JPS63307144A - Surface treating method for glass - Google Patents
Surface treating method for glassInfo
- Publication number
- JPS63307144A JPS63307144A JP62142549A JP14254987A JPS63307144A JP S63307144 A JPS63307144 A JP S63307144A JP 62142549 A JP62142549 A JP 62142549A JP 14254987 A JP14254987 A JP 14254987A JP S63307144 A JPS63307144 A JP S63307144A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- silicon oxide
- etching
- oxide film
- coating film
- 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
- 239000011521 glass Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 36
- 238000005530 etching Methods 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract 2
- 238000004381 surface treatment Methods 0.000 claims description 7
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000758 substrate Substances 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- 239000005361 soda-lime glass Substances 0.000 description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- 238000007654 immersion Methods 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000003746 surface roughness Effects 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
- 238000001771 vacuum 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
-
- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/036—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
-
- 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
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Photovoltaic Devices (AREA)
- Light Receiving Elements (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はガラスの表面処理法、特に太陽電池用ガラス基
板として最適な微細な表面凹凸構造を有するガラス基板
を、低コストでかつ制御性よく作製する方法に関するも
のである。[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a method for surface treatment of glass, particularly a glass substrate having a fine surface roughness structure suitable for use as a glass substrate for solar cells, at low cost and with good controllability. It is related to a method of manufacturing.
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（以下、ａ−８ｉと記す）を主
たる光電変換層に用いた太陽電池が、低コストで製造可
能な光電変換装置の１つとして注目されている。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（ＧａＡｓ、ＩｎＰなど）Ｋ比べて
極めて低いことが間順であり、これを解決するために、
電池の構造や作製方法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の反射損失を低減して短
絡電流を増大させることは重要であり、このため太＠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。In recent years, solar cells that use amorphous silicon (hereinafter referred to as a-8i), which is produced by glow discharge decomposition of silane gas, as the main photoelectric conversion layer, are one of the photoelectric conversion devices that can be manufactured at low cost. It is attracting attention as However, in such a-8i solar cells, the photoelectric conversion efficiency is extremely low compared to other crystalline semiconductors (GaAs, InP, etc.), and in order to solve this problem,
Various countermeasures have been devised for battery structures and manufacturing methods. In particular, it is important to reduce the reflection loss of light on the surface of the battery and increase the short-circuit current. Therefore, by making the thick @battery have an uneven structure and causing the incident light to undergo multiple reflection and refraction within the battery, long-wavelength light can be It is being considered to improve the collection efficiency for
上記凹凸構造を有した太陽電池を作製するためには、所
望の凹凸構造を有するガラス基板上に、太陽電池を作製
することが最も簡便な方法である。In order to produce a solar cell having the above-mentioned uneven structure, the simplest method is to produce the solar cell on a glass substrate having a desired uneven structure.
かかるガラス基板を作製する方法としては、ナチュラル
リソグラフィ法などのエツチング法が、凹凸構造の均一
性や大面積処理が容易であることなどの点から最も代表
的なものである。ナチュラルリングラフィ法の詳細はＨ
，Ｗ、 Ｄｅｃｋｍａｎ ａｎｄ Ｊ、 Ｈ。As a method for producing such a glass substrate, an etching method such as a natural lithography method is the most typical method because of the uniformity of the uneven structure and the ease of processing a large area. For details on the natural phosphorography method, see
, W., Deckman and J., H.
１）ｕｎｓｍｕｉｒ Ａｐｐｌ、Ｐｈｙｓ、Ｌｅｔｔ
、ＩＩ／ 、３７７（／り♂））に記載されているよう
に、ガラス上に直径３００ｎｍ稈度のポリマ球を配列し
た後イオンビーム等でガラス基板面をエツチングし、そ
の後ポリマ球を除去する方法である。1) unsmuir Appl, Phys, Lett
, II/, 377 (/ri♂)), after arranging polymer spheres with a diameter of 300 nm and culmivity on glass, the glass substrate surface is etched with an ion beam, etc., and then the polymer spheres are removed. It's a method.
しかしながら、上記ナチュラルリソグラフィー法に代表
される従来の方法では、いったんガラス上に塗布した耐
食材料をエツチング終了後に除去する必要があり、コス
ト的に必らずしも有利とはいえなかった。さらに耐食材
料をガラス上に塗布する工程の制御も容易ではなく、生
産性も悪いという問題点があった。However, in the conventional methods typified by the above-mentioned natural lithography method, it is necessary to remove the corrosion-resistant material once coated on the glass after etching is completed, which is not necessarily advantageous in terms of cost. Furthermore, it is not easy to control the process of applying the corrosion-resistant material onto the glass, and there are also problems in that productivity is poor.
本発明はかかる目的に基づいて研究の結果発明されたも
のであり、その要旨は、ガラス表面上に酸化珪素被膜を
形成した後かかる被膜をエツチングによって除去するこ
とにより該ガラス表面を凹凸化することを特徴とするガ
ラスの表面処理法に関するものである。The present invention was invented as a result of research based on this object, and its gist is to form a silicon oxide film on the glass surface and then remove the film by etching to make the glass surface uneven. The present invention relates to a glass surface treatment method characterized by:
本発明によれば、ガラスの表面に適当な凹凸構造が形成
されているので、この上にアルカリの溶出を防止するた
めの酸化珪素膜および透明導電膜を通常の方法によって
成膜するだけで、太陽電池用として最適な凹凸導電性ガ
ラス基板を提供することができる。According to the present invention, since an appropriate uneven structure is formed on the surface of the glass, a silicon oxide film and a transparent conductive film for preventing alkali elution are simply formed on the surface by a normal method. It is possible to provide an uneven conductive glass substrate that is optimal for use in solar cells.
本発明によりガラスの表面処理を行なうに際しては、ま
ず所望のガラスの表面に酸化珪素膜を形成する。かかる
膜を形成する方法としては、アルコキシシラン化合物と
水とアルコールを含有する酸化珪素被膜形成溶液を塗布
した後これを加水分解させる方法（以下、塗布法と呼ぶ
）、珪弗化水素酸の酸化珪素過飽和水溶液中に浸漬する
方法（以下、液相析出法と呼ぶ）、ＣＶＤ法、真空蒸着
法、スパッタリング法などの押々の方法が使用できる。When surface-treating glass according to the present invention, a silicon oxide film is first formed on the surface of the desired glass. Methods for forming such a film include a method in which a silicon oxide film forming solution containing an alkoxysilane compound, water, and alcohol is applied and then hydrolyzed (hereinafter referred to as the coating method), a method in which the silicon oxide film forming solution containing an alkoxysilane compound, water, and alcohol is hydrolyzed; Any method can be used, such as immersion in a silicon supersaturated aqueous solution (hereinafter referred to as liquid phase precipitation method), CVD method, vacuum evaporation method, and sputtering method.
中でも、塗布法および液相析出法は、低コストでの成膜
が可能でありかつ非平面上にも容易に成膜できるので、
本発明における被膜の形成方法としては最適である。上
記酸化珪素膜の膜厚は特に限定されないが、ガラス表面
への好適な凹凸の生成という見地から、ｔｏｎｍ〜／夕
Ｏｎｍ 程度が好適である。Among them, the coating method and liquid phase precipitation method enable film formation at low cost and can be easily formed even on non-flat surfaces.
This is the most suitable method for forming a film in the present invention. The thickness of the silicon oxide film is not particularly limited, but from the viewpoint of forming suitable irregularities on the glass surface, it is preferably about 100 to 200 nm.
上記ガラス上に形成された酸化珪素膜は、引き続きエツ
チングの工程によって除去される。かかるエツチングの
方法としては、いわゆるウェットエツチングやドライエ
ツチングのいずれも利用できるが、ウェットエツチング
がコスト的に有利であることから最適である。エツチン
グ液としては弗化水素および硫酸あるいは硝酸を含有す
る水溶液が最も代表的なものであるが、触媒や濃度調整
剤などを加えることもできる。The silicon oxide film formed on the glass is subsequently removed by an etching process. As such an etching method, both so-called wet etching and dry etching can be used, but wet etching is most suitable since it is advantageous in terms of cost. The most typical etching solution is an aqueous solution containing hydrogen fluoride and sulfuric acid or nitric acid, but catalysts, concentration regulators, etc. can also be added.
かかるエツチング液中に酸化珪素膜で被覆されたガラス
を保持することによりかかる酸化珪素膜がエツチングに
よって除去され、該ガラス表面に周期性の凹凸構造が形
成される。上記したエツチング液中でのガラスの保持時
間には、エツチング液中の弗化水素濃度、エツチング液
の湿度、酸化珪素被膜の膜厚、液のかくはんの有無など
に応じた最適時間が存在する。すなわち、エツチング時
間が短かすぎて酸化珪素被膜が残っている場合にはガラ
スの表面（正確にはガラス上の酸化珪素膜の表面）はほ
とんど平滑であり、エツチング時間が長すぎる場合には
一旦形成されたガラス表面の凹凸構造がだれてしまい、
はとんど平滑になる。By holding glass coated with a silicon oxide film in such an etching solution, the silicon oxide film is removed by etching, and a periodic uneven structure is formed on the glass surface. There is an optimum time for holding the glass in the above-mentioned etching solution depending on the concentration of hydrogen fluoride in the etching solution, the humidity of the etching solution, the thickness of the silicon oxide film, the presence or absence of stirring of the solution, etc. In other words, if the etching time is too short and a silicon oxide film remains, the surface of the glass (more precisely, the surface of the silicon oxide film on the glass) will be almost smooth, but if the etching time is too long, the surface will be flat. The uneven structure on the glass surface that has been formed will sag,
becomes almost smooth.
なお、本発明において表面が凹凸化されるガラスとして
はソーダライムガラスが代表として挙げられるが、シリ
カガラスやホウケイ酸ガラスなどの酸化ケイ素を含有す
るガラスであれば、もちろんこれらガラスを使用しても
よい。In the present invention, soda lime glass is a typical example of the glass whose surface is textured, but any glass containing silicon oxide such as silica glass or borosilicate glass may of course be used. good.
本発明により表面が凹凸化されたガラスは、太陽電池用
の透明導電膜を形成するガラス基板として最適であるが
、かかるガラス表面には微細な凹凸構造が形成されるこ
とにより正反射が抑制されるため、防眩用、その他各種
用途に対しても利用できる。Glass whose surface has been made uneven according to the present invention is most suitable as a glass substrate for forming a transparent conductive film for solar cells, but regular reflection is suppressed by forming a fine uneven structure on such a glass surface. Therefore, it can be used for anti-glare purposes and various other purposes.
〔実施例１〕
十分な洗浄処理を施したソーダライムガラス板を、珪弗
化水素酸の酸化珪素過飽和水溶液中に浸漬させ、酸化珪
素被膜を約１１００ｎ析出させた。[Example 1] A soda lime glass plate that had been thoroughly washed was immersed in a supersaturated silicon oxide aqueous solution of hydrosilicofluoric acid to deposit about 1100 nm of silicon oxide film.
上記酸化珪素被膜を有するソーダライムガラス板を、弗
酸、硝酸、水をそれぞれ重量比でｌ：、２ｒ：／２の割
合で混合して作製した２０”Ｃのエツチング液中に所定
時間浸漬した後、走査型電子顕微鏡（ＪＳＭ、ｚｔＳＩ
［、以下同じ）を用いてガラス表面の観察を行った。結
果は表−ｌのとおりであった。The soda lime glass plate having the silicon oxide coating was immersed for a predetermined time in a 20"C etching solution prepared by mixing hydrofluoric acid, nitric acid, and water in a weight ratio of l: and 2r:/2, respectively. After that, scanning electron microscopy (JSM, ztSI
[, hereinafter the same)] was used to observe the glass surface. The results were as shown in Table 1.
表−７
〔実施例λ〕
十分な洗浄処理を施したソーダライムガラス板を、珪弗
化水素酸の酸化珪素過飽和水溶液中に浸漬させ、酸化珪
素被膜を約１１００ｎ析出させた。Table 7 [Example λ] A soda lime glass plate that had been thoroughly washed was immersed in a supersaturated silicon oxide aqueous solution of hydrosilicofluoric acid to deposit about 1100 nm of silicon oxide film.
上記酸化珪素被膜を有するソーダライムガラス板を、弗
酸、硝酸、水をそれぞれ重量比で７：７７３１０の割合
で混合して作製した２０”Ｃのエツチング液中に所定時
間浸漬した後、走査型顕微鏡を用いてガラス表面の観察
を行った。結果は表−２のとおりであった。After immersing the soda lime glass plate having the silicon oxide coating in a 20"C etching solution prepared by mixing hydrofluoric acid, nitric acid, and water in a weight ratio of 7:77310 for a predetermined time, The glass surface was observed using a microscope.The results are shown in Table-2.
表−２
〔実施例３〕
十分な洗浄処理を施したソーダライムガラス板に酸化珪
素膜形成溶液（チッソ■製）を浸漬引き上げ法によって
塗布した後焼成し、酸化珪素被膜を約／ Ｊ Ｏｎｍ析
出させた。上記酸化珪素被膜を有するソーダライムガラ
ス板を、弗讃、硝酸、水をそれぞれ重量比で／：、２１
：／２の割合で混合して作製した。２（７”Ｃのエツチ
ング液中に所定時間浸漬した後、走査型電子顕微鏡を用
いてガラス表面の観察を行った。結果は表−３のとおり
であった。Table 2 [Example 3] A silicon oxide film forming solution (manufactured by Chisso ■) was coated on a soda lime glass plate that had been thoroughly cleaned by dipping and pulling up, followed by firing, and a silicon oxide film was deposited in an amount of about / J Onm. I let it happen. The above-mentioned soda lime glass plate having a silicon oxide coating was mixed with fluoride, nitric acid, and water in a weight ratio of /:, 21.
It was prepared by mixing at a ratio of :/2. After being immersed in a 2 (7"C) etching solution for a predetermined period of time, the glass surface was observed using a scanning electron microscope. The results are shown in Table 3.
表−３
〔実施例弘〕
十分な洗浄処理を施したソーダライムガラス板を、珪弗
化水素酸の酸化珪素過飽和水溶液中に浸漬させ、酸化珪
素被膜を約ｒｏｎｍ析出させた。Table 3 [Example Hiroshi] A soda lime glass plate that had been thoroughly washed was immersed in a supersaturated silicon oxide aqueous solution of hydrosilicofluoric acid to deposit a silicon oxide film of approximately ronm.
上記酸化珪素被膜を有するソーダライムガラス板を、弗
酸、硝酸、水をそれぞれ重量比で／：２♂：ｌλの割合
で混合して作製した。２０℃のエツチング液に所定時間
浸漬した徒、走査型電子顕微鏡を用いて表面の観察を行
った。結果は表−弘のとおりであった。The above-mentioned soda lime glass plate having a silicon oxide coating was prepared by mixing hydrofluoric acid, nitric acid, and water in a weight ratio of /:2♂:lλ. After being immersed in an etching solution at 20° C. for a predetermined time, the surface was observed using a scanning electron microscope. The results were as shown in Table 1.
表−グ
〔実施例！〕
十分な洗浄処理を施したソーダライムガラス板を、珪弗
化水素酸の酸化珪素過飽和水溶液中に浸漬させ、酸化珪
素被膜を約ｔｏｎｍ析出させた。Table-G [Example! ] A soda lime glass plate that had been thoroughly washed was immersed in a silicon oxide supersaturated aqueous solution of hydrosilicofluoric acid to precipitate a silicon oxide film of about tonm.
上記酸化珪素被膜を有するソーダライムガラス板を、弗
酸、硫酸、水をそれぞれ重量比で３：１００：１００
の割合で混合して作製したλＯ′Ｃのエツチング液に所
定の時間浸漬した後、走査型電子顕微鏡を用いて表面の
観察を行った。結果は表−夕のとおりであった。The above soda lime glass plate having a silicon oxide coating was mixed with hydrofluoric acid, sulfuric acid, and water in a weight ratio of 3:100:100, respectively.
After being immersed for a predetermined period of time in an etching solution of λO'C prepared by mixing at a ratio of 1, the surface was observed using a scanning electron microscope. The results were as shown in the table below.
表−！
〔実施例ｔ〕
実施例Ｊにおいて、エツチング液に４ｔ０秒浸漬させる
ことにより作製した凹凸表面を有するガラス基板（Ａ）
と処理を施さない平滑な表面を有するソーダライムガラ
ス基板（Ｂ）とを用いてａ−８ｉ太＠電池を作製し、そ
の特性を比較評価した。Table-! [Example t] Glass substrate (A) having an uneven surface prepared by immersing it in an etching solution for 4t0 seconds in Example J
An a-8i thick@ battery was prepared using the untreated soda lime glass substrate (B) having a smooth surface, and its characteristics were comparatively evaluated.
それぞれの基板Ａ、Ｂ上にモノシランガスを用いたＣＶ
Ｄ法によって約ａｏｎｍの酸化珪素膜を作製し、さらに
モツプチル錫トリクロライドの蒸気及びドーパントとし
て０Ｈ３０ＨＦ２ ガスを用いたＣＶＤ法によって約
弘ｓｏｎｍの酸化錫膜を作製した。CV using monosilane gas on each substrate A and B
A silicon oxide film with a thickness of about aonm was produced by the D method, and a tin oxide film of about aonm was further produced by a CVD method using motsbutyltin trichloride vapor and 0H30HF2 gas as a dopant.
次いでモノシラン（ＳｉＨ４）を主成分とする原料ガス
を用いて／Ｐａ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ａ−８ｉＯ：Ｅ（（Ｐ層〜／ｊｎｍ）／
ａ−８ｉ：！（（ｉ層〜ｔｏｏｎｍ）／μｃ−８ｉ（ｎ
層〜３０ｎｒｎ）の順に堆積させ、最後にＡｌ電極を真
空中（＃’−６Ｐａ）で蒸着し、有効前面積ｏ、ｏ３ｃ
ｒｌのセルを基板Ａ。Next, a-8iO:E((P layer~/jnm)/
a-8i:! ((i layer~toonm)/μc-8i(n
Finally, an Al electrode is deposited in vacuum (#'-6Pa) to reduce the effective front area o, o3c.
RL cell on substrate A.
Ｂ上にそれぞれ１２１ｒ個作製した。これらセルの太＠
電池特性をソーラーシュミレータ−光（ＡＭ／。121r pieces of each were produced on B. The thickness of these cells @
Solar simulator light (AM/.
１００ｍＷ／ｃｒ／Ｉ）を用いて測定したところ、基板
Ａ上に作製したセルの光電変換効率は基板Ｂ上に作製し
たセルの平均に比べて３％の向上がみられた。When measured using 100 mW/cr/I), the photoelectric conversion efficiency of the cells fabricated on substrate A was improved by 3% compared to the average of cells fabricated on substrate B.
このように、本発明によれば、低コストでかつ制御性よ
くガラス表面上に１１００−３００ｎ の周期をもった
凹凸構造を形成することができるので、安価で高性能の
太陽電池を再現性よくかつ容易に実現できる。さらに、
かかる凹凸表面を有するガラスは低反射性であるため防
眩用、装飾用の用速に対しても利用できる。使用される
ガラスは平板ガラスであっても、曲率をもった板ガラス
であっても、あるいは管状のものであってもかまわない
。As described above, according to the present invention, it is possible to form an uneven structure with a period of 1100-300n on a glass surface at low cost and with good controllability, so that inexpensive and high-performance solar cells can be produced with good reproducibility. And it can be easily realized. moreover,
Glass having such an uneven surface has low reflectivity and can therefore be used for anti-glare and decorative applications. The glass used may be flat glass, curved glass, or tubular.
第１図は実施例！の条件によるガラス表面処理における
エツチング液７５秒浸漬後の走査型電子顕微鏡写真を示
す。第２図は浸漬時間３０秒後の走査型電子顕微鏡写真
を示す。
竿 ２１」
手 続 補 正 書ｃ方式）
％式％
／ 事件の表示
特願昭ｔ２−／１１．２ｊゲタ号
−発明の名称
ガラスの表面処理法
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
（ｌθθ）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
（１）明細書第１３頁第１３行目に
「におけるエツチング液１５秒浸漬後の走査型電子」と
あるを
「におけるエツチング液１５秒浸漬後少Ｊヨ５Ｚ表−の
−′ｔ７ 査型電子」と補正する。
（２）明細書第１３頁第１４行目に
「・・・・・・・・・。第２図は浸漬時間３０秒後の」
とあるを
「・・・・・・・・・。第２図は浸漬時間３０秒後ｍの
亡 ゛ 六 」と補正する。Figure 1 is an example! A scanning electron micrograph is shown after 75 seconds of immersion in an etching solution during glass surface treatment under the following conditions. FIG. 2 shows a scanning electron micrograph after 30 seconds of immersion. 21 Procedural amendment (C method) % formula % / Indication of the case Patent application No. 11/11.2J Geta - Name of the invention Glass surface treatment method 3 Person making the amendment Relationship to the case Patent applicant Address: 4-8 Doshomachi, Higashi-ku, Osaka-shi, Osaka Name:
(lθθ) Shin Saiga, Representative of Nippon Sheet Glass Co., Ltd.
Og Agent 7, Contents of Amendment (1) On page 13, line 13 of the specification, the phrase "scanning electronics after 15 seconds of immersion in etching solution" has been replaced with "Scanning electronics after 15 seconds of immersion in etching solution of Correct it to -'t7 scanning electron' in the table. (2) On page 13, line 14 of the specification: ``......Figure 2 is after 30 seconds of immersion.''
The statement has been corrected to ``...... Figure 2 shows the disappearance of m after 30 seconds of immersion.''
Claims (3)
該被膜をエッチングにより除去することにより、該ガラ
ス表面を凹凸化することを特徴とするガラス表面処理法
。(1) Form a silicon oxide film on the glass surface in advance,
A glass surface treatment method characterized by making the glass surface uneven by removing the film by etching.
珪素過飽和水溶液中に浸漬することにより形成されたも
のであることを特徴とする、特許請求の範囲第１項に記
載のガラス表面処理法。(2) The glass according to claim 1, wherein the silicon oxide coating is formed by immersing the glass in a supersaturated silicon oxide aqueous solution of hydrosilicofluoric acid. Surface treatment method.
ン化合物と水とアルコールを含有する酸化珪素被膜形成
溶液を塗布した後、該アルコキシシラン化合物を加水分
解させることにより形成されたものであることを特徴と
する特許請求の範囲第１項に記載のガラス表面処理法。(3) The silicon oxide film is formed by applying a silicon oxide film forming solution containing an alkoxysilane compound, water, and alcohol to the glass surface, and then hydrolyzing the alkoxysilane compound. A glass surface treatment method according to claim 1, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62142549A JP2541986B2 (en) | 1987-06-08 | 1987-06-08 | Glass surface treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62142549A JP2541986B2 (en) | 1987-06-08 | 1987-06-08 | Glass surface treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63307144A true JPS63307144A (en) | 1988-12-14 |
| JP2541986B2 JP2541986B2 (en) | 1996-10-09 |
Family
ID=15317932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62142549A Expired - Lifetime JP2541986B2 (en) | 1987-06-08 | 1987-06-08 | Glass surface treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2541986B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5518490B2 (en) * | 2008-01-30 | 2014-06-11 | Ｈｏｙａ株式会社 | Substrate manufacturing method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6131329A (en) * | 1984-07-23 | 1986-02-13 | Nippon Sheet Glass Co Ltd | Matt glass plate and its production |
| JPS623046A (en) * | 1985-06-28 | 1987-01-09 | Asahi Glass Co Ltd | Formation of silicon oxide film |
-
1987
- 1987-06-08 JP JP62142549A patent/JP2541986B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6131329A (en) * | 1984-07-23 | 1986-02-13 | Nippon Sheet Glass Co Ltd | Matt glass plate and its production |
| JPS623046A (en) * | 1985-06-28 | 1987-01-09 | Asahi Glass Co Ltd | Formation of silicon oxide film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5518490B2 (en) * | 2008-01-30 | 2014-06-11 | Ｈｏｙａ株式会社 | Substrate manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2541986B2 (en) | 1996-10-09 |
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