the stacking order of each layer depending on the purpose.
以下、これらの太陽電池の構成について説明する。The configurations of these solar cells will be explained below.
帯状部材
本発明において用いられる帯状部材６０１は、フレキシ
ブルである材質のものが好適に用いられ、導電性のもの
であっても、また電気絶縁性のものであってもよい、さ
らには、それらは透光性のものであっても、また非透光
性のものであってもよいが、支持体６０１の側より光入
射が行われる場合には、もちろん透光性であることが必
要である。Band-shaped member The band-shaped member 601 used in the present invention is preferably made of a flexible material, and may be electrically conductive or electrically insulating. It may be either translucent or non-transparent, but of course it is required to be translucent when light is incident from the side of the support 601. .
具体的には、本発明において用いられる前記帯状部材を
挙げることができ、該帯状部材を用いることにより、作
製される太陽電池の軽量化、強度向上、運搬スペースの
低減等が図れる。Specifically, the above-mentioned band-shaped member used in the present invention can be mentioned, and by using the band-shaped member, the weight of the manufactured solar cell can be reduced, the strength can be improved, and the transportation space can be reduced.
電極
本太陽電池においては、当該素子の構成形態により適宜
の電極が選択使用される。それらの電極としては、下部
電極、上部電極（透明電極）、集電電極を挙げることが
できる。（ただし、ここでいう上部電極とは光の入射側
に設けられたものを示し、下部電極とは半導体層を挟ん
で上部電極に対向して設けられたものを示すこととする
。）これらの電極について以下に詳しく説明する。Electrode In the present solar cell, an appropriate electrode is selected and used depending on the configuration of the element. Examples of these electrodes include a lower electrode, an upper electrode (transparent electrode), and a current collecting electrode. (However, the upper electrode here refers to the one provided on the light incident side, and the lower electrode refers to the one provided opposite the upper electrode with the semiconductor layer in between.) The electrodes will be explained in detail below.
（Ｉ）下部電極
本発明において用いられる下部電極６０２としては、上
述した帯状部材６０１の材料が透光性であるか否かによ
って、光起電力発生用の光を照射する面が異なる故（た
とえば帯状部材６０１が金属等の非透光性の材料である
場合には、第６図（Ａ）で示したごとく透明電極６０６
側から光起電力発生用の光を照射する。）その設置され
る場所が異なる。(I) Lower electrode As the lower electrode 602 used in the present invention, the surface to which light for photovoltaic generation is irradiated differs depending on whether the material of the above-mentioned strip member 601 is translucent or not (for example, When the strip member 601 is made of a non-transparent material such as metal, a transparent electrode 606 is used as shown in FIG. 6(A).
Light for photovoltaic generation is irradiated from the side. ) The location where it is installed is different.
具体的には、第６図（Ａ）、（Ｃ）及び（Ｄ）のような
層構成の場合には帯状部材６０１とｎ型半導体層６０３
との間に設けられる。しかし、帯状部材６０１が導電性
である場合には、該帯状部材が下部電極を兼ねることが
できる。ただし、帯状部材６０１が導電性であってもシ
ート抵抗値が高い場合には、電流取り出し用の低抵抗の
電極として、あるいは基板表面での反射率を高め入射光
の有効利用を図る目的で電極６０２を設置してもよい。Specifically, in the case of layer configurations as shown in FIGS. 6(A), (C), and (D), the strip member 601 and the n-type semiconductor layer 603
established between. However, when the strip member 601 is conductive, the strip member 601 can also serve as the lower electrode. However, even if the strip member 601 is conductive, if the sheet resistance value is high, it may be used as a low-resistance electrode for current extraction, or as an electrode for increasing the reflectance on the substrate surface and effectively utilizing incident light. 602 may be installed.
第６図（Ｂ）の場合には透光性の帯状部材６０１が用い
られており、帯状部材６０１の側から光が入射されるの
で、電流取り出し及び当該電極での光反斜用の目的で、
下部電極６０２が帯状部材６０１と対向して半導体層を
挟んで設りられている。In the case of FIG. 6(B), a translucent band member 601 is used, and since light is incident from the side of the band member 601, it is used for the purpose of current extraction and light reversal at the electrode. ,
A lower electrode 602 is provided facing the strip member 601 with a semiconductor layer in between.
また、帯状部材６０１として電気絶縁性のものを用いる
場合には電流取り出し用の電極として、帯状部材６０１
とｎ型半導体層６０３との間に下部電極６０２が設けら
れる。In addition, when using an electrically insulating material as the strip member 601, the strip member 601 can be used as an electrode for taking out current.
A lower electrode 602 is provided between the n-type semiconductor layer 603 and the n-type semiconductor layer 603 .
電極材料としてはＡ ｇ Ａ ｕ ％ Ｐ ｔ ％
Ｎ ｉ ｓＣｒ％Ｃｕ、ＡＩ％Ｔｉ、Ｚｎ％Ｍｏ、Ｗ等
の金属又はこれらの合金が挙げられ、これ等の金属の薄
膜を真空蒸着、電子ビーム蒸着、スパツタリング等で形
成する。また、形成された金属薄膜は太陽電池の出力に
対して抵抗成分とならぬように配慮されねばならず、シ
ート抵抗値として好ましくは５ｏΩ以下、より好ましく
は１０Ω以下であることが望ましい。As electrode materials, A g A u % P t %
Examples include metals such as NisCr%Cu, AI%Ti, Zn%Mo, and W, or alloys thereof, and a thin film of these metals is formed by vacuum evaporation, electron beam evaporation, sputtering, or the like. Further, care must be taken so that the formed metal thin film does not become a resistance component with respect to the output of the solar cell, and it is desirable that the sheet resistance value is preferably 50Ω or less, more preferably 10Ω or less.
下部電極６０２とｎ型半導体層６０３との間に、図中に
は示されていないが、ＺｎＯ等の短絡防止及び拡散防止
のための緩衝層を設けても良い、該緩衝層の効果として
は電極６０２を構成する金属元素がｎ型半導体層中へ拡
散するのを防止するのみならず、若干の抵抗値をもたせ
ることで半導体層を挟んで設けられた下部電極６０２と
透明電極６０６との間にピンホール等の欠陥で発生する
ショートを防止すること、及び薄膜による多重干渉を発
生させ入射された光を太陽電池内に閉じ込める等の効果
を挙げることができる。Although not shown in the figure, a buffer layer of ZnO or the like for short circuit prevention and diffusion prevention may be provided between the lower electrode 602 and the n-type semiconductor layer 603.The effect of the buffer layer is as follows. This not only prevents the metal elements constituting the electrode 602 from diffusing into the n-type semiconductor layer, but also provides a slight resistance value between the lower electrode 602 and the transparent electrode 606, which are provided with the semiconductor layer in between. It can have effects such as preventing short circuits caused by defects such as pinholes, and confining incident light within the solar cell by generating multiple interference due to the thin film.
（ＩＩ）上部電極（透明電極）
本発明において用いられる透明電極６０６としては太陽
や白色蛍光灯等からの光を半導体層内に効率良く吸収さ
せるために光の透過率が８５％以上であることが望まし
く、さらに、電気的には太陽電池の出力に対して抵抗成
分とならぬようにシート抵抗値は１００Ω以下であるこ
とが望ましい。このような特性を備えた材料として５ｎ
Ｐ２ 、Ｉ ｎｚ Ｏｓ 、ＺｎＯ，Ｃｄ０１Ｃｄ２Ｓ
ｎ０４ 、Ｉ Ｔｏ （Ｉ ｎｚ ０ｓ ＋５ｎＯｚ
）などの金属酸化物や、Ａｕ、Ａｌ、Ｃｕ等の金属を極
めて薄く半透明状に成膜した金属薄膜等が挙げられる。(II) Upper electrode (transparent electrode) The transparent electrode 606 used in the present invention must have a light transmittance of 85% or more in order to efficiently absorb light from the sun, white fluorescent lamp, etc. into the semiconductor layer. Further, it is desirable that the sheet resistance value is 100Ω or less so as not to become a resistance component electrically with respect to the output of the solar cell. 5n is a material with such characteristics.
P2, InzOs, ZnO, Cd01Cd2S
n04 , I To (I nz 0s +5nOz
Examples include metal oxides such as ), and metal thin films made of metals such as Au, Al, and Cu in an extremely thin and translucent manner.
透明電極は第６図（Ａ）、（Ｃ）、（Ｄ）においてはｐ
型半導体層６０５層の上に積層され、第６図（Ｂ）にお
いては基板６０１の上に積層されるものであるため、互
いの密着性の良いものを選ぶことが必要である。これら
の作製方法としては、抵抗加熱蒸着法、電子ビーム加熱
蒸着法、スパッタリング法、スプレー法等を用いること
ができ所望に応じて適宜選択される。The transparent electrode is p in FIGS. 6(A), (C), and (D).
Since the semiconductor layer 605 is laminated on the substrate 601 in FIG. 6(B), it is necessary to select materials that have good adhesion to each other. As a method for producing these, a resistance heating evaporation method, an electron beam heating evaporation method, a sputtering method, a spray method, etc. can be used, and the method is appropriately selected depending on the need.
（ｍ）集電電極
本発明において用いられる集電電極６０７は、透明電極
６０６の表面抵抗値を低減させる目的で透明電極６０６
上に設けられる。電極材料とじてはＡｇ、Ｃｒ％Ｎｉ、
Ａｌ、Ａｇ、Ａｕ％Ｔｉ。(m) Current collector electrode The current collector electrode 607 used in the present invention is a transparent electrode 607 for the purpose of reducing the surface resistance value of the transparent electrode 606.
provided above. The electrode material is Ag, Cr%Ni,
Al, Ag, Au%Ti.
ｐｔ％Ｃｕ、Ｍｏ、Ｗ等の金属またはこれらの合金の薄
膜が挙げられる。これらの薄膜は積層させて用いること
ができる。また、半導体層への光入射光量が十分に確保
されるよう、その形状及び面積が適宜設計される。Examples include thin films of metals such as pt% Cu, Mo, and W, or alloys thereof. These thin films can be used in a stacked manner. Further, the shape and area of the semiconductor layer are appropriately designed so that a sufficient amount of light incident on the semiconductor layer is ensured.
たとえば、その形状は太陽電池の受光面に対して一様に
広がり、且つ受光面積に対してその面積は好ましくは１
５％以下、より好ましくは１０％以下であることが望ま
しい。For example, its shape should spread uniformly over the light-receiving surface of the solar cell, and its area should preferably be 1 with respect to the light-receiving area.
It is desirable that it be 5% or less, more preferably 10% or less.
また、シート抵抗値としては、好ましくは５０Ω以下、
より好ましくは１０Ω以下であることが望ましい。In addition, the sheet resistance value is preferably 50Ω or less,
More preferably, it is 10Ω or less.
ｉ型半導体層
本発明によって作製される太陽電池において好適に用い
られるｉ型半導体層を構成する半導体材料としては、ａ
−Ｓｉ ：Ｈ，ａ−Ｓｉ 二Ｆ、 ａ −Ｓｉ ：Ｈ
：Ｆ％ ａ−３ｉＣ：Ｈ，ａ−３ｉＣ：Ｆ、ａ−３ｉＣ
：Ｈ：Ｆ％ ａ−ＳｉＧｅ：Ｈ。i-type semiconductor layer Semiconductor materials constituting the i-type semiconductor layer suitably used in the solar cell produced by the present invention include a
-Si:H, a-Si 2F, a-Si:H
:F% a-3iC:H, a-3iC:F, a-3iC
:H:F% a-SiGe:H.
ａ−ＳｉＧｅ：Ｆ、ａ−ＳｉＧｅ：Ｈ：Ｆ、多結晶質Ｓ
ｉ ：Ｈ２多結晶質Ｓｉ ：Ｆ、多結晶質Ｓｉ ：Ｈ：
Ｆ等いわゆる■族及び■鉄合金系半導体材料の他、■−
■族及び■−ｖ族のいわゆる化合物半導体材料等が挙げ
られる。a-SiGe:F, a-SiGe:H:F, polycrystalline S
i:H2 Polycrystalline Si:F, Polycrystalline Si:H:
In addition to the so-called ■ group such as F and ■ iron alloy semiconductor materials, ■-
Examples include so-called compound semiconductor materials of group (1) and group (2)-v.
ｐ型半導体層及びｎ型半導体層
本発明によって作製される太陽電池において好適に用い
られるｐ型又はｎ型半導体層を構成する半導体材料とし
ては、前述したｉ型半導体層を構成する半導体材料に価
電子制御剤をドーピングすることによって得られる。P-Type Semiconductor Layer and N-Type Semiconductor Layer Semiconductor materials constituting the p-type or n-type semiconductor layer suitably used in the solar cell produced by the present invention include those having a value equal to the semiconductor material constituting the i-type semiconductor layer described above. Obtained by doping with an electronic control agent.
〔実施例１
以下、本発明の方法を用いた大面積太陽電池基板及び大
面積太陽電池製造の具体的実施例を示すが、本発明はこ
れらの実施例によって何ら限定されるものではない。[Example 1] Hereinafter, specific examples of manufacturing a large-area solar cell substrate and a large-area solar cell using the method of the present invention will be shown, but the present invention is not limited to these examples in any way.
（実施例１）
装置例１で説明した本発明の大面積太陽電池基板製造方
法を用いて帯状部材上複数工程の処理を施すことにより
、大面積太陽電池基板の連続製造を行った。(Example 1) Using the large area solar cell substrate manufacturing method of the present invention described in Apparatus Example 1, a plurality of steps were performed on a strip member to continuously manufacture a large area solar cell substrate.
まず基板送り出し機構を有する真空容器１０２に、十分
に脱脂、洗浄を行った５ＵＳ４３０ＢＡ製帯状部材１０
１ （幅４５ｃｍＸ長さ２００ｍ×厚さ０．０８ｍｍ）
の巻きつけられたボビン１０４をセットし、該帯状部材
１０）をガスゲート、各種処理空間、測定空間を介して
、帯状部材巻き取り機構を有する真空容器１０３まで通
し、たるみのない程度に張力調整を行った。First, a strip member 10 made of 5US430BA that has been thoroughly degreased and cleaned is placed in a vacuum container 102 having a substrate feeding mechanism.
1 (width 45cm x length 200m x thickness 0.08mm)
The bobbin 104 wound with is set, and the strip member 10) is passed through a gas gate, various processing spaces, and measurement spaces to a vacuum container 103 having a strip winding mechanism, and the tension is adjusted to the extent that there is no slack. went.
そこで、各真空容器１０２．１０３．１２０１１２１．
１２２を不図示のロータリーポンプで荒引きし、次いで
不図示のメカニカルブースターポンプな起動させ１０−
’Ｔｏｒｒ付近まで真空引きした後、不図示の油拡散ポ
ンプ（バリアン製ＨＳ−３２）にて５Ｘ１０−’Ｔｏｒ
ｒ以下まで真空引きした。Therefore, each vacuum container 102.103.1201121.
122 is roughly pumped with a rotary pump (not shown), and then a mechanical booster pump (not shown) is activated.
After evacuation to around 'Torr, 5X10-'Tor was applied using an oil diffusion pump (not shown, Varian HS-32).
The vacuum was evacuated to below r.
また前記帯状部材温度コントローラー１３３．１２３．
１２４．１３４をそれぞれ動作させ、該帯状部材１０１
の表面温度の制御を行った。Further, the band member temperature controller 133.123.
124 and 134 respectively, and the strip member 101
The surface temperature was controlled.
充分に脱ガスが行われた時点で、ガス導入管（不図示）
より、Ａｒガス２０ｓｅｃｍをＤＣスパッタ装置１２０
内及び１２２内に各々導入し、該ＤＣスパッタ装置内の
内圧が５ｍＴｏｒｒとなるよう前記油拡散ポンプ（不図
示）に取り付けられたスロットルバルブ（不図示）の開
度を調整した。圧力が安定したところで該ＤＣスパッタ
装置内のＡｇターゲット１２７、及びＺｎＯターゲツ１
−１２８と前記帯状部材の間にＤＣパワーを印可し、グ
ロー放電を生起せしめ、前記帯状部材上にＡｇ及びＺｎ
Ｏ薄膜を形成した。Once sufficient degassing has occurred, open the gas inlet pipe (not shown).
Then, Ar gas was applied at 20 sec to the DC sputtering device 120.
The opening degree of a throttle valve (not shown) attached to the oil diffusion pump (not shown) was adjusted so that the internal pressure in the DC sputtering device was 5 mTorr. Once the pressure stabilized, the Ag target 127 and the ZnO target 1 in the DC sputtering device were removed.
DC power is applied between -128 and the strip member to generate glow discharge, and Ag and Zn are deposited on the strip member.
An O thin film was formed.
また、それと同時に反射光強度法を用いた表面粗さ測定
手段１２１において前記白色光照射及び反射光受光部分
１２９と前記帯状部材１０１の間の間隔を保ちつつ光照
射を行い該帯状部材表面の凹凸形状の粗さを測定した。At the same time, the surface roughness measuring means 121 using the reflected light intensity method irradiates the white light while maintaining the distance between the reflected light receiving portion 129 and the strip member 101, thereby forming the irregularities on the surface of the strip member. The roughness of the shape was measured.
なおガスゲートにはゲートガス導入管１１２．１１３．
１１４．１１５よりゲートガスとしてＡｒガスを５０ｓ
ｅｃｍ流し、排気孔１１６．１１７．１１８．１１９よ
り不図示の油拡散ポンプで排気し、ガスゲート部内圧は
１ ｍ Ｔ ｏ ｒ １−となるように制御した。Note that the gas gate has gate gas introduction pipes 112, 113.
From 114.115, Ar gas was used as gate gas for 50 seconds.
ecm was flowed, and the gas was evacuated from the exhaust holes 116, 117, 118, and 119 using an oil diffusion pump (not shown), and the internal pressure of the gas gate section was controlled to be 1 m Tor 1-.
また、表面粗さ測定手段１２１にて前記帯状部材表面の
表面粗さをモニターにし、その結果によりＡｇ薄膜形成
時の前記帯状部材の表面温度に対して制御を行った。す
なわち、前記帯状部材の表面粗さの程度が大きい、ある
いは小さい方に変位したときには前記ＤＣスパッタ法を
用いたＡｇ薄膜形成手段１２０における前記帯状部材表
面温度を下げる、あるいは上げるように前記帯状部材加
熱手段１３３及び前記帯状部材表面温度コントローラ１
２３によって制御した。この反射性導電膜形成時の帯状
部材表面温度制御は、前述したように前記反射性導電膜
表面の粗さを制御する効果を期待して行ったものである
。In addition, the surface roughness of the surface of the strip member was monitored by a surface roughness measuring means 121, and the surface temperature of the strip member during the formation of the Ag thin film was controlled based on the results. That is, when the degree of surface roughness of the belt-shaped member is large or displaced to a small degree, the belt-shaped member is heated to lower or increase the surface temperature of the belt-shaped member in the Ag thin film forming means 120 using the DC sputtering method. Means 133 and the strip member surface temperature controller 1
Controlled by 23. This control of the surface temperature of the strip member during the formation of the reflective conductive film was carried out in anticipation of the effect of controlling the roughness of the surface of the reflective conductive film, as described above.
搬送を開始してから連続して大面積太陽電池基板の製造
を行い、本実施例の処理が終了した後、前記巻き取りボ
ビン１０５に巻き取られた前記帯状部材を冷却して取り
出し、中心線平均粗さの分布を長平方向について測定し
たところ、むらは２％以内に収まっていた。Large-area solar cell substrates are manufactured continuously after the start of transportation, and after the processing of this embodiment is completed, the strip member wound up on the winding bobbin 105 is cooled and taken out, and the center line is When the distribution of average roughness was measured in the longitudinal direction, the unevenness was within 2%.
更に、このようにして製造された大面積太陽電池基板を
切り出し、この上に第６図（Ａ）で示される層構成を有
するｐｉｎ型ａ−Ｓｉ太陽電池を作製し、太陽電池ユニ
ットセルの光電変換効率のむらをＡＭｌ、５ （１００
ｍＷ／ｃｍ’）光照射下にて前記帯状部材長手方向に亘
って測定したところ、５％以内に収まっていた。Furthermore, the large-area solar cell substrate produced in this way was cut out, and a pin type A-Si solar cell having the layer structure shown in FIG. The unevenness of conversion efficiency is AMl, 5 (100
When measured over the longitudinal direction of the strip member under light irradiation (mW/cm'), it was within 5%.
（実施例２）
本実施例では、表面粗さ測定手段１２】にて前記帯状部
材表面の表面粗さをモニターし、その結果によりＡｇ薄
膜形成時の前記帯状部材の表面温度と、ＺｎＯ薄膜形成
時の放電電力のふたつに対して制御を行った。すなわち
、前記帯状部材の表面粗さの程度が大きい、あるいは小
さい方に変位したときには前記ＤＣスパッタ法を用いた
Ａｇ薄膜形成手段１２０における前記帯状部材表面温度
を下げ、あるいは上げるように前記帯状部材加熱手段１
３３及び前記帯状部材表面温度コントローラ１２３によ
って制御し、また、前記ＤＣスパッタ法を用いたＺｎＯ
薄膜形成手段における放電電力を上げる、あるいは下げ
るように制御した。後者のＤＣ放電電力制御の効果とし
て、表面粗さの大きい基板に対するＺｎ○薄膜の緩衝効
果の調節を期待して行ったものである。(Example 2) In this example, the surface roughness of the surface of the strip member is monitored by the surface roughness measuring means 12, and the surface temperature of the strip member during the formation of the Ag thin film and the surface temperature of the strip member during the formation of the ZnO thin film are determined based on the results. Control was performed on two types of discharge power: That is, when the degree of surface roughness of the belt-shaped member is increased or decreased, the belt-shaped member is heated to lower or increase the surface temperature of the belt-shaped member in the Ag thin film forming means 120 using the DC sputtering method. Means 1
33 and the belt-shaped member surface temperature controller 123, and the ZnO using the DC sputtering method.
The discharge power in the thin film forming means was controlled to be increased or decreased. As the latter effect of DC discharge power control, this was done in anticipation of adjusting the buffering effect of the Zn○ thin film on a substrate with a large surface roughness.
上記の点をのぞいて実施例１と同様にして大面積太陽電
池基板の連続的製造及び評価を行ったところ、表面粗さ
のむらは２％、また、この大面積太陽電池基板を用いて
作製した太陽電池ユニットセルの光電変換効率のむらは
３％に収まっていた。これはＺｎＯの緩衝層としての効
果が適当に調節されたことによる効果が表われたものと
考えられる。A large area solar cell substrate was continuously manufactured and evaluated in the same manner as in Example 1 except for the above points, and the surface roughness unevenness was 2%. The variation in photoelectric conversion efficiency of the solar battery unit cells was within 3%. This is considered to be due to the effect that the effect of ZnO as a buffer layer was appropriately adjusted.
（実施例３）
本実施例においては、第５（Ｂ）図に示す装置を用いて
、大面積太陽電池基板の製造及び該大面積太陽電池基板
上への第６図（Ａ）に示す層構成を有するｐｉｎ型ａ−
３ｉ太陽電池の製造を連続して行った。(Example 3) In this example, using the apparatus shown in FIG. 5(B), a large area solar cell substrate was manufactured and a layer shown in FIG. 6(A) was deposited on the large area solar cell substrate. A pin type a-
The production of 3i solar cells was carried out continuously.
本実施例の工程中、大面積太陽電池基板製造の方法につ
いては実施例２と同様にして行った。During the process of this example, the method for producing a large area solar cell substrate was carried out in the same manner as in Example 2.
本実・施例における前記ｐｉｎ型ａ−３ｉ太陽電池は、
基板６０１上に反射性導電膜６０２、ｎ型半導体層６０
３、ｉ型半導体層６０４、ｐ型半導体層６０５、透明電
極６０６及び集電電極６０７をこの順に堆積形成した太
陽電池６００である。The pin type A-3i solar cell in this example is:
A reflective conductive film 602 and an n-type semiconductor layer 60 are formed on a substrate 601.
3. A solar cell 600 in which an i-type semiconductor layer 604, a p-type semiconductor layer 605, a transparent electrode 606, and a current collecting electrode 607 are deposited in this order.
なお、本実施例の太陽電池では透明電極６０６の側より
光の入射が行われることを前提としている。Note that in the solar cell of this example, it is assumed that light is incident from the transparent electrode 606 side.
第１のＲＦプラズマＣＶＤ法を用いた機能性堆積膜形成
手段５０７において、ｎ型ａ−Ｓｉ：Ｈ：Ｆ膜６０３の
形成を行った。マイクロ波プラズマＣＶＤ法を用いた機
能性堆積膜形成手段５０４にてｉ型ａ−３ｉ：Ｈ：Ｆ膜
６０４を形成した。更に、第２のＲＦプラズマＣＶＤ法
を用いた機能性堆積膜形成手段５０６において、ｐ型機
結晶（ｕ ｃ −上記ｔ ） Ｓ １ ： Ｈ： Ｆ
ｍ ６０５ （７）形成を行った。In the functional deposited film forming means 507 using the first RF plasma CVD method, an n-type a-Si:H:F film 603 was formed. An i-type a-3i:H:F film 604 was formed using a functional deposited film forming means 504 using a microwave plasma CVD method. Furthermore, in the functional deposited film forming means 506 using the second RF plasma CVD method, a p-type machine crystal (uc - the above t) S1:H:F
m 605 (7) formation was performed.
また、加熱蒸着法を用いた透明導電膜形成手段５１０に
てＩＴＯ膜６０６の形成、スクリーン印刷手段５１１に
て銀ペーストの集電電極６０７の印刷と加熱乾燥を行っ
た。Further, an ITO film 606 was formed using a transparent conductive film forming means 510 using a heating vapor deposition method, and a current collecting electrode 607 of silver paste was printed and heated and dried using a screen printing means 511.
各々のプラズマＣＶＤ装置内でプラズマを生起させ、ガ
ス流量、放電等が安定したところで帯状部材１０１を図
中左側から右側方向へ搬送させ、大面積太陽電池基板製
造工程に連続して、ｎ、ｉ、ｐ型半導体層を積層形成し
、その上に透明電極、集電電極の形成を行った。Plasma is generated in each plasma CVD apparatus, and when the gas flow rate, discharge, etc. are stabilized, the strip member 101 is conveyed from the left side to the right side in the figure, and successively continues to the large area solar cell substrate manufacturing process. , p-type semiconductor layers were laminated, and a transparent electrode and a current collecting electrode were formed thereon.
帯状部材１０１の全長に亘って太陽電池を積層形成した
後、冷却後取り出し、前記太陽電池ユニットセルの光電
変換効率のばらつきを実施例１と同様にして測定したと
ころ、光電変換効率のばらつきは２．５％に収まってい
た。After solar cells were layered over the entire length of the strip member 101, it was taken out after cooling and the variation in photoelectric conversion efficiency of the solar cell unit cells was measured in the same manner as in Example 1. As a result, the variation in photoelectric conversion efficiency was 2. It was within .5%.
更に、このようにして製造された太陽電池を用いて３５
ｃｍＸ７０ｃｍの太陽電池モジュールを作製した。作製
した太陽電池モジュールについて、特性評価を行ったと
ころ、光電変換効率で８．３％以上が得られ、更にモジ
ュール間の特性のバラツキは３％以内に収まっていた。Furthermore, using the solar cells manufactured in this way, 35
A solar cell module of cm×70 cm was produced. Characteristic evaluation of the produced solar cell module revealed that a photoelectric conversion efficiency of 8.3% or more was obtained, and the variation in characteristics between modules was within 3%.
これらのモジュールを接続して３ｋＷの電力供給システ
ムを作製することができた。By connecting these modules, we were able to create a 3kW power supply system.
（実施例４）
本実施例では、実施例３で作製したｐｉｎ型太陽電池に
おいて、ｉ型半導体層としてのａＳｉ ：Ｈ：Ｆ膜のか
わりにａ−３ｉＧｅ：Ｈ：Ｆ膜を用いた例を示す。(Example 4) This example describes an example in which an a-3iGe:H:F film is used instead of the aSi:H:F film as the i-type semiconductor layer in the pin-type solar cell manufactured in Example 3. show.
本実施例では、ｉ層の材質にａ−３ｉＧｅ：Ｈ：Ｆ膜を
用いた以外は実施例２で行ったのと同様の操作及び方法
で行い、他の工程は実施例３と同様の方法で行い、太陽
電池ユニットセル、太陽電池モジュールを作製した。In this example, the operations and methods were the same as in Example 2 except that an a-3iGe:H:F film was used as the material for the i-layer, and the other steps were the same as in Example 3. A solar cell unit cell and a solar cell module were fabricated.
作製した太陽電池ユニットセルの光電変換効率のばらつ
きを実施例１と同様にして調べたところ、３％に収まっ
ていた。When the variation in photoelectric conversion efficiency of the produced solar cell unit cells was investigated in the same manner as in Example 1, it was found to be within 3%.
また、作製した太陽電池モジュールについて、実施例１
と同様にして特性評価を行ったところ、光電変換効率は
平均で７．３％以上が得られ、更にモジュール間の特性
のばらつきは３％以内に収まっていた。In addition, regarding the produced solar cell module, Example 1
When characteristics were evaluated in the same manner as above, an average photoelectric conversion efficiency of 7.3% or more was obtained, and the variation in characteristics between modules was within 3%.
これらのモジュールを接続して３ｋＷの電力供給システ
ムを作製することができた。By connecting these modules, we were able to create a 3kW power supply system.
比較のため、前記表面粗さ測定手段を機能させないとい
う点を除いて本実施例とまったく同様にし・て太陽電池
子ジュールの製造を行い、同様の測定を行った結果、太
陽電池ユニットセルの光電変換効率のばらつきは１０％
、太陽電池モジュールの光電変換効率の平均６．３％、
モジュール間のばらつきは１２％にも及んでいることが
わかった。本実施例の太陽電池のｉｉがａ−ＳｉＧｅＨ
：Ｆであるため長波長感度が高く、基板の表面性の影響
を強く受けたものと考えられる。For comparison, a solar cell module was manufactured in exactly the same manner as in this example except that the surface roughness measuring means was not activated, and as a result of the same measurement, the photovoltaic value of the solar cell unit cell was Variation in conversion efficiency is 10%
, the average photoelectric conversion efficiency of the solar cell module is 6.3%,
It was found that the variation between modules was as high as 12%. ii of the solar cell of this example is a-SiGeH
:F, it has high long wavelength sensitivity, and is thought to be strongly influenced by the surface properties of the substrate.
［発明の効果］
本発明の方法により、帯状部材をその長手方向に連続的
に移動せしめながら、複数の太陽電池基板処理空間を順
次通過させ、該帯状部材の表面に複数工程の処理を施し
、大面積の太陽電池基板を連続的に製造する際に、前記
帯状部材の移動方向に対して少なくともひとつ以上の前
記太陽電池基板処理空間の後の空間において、前記帯状
部材表面の表面粗さをインプロセスで測定し、その測定
結果を用いて、少なくとも一種類以上の前記太陽電池基
板処理工程に対する制御パラメータをその場で決定する
ことによって、大面積に亘って均一な、かつ再現性良好
な太陽電池基板を製造することが可能となった。[Effects of the Invention] According to the method of the present invention, the strip member is continuously moved in its longitudinal direction and sequentially passed through a plurality of solar cell substrate processing spaces, and the surface of the strip member is subjected to multiple steps of processing, When manufacturing large-area solar cell substrates continuously, the surface roughness of the surface of the strip member is measured in a space after at least one solar cell substrate processing space in the moving direction of the strip member. By measuring in the process and using the measurement results to determine on the spot control parameters for at least one type of solar cell substrate processing process, solar cells can be made uniform over a large area and with good reproducibility. It has become possible to manufacture substrates.
更に、該大面積太陽電池基板を用いて、変換効率が高く
、かつ特性の揃った太陽電池を量産化することが可能と
なった。Furthermore, using the large-area solar cell substrate, it has become possible to mass-produce solar cells with high conversion efficiency and uniform characteristics.
また、大面積太陽電池基板の製造工程後、真空容器から
取り出して表面性の検査をするという工程が省かれるた
め、大面積太陽電池基板の製造工程後、真空を破らずに
連続して大面積太陽電池の製造工程に安定的につなげる
ことが可能となり、稼動率、歩留りの向上が図れ、その
結果として、安価で高効率の太陽電池を量産化すること
が可能となった。In addition, after the manufacturing process of large-area solar cell substrates, the process of removing them from the vacuum container and inspecting their surface properties is omitted, so after the manufacturing process of large-area solar cell substrates, large-area solar cell substrates can be continuously processed without breaking the vacuum. It has become possible to stably connect it to the solar cell manufacturing process, improving operating rates and yields, and as a result, it has become possible to mass-produce inexpensive, highly efficient solar cells.
すなわち、本発明の方法は、大面積太陽電池基板及び大
面積太陽電池の量産方法として好適に用いることができ
る。That is, the method of the present invention can be suitably used as a method for mass-producing large-area solar cell substrates and large-area solar cells.
第１図は本発明の方法を用いた大面積太陽電池基板製造
装置の一例の概念的模式図、
第２図は本発明において好適に用いられるガスゲート手
段の圧力勾配を模式的に示した図、第３図は本発明の方
法に好適に用いられる表面粗さ測定手段の一例の概念的
模式図、
第４図は本発明の方法に好適に用いられる表面粗さ測定
手段の他の一例の概念的模式図、第５図（Ａ）は第１図
の装置をさらに簡略に表わした概略図、
第５図（Ｂ）は第５図（Ａ）と同様の様式で本発明に用
いられる他の装置例の構成を表わした概略図、
第６図（Δ）乃至（Ｄ）はｐｉｎ型太陽電池（シングル
、タンデム、トリプル）の断面模式図である。
１０１・・・帯状部材
１０２．１０３・・・帯状部材の送り出し及び巻き取り
用真空容器
１０４・・・帯状部材の送り出し用ボビン１０５・・・
帯状部材の巻き取り用ボビン１０６．１０７・・・搬送
用ローラー
１０８．１０９．１３１．１３２・・・排気管１１０．
１１１・・・圧力計
１１２．１１３．１１４．１１５・・・ゲートガス導入
管
１１６．１１７．１１８．１１９・・・ゲートガス排気
管
１２０・・・反射性導電膜形成手段用真空容器１２１・
・・表面粗さ測定手段用真空容器１２２・・・緩衝層形
成手段用真空容器１２３・・・反射性導電膜形成用帯状
部材温度コントローラ
１２４・・・緩衝層形成用帯状部材温度コントローフ
１２５．１２６・・・帯状部材の支持・搬送用ローラー
１２７・・・反射性導電膜形成用ＤＣスパッタターゲッ
ト
１２８・・・緩衝層形成用ＤＣスパッタターゲット１２
９・・・白色光照射及び反射光受光部分１３０・・・光
伝送路
１３３．１３４・・・温度調整機構
３０１・・・帯状部材
３０２．３０３・・・支持・搬送用ローラー３０４・・
・白色光照射及び反射光受光部分３０５・・・光伝送路
３０６・・・光反射率計側装置
３０７・・・データ解析及び各種機器制御用コンピュー
タ
３０８．３０９・・・インターフェース３０６・・・反
射率計測装置
４０１・・・帯状部材
４ 。
４ 。
２．４０３・・・支持・搬送用ローラー４・・・表面粗
さ測定用の探針な有するドラム５・・・板バネ
６・・・変位検出器
７・・・スリップリング
８・・・伝送ケーブル
９・・・Ａ／Ｄコンバータ
０・・・データ解析及び各種機器制御用コンピュータ
１．４１２・・・インターフニース
ト・・帯状部材送りだし手段
２・・・帯状部材巻き取り手段
３・・・ガスゲート手段
４・・・表面粗さ測定手段
５・・・ＤＣスパッタ法による反射性導電膜形成手段
６・・・ＤＣスパッタ法による緩衝層形成手段７．５０
９・・・ＲＦプラズマＣＶＤ法による機能性堆積膜形成
手段
５０８・・・マイクロ波ＣＶＤ法による機能性堆積膜形
成手段
５１０・・・抵抗加熱法による透明導電膜形成手段５１
１・・・スクリーン印刷法による集電電極形成手段
６０１・・・帯状部材
６０２・・・下部電極
６０３．６０８．６１４．６１７ ・” ｎ型半導体層
６０４．６０９．６１５．６１８・・・ｉ型半導体層
６０５．６１０．６１６．６１９・・・ｐ型半導体層
６０６・・・上部電極（透明電極）
６０７・・・集電電極
６００．６００’ ６１１．６１２．６２０．６２１
．６２３・・・ｐｉｎ接合型太陽電池第２図
高
第３図
第４図
第６図（Ａ）
第６図（Ｂ）FIG. 1 is a conceptual diagram of an example of a large-area solar cell substrate manufacturing apparatus using the method of the present invention, FIG. 2 is a diagram schematically showing the pressure gradient of the gas gate means preferably used in the present invention, FIG. 3 is a conceptual diagram of an example of a surface roughness measuring means suitably used in the method of the present invention, and FIG. 4 is a conceptual diagram of another example of a surface roughness measuring means suitably used in the method of the present invention. FIG. 5(A) is a schematic diagram further simplifying the apparatus shown in FIG. 1, and FIG. A schematic diagram showing the configuration of an example device. FIGS. 6 (Δ) to (D) are schematic cross-sectional views of pin type solar cells (single, tandem, triple). 101...Band-shaped member 102.103...Vacuum container for feeding and winding up the band-shaped member 104...Bobbin 105 for feeding out the band-shaped member...
Bobbin for winding the strip member 106, 107... Conveyance roller 108, 109, 131, 132... Exhaust pipe 110.
111... Pressure gauge 112.113.114.115... Gate gas inlet pipe 116.117.118.119... Gate gas exhaust pipe 120... Vacuum container 121 for reflective conductive film forming means.
... Vacuum container for surface roughness measuring means 122 ... Vacuum container for buffer layer forming means 123 ... Band-like member temperature controller for forming reflective conductive film 124 ... Band-like member temperature controller for forming buffer layer 125.126 ... Roller for supporting and conveying the strip member 127 ... DC sputter target for forming a reflective conductive film 128 ... DC sputter target for forming a buffer layer 12
9...White light irradiation and reflected light receiving portion 130...Light transmission path 133, 134...Temperature adjustment mechanism 301...Strip member 302, 303...Supporting/conveying roller 304...
・White light irradiation and reflected light receiving portion 305...Optical transmission line 306...Light reflectance meter side device 307...Computer for data analysis and various equipment control 308.309...Interface 306...Reflection Rate measuring device 401...band-shaped member 4. 4. 2.403... Support/transport roller 4... Drum with a probe for surface roughness measurement 5... Leaf spring 6... Displacement detector 7... Slip ring 8... Transmission Cable 9...A/D converter 0...Computer for data analysis and various equipment control 1.412...Interphneist...Meands for feeding out strip 2...Means for winding up strip 3...Gas gate Means 4: Surface roughness measuring means 5: Reflective conductive film forming means by DC sputtering 6: Buffer layer forming means by DC sputtering 7.50
9 Functional deposited film forming means 508 by RF plasma CVD method Functional deposited film forming means 510 by microwave CVD method Transparent conductive film forming means 51 by resistance heating method
1... Means for forming current collecting electrode by screen printing method 601... Band-shaped member 602... Lower electrode 603.608.614.617 ``N-type semiconductor layer 604.609.615.618...I-type Semiconductor layer 605.610.616.619...p-type semiconductor layer 606...upper electrode (transparent electrode) 607...collecting electrode 600.600' 611.612.620.621
．． 623...Pin junction solar cell Figure 2 High Figure 3 Figure 4 Figure 6 (A) Figure 6 (B)
Claims (1)
ら、複数の太陽電池基板処理空間を順次通過させ、該帯
状部材の表面に複数工程の処理を施し、大面積の太陽電
池基板を連続的に製造する方法であり、 前記帯状部材の移動方向に対して少なくともひとつ以上
の前記太陽電池基板処理空間の後の空間において、前記
帯状部材表面の状態をインプロセスで測定し、その測定
結果を用いて、前記太陽電池基板処理空間における処理
工程の少なくとも一種類以上の制御パラメータをその場
で決定することを特徴とする大面積太陽電池基板の連続
製造方法。[Claims] While continuously moving the strip member in its longitudinal direction, the strip member is sequentially passed through a plurality of solar cell substrate processing spaces, and the surface of the strip member is subjected to a plurality of processing steps, so that a large area of solar cells can be processed. A method for continuously manufacturing battery substrates, the method comprising: measuring the state of the surface of the strip member in-process in a space after at least one solar cell substrate processing space in the moving direction of the strip member; A continuous manufacturing method for large-area solar cell substrates, characterized in that the measurement results are used to determine on the spot at least one type of control parameter for a processing step in the solar cell substrate processing space.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2140433A JPH0432268A (en) | 1990-05-29 | 1990-05-29 | Continuous manufacture of large area solar cell substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2140433A JPH0432268A (en) | 1990-05-29 | 1990-05-29 | Continuous manufacture of large area solar cell substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0432268A true JPH0432268A (en) | 1992-02-04 |
Family
ID=15268558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2140433A Pending JPH0432268A (en) | 1990-05-29 | 1990-05-29 | Continuous manufacture of large area solar cell substrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0432268A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5577977A (en) * | 1993-12-22 | 1996-11-26 | Nippondenso Co., Ltd. | Starter equipped with planetary gear reduction mechanism |
| US11764858B2 (en) | 2022-01-26 | 2023-09-19 | Emeric S. Bennett | Communicating polarization-dependent information over a free space channel |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56152276A (en) * | 1980-04-25 | 1981-11-25 | Teijin Ltd | Solar cell made of amorphous silicon thin film |
| JPS57162420A (en) * | 1981-03-16 | 1982-10-06 | Atlantic Richfield Co | Method and device for optically controlling layer thickness |
| JPS59211287A (en) * | 1983-05-16 | 1984-11-30 | Fuji Electric Corp Res & Dev Ltd | Device for manufacturing photoelectric converter |
-
1990
- 1990-05-29 JP JP2140433A patent/JPH0432268A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56152276A (en) * | 1980-04-25 | 1981-11-25 | Teijin Ltd | Solar cell made of amorphous silicon thin film |
| JPS57162420A (en) * | 1981-03-16 | 1982-10-06 | Atlantic Richfield Co | Method and device for optically controlling layer thickness |
| JPS59211287A (en) * | 1983-05-16 | 1984-11-30 | Fuji Electric Corp Res & Dev Ltd | Device for manufacturing photoelectric converter |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5577977A (en) * | 1993-12-22 | 1996-11-26 | Nippondenso Co., Ltd. | Starter equipped with planetary gear reduction mechanism |
| US11764858B2 (en) | 2022-01-26 | 2023-09-19 | Emeric S. Bennett | Communicating polarization-dependent information over a free space channel |
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