201236175 六、發明說明： 【發明所屬之技術領域】 本發明係有關附太陽能電池用複合膜之透明基板及其 製造方法。更詳言之’係有關具有高的發電效率之附太陽 能電池用透明基板及其製造方法。 【先前技術】 目前’基於環境保護立場，已朝乾淨能源之硏究開發 、實用化進展，太陽能電池由於作爲能源之太陽光無窮盡 ’且爲無公害等而備受矚目。以往，太陽能電池係使用單 晶矽或多晶矽之塊體太陽能電池。 另一方面’使用非晶矽等之半導體之所謂薄膜半導體 太陽能電池（以下稱爲薄膜太陽能電池）係於玻璃或不鏽 鋼等之便宜基板上，形成僅必要量之光電變換層之半導體 層之構造。因此，薄膜太陽能電池由於薄型、量輕、製造 成本便宜、可容易大面積化等，認爲往後將成爲太陽能電 池之主流。 . 太陽能電池之膜形成一般係利用濺鍍法、CVD法等 之真空成膜法進行。然而，維持大型真空成膜裝置並運轉 必須較大成本’故藉由將膜形成替換成濕式成膜法，而期 待大幅改善運轉成本。 作爲由濕式成膜法所得之太陽能電池所挪用之透明導 電膜揭示有將分散有導電氧化物超微粒子之塗覆液塗佈於 玻璃基板之基體上，並使之硬化之薄膜太陽能電池用透明 201236175 導電膜之製造方法（專利文獻1)。 然而’以上述製造方法，目的係在於提高超準直（ super straight )型太陽能電池之玻璃基板上之透明導電膜 之濁度’而未考慮玻璃基板與透明電極膜之介面之反射光 降低。 於超準直型太陽能電池通常係於折射率約K5的玻璃 基板上’形成折射率約2.0之二氧化錫之透明電極膜，由 於玻璃基板與透明電極膜之折射率差，使來自玻璃基板之 入射光之一部分反射，而減少到達光電轉換層之光量減少 ，而使太陽能電池之轉換效率降低。 [先前技術文獻] [專利文獻] [專利文獻〗]特開平1 0- 1 2 05 9號公報 【發明內容】 [發明欲解決之課題] 本發明之課題係於自透明基板側使太陽光入射之太陽 能電池中，使入射至透明基板之光在透明基板與透明電極 膜之介面反射，藉此抑制太陽能電池之轉換效率之降低。 [用以解決課題之手段] 本發明藉由以下所示之構成而解決上述課題，係關於 在透明基板與透明電極膜之冏具有透明膜之附有太陽能電 -6 - 201236175 池用複合膜之透明基板以及其製造方法以及使用附有該複 合膜之基板之太陽能電池。 π] —種附太陽能電池用複合膜之透明基板’其爲在 透明基板與透明電極膜之間具有透明膜之附太陽能電池用 複合膜之透明基板，其特徵爲透明膜含有透光性黏合劑’ 且折射率爲(式中m表示透明基板之折射率， n2表示透明膜之折射率，及n3表示透明電極膜之折射率 )° [2] 如上述[1 ]劑載之附太陽能電池用複合膜之透明 基板，其中透明膜之折射率爲1.5〜1.9。 [3] 如上述[1]或[2]記載之附太陽能電池用複合膜之 透明基板，其中透明膜之厚度爲〇·〇卜〇·5μΐΏ。 [4] 如上述[1]至[3]中任一項記載之附太陽能電池用 複合膜之透明基板，其中透明膜之透光性黏合劑包含利用 加熱而硬化之聚合物型黏合劑及/或非聚合物型黏合劑。 [5] 如上述[1]至[4]中任一項記載之附太陽能電池用 複合膜之透明基板，其中透明膜進而含有自ΙΤΟ、ΖηΟ、 ΑΤΟ及Ti02所組成群組選出之至少一種氧化物粒子。 [6] 一種附太陽能電池用複合膜之透明基板之製造方 法，其爲依序具有透明基板、透明膜及透明電極膜之附太 陽能電池用複合膜之透明基板之製造方法，其係利用濕式 塗佈法將透明膜用組成物塗佈於透明基板上，形成透明塗 膜後，使具有透明塗膜之透明基板經燒成或硬化，形成透 明膜，進而於透明膜上形成透明電極膜。 201236175 [7] 如上述[6]記載之附太陽能電池用複合膜之透明 基板之製造方法，其中透明導電塗膜之燒成溫度爲130~ 2 5(TC。 [8] 如上述[6]或[7]記載之附太陽能電池用複合膜之 透明基板之製造方法，其中透明膜用組成物之濕式塗佈法 爲噴佈塗佈法、分佈塗佈法、旋轉塗佈法、刮刀塗佈法、 狹縫塗佈法、噴墨塗佈法、模嘴塗佈法、網版印刷法、平 版印刷法、或凹版印刷法。 [9] 一種太陽能電池，其係包含上述[1]至[5]中任一 項記載之附太陽能電池用複合膜之透明基板。 [發明效果] 依據本發明[1 ]，可簡便地獲得可抑制入射至透明基 板之光在透明基板-透明電極膜介面之反射，藉由增加朝 光電轉換層之入光量而提高發電效率之太陽能電池。 依據本發明[6]，可不使用昂貴之真空設備即可形成 透明膜，而可以簡便、低成本地製造發電效率高之太陽能 電池。 【實施方式】 以下基於實施形態具體說明本發明。又，％只要未特 別表示，則爲數値特有之情況除外之質量％。 [附太陽能電池用複合膜之透明基板] -8- 201236175 本發明之附太陽能電池用複合膜之透明基板（以下稱 爲附複合膜之透明基板）爲在透明基板與透明電極膜之間 具有透明膜之附太陽能電池用複合膜之透明基板，其特徵 爲該透明膜含有透光性黏合劑，折射率爲ηι<η2<η3 (式中 〜表示透明基板之折射率，n2表示透明膜之折射率，及 n3表示透明電極膜之折射率）。 圖1顯示本發明之附太陽能電池用複合膜之透明基板 之超準直形態太陽能電池之剖面示意圖。附透明膜之基板 10係於透明基板2與透明電極膜4之間具有透明膜3。該 透明膜3上形成光電轉換層5及反射電極膜6，構成超準 直型太陽能電池1。太陽光自透明基板2側入射。此處， η!表示透明基板之折射率，n2表示透明膜之折射率，及 n3表示透明電極膜之折射率時，若爲ηι<η2<η3，則可抑制 透明基板·透明膜介面之反射，可提高太陽能電池之發電 效率。 透明基板並未特別限定，舉例有玻璃基板等。透明電 極膜亦未特別限定，舉例有二氧化錫膜等。 透明膜含有透光性黏合劑，折射率爲1 · 5〜1 · 9時，由 於透明基板-透明膜介面之反射抑制優異，故而較佳。且 ，透明膜之厚度爲0.01〜0·5μιη時，由密著性之觀點而言 較佳。 且’透明膜亦較好設爲2層以上，該情況下，較好形 成爲折射率自透明基板朝向透明電極膜緩慢升高。 201236175 《透明膜用組成物》 透明膜係由透明膜用組成物製造，透明膜用組成物含 有透光性黏合劑。 透光性黏合劑包含利用加熱而硬化之聚合物型黏合劑 及/或非聚合物型黏合劑時，塗佈後之硬化容易，由密著 性之觀點而言較佳。至於聚合物型黏合劑，舉例有折射率 爲1.3〜1.6範圍之丙烯酸樹脂 '聚碳酸酯、聚酯、醇酸樹 脂、聚胺基甲酸酯、丙烯酸胺基甲酸酯、聚苯乙烯、聚乙 縮醛、聚醯胺、聚乙烯醇、聚乙酸乙烯酯、纖維素及矽氧 院聚合物等。且，聚合物型黏合劑較好含有折射率爲 1 .3〜1 · ό之範圍之自銘、砂、駄、鉻、鐘、鐵、銘、錬、 銀、銅、鋅、鉬及錫之金屬皂、金屬錯合物、金屬烷氧化 物及金屬烷氧化物之水解體所成組群選出之至少一種。 至於非聚合型黏合劑舉例有金屬皂、金屬錯合物、金 屬烷氧化物、金屬烷氧化物之水解體、烷氧基矽烷、鹵矽 院類、2-烷氧基乙醇、Θ·二酮及乙酸烷酯等。且，金屬 巷、金屬錯合物或金屬烷氧化物中含有之金屬較好爲鋁、 矽、鈦、鉻、錳、鐵、鈷、鎳、銀 '銅、鋅、鉬、錫、銦 或銻’更佳爲矽、鈦之烷氧化物（例如四乙氧基矽烷、四 甲氧基矽烷、丁氧基矽烷）。至於鹵矽烷類舉例有三氯矽 院。至於2-烷氧基乙醇舉例有2-正丙氧基乙醇、2-正丁 氧基乙醇'2-己氧基乙醇等，至於二酮舉例有2,4-戊 二酮、3-異丙基-2,4 -戊二酮、2,2-二甲基·3,5-己二酮等， 至於乙酸烷酯舉例有乙酸正丙酯、乙酸異丙酯等。該等聚 -10- 201236175 合物型黏合劑、非聚合物型黏合劑可藉由加熱而硬化而形 成具有高密著性之透明膜。 使金屬烷氧化物硬化時，較好含有用以開始水解反應 之水以及作爲觸媒之鹽酸、硝酸、磷酸（h3po4 )、硫酸 等之酸，或氨水、氫氧化鈉等之鹼，自加熱硬化後，觸媒 易揮發、不易殘留、不殘留鹵素、不殘留耐水性弱之p、 硬化後之密著性等觀點而言，更好爲硝酸。 透光性黏合劑之含有比例相對於除後述分散介質以外 之透明膜用組成物：100質量份，較好爲10〜90質量份， 若爲3 0~8 0質量份則更佳。若爲1 〇質量份以上，則與透 明基板或透明電極膜之接著力良好，若爲90質量份以下 ’則成膜時不易產生膜不均。且，作爲黏合劑使用金屬烷 氧化物’作爲觸媒使用硝酸時，相對於金屬烷氧化物： 1〇〇質量份’硝酸爲1〜10質量份時，由黏合劑之硬化速 度、硝酸之殘存量之觀點而言較佳。 透明膜用組成物中較好含氧化物粒子，氧化物粒子在 透明膜中產生使來自光電轉換層之返回光返回至光電轉換 層側之薄膜太陽能電池內之光閉鎖之效果，而可提高太陽 能電池之轉換效率。又’氧化物粒子就透光性、安定性、 耐候性之觀點而言亦較佳。作爲氧化物粒子，舉例有I TO (Indium Tin Oxide:銦錫氧化物，折射率：2) ； ΑΤΟ ( Antimony Tin Oxide :摻銻氧化錫，折射率：2 );含有自 Al、Co、Fe、In、Sn及Ti所成組群選出之至少一種金屬 之ZnO粉末（折射率：2) ;Si〇2(折射率：1.45)、 -11 - 201236175201236175 VI. Description of the Invention: [Technical Field] The present invention relates to a transparent substrate with a composite film for a solar cell and a method of manufacturing the same. More specifically, it relates to a transparent substrate for solar cells having high power generation efficiency and a method of manufacturing the same. [Prior Art] At present, based on the environmental protection standpoint, the development of clean energy and the development of practical use have progressed, and solar cells have attracted attention because of the inexhaustible sunlight as an energy source. Conventionally, solar cells have used monocrystalline or polycrystalline silicon solar cells. On the other hand, a so-called thin film semiconductor solar cell (hereinafter referred to as a thin film solar cell) using a semiconductor such as amorphous germanium is a structure in which a semiconductor layer of only a necessary amount of a photoelectric conversion layer is formed on an inexpensive substrate such as glass or stainless steel. Therefore, thin-film solar cells are considered to be the mainstream of solar cells in the future because of their thinness, light weight, low manufacturing cost, and ease of large-area. The film formation of a solar cell is generally carried out by a vacuum film formation method such as a sputtering method or a CVD method. However, maintaining a large vacuum film forming apparatus and operating it requires a large cost, so that the operation cost is greatly improved by replacing the film formation with the wet film forming method. The transparent conductive film which is used as a solar cell obtained by the wet film formation method discloses that a coating liquid in which fine particles of conductive oxide are dispersed is applied onto a substrate of a glass substrate, and the thin film solar cell is cured. 201236175 A method for producing a conductive film (Patent Document 1). However, the above manufacturing method aims to increase the turbidity of the transparent conductive film on the glass substrate of the super straight type solar cell without considering the decrease in the reflected light of the interface between the glass substrate and the transparent electrode film. The super-collimated solar cell is usually formed on a glass substrate having a refractive index of about K5 to form a transparent electrode film of tin dioxide having a refractive index of about 2.0, which is derived from the glass substrate due to the difference in refractive index between the glass substrate and the transparent electrode film. One of the incident light is partially reflected, and the amount of light reaching the photoelectric conversion layer is reduced, and the conversion efficiency of the solar cell is lowered. [PRIOR ART DOCUMENT] [Patent Document] [Patent Document] Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. In the solar cell, light incident on the transparent substrate is reflected on the interface between the transparent substrate and the transparent electrode film, thereby suppressing a decrease in conversion efficiency of the solar cell. [Means for Solving the Problem] The present invention solves the above-described problems by the configuration described below, and relates to a composite film for solar cell -6 - 201236175 having a transparent film between a transparent substrate and a transparent electrode film. A transparent substrate, a method of manufacturing the same, and a solar cell using the substrate to which the composite film is attached. π] - a transparent substrate with a composite film for a solar cell, which is a transparent substrate with a composite film for a solar cell having a transparent film between a transparent substrate and a transparent electrode film, characterized in that the transparent film contains a light-transmitting adhesive And the refractive index is (where m represents the refractive index of the transparent substrate, n2 represents the refractive index of the transparent film, and n3 represents the refractive index of the transparent electrode film). [2] For the solar cell of the above [1] agent A transparent substrate of a composite film, wherein the transparent film has a refractive index of 1.5 to 1.9. [3] The transparent substrate with a composite film for a solar cell according to the above [1] or [2], wherein the transparent film has a thickness of 〇·〇卜〇·5 μΐΏ. [4] The transparent substrate with a composite film for a solar cell according to any one of the above [1], wherein the transparent adhesive of the transparent film comprises a polymer type adhesive which is cured by heating and/or Or a non-polymeric binder. [5] The transparent substrate with a composite film for a solar cell according to any one of the above [1], wherein the transparent film further contains at least one selected from the group consisting of ruthenium, ΖnΟ, ruthenium and TiO2. Particles. [6] A method for producing a transparent substrate with a composite film for a solar cell, which is a method for producing a transparent substrate with a composite film for a solar cell having a transparent substrate, a transparent film, and a transparent electrode film, which is a wet type In the coating method, the transparent film composition is applied onto a transparent substrate to form a transparent coating film, and then the transparent substrate having the transparent coating film is fired or cured to form a transparent film, and a transparent electrode film is formed on the transparent film. [6] The method for producing a transparent substrate with a composite film for a solar cell according to the above [6], wherein the transparent conductive coating film has a firing temperature of 130 to 25 (TC. [8] as described above [6] or [7] The method for producing a transparent substrate with a composite film for a solar cell according to the invention, wherein the wet coating method for the transparent film composition is a spray coating method, a distribution coating method, a spin coating method, or a knife coating method. Method, slit coating method, inkjet coating method, die coating method, screen printing method, lithography method, or gravure printing method. [9] A solar cell comprising the above [1] to [ (5) The transparent substrate of the composite film for a solar cell according to any one of the inventions. [Effect of the Invention] According to the invention [1], it is possible to easily suppress the light incident on the transparent substrate on the transparent substrate-transparent electrode film interface. Reflecting, a solar cell that increases power generation efficiency by increasing the amount of light entering the photoelectric conversion layer. According to the invention [6], a transparent film can be formed without using an expensive vacuum device, and power generation efficiency can be easily and inexpensively manufactured. Solar battery. MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below based on the embodiment. The % is not particularly indicated, and is a mass % excluding the ones unique to the number. [Transparent substrate with composite film for solar cell] -8- 201236175 Attachment of the present invention A transparent substrate of a composite film for a solar cell (hereinafter referred to as a transparent substrate with a composite film) is a transparent substrate with a composite film for a solar cell having a transparent film between a transparent substrate and a transparent electrode film, and is characterized in that the transparent film contains The translucent adhesive has a refractive index of ηι < η2 < η 3 (wherein 〜 represents the refractive index of the transparent substrate, n2 represents the refractive index of the transparent film, and n3 represents the refractive index of the transparent electrode film). Figure 1 shows the present invention. A schematic cross-sectional view of a super-collimated solar cell with a transparent substrate for a composite film for a solar cell. The substrate 10 with a transparent film is provided with a transparent film 3 between the transparent substrate 2 and the transparent electrode film 4. The transparent film 3 forms a photovoltaic The conversion layer 5 and the reflective electrode film 6 constitute a super-collimation type solar cell 1. The sunlight is incident from the side of the transparent substrate 2. Here, η! represents a transparent substrate. When the refractive index, n2 represents the refractive index of the transparent film, and n3 represents the refractive index of the transparent electrode film, if ηι < η2 < η3, the reflection of the transparent substrate and the transparent film interface can be suppressed, and the power generation efficiency of the solar cell can be improved. The transparent substrate is not particularly limited, and examples thereof include a glass substrate, etc. The transparent electrode film is not particularly limited, and examples thereof include a tin oxide film, etc. The transparent film contains a light-transmitting adhesive, and when the refractive index is 1 · 5 to 1 · 9, The transparent substrate-transparent film interface is preferably excellent in reflection suppression, and when the thickness of the transparent film is 0.01 to 0.5 μm, it is preferable from the viewpoint of adhesion. In the case of two or more layers, it is preferred to form the refractive index from the transparent substrate toward the transparent electrode film to rise slowly. 201236175 "Composition for transparent film" The transparent film is produced from a composition for a transparent film, and the composition for a transparent film contains a light-transmitting adhesive. When the light-transmitting adhesive contains a polymer type binder and/or a non-polymer type binder which are cured by heating, the curing after application is easy, and it is preferable from the viewpoint of adhesion. As the polymer type binder, for example, an acrylic resin having a refractive index of 1.3 to 1.6 'polycarbonate, polyester, alkyd resin, polyurethane, urethane, polystyrene, poly Acetal, polyamine, polyvinyl alcohol, polyvinyl acetate, cellulose, and oxygenated polymer. Further, the polymer type binder preferably contains a range of refractive index of 1.3 to 1 · 自 from the range of sand, bismuth, chrome, bell, iron, samarium, samarium, silver, copper, zinc, molybdenum and tin. At least one selected from the group consisting of a metal soap, a metal complex, a metal alkoxide, and a metal alkoxide hydrolyzate. Examples of the non-polymerizable binder include metal soaps, metal complexes, metal alkoxides, hydrolyzates of metal alkoxides, alkoxy decanes, haloximes, 2-alkoxyethanols, hydrazines. And alkyl acetate and the like. Moreover, the metal contained in the metal lane, the metal complex or the metal alkoxide is preferably aluminum, bismuth, titanium, chromium, manganese, iron, cobalt, nickel, silver 'copper, zinc, molybdenum, tin, indium or bismuth. More preferably, it is a titanium alkoxide (e.g., tetraethoxy decane, tetramethoxy decane, butoxy decane). As for the halodecanes, there are exemplified triclosan. As the 2-alkoxyethanol, 2-n-propoxyethanol, 2-n-butoxyethanol '2-hexyloxyethanol and the like are exemplified, and as the diketone, 2,4-pentanedione and 3-isopropyl are exemplified. Examples are benzyl-2,4-pentanedione, 2,2-dimethyl-3,5-hexanedione, and the like. Examples of the alkyl acetate include n-propyl acetate and isopropyl acetate. These poly-10-201236175 composite adhesives and non-polymeric adhesives can be hardened by heating to form a transparent film having high adhesion. When the metal alkoxide is hardened, it preferably contains water for starting the hydrolysis reaction, an acid such as hydrochloric acid, nitric acid, phosphoric acid (h3po4) or sulfuric acid as a catalyst, or an alkali such as ammonia water or sodium hydroxide, which is hardened by heating. After that, the catalyst is more volatile, does not easily remain, does not remain halogen, does not leave p which is weak in water resistance, and has good adhesion after hardening. The content of the light-transmitting adhesive is preferably from 10 to 90 parts by mass, more preferably from 10 to 80 parts by mass, per 100 parts by mass of the composition for a transparent film other than the dispersion medium to be described later. When the amount is 1 part by mass or more, the adhesion to the transparent substrate or the transparent electrode film is good, and when it is 90 parts by mass or less, film unevenness is less likely to occur at the time of film formation. In the case where nitric acid is used as the binder as the binder, the curing rate of the binder and the residual of the nitric acid are 1 to 10 parts by mass with respect to the metal alkoxide: 1 part by mass of the nitric acid. It is preferred from the viewpoint of quantity. The composition for a transparent film preferably contains oxide particles, and the oxide particles have an effect of blocking light returning from the photoelectric conversion layer to the photoelectric conversion layer side of the thin film solar cell in the transparent film, thereby improving solar energy. Battery conversion efficiency. Further, the oxide particles are also preferable from the viewpoint of light transmittance, stability, and weather resistance. Examples of the oxide particles include I TO (Indium Tin Oxide: indium tin oxide, refractive index: 2); ΑΤΟ (Antimony Tin Oxide: antimony-doped tin oxide, refractive index: 2); and include from Al, Co, Fe, ZnO powder of at least one metal selected from the group consisting of In, Sn and Ti (refractive index: 2); Si〇2 (refractive index: 1.45), -11 - 201236175
Ti〇2 (折射率：2.7 ) ; Zr〇2 (折射率：2 )，較好含有自 ITO、ZnO、ΑΤΟ及Ti02所組成之群選出之至少一種之氧 化物粒子。又，氧化物粒子之平均粒徑爲在分散介質中保 持安定性，較好在 10〜l〇〇nm之範圍，其中，更好爲 20〜60nm 之範圍。此處，平均粒徑係使用利用 QUANTACHROME AUTOSORB-1 之比表面積測定之 BET 法而測定。 氧化物粒子，相對於除分散介質以外之透明膜用組成 物：100質量份，較好爲10〜90質量份，若爲20〜70質量 份則更佳。若爲1 0重量份以上，則可期待來自光電轉換 層之返回光朝光電轉換層側返回之效果。若爲90質量份 以下，則維持了透明膜自身之強度、以及透明膜用組成物 與透明基板或透明電極膜之接著力。 透明膜用組成物爲提高成膜性，較好含有分散介質。 作爲分散介質，舉例有水；甲醇、乙醇、異丙醇、丁醇等 之醇類；丙酮、甲基乙基酮、環己酮、異佛爾酮等之酮類 ;甲苯、二甲苯、己烷、環己烷等之烴類；N，N-二甲基甲 醯胺、N，N-二甲基乙醯胺等之醯胺類；二甲基亞颯等之亞 颯類；或乙二醇等之二醇類；乙基纖維素等之二醇醚類等 。分散介質之含量，爲了獲得良好成膜性，相對於透明膜 用組成物：100質量份，較好爲65〜99質量份。 又，透光性黏合劑較好對應於所使用之其他成分添加 偶合劑。此係因爲可提高透明基板與透明膜之密著性、以 及透明膜與透明甩極膜之密辨性，進而亦提高透光性黏合 -12- 201236175 劑與氧化物粒子之密著性之故。作爲偶合劑舉例有矽烷偶 合劑、鋁偶合劑及鈦偶合劑等。 作爲矽烷偶合劑，舉例有乙烯基三乙氧基矽烷、7-縮水甘油氧基丙基三甲氧基矽烷、r-甲基丙烯醯氧基丙 基三甲氧基矽烷等。作爲鋁偶合劑，舉例有式（1 )所示 之含有乙醯基烷氧基之鋁偶合劑， 【化1 CH3Ti〇2 (refractive index: 2.7); Zr〇2 (refractive index: 2) preferably contains at least one of oxide particles selected from the group consisting of ITO, ZnO, ruthenium and TiO 2 . Further, the average particle diameter of the oxide particles is such that it maintains stability in the dispersion medium, and is preferably in the range of 10 to 10 nm, and more preferably in the range of 20 to 60 nm. Here, the average particle diameter is measured by a BET method using a specific surface area measurement of QUANTACHROME AUTOSORB-1. The oxide particles are preferably 10 to 90 parts by mass, more preferably 10 to 70 parts by mass, per 100 parts by mass of the composition for a transparent film other than the dispersion medium. When the amount is 10 parts by weight or more, the effect of returning the return light from the photoelectric conversion layer toward the photoelectric conversion layer side can be expected. When the amount is 90 parts by mass or less, the strength of the transparent film itself and the adhesion between the composition for the transparent film and the transparent substrate or the transparent electrode film are maintained. The composition for a transparent film preferably contains a dispersion medium in order to improve film formability. Examples of the dispersion medium include water; alcohols such as methanol, ethanol, isopropanol, and butanol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and isophorone; toluene, xylene, and a hydrocarbon such as an alkane or a cyclohexane; an amide such as N,N-dimethylformamide or N,N-dimethylacetamide; a hydrazine such as dimethyl hydrazine; or Glycols such as diols; glycol ethers such as ethyl cellulose; and the like. The content of the dispersion medium is preferably from 65 to 99 parts by mass per 100 parts by mass of the composition for the transparent film in order to obtain good film formability. Further, the light-transmitting adhesive preferably contains a coupling agent in accordance with the other components used. This is because the adhesion between the transparent substrate and the transparent film and the adhesion between the transparent film and the transparent ruthenium film can be improved, and the adhesion of the light-transmitting adhesive -12-201236175 to the oxide particles is also improved. . As the coupling agent, a decane coupling agent, an aluminum coupling agent, a titanium coupling agent and the like are exemplified. As the decane coupling agent, vinyl triethoxy decane, 7-glycidoxypropyl trimethoxy decane, r-methyl propylene methoxy propyl trimethoxy decane, and the like are exemplified. As the aluminum coupling agent, an aluminum coupling agent containing an ethoxylated alkoxy group represented by the formula (1), for example, 1 CH3
CH 3 3CH 3 3
CH3~CH—〇—AI-—O—C Η—CH ΟCH3~CH—〇—AI——O—C Η—CH Ο
且，至於鈦偶合劑’舉例有式（2 )〜（4 )所示之具 有二烷基焦磷酸基之鈦偶合劑， -13- 201236175Further, as for the titanium coupling agent', a titanium coupling agent having a dialkyl pyrophosphate group represented by the formulas (2) to (4) is exemplified, -13-201236175
及式（5)所示之具有二烷基磷酸基之鈦偶合劑， 【化5】 (C8H170)4Ti[P(〇Ci3H27)2〇H] ( 5 ) 偶合劑相對於透明膜用組成物：1 00質量份較好爲 0.01〜5質量份，若爲〇_1〜2質量份，則更佳。若爲0.01 質量份以上，則可見到與透明基板或透明電極膜之接著力 提高、或顯著見到氧化物粒子分散性之提高效果，若多於 5質量份，則容易產生膜不均。 又，透明膜用組成物較好對應於所使用之成分添加水 溶性纖維素衍生物。水溶性纖維素衍生物爲非離子化界面 活性劑，相較於其他界面活性劑’即使以少量添加其使氧 化物粒子分散之能力極高’且藉由添加水溶性纖維素衍生 物，亦可提高所形成之透明膜之透明性。至於水溶性纖維 -14- 201236175 素衍生物，舉例有羥丙基纖維素、羥丙基甲基纖維素等。 水溶性纖維素衍生物之添加量，相對於透明膜用組成物： 100質量份，較好爲0.2〜5質量份。 又，透明電極膜亦可由與透明膜用組成物同樣之組成 物形成，但透明電極膜用組成物係調配成硬化後之透明電 極膜之折射率高於透明膜之折射率。 [附太陽能電池用複合膜之透明基板之製造方法] 本發明之附複合膜之透明基板之製造方法，爲依序具 有透明基板、透明膜及透明電極膜之附太陽能電池用複合 膜之透明基板之製造方法，係於透明基板上，利用濕式塗 佈法塗佈透明膜用組成物，形成透明塗膜後，使具有透明 塗膜之透明基板經燒成或硬化，形成透明膜，進而於透明 膜上形成透明電極膜。 透明基板及透明電極膜如上述。 透明膜用組成物可將上述所需成分，依據常用方法， 利用漆料搖晃器（paint shaker)、球磨機、砂磨機 '批 式介質分散機（centri mill )、三輥磨機等予以混合，將 透光性黏合劑及視情況之氧化物粒子等分散而製造。當然 ’亦可利用通常之攪拌操作製造。又，將氧化物粒子除外 之成分混合後，與包含另外分散之氧化物粒子之分散介質 混合，自容易獲得均質透明膜用組成物之觀點而言，則較 佳。 首先，利用濕式塗佈法於透明基板上塗佈上述透明膜 -15- 201236175 用組成物。此處之塗佈較好成爲燒成後之厚度爲 0.01〜0.5μηι。接著，該塗膜較好在溫度20〜120°c，更好 25~60°C乾燥1〜30分鐘，較好2〜10分鐘。如此形成透明 塗膜。 於透明基板上，利用濕式塗佈法塗佈透明膜用組成物 之方法’較好爲噴佈塗佈法、分佈塗佈法、旋轉塗佈法、 刮刀塗佈法、狹縫塗佈法、噴墨塗佈法、模嘴塗佈法、網 版印刷法、平版印刷法、或凹版印刷法之任一者，但不限 於該等，而可利用所有方法。 噴霧塗佈法爲藉由壓縮氣體將透明膜用組成物以霧狀 塗佈於基材上，或將分散體本身加壓成霧狀而塗佈於基材 上之方法，分佈塗佈法爲例如將透明膜用組成物裝入注射 器中，藉由按壓該注射器之活塞桿而自注射器前端之微細 噴嘴噴出分散體而塗佈於基材上之方法。旋轉塗佈法係將 透明膜用組成物滴加於旋轉中之基材上，將該滴下之透明 膜用組成物利用其離心力而擴及基材周緣之方法，刮刀塗 佈法係使與刮刀前端空出特定間隙之基材可於水平移動地 設置，對該刮刀更上游側之基材供給透明膜用組成物，使 基材朝下游側水平移動之方法，狹縫塗佈法爲使透明膜用 組成物自狹小狹縫流出而塗佈於基材上之方法，噴墨塗佈 法爲將透明膜用組成物塡充於市售之噴墨印表機之墨水匣 中，於基材上噴墨印刷之方法。網版印刷法爲利用紗作爲 圖型指示材，透過於其上作成之版圖像而將透明膜用組成 物轉印於基材上之方法。平版印刷法係將附於版上之透明 -16- 201236175 膜用組成物，未直接附著於基材上，而自版暫時轉印至橡 膠薄板上’自橡膠薄板再轉印於基材上之利用透明膜用組 成物之撥水性之印刷方法。模嘴塗佈法係將供給至模嘴內 之透明膜用組成物自以多歧管分配之狹縫擠出至薄膜上， 而塗佈行進中之基材表面之方法。模嘴塗佈法有狹口塗佈 方式或滑動塗佈方式、簾塗方式。 最後，將具有透明塗膜之透明基板於大氣中或氮氣或 氬氣之惰性氣體環境中，較好在1 3 0〜2 5 0 °c ，更好在 180〜220 °C之溫度，保持5〜60分鐘，較好保持15〜40分鐘 而燒成。 具有塗膜之透明基板之燒成溫度設爲13 0〜2 50 °C之範 圍之理由係’於未達1 3 0 °C時，會於透明膜上產生硬化不 足之缺點。又，超過250 °C時，無法產生低溫製程之生產 上之益處’亦即製造成本增大，而使生產性降低。 具有塗膜之透明基板之燒成時間設爲5〜60分鐘之範 圍之理由係，於燒成時間未達下限値時，於透明膜中之黏 合劑燒成不足而產生缺陷。燒成時間若超過上限値，則會 增大必要以上之製造成本而產生生產性降低之缺點之故。 再者，於透明膜上形成透明電極膜之方法並未特別限 定’宜爲真空成膜法等之公知方法。 由上述，可形成本發明之附太陽能電池用複合膜之基 板。如此，本發明之製造方法藉由於透明膜之形成中使用 濕式塗佈法’由於儘可能排除真空蒸鍍法或濺鍍法等之真 空製程，故可更廉價地製造透明膜。 -17- 201236175 [實施例] 以下，利用實施例詳細說明本發明，但本發明不限定 於該等。 以成爲表1所示組成（數値表示質量份）之方式’以 合計爲60g，裝入100cm3之玻璃瓶中，使用直徑：〇.3mm 之氧化锆珠粒（MICROHICA，昭和蜆殻石油製）：100g ，藉由漆料搖晃器分散6小時，製作實施例1〜5、比較例 2之透明膜用組成物。此處，作爲黏合劑使用之Si02結合 劑1〜3、非聚合物型黏合劑1、2、混合溶劑1如下述製作 [Si02結合劑1] 使用50cm3之玻璃製4頸燒瓶，添加140g四乙氧基 矽烷及14(^之乙醇，邊攪拌邊一次添加將1.78之60%硝 酸溶解於120g純水中之溶液，隨後在50°C反應3小時而 製造。 [Si02結合劑2] 使用50cm3之玻璃製4頸燒瓶，添加85g四乙氧基矽 烷及l〇〇g之乙醇，邊攪拌邊於室溫使用管泵以10〜15分 鐘之時間投入將〇.〇9g之60%硝酸溶解於ll〇g純水中之 溶液。隨後，於所得混合溶液中，使用管栗以1 0〜1 5分鐘 之時間投入預先混合之4 5 g三-第三丁氧化鋁及6 0 g乙醇 之混合溶液。在审溫揽拌3 0分鐘左右後，於5 0 °C反應3 -18- 201236175 小時而製造。 [Si〇2結合劑3] 乙氧基 3 5 %硝 小時而 使用50cm3之玻璃製4頸燒瓶，添加U5g E 矽烷及175g之乙醇，邊攪拌邊—次添加將i 4g< 酸溶解於1 1 〇 g純水中之溶液，隨後在4 5 °C反應： 製造。 [非聚合物型黏合劑1 ] 與3-異 係使用 量比1 非聚合物型黏合劑1係使用2 -正丁氧基乙醇 丙基-2,4-戊二酮之混合液，非聚合物型黏合劑2 2,2-二甲基-3,5-己二酮與乙酸異丙酯之混合液（賽 [混合溶劑1] 基甲醯 混合溶劑1係使用異丙醇、乙醇及N，N-二 胺之混合液（質量比4 : 2 : 1 )。 [實施例1〜6、比較例2 ] 表1戶斤 玻璃基 中顯示 實施例1、比較例2之透明膜用組成物，W 示之濕式塗佈法，於作爲透明基板之1mm厚之齒 板上成膜後，在20(TC大氣中燒成30分鐘。表1 燒成後之透明膜之膜厚。 -19- 201236175 [折射率評價] 關於折射率評價，針對實施例1〜5、比較例2所示之 透明膜用組成物，對於光學常數已知之鹼玻璃基板（1.54 )利用濕式塗佈法（旋轉塗佈法、模嘴塗佈法、平版印刷 法）成膜透明膜後，在200 °C燒成30分鐘，藉此形成厚 度0.1〜2 μηι之透明膜。對於該膜，使用分光橢圓偏振裝置 (J. A. Wollam Japan (股）製 Μ-2000)測定，針對透明 膜部分進行數據解析，求得光學常數。由解析之光學常數 ，求得63 3 nm之値作爲折射率。表1顯示該等結果。 [密著性評價] 針對密著性評價，以依據膠帶測試（】IS K-5600 )之 方法進行評價。使用評價折射率之試料。使膠帶對於透明 膜予以密著，於剝離時，將透明膜剝離，藉由捲曲狀態之 程度，以優、可、不佳之三階段予以評價》透明膜未貼附 於膠帶側，僅接著膠帶剝離時評價爲優，接著膠帶剝離時 混雜有鹼玻璃基板露出之狀態時，評價爲可，因接著膠帶 撕下而使鹼玻璃基板表面全面露出時評價爲不佳。表1顯 示該等結果。 [發電特性之評價] 爲了進行太陽能電池之發電評價，製作圖1所示之超 準直型太陽能電池1。於折射率測定中使用之透明基板2 之透明膜3上，藉使用磁控管連線式濺鍍裝置之濺鑛法， -20- 201236175 形成表面具有凹凸紋理且摻雜F (氟）之厚度：8 OOnm之 表面電極膜（Sn02膜，折射率：2.0 )作爲透明導電膜4 。對該透明電極膜4使用雷射加工法圖案化藉此成爲陣列 狀，同時形成將該等予以電性相互連接之配線。接著，於 透明電極膜4上，使用電漿CVD法，形成光電轉換層5 。該光電轉換層5於其實施例中自透明基板2側起依序層 合p型a-Si:H (非晶質碳化矽）、i型a-Si (非晶質矽） 及η型// c-Si (微結晶碳化矽）所成之膜。光電轉換層5 使用雷射加工法進行圖案化。於該光電轉換層5上，利用 濺鍍法，形成厚度：80nni之透明導電層（ZnO層）（未圖 示）及厚度：2 00nm之Ag膜之反射電極膜6後，使用雷射 加工法進行圖案化，製作超準直型太陽能電池1。 至於太陽能電池之評價方法，係對使用雷射加工法實 施圖案化之加工後之基板上實施引線配線，對確認I-V特 性曲線時之輸出特性及短路電流密度（Jsc )之値，進行 與使用除未形成透明膜以外，以與實施例同樣方法獲得之 光電轉換層，均利用濺鍍法形成透明導電膜、導電性反射 膜之比較例1之太陽能電池設爲1 00時之相對輸出評價。 表1顯示該等結果。 此處，均利用濺鑛法形成之薄膜太陽能電池，係如圖 1所示，首先準備於一面上形成有厚度50nm之8丨02層（ 未圖示）之玻璃基板作爲基板2，在該Si 02層上形成表面 具有凹凸紋理且摻雜F (氟）之厚度8 OOnm之透明電極膜 (Sn02膜）4。該透明電極膜4使用雷射加工法圖案化藉 -21 - 201236175 此成爲陣列狀同時形成使其等電性相互 於透明電極膜4上，使用電漿CVD法 5。該光電轉換層5於其實施例中自透 層合P型a-Si:H (非晶質碳化矽）、i )及η型// c-Si (微結晶碳化矽）所成 5使用雷射加工法進行圖案化後’利用 轉換層5上形成厚度80nm之透明導電 圖示）及厚度200nm之Ag膜之反射電 6者。 連接之配線。接著 ，形成光電轉換層 明基板2側起依序 型a-Si (非晶質矽 之膜。光電轉換層 濺鍍法，於該光電 層（ΖηΟ層）（未 極膜（銀電極層） -22- 201236175 表1 實施例 1 實施例 2 實施例 3 實施例 4 實施例 5 比較例 1 比較例 2 透明氧 化物粒 子1 透明氧 化物粒 子2 黏合劑 種類 ZnO ΑΤΟ Zr02 Ti02 Ti02 — — 平均粒 徑(nm) 25 20 30 30 35 一 — 比例(％) 10 10 Ti02 20 ITO 27 Zr02 20 ΑΤΟ — 種類 — — — 平均粒 徑(nm) — 20 30 30 35 — — 比例(％) 種類 si〇2 黏 合劑1 2 非聚合 物型黏 合劑1 2 Si〇2 黏 合劑2 3 非聚合 物型黏 合劑2 2 Si02 黏 合劑3 Si〇2 黏 合劑1 比例(％) 20 10 30 5 10 — 25 分散 介質 種類 IPA Et-OH IPA Et-OH 混合溶 劑1 — IPA 比例(％) 80 78 48 65 68 — 75 成膜 濕式塗 佈法 旋轉塗 佈法 平版印 刷法 旋轉塗 佈法 平版印 刷法 模嘴塗 佈法 — 旋轉塗 佈法 燒成後 膜厚 (μιη) 0.1 0.3 0.4 1 2 — 0.3 ,1.55 1.60 — 1.40 評價 折射率 1.65 1.85 1.65 密著性 優 優 優 優 優 — 優 Jsc增加 率(％) 3 4 3 2 2 0 -5 所有中，折射率均爲 13 ( 2.0 ) ’ Jsc 增加 如表1所了解，實施例1… 1.55〜1.85，滿足 η, ( 1.54) <n2 ;c降低5%。認爲係因 2〜4%。且，實施例1〜5之透明膜密著性亦良好。相對於 此，折射率小如1.40之比較例2 | -23- 201236175 於透明基板與透明膜之介面，由於入射之太陽光反射之故 0 本發明之附太陽能電池用複合膜之基板，藉由以濕式 塗佈法塗佈於透明基板上，並燒成，可減低通過透明基板 之光於透明基板-透.明電極膜介面之反射光，故而就提高 各種太陽能電池之光電轉換效率方面非常有用。 【圖式簡單說明】 圖1爲超準直型太陽能電池之剖面示意圖。 【主要元件符號說明】 1 :超準直型太陽能電池 2 :透明基板 3 :透明膜 4 :透明電極膜 5 :光電轉換層 6 :反射電極膜 1 0 ·'附複合膜之透明基板 -24-And a titanium coupling agent having a dialkyl phosphate group represented by the formula (5), (C8H170)4Ti[P(〇Ci3H27)2〇H] (5) a coupling agent with respect to a composition for a transparent film: The amount of 100 parts by mass is preferably 0.01 to 5 parts by mass, more preferably 〇1 to 2 parts by mass. When the amount is 0.01 parts by mass or more, the adhesion to the transparent substrate or the transparent electrode film is improved, or the effect of improving the dispersibility of the oxide particles is remarkably observed. When the amount is more than 5 parts by mass, film unevenness is likely to occur. Further, the composition for a transparent film preferably contains a water-soluble cellulose derivative in accordance with the component to be used. The water-soluble cellulose derivative is a non-ionizing surfactant, and the ability to disperse the oxide particles is extremely high compared to other surfactants, and by adding a water-soluble cellulose derivative, Improve the transparency of the formed transparent film. As the water-soluble fiber -14-201236175-derived derivatives, hydroxypropylcellulose, hydroxypropylmethylcellulose and the like are exemplified. The amount of the water-soluble cellulose derivative to be added is preferably 0.2 to 5 parts by mass based on 100 parts by mass of the composition for a transparent film. Further, the transparent electrode film may be formed of the same composition as the composition for a transparent film, but the composition of the transparent electrode film is adjusted so that the refractive index of the cured transparent electrode film is higher than that of the transparent film. [Manufacturing method of a transparent substrate with a composite film for a solar cell] The method for producing a transparent substrate with a composite film according to the present invention is a transparent substrate with a composite film for a solar cell including a transparent substrate, a transparent film, and a transparent electrode film. The manufacturing method is based on a transparent substrate, and the composition for a transparent film is applied by a wet coating method to form a transparent coating film, and then the transparent substrate having the transparent coating film is fired or cured to form a transparent film, and further A transparent electrode film is formed on the transparent film. The transparent substrate and the transparent electrode film are as described above. The composition for a transparent film can be mixed with the above-mentioned desired components by a paint shaker, a ball mill, a sand mill 'centri mill, a three-roll mill, etc. according to a usual method. It is produced by dispersing a light-transmitting adhesive, and optionally oxide particles. Of course, it can also be manufactured by a usual stirring operation. Further, it is preferable to mix the components other than the oxide particles and to mix with the dispersion medium containing the separately dispersed oxide particles, from the viewpoint of easily obtaining a composition for a homogeneous transparent film. First, the composition for the above transparent film -15-201236175 was applied onto a transparent substrate by a wet coating method. The coating here is preferably a thickness of 0.01 to 0.5 μm after firing. Next, the coating film is preferably dried at a temperature of 20 to 120 ° C, more preferably 25 to 60 ° C for 1 to 30 minutes, preferably 2 to 10 minutes. The transparent coating film is thus formed. The method of coating a composition for a transparent film by a wet coating method on a transparent substrate is preferably a spray coating method, a distribution coating method, a spin coating method, a knife coating method, or a slit coating method. Any of the inkjet coating method, the nozzle coating method, the screen printing method, the lithography method, or the gravure printing method, but is not limited thereto, and all methods can be utilized. The spray coating method is a method in which a transparent film composition is applied to a substrate in a mist form by a compressed gas, or the dispersion itself is pressed into a mist to be applied onto a substrate, and the distribution coating method is For example, a method in which a composition for a transparent film is placed in a syringe and a piston rod of the syringe is pressed to eject a dispersion from a fine nozzle at a tip end of the syringe to be applied to a substrate. In the spin coating method, a composition for a transparent film is dropped onto a substrate to be rotated, and the composition for the transparent film to be dropped is expanded to the periphery of the substrate by centrifugal force thereof, and the blade coating method is used to make a blade. The substrate having a certain gap at the front end can be horizontally moved, and the composition for the transparent film is supplied to the substrate on the upstream side of the blade to horizontally move the substrate toward the downstream side, and the slit coating method is transparent. A method in which a film composition is discharged from a narrow slit and applied to a substrate, and the inkjet coating method is a method of filling a transparent film composition into an ink cartridge of a commercially available ink jet printer. The method of inkjet printing. The screen printing method is a method in which a yarn is used as a pattern indicating material, and a composition for a transparent film is transferred onto a substrate by a plate image formed thereon. The lithography method is attached to the transparent 16-201236175 film composition on the plate, which is not directly attached to the substrate, but is temporarily transferred from the plate to the rubber sheet and then transferred from the rubber sheet to the substrate. A printing method using water repellency of a composition for a transparent film. The die coating method is a method in which a transparent film supplied to a die is extruded from a slit which is distributed by a manifold to a film to coat a surface of a substrate in progress. The die coating method has a slit coating method, a sliding coating method, and a curtain coating method. Finally, the transparent substrate having the transparent coating film is placed in the atmosphere or in an inert gas atmosphere of nitrogen or argon, preferably at a temperature of 130 to 250 ° C, more preferably at a temperature of 180 to 220 ° C. ~60 minutes, preferably kept for 15~40 minutes and burned. The reason why the firing temperature of the transparent substrate having a coating film is set to a range of 130 to 2 50 °C is that the hardness of the transparent film is insufficient at 130 °C. Further, when the temperature exceeds 250 °C, the production benefit of the low-temperature process cannot be produced, that is, the manufacturing cost is increased, and the productivity is lowered. The reason why the firing time of the transparent substrate having the coating film is in the range of 5 to 60 minutes is that when the firing time is less than the lower limit, the binder in the transparent film is insufficiently burned to cause defects. When the firing time exceeds the upper limit, the manufacturing cost of more than necessary is increased, and the productivity is lowered. Further, the method of forming the transparent electrode film on the transparent film is not particularly limited to a known method such as a vacuum film forming method. From the above, the substrate of the composite film for a solar cell of the present invention can be formed. As described above, in the production method of the present invention, since the wet coating method is used for the formation of the transparent film, the transparent film can be manufactured at a lower cost because the vacuum processing such as the vacuum deposition method or the sputtering method is eliminated as much as possible. -17-201236175 [Examples] Hereinafter, the present invention will be described in detail by way of examples, but the invention is not limited thereto. In the case of the composition shown in Table 1 (the number of parts indicated by mass), the total amount is 60 g, and it is placed in a glass bottle of 100 cm3, and zirconia beads having a diameter of 〇.3 mm (MICROHICA, manufactured by Showa Shell Co., Ltd.) are used. 100 g was dispersed by a paint shaker for 6 hours to prepare compositions for transparent films of Examples 1 to 5 and Comparative Example 2. Here, the SiO 2 bonding agent 1 to 3 used as the binder, the non-polymer type binder 1 and 2, and the mixed solvent 1 were prepared as follows [SiO 2 bonding agent 1] Using a 50 cm 3 glass four-necked flask, 140 g of four B was added. Oxydecane and 14 (ethanol) were prepared by adding a solution of 1.78 of 60% nitric acid in 120 g of pure water with stirring, followed by reaction at 50 ° C for 3 hours. [Si02 Bond 2] 50 cm 3 was used. A glass four-necked flask was charged with 85 g of tetraethoxy decane and 1 g of ethanol, and a tube pump was used at room temperature for 10 to 15 minutes while stirring to dissolve 60.〇9 g of 60% nitric acid in ll. 〇g a solution of pure water. Subsequently, in the obtained mixed solution, a mixed solution of 45 g of tri-tert-butyl alumina and 60 g of ethanol mixed in a period of 10 to 15 minutes is used. After the temperature is about 30 minutes, it is produced by reacting at 30 ° C for 3 -18-201236175 hours. [Si〇2 binder 3] Ethoxy 3 5 % nitric acid and 50 cm 3 glass 4 Neck flask, adding U5g E decane and 175g of ethanol, while stirring - i 4g < acid dissolved in 1 1 〇g pure water The solution, which is then reacted at 45 ° C: Manufacture. [Non-Polymeric Adhesive 1] vs. 3-Heterogeneous Use Ratio 1 Non-Polymeric Adhesive 1 Use 2-n-butoxyethanolpropyl-2 , a mixture of 4-pentanedione, a mixture of 2,2-dimethyl-3,5-hexanedione and isopropyl acetate, a non-polymeric binder (race [mixed solvent 1]) The mixed solvent 1 was a mixture of isopropyl alcohol, ethanol, and N,N-diamine (mass ratio 4:2:1). [Examples 1 to 6 and Comparative Example 2] Table 1 shows the implementation of the glass base. The composition for a transparent film of Example 1 and Comparative Example 2, which was formed by a wet coating method on a 1 mm-thick tooth plate as a transparent substrate, was fired at 20 (TC atmosphere for 30 minutes). Film thickness of the transparent film after the firing. -19-201236175 [Refractive index evaluation] For the evaluation of the refractive index, the compositions for the transparent film shown in Examples 1 to 5 and Comparative Example 2 were used for the alkali glass having an optical constant. The substrate (1.54) was formed into a transparent film by a wet coating method (a spin coating method, a die coating method, or a lithography method), and then baked at 200 ° C for 30 minutes to form a thickness of 0.1 to 2 A transparent film of ηι was used, and the film was measured by a spectroscopic ellipsometry apparatus (manufactured by JA Wollam Japan Co., Ltd.), and data was analyzed for the transparent film portion to obtain an optical constant. From the optical constant of analysis, 63 was obtained. The refractive index of 3 nm was used as the refractive index. The results are shown in Table 1. [Adhesion evaluation] For the adhesion evaluation, the evaluation was performed by the method according to the tape test (] IS K-5600). A sample for evaluating the refractive index was used. The adhesive tape is adhered to the transparent film, and when the film is peeled off, the transparent film is peeled off, and the film is evaluated in three stages of excellent, acceptable, and poor in the state of being curled. The transparent film is not attached to the tape side, and only the tape is peeled off. In the case where the alkali glass substrate was exposed in the case where the tape was peeled off, the evaluation was considered to be satisfactory, and the surface of the alkali glass substrate was evaluated to be poor when the tape was peeled off. Table 1 shows these results. [Evaluation of power generation characteristics] In order to perform power generation evaluation of a solar cell, the supercollimation type solar cell 1 shown in Fig. 1 was produced. On the transparent film 3 of the transparent substrate 2 used in the refractive index measurement, by using the sputtering method of the magnetron-connected sputtering apparatus, -20-201236175 forms a surface having a textured texture and a thickness of doping F (fluorine) A surface electrode film (Sn02 film, refractive index: 2.0) of 8.0 nm was used as the transparent conductive film 4. The transparent electrode film 4 is patterned by a laser processing method to form an array, and wirings electrically connected to each other are formed. Next, a photoelectric conversion layer 5 is formed on the transparent electrode film 4 by a plasma CVD method. In the embodiment, the photoelectric conversion layer 5 sequentially laminates p-type a-Si:H (amorphous niobium carbide), i-type a-Si (amorphous niobium), and n-type/ from the transparent substrate 2 side. / c-Si (microcrystalline niobium carbide) film. The photoelectric conversion layer 5 is patterned using a laser processing method. On the photoelectric conversion layer 5, a transparent conductive layer (ZnO layer) having a thickness of 80 nni (not shown) and a reflective electrode film 6 of an Ag film having a thickness of 200 nm were formed by a sputtering method, and then laser processing was used. Patterning was performed to produce a super-collimated solar cell 1. As for the evaluation method of the solar cell, the lead wire is applied to the substrate after the patterning process by the laser processing method, and the output characteristics and the short-circuit current density (Jsc) when the IV characteristic curve are confirmed are used and used. The photoelectric conversion layer obtained in the same manner as in the Example, except that the transparent film was not formed, was evaluated by the relative output of the solar cell of Comparative Example 1 in which the transparent conductive film and the conductive reflective film were formed by sputtering. Table 1 shows these results. Here, as shown in Fig. 1, a thin film solar cell formed by a sputtering method is prepared by first forming a glass substrate having a thickness of 50 nm of 8 丨 02 layers (not shown) as a substrate 2 on the surface. On the 02 layer, a transparent electrode film (Sn02 film) 4 having a concave-convex texture on the surface and doped with F (fluorine) and having a thickness of 800 nm was formed. The transparent electrode film 4 is patterned by a laser processing method in the form of an array to form an isoelectric property on the transparent electrode film 4, and a plasma CVD method 5 is used. In the embodiment, the photoelectric conversion layer 5 is self-transmissively laminated with P-type a-Si:H (amorphous niobium carbide), i) and n-type / c-Si (microcrystalline niobium carbide). After the patterning method by the shot processing method, "the transparent conductive pattern having a thickness of 80 nm formed on the conversion layer 5" and the reflected electricity of the Ag film having a thickness of 200 nm were used. Wiring for connection. Next, a side of the photoelectric conversion layer on the bright substrate 2 side is formed as a-Si (amorphous germanium film. Photoelectric conversion layer sputtering method, the photovoltaic layer (ΖηΟ layer) (unpolar film (silver electrode layer) - 22-201236175 Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Transparent oxide particles 1 Transparent oxide particles 2 Adhesive type ZnO ΑΤΟ Zr02 Ti02 Ti02 — — Average particle diameter ( Nm) 25 20 30 30 35 I—Proportion (%) 10 10 Ti02 20 ITO 27 Zr02 20 ΑΤΟ — Species — — — Average particle size (nm) — 20 30 30 35 — — Proportion (%) Type si〇2 Adhesive 1 2 Non-polymeric binder 1 2 Si〇2 Adhesive 2 3 Non-polymeric binder 2 2 Si02 Adhesive 3 Si〇2 Adhesive 1 Proportion (%) 20 10 30 5 10 — 25 Dispersion medium type IPA Et-OH IPA Et-OH Mixed Solvent 1 - IPA Proportion (%) 80 78 48 65 68 — 75 Film Forming Wet Coating Rotating Coating Lithography Twirl Coating Plating Method Mold Coating Method — Film thickness after firing by spin coating (μιη) 0.1 0.3 0.4 1 2 — 0.3 , 1.55 1.60 — 1.40 Evaluation of refractive index 1.65 1.85 1.65 Adhesion excellent and excellent excellent - excellent Jsc increase rate (%) 3 4 3 2 2 0 -5 All, the refractive index is 13 (2.0) ' Jsc increase as understood in Table 1, Example 1...1.55~1.85, satisfies η, (1.54) <n2;c decreases by 5%. It is considered to be 2 to 4%. Moreover, the transparent film of Examples 1 to 5 The adhesion is also good. In contrast, the refractive index is as small as 1.40. Comparative Example 2 | -23- 201236175 The interface between the transparent substrate and the transparent film is reflected by the incident sunlight. The substrate of the film is coated on a transparent substrate by a wet coating method and fired, thereby reducing the light transmitted through the transparent substrate to the transparent substrate-transparent electrode film interface, thereby improving various solar cells. The photoelectric conversion efficiency is very useful. [Simplified schematic diagram] Figure 1 is a schematic cross-sectional view of a super-collimated solar cell. [Main component symbol description] 1 : Super-collimated solar cell 2: transparent substrate 3: transparent film 4 : Transparent Electrode Film 5 : Photoelectric Conversion Layer 6 :Reflective electrode film 1 0 ·'Transparent substrate with composite film -24-