JPH11261090A - Solar battery substrate and its manufacture - Google Patents
Solar battery substrate and its manufactureInfo
- Publication number
- JPH11261090A JPH11261090A JP10056907A JP5690798A JPH11261090A JP H11261090 A JPH11261090 A JP H11261090A JP 10056907 A JP10056907 A JP 10056907A JP 5690798 A JP5690798 A JP 5690798A JP H11261090 A JPH11261090 A JP H11261090A
- Authority
- JP
- Japan
- Prior art keywords
- insulating film
- film
- solar cell
- insulating
- metal plate
- 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.)
- Withdrawn
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 48
- 238000003980 solgel method Methods 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000009413 insulation Methods 0.000 claims abstract description 12
- 239000002585 base Substances 0.000 claims description 45
- 239000007772 electrode material Substances 0.000 claims description 17
- 150000004703 alkoxides Chemical class 0.000 claims description 13
- -1 methacryloxy group Chemical group 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000002562 thickening agent Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 150000002484 inorganic compounds Chemical group 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 22
- 239000000377 silicon dioxide Substances 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 239000002344 surface layer Substances 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 238000001579 optical reflectometry Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 149
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229910021417 amorphous silicon Inorganic materials 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 229910018137 Al-Zn Inorganic materials 0.000 description 1
- 229910018573 Al—Zn Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- ZZRGHKUNLAYDTC-UHFFFAOYSA-N ethoxy(methyl)silane Chemical compound CCO[SiH2]C ZZRGHKUNLAYDTC-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002365 multiple layer Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide 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
- Surface Treatment Of Glass (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、可撓性，耐熱性，絶縁
性，電極材との密着性に優れた太陽電池用絶縁基板及び
その製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insulating substrate for a solar cell which is excellent in flexibility, heat resistance, insulation and adhesion to an electrode material, and a method of manufacturing the same.
【０００２】[0002]
【従来の技術】非晶質Ｓｉ等からなる太陽電池を形成す
る基板には、ガラス板や金属板が使用されている。なか
でも、金属板は、ガラス板に比較して優れた可撓性を活
用した基板材料として着目されている。金属板を太陽電
池用基板として使用する場合、基板表面を絶縁処理する
必要があり、樹脂系絶縁皮膜，無機系絶縁皮膜等が提案
されている。たとえば、特開昭５９−４７７７６号公報
では、スピナー，スプレー，浸漬法で液状樹脂をステン
レス鋼基板の表面に塗布し、高温焼成することにより厚
み２μｍ程度の高分子樹脂皮膜を形成している。また、
特開昭５９−４７７７５号公報では、スパッタリング，
蒸着，イオンプレーティング，プラズマＣＶＤ，熱分解
ＣＶＤ等でＳｉＯ 2 ，Ａｌ2 Ｏ3 ，ＳｉＮX ，非晶質Ｓ
ｉ等の絶縁皮膜を形成している。2. Description of the Related Art A solar cell made of amorphous Si or the like is formed.
A glass plate or a metal plate is used for the substrate. Inside
However, metal plates take advantage of their superior flexibility compared to glass plates.
It is drawing attention as a substrate material used. Metal plate with solar power
When used as a pond substrate, insulate the substrate surface
It is necessary to propose resin-based insulation film, inorganic insulation film, etc.
Have been. For example, JP-A-59-47776 discloses
Then, spin the liquid resin by spinner, spray and immersion method.
It is applied to the surface of a
Only a polymer resin film of about 2 μm is formed. Also,
In JP-A-59-47775, sputtering,
Evaporation, ion plating, plasma CVD, thermal decomposition
SiO by CVD etc. Two , AlTwo OThree , SiNX , Amorphous S
An insulating film such as i is formed.
【０００３】[0003]
【発明が解決しようとする課題】樹脂系絶縁皮膜は、可
撓性があり、耐衝撃性にも優れている。しかし、太陽電
池として働く非晶質Ｓｉの堆積時に加熱されると、熱分
解してガスを発生し易く、非晶質Ｓｉ層に欠陥を導入す
る原因となる。また、耐湿性も十分でないことから、耐
久性の点で問題がある。他方、スパッタリング，蒸着，
イオンプレーティング，プラズマＣＶＤ，熱分解ＣＶＤ
等で無機系絶縁皮膜を設ける方法では、絶縁皮膜が必要
厚みに成長するまで時間がかかり、製造コストが高くな
る。The resin-based insulating film is flexible and has excellent impact resistance. However, when heated during the deposition of amorphous Si that acts as a solar cell, it is likely to thermally decompose and generate gas, which may introduce defects into the amorphous Si layer. In addition, since moisture resistance is not sufficient, there is a problem in durability. On the other hand, sputtering, evaporation,
Ion plating, plasma CVD, thermal decomposition CVD
In the method of providing an inorganic insulating film by the method described above, it takes time until the insulating film grows to a required thickness, and the manufacturing cost increases.
【０００４】更に、無機系絶縁皮膜の上層に電極材及び
非晶質Ｓｉ層を積層する過程で、熱膨張係数の違いから
無機系絶縁皮膜に微小なクラックが生じると、太陽電池
のセル間で短絡を発生させることになる。しかも、シリ
カ系皮膜は、絶縁性に優れているものの、シリコンの有
機系化合物を主成分とする浴から製膜されたものである
ため、硬化時にＣＨ3 基が残存し易い欠点がある。ＣＨ
3 基が残存しているシリカ系皮膜の上に電極材を積層す
ると、電極材／シリカ系皮膜の界面で剥離が生じ、良好
な太陽電池を構成できなくなる。本発明は、このような
問題を解消すべく案出されたものであり、それぞれ異な
った機能が付与された下地絶縁膜及び表層絶縁膜をゾル
−ゲル法で金属板表面に形成することにより、ピンホー
ル欠陥の発生を抑え絶縁抵抗が高く、電極材や非晶質Ｓ
ｉ層の積層時にクラックの発生を抑制でき、電極材／絶
縁層の界面剥離を抑制した太陽電池用絶縁基板を提供す
ることを目的とする。Further, in the process of laminating the electrode material and the amorphous Si layer on the inorganic insulating film, if a minute crack occurs in the inorganic insulating film due to a difference in thermal expansion coefficient, the solar cell may have a problem. This will cause a short circuit. In addition, although the silica-based film is excellent in insulating properties, it is formed from a bath containing an organic compound of silicon as a main component, and therefore has a disadvantage that CH 3 groups are likely to remain during curing. CH
If the electrode material is laminated on the silica-based film in which the three groups remain, peeling occurs at the interface between the electrode material and the silica-based film, and a favorable solar cell cannot be formed. The present invention has been devised to solve such a problem, and a base insulating film and a surface insulating film each having a different function are formed on a metal plate surface by a sol-gel method. It suppresses the occurrence of pinhole defects, has a high insulation resistance,
It is an object of the present invention to provide an insulating substrate for a solar cell in which cracks can be suppressed from occurring during the lamination of an i-layer and interface separation between an electrode material and an insulating layer is suppressed.
【０００５】[0005]
【課題を解決するための手段】本発明の太陽電池用絶縁
基板は、その目的を達成するため、金属板を基板とし、
ゾル−ゲル法で形成された絶縁抵抗の高い下地絶縁膜
と、組成が異なる浴を用いたゾル−ゲル法で形成され電
極材に対する密着性に優れた表層絶縁膜が形成されてい
ることを特徴とする。下地絶縁膜及び表層絶縁膜は、そ
れぞれ膜厚０．５〜１０μｍの酸化物層で形成される。
下地絶縁膜や表層絶縁膜には、可視光反射率７０％以上
の無機化合物等の絶縁性無機粉末を分散させることがで
きる。表層絶縁膜としては、表面にＯＨ基を配向された
膜が好ましい。下地絶縁膜と表層絶縁膜との間には、更
にゾル−ゲル法による単数又は複数の絶縁層が設けるこ
ともできる。In order to achieve the object, an insulating substrate for a solar cell according to the present invention comprises a metal plate as a substrate,
It features a base insulating film with high insulation resistance formed by the sol-gel method and a surface insulating film with excellent adhesion to electrode materials formed by the sol-gel method using baths having different compositions. And The base insulating film and the surface insulating film are each formed of an oxide layer having a thickness of 0.5 to 10 μm.
An insulating inorganic powder such as an inorganic compound having a visible light reflectance of 70% or more can be dispersed in the base insulating film and the surface insulating film. As the surface insulating film, a film having OH groups oriented on the surface is preferable. Between the base insulating film and the surface insulating film, one or more insulating layers can be further provided by a sol-gel method.
【０００６】下地絶縁膜は、アルコキシシラン，（１）
の構造を持つオルガノアルコキシシラン，金属アルコキ
シド，水，酸及び増粘剤を有機溶媒に溶解させた溶液に
金属板を浸漬，塗布，スプレー等で接触させ、金属板に
付着した溶液を乾燥・焼成することにより形成される。
次いで、異なる組成の溶液に金属板を接触させ、同様な
乾燥・焼成により表層絶縁膜を形成する。金属アルコキ
シドとしては、金属アルコキシドとしてアルミニウムア
ルコキシド，チタンアルコキシド，アルカリ金属又はア
ルカリ土類金属を含むアルコキシドの１種類又は２種以
上が使用される。The underlying insulating film is made of an alkoxysilane, (1)
A metal plate is immersed in a solution of an organoalkoxysilane, metal alkoxide, water, acid, and a thickener dissolved in an organic solvent with a structure of dipping, coating, spraying, etc., and the solution attached to the metal plate is dried and fired. It is formed by doing.
Next, a metal plate is brought into contact with a solution having a different composition, and a surface insulating film is formed by similar drying and firing. As the metal alkoxide, one or two or more of alkoxides containing aluminum alkoxide, titanium alkoxide, alkali metal or alkaline earth metal as the metal alkoxide are used.
【０００７】 Ｘ：ビニル基，エポキシ基，アミノ基，メタクリロキシ
基又はメルカプト基 Ｒ：アルキル基[0007] X: vinyl group, epoxy group, amino group, methacryloxy group or mercapto group R: alkyl group
【０００８】[0008]
【作用】ゾル−ゲル法は、金属板表面に酸化物層を形成
させる方法として従来から使用されており、比較的低温
で酸化物層を形成できる長所をもっている。しかし、従
来のゾル−ゲル法では、膜厚が１μｍ以下の薄膜が得ら
れるに過ぎない。このような薄膜は、多数のピンホール
を含み絶縁性が十分でないことから、太陽電池用基板の
絶縁層として使用できない。ところで、本発明者等は、
オルガノアルコキシシランを膜強化剤として、ヒドロキ
シアルキルセルロースを増粘剤としてアルコキシドに添
加したコーティング溶液を使用すると、比較的厚膜の酸
化物層が形成されることを見出し、特開平９−２０６６
８０号公報で紹介した。基本となるゾル−ゲル浴は、ア
ルミニウムアルコキシド，アルコキシシラン，オルガノ
アルコキシシラン，アルカリ金属及び／又はアルカリ土
類金属の１種又は２種以上を含むアルコキシド，アルコ
ールアミン，水を含み、各アルコキシドを溶解させるた
めアルコール系の溶剤を使用する。アルコール系溶剤に
溶解したアルコキシドは、水添加によって加水分解し、
水酸化物となる。しかし、急激な加水分解では沈澱物が
生成するので、アルコールアミンの添加によって加水分
解の反応速度を調整する。The sol-gel method has been conventionally used as a method for forming an oxide layer on the surface of a metal plate, and has an advantage that an oxide layer can be formed at a relatively low temperature. However, in the conventional sol-gel method, only a thin film having a thickness of 1 μm or less can be obtained. Such a thin film cannot be used as an insulating layer of a solar cell substrate because it has many pinholes and has insufficient insulation. By the way, the present inventors,
It has been found that a relatively thick oxide layer can be formed by using a coating solution containing organoalkoxysilane as a film strengthening agent and hydroxyalkylcellulose as a thickener added to an alkoxide.
No. 80 was introduced. The basic sol-gel bath contains an aluminum alkoxide, an alkoxysilane, an organoalkoxysilane, an alkoxide containing one or more of an alkali metal and / or an alkaline earth metal, an alcoholamine, and water, and dissolves each alkoxide. An alcohol-based solvent is used for this purpose. The alkoxide dissolved in the alcohol solvent is hydrolyzed by adding water,
Becomes hydroxide. However, a precipitate is formed by rapid hydrolysis. Therefore, the reaction rate of the hydrolysis is adjusted by adding an alcoholamine.
【０００９】このゾル−ゲル浴を金属板に浸漬，塗布，
スプレー等でコーティングすると、アルミニウムアルコ
キシド，アルコキシシラン，アルカリ金属，アルカリ土
類金属のアルコキシド等の加水分解された水酸化物が付
着する。この状態で金属板を加熱すると合成反応が進行
し、金属板の表面に酸化物層が形成される。このときの
加熱は、１００〜６００℃程度で、従来の無機系酸化物
を焼き付ける温度に比較して大幅に低い。そのため、金
属板に熱的な悪影響を及ぼすことなく、しかも酸化物本
来の優れた絶縁性を呈する絶縁層となる。形成された絶
縁層は、従来のゾル−ゲル法による酸化物層と異なり、
オルガノアルコキシシラン添加によりシリカの網目構造
の結合が強化され、ヒドロキシアルキルセルロースの添
加により急激な溶剤の蒸発に伴うクラックの発生が抑制
されることから厚く成長し、金属板に対する密着性も良
好である。This sol-gel bath is immersed in a metal plate, coated,
When coated with a spray or the like, a hydrolyzed hydroxide such as an aluminum alkoxide, an alkoxysilane, an alkoxide of an alkali metal or an alkaline earth metal adheres. When the metal plate is heated in this state, the synthesis reaction proceeds, and an oxide layer is formed on the surface of the metal plate. The heating at this time is about 100 to 600 ° C., which is much lower than the temperature at which conventional inorganic oxides are baked. For this reason, the insulating layer does not adversely affect the metal plate thermally and exhibits excellent insulating properties inherent to the oxide. The formed insulating layer is different from the oxide layer formed by the conventional sol-gel method,
The addition of the organoalkoxysilane strengthens the bonding of the silica network structure, and the addition of hydroxyalkyl cellulose suppresses the generation of cracks due to the rapid evaporation of the solvent, so that it grows thickly and has good adhesion to the metal plate. .
【００１０】本発明にあっては、図１に示すように金属
板１の表面にゾル−ゲル法で下地絶縁膜２を形成する。
下地絶縁膜２には高い絶縁特性が要求されるため、金属
酸化物を用いる。代表的にはシリカ系，アルミナ系，チ
タニア系等の絶縁膜があるが、なかでもシリカ系の膜が
高い絶縁抵抗を示す。下地絶縁膜は、要求される絶縁特
性を付与する上で０．５〜１０μｍの膜厚をもつことが
好ましい。０．５μｍに満たない膜厚では、下地絶縁膜
に含まれているピンホール等の欠陥により影響が大きく
なり、絶縁特性が低下する。しかし、１０μｍを超える
厚膜に下地絶縁膜を形成すると、広幅のクラックが発生
し易く、却って絶縁特性を低下させる。In the present invention, a base insulating film 2 is formed on a surface of a metal plate 1 by a sol-gel method as shown in FIG.
Since a high insulating property is required for the base insulating film 2, a metal oxide is used. Typically, there are insulating films such as silica-based, alumina-based, and titania-based. Among them, silica-based films exhibit high insulation resistance. The base insulating film preferably has a thickness of 0.5 to 10 μm in order to provide required insulating properties. If the film thickness is less than 0.5 μm, the influence becomes large due to defects such as pinholes contained in the base insulating film, and the insulating characteristics deteriorate. However, if the base insulating film is formed as a thick film having a thickness of more than 10 μm, a wide crack is easily generated, and the insulating characteristics are rather deteriorated.
【００１１】下地絶縁膜２の上に、更に表層絶縁膜３を
同様なゾル−ゲル法で形成する。表層絶縁膜３によって
下地絶縁膜２のピンホールやミクロクラック等が封鎖さ
れるため、下地絶縁膜２の絶縁特性が更に向上する。た
だし、表層絶縁膜３には、その上に電極となる金属層が
形成されることから、電極材に対する密着性に優れた膜
を形成する必要がある。電極材と同一の金属を含む膜で
あれば、電極材に対する密着性に優れた膜となる。電極
材としてはＡｌが一般的であり、絶縁性も必要とされる
ことからアルミナ系酸化物が表層絶縁膜として有効であ
る。代表的には、ゼオライトの絶縁膜がある。表層絶縁
膜３も、要求される密着性を確保する上で０．５〜１０
μｍの膜厚をもつことが好ましい。０．５μｍに満たな
い膜厚では電極材に対する密着性改善効果が小さく、逆
に１０μｍを超える厚膜では表層絶縁膜にクラックが発
生し易く、下地絶縁膜との密着性が高い場合に下地絶縁
膜まで及ぶクラックとなって却って絶縁性を低下させ
る。On the base insulating film 2, a surface insulating film 3 is further formed by a similar sol-gel method. Since the pinholes, microcracks, and the like of the base insulating film 2 are blocked by the surface insulating film 3, the insulating properties of the base insulating film 2 are further improved. However, since a metal layer serving as an electrode is formed on the surface insulating film 3, it is necessary to form a film having excellent adhesion to the electrode material. If the film contains the same metal as the electrode material, the film has excellent adhesion to the electrode material. Al is generally used as an electrode material, and since an insulating property is also required, an alumina-based oxide is effective as a surface insulating film. Typically, there is a zeolite insulating film. The surface insulating film 3 also has a thickness of 0.5 to 10 to secure the required adhesion.
It preferably has a thickness of μm. If the film thickness is less than 0.5 μm, the effect of improving the adhesion to the electrode material is small. Conversely, if the film thickness exceeds 10 μm, cracks are likely to occur in the surface insulating film, and if the adhesion to the underlying insulating film is high, the base insulating The cracks extend to the film, which in turn lowers the insulation.
【００１２】また、電極材との密着性改善に有効なＯＨ
基を表面に配向させた表層絶縁膜３を形成すると、電極
材／絶縁膜界面での剥離が防止される。ＯＨ基を表面に
配向させた絶縁膜は、たとえばチタンアルコキシドのよ
うな加水分解され易いものを金属アルコキシドとして使
用して有機物の残留が少ない状態にすること、或いは親
水基をもつオルガノアルコキシシランを使用し表層に水
が吸着し易い状態にすることによって製膜される。因み
に、絶縁抵抗の高いシリカ系絶縁膜で金属板１を２層コ
ートすると、十分な絶縁特性が得られるものの、絶縁膜
の上に形成される電極材が剥離し易くなる。すなわち、
アルコキシシランを含むゾル−ゲル浴を金属板１に付着
させ、加熱硬化してシリカ系絶縁膜にするとき、クラッ
クの発生を防止するため３００〜５００℃の比較的低温
で加熱されるが、加熱時に分解されることなくＣＨ3 基
等が絶縁層表面に残留し易い。残留ＣＨ3 基は、絶縁膜
の上に電極層を積層する際、絶縁膜と電極層との密着性
に悪影響を及ぼし、形成された電極層が剥離し易くな
る。OH which is effective for improving the adhesion to the electrode material
When the surface insulating film 3 having the bases oriented on the surface is formed, peeling at the electrode material / insulating film interface is prevented. An insulating film having an OH group oriented on the surface may be made of an easily hydrolyzable material such as titanium alkoxide as a metal alkoxide so as to reduce residual organic substances, or using an organoalkoxysilane having a hydrophilic group. The film is formed by making the surface layer easily absorb water. Incidentally, if the metal plate 1 is coated with two layers of a silica-based insulating film having a high insulation resistance, sufficient insulating properties can be obtained, but the electrode material formed on the insulating film is easily peeled off. That is,
When a sol-gel bath containing alkoxysilane is applied to the metal plate 1 and cured by heating to form a silica-based insulating film, the sol-gel bath is heated at a relatively low temperature of 300 to 500 ° C. to prevent cracks. CH 3 groups and the like easily remain on the surface of the insulating layer without being sometimes decomposed. When the electrode layer is laminated on the insulating film, the remaining CH 3 groups have an adverse effect on the adhesion between the insulating film and the electrode layer, and the formed electrode layer is easily peeled off.
【００１３】少なくとも２工程のゾル−ゲル法で金属板
１の表面に、図１（ａ）に示すように下地絶縁層２及び
表層絶縁層３を形成するとき、下地絶縁層２で優れた絶
縁特性が得られ、表層絶縁層３で電極材に対する密着性
が改善される。その結果、太陽電池用に適した絶縁基板
となる。酸化物，窒化物，炭化物等の絶縁性粉末を分散
させたゾル−ゲル浴を使用すると、絶縁性粉末４が分散
した厚膜の絶縁膜が得られる。絶縁性粉末４は、下地絶
縁膜２及び表層絶縁膜３に分散させ（図１ｂ）、表層絶
縁膜３のみに分散させ（図１ｃ）、或いは下地絶縁膜２
のみに分散させてもよい。絶縁性粉末４は、クラック発
生を抑制する作用を呈し、絶縁膜２，３の厚膜化を容易
にする。なかでも、可視光反射特性が高い粉末を絶縁性
粉末４として使用すると、太陽電池を構成したときの入
射光の多重反射が促進され、光電変換効率が向上する。
可視光反射特性が高い粉末としては、Ａｌ2 Ｏ3 ，Ｚｎ
Ｏ，ＭｇＯ，ＳｉＯ2 ，ＴｉＯ2 ，ＺｎＯ，ＭｇＯ，Ｃ
ａＣＯ3 ，ＭｇＣＯ3 等がある。When the base insulating layer 2 and the surface insulating layer 3 are formed on the surface of the metal plate 1 by the sol-gel method in at least two steps as shown in FIG. Characteristics are obtained, and the adhesion to the electrode material is improved by the surface insulating layer 3. As a result, an insulating substrate suitable for a solar cell is obtained. When a sol-gel bath in which insulating powders such as oxides, nitrides, and carbides are dispersed is used, a thick insulating film in which the insulating powders 4 are dispersed can be obtained. The insulating powder 4 is dispersed in the base insulating film 2 and the surface insulating film 3 (FIG. 1B), dispersed only in the surface insulating film 3 (FIG. 1C), or
Alternatively, they may be dispersed only. The insulating powder 4 has a function of suppressing the occurrence of cracks, and facilitates increasing the thickness of the insulating films 2 and 3. In particular, when a powder having high visible light reflection characteristics is used as the insulating powder 4, multiple reflection of incident light when a solar cell is formed is promoted, and the photoelectric conversion efficiency is improved.
Powders having high visible light reflection characteristics include Al 2 O 3 and Zn.
O, MgO, SiO 2 , TiO 2 , ZnO, MgO, C
there is aCO 3, MgCO 3, and the like.
【００１４】下地絶縁膜２はゾル−ゲル浴と金属板１の
表面との接触界面で成長し、表層絶縁膜３はゾル−ゲル
浴と下地絶縁膜２との接触界面で成長する。そのため、
形成される絶縁膜２，３は、金属板１の表面形態を正確
に倣った均一膜厚となる。そこで、金属板１を凹凸やウ
ネリのある表面（図１ｄ）にすると、その表面凹凸を倣
った酸化物第１層２が形成される。凹凸やウネリのある
酸化物第１層２は、入射光の乱反射や多重反射を促進さ
せ、光閉じ込め効果によって光電変換効率を向上させ
る。たとえば、Ｒz １．０μｍ，Ｒmax １．４μｍの表
面粗さ及び圧延方向のウネリをもつ微細な凹凸が金属板
１の表面に形成されていると、その上に形成された絶縁
皮膜が基材の表面凹凸やウネリを倣ったものとなり、入
射光の多重散乱反射が促進される。このような表面粗さ
やウネリは、仕上げ冷間圧延時の圧延率を２０％以上，
圧延速度を４００ｍ／分以上とし、研磨番手＃１００〜
＃４００で研磨したワークロールを使用して仕上げ圧延
等を施すことにより金属板１に付けることができる。The base insulating film 2 grows at the contact interface between the sol-gel bath and the surface of the metal plate 1, and the surface insulating film 3 grows at the contact interface between the sol-gel bath and the base insulating film 2. for that reason,
The formed insulating films 2 and 3 have a uniform film thickness that accurately follows the surface morphology of the metal plate 1. Therefore, when the metal plate 1 is made to have a surface having unevenness and undulation (FIG. 1d), the first oxide layer 2 is formed following the surface unevenness. The first oxide layer 2 having irregularities and undulations promotes irregular reflection and multiple reflection of incident light, and improves photoelectric conversion efficiency by a light confinement effect. For example, if fine irregularities having a surface roughness of Rz 1.0 μm and Rmax 1.4 μm and a undulation in the rolling direction are formed on the surface of the metal plate 1, the insulating film formed thereon has a base. The material imitates the surface unevenness and undulation of the material, and multiple scattering reflection of incident light is promoted. Such surface roughness and undulation can reduce the rolling reduction during finish cold rolling by 20% or more.
The rolling speed is 400 m / min or more, and the grinding number is # 100 ~
The work roll polished at # 400 can be attached to the metal plate 1 by performing finish rolling or the like.
【００１５】下地絶縁膜２と表層絶縁膜３との間には、
更にゾル−ゲル法によって単層又は複層の中間絶縁膜を
設けることができる。下地絶縁膜と表層絶縁膜との密着
性が高いほど、加熱等により表層絶縁膜に発生するクラ
ックが伝播して下地絶縁膜までもが割れることがある。
クラックの発生は、下地絶縁膜と表層絶縁膜との間で熱
膨張係数が違うことに起因する。そこで、下地絶縁膜と
表層絶縁膜との間に、中間的な組成をもつ中間層を設け
ることによってクラックの発生及び伝播が防止される。
たとえば、下地絶縁膜をシリカ膜，表層絶縁膜をゼオラ
イト膜とする場合、中間層にはシリカ比率の高い膜を形
成する。中間層用のゾル−ゲル浴は、アルコキシシラン
の濃度を高くする以外はゼオライトコーティング用のゾ
ル−ゲル浴と同様に調製される。Between the underlying insulating film 2 and the surface insulating film 3,
Further, a single-layer or multiple-layer intermediate insulating film can be provided by a sol-gel method. As the adhesion between the base insulating film and the surface insulating film is higher, cracks generated in the surface insulating film due to heating or the like may propagate and break even the base insulating film.
The generation of cracks is caused by a difference in thermal expansion coefficient between the base insulating film and the surface insulating film. Therefore, by providing an intermediate layer having an intermediate composition between the base insulating film and the surface insulating film, generation and propagation of cracks are prevented.
For example, when the base insulating film is a silica film and the surface insulating film is a zeolite film, a film having a high silica ratio is formed in the intermediate layer. The sol-gel bath for the intermediate layer is prepared similarly to the sol-gel bath for zeolite coating except for increasing the concentration of alkoxysilane.
【００１６】[0016]
【実施例】実施例１：メチルエトキシシラン：１．０モ
ル，リン酸：０．０５モル，水：４．０モルをブタノー
ル：７．０モルに溶解した後、１質量％のヒドロキシプ
ロピルセルロースを添加し、２４時間撹拌して下地絶縁
膜用ゾル−ゲル浴を調製した。得られたゾル−ゲル浴
は、透明で、１００時間撹拌放置しても安定であった。
アルミニウムイソプロポキシド：１．０モル，オルトケ
イ酸テトラエチル：２．５モル，ナトリウムメトキシ
ド：１．０モル，トリイソプロパノールアミン：４．０
モル，水：７．０モルをブチルセルソルブ：１５モルに
溶解し、２４時間撹拌して表層絶縁膜用ゾル−ゲル浴を
調製した。得られたゾル−ゲル浴は、透明で、１００時
間撹拌放置しても安定であった。板厚０．１５ｍｍのス
テンレス鋼板を脱脂し、下地絶縁膜用ゾル−ゲル浴をロ
ールコータで塗布し、４００℃で１分間焼成することに
より膜厚１．３μｍの下地絶縁膜を形成した。３０分か
けて放冷した後、表層絶縁膜用ゾル−ゲル浴をロールコ
ータで塗布し、４００℃で１分間焼成することにより膜
厚１．３μｍの表層絶縁膜を形成した。形成された下地
絶縁膜及び表層絶縁膜は、何れも均一で緻密な構造をも
つ透明膜であった。EXAMPLES Example 1 1.0 mol of methylethoxysilane, 0.05 mol of phosphoric acid, 4.0 mol of water were dissolved in 7.0 mol of butanol, and then 1% by mass of hydroxypropylcellulose was dissolved. Was added and stirred for 24 hours to prepare a sol-gel bath for a base insulating film. The resulting sol-gel bath was transparent, and was stable even after stirring for 100 hours.
Aluminum isopropoxide: 1.0 mol, tetraethyl orthosilicate: 2.5 mol, sodium methoxide: 1.0 mol, triisopropanolamine: 4.0
Mol and water: 7.0 mol were dissolved in 15 mol of butyl cellosolve and stirred for 24 hours to prepare a sol-gel bath for a surface insulating film. The resulting sol-gel bath was transparent, and was stable even after stirring for 100 hours. A stainless steel plate having a thickness of 0.15 mm was degreased, a sol-gel bath for a base insulating film was applied by a roll coater, and baked at 400 ° C. for 1 minute to form a base insulating film having a thickness of 1.3 μm. After allowing to cool for 30 minutes, a sol-gel bath for a surface insulating film was applied by a roll coater and baked at 400 ° C. for 1 minute to form a surface insulating film having a thickness of 1.3 μm. The formed base insulating film and surface insulating film were both transparent films having a uniform and dense structure.
【００１７】実施例２：基板を溶融５５％Ａｌ−Ｚｎめ
っき鋼板とし、実施例１と同じ条件でコーティングし
た。形成された下地絶縁膜及び表層絶縁膜は、共に膜厚
が１．４μｍで、均一で緻密な構造をもつ透明膜であっ
た。 実施例３：実施例１の下地絶縁膜用ゾル−ゲル浴及び表
層絶縁膜用ゾル−ゲル浴にＡｌ2Ｏ3 ：２０重量部を添
加し、ロールコータの周速を上げる以外は実施例１と同
じ条件でコーティングした。形成された下地絶縁膜及び
表層絶縁膜は、共に膜厚が４．２μｍで、均一で緻密な
構造をもつ白色膜であった。Example 2 A substrate was made of a 55% Al-Zn plated steel sheet and coated under the same conditions as in Example 1. Each of the base insulating film and the surface insulating film thus formed was a transparent film having a thickness of 1.4 μm and a uniform and dense structure. Example 3 Example 1 was repeated except that 20 parts by weight of Al 2 O 3 was added to the sol-gel bath for the base insulating film and the sol-gel bath for the surface insulating film of Example 1, and the peripheral speed of the roll coater was increased. Coating was performed under the same conditions as described above. The formed base insulating film and surface insulating film were both white films having a thickness of 4.2 μm and a uniform and dense structure.
【００１８】実施例４：表面粗さを調節するために冷間
圧延した板厚０．１５ｍｍの溶融Ａｌめっき鋼板を脱脂
し、実施例１と同じ下地絶縁膜用ゾル−ゲル浴を用いて
引上げ法でコーティングした後、４００℃で２分間焼成
した。形成された下地絶縁膜は、膜厚が０．５μｍで、
均一で緻密な構造をもつ透明膜であった。次いで、実施
例１のゾル−ゲル浴にＴｉＯ2 粉末１０重量部を添加し
た表層絶縁膜用ゾル−ゲル浴を用い、引上げ法でコーテ
ィングした後、４００℃で２分間焼成した。形成された
下地絶縁膜は、膜厚が１．５μｍで、均一で緻密な構造
をもつ白色膜であった。Example 4 A 0.15 mm thick hot-dip Al-plated steel sheet cold-rolled to adjust its surface roughness was degreased and pulled up using the same sol-gel bath for a base insulating film as in Example 1. After coating by the method, it was baked at 400 ° C. for 2 minutes. The formed base insulating film has a thickness of 0.5 μm,
The transparent film had a uniform and dense structure. Then, the sol-gel bath of Example 1 was coated with a sol-gel bath for a surface insulating film in which 10 parts by weight of TiO 2 powder was added, coated by a pull-up method, and baked at 400 ° C. for 2 minutes. The base insulating film thus formed was a white film having a thickness of 1.5 μm and a uniform and dense structure.
【００１９】実施例５：表面粗さをＲz １．２８μｍ，
Ｒmax １．６３μｍに調整し、且つ表面粗さに一方向の
うねりをつけたステンレス鋼板を使用する以外は、実施
例１と同じゾル−ゲル浴を用いてステンレス鋼板をコー
ティングした。形成された下地絶縁膜及び表層絶縁膜
は、共に膜厚１．２μｍで、均一で緻密な構造をもつ白
色膜であり、ステンレス鋼板の表面形態を正確に倣って
一方向のうねりが付けられていた。 比較例１：実施例１と同じ方法で、膜厚１．３μｍの下
地絶縁膜のみを形成した。 比較例２：実施例３と同じ方法で、膜厚４．０μｍの下
地絶縁膜のみを形成した。Example 5: Surface roughness R z 1.28 μm,
A stainless steel plate was coated using the same sol-gel bath as in Example 1, except that a stainless steel plate adjusted to R max of 1.63 μm and having a surface roughness with unidirectional undulation was used. The formed base insulating film and surface insulating film are both white films having a thickness of 1.2 μm and a uniform and dense structure, and are provided with unidirectional undulations that accurately follow the surface morphology of the stainless steel plate. Was. Comparative Example 1 In the same manner as in Example 1, only a 1.3 μm-thick underlying insulating film was formed. Comparative Example 2: In the same manner as in Example 3, only a base insulating film having a thickness of 4.0 μm was formed.
【００２０】比較例３：実施例１と同じ方法で膜厚１．
３μｍの第１層絶縁膜を形成した後、その上に第１層と
同様の酸化皮膜を第２層絶縁膜として形成した。第１層
及び第２層共に、絶縁膜の膜厚は１．３μｍであり、何
れも均一で緻密な構造をもつ透明膜であった。 比較例４：Ａｌ2 Ｏ3 に替えてＣｕＯを添加したゾル−
ゲル浴を用いる以外は、実施例３と同じ方法で絶縁膜を
形成した。形成された絶縁膜は、第１層及び第２層共に
膜厚３．９μｍで、均一且つ緻密な構造をもつ灰色膜で
あった。Comparative Example 3: The same method as in Example 1 was used to form a film having a thickness of 1.
After forming a first layer insulating film of 3 μm, an oxide film similar to the first layer was formed thereon as a second layer insulating film. Both the first layer and the second layer had a thickness of the insulating film of 1.3 μm, and both were transparent films having a uniform and dense structure. Comparative Example 4: Instead of Al 2 O 3 sol was added CuO -
An insulating film was formed in the same manner as in Example 3 except that a gel bath was used. The formed insulating film was a gray film having a uniform and dense structure with a thickness of 3.9 μm for both the first layer and the second layer.
【００２１】実施例１〜５及び比較例１〜４で絶縁膜が
形成された金属板を太陽電池用基板として使用し、常法
に従って次のようにして太陽電池を形成した。先ず、加
熱した基板表面に酸化インジウム及び酸化錫の混合物を
蒸着させ、下部電極を所定間隔で形成した。そして、下
部電極上に非晶質Ｓｉ膜をプラズマＣＶＤ法で形成し、
下部電極に対応する透光性上部電極として酸化インジウ
ム膜を非晶質Ｓｉ膜上にスパッタリング法で形成した。
更に、透光性上部電極の上に高分子樹脂を一様に塗布
し、焼成することにより、透光性パシベーション膜を形
成した。Using the metal plates on which the insulating films were formed in Examples 1 to 5 and Comparative Examples 1 to 4 as solar cell substrates, solar cells were formed in the following manner according to a conventional method. First, a mixture of indium oxide and tin oxide was deposited on the heated substrate surface to form lower electrodes at predetermined intervals. Then, an amorphous Si film is formed on the lower electrode by a plasma CVD method,
An indium oxide film was formed as a light-transmitting upper electrode corresponding to the lower electrode on the amorphous Si film by a sputtering method.
Further, a high-molecular resin was uniformly applied on the light-transmitting upper electrode and baked to form a light-transmitting passivation film.
【００２２】得られた各太陽電池について、山下電装株
式会社製のソーラシミュレータを用いて光電変換効率を
測定した。実施例１〜４の基板を使用した太陽電池で
は、１０％の光電変換効率を示した。ウネリのあるステ
ンレス鋼板を使用した実施例５では、１１％と高い光電
変換効率が得られた。これに対し、比較例１の基板を使
用した太陽電池では、絶縁膜に微細なクラックやピンホ
ールが発生しており、光電変換効率も０〜７％の低い範
囲でばらついていた。比較例２の基板を使用した太陽電
池でも、絶縁膜に微細なクラックやピンホールが発生
し、光電変換効率も２〜８％の低い範囲でばらついてい
た。比較例３の基板を使用した場合、金属質の電極と絶
縁膜との界面に全面剥離が生じたため、太陽電池を構成
できなかった。比較例４の基板を使用した太陽電池で
は、添加したＣｕＯの可視光反射率が低いため、光電変
換効率も６％と低い値を示した。この対比から明らかな
ように、実施例１〜５で絶縁膜が形成された金属板は、
何れも高性能の太陽電池用絶縁基板として使用されるこ
とが判る。For each of the obtained solar cells, the photoelectric conversion efficiency was measured using a solar simulator manufactured by Yamashita Denso Co., Ltd. The solar cells using the substrates of Examples 1 to 4 exhibited a photoelectric conversion efficiency of 10%. In Example 5 using a stainless steel plate with undulation, a high photoelectric conversion efficiency of 11% was obtained. On the other hand, in the solar cell using the substrate of Comparative Example 1, fine cracks and pinholes occurred in the insulating film, and the photoelectric conversion efficiency also varied in a low range of 0 to 7%. Also in the solar cell using the substrate of Comparative Example 2, fine cracks and pinholes occurred in the insulating film, and the photoelectric conversion efficiency also varied in a low range of 2 to 8%. When the substrate of Comparative Example 3 was used, a solar cell could not be constructed because the entire surface of the interface between the metal electrode and the insulating film was peeled off. In the solar cell using the substrate of Comparative Example 4, the visible light reflectance of the added CuO was low, so that the photoelectric conversion efficiency also showed a low value of 6%. As is clear from this comparison, the metal plates on which the insulating films were formed in Examples 1 to 5 were:
It can be seen that all of them are used as high-performance insulating substrates for solar cells.
【００２３】[0023]
【発明の効果】以上に説明したように、本発明の太陽電
池用基板は、絶縁層として有効な膜厚の下地絶縁膜及び
表層絶縁膜の少なくとも２層をゾル−ゲル法で金属板の
表面に形成しているため、従来の有機系絶縁層に比較し
て耐熱性，耐湿性に優れ、非晶質Ｓｉ堆積時等にガスを
発生することがなく、しかも優れた密着性で金属質の電
極を形成できる。ゾル−ゲル法で形成される絶縁膜は、
従来の無機系絶縁層に比較すると非常に簡便な方法で形
成され、優れた絶縁特性を呈する絶縁層となる。しか
も、下地絶縁膜の上に表層絶縁膜を形成するため、下地
絶縁膜の絶縁抵抗が改善されると共に、電極材／絶縁膜
界面での剥離が防止される。As described above, in the solar cell substrate of the present invention, at least two layers of a base insulating film and a surface insulating film having a film thickness effective as an insulating layer are formed on the surface of a metal plate by a sol-gel method. Since it is formed on the substrate, it has excellent heat resistance and moisture resistance as compared with the conventional organic insulating layer, does not generate gas at the time of depositing amorphous Si, and has excellent adhesiveness. Electrodes can be formed. The insulating film formed by the sol-gel method,
Compared to a conventional inorganic insulating layer, the insulating layer is formed by a very simple method and has excellent insulating properties. In addition, since the surface insulating film is formed on the base insulating film, the insulation resistance of the base insulating film is improved, and separation at the electrode material / insulating film interface is prevented.
【図１】 ゾル−ゲル法で下地絶縁膜及び表層絶縁膜の
２層が形成された金属板（ａ），絶縁粉末を分散させた
下地絶縁膜及び表層絶縁膜をもつ金属板（ｂ），表層絶
縁膜のみに絶縁粉末を分散させた金属板（ｃ）及び表面
にうねりを付けた金属板表面に形成された絶縁膜（ｄ）
の各断面図FIG. 1 shows a metal plate (a) having two layers of a base insulating film and a surface insulating film formed by a sol-gel method, a metal plate having a base insulating film and a surface insulating film in which insulating powder is dispersed (b), A metal plate (c) in which insulating powder is dispersed only in a surface insulating film and an insulating film (d) formed on the surface of a metal plate having undulations on its surface
Each sectional view
Claims (8)
された絶縁抵抗の高い下地絶縁膜と、組成の異なる浴を
用いたゾル−ゲル法で形成され電極材に対する密着性に
優れた表層絶縁膜が形成されていることを特徴とする太
陽電池用絶縁基板。1. A metal plate as a substrate, a base insulating film having a high insulation resistance formed by a sol-gel method, and excellent adhesion to an electrode material formed by a sol-gel method using baths having different compositions. An insulating substrate for a solar cell, wherein a surface insulating film is formed.
いる請求項１記載の太陽電池用絶縁基板。2. The insulating substrate for a solar cell according to claim 1, wherein OH groups are oriented on the surface of the surface insulating film.
厚０．５〜１０μｍの酸化物層である請求項１又は２記
載の太陽電池用絶縁基板。3. The insulating substrate for a solar cell according to claim 1, wherein each of the base insulating film and the surface insulating film is an oxide layer having a thickness of 0.5 to 10 μm.
性無機粉末が分散している請求項１〜３の何れかに記載
の太陽電池用絶縁基板。4. The solar cell insulating substrate according to claim 1, wherein an insulating inorganic powder is dispersed in the base insulating film and / or the surface insulating film.
上の無機化合物である請求項４記載の太陽電池用絶縁基
板。5. The insulating substrate for a solar cell according to claim 4, wherein the insulating inorganic powder is an inorganic compound having a visible light reflectance of 70% or more.
−ゲル法による単数又は複数の絶縁層が設けられている
請求項１〜５の何れかに記載の太陽電池用絶縁基板。6. The solar cell insulating substrate according to claim 1, wherein one or more insulating layers are provided between the base insulating film and the surface insulating film by a sol-gel method.
オルガノアルコキシシラン，金属アルコキシド，水，酸
及び増粘剤を有機溶媒に溶解させた溶液に金属板を接触
させ、金属板に付着した溶液を乾燥・焼成して下地絶縁
膜を形成した後、異なる組成の溶液に金属板を接触さ
せ、金属板に付着した溶液を乾燥・焼成して表層絶縁膜
を形成することを特徴とする太陽電池用絶縁基板の製造
方法。 Ｘ：ビニル基，エポキシ基，アミノ基，メタクリロキシ
基又はメルカプト基 Ｒ：アルキル基7. A solution in which an alkoxysilane, an organoalkoxysilane having a structure of (1), a metal alkoxide, water, an acid and a thickener are dissolved in an organic solvent, the metal plate is brought into contact with the solution, and the solution adhered to the metal plate. A solar cell characterized in that after drying and baking to form a base insulating film, a metal plate is brought into contact with a solution having a different composition, and the solution attached to the metal plate is dried and fired to form a surface insulating film. Of manufacturing insulating substrates for semiconductors. X: vinyl group, epoxy group, amino group, methacryloxy group or mercapto group R: alkyl group
ルコキシド，チタンアルコキシド，アルカリ金属又はア
ルカリ土類金属を含むアルコキシドの１種類又は２種以
上を使用する請求項７記載の太陽電池用絶縁基板の製造
方法。8. The method for producing an insulating substrate for a solar cell according to claim 7, wherein one or more of aluminum alkoxide, titanium alkoxide, alkoxide containing an alkali metal or an alkaline earth metal is used as the metal alkoxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10056907A JPH11261090A (en) | 1998-03-09 | 1998-03-09 | Solar battery substrate and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10056907A JPH11261090A (en) | 1998-03-09 | 1998-03-09 | Solar battery substrate and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11261090A true JPH11261090A (en) | 1999-09-24 |
Family
ID=13040535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10056907A Withdrawn JPH11261090A (en) | 1998-03-09 | 1998-03-09 | Solar battery substrate and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11261090A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001185747A (en) * | 1999-12-24 | 2001-07-06 | Nisshin Steel Co Ltd | Insulation board superior in heat resistance for solar cells and its manufacturing method |
| US6441301B1 (en) | 2000-03-23 | 2002-08-27 | Matsushita Electric Industrial Co., Ltd. | Solar cell and method of manufacturing the same |
| JP2007502536A (en) * | 2003-08-12 | 2007-02-08 | サンドビック インテレクチュアル プロパティー アクティエボラーグ | New metal strip |
| JP2013089697A (en) * | 2011-10-14 | 2013-05-13 | Nippon Steel Sumikin Materials Co Ltd | Stainless foil with insulation coating for solar battery and method for manufacturing the same |
| JP2014516467A (en) * | 2011-03-08 | 2014-07-10 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Aluminum oxide-based metal wiring barrier |
-
1998
- 1998-03-09 JP JP10056907A patent/JPH11261090A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001185747A (en) * | 1999-12-24 | 2001-07-06 | Nisshin Steel Co Ltd | Insulation board superior in heat resistance for solar cells and its manufacturing method |
| US6441301B1 (en) | 2000-03-23 | 2002-08-27 | Matsushita Electric Industrial Co., Ltd. | Solar cell and method of manufacturing the same |
| JP2007502536A (en) * | 2003-08-12 | 2007-02-08 | サンドビック インテレクチュアル プロパティー アクティエボラーグ | New metal strip |
| JP2014516467A (en) * | 2011-03-08 | 2014-07-10 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Aluminum oxide-based metal wiring barrier |
| JP2013089697A (en) * | 2011-10-14 | 2013-05-13 | Nippon Steel Sumikin Materials Co Ltd | Stainless foil with insulation coating for solar battery and method for manufacturing the same |
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