JPS60176947A - Production of silicon oxide film - Google Patents
Production of silicon oxide filmInfo
- Publication number
- JPS60176947A JPS60176947A JP59031139A JP3113984A JPS60176947A JP S60176947 A JPS60176947 A JP S60176947A JP 59031139 A JP59031139 A JP 59031139A JP 3113984 A JP3113984 A JP 3113984A JP S60176947 A JPS60176947 A JP S60176947A
- Authority
- JP
- Japan
- Prior art keywords
- silicon oxide
- oxide film
- substrate
- solution
- aqueous solution
- 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
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
- Y02E10/548—Amorphous silicon PV cells
Abstract
Description
【発明の詳細な説明】
ａ 産業上の利用分野
本発明は基材上に酸化珪素被膜を製造する方法に関し、
更に詳しくは太陽電池基板に適した凹凸形状を有する透
明基板を製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION a. Industrial Application Field The present invention relates to a method for producing a silicon oxide coating on a substrate,
More specifically, the present invention relates to a method of manufacturing a transparent substrate having an uneven shape suitable for a solar cell substrate.
ｂ 従来技術
今日、いろいろな材料の表面を酸化珪素膜で被覆するこ
とが広く行なわれている。例えばガラス表面に酸化チタ
ン膜と酸化珪素の交互多層膜を形成することにより、表
面の反射効果を減じることが古くから行なわれている。b. Prior Art Today, it is widely practiced to coat the surfaces of various materials with silicon oxide films. For example, it has long been practiced to reduce the reflection effect of the surface by forming alternating multilayer films of titanium oxide and silicon oxide on the glass surface.
あるいは金属・合金材料の保護膜としてその表面に酸化
珪素被膜を形成させることも広く行なわれている。更に
は、液晶表示パネル、太陽電池用基板ガラスにソーダラ
イムガラスまたはホウ珪酸ガラスなどアルカリ含有ガラ
スを用いる場合、ガラスからのアルカリ虚分の溶出を防
止する目的で、これらガラスの表面を酸化珪素膜で被覆
することが行なわれる。特にガラスからのアルカリ成分
の溶出防止は、液晶表示あるいは太陽電池の寿命を維持
する上で、欠くことのできない技術となっている。Alternatively, it is widely practiced to form a silicon oxide film on the surface of metal/alloy materials as a protective film. Furthermore, when alkali-containing glasses such as soda lime glass or borosilicate glass are used for substrate glass for liquid crystal display panels and solar cells, the surfaces of these glasses are coated with a silicon oxide film in order to prevent the elution of alkaline vacancies from the glass. The coating is carried out with In particular, preventing the elution of alkaline components from glass has become an indispensable technology for maintaining the lifespan of liquid crystal displays or solar cells.
ガラスの表面に酸化珪素被膜を形成させるＫは、従来よ
り真空恭着・スパッター・ＣＶＤあるいは浸漬塗布法（
ティッピング法）等の方法が多く用いられてきた。しか
しながら、これらの方法は装置あるいは付帯設備が高価
であるため、酸化珪素被覆に要するコストが高くなる他
、小さなガラスしか処理できないという欠点があった。K, which forms a silicon oxide film on the surface of glass, has traditionally been applied by vacuum deposition, sputtering, CVD, or dip coating (
Tipping method) and other methods have been widely used. However, these methods have the disadvantage that the equipment or ancillary equipment is expensive, which increases the cost required for silicon oxide coating, and that only small pieces of glass can be processed.
そこで、これら従来の酸化珪素被膜形成方法の欠点に鑑
み、珪弗化水素酸の酸化珪素飽和水溶液にホウ酸を添加
した処理液を用いた新しい酸化珪素被膜形成方法が提案
されている。（特開昭Ｓ７−／９乙７グゲ）。In view of these drawbacks of the conventional methods for forming silicon oxide films, a new method for forming silicon oxide films has been proposed using a treatment solution in which boric acid is added to a saturated silicon oxide aqueous solution of hydrosilicofluoric acid. (Unexamined Japanese Patent Publication Showa S7-/9 Otsu 7 Guge).
又、一方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−３ｊ−）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１７で注１−１を浴びている。On the other hand, in recent years, solar cells using amorphous silicon (a-3j-), which is produced by glow discharge decomposition of silane gas, are one of the photoelectric conversion devices that can be manufactured at low cost. is bathed in
しかし、かかるａ−８ｉ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Ｓｉ、ＧａＡｓなど）
Ｋ比べ極めて低いことが問題となり、（−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（・づる光反射損失を低減
し短絡電流を増大さゼ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層１
〕１させることにより長波長光に対する収集効率を向上
さセることか考えられている。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か発生したり膜
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。従って高度に制御さ
れた凹凸の度合か必要とされていた。However, in such an A-8i solar cell, its photoelectric conversion efficiency is higher than that of other crystalline semiconductors (crystalline Si, GaAs, etc.).
In order to solve this problem, various countermeasures have been devised for manufacturing methods and battery structures. In particular, it is necessary to reduce light reflection loss on the surface of the battery and reduce short-circuit current. It is important to increase the amount of light reflected by the solar cell, and for this reason, the solar cell is made to have an uneven structure so that the incident light is reflected within the cell by a multi-reflection layer 1.
] 1, it is considered that the collection efficiency for long wavelength light can be improved. However, if the degree of unevenness is too large, defects such as pinholes are likely to occur, and the film thickness is likely to become non-uniform, which will actually reduce the characteristics of the solar cell (particularly the open circuit voltage and yield rate). Therefore, a highly controlled degree of unevenness was required.
Ｃ発明の目的
本発明は、珪弗化水素酸の酸化珪素飽和水溶液にホウ酸
を添加した処理液を用いた酸化珪素被膜製造方法を改良
し、連続的でかつ安価であり、凹凸の形状精度が調整さ
れ、大面積でも製造出来る、凹凸形状を有する太陽電池
基板に適する酸化珪素被膜σ）製造方法を提供すること
にある。C.Object of the Invention The present invention improves a method for manufacturing a silicon oxide film using a treatment solution in which boric acid is added to a saturated silicon oxide aqueous solution of hydrosilicofluoric acid, which is continuous and inexpensive, and improves the shape accuracy of irregularities. It is an object of the present invention to provide a method for manufacturing a silicon oxide film σ) suitable for a solar cell substrate having an uneven shape, which can be adjusted and manufactured even on a large area.
ｄ 発明の構成
本発明は、暴利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することにより、該暴利
表面」二に酸化珪素被膜を製造する方法において該処理
液中に酸化珪素のかたまりが浮遊し、かつ該処理液が浸
漬した基材表面で０．２〜ｇ。Ｏｃｍ、’ｍｉｎの速度
で流動する状態で該基材を処理液に浸漬させ、該基材表
面に凹凸形状を有する酸化珪素被膜を形成させることを
特徴とする酸化珪素破膜の製造方法である。d.Structure of the Invention The present invention provides a method for producing a silicon oxide coating on the surface of a profiteer by immersing the profiteer in a treatment solution in which boric acid is added to a saturated silicon oxide aqueous solution of hydrosilicofluoric acid. A lump of silicon oxide is floating in the solution, and the weight on the surface of the substrate immersed in the treatment solution is 0.2 to 0.2 g. A method for producing a broken silicon oxide film, which comprises immersing the base material in a treatment liquid while flowing at a flow rate of Ocm, min, to form a silicon oxide film having an uneven shape on the surface of the base material. .
ここで暴利には酸化珪素を含むガラス、セラミックス、
プラスチック等があげられる。Here, profiteering includes glass, ceramics containing silicon oxide,
Examples include plastic.
又、使用する処理液の調整法としては２モル／！−
４の濃度以−にの珪弗化水素酸水溶液匂酸化珪素を飽和
し、しかる復水で希釈し珪弗化水素酸の濃度を一モル／
ｌ以下としたものが望ましい。この様な処理液調整法が
望ましい理由は、被膜形成速度るからである。ここで処
理液として用いる珪弗化水素酸の望ましい濃度は７〜２
モル／ｌであるが、この濃度の珪弗化水素酸水溶液を直
接調整した後酸化珪素を飽和するよりも、本発明のよう
にあらかじめ高濃度の珪弗化水素酸水溶液を調整した後
酸化珪素を飽和し、しかる後珪弗化水素酸の濃度がｌ−
２モル／ｅとなるよう水で希釈した方が酸化珪素被膜の
形成速度が速く、かつ形成される凹凸が大きく、数も多
くなるからである。Also, the method for adjusting the processing solution used is 2 mol/! - Saturate aqueous solution of hydrosilicofluoric acid with a concentration of 4 or higher and dilute silicon nitride with the appropriate condensate to adjust the concentration of hydrosilicofluoric acid to 1 mol/ml.
It is desirable that it be less than l. The reason why such a treatment liquid adjustment method is desirable is that it increases the film formation rate. The desirable concentration of hydrosilicofluoric acid used as the treatment liquid here is 7 to 2.
mol/l, but rather than directly preparing an aqueous solution of hydrosilicofluoric acid with this concentration and then saturating the silicon oxide, as in the present invention, preparing an aqueous solution of hydrosilicic acid with a high concentration in advance and then saturating the silicon oxide. is saturated, and then the concentration of hydrosilicofluoric acid is l-
This is because diluting with water to 2 mol/e results in faster formation of the silicon oxide film, and the formed irregularities are larger and more numerous.
上記処理液にホウ酸を添加して行くとしだいに酸化珪素
の過飽和状態となって処理液中から酸化珪素の析出が始
まる。本発明の酸化珪素被膜の製造方法は、上記析出酸
化珪素を被膜として得る方法である。As boric acid is added to the treatment liquid, silicon oxide gradually becomes supersaturated, and silicon oxide begins to precipitate from the treatment liquid. The method for producing a silicon oxide film of the present invention is a method for obtaining the above-mentioned precipitated silicon oxide as a film.
ホウ酸の添力１１速度は、ポウ＃濃ｊ勺かＯ，Ｓモル／
βであり処理液が」１記方法により調整された珪弗化水
素酸の酸化珪素含有水溶液（珪弗化水素酸が／−２モル
／ｌ）である時は、Ｏ，０５〜／ｍｎ／ｍｉ、ｎである
ことが好まれる。ここで添加量がＯ，ＯＳよりＡ＞ ｌ
’ｔ イ、Ｉ−耐什往＊被股が形成されず、ｔｍｒｙｍ
１ｎより多いと、処理液中に大きな酸化珪素の固りが生
じ沈殿となるために凹凸形状を有する、酸化珪素被膜を
安定的に形成することが出来ない。良好な凹凸形状を持
った酸化珪素被膜を得るためには、処理液中に適度な大
きさの酸化珪素の固りが浮遊することが必要である。又
出来上がる酸化珪素被膜の凹凸の大きさおよび数は、処
理液の基材表面ての流動速度、およびホウ酸の添加速度
によって変化させることが出来、一般的には処理液の流
動速度が遅いほど、ホウ酸の添加速度が速いほど凹凸は
大きくなる。The addition rate of boric acid is 11 mol/O, S mol/
β and the treatment liquid is a silicon oxide-containing aqueous solution of hydrosilicofluoric acid prepared by the method described in 1. mi, n are preferred. Here, the amount added is O, A> l from OS
't I, I-resistant
When the amount is more than 1n, large silicon oxide particles form in the treatment solution and become precipitates, making it impossible to stably form a silicon oxide film having an uneven shape. In order to obtain a silicon oxide film with a good uneven shape, it is necessary that appropriately sized silicon oxide lumps be suspended in the processing liquid. In addition, the size and number of unevenness in the silicon oxide film that is completed can be changed by the flow rate of the treatment liquid over the substrate surface and the addition rate of boric acid; generally, the slower the flow rate of the treatment liquid, the better the , the faster the addition rate of boric acid, the larger the unevenness becomes.
処理液の流動により、酸化珪素の固りが処理液中に浮遊
することが、良好な凹凸形状を持った酸化珪素被膜を形
成するのに必要であるが、こごで＃遊する酸化珪素の固
りには／ｊμｍ以上の大きさを持った酸化珪素の固りが
含まれていることが好まれる。ここで／、５μｍより小
さい酸化珪素の固りだけでは良好な凹凸形状を持った酸
化珪素被膜が得られず、平担な酸化珪素被膜が得られる
（特願昭ｓｇ−／３ｑｒ／７）ためである。It is necessary for silicon oxide particles to float in the processing solution due to the flow of the processing solution in order to form a silicon oxide film with a good uneven shape. It is preferable that the solids include silicon oxide solids having a size of /j μm or more. Here/, since a silicon oxide film with a good uneven shape cannot be obtained only by silicon oxide lumps smaller than 5 μm, a flat silicon oxide film can be obtained (Patent Application Showa sg-/3qr/7). It is.
析出する酸化珪素の固りを処理液中（で浮遊し、又添加
したホウ酸を処理液に混合するために処理液を流動させ
るが、処理液の浸漬暴利表面での流速が０．２〜ｇ、
Ｏｃｍ／ｍｉｎであることが好まれる。流速がｏ、 ２
ｃｍ７ｍ１ｎ より遅いと、処理液中に酸化珪素の沈殿
が生じやすくなり、望みの凹凸形状を持った酸化珪素被
膜が得られない。又流速がざ、Ｏａｍ／ｍｉｎより早い
と、流れが乱流となりやすく、ムラの多い膜となるので
好ましくない。The treatment liquid is made to flow in order to float the precipitated silicon oxide solids in the treatment liquid and mix the added boric acid into the treatment liquid, but the flow rate of the treatment liquid on the immersed surface is 0.2~ g,
Ocm/min is preferred. The flow rate is o, 2
If it is slower than cm7m1n, silicon oxide tends to precipitate in the treatment solution, making it impossible to obtain a silicon oxide film with the desired uneven shape. Furthermore, if the flow rate is faster than Oam/min, the flow tends to become turbulent, resulting in an uneven film, which is not preferable.
処理液を流動させる方法はどの様な方法であってもかま
わないが、処理液を流出させその後循環ポンプ等で循環
させる方法等が簡哨であり、好まれる。又処理液の流れ
は浸漬した基相面に対して層状に流れる事が好まれる。Any method may be used to flow the treatment liquid, but a method in which the treatment liquid is flowed out and then circulated using a circulation pump or the like is simple and preferred. Further, it is preferable that the treatment liquid flows in a layered manner with respect to the immersed base phase surface.
これは処理液が乱流て流れる場合には上述の様にムラの
多い膜となるためである。This is because when the processing liquid flows turbulently, the film becomes uneven as described above.
以下（で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１
大きさが１０（７（ｍｍ）Ｘ１００（ｍｍ） の厚味／
（ｍｍ）のソーダライムガラスをｏ３％濃度（ｆｆｉｉ
ｔ％）のＨＦ水溶液中に１０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 Examples Example 1 Size: 10 (7 (mm) x 100 (mm) Thickness/
(mm) of soda lime glass with O3% concentration (ffii
After immersing the glass in a HF aqueous solution of (t%) for 10 minutes, it 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）から成り、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３３”Ｃとなるよう、水はヒーター（ψ）で加熱さ
れ、かつ温度分布均一化のため攪拌器Ｄ）で攪拌されて
いる。内槽は前部（ｇ）、中部（７）、後部（ｇ）から
成り、その内部には２モル／ｌの珪弗化水素酸に酸化珪
素を飽和し、しかる抜水で１モル／βに希釈した３１の
処理液が満たしである。内槽後部（ざ）の処理液は循環
ポンプ（／のによりろ過されることなく内槽前部（乙）
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ｇ％に設定した。（ここで全処理液
量は約３４であり処理槽中部の底面積は約１３０ｃｍ２
であるので、浸漬する基材ガラス板表面での液流速は約
１．ｔｃｍ７ｍ１ｎと予想される。）液（／／）を０．
２ｍ ／ ７分で連続的に滴下し、７０時間保持した。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 water was heated with a heater (ψ) so that the temperature of this water was 33"C, and was stirred with an agitator D) to make the temperature distribution uniform. The inner tank was placed in the front part (g). , the middle part (7), and the rear part (g), and inside it there is a treatment solution of 31, which is saturated with silicon oxide in 2 mol/l of hydrosilicofluoric acid and diluted to 1 mol/β by draining the water. The treated liquid in the rear part of the inner tank is not filtered by the circulation pump (/) and is transferred to the front part of the inner tank (B).
be returned to. Here, the ratio of the amount of processing liquid circulated per 7 minutes to the total amount of processing liquid was set to g%. (Here, the total amount of treated liquid is about 34 cm, and the bottom area of the middle part of the processing tank is about 130 cm2.
Therefore, the liquid flow rate on the surface of the substrate glass plate to be immersed is approximately 1. It is expected to be tcm7m1n. ) liquid (//) to 0.
It was continuously dropped at 2m/7min and held for 70 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から１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. Circulation of the reaction solution and addition of the aqueous boric acid solution were continued for 1 hour, after which the sample was taken out, washed and dried.
得られた被膜の厚みは約１００ｑＡであり、同被膜の電
子顕微鏡観察の結果直径３００〜ｊ；０ＯＯＡ高２図に
示す。The thickness of the obtained coating was approximately 100 qA, and the results of electron microscopic observation of the coating were shown in Figure 2: Diameter: 300~J; 0OOA, Height: 2.
凹凸の形状、および栄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
わすことができる。ここで得られた試料のへイス率を航
空機用メタクリル樹脂板の曇価測定法（ＪＩＳ、に−６
７／Ｚ（／９７７））により測定したら約２％であり、
表面に凹凸のない５１０２膜をコートした試料のへイス
率０．２％とくらべると大きな値であった。The shape of the unevenness and the number per crown area can be expressed as the degree of scattering (haze rate) for incident light as a comprehensive effect. The haze rate of the sample obtained here was determined by the Haze Value Measuring Method for Methacrylic Resin Boards for Aircraft (JIS, 6-6).
7/Z (/977)), it is about 2%,
This was a large value compared to the Heis ratio of 0.2% for the sample coated with 5102 film, which has no irregularities on the surface.
処理液の循環量を全処理液１ｊＪ： ｖｃ対し７分間当
り＠Ｌ３％（処理液の流速約０．乙Ｃｍ／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十に約１０ＯＯＡの
厚さの酸化珪素被膜を形成した。Except that the circulation rate of the treatment liquid was changed to 1JJ:vc of the total treatment liquid per 7 minutes @L3% (flow rate of treatment liquid approximately 0.Cm/m1n), and the immersion time of the sample was changed to 3 hours. A silicon oxide film with a thickness of about 1000A was formed on each sample by the same method as in Example.
？；Ｊら、１１だ酸化珪素被膜は厚み約１０ｏｏＸの膜
であり、試料の電子顕Ｒ鏡観察により試料にｉ」実施例
／と同様の直径３００−！；０００Ａ高さ、２００〜３
０００Ａの略おわん形をした多数の凹凸が存在すること
が確Ｊ、をさ才］だ。? J et al., 11 The silicon oxide film is a film with a thickness of about 1000X, and by electron microscopy observation of the sample, it was observed that the sample had a diameter of 300mm, similar to Example 1. ;000A height, 200~3
It is certain that there are many roughly bowl-shaped irregularities of 000A.
又得ら才また試料のへイス率は７％であ一す、実施例２
（てより得られた試料は実施例／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か増力１１
１〜でいることか予想される。In addition, the heis ratio of the sample was 7%, Example 2
(The sample obtained by this method was higher than the sample obtained by Example/by the increase in the ratio of unevenness with deep arcs or the number of unevenness by 11
It is expected that it will be 1~.
実施例３
実施例２によ−、て製造された凹凸形状を有する酸化珪
素被膜つき基板カラス（以後ＡＯと呼ぶ）をリン入り酸
化珪素形成液（東京応化−Ｌ業社製ＯＣＤ溶液）（で浸
漬し、その後ｓｏｏ”ｃで焼成を行ない膜厚約１０００
大の酸化珪素被膜を形成した。Example 3 A substrate glass with a silicon oxide film having an uneven shape (hereinafter referred to as AO) manufactured in Example 2 was treated with a silicon oxide forming solution containing phosphorus (OCD solution manufactured by Tokyo Ohka-L Gyo Co., Ltd.). immersed, then baked in soo'c to a film thickness of about 1000
A large silicon oxide film was formed.
（以後この基板をＡＩとｌＰｐぶ）へイス率は７％から
３％へと変化した。(Hereinafter, this substrate will be referred to as AI and lPp.) The heis ratio changed from 7% to 3%.
又同様にＡＯのカラス基板上にスパンタ法により約２０
ＯＡの膜厚の酸化珪素被＋１！、％を形成１−だ。（以
後この基板をＡ２と呼ぶ）へイス率ｏＪ７％から乙％へ
変化した。Similarly, about 20
Silicon oxide film thickness of OA +1! , forming 1-%. (Hereinafter, this board will be referred to as A2) The Heis ratio changed from oJ7% to Otsu%.
又別に実施例Ωと同様なカラス基板を珪弗化水素酸の酸
化月未飽和水溶液にホウ酸を添加１〜だ処理液に浸漬１
−平滑度の高い酸化珪素形成液１０００λを作成した比
較用基板Ｂを作成した（特凰１昭５ｇ−７３７２／７）
これら基板を用いてアモルファスＳコ−の太１ｍ ’、
’ｌＬＧを作成した。作成手順を以下に示す。Separately, a glass substrate similar to Example Ω was immersed in an unsaturated aqueous solution of hydrosilicofluoric acid with boric acid added to it.
- Comparative substrate B was prepared using 1000λ of silicon oxide forming liquid with high smoothness (Tokuo 1 Showa 5g-7372/7) Using these substrates, a 1 m thick amorphous S coat,
'lLG was created. The creation procedure is shown below.
基板Ａ Ｏ＋ Ａ ］、 ＋ Ａ２ ＋Ｂ上にモノフヂ
ル８トリクロライドの然気及びドーパントとしてａｎ：
＼０ＨＦ２カスを用いＣＶＤ法によって、２０００Ａの
酸化錫透明導電膜を形成した。次いてモノシラン（Ｓ］
、Ｈ４）ガスを主成分とする原料カスを用いて１０ＯＰ
ａ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
（１）Ｐ型半導体層（ホウ素１’ −）（１） ａ−３
ＩＣ’Ｈｒをそれぞれ順番Ｃ（堆積さゼ、最後にＡ／組
電極約５ｏｏＸ）を真空中（約１Ｏ−４Ｐａ）で蒸着法
により作成した。On the substrate A O+ A ], + A2 + B, an air of monofiltrate 8 trichloride and an as a dopant:
A 2000A tin oxide transparent conductive film was formed by CVD using \0HF2 residue. Next, monosilane (S)
, H4) 10OP using raw material waste whose main component is gas
(1) P-type semiconductor layer (boron 1'-) (1) a-3 using a capacitively coupled high-frequency glow discharge device under a pressure of about a
IC'Hr was prepared by vapor deposition in order C (deposition, finally A/set of electrodes about 50X) in vacuum (about 10-4 Pa).
得らねた太陽電池ＫＡ、Ｍ／の１００ｍＷ／Ｃｍ２（１
’）光を照射し、負荷を無限大とした時の起電圧（開放
電圧。100 mW/Cm2 (1
') Electromotive force (open circuit voltage) when light is irradiated and the load is infinite.
■）および負荷をＯ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；ｍ４／Ｃｍ２）を測定した。(2) and the current value per unit surface area of the solar cell (short circuit current; m4/Cm2) when the load was O.
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Ａ Ｏ、Ａ
、 ｌ ＋ Ａ、 ２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、性能が向上してい
ることかわかる。Table 1 shows the measurement results obtained. As is clear from the table, substrates A O, A using a silicon oxide film with an uneven shape
, l + A, 2 showed a larger short-circuit current value than the substrate B using a smooth silicon oxide film, indicating that the performance was improved.
ここで上記実施例では基材として酸化珪素を含むカラス
を用い、又形状も１００ｍｍ×１００ｍｍとし、々几皿
■−扁≠、断賂酊■に９斤な。たが、【の酔什柱去姑第
／ 表
膜は、付着被膜であるので着色カラスをはじめとするそ
の他の力゛ラス板、プラスザック析、七うミックス飯な
どあらゆる材料を使用することができる。又形状も／
００ ｍ’ｍ Ｘ ／ ００ ｍｍに限らず大板化出来
、ヌ処理工程も酸化珪素の飽和状態が続く限り連続的Ｋ
Ｍ材を浸漬することかできる。Here, in the above embodiment, glass containing silicon oxide was used as the base material, and the shape was 100 mm x 100 mm, and the size of the plate was 9 loaves. However, since the surface film is an adhesive film, it is possible to use all kinds of materials such as colored glass, other strength glass plates, plus sack analysis, and mixed rice. can. Also the shape/
00 mm
M material can be immersed.
ｆ 発明の効果
本発明によれば、大板形状の基材に簡単に凹凸の精度の
調整された凹凸形状を有する戯・化珪素被膜を形成する
ことができる。この様にして形成された凹凸形状を有す
る酸化珪素被服体は、基材が透明材料である場合は太陽
電池基板として、その第２図
特許庁長官殿
／ 事件の表示
特願昭５９−３／／３９号
→’ＭＨｊ酬−□−一−シ
ー 発明の名称
酸化珪素被膜の製造方法
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
（ｇｏｏ） 日本板硝子株式会社代表者 刺 賀 信
雄
グ代理人
２ 補正の対象 明細、−１＝１２Ｎや簡単な説明」の
欄。f. Effects of the Invention According to the present invention, it is possible to easily form a silicon oxide coating having an uneven shape with the accuracy of the unevenness adjusted on a large plate-shaped base material. The silicon oxide covering body having the uneven shape formed in this way can be used as a solar cell substrate when the base material is a transparent material. / No. 39 → 'MHj Compensation-□-1-C Name of the invention Method for manufacturing silicon oxide film 3 Relationship to the case of the person making the amendment Patent applicant address 4-8 Doshomachi, Higashi-ku, Osaka-shi, Osaka Name Name
(goo) Shin Saiga, Representative of Nippon Sheet Glass Co., Ltd.
Ogu agent 2 Target of correction Details, -1=12N and brief explanation" column.
７ 補ｆｌヨの内容
明細占第１Ｓ頁７〜ざ行目に「第、２図は・−・電子顕
微鏡写真である。」とあるのを［第２図は実施例／によ
り得られた酸化珪素被膜に生成している略おわん形粒子
の構造を示す図面に代る電子顕微鏡写真である。１と補
正する。7 In the Supplementary Contents Specification, page 1S, lines 7 to 11, it says "Figure 2 is an electron micrograph." This is an electron micrograph in place of a drawing showing the structure of approximately bowl-shaped particles formed in a silicon coating. Correct it to 1.
Claims (3)
ウ酸を添加した処理液に浸漬することにより、該基材表
面上に酸化珪素被膜を製造する方法において、該処理液
中に酸化珪素のかたまりが浮遊し、かつ該処理液が浸漬
した基材表面で０．２〜ｇ、ＯＣｍ／ｍｉｎの速度で流
動する状態で該基材を処理液に浸漬させ、該基材表面に
凹凸形状を有する酸化珪素被膜を形成させることを特徴
とする酸化珪素被膜の製造方法。(1) In a method of manufacturing a silicon oxide film on the surface of a substrate by immersing the substrate in a treatment solution in which boric acid is added to a saturated aqueous solution of silicon oxide of hydrosilicofluoric acid, the method includes: The substrate is immersed in the treatment liquid in a state in which lumps of silicon oxide are suspended in the treatment liquid and the treatment liquid flows at a rate of 0.2 to OCm/min on the surface of the immersed substrate. 1. A method for producing a silicon oxide film, comprising forming a silicon oxide film having an uneven shape.
層流である特許請求の範囲第１項記載の酸化珪素被膜の
製造方法。(2) The method for producing a silicon oxide film according to claim 1, wherein the flow of the treatment liquid is a laminar flow parallel to the surface of the substrate immersed.
操作によるものである特許請求の範囲第７項又（４）該
凹凸形状を有する酸化珪素被膜が直径３００〜５ｏｏｏ
Ｘｙ高さ２００〜３ｏｏｏＡの多数の凸部を有ず〜る膜
である特許請求の範囲第１項ないし第３項記載の酸化珪
素被膜の製造方法。(3) The flow of the processing liquid is caused by the outflow operation and circulation operation of the processing liquid, or (4) the silicon oxide coating having the uneven shape has a diameter of 300 to 500 mm.
4. The method for producing a silicon oxide film according to claim 1, wherein the film has a large number of convex portions with an Xy height of 200 to 3 oooA.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59031139A JPS60176947A (en) | 1984-02-21 | 1984-02-21 | Production of silicon oxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59031139A JPS60176947A (en) | 1984-02-21 | 1984-02-21 | Production of silicon oxide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60176947A true JPS60176947A (en) | 1985-09-11 |
| JPH0413301B2 JPH0413301B2 (en) | 1992-03-09 |
Family
ID=12323103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59031139A Granted JPS60176947A (en) | 1984-02-21 | 1984-02-21 | Production of silicon oxide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60176947A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5114760A (en) * | 1989-04-01 | 1992-05-19 | Nippon Sheet Glass Co., Ltd. | Method for manufacturing layer-built material with silicon dioxide film containing organic colorant and the layer-built material manufactured thereby |
| US5232781A (en) * | 1989-04-01 | 1993-08-03 | Nippon Sheet Glass Co., Ltd. | Method for manufacturing layer-built material with silicon dioxide film containing organic colorant and the layer-built material manufactured thereby |
| US5326720A (en) * | 1990-10-25 | 1994-07-05 | Nippon Sheet Glass Co., Ltd. | Method for producing silicon dioxide film which prevents escape of Si component to the environment |
| JP2005500702A (en) * | 2001-08-23 | 2005-01-06 | パシフィック ソーラー ピー ティ ワイ リミテッド | Glass bead coating method |
| JP2009515328A (en) * | 2005-11-04 | 2009-04-09 | インターナショナル・ビジネス・マシーンズ・コーポレーション | Semiconductor transistor with contact hole close to the gate |
| JP2016528149A (en) * | 2013-07-29 | 2016-09-15 | エージェンシー フォー サイエンス，テクノロジー アンド リサーチ | Super hydrophilic coating |
-
1984
- 1984-02-21 JP JP59031139A patent/JPS60176947A/en active Granted
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5114760A (en) * | 1989-04-01 | 1992-05-19 | Nippon Sheet Glass Co., Ltd. | Method for manufacturing layer-built material with silicon dioxide film containing organic colorant and the layer-built material manufactured thereby |
| US5232781A (en) * | 1989-04-01 | 1993-08-03 | Nippon Sheet Glass Co., Ltd. | Method for manufacturing layer-built material with silicon dioxide film containing organic colorant and the layer-built material manufactured thereby |
| US5326720A (en) * | 1990-10-25 | 1994-07-05 | Nippon Sheet Glass Co., Ltd. | Method for producing silicon dioxide film which prevents escape of Si component to the environment |
| JP2005500702A (en) * | 2001-08-23 | 2005-01-06 | パシフィック ソーラー ピー ティ ワイ リミテッド | Glass bead coating method |
| JP2009515328A (en) * | 2005-11-04 | 2009-04-09 | インターナショナル・ビジネス・マシーンズ・コーポレーション | Semiconductor transistor with contact hole close to the gate |
| US7985643B2 (en) | 2005-11-04 | 2011-07-26 | International Business Machines Corporation | Semiconductor transistors with contact holes close to gates |
| JP2016528149A (en) * | 2013-07-29 | 2016-09-15 | エージェンシー フォー サイエンス，テクノロジー アンド リサーチ | Super hydrophilic coating |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0413301B2 (en) | 1992-03-09 |
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