JPS60175465A - Solar battery substrate - Google Patents
Solar battery substrateInfo
- Publication number
- JPS60175465A JPS60175465A JP59031140A JP3114084A JPS60175465A JP S60175465 A JPS60175465 A JP S60175465A JP 59031140 A JP59031140 A JP 59031140A JP 3114084 A JP3114084 A JP 3114084A JP S60175465 A JPS60175465 A JP S60175465A
- Authority
- JP
- Japan
- Prior art keywords
- silicon oxide
- substrate
- oxide film
- solar cell
- tank
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 43
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004327 boric acid Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 206010016334 Feeling hot Diseases 0.000 claims description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000919 ceramic Substances 0.000 abstract description 3
- 238000007598 dipping method Methods 0.000 abstract 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 230000001788 irregular Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000000113 methacrylic resin Substances 0.000 description 2
- 230000004083 survival effect Effects 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
-
- 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
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Surface Treatment Of Glass (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
【発明の詳細な説明】
ａ 産業上の利用分野
本発明は太ｌｌ！電池基板に関し、特に光電変換効率の
良好な太陽電池基板に関する。[Detailed Description of the Invention] a. Field of Industrial Application The present invention is very useful! The present invention relates to a battery substrate, and particularly to a solar cell substrate with good photoelectric conversion efficiency.
ｂ 従来技術
近年シランガスをグロー放電分解することなどにより作
製される非晶質シリコン（ａ−ｓｉ）を用いた太陽電池
が低コストで製造可能な光電変換装置の一つとして注目
を浴びている。しかしかかるａ−ｓｉ太陽電池において
は、その光電変換効率が他の結晶半導体（結晶ｓ ｉ、
ＧａＡｓなど）に比べ極めて低いことが問題となり、
これを解決するため作製方法や電池の構造に対し種々の
対策が考案されている。特に電池の表面における光反射
損失を低減し短絡電流を増大させることは重要であり、
このため太陽電池を凹凸構造にして、入射光を電池内で
多重反射屈折させることにより長波長光に対する収集効
率を向上させることが考えられている。B. Prior Art In recent years, solar cells using amorphous silicon (a-si), which are manufactured by glow discharge decomposition of silane gas, have been attracting attention as one of the photoelectric conversion devices that can be manufactured at low cost. However, in such an a-si solar cell, its photoelectric conversion efficiency is lower than that of other crystalline semiconductors (crystal s i,
The problem is that it is extremely low compared to other materials (such as GaAs).
To solve this problem, various countermeasures have been devised for manufacturing methods and battery structures. In particular, it is important to reduce light reflection loss on the surface of the battery and increase short-circuit current.
For this reason, it has been considered to improve the collection efficiency for long wavelength light by making the solar cell have an uneven structure so that the incident light is subjected to multiple reflection and refraction within the cell.
しかしながら凹凸の度合いが大き過ぎるとピンホール等
の欠陥が発生したり膜厚が不均一になりやすく、かえっ
て太陽電池の特性（特に開放電圧・良品率）が低下する
。従ってこの様な凹凸構造を有する太陽型−池において
は、凹凸の程度を最適化する必要があった。However, if the degree of unevenness is too large, defects such as pinholes may occur or the film thickness may become non-uniform, which may actually reduce the characteristics of the solar cell (particularly the open circuit voltage and yield rate). Therefore, in a solar pond having such an uneven structure, it is necessary to optimize the degree of the unevenness.
Ｃ発明の目的
本発明の目的は、太陽光の収集効率の高い太陽電池基板
を提供することであり、さらに詳しくは開放電圧および
良品率の高い凹凸形状被膜を有する太陽電池が得られる
太陽電池基板を提供することである。C.Object of the Invention The object of the present invention is to provide a solar cell substrate with high sunlight collection efficiency, and more specifically, a solar cell substrate from which a solar cell having a concavo-convex shaped coating with a high open-circuit voltage and high yield rate can be obtained. The goal is to provide the following.
ｄ 発明の構成
本発明は、ヘイズ率が７％以上であり、直径３００〜５
ｏｏｏ人、高さ、２００〜３０００大の多数の凸部を持
った酸化珪素被膜を有することを特徴とする太陽電池基
板である。d Structure of the invention The present invention has a haze rate of 7% or more and a diameter of 300 to 5
ooo This is a solar cell substrate characterized by having a silicon oxide film having a large number of convex portions of 200 to 3000 in height.
ここで本発明の酸化珪素被膜のへイス率は航空機用メタ
クリル樹脂板の曇価測定法（ＪＩＳ。Here, the heis ratio of the silicon oxide coating of the present invention is determined by the haze value measurement method for aircraft methacrylic resin plates (JIS).
Ｋ−３７／＋（／９７７’））により測定して７％以上
であるが、ヘイズ率／％より小さな酸化珪素被膜では上
述の様な多重反射屈折による太陽電池の効率の向上があ
まり得られないため好ましくない。又本発明の酸化珪素
被膜の有する凹凸形状は、直径３’ ＯＯ〜３０００Ａ
ｊ高さ２００〜３０００にの略おわん状の凹凸形状で
ある。直径３００Ａより小さいもの、高さ２０ＯＡより
低いものでは高いヘイズ率を実現するために、数多い凹
凸を必要とし、数多い凹凸形状を形成することは、生産
性が悪くなることが多いので好ましくない。又直径５ｃ
ｉｏｏ大より大きなもの、高さ３０００により高いもの
ではその上に順次積層するａ−８ｉのＰ層（膜厚約／５
ｏＡ）に亀裂を生じやすくなるなどの欠点となるため好
ましくない。凹凸の形状は、上部からの圧力などによっ
て上記ａ−８ｉ層に亀裂等が生じにくい略おわん状の凹
凸が好まれる。K-37/+ (/977')) is 7% or more, but a silicon oxide film with a haze ratio smaller than /% does not significantly improve the efficiency of solar cells due to multiple catadioptric refraction as described above. This is not desirable because there is no such thing. Moreover, the uneven shape of the silicon oxide film of the present invention has a diameter of 3' OO to 3000A.
j It has an approximately bowl-shaped uneven shape with a height of 200 to 3000 mm. A diameter smaller than 300 A and a height lower than 20 OA require a large number of irregularities in order to achieve a high haze rate, and forming a large number of uneven shapes is not preferable because productivity often deteriorates. Also diameter 5c
If the size is larger than IOO, or if the height is higher than 3000, a P layer of A-8i (thickness of about /5
This is not preferable because it causes drawbacks such as the possibility of cracking in the oA). As for the shape of the unevenness, a substantially bowl-shaped unevenness is preferable because it is difficult to cause cracks or the like in the a-8i layer due to pressure from above.
ここで太陽電池基板として使用出来る基板材料としては
、酸化珪素を含むガラス、セラミツクス。Substrate materials that can be used as solar cell substrates include glass and ceramics containing silicon oxide.
プラスチツタ等の透明材料があげられる。基板の厚みは
基板材がガラスの場合ＯＪ〜ｒｍｍが好まれ、特に八ｌ
へ３．０ｍｍが好ましい。プラスチック材の場合フィル
ム状からｓｍｍ厚程度の板厚を持った状態まで使用出来
る。ここで基板の厚みは光の透過率の極端な低下が起こ
らず、又太陽電池としての強度の得られる厚みであれば
どの様な厚みであっても良い。Examples include transparent materials such as plastic ivy. The thickness of the substrate is preferably OJ~rmm when the substrate material is glass, especially 8 l.
3.0 mm is preferable. In the case of plastic materials, it can be used from a film to a plate with a thickness of about smm. Here, the thickness of the substrate may be any thickness as long as it does not cause an extreme decrease in light transmittance and provides sufficient strength as a solar cell.
ここで、上記凹凸形状を有する酸化珪素被膜の形成には
、例えば珪弗化水素酸の酸化珪素飽和水溶液にホウ酸を
添加して酸化珪素のかたまりが浮遊している状態にした
処理液中に、処理液が浸漬した基材表面で０．２〜Ｉ！
′、ＯＣｍ／ｍｉｎ の速度で流動する状態で基材を浸
漬し、基材表面に凹凸形状を有する酸化珪素被膜を析出
させる方法が利用出来る。Here, to form the silicon oxide film having the above-mentioned uneven shape, for example, boric acid is added to a silicon oxide saturated aqueous solution of hydrosilicofluoric acid to create a state in which silicon oxide lumps are suspended. , 0.2 to I! on the surface of the substrate immersed in the treatment solution.
A method can be used in which the substrate is immersed in a flowing state at a flow rate of 1, OCm/min, and a silicon oxide film having an uneven shape is deposited on the surface of the substrate.
上記透明基材を上記方法で処理することにより、直径３
００〜！；０００Ａ＋高さ、２００〜３０００Ａの略お
わん状の凹凸形状を持った酸化珪素被膜が実現される。By treating the transparent base material with the above method, a diameter of 3
00～! ;000A+height, a silicon oxide film having an approximately bowl-shaped uneven shape of 200 to 3000A is realized.
又、本発明の酸化珪素被膜は、上記透明暴利を上記方法
で処理し、その後さらにその土に酸化珪素被膜を均一な
厚みで作成する事によっても得られる。The silicon oxide coating of the present invention can also be obtained by treating the above-mentioned transparent profiteer by the above-mentioned method, and then further forming a silicon oxide coating with a uniform thickness on the soil.
２層目の均一な厚みを有する酸化珪素被膜の作成には通
常の酸化珪素被膜の製造方法が使用出来る。具体的には
、（１）有機シリコン化合物をコーディングした後に１
ｌｏｏ〜Ｓ００°Ｃに加熱して５１０２焼成膜を得る方
法（２）スパッタ法（３ＬＧＶＤ法（４）珪弗化水素酸
の酸化珪素飽和水溶液（（ホウ酸を添加させ５ｉ０２膜
を析出させる方法（特開昭３７−／９４７４１）などが
挙げられる。A normal silicon oxide film manufacturing method can be used to create the second layer of silicon oxide film having a uniform thickness. Specifically, (1) after coating the organosilicon compound,
(2) Sputtering method (3LGVD method (4) A saturated silicon oxide aqueous solution of hydrosilicofluoric acid ((Method of adding boric acid to precipitate a 5i02 film) JP-A-37-/94741).
酸化珪素被膜を２層構造とする事は、第１層の凹凸形状
の急傾斜を有する部分を平滑化して、上部に積層するａ
−８ｉ層に亀裂等が発生するのを防１１−するため、得
られる太陽電池の欠点が少なくなり、好ましい。゛こご
で第２層を形成する時の好ましい厚みはＳＯ〜、！（１
１（ＩＩ（７Ａである。５ＯＡよりうすいＩすみでは」
二記第２層の効果が十分でなく、又、２００ＯＡより厚
いと第１層の凹凸形状がつぶされる事となるので好まし
くない。特に１０ｏｏ＞ ｐａ１後の膜厚が望ましい。The two-layer structure of the silicon oxide film is achieved by smoothing the steeply sloped parts of the first layer and then layering it on top.
-8 It is preferable to prevent cracks and the like from occurring in the i layer, so that the resulting solar cell has fewer defects.゛The preferred thickness when forming the second layer here is SO~,! (1
1 (II) (7A. In the I corner, which is thinner than 5OA.)
2) The effect of the second layer is not sufficient, and if it is thicker than 200 OA, the uneven shape of the first layer will be crushed, which is not preferable. In particular, a film thickness after 10oo>pa1 is desirable.
又第２層の形成は第１層により得られるヘイズ率の低下
を導くために、酸化珪素被膜を２層の構造とする時には
第１層目においてヘイズ率が２．３％以上であることが
望ましい。In addition, since the formation of the second layer leads to a decrease in the haze rate obtained by the first layer, when the silicon oxide film has a two-layer structure, the haze rate in the first layer should be 2.3% or more. desirable.
第１層のへイス率が２．５％より少ないと２層目の被覆
によりヘイズ率が小さくなりすぎて凹凸形状の効果が小
さくなり好ましくない。If the haze ratio of the first layer is less than 2.5%, the haze ratio becomes too small due to the coating of the second layer, and the effect of the uneven shape becomes undesirable.
以下に本発明を実施例に基き説明する。The present invention will be explained below based on examples.
ｅ 実施例
実施例／
大きさがｉｏｏ （ｍｍ）ｘ１０ｃ＋ （ｍｍ）の厚味
／（ｍｍ）ノソーダライムガラスをｏ、！％濃度（重量
％）のＨＦ水溶液中に７０分間浸漬した後、十分に洗浄
し乾燥し試料ガラスとした。次に試料を浸漬するための
浸漬槽を用意する。e Example Example / Size is ioo (mm) x 10c + (mm) Thickness / (mm) No soda lime glass o,! % concentration (weight %) for 70 minutes, the sample glass was thoroughly washed and dried to obtain a sample glass. Next, prepare an immersion tank for immersing the sample.
浸漬槽は外槽（１）と内槽（２）がら成り、内槽と外槽
の間には水（３）が満しである。実験では、この水の温
度が３！；、’Ｃとなるよう、水はヒーター（４）で加
熱され、かつ温度分布均一化のため攪拌Ｈ（ｊ）で攪拌
されている。内槽は前部（６）、中部（７）。The immersion tank consists of an outer tank (1) and an inner tank (2), and the space between the inner tank and the outer tank is filled with water (3). In the experiment, the temperature of this water was 3! ;, 'C, the water is heated by a heater (4) and stirred by stirring H(j) to make the temperature distribution uniform. The inner tank is the front part (6) and the middle part (7).
後部（ざ）から成り、その各部には２モル／ｌの珪弗化
水素酸に酸化珪素を飽和し、しがる接水で１モル／４に
希釈した３１の処理液が満たしである。Each part is filled with a treatment solution of 31, which is saturated with silicon oxide in 2 mol/l of hydrofluorosilicic acid and diluted to 1 mol/4 with water.
内槽後部（ざ）の処理液は循環ポンプ（ｌｏ）により内
槽前部（６）へ戻される。ここで全処理液量に対する７
分間当りの処理液循環量の割合はざ％に設定した。（こ
こで全処理液量は約３４であり、処理中
槽害部の底面積は約／ ！； ００ｍ２であるので、浸
漬する基材ガラス表面での液流速は約へ４Ｃｍ／ｍｉｎ
と予想される。）
この反応液にＯ０！；モル／ｌの濃度のホウ酸水溶液（
／ｌ）をｏ、２ｍ１１分で連続的に滴下し、１０時間保
持した。The processing liquid at the rear part of the inner tank is returned to the front part (6) of the inner tank by a circulation pump (lo). Here, 7 for the total amount of treated liquid
The rate of processing liquid circulation per minute was set at %. (Here, the total amount of treated liquid is about 34 cm, and the bottom area of the tank during treatment is about /!; 00 m2, so the liquid flow rate on the surface of the substrate glass to be immersed is about 4 Cm/min.
It is expected to be. ) O0 to this reaction solution! ; an aqueous boric acid solution with a concentration of mol/l (
/l) was continuously added dropwise to 2ml over 11 minutes and held for 10 hours.
その後この反応液に試料（９）を内槽中央部（７）に垂
直状に浸漬・保持する。反応処理液の循環およびホウ酸
水溶液の添加を続けながらｔ時間保持し、その後試料を
取り出し洗浄乾燥した。Thereafter, a sample (9) is vertically immersed and held in the reaction solution in the center part (7) of the inner tank. The reaction treatment solution was kept circulating and the boric acid aqueous solution was continued to be added for t hours, and then the sample was taken out, washed and dried.
得られ、た被膜の厚みは約１０ｏｏ’ｊ、であり、同被
膜の電子顕微鏡観察の結果直径３００〜５ｏｏｏＸ、高
２図に示す。The thickness of the obtained film was about 1000 mm, and the result of electron microscopic observation of the film was 300 to 500 mm in diameter, as shown in Figure 2.
凹凸の形状、および単位面積あたりの数はその総合効果
として、入射光に対する散乱度合（ヘイズ率）として表
わすことが出来る。ここで、得られた表裏両面に凹凸形
状を持った上記試料のヘイズ率は２％であり、試料の両
面に凹凸のない５ｉ０２膜をコートした試料のへイス率
００．２％とくらべると大きな値であった。ここでヘイ
ズ率の測定は航空機用メタクリル樹脂板の曇価測定法（
ＪＩＳ。The overall effect of the shape of the unevenness and the number per unit area can be expressed as the degree of scattering (haze rate) for incident light. Here, the haze rate of the sample obtained above with uneven shapes on both the front and back sides is 2%, which is larger than the haze rate of 00.2% of the sample coated with a 5i02 film without unevenness on both sides of the sample. It was a value. Here, the haze rate is measured using the haze value measurement method for aircraft methacrylic resin plates (
J.I.S.
Ｋ−乙７／グ（／９７７））により測定した。Measured using K-Otsu 7/G (/977)).
実施例λ
処理液の循環量を全処理液量に対し１分間当り＠３％（
処理液の流速約ｃ＋、４０ｍ／ｍ１ｎ）となる様に変更
し、試料の浸漬時間を３時間に変更した以外は実施例／
と同様の方法により試料上に約１０００にの厚さの酸化
珪素被膜を形成した。Example λ The circulation rate of the processing liquid was @3% per minute (of the total processing liquid amount)
Example/Except that the flow rate of the treatment liquid was changed to approximately c+, 40 m/m1n), and the immersion time of the sample was changed to 3 hours.
A silicon oxide film with a thickness of about 1,000 mm was formed on the sample using the same method as described above.
得られた酸化珪素被膜は厚み約１０ＯＯＡの膜であり、
試料の電子顕微鏡観察により試料には実施例／と同様の
直径３００−、−！；０ＯＯＡ 、高さ、！００〜３０
００Ａの略おわん形をした多数の凹凸が存在することが
確認された。The obtained silicon oxide film has a thickness of about 10OOA,
Electron microscopic observation of the sample revealed that the sample had a diameter of 300-,-! ;0OOA, height,! 00-30
It was confirmed that there were a large number of approximately bowl-shaped irregularities of 00A.
又得られた試料両面に凹凸形状を持った上記試料のへイ
ス率は７％であり、実施例λにより得られた試料は実施
例１により得られた試料より深い弧を持つ凹凸の割合ま
たは凹凸の数が増加していることが予想される。In addition, the Heis ratio of the above-mentioned sample with uneven shapes on both sides of the obtained sample was 7%, and the sample obtained in Example λ had a higher ratio of unevenness with deeper arcs than the sample obtained in Example 1. It is expected that the number of irregularities will increase.
実施例３
実施例２ＶＣよって製造された凹凸形状を有する酸化珪
素被膜つき基板ガラス（以後ＡＯと呼ぶ）をリン入り酸
化珪素形成液（東京応化工業社製００Ｄ溶液）に浸漬し
、その後ＳＯＯ°Ｃで焼成を行ない膜厚約／に１（Ｊ（
ＩＩＡの酸化珪素被膜を試料両面に形成した。（以後口
の基板をＡ／と呼ぶ）ヘイズ率は７％から３％へと変化
した。Example 3 A substrate glass with a silicon oxide film having an uneven shape manufactured by Example 2 VC (hereinafter referred to as AO) was immersed in a silicon oxide forming solution containing phosphorus (00D solution manufactured by Tokyo Ohka Kogyo Co., Ltd.), and then heated to SOO°C. The film thickness was approximately 1 (J).
A silicon oxide film of IIA was formed on both sides of the sample. (The substrate at the mouth is hereinafter referred to as A/) The haze rate changed from 7% to 3%.
又同様ＫＡＯのガラス基板上にスパッタ法により約２０
０・Ａの膜厚の酸化珪素被膜を試料片面圧形成した。（
以後この基板をＡ２と呼ぶ）ヘイズ率は７％から４％へ
変化した。Similarly, about 20
A silicon oxide film with a thickness of 0.A was formed on one side of the sample. (
(Hereafter this substrate is referred to as A2) The haze rate changed from 7% to 4%.
又別に実施例２と同様なガラス基板を珪弗化水素酸の酸
化珪素飽和水溶液にホウ酸を添加した処理液に浸漬し平
滑度の高い酸化珪素被膜約７０００大を作成した比較用
基板Ｂを作成した。（特願昭３ｇ−／３’７２／７）
これらＡＯ，Ａ／ＩＪ層構造側のＡ２基板、Ｂ基板を用
いてアモルファスＳｉの太陽電池を作成した。作成手順
を以下に示す。Separately, a comparative substrate B was prepared, in which a glass substrate similar to that of Example 2 was immersed in a treatment solution in which boric acid was added to a saturated aqueous solution of silicon oxide of hydrofluorosilicic acid to form a highly smooth silicon oxide film of about 7,000 square meters. Created. (Japanese Patent Application No. 3G-/3'72/7) An amorphous Si solar cell was fabricated using the A2 substrate and B substrate on the side of the AO and A/IJ layer structures. The creation procedure is shown below.
基板ＡＯ，Ａ１．Ａ２．Ｂ上にモノブチル錫トリクロラ
イドの然気及びドーパントとして０Ｈ３０ＨＦ２ガスを
用いＣＶＤ法によって、２ｏｏｏ＠の酸化錫透明導電膜
を形成した。次いでモノシラン（ＳｉＨ４）ガスを主成
分とする原料ガスを用いて１０ＯＰａ程度の圧力下で容
量結合型高周波グロー放電装置により、（Ｊ） ｐ型ず
導体層（ホウ素ドープのａ−３ｉＧ’Ｈ＋約／３（Ｄ、
厚）
（２）真性半導体層（ａ−！３ｉ°Ｈ１約５ｏｏｏ＞厚
）（３） ｎ型半導体層（リンドープのマイクロクリス
タリン５ｉ（ｚｚｃ−３ｉ） ：Ｈ，約３０ＯＡ厚）を
それぞれ順番に堆積させ、最後にＡｄａ＆ （約ＳＯＯ
人）を真空中（約／（１−４Ｐａ）で蒸着法により作成
した。Substrates AO, A1. A2. A 2ooo@ tin oxide transparent conductive film was formed on B by a CVD method using monobutyltin trichloride in air and 0H30HF2 gas as a dopant. Next, using a capacitively coupled high-frequency glow discharge device under a pressure of about 10 OPa using a source gas containing monosilane (SiH4) gas as the main component, a (J) p-type conductor layer (boron-doped a-3iG'H + approx./ 3(D,
Thickness) (2) Intrinsic semiconductor layer (a-!3i°H1 approx. 5ooo>thickness) (3) N-type semiconductor layer (phosphorus-doped microcrystalline 5i (zzc-3i): H, approx. 30OA thick) are deposited in order. Finally, Ada & (approximately SOO
(1-4 Pa) in vacuum (approximately 1-4 Pa) by vapor deposition.
に記Ａｌ電極を作成する際基板上ＶＣ直径、２ｍｍの穴
があいたマスクをのせておき、直径、２ｍｍの太陽電池
をノＯケ作成した。When creating the Al electrode described in 2. above, a mask with a hole 2 mm in diameter was placed on the VC substrate, and a solar cell with a diameter of 2 mm was drilled.
イ（Ｉら）また太陽電池にＡＭ／の１００ｍＷ／Ｃｍ２
（７）光を照射し、負荷を無限大とした時の起電力（
開放電圧；ｖ）および負荷を０とした時の太陽電池単位
表面積あたりの電流値（短絡電流；ｍＡ／Ｃｍ２）およ
び正常な特性を示す太陽電池の割合（生存率；％）を測
定した。I (I et al.) Also, 100mW/Cm2 of AM/ for solar cells.
(7) Electromotive force when light is irradiated and the load is infinite (
The open circuit voltage (v), the current value per unit surface area of the solar cell (short-circuit current; mA/Cm2) when the load was set to 0, and the percentage of solar cells exhibiting normal characteristics (survival rate; %) were measured.
第１表に得られた測定結果を示す。表より明らかな様に
凹凸形状を持つ酸化珪素被膜を用いた基板ＡＯ，Ａ／、
Ａ−が平滑な酸化珪素被膜を用いた基板Ｂよりも大きな
短絡電流値を示していることがわかる。又、酸化珪素被
膜を２層の構造とすることにより、太陽電池を作成した
時により性能が高く（開放電圧低下の度合が少ない）、
より生存率の高い太陽電池基板が提供されていることが
わかる。Table 1 shows the measurement results obtained. As is clear from the table, substrates AO, A/, using silicon oxide films with uneven shapes,
It can be seen that substrate A- has a larger short circuit current value than substrate B using a smooth silicon oxide film. In addition, by making the silicon oxide film have a two-layer structure, the performance is higher when creating a solar cell (less degree of open circuit voltage drop),
It can be seen that a solar cell substrate with a higher survival rate is provided.
ここで上記実施例では暴利として酸化珪素を含むガラス
を用い、又形状も１００ｍｍ×１００ｍｍとし、処理工
程も断続的に行なったが、前記酸化珪素被膜は付着被膜
であるのでその他のガラス板、プラスチック板、セラミ
ックス板などあらゆる材料を使用することができる。又
形状もｌｏｏｍｍｘｉｏｏｍｍに限らず大型化出来、又
処理工程も酸化珪素の飽和第 ｌ 表
状態が続く限り連続的に基材を浸漬することが出来る。Here, in the above example, glass containing silicon oxide was used as the profiteer, the shape was 100 mm x 100 mm, and the treatment process was performed intermittently, but since the silicon oxide film is an adhesive film, other glass plates, plastic Any material can be used, such as a plate or a ceramic plate. In addition, the shape is not limited to loommxioomm, but it can be made larger, and the treatment process can be such that the substrate is continuously immersed as long as the saturated state of silicon oxide continues.
ここで、又上記実施例では、太陽電池基板として基板の
両面に凸凹形状の酸化珪素被膜を作成したが、少なくと
も太＠電池を積層する側に凹凸形状を持っていれば、太
＠電池としての性能向上に効果があることは言うまでも
ない。又太陽電池を積層していない側の基板表面には、
反射防止膜を設けることが好ましいが、なくてもかまわ
ない。Here, and in the above example, a silicon oxide film with an uneven shape was created on both sides of the substrate as a solar cell substrate, but if the uneven shape is formed on the side where the thick@cell is laminated at least, the silicon oxide film can be used as a thick@cell. Needless to say, this is effective in improving performance. Also, on the surface of the substrate on the side where the solar cells are not stacked,
Although it is preferable to provide an antireflection film, it is not necessary.
又、上記実施例のへイス率の測定値は基板両面に凹凸を
形成したものであり、片面に凹凸を制限しｆ 発明の効
果
本発明によれば、太陽電池基板として適当な凹凸形状を
有する太陽電池基板が、部用な方法により得られている
。又コ重のコ〜１・膜を作成することにより、特性のよ
り向上した、生産性の高い太陽電池基板を提供している
。In addition, the measured value of the Heiss ratio in the above example was obtained by forming unevenness on both sides of the substrate, and the unevenness was limited to one side. Solar cell substrates have been obtained by conventional methods. In addition, by creating a 1-layer film, a solar cell substrate with improved characteristics and high productivity is provided.
第１図は本願発明の実施例を示す循環系統説明図、第２
図は本発明の凹凸形状を持った酸化珪素被膜を有する太
陽電池基板の電子顕微鏡写真である。
（１） 外構 （２） 内槽
（３） 水 （４’） ヒーター
Ｄ） 攪拌器 （６） 内槽前部
（７） 内槽中央部 （ざ） 内槽後部（９） ガラス
（ｌＯ）循環ポンプ
（ｌｌ） ホウ酸水溶液 、
４
第１図
覚２図
手 続 補 正 書（方式）
／ 事件の表示
特願昭５ｑ−３１１ｔｉｏ号
一＝＝号
！ 発明の名称
太＠電池基板
３ 補正をする者
事件との関係 特許出願人
住 所 大阪府大阪市東区道修町４丁目８番地名 称
（４′０θ）日本板硝子株式会社代表者 刺 賀 信
雄
グ代理人
７ 補正の内容
明細書第１＆頁９〜／／行目に「第２図は・・・・・・
子顕微鏡写真である。」とあるのを１第２図は実施例／
により得られた太陽電池基板表面の略おわん形粒子の構
造を示す図面に代る電子顕微鏡ず真である。」と補正す
る。Fig. 1 is an explanatory diagram of a circulation system showing an embodiment of the present invention;
The figure is an electron micrograph of a solar cell substrate having a silicon oxide film having an uneven shape according to the present invention. (1) Exterior (2) Inner tank (3) Water (4') Heater D) Stirrer (6) Front part of the inner tank (7) Center part of the inner tank (Za) Rear part of the inner tank (9) Glass (lO) Circulation pump (ll) Boric acid aqueous solution, 4 Figure 1 Figure 2 Procedure Amendment (Method) / Incident Display Patent Application No. 1 == No. 1 = = No. 311 of Showa 5Q-311! Name of the invention: Fat@Battery Substrate 3 Relationship with the case of the person making the amendment Patent applicant address: 4-8 Doshomachi, Higashi-ku, Osaka-shi, Osaka Name:
(4'0θ) Shin Saiga, Representative of Nippon Sheet Glass Co., Ltd.
Ogu Agent 7 In the statement of contents of the amendment, from page 1 & page 9 to line //, it says "Figure 2 is..."
This is a microscopic photograph of a child. ” 1. Figure 2 shows an example/
This is an electron microscope photograph in place of a drawing showing the structure of approximately bowl-shaped particles on the surface of a solar cell substrate obtained by. ” he corrected.
Claims (2)
０００に高さ２００〜３０００λの多数の凸部を持った
酸化珪素被膜を有することを特徴とする太陽電池基板。(1) Has a Heiss ratio of 7% or more and a diameter of 300-! ;
A solar cell substrate characterized in that it has a silicon oxide film having a large number of convex portions with a height of 200 to 3000λ.
００にの多数の凸部を持った酸化珪素被膜が、珪弗化水
素酸の酸化珪素飽和水溶液にホウ酸を添加した処理液か
らの析出膜である特許請求の範囲第１項記載の太陽電池
基板。 Ｃ’ｌ ｆｉｎ、 径３００−３０００ Ａ ＋ 高す
−２００〜３０００ Ａ （’） 多ｆｌの凸部を持っ
た酸化珪素被膜が、珪弗化水素酸の酸化珪素飽和水溶液
にホウ酸を添加した処理液からの析出膜上に、厚さ３０
〜２０００にの均一厚の酸化珪素の被膜を設けたもので
ある特許請求の範囲、第７項記載の太陽電池基板。(2) Diameter 300~! ;000A+height-oo~30
The solar cell according to claim 1, wherein the silicon oxide film having a large number of convex portions is a deposited film from a treatment solution obtained by adding boric acid to a saturated silicon oxide aqueous solution of hydrosilicofluoric acid. substrate. C'l fin, Diameter 300-3000 A + Height -200-3000 A (') A silicon oxide coating with multi-fl convex parts is formed by adding boric acid to a silicon oxide saturated aqueous solution of hydrosilicofluoric acid. A layer with a thickness of 30 mm is deposited on the deposited film from the treatment solution.
8. The solar cell substrate according to claim 7, wherein the solar cell substrate is provided with a silicon oxide coating having a uniform thickness of 2,000 to 2,000 mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59031140A JPS60175465A (en) | 1984-02-21 | 1984-02-21 | Solar battery substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59031140A JPS60175465A (en) | 1984-02-21 | 1984-02-21 | Solar battery substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60175465A true JPS60175465A (en) | 1985-09-09 |
| JPH0438147B2 JPH0438147B2 (en) | 1992-06-23 |
Family
ID=12323130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59031140A Granted JPS60175465A (en) | 1984-02-21 | 1984-02-21 | Solar battery substrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60175465A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6245079A (en) * | 1985-08-22 | 1987-02-27 | Kanegafuchi Chem Ind Co Ltd | Substrate for solar cell and manufacture thereof |
| US4732621A (en) * | 1985-06-17 | 1988-03-22 | Sanyo Electric Co., Ltd. | Method for producing a transparent conductive oxide layer and a photovoltaic device including such a layer |
| JPH01219043A (en) * | 1988-02-26 | 1989-09-01 | Nippon Sheet Glass Co Ltd | Transparent conductive glass substrate and solar-cell module |
| JPH0650359U (en) * | 1992-11-30 | 1994-07-08 | 日本特殊陶業株式会社 | Semiconductor package terminal correction jig |
| JP2002237610A (en) * | 2001-02-08 | 2002-08-23 | Nippon Sheet Glass Co Ltd | Photoelectric converter and its manufacturing method |
| US6504139B1 (en) | 1999-05-28 | 2003-01-07 | Nippon Sheet Glass Co., Ltd. | Substrate for photoelectric conversion device, method of manufacturing the same, and photoelectric conversion device using the same |
| WO2003017377A1 (en) * | 2001-08-10 | 2003-02-27 | Nippon Sheet Glass Company, Limited | Glass plate having electroconductive film formed thereon |
| WO2010050189A1 (en) | 2008-10-29 | 2010-05-06 | 株式会社アルバック | Method for manufacturing solar cell, etching device, and cvd device |
-
1984
- 1984-02-21 JP JP59031140A patent/JPS60175465A/en active Granted
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4732621A (en) * | 1985-06-17 | 1988-03-22 | Sanyo Electric Co., Ltd. | Method for producing a transparent conductive oxide layer and a photovoltaic device including such a layer |
| JPS6245079A (en) * | 1985-08-22 | 1987-02-27 | Kanegafuchi Chem Ind Co Ltd | Substrate for solar cell and manufacture thereof |
| JPH0566753B2 (en) * | 1985-08-22 | 1993-09-22 | Kanegafuchi Chemical Ind | |
| JPH01219043A (en) * | 1988-02-26 | 1989-09-01 | Nippon Sheet Glass Co Ltd | Transparent conductive glass substrate and solar-cell module |
| JPH0650359U (en) * | 1992-11-30 | 1994-07-08 | 日本特殊陶業株式会社 | Semiconductor package terminal correction jig |
| US6504139B1 (en) | 1999-05-28 | 2003-01-07 | Nippon Sheet Glass Co., Ltd. | Substrate for photoelectric conversion device, method of manufacturing the same, and photoelectric conversion device using the same |
| JP2002237610A (en) * | 2001-02-08 | 2002-08-23 | Nippon Sheet Glass Co Ltd | Photoelectric converter and its manufacturing method |
| WO2003017377A1 (en) * | 2001-08-10 | 2003-02-27 | Nippon Sheet Glass Company, Limited | Glass plate having electroconductive film formed thereon |
| WO2010050189A1 (en) | 2008-10-29 | 2010-05-06 | 株式会社アルバック | Method for manufacturing solar cell, etching device, and cvd device |
| US8420436B2 (en) | 2008-10-29 | 2013-04-16 | Ulvac, Inc. | Method for manufacturing solar cell, etching device, and CVD device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0438147B2 (en) | 1992-06-23 |
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