JP2011088794A - Glass plate for solar cell - Google Patents

Glass plate for solar cell Download PDF

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JP2011088794A
JP2011088794A JP2009245053A JP2009245053A JP2011088794A JP 2011088794 A JP2011088794 A JP 2011088794A JP 2009245053 A JP2009245053 A JP 2009245053A JP 2009245053 A JP2009245053 A JP 2009245053A JP 2011088794 A JP2011088794 A JP 2011088794A
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glass plate
solar cell
content
thermal expansion
glass
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Takashi Murata
隆 村田
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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    • 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
    • Y02E10/542—Dye sensitized solar cells
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Photovoltaic Devices (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass plate for a solar cell having 60-100×10<SP>-7</SP>/°C thermal expansion coefficient, high strain point and small alkali metal oxide content to improve the reliability or the characteristics of the solar cell and to reduce the manufacture cost of the solar cell. <P>SOLUTION: The glass plate for the solar cell contains by mass% 40-80% SiO<SB>2</SB>, 0-20% Al<SB>2</SB>O<SB>3</SB>, 0-10% B<SB>2</SB>O<SB>3</SB>and 5-65% alkaline earth metal oxide (MgO, CaO, SrO, BaO) and has ≤5% alkali metal oxide (Li<SB>2</SB>O, Na<SB>2</SB>O, K<SB>2</SB>O) and 60-100×10<SP>-7</SP>/°C thermal expansion coefficient at 30-380°C. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は、太陽電池用ガラス板に関し、特に色素増感型太陽電池、ＣＩＧＳ太陽電池、単結晶シリコン太陽電池、多結晶シリコン太陽電池、アモルファスシリコン太陽電池、薄膜化合物太陽電池等に好適な太陽電池用ガラス板に関する。なお、本発明でいう「太陽電池用ガラス板」には、太陽電池用カバーガラスと太陽電池用基材の双方が含まれる。   The present invention relates to a glass plate for a solar cell, and particularly a solar cell suitable for a dye-sensitized solar cell, a CIGS solar cell, a single crystal silicon solar cell, a polycrystalline silicon solar cell, an amorphous silicon solar cell, a thin film compound solar cell, and the like. It relates to a glass plate. In addition, both the cover glass for solar cells and the base material for solar cells are contained in the "glass plate for solar cells" as used in the field of this invention.

太陽電池は、光起電力効果を利用し、光エネルギーを直接電力に変換するデバイスである。現在、シリコン太陽電池の他、種々の化合物半導体等を素材にした太陽電池が実用化されている。特に、色素増感太陽電池は、低コストで製造できるため、次世代の太陽電池として期待されている（特許文献１参照）。   A solar cell is a device that uses the photovoltaic effect to convert light energy directly into electric power. Currently, in addition to silicon solar cells, solar cells using various compound semiconductors and the like have been put into practical use. In particular, since dye-sensitized solar cells can be manufactured at low cost, they are expected as next-generation solar cells (see Patent Document 1).

色素増感太陽電池は、次のようにして製造される。まずガラス板上にアルカリ拡散を防止するためのバリアコート等を形成した後、ＦＴＯ等の導電膜を５００℃〜５５０℃の温度で形成し、更にその上にＴｉＯ２の多孔質体を５００〜５５０℃の温度で焼成し、続いてこの基板と対向基板をガラスフリット等によりシールした後、内部に電解液を注入する。 The dye-sensitized solar cell is manufactured as follows. First, after forming a barrier coat or the like for preventing alkali diffusion on a glass plate, a conductive film such as FTO is formed at a temperature of 500 ° C. to 550 ° C., and a porous body of TiO 2 is further formed thereon on a 500 to 500 ° C. After baking at a temperature of 550 ° C., the substrate and the counter substrate are sealed with a glass frit or the like, and then an electrolytic solution is injected therein.

特開平１−２２０３８０号公報Japanese Patent Laid-Open No. 1-220380

太陽電池用ガラス板には、次の特性が要求される。   The following characteristics are required for a glass plate for a solar cell.

（１）熱膨張係数が周辺部材の熱膨張係数に整合すること、具体的には熱膨張係数が６０〜１００×１０−７／℃であること。このようにすれば、熱膨張差による膜の剥離等を防止することができる。また、このようにすれば、ガラス板とガラスフリットの熱膨張係数が整合するため、ガラスフリットにより適正にシールすることができ、結果として、太陽電池内部の気密性が維持されて、長期に亘って、電解液の劣化を防ぐことができる。 (1) The thermal expansion coefficient matches the thermal expansion coefficient of the peripheral member, specifically, the thermal expansion coefficient is 60 to 100 × 10 −7 / ° C. In this way, peeling of the film due to a difference in thermal expansion can be prevented. In this case, since the thermal expansion coefficients of the glass plate and the glass frit are matched, the glass frit can be properly sealed, and as a result, the hermeticity inside the solar cell is maintained, and a long period of time can be maintained. Thus, deterioration of the electrolytic solution can be prevented.

（２）高い耐熱性を有すること、換言すれば耐熱性の指標である歪点が高いこと。歪点が高いと、薄膜化合物を高温で形成することができ、結果として、膜品位を高めることができる。 (2) High heat resistance, in other words, a high strain point, which is an index of heat resistance. When the strain point is high, the thin film compound can be formed at a high temperature, and as a result, the film quality can be improved.

（３）ガラス組成中のアルカリ金属酸化物の含有量が少ないこと。アルカリ金属酸化物の含有量が多いと、ＳｉＯ２のバリアコート等を形成しない限り、熱処理工程でガラス板に含まれるアルカリ成分が膜中に拡散して、膜特性が変化し、またガラス板の熱膨張係数が変化して、ガラス板に反り等の問題が発生しやすくなる。なお、ガラス板上にバリアコート等を形成すると、上記問題は解消するが、太陽電池の製造コストが高騰してしまう。 (3) The content of alkali metal oxide in the glass composition is small. If the content of the alkali metal oxide is large, unless the SiO 2 barrier coat or the like is formed, the alkali component contained in the glass plate diffuses in the film in the heat treatment process, and the film characteristics change. The coefficient of thermal expansion changes, and problems such as warpage of the glass plate are likely to occur. In addition, when a barrier coat etc. are formed on a glass plate, the said problem will be eliminated, but the manufacturing cost of a solar cell will rise.

従来、ガラス板の熱膨張係数を６０〜１００×１０−７／℃に調整するために、ガラス組成中のアルカリ金属酸化物を増量していたが、このような場合、歪点が低下することに加えて、ガラス板上にバリアコート等を形成する必要があった。したがって、熱膨張係数、歪点、アルカリ金属酸化物の含有量は、所謂トレードオフの関係にあり、上記要求特性（１）〜（３）の両立は困難であった。このため、従来の太陽電池用ガラス板は、上記要求特性（１）〜（３）を充足していなかった。 Conventionally, in order to adjust the thermal expansion coefficient of a glass plate to 60 to 100 × 10 −7 / ° C., the amount of alkali metal oxide in the glass composition has been increased, but in such a case, the strain point is lowered. In addition, it was necessary to form a barrier coat or the like on the glass plate. Therefore, the thermal expansion coefficient, strain point, and alkali metal oxide content are in a so-called trade-off relationship, and it is difficult to satisfy the required characteristics (1) to (3). For this reason, the conventional glass plate for solar cells has not satisfied the said required characteristics (1)-(3).

そこで、本発明は、６０〜１００×１０−７／℃の熱膨張係数を有するとともに、歪点が高く、且つアルカリ金属酸化物の含有量が少ない太陽電池用ガラス板を創案することにより、太陽電池の信頼性や特性を高めつつ、太陽電池の製造コストを低廉化することを技術的課題とする。 Therefore, the present invention creates a glass plate for a solar cell having a thermal expansion coefficient of 60 to 100 × 10 −7 / ° C., a high strain point, and a low alkali metal oxide content. The technical problem is to reduce the manufacturing cost of solar cells while improving the reliability and characteristics of the cells.

本発明者は、鋭意努力の結果、ガラス組成中の各成分の含有量および熱膨張係数を規制することにより、上記技術的課題を解決することを見出し、本発明として提案するものである。すなわち、本発明の太陽電池用ガラス板は、ガラス組成として、質量％で、ＳｉＯ２ ４０〜８０％、Ａｌ２Ｏ３ ０〜２０％、Ｂ２Ｏ３ ０〜１０％、アルカリ土類金属酸化物（ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ） ５〜６５％を含有するとともに、アルカリ金属酸化物（Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ）の含有量が５％以下であり、且つ３０〜３８０℃における熱膨張係数が６０〜１００×１０−７／℃であることを特徴とする。ここで、「３０〜３８０℃における熱膨張係数」は、ディラトメーターで測定した値を指し、３０〜３８０℃における平均値を指す。 As a result of diligent efforts, the present inventor has found that the above technical problem can be solved by regulating the content and thermal expansion coefficient of each component in the glass composition, and proposes the present invention. That is, the glass plate for solar cells of the present invention has, as a glass composition, mass%, SiO 2 40-80%, Al 2 O 3 0-20%, B 2 O 3 0-10%, alkaline earth metal oxidation. Product (MgO, CaO, SrO, BaO) 5 to 65%, the content of alkali metal oxides (Li 2 O, Na 2 O, K 2 O) is 5% or less, and 30 to 380 The thermal expansion coefficient at 60 ° C. is 60 to 100 × 10 −7 / ° C. Here, “thermal expansion coefficient at 30 to 380 ° C.” indicates a value measured by a dilatometer, and indicates an average value at 30 to 380 ° C.

第二に、本発明の太陽電池用ガラス板は、ガラス組成として、質量％で、ＳｉＯ２ ４０〜７０％、Ａｌ２Ｏ３ ０〜１５％、Ｂ２Ｏ３ ０〜５％、アルカリ土類金属酸化物 １０〜６０％を含有するとともに、アルカリ金属酸化物の含有量が５％以下であり、且つ３０〜３８０℃における熱膨張係数が６０〜１００×１０−７／℃であることを特徴とする。 Second, the glass plate for a solar cell of the present invention has a glass composition, in mass%, SiO 2 40~70%, Al 2 O 3 0~15%, B 2 O 3 0~5%, an alkaline earth The metal oxide contains 10 to 60%, the alkali metal oxide content is 5% or less, and the thermal expansion coefficient at 30 to 380 ° C. is 60 to 100 × 10 −7 / ° C. And

第三に、本発明の太陽電池用ガラス板は、ガラス組成として、質量％で、ＳｉＯ２ ４０〜５５％、Ａｌ２Ｏ３ ０〜１０％、Ｂ２Ｏ３ ０〜０．５％、アルカリ土類金属酸化物 ３５〜６０％を含有するとともに、アルカリ金属酸化物の含有量が０．１％以下であり、且つ３０〜３８０℃における熱膨張係数が６０〜９５×１０−７／℃であることを特徴とする。 Thirdly, the glass plate for a solar cell of the present invention has a glass composition, in mass%, SiO 2 40~55%, Al 2 O 3 0~10%, B 2 O 3 0~0.5%, alkali While containing 35-60% of earth metal oxide, the content of alkali metal oxide is 0.1% or less, and the thermal expansion coefficient at 30-380 ° C. is 60-95 × 10 −7 / ° C. It is characterized by being.

第四に、本発明の太陽電池用ガラス板は、歪点が６５０℃以上であることを特徴とする。ここで、「歪点」は、ＡＳＴＭ Ｃ３３６−７１に準拠した方法で測定した値を指す。   Fourthly, the glass plate for solar cells of the present invention is characterized in that the strain point is 650 ° C. or higher. Here, “strain point” refers to a value measured by a method based on ASTM C336-71.

第五に、本発明の太陽電池用ガラス板は、１０４．０ｄＰａ・ｓにおける温度が１２５０℃以下であることを特徴とする。ここで、「１０４．０ｄＰａ・ｓにおける温度」は、白金球引き上げ法で測定した値を指す。 Fifth, the glass plate for a solar cell of the present invention is characterized in that the temperature at 10 4.0 dPa · s is 1250 ° C. or lower. Here, “temperature at 10 4.0 dPa · s” refers to a value measured by a platinum ball pulling method.

第六に、本発明の太陽電池用ガラス板は、液相粘度が１０４．０ｄＰａ・ｓ以上であることを特徴とする。ここで、「液相粘度」は、液相温度における粘度を白金球引き上げ法で測定した値を指す。また、「液相温度」は、標準篩３０メッシュ（篩目開き５００μｍ）を通過し、５０メッシュ（篩目開き３００μｍ）に残るガラス粉末を白金ボートに入れ、温度勾配炉中に２４時間保持して、結晶の析出する温度を測定した値を指す。 Sixth, the glass plate for a solar cell of the present invention has a liquid phase viscosity of 10 4.0 dPa · s or more. Here, “liquid phase viscosity” refers to a value obtained by measuring the viscosity at the liquid phase temperature by a platinum ball pulling method. In addition, the “liquid phase temperature” passes through a standard sieve 30 mesh (a sieve opening of 500 μm), and the glass powder remaining in a 50 mesh (a sieve opening of 300 μm) is put in a platinum boat and kept in a temperature gradient furnace for 24 hours. The value at which the temperature at which crystals precipitate is measured.

第七に、本発明の太陽電池用ガラス板は、フロート法により成形されてなることを特徴とする。このようにすれば、安価に大量にガラス板を成形することができる。   Seventh, the glass plate for a solar cell of the present invention is formed by a float process. In this way, a large number of glass plates can be formed at a low cost.

第八に、本発明の太陽電池用ガラス板は、ロールアウト法により成形されてなることを特徴とする。   Eighth, the glass plate for a solar cell of the present invention is formed by a roll-out method.

上記のように各成分の含有量を限定した理由を以下に詳述する。なお、以下の％表示は、特に限定がある場合を除き、質量％を指す。   The reason for limiting the content of each component as described above will be described in detail below. In addition, the following% display points out the mass% except the case where there is especially limitation.

ＳｉＯ２は、ガラスネットワークを形成する成分である。ＳｉＯ２の含有量は４０〜８０％、好ましくは４０〜７０％、より好ましくは４４〜６０％、更に好ましくは４４〜５５％、更に好ましくは４５〜５２％である。ＳｉＯ２の含有量が８０％より多くなると、ガラスを溶融、成形し難くなったり、熱膨張係数が低くなり、周辺材料の熱膨張係数に整合し難くなる。一方、ＳｉＯ２の含有量が４０％より少なくなると、熱膨張係数が高くなり過ぎて、耐熱衝撃性が低下したり、ガラス化し難くなる傾向がある。 SiO 2 is a component that forms a glass network. The content of SiO 2 is 40 to 80%, preferably 40 to 70%, more preferably 44 to 60%, still more preferably 44 to 55%, still more preferably 45 to 52%. When the content of SiO 2 exceeds 80%, it becomes difficult to melt and mold the glass, or the thermal expansion coefficient becomes low, and it becomes difficult to match the thermal expansion coefficient of the surrounding materials. On the other hand, when the content of SiO 2 is less than 40%, the thermal expansion coefficient becomes too high, and the thermal shock resistance tends to be lowered or vitrification tends to be difficult.

Ａｌ２Ｏ３は、歪点やヤング率を高める成分である。Ａｌ２Ｏ３の含有量は０〜２０％、好ましくは１〜１７％、より好ましくは２〜１６％、更に好ましくは３〜９％、特に好ましくは３〜８％である。Ａｌ２Ｏ３の含有量が２０％より多くなると、耐失透性が低下するとともに、高温粘性が高くなり、溶融性が低下する傾向がある。Ａｌ２Ｏ３の含有量が少なくなると、熱膨張係数が高くなり過ぎたり、耐熱衝撃性が低下したり、歪点が低下する傾向があり、太陽電池を製造する際の熱処理工程でガラス板に割れが発生したり、熱変形や熱収縮が生じやすくなる。 Al 2 O 3 is a component that increases the strain point and Young's modulus. The content of Al 2 O 3 is 0 to 20%, preferably 1 to 17%, more preferably 2 to 16%, still more preferably 3 to 9%, and particularly preferably 3 to 8%. When the content of Al 2 O 3 is more than 20%, the devitrification resistance decreases, the high temperature viscosity increases, and the meltability tends to decrease. When the content of Al 2 O 3 decreases, the thermal expansion coefficient tends to be too high, the thermal shock resistance tends to decrease, or the strain point tends to decrease, and the glass plate is subjected to a heat treatment process when manufacturing a solar cell. Cracks are likely to occur, and thermal deformation and shrinkage are likely to occur.

Ｂ２Ｏ３は、溶融性を高めるとともに、失透を抑制する成分である。Ｂ２Ｏ３の含有量は０〜１０％であり、０〜８％、０〜５％、０〜１％、０〜０．５％、０〜０．４％、０〜０．３％、０〜０．２％、特に０〜０．１％が好ましい。Ｂ２Ｏ３の含有量が１０％より多くなると、歪点やヤング率が低下しやすくなる。特に、歪点が低下すると、高温の熱処理、特に高温の成膜時に、ガラス板に熱反り、熱変形、熱収縮等が生じて、高品位の膜を形成し難くなり、結果として、太陽電池の光電変換効率を高め難くなる。また、Ｂ２Ｏ３含有量が多くなると、１０４．０ｄＰａ・ｓにおける温度が低下しやすくなるため、液相温度が低下しても、液相粘度が低下する傾向がある。 B 2 O 3 is a component that increases meltability and suppresses devitrification. The content of B 2 O 3 is 0 to 10%, 0 to 8%, 0 to 5%, 0 to 1%, 0 to 0.5%, 0 to 0.4%, 0 to 0.3%. 0 to 0.2%, particularly 0 to 0.1% is preferable. When the content of B 2 O 3 is more than 10%, the strain point and Young's modulus are likely to be lowered. In particular, when the strain point is lowered, it becomes difficult to form a high-quality film due to thermal warping, thermal deformation, thermal shrinkage, etc. on the glass plate during high-temperature heat treatment, particularly during high-temperature film formation. It is difficult to increase the photoelectric conversion efficiency. Further, when the content of B 2 O 3 increases, 10 4.0 and the temperature tends to decrease in dPa · s, even the liquidus temperature decreases, the liquidus viscosity tends to decrease.

アルカリ土類金属酸化物の含有量は５〜６５％、好ましくは１５〜５５％、より好ましくは２５〜５５％、更に好ましくは３３〜５３％、特に好ましくは３８〜５０％である。アルカリ土類金属酸化物の含有量が６５％より多くなると、密度や熱膨張係数が過度に上昇し、また耐失透性が低下する傾向がある。一方、アルカリ土類金属酸化物の含有量が５％より少なくなると、熱膨張係数が低下したり、溶融性や耐熱性が低下する。   The content of the alkaline earth metal oxide is 5 to 65%, preferably 15 to 55%, more preferably 25 to 55%, still more preferably 33 to 53%, and particularly preferably 38 to 50%. When the content of the alkaline earth metal oxide is more than 65%, the density and the coefficient of thermal expansion increase excessively, and the devitrification resistance tends to decrease. On the other hand, when the content of the alkaline earth metal oxide is less than 5%, the thermal expansion coefficient is lowered, and the meltability and heat resistance are lowered.

ＭｇＯは、歪点を高める成分である。ＭｇＯの含有量は０〜１０％、０〜５％、０〜３％、０〜１％、特に０〜０．１％が好ましい。ＭｇＯの含有量が多くなると、熱膨張係数が高くなり過ぎたり、密度が高くなったり、耐失透性が低下する傾向がある。   MgO is a component that increases the strain point. The content of MgO is preferably 0 to 10%, 0 to 5%, 0 to 3%, 0 to 1%, particularly preferably 0 to 0.1%. When the content of MgO increases, the thermal expansion coefficient tends to be too high, the density increases, and the devitrification resistance tends to decrease.

ＣａＯは、歪点をあまり低下させずに、高温粘性を低下させる成分である。ＣａＯの含有量は０〜１０％、０〜８％、０〜７％、特に０〜６％が好ましい。ＣａＯの含有量が多くなると、熱膨張係数が高くなり過ぎたり、密度が高くなったり、耐失透性が低下する傾向がある。   CaO is a component that lowers the high temperature viscosity without significantly reducing the strain point. The content of CaO is preferably 0 to 10%, 0 to 8%, 0 to 7%, particularly preferably 0 to 6%. When the content of CaO increases, the thermal expansion coefficient tends to be too high, the density increases, and the devitrification resistance tends to decrease.

ＳｒＯは、耐失透性を低下させずに、高温粘性を低下させるとともに、熱膨張係数を高める成分である。ＳｒＯの含有量は０〜２５％、０〜２０％、０〜１７％、２〜１６％、７〜１６％、特に９〜１６％が好ましい。ＳｒＯの含有量が多くなると、熱膨張係数や密度が高くなり過ぎたり、ガラス組成のバランスが損なわれて、逆に耐失透性が低下しやすくなる。   SrO is a component that increases the thermal expansion coefficient while lowering the high-temperature viscosity without reducing the devitrification resistance. The content of SrO is preferably 0 to 25%, 0 to 20%, 0 to 17%, 2 to 16%, 7 to 16%, particularly preferably 9 to 16%. When the content of SrO increases, the coefficient of thermal expansion and the density become too high, or the balance of the glass composition is impaired, and conversely, the devitrification resistance tends to decrease.

ＢａＯは、耐失透性を低下させずに、高温粘性を低下させるとともに、熱膨張係数を高める成分である。ＢａＯの含有量は０〜４０％、５〜３５％、１０〜３５％、１５〜３５％、２０〜３３％、２５〜３３％、特に２４〜３２％が好ましい。ＢａＯの含有量が多くなると、熱膨張係数が高くなり過ぎたり、密度が高くなったり、ガラス組成のバランスが損なわれて、逆に耐失透性が低下しやすくなる。   BaO is a component that lowers the high temperature viscosity without increasing the devitrification resistance and increases the coefficient of thermal expansion. The BaO content is preferably 0 to 40%, 5 to 35%, 10 to 35%, 15 to 35%, 20 to 33%, 25 to 33%, particularly preferably 24 to 32%. When the content of BaO increases, the coefficient of thermal expansion becomes too high, the density increases, the balance of the glass composition is impaired, and devitrification resistance tends to decrease.

アルカリ金属酸化物は、高温粘性を低下させるとともに、熱膨張係数を調整する成分であるが、その含有量が５％より多いと、歪点が低下したり、熱膨張係数が高くなり過ぎ、またガラス板上にアルカリバリア膜を形成しなければならず、太陽電池の製造コストが高騰する。よって、アルカリ金属酸化物の含有量は５％以下であり、１％以下、０．５％以下、特に０．１％以下が好ましい。   Alkali metal oxide is a component that lowers the viscosity at high temperature and adjusts the coefficient of thermal expansion. However, if its content is more than 5%, the strain point decreases, the coefficient of thermal expansion becomes too high, and An alkali barrier film must be formed on the glass plate, which increases the manufacturing cost of the solar cell. Therefore, the content of the alkali metal oxide is 5% or less, preferably 1% or less, 0.5% or less, and particularly preferably 0.1% or less.

上記成分以外にも以下の成分を含有してもよい。   In addition to the above components, the following components may be contained.

ＺｒＯ２は、歪点やヤング率を高める成分であり、また１０４．０ｄＰａ・ｓ付近の粘度を高める成分である。ＺｒＯ２の含有量は０〜１０％、０〜８％、０〜７％、０．０１〜７％、０．０１〜６％、０．５〜６％、特に１〜６％が好ましい。ＺｒＯ２の含有量が１０％より多くなると、耐失透性が低下したり、密度が高くなり過ぎる。特に、ＳｒＯ＋ＺｒＯ２（ＳｒＯとＺｒＯ２の合量）の含有量が多くなると、耐失透性が顕著に低下する傾向がある。このため、ＳｒＯ＋ＺｒＯ２の含有量は０〜１８％、２〜１７％、５〜１７％、特に１０〜１６％が好ましい。 ZrO 2 is a component that increases the strain point and Young's modulus, and is a component that increases the viscosity in the vicinity of 10 4.0 dPa · s. The content of ZrO 2 is preferably 0 to 10%, 0 to 8%, 0 to 7%, 0.01 to 7%, 0.01 to 6%, 0.5 to 6%, particularly preferably 1 to 6%. When the content of ZrO 2 is more than 10%, the devitrification resistance is lowered or the density is too high. In particular, when the content of SrO + ZrO 2 (the total amount of SrO and ZrO 2 ) increases, the devitrification resistance tends to be significantly reduced. For this reason, the content of SrO + ZrO 2 is preferably 0 to 18%, 2 to 17%, 5 to 17%, particularly preferably 10 to 16%.

Ｆｅ２Ｏ３は、透過率に影響を及ぼす成分である。Ｆｅ２Ｏ３の含有量は０〜０．０５％、１ｐｐｍ〜０．０３％、０．００５〜０．０２％、特に０．００５〜０．０１５％が好ましい。Ｆｅ２Ｏ３の含有量が多くなると、可視域の透過率が低下し過ぎて、太陽電池素子に照射される太陽光の量が低減する上に、ソラリゼーションが起こりやすくなり、結果として、太陽電池の光電変換効率が低下しやすくなる。また、Ｆｅ２Ｏ３の含有量が少なくなると、高純度のガラス原料の使用量が増加し、ガラス板の製造コストが高騰しやすくなり、また紫外域の透過率が高くなり過ぎて、ガラス板上に存在する樹脂の劣化を招き、太陽電池の寿命が短くなるおそれがある。 Fe 2 O 3 is a component that affects the transmittance. The content of Fe 2 O 3 is preferably 0 to 0.05%, 1 ppm to 0.03%, 0.005 to 0.02%, particularly preferably 0.005 to 0.015%. When the content of Fe 2 O 3 is increased, the transmittance in the visible region is excessively decreased, and the amount of sunlight irradiated to the solar cell element is reduced, and solarization is likely to occur. As a result, the solar cell The photoelectric conversion efficiency is likely to decrease. In addition, when the content of Fe 2 O 3 is reduced, the amount of high-purity glass raw material used is increased, the manufacturing cost of the glass plate is likely to increase, and the transmittance in the ultraviolet region is too high. The resin existing above may be deteriorated and the life of the solar cell may be shortened.

ＴｉＯ２は、ソラリゼーションを抑制する成分である。ＴｉＯ２の含有量は０〜１０％、０〜５％、０〜３％、０．００１〜１％、特に０．００５〜０．１％が好ましい。ＴｉＯ２の含有量が多くなると、耐失透性が低下したり、ガラスが着色しやすくなる。 TiO 2 is a component that suppresses solarization. The content of TiO 2 is preferably 0 to 10%, 0 to 5%, 0 to 3%, 0.001 to 1%, particularly preferably 0.005 to 0.1%. When the content of TiO 2 increases, the devitrification resistance decreases and the glass tends to be colored.

ＺｎＯは、ヤング率や溶融性を高める成分である。ＺｎＯの含有量は０〜１０％、０〜５％、０〜３％、０〜１％、特に０〜０．５％が好ましい。ＺｎＯの含有量が多くなると、密度や熱膨張係数が高くなり過ぎ、また耐失透性や歪点が低下する傾向がある。   ZnO is a component that enhances Young's modulus and meltability. The content of ZnO is preferably 0 to 10%, 0 to 5%, 0 to 3%, 0 to 1%, particularly preferably 0 to 0.5%. When the content of ZnO increases, the density and thermal expansion coefficient become too high, and devitrification resistance and strain point tend to decrease.

Ａｓ２Ｏ３は、清澄剤として作用する成分である。しかし、Ａｓ２Ｏ３は、フロート法で成形を行う場合、Ｓｎバスを汚染する。このため、Ａｓ２Ｏ３の含有量は０〜１％、０〜０．８％、０〜０．５％、特に０〜０．３％が好ましく、実質的に含有しないことが望ましい。実質的にＡｓ２Ｏ３を含有しない態様にすれば、近年の環境的要請も満たすことができる。なお、ここで、「実質的にＡｓ２Ｏ３を含有しない」とは、ガラス組成中のＡｓ２Ｏ３の含有量が５００ｐｐｍ以下の場合を指す。 As 2 O 3 is a component that acts as a fining agent. However, As 2 O 3 contaminates the Sn bath when forming by the float method. For this reason, the content of As 2 O 3 is preferably 0 to 1%, 0 to 0.8%, 0 to 0.5%, particularly preferably 0 to 0.3%, and is preferably not substantially contained. If the embodiment does not substantially contain As 2 O 3 , recent environmental requirements can be satisfied. Here, “substantially does not contain As 2 O 3 ” refers to the case where the content of As 2 O 3 in the glass composition is 500 ppm or less.

Ｓｂ２Ｏ３は、清澄剤として作用する成分である。しかし、Ｓｂ２Ｏ３は、フロート法で成形を行う場合、Ｓｎバスを汚染する。このため、Ｓｂ２Ｏ３の含有量は０〜１％、０〜０．８％、０〜０．５％、特に０〜０．３％が好ましく、実質的に含有しないことが望ましい。実質的にＳｂ２Ｏ３を含有しない態様にすれば、近年の環境的要請も満たすことができる。なお、ここで、「実質的にＳｂ２Ｏ３を含有しない」とは、ガラス組成中のＳｂ２Ｏ３の含有量が５００ｐｐｍ以下の場合を指す。 Sb 2 O 3 is a component that acts as a fining agent. However, Sb 2 O 3 contaminates the Sn bath when forming by the float method. For this reason, the content of Sb 2 O 3 is preferably 0 to 1%, 0 to 0.8%, 0 to 0.5%, particularly preferably 0 to 0.3%, and is preferably not substantially contained. If the embodiment does not substantially contain Sb 2 O 3 , recent environmental requirements can be satisfied. Here, “substantially does not contain Sb 2 O 3 ” indicates a case where the content of Sb 2 O 3 in the glass composition is 500 ppm or less.

ＳｎＯ２は、清澄剤として作用する成分である。ＳｎＯ２の含有量は０．００１〜２％、０．００５〜１．５％、０．０１〜１％、０．０５〜０．５％、特に０．０５〜０．３％が好ましい。ＳｎＯ２の含有量が多くなると、耐失透性が低下する。なお、ＳｎＯ２の導入源として、ＳｎＯ２を主成分とする原料を用いても良いが、他の原料に含まれる微量成分から含有させても差し支えなく、電極成分の溶出により含有させても差し支えない。 SnO 2 is a component that acts as a fining agent. The content of SnO 2 is preferably 0.001 to 2 %, 0.005 to 1.5%, 0.01 to 1%, 0.05 to 0.5%, particularly preferably 0.05 to 0.3%. When the content of SnO 2 increases, the devitrification resistance decreases. As introduced source of SnO 2, may be used a raw material composed mainly of SnO 2, but not safely be contained from trace components contained in other raw materials, it can safely be contained by dissolution of the electrode components Absent.

Ｃｌ、Ｆ等のハロゲン化物は、清澄剤として作用する成分である。ハロゲン化物の含有量は、環境的影響を考慮すると、０〜１％、０〜０．５％、０〜０．１％、０〜０．０１％、特に０〜０．００１％が好ましい。   Halides such as Cl and F are components that act as fining agents. The content of the halide is preferably 0 to 1%, 0 to 0.5%, 0 to 0.1%, 0 to 0.01%, particularly preferably 0 to 0.001% in consideration of environmental influences.

ＳＯ３は、清澄剤として作用する成分である。ＳＯ３の含有量は０〜１％、０〜０．５％、０〜０．１％、０〜０．０１％、特に０〜０．００１％が好ましい。 SO 3 is a component that acts as a fining agent. The content of SO 3 is preferably 0 to 1%, 0 to 0.5%, 0 to 0.1%, 0 to 0.01%, particularly preferably 0 to 0.001%.

Ｎｂ２Ｏ５、Ｌａ２Ｏ３等の希土類酸化物は、ヤング率を高める成分である。しかし、希土類酸化物は、原料自体のコストが高く、また耐失透性を低下させる成分である。よって、希土類酸化物の含有量は３％以下、２％以下、１％以下、特に０．５％以下が好ましい。 Rare earth oxides such as Nb 2 O 5 and La 2 O 3 are components that increase the Young's modulus. However, the rare earth oxide is a component that increases the cost of the raw material itself and reduces devitrification resistance. Therefore, the rare earth oxide content is preferably 3% or less, 2% or less, 1% or less, and particularly preferably 0.5% or less.

上記成分以外にも、ガラス特性を損なわない範囲で、他の成分を１０％まで導入することができる。   In addition to the above components, other components can be introduced up to 10% as long as the glass properties are not impaired.

上記の各成分の好適な含有範囲を適宜組み合わせて、好適なガラス組成範囲を構成することは当然に可能であるが、その中にあって、太陽電池用ガラス板として、より好適なガラス組成範囲は、
（１）ＳｉＯ２ ４０〜７０％、Ａｌ２Ｏ３ ０〜１５％、Ｂ２Ｏ３ ０〜５％、ＭｇＯ ０〜５％、ＣａＯ ０〜１０％、ＳｒＯ ０〜２０％、ＢａＯ １０〜５０％、Ｒ２Ｏ ０〜５％含有、
（２）ＳｉＯ２ ４４〜６５％、Ａｌ２Ｏ３ ０〜１０％、Ｂ２Ｏ３ ０〜３％、ＭｇＯ ０〜２％、ＣａＯ ０〜８％、ＳｒＯ ５〜２０％、ＢａＯ １５〜４５％、アルカリ金属酸化物 ０〜５％、アルカリ土類金属酸化物 ２０〜６０％含有、
（３）ＳｉＯ２ ４４〜６５％、Ａｌ２Ｏ３ ０〜１０％、Ｂ２Ｏ３ ０〜３％、ＭｇＯ ０〜２％、ＣａＯ ０〜８％、ＳｒＯ ５〜２０％、ＢａＯ １５〜４５％、アルカリ金属酸化物 ０〜３％、アルカリ土類金属酸化物 ２０〜６０％含有、
（４）ＳｉＯ２ ４４〜６２％、Ａｌ２Ｏ３ ０〜１０％、Ｂ２Ｏ３ ０〜３％、ＭｇＯ ０〜２％、ＣａＯ ０〜８％、ＳｒＯ ７〜２０％、ＢａＯ ２０〜４５％、アルカリ金属酸化物 ０〜１％、アルカリ土類金属酸化物 ３３〜５５％含有、
（５）ＳｉＯ２ ４４〜５５％、Ａｌ２Ｏ３ ０〜８％、Ｂ２Ｏ３ ０〜１％、ＭｇＯ ０〜２％、ＣａＯ ０〜８％、ＳｒＯ ９〜１８％、ＢａＯ ２３〜３８％、ＳｒＯ＋ＺｒＯ２ ９〜１８％、アルカリ金属酸化物 ０〜０．１％、アルカリ土類金属酸化物 ３５〜５０％含有、である。上記のようにガラス組成範囲を規制すれば、耐失透性を大幅に改善しつつ、耐熱性や熱膨張係数を高めることが可能になる。 Although it is naturally possible to configure a suitable glass composition range by appropriately combining the preferred content ranges of the above components, there is a more suitable glass composition range as a solar cell glass plate. Is
(1) SiO 2 40~70%, Al 2 O 3 0~15%, B 2 O 3 0~5%, 0~5% MgO, CaO 0~10%, SrO 0~20%, BaO 10~50 %, R 2 O 0-5% contained,
(2) SiO 2 44~65%, Al 2 O 3 0~10%, B 2 O 3 0~3%, 0~2% MgO, CaO 0~8%, SrO 5~20%, BaO 15~45 %, Alkali metal oxide 0 to 5%, alkaline earth metal oxide 20 to 60% contained,
(3) SiO 2 44~65%, Al 2 O 3 0~10%, B 2 O 3 0~3%, 0~2% MgO, CaO 0~8%, SrO 5~20%, BaO 15~45 %, Alkali metal oxide 0 to 3%, alkaline earth metal oxide 20 to 60% containing,
(4) SiO 2 44~62%, Al 2 O 3 0~10%, B 2 O 3 0~3%, 0~2% MgO, CaO 0~8%, SrO 7~20%, BaO 20~45 %, Alkali metal oxide 0 to 1%, alkaline earth metal oxide 33 to 55% contained,
(5) SiO 2 44~55%, Al 2 O 3 0~8%, B 2 O 3 0~1%, 0~2% MgO, CaO 0~8%, SrO 9~18%, BaO 23~38 %, SrO + ZrO 2 9-18%, alkali metal oxide 0-0.1%, alkaline earth metal oxide 35-50%. If the glass composition range is regulated as described above, the heat resistance and the thermal expansion coefficient can be increased while greatly improving the devitrification resistance.

本発明の太陽電池用ガラス板において、３０〜３８０℃における熱膨張係数は６０〜１００×１０−７／℃であり、５５〜９５×１０−７／℃、６０〜９５×１０−７／℃、６５〜９５×１０−７／℃、特に７０〜９０×１０−７／℃が好ましい。ガラス板の熱膨張係数を上記範囲に規制すれば、金属、有機系接着剤、ガラスフリット、ＦＴＯ膜、ＴｉＯ２多孔質体の熱膨張係数に整合しやすくなり、これらの部材の剥離、熱膨張差による反り、割れを防止することができる。 In the glass plate for a solar cell of the present invention, the thermal expansion coefficient at 30 to 380 ° C. is 60~100 × 10 -7 / ℃, 55~95 × 10 -7 / ℃, 60~95 × 10 -7 / ℃ 65 to 95 × 10 −7 / ° C., and particularly preferably 70 to 90 × 10 −7 / ° C. If the thermal expansion coefficient of the glass plate is regulated within the above range, it becomes easy to match the thermal expansion coefficient of the metal, organic adhesive, glass frit, FTO film, and TiO 2 porous material, and peeling and thermal expansion of these members are facilitated. Warpage and cracking due to the difference can be prevented.

本発明の太陽電池用ガラス板において、歪点は６５０℃以上、６６０℃以上、６６５℃以上、６７０℃以上、６８０℃以上、特に６９５℃以上が好ましい。歪点が高い程、高温で成膜できるため、膜品位を高めることができ、太陽電池の光電変換効率を高めることができる。また、歪点が高い程、薄膜化合物太陽電池等の成膜工程（例えば、ガラス板上に透明電極を形成するための熱ＣＶＤ工程）で熱変形や熱収縮等が生じ難くなる。   In the glass plate for a solar cell of the present invention, the strain point is preferably 650 ° C. or higher, 660 ° C. or higher, 665 ° C. or higher, 670 ° C. or higher, 680 ° C. or higher, particularly 695 ° C. or higher. As the strain point is higher, the film can be formed at a higher temperature, so that the film quality can be improved and the photoelectric conversion efficiency of the solar cell can be increased. In addition, as the strain point is higher, thermal deformation, thermal contraction, and the like are less likely to occur in a film formation process (for example, a thermal CVD process for forming a transparent electrode on a glass plate) such as a thin film compound solar cell.

本発明の太陽電池用ガラス板において、液相粘度は１０４．０ｄＰａ・ｓ以上、１０４．３ｄＰａ・ｓ以上、１０４．５ｄＰａ・ｓ以上、特に１０４．７ｄＰａ・ｓ以上が好ましい。一般的に、耐失透性が低いと、成形時に失透ブツが発生し、ガラス板に成形し難くなる。具体的には、液相粘度が１０４．０ｄＰａ・ｓ未満であると、フロート法やロールアウト法でガラス板を成形し難くなる。よって、液相粘度が１０４．０ｄＰａ・ｓ未満であると、太陽電池用ガラス板の成形方法に不当な制約が課されて、所望の表面形状を有するガラス板を成形し難くなる。なお、液相粘度が高い程、耐失透性が良好である。ガラス特性の改良は、一般的に、他のガラス特性を低下させることにより達成される。つまり、ガラス特性の改良は、一般的に、他のガラス特性の低下を招き、特性同士がトレードオフの関係になりやすい。ここで、粘度、密度、熱膨張係数等とのバランスを考慮すると、液相粘度は１０６．５ｄＰａ・ｓ以下が目安になる。 In the glass plate for a solar cell of the present invention, the liquid phase viscosity is 10 4.0 dPa · s or more, 10 4.3 dPa · s or more, 10 4.5 dPa · s or more, and particularly 10 4.7 dPa · s or more. Is preferred. Generally, when the devitrification resistance is low, devitrification is generated at the time of molding, and it becomes difficult to mold the glass plate. Specifically, when the liquid phase viscosity is less than 10 4.0 dPa · s, it is difficult to form a glass plate by a float method or a roll-out method. Therefore, if the liquid phase viscosity is less than 10 4.0 dPa · s, an unreasonable restriction is imposed on the method for forming the solar cell glass plate, and it becomes difficult to form a glass plate having a desired surface shape. The higher the liquidus viscosity, the better the devitrification resistance. Improvement of glass properties is generally achieved by reducing other glass properties. That is, the improvement of the glass characteristics generally causes a decrease in other glass characteristics, and the characteristics tend to be in a trade-off relationship. Here, in consideration of the balance with the viscosity, density, coefficient of thermal expansion, etc., the liquid phase viscosity is 10 6.5 dPa · s or less as a guide.

本発明の太陽電池用ガラス板において、液相温度は１２００℃以下、１１５０℃以下、特に１１３０℃以下が好ましい。液相温度が１２００℃より高いと、太陽電池用ガラス板の成形方法に不当な制約が課されて、所望の表面形状を有するガラス板を成形し難くなる。なお、液相温度が低い程、耐失透性が良好である。ここで、粘度、密度、熱膨張係数等とのバランスを考慮すると、液相温度は８５０℃以上が目安になる。   In the glass plate for a solar cell of the present invention, the liquidus temperature is preferably 1200 ° C. or lower, 1150 ° C. or lower, particularly preferably 1130 ° C. or lower. If the liquidus temperature is higher than 1200 ° C., unreasonable restrictions are imposed on the method for forming the glass plate for solar cells, and it becomes difficult to form a glass plate having a desired surface shape. In addition, devitrification resistance is so favorable that liquid phase temperature is low. Here, considering the balance with viscosity, density, coefficient of thermal expansion, etc., the liquidus temperature is 850 ° C. or higher.

本発明の太陽電池用ガラス板において、密度は３．７ｇ／ｃｍ３以下、特に３．５ｇ／ｃｍ３以下が好ましい。密度が低い程、ガラス板が軽量化するため、太陽電池を軽量化することができる。 In the glass plate for a solar cell of the present invention, the density is preferably 3.7 g / cm 3 or less, particularly preferably 3.5 g / cm 3 or less. The lower the density, the lighter the glass plate, so the solar cell can be lightened.

本発明の太陽電池用ガラス板において、１０４．０ｄＰａ・ｓにおける温度は１２５０℃以下、１２００℃以下、特に１１６０℃以下が好ましい。１０４．０ｄＰａ・ｓにおける温度が１２５０℃より高くなると、フロート法でガラス板を成形する場合、成形体への負荷が大きくなるため、成形体の耐久性が低下して、ガラス板の製造コストが高騰しやすくなる。一方、１０４．０ｄＰａ・ｓにおける温度が低過ぎると、成形温度が低下して、液相粘度が低下しやすくなる。このため、１０４．０ｄＰａ・ｓにおける温度は１０００℃以上、１０５０℃以上、特に１１００℃以上が好ましい。 In the glass plate for a solar cell of the present invention, the temperature at 10 4.0 dPa · s is preferably 1250 ° C. or less, 1200 ° C. or less, and particularly preferably 1160 ° C. or less. When the temperature at 10 4.0 dPa · s is higher than 1250 ° C., when a glass plate is molded by the float process, the load on the molded body increases, so that the durability of the molded body decreases and the glass plate is manufactured. Costs are likely to rise. On the other hand, when the temperature at 10 4.0 dPa · s is too low, the molding temperature is lowered, and the liquid phase viscosity tends to be lowered. For this reason, the temperature at 10 4.0 dPa · s is preferably 1000 ° C. or higher, 1050 ° C. or higher, and particularly preferably 1100 ° C. or higher.

本発明の太陽電池用ガラス板において、１０２．５ｄＰａ・ｓにおける温度は１５００℃以下、１４５０℃以下、特に１４００℃以下が好ましい。１０２．５ｄＰａ・ｓにおける温度が低い程、溶融時に溶融ガラス中に存在する気泡の浮上速度が速くなるため、ガラス板中の泡を低減しやすくなり、ガラス板の泡品位が向上する。１０２．５ｄＰａ・ｓにおける温度が１５００℃より高いと、溶融時に溶融ガラス中に存在する気泡の浮上速度が遅くなるため、ガラス板中の泡を低減し難くなり、ガラス板の泡品位が低下する。また、高温粘度１０２．５ｄＰａ・ｓにおける温度が１５００℃より高いと、炉体耐火物の耐久性が低下するため、溶融炉等の耐久性が低下し、ガラス板の製造コストが高騰する。 In the glass plate for a solar cell of the present invention, the temperature at 10 2.5 dPa · s is preferably 1500 ° C. or lower, 1450 ° C. or lower, particularly preferably 1400 ° C. or lower. The lower the temperature at 10 2.5 dPa · s, the faster the bubbles rise in the molten glass at the time of melting, so it becomes easier to reduce bubbles in the glass plate and the bubble quality of the glass plate is improved. When the temperature at 10 2.5 dPa · s is higher than 1500 ° C., the rising speed of the bubbles present in the molten glass at the time of melting becomes slow, so it is difficult to reduce the bubbles in the glass plate, and the bubble quality of the glass plate is descend. Further, when the temperature at a high temperature viscosity of 10 2.5 dPa · s is higher than 1500 ° C., the durability of the furnace refractory decreases, so the durability of the melting furnace decreases, and the manufacturing cost of the glass plate increases. .

本発明の太陽電池用ガラス板において、ガラス板の板厚は３．０ｍｍ以下、２．０ｍｍ以下、１．５ｍｍ以下、０．７ｍｍ以下、特に０．５ｍｍ以下が好ましい。ガラス板の板厚が小さい程、ガラス板が軽量化するため、太陽電池を軽量化することができる。また、太陽電池の製造工程でガラス板上に成膜する場合、ガラス板の板厚が小さいと、成膜に際し、高速加熱が可能になるため、太陽電池の製造効率を高めることができる。   In the glass plate for a solar cell of the present invention, the thickness of the glass plate is preferably 3.0 mm or less, 2.0 mm or less, 1.5 mm or less, 0.7 mm or less, particularly 0.5 mm or less. Since the glass plate becomes lighter as the plate thickness of the glass plate is smaller, the solar cell can be made lighter. In addition, when a film is formed on a glass plate in the manufacturing process of the solar cell, if the thickness of the glass plate is small, high-speed heating is possible at the time of film formation, so that the manufacturing efficiency of the solar cell can be increased.

本発明の太陽電池用ガラス板は、所望のガラス組成になるように、ガラス原料を調合したガラスバッチを連続溶融炉に投入した上で、このガラスバッチを加熱溶融し、脱泡した後、成形装置に供給して、溶融ガラスを板状に成形し、徐冷することにより、製造することができる。   The glass plate for a solar cell of the present invention is molded after a glass batch prepared by mixing glass raw materials is put into a continuous melting furnace so as to have a desired glass composition, and the glass batch is heated and melted and defoamed. It can manufacture by supplying to an apparatus, shape | molding molten glass in plate shape, and cooling slowly.

本発明の太陽電池用ガラス板は、フロート法またはロールアウト法により成形されてなることが好ましい。フロート法は、安価に大量にガラス板を成形することができる。ロールアウト法は、成形時にガラス板の表面に凹凸形状等を付与することができる。   The solar cell glass plate of the present invention is preferably formed by a float method or a roll-out method. The float process can form a large number of glass plates at a low cost. The roll-out method can impart an uneven shape or the like to the surface of the glass plate during molding.

以下、本発明を実施例に基づいて説明する。   Hereinafter, the present invention will be described based on examples.

表１は、本発明の実施例（試料Ｎｏ．１〜３）を示している。   Table 1 shows examples of the present invention (sample Nos. 1 to 3).

次のようにして、各試料を作製した。まず表中に記載のガラス組成となるように、ガラス原料を調合し、白金ポットを用いて１５５０℃で５時間溶融した。次に、カーボン板の上に溶融ガラスを流し出して、板状に成形した。得られたガラス板について、各種の評価（密度、歪点、徐冷点、軟化点、熱膨張係数、高温粘度、液相温度、液相粘度）を行った。その結果を表１に示す。   Each sample was produced as follows. First, glass raw materials were prepared so as to have the glass composition described in the table, and melted at 1550 ° C. for 5 hours using a platinum pot. Next, molten glass was poured out on the carbon plate and formed into a plate shape. Various evaluations (density, strain point, annealing point, softening point, thermal expansion coefficient, high temperature viscosity, liquidus temperature, liquidus viscosity) were performed on the obtained glass plate. The results are shown in Table 1.

Figure 2011088794
Figure 2011088794

密度は、周知のアルキメデス法により測定した値である。   The density is a value measured by a well-known Archimedes method.

歪点Ｐｓは、ＡＳＴＭ Ｃ３３６の方法に基づいて測定した値である。   The strain point Ps is a value measured based on the method of ASTM C336.

徐冷点Ｔａは、ＡＳＴＭ Ｃ３３６の方法に基づいて測定した値である。   The annealing point Ta is a value measured based on the method of ASTM C336.

軟化点Ｔｓは、ＡＳＴＭ Ｃ３３８の方法に基づいて測定した値である。   The softening point Ts is a value measured based on the method of ASTM C338.

１０４．０ｄＰａ・ｓ、１０３．０ｄＰａ・ｓ、１０２．５ｄＰａ・ｓにおける温度は、白金球引き上げ法で測定した値である。 The temperatures at 10 4.0 dPa · s, 10 3.0 dPa · s, and 10 2.5 dPa · s are values measured by a platinum ball pulling method.

熱膨張係数αは、ディラトメーターを用いて、３０〜３８０℃における平均値を測定した値である。   Thermal expansion coefficient (alpha) is the value which measured the average value in 30-380 degreeC using the dilatometer.

液相温度は、標準篩３０メッシュ（篩目開き５００μｍ）を通過し、５０メッシュ（篩目開き３００μｍ）に残るガラス粉末を白金ボートに入れ、温度勾配炉中に２４時間保持して、結晶の析出する温度を測定した値である。   The liquidus temperature passes through a standard sieve 30 mesh (500 μm sieve opening), the glass powder remaining in 50 mesh (300 μm sieve opening) is placed in a platinum boat, and kept in a temperature gradient furnace for 24 hours. It is the value which measured the temperature which precipitates.

液相粘度は、液相温度における粘度を白金球引き上げ法で測定した値である。   The liquid phase viscosity is a value obtained by measuring the viscosity at the liquid phase temperature by a platinum ball pulling method.

表１から明らかなように、試料Ｎｏ．１〜３は、密度が３．２３〜３．３７ｇ／ｃｍ３、熱膨張係数が７１〜７３×１０−７／℃、歪点が６６４〜７０１℃、液相温度が１０５５〜１１３０℃、液相粘度が１０４．３〜１０４．９ｄＰａ・ｓ、１０４．０ｄＰａ・ｓにおける温度が１４００℃以下、１０２．５ｄＰａ・ｓにおける温度が１２５０℃以下であり、且つアルカリ金属酸化物を含有していない。したがって、試料Ｎｏ．１〜３は、耐熱性が良好であり、且つバリアコート等が不要である。このため、試料Ｎｏ．１〜３を用いると、光電変換効率が高い太陽電池を安価に製造することができる。また、試料Ｎｏ．１〜３は、ガラスフリット等の周辺部材の熱膨張係数に整合しているため、太陽電池の信頼性を高めることができる。さらに、試料Ｎｏ．１〜３は、高温粘性が低いため、低温で溶融可能であり、且つ泡品位を高めることができる。しかも、試料Ｎｏ．１〜３は、液相粘度が高いため、フロート法により成形することができる。 As is clear from Table 1, sample No. 1 to 3 have a density of 3.23 to 3.37 g / cm 3 , a thermal expansion coefficient of 71 to 73 × 10 −7 / ° C., a strain point of 664 to 701 ° C., a liquidus temperature of 1055 to 1130 ° C., a liquid The phase viscosity is 10 4.3 to 10 4.9 dPa · s, the temperature at 10 4.0 dPa · s is 1400 ° C. or less, the temperature at 10 2.5 dPa · s is 1250 ° C. or less, and the alkali metal oxidation Contains no products. Therefore, sample no. Nos. 1 to 3 have good heat resistance and do not require a barrier coat or the like. For this reason, sample no. When 1 to 3 are used, a solar cell with high photoelectric conversion efficiency can be manufactured at low cost. Sample No. 1 to 3 match the thermal expansion coefficient of a peripheral member such as a glass frit, so that the reliability of the solar cell can be improved. Furthermore, sample no. Since 1-3 are low in high temperature viscosity, they can be melted at a low temperature and can improve foam quality. In addition, Sample No. Nos. 1 to 3 can be molded by the float process because the liquid phase viscosity is high.

以上に説明した通り、本発明の太陽電池用ガラス板は、太陽電池用カバーガラス、太陽電池用基材として好適である。また、本発明の太陽電池用ガラスは、色素増感型太陽電池、ＣＩＧＳ太陽電池、単結晶シリコン太陽電池、多結晶シリコン太陽電池、アモルファスシリコン太陽電池、薄膜化合物太陽電池等に好適である。   As explained above, the solar cell glass plate of the present invention is suitable as a solar cell cover glass and a solar cell substrate. Moreover, the glass for solar cells of the present invention is suitable for dye-sensitized solar cells, CIGS solar cells, single crystal silicon solar cells, polycrystalline silicon solar cells, amorphous silicon solar cells, thin film compound solar cells, and the like.

Claims (8)

ガラス組成として、質量％で、ＳｉＯ２ ４０〜８０％、Ａｌ２Ｏ３ ０〜２０％、Ｂ２Ｏ３ ０〜１０％、アルカリ土類金属酸化物 ５〜６５％を含有するとともに、アルカリ金属酸化物の含有量が５％以下であり、且つ３０〜３８０℃における熱膨張係数が６０〜１００×１０−７／℃であることを特徴とする太陽電池用ガラス板。 As a glass composition, it contains 40 to 80% of SiO 2 , 0 to 20% of Al 2 O 3, 0 to 10% of B 2 O 3 , 5 to 65% of alkaline earth metal oxide, and an alkali metal. The glass plate for solar cells, wherein the oxide content is 5% or less and the thermal expansion coefficient at 30 to 380 ° C is 60 to 100 x 10-7 / ° C. ガラス組成として、質量％で、ＳｉＯ２ ４０〜７０％、Ａｌ２Ｏ３ ０〜１５％、Ｂ２Ｏ３ ０〜５％、アルカリ土類金属酸化物 １０〜６０％を含有するとともに、アルカリ金属酸化物の含有量が５％以下であり、且つ３０〜３８０℃における熱膨張係数が６０〜１００×１０−７／℃であることを特徴とする請求項１に記載の太陽電池用ガラス板。 The glass composition contains 40 to 70% SiO 2 , 0 to 15% Al 2 O 3 , 0 to 5% B 2 O 3 , 10 to 60% alkaline earth metal oxide, and 10% to 60% alkali metal by mass%. 2. The glass plate for a solar cell according to claim 1, wherein the oxide content is 5% or less and the thermal expansion coefficient at 30 to 380 ° C. is 60 to 100 × 10 −7 / ° C. 3. ガラス組成として、質量％で、ＳｉＯ２ ４０〜５５％、Ａｌ２Ｏ３ ０〜１０％、Ｂ２Ｏ３ ０〜０．５％、アルカリ土類金属酸化物 ３５〜６０％を含有するとともに、アルカリ金属酸化物の含有量が０．１％以下であり、且つ３０〜３８０℃における熱膨張係数が６０〜９５×１０−７／℃であることを特徴とする請求項１または２に記載の太陽電池用ガラス板。 As a glass composition, while containing 40 to 55% of SiO 2 , 0 to 10% of Al 2 O 3, 0 to 0.5% of B 2 O 3 , and 35 to 60% of an alkaline earth metal oxide, The content of alkali metal oxide is 0.1% or less, and the thermal expansion coefficient at 30 to 380 ° C is 60 to 95 × 10 -7 / ° C. Glass plate for solar cells. 歪点が６５０℃以上であることを特徴とする請求項１〜３のいずれかに記載の太陽電池用ガラス板。   The glass plate for a solar cell according to any one of claims 1 to 3, wherein the strain point is 650 ° C or higher. １０４．０ｄＰａ・ｓにおける温度が１２５０℃以下であることを特徴とする請求項１〜４のいずれかに記載の太陽電池用ガラス板。 The glass plate for a solar cell according to any one of claims 1 to 4, wherein the temperature at 10 4.0 dPa · s is 1250 ° C or lower. 液相粘度が１０４．０ｄＰａ・ｓ以上であることを特徴とする請求項１〜５のいずれかに記載の太陽電池用ガラス板。 Liquid phase viscosity is 10 < 4.0 > dPa * s or more, The glass plate for solar cells in any one of Claims 1-5 characterized by the above-mentioned. フロート法により成形されてなることを特徴とする請求項１〜６のいずれかに記載の太陽電池用ガラス板。   The glass plate for solar cells according to any one of claims 1 to 6, which is formed by a float process. ロールアウト法により成形されてなることを特徴とする請求項１〜６のいずれかに記載の太陽電池用ガラス板。   The glass plate for a solar cell according to any one of claims 1 to 6, which is formed by a roll-out method.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012254918A (en) * 2011-05-18 2012-12-27 Nippon Electric Glass Co Ltd High-refractive-index glass
US20140376868A1 (en) 2012-01-12 2014-12-25 Schott Ag Highly transmissive glasses with high solarisation resistance, use thereof and method for production thereof
JPWO2018051987A1 (en) * 2016-09-16 2019-06-27 Ａｇｃ株式会社 Glass substrate and laminated substrate

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6374935A (en) * 1986-09-17 1988-04-05 Nippon Electric Glass Co Ltd Glass composition for substrate, having improved chemical resistance
JPH05232458A (en) * 1991-08-12 1993-09-10 Corning Inc Flat panel display device
JPH08133778A (en) * 1994-09-14 1996-05-28 Asahi Glass Co Ltd Glass composition and substrate for plasma display
JPH08333133A (en) * 1995-03-02 1996-12-17 Corning Inc Glass for display panel
JPH09255356A (en) * 1996-03-18 1997-09-30 Asahi Glass Co Ltd Glass composition for substrate
JPH10506088A (en) * 1994-09-19 1998-06-16 コーニング インコーポレイテッド Base glass for plasma display panel
JP2003508339A (en) * 1999-09-04 2003-03-04 カール−ツァイス−スティフツング Aluminoborosilicate glass containing alkaline earth metal and use of this glass
JP2005089286A (en) * 2003-08-12 2005-04-07 Nippon Electric Glass Co Ltd Glass base plate for flat panel display device
JP2008222542A (en) * 2007-02-16 2008-09-25 Nippon Electric Glass Co Ltd Glass substrate for solar battery
JP2008280189A (en) * 2007-05-08 2008-11-20 Nippon Electric Glass Co Ltd Glass substrate for solar cell, and method of manufacturing the same

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6374935A (en) * 1986-09-17 1988-04-05 Nippon Electric Glass Co Ltd Glass composition for substrate, having improved chemical resistance
JPH05232458A (en) * 1991-08-12 1993-09-10 Corning Inc Flat panel display device
JPH08133778A (en) * 1994-09-14 1996-05-28 Asahi Glass Co Ltd Glass composition and substrate for plasma display
JPH10506088A (en) * 1994-09-19 1998-06-16 コーニング インコーポレイテッド Base glass for plasma display panel
JPH08333133A (en) * 1995-03-02 1996-12-17 Corning Inc Glass for display panel
JPH09255356A (en) * 1996-03-18 1997-09-30 Asahi Glass Co Ltd Glass composition for substrate
JP2003508339A (en) * 1999-09-04 2003-03-04 カール−ツァイス−スティフツング Aluminoborosilicate glass containing alkaline earth metal and use of this glass
JP2005089286A (en) * 2003-08-12 2005-04-07 Nippon Electric Glass Co Ltd Glass base plate for flat panel display device
JP2008222542A (en) * 2007-02-16 2008-09-25 Nippon Electric Glass Co Ltd Glass substrate for solar battery
JP2008280189A (en) * 2007-05-08 2008-11-20 Nippon Electric Glass Co Ltd Glass substrate for solar cell, and method of manufacturing the same

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012254918A (en) * 2011-05-18 2012-12-27 Nippon Electric Glass Co Ltd High-refractive-index glass
JP2012254920A (en) * 2011-05-18 2012-12-27 Nippon Electric Glass Co Ltd Glass
US20140376868A1 (en) 2012-01-12 2014-12-25 Schott Ag Highly transmissive glasses with high solarisation resistance, use thereof and method for production thereof
JP2015508385A (en) * 2012-01-12 2015-03-19 ショット・アーゲー Highly permeable glasses with high solarization resistance, their use and methods for their production
US20190152841A1 (en) * 2012-01-12 2019-05-23 Schott Ag Highly transmissive glasses with high solarisation resistance, use thereof and method for production thereof
US10759692B2 (en) 2012-01-12 2020-09-01 Schott Ag Highly transmissive glasses with high solarisation resistance, use thereof and method for production thereof
US11084754B2 (en) 2012-01-12 2021-08-10 Schott Ag Highly transmissive glasses with high solarisation resistance, use thereof and method for production thereof
JPWO2018051987A1 (en) * 2016-09-16 2019-06-27 Ａｇｃ株式会社 Glass substrate and laminated substrate

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