JP2016113340A - Glass sheet fro solar battery - Google Patents

Glass sheet fro solar battery Download PDF

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JP2016113340A
JP2016113340A JP2014254977A JP2014254977A JP2016113340A JP 2016113340 A JP2016113340 A JP 2016113340A JP 2014254977 A JP2014254977 A JP 2014254977A JP 2014254977 A JP2014254977 A JP 2014254977A JP 2016113340 A JP2016113340 A JP 2016113340A
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JP6497576B2 (en
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真人 六車
Masato Rokusha
真人 六車
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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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Abstract

PROBLEM TO BE SOLVED: To enhance photoelectric conversion efficiency of a CIGS-based solar battery by providing a glass sheet capable of rationalizing distribution of alkali ions even when reducing deposition temperature of the CIGS film and rationalizing crystal quality of the CIGS film.SOLUTION: The glass sheet for solar battery contains, by mass%, SiOof 50 to 80%, AlOof 0 to 30%, BOof 0 to 20%, MgO of 0 to 20%, CaO of 0 to 20%, NaO of 4.4 to 30%, KO of 0 to 20%, ZrOof 0 to 5% as glass composition.SELECTED DRAWING: None

Description

本発明は、太陽電池用ガラス板に関し、特にＣＩＳ系太陽電池、ＣＩＧＳ系太陽電池に代表されるカルコパイライト系太陽電池、ＣＺＴＳ系太陽電池に代表されるケステライト系太陽電池、ＣｄＴｅ系太陽電池、色素増感太陽電池、アモルファスシリコン太陽電池等の各種太陽電池の基材又はカバーガラスに好適な太陽電池用ガラス板に関する。   The present invention relates to a glass plate for solar cells, and in particular, CIS solar cells, chalcopyrite solar cells typified by CIGS solar cells, kesterite solar cells typified by CZTS solar cells, CdTe solar cells, and dyes The present invention relates to a glass plate for a solar cell suitable for a base material or a cover glass of various solar cells such as a sensitized solar cell and an amorphous silicon solar cell.

薄膜太陽電池、例えばＣＩＧＳ系太陽電池では、Ｃｕ、Ｉｎ、Ｇａ、Ｓｅからなるカルコパイライト型化合物半導体、Ｃｕ（Ｉｎ,Ｇａ）Ｓｅ２が光電変換膜としてガラス基材上に形成される。 In a thin film solar cell, for example, a CIGS solar cell, a chalcopyrite compound semiconductor made of Cu, In, Ga, and Se, Cu (In, Ga) Se 2 is formed on a glass substrate as a photoelectric conversion film.

カルコパイライト型化合物は、ガラス基材上に多元蒸着法、セレン化法等によりＣｕ、Ｉｎ、Ｇａ、Ｓｅを塗布して、５００℃程度以上の熱処理を行うことにより形成される。   A chalcopyrite type compound is formed by applying Cu, In, Ga, and Se on a glass substrate by a multi-source deposition method, a selenization method, or the like, and performing a heat treatment at about 500 ° C. or higher.

ＣＩＧＳ系太陽電池を作製する際、ＣＩＧＳ膜を高温で成膜すると、アルカリイオンがガラス基材からＣＩＧＳ膜に拡散するため、ＣＩＧＳ膜の結晶品位が改善されて、光電変換効率が向上すると考えられていた。そこで、ガラス基材の耐熱性を高めるために、高歪点ガラス板を使用することが検討されている。例えば、特許文献１には、５５０℃以上の高温で光電変換膜を成膜するために、高歪点ガラス板を用いることが記載されている。特許文献２には、歪点が６００℃超の高歪点ガラス板が記載されている。   When a CIGS solar cell is manufactured, if a CIGS film is formed at a high temperature, alkali ions diffuse from the glass substrate to the CIGS film, so that the crystal quality of the CIGS film is improved and the photoelectric conversion efficiency is considered to be improved. It was. Then, in order to improve the heat resistance of a glass base material, using a high strain point glass plate is examined. For example, Patent Document 1 describes that a high strain point glass plate is used to form a photoelectric conversion film at a high temperature of 550 ° C. or higher. Patent Document 2 describes a high strain point glass plate having a strain point exceeding 600 ° C.

特開平１１−１３５８１９号公報JP-A-11-135819 特開２０１３−０１８６９８号公報JP2013-018698A

ところで、ＣＩＧＳ系太陽電池において、膜構成元素、特にＩｎ，Ｇａ元素の深さ方向の組成プロファイルを最適化すると、ＣＩＧＳ膜中の深さ方向のバンドギャップ構造を最適化することができる。深さ方向の組成プロファイルを最適化するためには、セレン化法ではプリカーサ膜を多層化し、多元蒸着法では各蒸着源からの蒸着量を厳密に管理することになる。   By the way, in the CIGS solar cell, when the composition profile in the depth direction of the film constituent elements, particularly In and Ga elements, is optimized, the band gap structure in the depth direction in the CIGS film can be optimized. In order to optimize the composition profile in the depth direction, the precursor film is multilayered in the selenization method, and the deposition amount from each deposition source is strictly controlled in the multi-source deposition method.

しかし、ＣＩＧＳ膜の成膜温度が高過ぎる場合、膜成分が、熱拡散によりＣＩＧＳ膜内を移動し易くなる。このため、ＣＩＧＳ膜中の深さ方向のバンドギャップ構造を最適化し難くなる。また、ＣｕＳｅ２に代表される低抵抗相が形成されて、ＣＩＧＳ膜のシャントが発生する確率も高まる。結果として、ＣＩＧＳ膜の成膜温度が高過ぎると、ＣＩＧＳ系太陽電池の光電変換効率が低下する虞がある。 However, when the film formation temperature of the CIGS film is too high, the film component easily moves in the CIGS film due to thermal diffusion. For this reason, it becomes difficult to optimize the band gap structure in the depth direction in the CIGS film. In addition, a low resistance phase typified by CuSe 2 is formed, and the probability that a shunt of the CIGS film is generated increases. As a result, if the deposition temperature of the CIGS film is too high, the photoelectric conversion efficiency of the CIGS solar cell may be reduced.

一方、ＣＩＧＳ膜の成膜温度を低下させると、成膜装置の低コスト化、成膜工程の短時間化、成膜後のＣＩＧＳ膜の蒸発又は揮発の防止、ＣＩＧＳ膜の深さ方向バンドギャップ構造の最適化を図ることができると考えられるが、特許文献１、２に記載の高歪点ガラス板を基材に用いる場合、ＣＩＧＳ膜の成膜温度を低下させると、アルカリイオン、特にナトリウムイオンの拡散が不十分になり、ＣＩＧＳ膜の結晶品位の改善効果を享受できなくなる。   On the other hand, when the film formation temperature of the CIGS film is lowered, the cost of the film formation apparatus is reduced, the film formation process is shortened, evaporation or volatilization of the CIGS film after film formation is prevented, and the band gap in the depth direction of the CIGS film Although it is considered that the structure can be optimized, when the high strain point glass plate described in Patent Documents 1 and 2 is used as a base material, alkali ions, particularly sodium, can be obtained by reducing the film formation temperature of the CIGS film. Ion diffusion becomes insufficient, and the effect of improving the crystal quality of the CIGS film cannot be enjoyed.

また、汎用のソーダ石灰ガラス板は、ガラス組成中にＮａ２Ｏを１２〜１４質量％含み、歪点が５１０℃程度と低いため、ＣＩＧＳ膜の成膜時にナトリウムイオンをＣＩＧＳ膜へ拡散させ易い性質を有している。その一方で、ソーダ石灰ガラス板は、耐候性が低いため、ガラス中のアルカリ成分が大気中の水分や炭酸ガス成分と結合することにより、ガラス基材の表面にアルカリ塩を不均質に析出させ易い性質を有する。析出したアルカリ塩は、洗浄により表面から脱離するが、この場合、ガラス基材の表面近傍のアルカリ分布が不均質になる。結果的に、ガラス基材からのアルカリ成分、特にナトリウムイオンの拡散が不均質になり、ガラス基材上にＣＩＧＳ結晶を均質に形成することが困難になる。なお、汎用のソーダ石灰ガラスは、低温（例えば５５０℃未満）の熱処理でも、熱変形や熱収縮のばらつきが大きいため、パターニング不良を招来させる虞もある。 Moreover, since a general-purpose soda-lime glass plate contains 12 to 14% by mass of Na 2 O in the glass composition and has a strain point as low as about 510 ° C., it is easy to diffuse sodium ions into the CIGS film when forming the CIGS film. It has properties. On the other hand, because soda-lime glass plates have low weather resistance, alkali salts in the glass combine with moisture and carbon dioxide components in the air to cause alkali salts to be deposited heterogeneously on the surface of the glass substrate. Easy to use. The precipitated alkali salt is detached from the surface by washing, but in this case, the alkali distribution in the vicinity of the surface of the glass substrate becomes inhomogeneous. As a result, the diffusion of alkali components, particularly sodium ions, from the glass substrate becomes inhomogeneous, making it difficult to form CIGS crystals uniformly on the glass substrate. Note that general-purpose soda-lime glass has a large variation in thermal deformation and thermal shrinkage even at a low temperature (for example, less than 550 ° C.), and may cause a patterning failure.

そこで、本発明は、上記事情に鑑みなされたものであり、その技術的課題は、ＣＩＧＳ膜の成膜温度を低下させても、アルカリイオンの拡散を適正化し得るガラス板を創案することにより、ＣＩＧＳ膜の結晶品位を適正化し、ＣＩＧＳ系太陽電池の光電変換効率を高めることである。   Therefore, the present invention has been made in view of the above circumstances, and its technical problem is to devise a glass plate that can optimize the diffusion of alkali ions even when the film formation temperature of the CIGS film is lowered. It is to optimize the crystal quality of the CIGS film and increase the photoelectric conversion efficiency of the CIGS solar cell.

本発明者は、鋭意検討した結果、ガラス組成範囲を厳密に規制することにより、上記技術的課題を解決し得ることを見出し、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 ５０〜８０％、Ａｌ２Ｏ３ ０〜３０％、Ｂ２Ｏ３ ０〜２０％、ＭｇＯ ０〜２０％、ＣａＯ ０〜２０％、Ｎａ２Ｏ ４．４〜３０％、Ｋ２Ｏ ０〜２０％、ＺｒＯ２ ０〜５％を含有することを特徴とする。 As a result of intensive studies, the present inventor has found that the above technical problem can be solved by strictly regulating the glass composition range, and proposes the present invention. That is, the glass plate for a solar cell of the present invention has a glass composition, in mass%, SiO 2 50~80%, Al 2 O 3 0~30%, B 2 O 3 0~20%, MgO 0~20% CaO 0 to 20%, Na 2 O 4.4 to 30%, K 2 O 0 to 20%, ZrO 2 0 to 5%.

本発明の太陽電池用ガラス板は、上記のようにガラス組成範囲を規制している。このようにすれば、ＣＩＧＳ膜の成膜温度を低下させても、ナトリウムイオンの拡散を適正化させることができる。またＣＩＧＳ膜の剥離を抑制することができる。更にガラス表面へのアルカリ塩の偏析や不均質なアルカリ脱離を抑制することができる。結果として、太陽電池の光電変換効率を高めることができる。   The glass plate for solar cells of the present invention regulates the glass composition range as described above. In this way, diffusion of sodium ions can be optimized even if the film formation temperature of the CIGS film is lowered. Moreover, peeling of the CIGS film can be suppressed. Furthermore, segregation of alkali salts on the glass surface and heterogeneous alkali desorption can be suppressed. As a result, the photoelectric conversion efficiency of the solar cell can be increased.

また、上記のようにガラス組成範囲を規制すれば、高温粘性を低下させつつ、液相粘度を高め易くなり、高品位なガラス板を高い歩留りで作製し易くなる。更に安価な原料構成が選択可能になるため、ガラス板の製造コストを低廉化することができる。   Moreover, if the glass composition range is regulated as described above, it becomes easy to increase the liquid phase viscosity while reducing the high-temperature viscosity, and it becomes easy to produce a high-quality glass plate with a high yield. Furthermore, since an inexpensive raw material structure can be selected, the manufacturing cost of the glass plate can be reduced.

第二に、本発明の太陽電池用ガラス板は、質量比Ｎａ２Ｏ／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）が０．３〜１．０であることが好ましい。ここで、「ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ」は、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ、Ｌｉ２Ｏ、Ｎａ２Ｏ及びＫ２Ｏの合量を指す。「Ｎａ２Ｏ／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）」は、Ｎａ２Ｏの含有量をＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏの含有量で割った値を指す。 Second, the glass plate for a solar cell of the present invention, it is preferred weight ratio Na 2 O / (MgO + CaO + SrO + BaO + Li 2 O + Na 2 O + K 2 O) is 0.3 to 1.0. Here, “MgO + CaO + SrO + BaO + Li 2 O + Na 2 O + K 2 O” refers to the total amount of MgO, CaO, SrO, BaO, Li 2 O, Na 2 O and K 2 O. “Na 2 O / (MgO + CaO + SrO + BaO + Li 2 O + Na 2 O + K 2 O)” refers to a value obtained by dividing the content of Na 2 O by the content of MgO + CaO + SrO + BaO + Li 2 O + Na 2 O + K 2 O.

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 ５０〜８０％、Ａｌ２Ｏ３ ５〜１８％、Ｂ２Ｏ３ ０〜４％、ＭｇＯ ０〜３．４％、ＣａＯ ０〜２％未満、ＭｇＯ＋ＣａＯ ２〜５．４％、Ｌｉ２Ｏ ０〜２％、Ｎａ２Ｏ ４．６〜３０％、Ｋ２Ｏ ０〜４％未満、ＺｒＯ２ ０〜３％、ＳｉＯ２＋Ａｌ２Ｏ３＋ＭｇＯ＋ＣａＯ＋Ｎａ２Ｏ＋Ｋ２Ｏ ９０％以上を含有することが好ましい。ここで、「ＭｇＯ＋ＣａＯ」は、ＭｇＯとＣａＯの合量を指す。「ＳｉＯ２＋Ａｌ２Ｏ３＋ＭｇＯ＋ＣａＯ＋Ｎａ２Ｏ＋Ｋ２Ｏ」は、ＳｉＯ２、Ａｌ２Ｏ３、ＭｇＯ、ＣａＯ、Ｎａ２Ｏ及びＫ２Ｏの合量を指す。 Thirdly, the glass plate for a solar cell of the present invention has a glass composition, in mass%, SiO 2 50~80%, Al 2 O 3 5~18%, B 2 O 3 0~4%, MgO 0~ 3.4%, CaO less than 0~2%, MgO + CaO 2~5.4% , Li 2 O 0~2%, Na 2 O 4.6~30%, K 2 O less than 0~4%, ZrO 2 0 to 3%, preferably contains SiO 2 + Al 2 O 3 + MgO + CaO + Na 2 O + K 2 O 90% or more. Here, “MgO + CaO” refers to the total amount of MgO and CaO. “SiO 2 + Al 2 O 3 + MgO + CaO + Na 2 O + K 2 O” refers to the total amount of SiO 2 , Al 2 O 3 , MgO, CaO, Na 2 O and K 2 O.

第四に、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 ５０〜８０％、Ａｌ２Ｏ３ ０〜３０％、Ｂ２Ｏ３ ０〜３．５％、ＭｇＯ ３．４超〜２０％、ＣａＯ １．０超〜２０％、Ｎａ２Ｏ ５．５〜２３％、Ｋ２Ｏ １．４〜２０％、ＺｒＯ２ ０〜１．９％を含有し、質量比Ｎａ２Ｏ／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）が０．４７〜０．７９であることが好ましい。 Fourth, the glass plate for a solar cell of the present invention has a glass composition, in mass%, SiO 2 50~80%, Al 2 O 3 0~30%, B 2 O 3 0~3.5%, MgO 3.4 super to 20%, CaO 1.0 super ~20%, Na 2 O 5.5~23% , K 2 O 1.4~20%, containing ZrO 2 0 to 1.9%, by weight The ratio Na 2 O / (MgO + CaO + SrO + BaO + Li 2 O + Na 2 O + K 2 O) is preferably 0.47 to 0.79.

第五に、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 ５０〜８０％、Ａｌ２Ｏ３ ３〜３０％、Ｂ２Ｏ３ ０〜１．５％未満、ＭｇＯ ３．４超〜２０％、ＣａＯ １．０超〜２０％、Ｎａ２Ｏ ４．４〜２３％、Ｋ２Ｏ ０．５〜２０％、ＺｒＯ２ ０〜１．９％を含有し、質量比Ｎａ２Ｏ／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）が０．４６〜０．８２であることが好ましい。 Fifth, the glass plate for solar cells of the present invention has, as a glass composition, mass%, SiO 2 50 to 80%, Al 2 O 3 3 to 30%, B 2 O 3 0 to less than 1.5%, MgO more than 3.4 to 20%, CaO more than 1.0 to 20%, Na 2 O 4.4 to 23%, K 2 O 0.5 to 20%, ZrO 2 0 to 1.9%, it is preferred weight ratio Na 2 O / (MgO + CaO + SrO + BaO + Li 2 O + Na 2 O + K 2 O) is from 0.46 to 0.82.

第六に、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 ５０〜８０％、Ａｌ２Ｏ３ １０〜３０％、Ｂ２Ｏ３ ０〜１０％、ＭｇＯ ３．３超〜２０％、ＣａＯ ０〜２０％、Ｎａ２Ｏ １１．５超〜３０％、Ｋ２Ｏ ０〜１．５％、ＺｒＯ２ ０〜３％未満を含有することが好ましい。 Sixth, a glass plate for a solar cell of the present invention has a glass composition, in mass%, SiO 2 50~80%, Al 2 O 3 10~30%, B 2 O 3 0~10%, MgO 3. 3 super ~20%, CaO 0~20%, Na 2 O 11.5 super ~30%, K 2 O 0~1.5% , preferably contains ZrO 2 less than 0-3%.

第七に、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 ５０〜８０％、Ａｌ２Ｏ３ ４．７超〜３０％、Ｂ２Ｏ３ ０〜３．５％、ＭｇＯ ４．０超〜２０％、ＣａＯ ０．３〜２０％、Ｎａ２Ｏ ４．９〜２３％、Ｋ２Ｏ １．４〜２０％、ＺｒＯ２ ０〜１．９％を含有し、質量比Ｎａ２Ｏ／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）が０．４６〜０．８０であることが好ましい。 Seventh, the glass plate for solar cells of the present invention has a glass composition of 50% by mass, SiO 2 50-80%, Al 2 O 3 more than 4.7-30%, B 2 O 3 0-3.5. %, MgO more than 4.0 to 20%, CaO 0.3 to 20%, Na 2 O 4.9 to 23%, K 2 O 1.4 to 20%, ZrO 2 0 to 1.9%. The mass ratio Na 2 O / (MgO + CaO + SrO + BaO + Li 2 O + Na 2 O + K 2 O) is preferably 0.46 to 0.80.

第八に、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 ５０〜８０％、Ａｌ２Ｏ３ ２．５〜３０％、Ｂ２Ｏ３ ０〜２０％、ＭｇＯ ３．１〜２０％、ＣａＯ １．０超〜２０％、Ｎａ２Ｏ ４．４〜２３％、Ｋ２Ｏ １〜２０％、ＺｒＯ２ ０〜１．９％を含有し、質量比Ｎａ２Ｏ／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）が０．４６〜０．８１であることが好ましい。 Eighth, the glass plate for solar cells of the present invention has, as a glass composition, mass%, SiO 2 50-80%, Al 2 O 3 2.5-30%, B 2 O 3 0-20%, MgO. 3.1 to 20%, CaO 1.0 super ~20%, Na 2 O 4.4~23% , K 2 O 1~20%, containing ZrO 2 0~1.9%, the weight ratio Na 2 O / (MgO + CaO + SrO + BaO + Li 2 O + Na 2 O + K 2 O) is preferably 0.46 to 0.81.

第九に、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 ５０〜８０％、Ａｌ２Ｏ３ ３〜３０％、Ｂ２Ｏ３ ０〜３％、ＭｇＯ ３．２〜５．１％、ＣａＯ １．０超〜２０％、Ｎａ２Ｏ ６〜２３％、Ｋ２Ｏ ２〜２０％、ＺｒＯ２ ０〜５％未満を含有し、質量比Ｎａ２Ｏ／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）が０．４９〜０．７８であることが好ましい。 Ninth, the glass plate for solar cells of the present invention has, as a glass composition, mass%, SiO 2 50 to 80%, Al 2 O 3 3 to 30%, B 2 O 3 0 to 3%, MgO 3. 2 to 5.1%, CaO more than 1.0 to 20%, Na 2 O 6 to 23%, K 2 O 2 to 20%, ZrO 2 less than 0 to 5%, and a mass ratio of Na 2 O / ( MgO + CaO + SrO + BaO + Li 2 O + Na 2 O + K 2 O) is preferably 0.49 to 0.78.

第十に、本発明の太陽電池用ガラス板は、歪点が５６０℃以下であることが好ましい。このようにすれば、ＣＩＧＳ膜の成膜温度を低下させた場合に、アルカリイオン、特にナトリウムイオンの拡散を適正化し易くなる。また成膜装置で使用するエネルギーの低減、太陽電池製造装置への負荷の低減、成膜時の高温工程でのＣＩＧＳ膜成分の揮発や蒸発を抑制し得るため、光電変換膜を安価に形成することができる。更にＣＩＧＳ膜成分の過剰拡散を抑制し得るため、バンドギャップ構造の最適化が容易になる。結果として、光電変換効率の高い太陽電池を安価に作製することができる。ここで、「歪点」は、ＡＳＴＭ Ｃ３３６−７１に基づいて測定した値を指す。   10thly, it is preferable that the glass plate for solar cells of this invention has a strain point of 560 degrees C or less. This makes it easier to optimize the diffusion of alkali ions, particularly sodium ions, when the film formation temperature of the CIGS film is lowered. In addition, the photoelectric conversion film can be formed at low cost because the energy used in the film forming apparatus, the load on the solar cell manufacturing apparatus can be reduced, and the volatilization and evaporation of the CIGS film component in the high temperature process during film formation can be suppressed. be able to. Furthermore, since excessive diffusion of CIGS film components can be suppressed, optimization of the band gap structure is facilitated. As a result, a solar cell with high photoelectric conversion efficiency can be manufactured at low cost. Here, the “strain point” refers to a value measured based on ASTM C336-71.

第十一に、本発明の太陽電池用ガラス板は、ナトリウム溶出量が０．３ｍｇ以下であることが好ましい。このようにすれば、大気中の水分や炭酸ガス成分とガラス中のアルカリ成分とが反応し難くなるため、ガラス表面のアルカリ成分の偏析を抑制することができる。結果として、ガラス基材の面方向に均質な光電変換膜を形成し易くなる。ここで、「ナトリウム溶出量」は、ＪＩＳ Ｒ ３５０２に基づく方法により測定した値であり、例えばナトリウム溶出量の特定に際し、原子吸光分析装置を用いることができる。   11thly, it is preferable that the amount of sodium elution of the glass plate for solar cells of this invention is 0.3 mg or less. If it does in this way, since it becomes difficult for the water | moisture content in the air | atmosphere, a carbon dioxide component, and the alkali component in glass to react, segregation of the alkali component on the glass surface can be suppressed. As a result, it becomes easy to form a homogeneous photoelectric conversion film in the surface direction of the glass substrate. Here, the “sodium elution amount” is a value measured by a method based on JIS R 3502, and for example, an atomic absorption analyzer can be used in specifying the sodium elution amount.

第十二に、本発明の太陽電池用ガラス板は、熱膨張係数が８０〜１１０×１０−７／℃であることが好ましい。このようにすれば、ガラス板と光電変換膜、電極膜との熱膨張係数差による膜剥離を低減することができる。また光電変換膜に発生する応力を適正化することができる。結果として、太陽電池の光電変換効率を高めることができる。ここで、「熱膨張係数」は、ディラトメーターにより３０〜３８０℃における平均熱膨張係数を測定した値を指す。 12thly, it is preferable that the thermal expansion coefficient of the glass plate for solar cells of this invention is 80-110 * 10 < -7 > / degreeC. In this way, film peeling due to a difference in thermal expansion coefficient between the glass plate, the photoelectric conversion film, and the electrode film can be reduced. In addition, the stress generated in the photoelectric conversion film can be optimized. As a result, the photoelectric conversion efficiency of the solar cell can be increased. Here, the “thermal expansion coefficient” refers to a value obtained by measuring an average thermal expansion coefficient at 30 to 380 ° C. using a dilatometer.

第十三に、本発明の太陽電池用ガラス板は、１０４．０ｄＰａ・ｓにおける温度が１２００℃未満であることが好ましい。このようにすれば、板成形に必要なエネルギーを低減することができる。特にフロート法でガラス板を安価に作製することができる。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。 Thirteenth, a glass plate for a solar cell of the present invention, it is preferable that the temperature at 10 4.0 dPa · s is lower than 1200 ° C.. If it does in this way, energy required for plate fabrication can be reduced. In particular, a glass plate can be produced at low cost by the float process. Here, “temperature at 10 4.0 dPa · s” refers to a value measured by a platinum ball pulling method.

第十四に、本発明の太陽電池用ガラス板は、１０２．５ｄＰａ・ｓにおける温度が１６００℃未満であることが好ましい。このようにすれば、ガラス溶解窯への負荷が低減されるため、ガラス溶融に必要なエネルギーを低減でき、ガラス板を安価に作製することができる。ここで、「１０２．５ｄＰａ・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。 Fourteenth, the glass plate for a solar cell of the present invention preferably has a temperature at 10 2.5 dPa · s of less than 1600 ° C. In this way, since the load on the glass melting furnace is reduced, the energy required for melting the glass can be reduced, and a glass plate can be produced at a low cost. Here, “temperature at 10 2.5 dPa · s” refers to a value measured by a platinum ball pulling method.

第十五に、本発明の太陽電池用ガラス板は、液相粘度が１０３．７ｄＰａ・ｓ以上であることが好ましい。このようにすれば、フロート法、オーバーフローダウンドロー法等により、表面品位が高いガラス板を作製し易くなる。ここで、「液相粘度」は、液相温度におけるガラスの粘度を白金球引き上げ法で測定した値を指す。「液相温度」は、標準篩３０メッシュ（５００μｍ）を通過し、５０メッシュ（３００μｍ）に残るガラス粉末を白金ボートに入れた後、この白金ボートを温度勾配炉中に２４時間保持して、結晶が析出する温度を測定した値を指す。 15thly, it is preferable that the liquid phase viscosity of the glass plate for solar cells of this invention is 10 3.7 dPa * s or more. If it does in this way, it will become easy to produce a glass plate with high surface quality by the float method, the overflow down draw method, etc. Here, “liquid phase viscosity” refers to a value obtained by measuring the viscosity of glass at the liquid phase temperature by a platinum ball pulling method. “Liquid phase temperature” is obtained by passing glass powder remaining on 50 mesh (300 μm) through a standard sieve 30 mesh (500 μm) into a platinum boat, and then holding the platinum boat in a temperature gradient furnace for 24 hours. The value at which the temperature at which crystals precipitate is measured.

第十六に、本発明の太陽電池用ガラス板は、イオン交換による表面圧縮応力層を有していないことが好ましい。このようにすれば、イオン交換処理が不要になるため、ガラス板の製造コストを低廉化し易くなる。   16thly, it is preferable that the glass plate for solar cells of this invention does not have the surface compressive-stress layer by ion exchange. In this way, the ion exchange process is not necessary, and the manufacturing cost of the glass plate can be easily reduced.

第十七に、本発明の太陽電池用ガラス板は、イオン交換による表面圧縮応力層を有していることが好ましい。このようにすれば、ガラス板の機械的強度を高めることができる。   17thly, it is preferable that the glass plate for solar cells of this invention has the surface compressive-stress layer by ion exchange. If it does in this way, the mechanical strength of a glass plate can be raised.

第十八に、本発明の太陽電池用ガラス板は、圧縮応力層の圧縮応力値が２００〜１２００ＭＰａ、圧縮応力層の厚みが５〜６０μｍであることが好ましい。   Eighteenth, in the glass plate for a solar cell of the present invention, it is preferable that the compressive stress layer has a compressive stress value of 200 to 1200 MPa and the compressive stress layer has a thickness of 5 to 60 μm.

第十九に、本発明の太陽電池用ガラス板は、カルコパイライト太陽電池の基材に用いることが好ましい。   Nineteenth, the glass plate for a solar cell of the present invention is preferably used for a base material of a chalcopyrite solar cell.

第二十に、本発明の太陽電池用ガラス板は、薄膜太陽電池又は色素増感太陽電池の基材に用いることが好ましい。   20thly, it is preferable to use the glass plate for solar cells of this invention for the base material of a thin film solar cell or a dye-sensitized solar cell.

第二十一に、本発明の太陽電池用ガラス板は、太陽電池のカバーガラスに用いることが好ましい。このようにすれば、基材とカバーガラスの熱膨張特性を一致させることができるため、基材とカバーガラスの熱膨張係数差による太陽電池（特に薄膜太陽電池）の反りを改善することができる。   21stly, it is preferable to use the glass plate for solar cells of this invention for the cover glass of a solar cell. In this way, since the thermal expansion characteristics of the base material and the cover glass can be matched, the warpage of the solar cell (particularly, the thin film solar cell) due to the difference in thermal expansion coefficient between the base material and the cover glass can be improved. .

第二十二に、本発明のガラス板は、ガラス組成として、質量％で、ＳｉＯ２ ５０〜８０％、Ａｌ２Ｏ３ ４．７超〜３０％、Ｂ２Ｏ３ ０〜１．５％未満、ＭｇＯ ３．４超〜２０％、ＣａＯ １．０超〜２０％、Ｎａ２Ｏ ５．６〜２３％、Ｋ２Ｏ １．４〜２０％、ＺｒＯ２ ０〜１．９％、ＺｎＯ ０〜５％を含有し、質量比Ｎａ２Ｏ／（Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ＋ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）が０．４９〜０．８０であることを特徴とする。 Twenty-secondly, the glass plate of the present invention has a glass composition of 50% by mass, SiO 2 50-80%, Al 2 O 3 more than 4.7-30%, B 2 O 3 0-1.5%. less, MgO 3.4 super to 20%, CaO 1.0 super ~20%, Na 2 O 5.6~23% , K 2 O 1.4~20%, ZrO 2 0~1.9%, ZnO containing 0 to 5%, the weight ratio Na 2 O / (Li 2 O + Na 2 O + K 2 O + MgO + CaO + SrO + BaO) is characterized in that it is a 0.49 to 0.80.

第二十三に、本発明のガラスは、ガラス組成として、質量％で、ＳｉＯ２ ５０〜８０％、Ａｌ２Ｏ３ ０〜３０％、Ｂ２Ｏ３ ０〜２０％、ＭｇＯ ０〜２０％、ＣａＯ ０〜２０％、Ｎａ２Ｏ ４．４〜３０％、Ｋ２Ｏ ０〜２０％、ＺｒＯ２ ０〜５％を含有することを特徴とする。なお、本発明のガラスは、各種太陽電池の基材やカバーガラスに限られず、太陽電池に用いられるガラス管に適用することもできる。 Twenty-third, the glass of the present invention has a glass composition of 50% by mass, SiO 2 50-80%, Al 2 O 3 0-30%, B 2 O 3 0-20%, MgO 0-20%. CaO 0 to 20%, Na 2 O 4.4 to 30%, K 2 O 0 to 20%, ZrO 2 0 to 5%. In addition, the glass of this invention is not restricted to the base material and cover glass of various solar cells, It can also apply to the glass tube used for a solar cell.

本発明の太陽電池用ガラスは、ガラス組成として、質量％で、ＳｉＯ２ ５０〜８０％、Ａｌ２Ｏ３ ０〜３０％、Ｂ２Ｏ３ ０〜２０％、ＭｇＯ ０〜２０％、ＣａＯ ０〜２０％、Ｎａ２Ｏ ４．４〜３０％、Ｋ２Ｏ ０〜２０％、ＺｒＯ２ ０〜５％を含有することを特徴とする。上記のように、各成分の含有量を規制した理由を下記に示す。なお、各成分の含有範囲の説明において、％表示は、質量％を指す。 The glass for solar cells of the present invention has a glass composition of 50% by mass, SiO 2 50-80%, Al 2 O 3 0-30%, B 2 O 3 0-20%, MgO 0-20%, CaO 0. ~20%, Na 2 O 4.4~30% , K 2 O 0~20%, characterized in that it contains ZrO 2 0 to 5%. The reason why the content of each component is regulated as described above is shown below. In addition, in description of the containing range of each component,% display points out the mass%.

ＳｉＯ２は、ガラスネットワークを形成する成分である。その含有量は５０〜８０％である。ＳｉＯ２の含有量が多過ぎると、高温粘度が不当に高くなり、溶融性や成形性が低下し易くなることに加えて、熱膨張係数が低くなり過ぎて、ＣＩＧＳ系太陽電池の電極膜、ＣＩＧＳ膜の熱膨張係数に整合させ難くなる。一方、ＳｉＯ２の含有量が少な過ぎると、耐失透性、化学的耐久性、耐候性が低下し易くなる。また原料コストが高騰し易くなる。更に熱膨張係数が高くなり過ぎて、耐熱衝撃性が低下し易くなり、結果として、成膜工程でガラス板に割れが発生し易くなる。したがって、ＳｉＯ２の好適な下限範囲は５５％以上、５８％以上、特に６１％以上であり、好適な上限範囲は７５％以下、７０％以下、特に６７％以下である。 SiO 2 is a component that forms a glass network. Its content is 50-80%. If the content of SiO 2 is too large, the high temperature viscosity becomes unreasonably high and the meltability and moldability tend to decrease, and the thermal expansion coefficient becomes too low, so that the electrode film of the CIGS solar cell, It becomes difficult to match the coefficient of thermal expansion of the CIGS film. On the other hand, if the content of SiO 2 is too small, devitrification resistance, chemical durability, weather resistance tends to decrease. In addition, the raw material cost is likely to increase. Furthermore, since the thermal expansion coefficient becomes too high, the thermal shock resistance tends to be lowered, and as a result, the glass plate is easily cracked in the film forming process. Therefore, the preferable lower limit range of SiO 2 is 55% or more, 58% or more, particularly 61% or more, and the preferable upper limit range is 75% or less, 70% or less, particularly 67% or less.

Ａｌ２Ｏ３は、歪点を高める成分であると共に、耐候性、化学的耐久性を高める成分であり、更にはガラス表面の硬度を高める成分である。またアルカリイオンの拡散性を高める成分である。Ａｌ２Ｏ３の含有量は０〜３０％である。Ａｌ２Ｏ３の含有量が多過ぎると、高温粘度が不当に高くなり、溶融性や成形性が低下し易くなる。一方、Ａｌ２Ｏ３の含有量が少な過ぎると、歪点が低下し易くなる。なお、ガラスの表面硬度が高いと、ＣＩＧＳ系太陽電池のパターニングにおいて、ＣＩＧＳ膜を除去する工程で、ガラス板が破損し難くなる。Ａｌ２Ｏ３の好適な下限範囲は２．５％以上、３％以上、４％以上、４．７超％、５％以上、７％以上、特に１０％以上であり、好適な上限範囲は２５％以下、２０％以下、１８％以下、特に１５％以下である。 Al 2 O 3 is a component that increases the strain point, is a component that increases the weather resistance and chemical durability, and further is a component that increases the hardness of the glass surface. Moreover, it is a component which improves the diffusibility of alkali ion. The content of Al 2 O 3 is 0 to 30%. When the content of Al 2 O 3 is too large, the high temperature viscosity becomes unduly high, the meltability and the formability tends to decrease. On the other hand, when the content of Al 2 O 3 is too small, the strain point tends to decrease. In addition, when the surface hardness of glass is high, it will become difficult to damage a glass plate at the process of removing a CIGS film | membrane in the patterning of a CIGS type | system | group solar cell. The preferable lower limit range of Al 2 O 3 is 2.5% or more, 3% or more, 4% or more, more than 4.7%, 5% or more, 7% or more, particularly 10% or more, and the preferable upper limit range is 25% or less, 20% or less, 18% or less, especially 15% or less.

Ｂ２Ｏ３は、高温粘度を低下させて、溶融温度や成形温度を低下させる成分であり、また耐失透性を改善する成分であるが、溶融時の成分蒸発に伴い、炉耐火物材料を消耗させる成分であり、また原料コストを高騰させる成分である。よって、Ｂ２Ｏ３は任意成分であり、好適な上限範囲は２０％以下、１０％以下、５％以下、４％以下、３．５２％以下、３．５％以下、３％以下、１．５％未満、特に１％以下である。 B 2 O 3 is a component that lowers the high-temperature viscosity and lowers the melting temperature and molding temperature, and is a component that improves devitrification resistance. However, along with component evaporation at the time of melting, the furnace refractory material It is a component that consumes the raw material, and a component that raises the raw material cost. Therefore, B 2 O 3 is an optional component, and a preferable upper limit range is 20% or less, 10% or less, 5% or less, 4% or less, 3.52% or less, 3.5% or less, 3% or less, 1 Less than 5%, especially 1% or less.

ＭｇＯは、高温粘度を低下させて、溶融性や成形性を高める成分である。また、ＭｇＯは、アルカリ土類酸化物の中では、ガラスを割れ難くする効果が大きい成分である。しかし、ＭｇＯは、液相粘度を低下させ易い成分である。またＣａＯと共存する場合に、ＣａＭｇＳｉＯ系の失透結晶を析出させ易い成分である。よって、ＭｇＯの含有量は０〜２０％である。ＭｇＯの好適な下限範囲は１％以上、２％超、３．１％以上、３．１％超、３．２％以上、３．３％超、３．４％超、特に３．５％以上であり、高温粘性の低下を優先する場合、３．７％以上、特に４％超であり、ＭｇＯの好適な上限範囲は１０％以下、８％以下、６％以下、５．１％以下、特に５％以下であり、耐失透性の向上を優先する場合、４％以下、４％未満、３．４％以下、特に３％以下である。   MgO is a component that increases the meltability and moldability by reducing the high-temperature viscosity. Further, MgO is a component having a great effect of making glass difficult to break among alkaline earth oxides. However, MgO is a component that tends to lower the liquid phase viscosity. Further, when it coexists with CaO, it is a component that easily precipitates CaMgSiO-based devitrified crystals. Therefore, the content of MgO is 0 to 20%. The preferred lower limit range of MgO is 1% or more, more than 2%, more than 3.1%, more than 3.1%, more than 3.2%, more than 3.3%, more than 3.4%, especially 3.5% In the case where priority is given to lowering the high temperature viscosity, it is 3.7% or more, particularly more than 4%, and the preferred upper limit range of MgO is 10% or less, 8% or less, 6% or less, 5.1% or less When the priority is given to improving devitrification resistance, it is 4% or less, less than 4%, 3.4% or less, particularly 3% or less.

ＣａＯは、高温粘度を低下させて、溶融性や成形性を高める成分である。また、アルカリ土類成分の内、最も安価に導入し得る成分である。ＣａＯの含有量は０〜２０％である。ＣａＯの含有量が多過ぎると、耐失透性が低下して、ガラス板に成形し難くなる。ＣａＯの好適な下限範囲は０．３％以上、０．５％以上、１％超、１．５％超であり、高温粘性と原料コストの低下を優先する場合、２％超、特に３％以上であり、好適な上限範囲は１０％以下、８％以下、特に５％以下であり、耐失透性の向上を優先する場合、３％以下、特に２％未満である。   CaO is a component that increases the meltability and moldability by reducing the high-temperature viscosity. In addition, among alkaline earth components, it is a component that can be introduced at the lowest cost. The content of CaO is 0 to 20%. When there is too much content of CaO, devitrification resistance will fall and it will become difficult to shape | mold into a glass plate. The preferable lower limit range of CaO is 0.3% or more, 0.5% or more, more than 1%, more than 1.5%. If priority is given to high temperature viscosity and lower raw material costs, more than 2%, especially 3% The upper limit is preferably 10% or less, 8% or less, particularly 5% or less. When priority is given to improving devitrification resistance, it is 3% or less, particularly less than 2%.

ＳｒＯは、高温粘度を低下させて、溶融性や成形性を高める成分であり、またアルカリ溶出量を低減させる成分であり、更にＣＩＧＳ膜へのアルカリイオン拡散量を調整し得る成分であるが、原料コストを高騰させる成分である。よって、ＳｒＯは任意成分であり、その含有量は０〜２０％が好ましい。ＳｒＯの含有量が多過ぎると、長石族の失透結晶が析出し易くなり、また密度が増大して、太陽電池の支持部材のコストが高騰し易くなる。更にガラス基材からアルカリイオンの拡散を不当に抑制する虞がある。ＳｒＯのより好適な範囲は８％以下、５％以下、３％以下、２％以下、２％未満、特に１％以下である。   SrO is a component that lowers the high-temperature viscosity and improves meltability and moldability, and is a component that reduces the amount of alkali elution, and is a component that can adjust the amount of alkali ion diffusion into the CIGS film. It is a component that increases raw material costs. Therefore, SrO is an optional component, and its content is preferably 0 to 20%. When the content of SrO is too large, feldspar group devitrified crystals are likely to be precipitated, and the density is increased, and the cost of the solar cell support member is likely to increase. Furthermore, there is a risk of unduly suppressing the diffusion of alkali ions from the glass substrate. A more preferable range of SrO is 8% or less, 5% or less, 3% or less, 2% or less, less than 2%, particularly 1% or less.

ＢａＯは、高温粘度を低下させて、溶融性や成形性を高める成分であり、またアルカリ溶出量を低減させる成分であり、更にＣＩＧＳ膜へのアルカリイオン拡散量を調整し得る成分であるが、原料コストを高騰させる成分である。よって、ＢａＯは任意成分であり、その含有量は０〜２０％が好ましい。ＢａＯの含有量が多過ぎると、バリウム長石族の失透結晶が析出し易くなり、また密度が増大して、太陽電池の支持部材のコストが高騰し易くなる。更にガラス基材からアルカリイオンの拡散を不当に抑制する虞がある。ＢａＯのより好適な範囲は８％以下、５％以下、３％以下、２％以下、２％未満、特に１％以下である。   BaO is a component that lowers the high-temperature viscosity to improve meltability and moldability, and is a component that reduces the amount of alkali elution, and is a component that can adjust the amount of alkali ion diffusion into the CIGS film. It is a component that increases raw material costs. Therefore, BaO is an optional component, and its content is preferably 0 to 20%. If the content of BaO is too large, devitrified crystals of the barium feldspar group are likely to precipitate, the density increases, and the cost of the solar cell support member is likely to increase. Furthermore, there is a risk of unduly suppressing the diffusion of alkali ions from the glass substrate. A more preferable range of BaO is 8% or less, 5% or less, 3% or less, 2% or less, less than 2%, particularly 1% or less.

Ｌｉ２Ｏは、熱膨張係数を調整し得る成分であり、また高温粘度を低下させて、溶融性や成形性を高める成分であるが、原料コストを高騰させる成分であり、更にアルカリイオン同士の拡散の競合により、ナトリウムイオンの拡散を抑制させる成分である。よって、Ｌｉ２Ｏは任意成分であり、その含有量は１０％以下、２％以下、１％以下、特に０．１％未満が好ましい。 Li 2 O is a component that can adjust the coefficient of thermal expansion, and is a component that lowers the high-temperature viscosity and improves the meltability and moldability, but is a component that raises the raw material cost, and further between alkali ions. It is a component that suppresses diffusion of sodium ions due to diffusion competition. Therefore, Li 2 O is an optional component, and its content is preferably 10% or less, 2% or less, 1% or less, particularly preferably less than 0.1%.

Ｎａ２Ｏは、熱膨張係数を調整し得る成分であり、また高温粘度を低下させて、溶融性や成形性を高める成分である。また、Ｎａ２Ｏは、ＣＩＧＳ系太陽電池において、ＣＩＧＳ結晶の成長に効果的な成分であり、光電変換効率を高めるために重要な成分である。よって、Ｎａ２Ｏの含有量は４．４〜３０％である。Ｎａ２Ｏの含有量が多過ぎると、歪点が低下し過ぎたり、熱膨張係数が不当に上昇して、耐熱衝撃性が低下し易くなる。結果として、成膜工程で、ガラス板に熱収縮や熱変形が生じたり、割れが発生し易くなる。また太陽電池膜へ不当な応力が発生し易くなる。Ｎａ２Ｏの好適な下限範囲は４．６％以上、４．６％超、４．９％以上、５％以上、特に５．５％以上であり、ＣＩＧＳ結晶の成長を優先する場合、６％以上、７％以上、９％以上、１０％以上、特に１１．５％超であり、好適な上限範囲は２３％以下、２２％以下、２０％以下、１８％以下、特に１５％以下、歪点の維持を優先する場合、１３％以下、特に１１％以下である。 Na 2 O is a component that can adjust the thermal expansion coefficient, and is a component that lowers the high-temperature viscosity and improves the meltability and moldability. Na 2 O is an effective component for the growth of CIGS crystals in CIGS solar cells, and is an important component for increasing the photoelectric conversion efficiency. Therefore, the content of Na 2 O is 4.4 to 30%. When the content of Na 2 O is too large, or too low the strain point, the thermal expansion coefficient becomes unduly increased, thermal shock resistance tends to decrease. As a result, in the film forming process, the glass plate is likely to undergo thermal contraction or thermal deformation, or cracks are likely to occur. In addition, undue stress is likely to occur on the solar cell film. A preferable lower limit range of Na 2 O is 4.6% or more, more than 4.6%, 4.9% or more, 5% or more, particularly 5.5% or more. When priority is given to the growth of CIGS crystal, 6 % Or more, 7% or more, 9% or more, 10% or more, particularly more than 11.5%, and a preferable upper limit range is 23% or less, 22% or less, 20% or less, 18% or less, particularly 15% or less, When priority is given to maintaining the strain point, it is 13% or less, particularly 11% or less.

Ｋ２Ｏは、熱膨張係数を調整し得る成分であり、また高温粘度を低下させて、溶融性や成形性を高める成分である。その一方で、Ｋ２Ｏの導入量は、カリウムイオンの拡散がナトリウムイオンの拡散と競合するため、ある程度規制される。また、Ａｌ２Ｏ３を多く含むガラス系において、Ｋ２Ｏの含有量が多過ぎると、カリウム長石族の失透が形成され易くなる。更に、Ｋ２Ｏの含有量が多過ぎると、ＣＩＧＳ膜へのナトリウムイオンの拡散量が減少して、高品位のＣＩＧＳ膜を形成し難くなったり、原料コストが高騰し易くなる。更に、Ｋ２Ｏの含有量が多過ぎると、熱膨張係数が不当に高くなって、耐熱衝撃性が低下し易くなる。結果として、成膜工程で、ガラス板に熱収縮や熱変形が生じたり、割れが発生し易くなる。よって、Ｋ２Ｏの含有量は０〜２０％であり、好適な下限範囲は０．４５％以上、０．５％以上、１％以上、１．３４％以上、特に１．４％以上であり、高温粘度の低下を優先する場合、２％以上、３．３９％以上、特に４．５％以上であり、好適な上限範囲は１０％以下、８％以下、７％以下、６％以下、特に５％以下であり、耐失透性の向上やナトリウムイオンの拡散性を優先する場合、４％以下、４％未満、特に１．５％以下である。 K 2 O is a component that can adjust the thermal expansion coefficient, and is a component that lowers the high-temperature viscosity and improves the meltability and moldability. On the other hand, the amount of K 2 O introduced is regulated to some extent because the diffusion of potassium ions competes with the diffusion of sodium ions. Further, in a glass system containing a large amount of Al 2 O 3 , when the content of K 2 O is too large, devitrification of the potassium feldspar group is likely to be formed. Furthermore, when the content of K 2 O is too large, the amount of sodium ions diffused into the CIGS film decreases, making it difficult to form a high-quality CIGS film and increasing the raw material cost. Further, when the content of K 2 O is too large, the thermal expansion coefficient becomes unduly high, the thermal shock resistance tends to decrease. As a result, in the film forming process, the glass plate is likely to undergo thermal contraction or thermal deformation, or cracks are likely to occur. Therefore, the content of K 2 O is 0 to 20%, and a preferable lower limit range is 0.45% or more, 0.5% or more, 1% or more, 1.34% or more, particularly 1.4% or more. Yes, when priority is given to lowering the high temperature viscosity, it is 2% or more, 3.39% or more, particularly 4.5% or more, and the preferred upper limit range is 10% or less, 8% or less, 7% or less, 6% or less When the priority is given to improving devitrification resistance and sodium ion diffusivity, it is 4% or less, less than 4%, particularly 1.5% or less.

ＳｉＯ２＋Ａｌ２Ｏ３＋ＭｇＯ＋ＣａＯ＋Ｎａ２Ｏ＋Ｋ２Ｏは、ガラス組成中の主要成分の合量である。ＳｉＯ２＋Ａｌ２Ｏ３＋ＭｇＯ＋ＣａＯ＋Ｎａ２Ｏ＋Ｋ２Ｏの含有量が少な過ぎると、高価な成分を導入する必要があり、原料コストが高騰する虞がある。よって、ＳｉＯ２＋Ａｌ２Ｏ３＋ＭｇＯ＋ＣａＯ＋Ｎａ２Ｏ＋Ｋ２Ｏの好適な範囲は８５％以上である。好ましい下限範囲は９０％以上、９２％以上、９５％以上、特に９８％以上である。一方、清澄剤、着色剤を導入したり、不純物を含む原料を使用する場合、ＳｉＯ２＋Ａｌ２Ｏ３＋ＭｇＯ＋ＣａＯ＋Ｎａ２Ｏ＋Ｋ２Ｏの上限含有量が制限される。好適な上限範囲は９９．９５％以下、９９．９％以下、特に９９．８％以下である。 SiO 2 + Al 2 O 3 + MgO + CaO + Na 2 O + K 2 O is the total amount of main components in the glass composition. When the content of SiO 2 + Al 2 O 3 + MgO + CaO + Na 2 O + K 2 O is too small, it is necessary to introduce an expensive component, there is a concern that the raw material cost is high. Therefore, a suitable range of SiO 2 + Al 2 O 3 + MgO + CaO + Na 2 O + K 2 O is 85% or more. A preferable lower limit range is 90% or more, 92% or more, 95% or more, and particularly 98% or more. On the other hand, when a refining agent and a colorant are introduced or a raw material containing impurities is used, the upper limit content of SiO 2 + Al 2 O 3 + MgO + CaO + Na 2 O + K 2 O is limited. A preferable upper limit range is 99.95% or less, 99.9% or less, and particularly 99.8% or less.

ＭｇＯとＣａＯは、アルカリ土類金属酸化物の中では、高温粘度を低下させることにより、ガラス溶解窯内の上昇流、下降流、バッチ投入口方向への後退流の移動速度を高めて、溶融ガラスを均質化させる成分である。また、ＭｇＯ＋ＣａＯは、アルカリ土類金属酸化物の中では、ガラスの割れ難さを最も維持させると共に、密度を最も低下させる２成分の総和である。ＭｇＯ＋ＣａＯの含有量が多過ぎると、耐失透性が低下し易くなる。一方、ＭｇＯ＋ＣａＯの含有量が少な過ぎると、ガラス溶解窯内で溶融ガラスの移動速度が低下して、溶融ガラスが均質化されず、結果として、溶融性や成形性が低下する傾向がある。よって、ＭｇＯ＋ＣａＯの含有量は０〜４０％である。好適な下限は１％以上、２％以上、２％超、３％以上、４．２％以上、特に４．５％以上であり、溶融ガラスの均質化を優先する場合、５％以上、特に６％以上であり、好適な下限は１２％以下、１０％以下、９％以下、８％以下、特に８％未満であり、耐失透性の向上を優先する場合、５．４％以下、特に５％以下である。なお、「ＭｇＯ＋ＣａＯ」は、ＭｇＯとＣａＯの合量である。   Among alkaline earth metal oxides, MgO and CaO are melted by reducing the high-temperature viscosity, thereby increasing the moving speed of the upward flow, downward flow, and backward flow in the batch inlet direction in the glass melting furnace. It is a component that homogenizes glass. Further, MgO + CaO is the total of two components that most maintain the difficulty of breaking the glass and reduce the density most among the alkaline earth metal oxides. When there is too much content of MgO + CaO, devitrification resistance will fall easily. On the other hand, when there is too little content of MgO + CaO, the moving speed of a molten glass will fall in a glass melting furnace, a molten glass will not be homogenized, and there exists a tendency for a meltability and a moldability to fall as a result. Therefore, the content of MgO + CaO is 0 to 40%. The preferred lower limit is 1% or more, 2% or more, more than 2%, 3% or more, 4.2% or more, particularly 4.5% or more. When priority is given to homogenization of molten glass, 5% or more, especially 6% or more, and the preferred lower limit is 12% or less, 10% or less, 9% or less, 8% or less, particularly less than 8%. When priority is given to improving devitrification resistance, 5.4% or less, In particular, it is 5% or less. “MgO + CaO” is the total amount of MgO and CaO.

Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏは、アルカリ金属酸化物の総量である。Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏの含有量が多過ぎると、熱膨張係数が高くなり過ぎて、耐熱衝撃性が低下し易くなる。結果として、成膜工程で、ガラス板に熱収縮や熱変形が生じたり、割れが発生し易くなる。一方、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏの含有量が少な過ぎると、熱膨張係数が低くなり、光電変換膜との熱膨張係数の不一致により膜剥がれが発生し易くなる。また、光電変換効率を高める効果を享受し難くなる。よって、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏの含有量は５．２〜４０％が好ましい。好適な下限範囲は５．５％以上、６％以上、８％以上、特に１０％以上であり、好適な上限範囲は３０％以下、２５％以下、２２％以下、２０％以下、１７％以下、特に１５％以下である。なお、「Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ」は、Ｌｉ２Ｏ、Ｎａ２Ｏ及びＫ２Ｏの合量である。 Li 2 O + Na 2 O + K 2 O is the total amount of alkali metal oxides. When the content of Li 2 O + Na 2 O + K 2 O is too large, the thermal expansion coefficient becomes too high, the thermal shock resistance tends to decrease. As a result, in the film forming process, the glass plate is likely to undergo thermal contraction or thermal deformation, or cracks are likely to occur. On the other hand, when the content of Li 2 O + Na 2 O + K 2 O is too small, the thermal expansion coefficient is lowered, film peeling tends to occur due to discrepancies between the thermal expansion coefficients of the photoelectric conversion layer. Moreover, it becomes difficult to enjoy the effect of increasing the photoelectric conversion efficiency. Therefore, the content of Li 2 O + Na 2 O + K 2 O is preferably 5.2 to 40%. The preferred lower limit range is 5.5% or more, 6% or more, 8% or more, particularly 10% or more, and the preferred upper limit range is 30% or less, 25% or less, 22% or less, 20% or less, 17% or less. In particular, it is 15% or less. “Li 2 O + Na 2 O + K 2 O” is the total amount of Li 2 O, Na 2 O and K 2 O.

Ｎａ２Ｏ／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）は、ガラスネットワークを修飾する成分の合量に対するＮａ２Ｏの比率である。Ｎａ２Ｏ／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）が少ないと、ナトリウムイオンが少なくなること、ナトリウムイオンの拡散を抑制するアルカリ土類が多くなること、或いはナトリウムイオンの拡散と競合するアルカリイオンが多くなることにより、ＣＩＧＳ膜へ拡散するナトリウムイオンが少なくなる。結果として、太陽電池の高効率化を達成し難くなる。一方、Ｎａ２Ｏ／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）が大きいと、ガラスネットワークを修飾する成分の内、Ｎａ２Ｏの割合が高くなり過ぎて、耐候性が低下する虞がある。また、ガラス表面へアルカリ塩が偏析して、均質なＣＩＧＳ膜を成膜し難くなったり、歪点が低くなり過ぎて、ナトリウムイオンがＣＩＧＳ膜に過剰に供給されて、太陽電池の光電変換効率が低下する虞がある。よって、質量比Ｎａ２Ｏ／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）は０．３〜１．０が好ましい。好適な下限範囲は０．４６以上、０．４７以上、０．４９以上、０．４９５以上、０．５０以上、０．５１以上、０．５２以上、０．５３以上、０．５４以上、特に０．５５以上であり、好適な下限範囲は０．８２以下、０．８１以下、０．８０以下、０．７９以下、０．７８以下、０．７５以下、０．７０以下、０．６５以下、０．６０以下、特に０．５８以下である。 Na 2 O / (MgO + CaO + SrO + BaO + Li 2 O + Na 2 O + K 2 O) is the ratio of Na 2 O to the total amount of components that modify the glass network. Na When 2 O / (MgO + CaO + SrO + BaO + Li 2 O + Na 2 O + K 2 O) is less, the sodium ion is reduced, it becomes large to suppress the alkaline earth diffusion of sodium ions, or alkali ions to compete with the diffusion of sodium ions Increasing the number reduces sodium ions diffusing into the CIGS film. As a result, it becomes difficult to achieve high efficiency of the solar cell. On the other hand, if Na 2 O / (MgO + CaO + SrO + BaO + Li 2 O + Na 2 O + K 2 O) is large, the proportion of Na 2 O among the components that modify the glass network becomes too high, and the weather resistance may be lowered. Also, alkali salts segregate on the glass surface, making it difficult to form a homogeneous CIGS film, or the strain point becomes too low, so that sodium ions are excessively supplied to the CIGS film, and the photoelectric conversion efficiency of the solar cell May decrease. Therefore, the mass ratio Na 2 O / (MgO + CaO + SrO + BaO + Li 2 O + Na 2 O + K 2 O) is preferably 0.3 to 1.0. Suitable lower limit ranges are 0.46 or more, 0.47 or more, 0.49 or more, 0.495 or more, 0.50 or more, 0.51 or more, 0.52 or more, 0.53 or more, 0.54 or more, Particularly, it is 0.55 or more, and preferable lower limit ranges are 0.82 or less, 0.81 or less, 0.80 or less, 0.79 or less, 0.78 or less, 0.75 or less, 0.70 or less, 0. 65 or less, 0.60 or less, particularly 0.58 or less.

Ｎａ２Ｏ／（Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）は、一価のカチオンであるアルカリイオンが拡散する際に、ナトリウムイオンが拡散する優先度合いを示している。Ｎａ２Ｏ／（Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）が少ないと、ＣＩＧＳ膜へ拡散するアルカリイオンの内、ナトリウムイオンの割合が少ないことを示し、太陽電池の高効率化を達成し難くなる。よって、質量比Ｎａ２Ｏ／（Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）は０．１〜１．０が好ましい。好適な下限範囲は０．５以上、０．６以上、０．７以上、特に０．７５以上であり、好適な上限範囲は０．９５以下、０．９以下、０．８５以下、特に０．８以下である。なお、「Ｎａ２Ｏ／（Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）」は、Ｎａ２Ｏの含有量をＬｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏの含有量で割った値である。 Na 2 O / (Li 2 O + Na 2 O + K 2 O) indicates a priority level in which sodium ions diffuse when alkali ions that are monovalent cations diffuse. When Na 2 O / (Li 2 O + Na 2 O + K 2 O) is small, among the alkali ions diffusing into the CIGS film, it indicates that the proportion of sodium ions is small, it becomes difficult to achieve high efficiency of solar cells. Therefore, the mass ratio Na 2 O / (Li 2 O + Na 2 O + K 2 O) is preferably 0.1 to 1.0. The preferred lower limit range is 0.5 or more, 0.6 or more, 0.7 or more, particularly 0.75 or more, and the preferred upper limit range is 0.95 or less, 0.9 or less, 0.85 or less, especially 0. .8 or less. “Na 2 O / (Li 2 O + Na 2 O + K 2 O)” is a value obtained by dividing the content of Na 2 O by the content of Li 2 O + Na 2 O + K 2 O.

ＺｒＯ２は、高温粘度を上げずに、歪点を高める成分である。しかし、ＺｒＯ２の含有量が多過ぎると、密度や原料コストが高くなり易く、またガラスが割れ易くなり、更にはＺｒＯ２系の失透結晶が析出し易くなり、ガラス板に成形し難くなる。よって、ＺｒＯ２は任意成分であり、好適な上限範囲は５％以下、５％未満、４．５％以下、３％以下、３％未満、１．９５％以下、１．９％以下、１．８％以下、１％以下、特に０．５％以下が好ましい。 ZrO 2 is a component that increases the strain point without increasing the high-temperature viscosity. However, if the content of ZrO 2 is too large, the density and raw material cost are likely to be high, the glass is liable to be broken, and further, ZrO 2 -based devitrified crystals are liable to precipitate, making it difficult to form a glass plate. . Therefore, ZrO 2 is an optional component, and the preferred upper limit range is 5% or less, less than 5%, 4.5% or less, 3% or less, less than 3%, 1.95% or less, 1.9% or less, 1% or less, 0.8% or less, 1% or less, and particularly preferably 0.5% or less.

上記成分以外にも、例えば、以下の成分を導入してもよい。   In addition to the above components, for example, the following components may be introduced.

ガラス中のＦｅはＦｅ２＋又はＦｅ３＋の状態で存在するが、特にＦｅ２＋は近赤外領域に強い光吸収特性を有する。このため、Ｆｅ２＋は、大容量のガラス溶解窯において、ガラス溶解窯内の輻射エネルギーを吸収し易く、溶融効率を高める効果を有する。また、Ｆｅ３＋は、鉄の価数変化の際に酸素を放出するため、清澄効果も有する。 Fe in the glass exists in the state of Fe 2+ or Fe 3+ , and especially Fe 2+ has strong light absorption characteristics in the near infrared region. For this reason, Fe <2+> has the effect of being easy to absorb the radiant energy in a glass melting furnace, and improving a melting efficiency in a large capacity | capacitance glass melting furnace. Fe 3+ also has a clarification effect because it releases oxygen when the valence of iron changes.

ガラス板の製造コストを低廉化するために、高純度原料（Ｆｅ２Ｏ３の含有量が極めて少ない原料）の使用を制限して、少量のＦｅ２Ｏ３を含む原料を使用することが好ましい。一方、Ｆｅ２Ｏ３の含有量が多過ぎると、太陽光を吸収し易くなるため、太陽電池の表面温度が上昇し易くなり、結果として、太陽電池の光電変換効率が低下する虞がある。また、Ｆｅ２Ｏ３の含有量が多過ぎると、窯の輻射エネルギーが、エネルギー源の近傍で吸収されて、窯の中央部に到達せず、ガラス溶解窯の熱分布にムラが生じ易くなる。よって、Ｆｅ２Ｏ３の含有量は０〜１％、特に０．０１〜１％が好ましい。また、Ｆｅ２Ｏ３の好適な下限範囲は０．０２％超、０．０３％超、特に０．０５％超である。なお、本発明では、酸化鉄は、Ｆｅの価数に係らず、「Ｆｅ２Ｏ３」に換算して表記するものとする。 In order to reduce the manufacturing cost of the glass plate, it is preferable to use a raw material containing a small amount of Fe 2 O 3 by restricting the use of a high-purity raw material (a raw material having a very low content of Fe 2 O 3 ). . On the other hand, when the content of Fe 2 O 3 is too large, it is easy to absorb sunlight, so that the surface temperature of the solar cell is likely to rise, and as a result, the photoelectric conversion efficiency of the solar cell may be reduced. Further, when the content of Fe 2 O 3 is too large, the radiation energy of the kilns, are absorbed in the vicinity of the energy source, does not reach the central portion of the furnace, it tends to occur unevenness in the heat distribution of the glass melting furnace . Therefore, the content of Fe 2 O 3 is preferably 0 to 1%, particularly preferably 0.01 to 1%. Further, the preferable lower limit range of Fe 2 O 3 is more than 0.02%, more than 0.03%, particularly more than 0.05%. In the present invention, iron oxide is expressed in terms of “Fe 2 O 3 ” regardless of the valence of Fe.

ＴｉＯ２は、紫外線による着色を防止すると共に、耐候性を高める成分である。しかし、ＴｉＯ２の含有量が多過ぎると、ガラスが失透したり、ガラスが茶褐色に着色したり、原料コストが高騰し易くなる。よって、ＴｉＯ２の含有量は０〜１０％、特に０〜０．１％未満が好ましい。 TiO 2 is a component that prevents coloring by ultraviolet rays and enhances weather resistance. However, if the content of TiO 2 is too large, the glass is devitrified, the glass is colored brown, or the raw material cost is likely to increase. Therefore, the content of TiO 2 is preferably 0 to 10%, particularly preferably less than 0 to 0.1%.

Ｐ２Ｏ５は、耐失透性を高める成分、特にＺｒＯ２系の失透結晶の析出を抑制する成分であり、またガラスを割れ難くする成分である。しかし、Ｐ２Ｏ５の含有量が多過ぎると、ガラスが乳白色に分相し易くなり、また原料コストが高騰し易くなる。よって、Ｐ２Ｏ５の含有量は０〜１０％、０〜０．２％、特に０〜０．１％未満が好ましい。 P 2 O 5 is a component that enhances devitrification resistance, particularly a component that suppresses precipitation of ZrO 2 -based devitrification crystals, and is a component that makes glass difficult to break. However, when the content of P 2 O 5 is too large, the glass tends to undergo phase separation milky, also raw material cost tends to rise. Therefore, the content of P 2 O 5 is preferably 0 to 10%, 0 to 0.2%, particularly preferably less than 0 to 0.1%.

ＺｎＯは、高温粘度を低下させる成分である。ＺｎＯの含有量が多過ぎると、耐失透性が低下し易くなり、原料コストが高騰し易くなる。よって、ＺｎＯの含有量は０〜１０％、０〜５％、０〜１％、０〜０．１％が好ましい。   ZnO is a component that lowers the high temperature viscosity. When there is too much content of ZnO, devitrification resistance will fall easily and raw material cost will rise easily. Therefore, the content of ZnO is preferably 0 to 10%, 0 to 5%, 0 to 1%, or 0 to 0.1%.

ＳＯ３は、清澄剤として作用する成分であり、その含有量は０〜１％、特に０．０１〜０．３％が好ましい。なお、フロート法で成形すると、大量のガラス板を安価に作製し得るが、この場合、清澄剤として芒硝を用いることが好ましい。 SO 3 is a component that acts as a fining agent, and its content is preferably 0 to 1%, particularly preferably 0.01 to 0.3%. In addition, when it shape | molds by a float glass process, a large amount of glass plates can be produced cheaply, but in this case, it is preferable to use mirabilite as a clarifier.

Ｃｌは、清澄剤として作用する成分であり、その含有量は０〜０．５％、０．０１〜０．１％、特に０．００１〜０．０６％が好ましい。また、Ｃｌは、アルカリ塩として導入することが好ましい。   Cl is a component that acts as a fining agent, and its content is preferably 0 to 0.5%, 0.01 to 0.1%, particularly preferably 0.001 to 0.06%. Further, Cl is preferably introduced as an alkali salt.

Ｓｂ２Ｏ３は、清澄剤として作用する成分であるが、フロート法でガラス板を成形する場合、ガラスを着色させる成分であり、また環境的負荷が懸念される成分である。よって、Ｓｂ２Ｏ３の含有量は０〜１％、特に０〜０．１％未満が好ましい。 Sb 2 O 3 is a component that acts as a fining agent. However, when a glass plate is formed by the float process, Sb 2 O 3 is a component that colors the glass and is a component that is concerned about the environmental burden. Therefore, the content of Sb 2 O 3 is preferably 0 to 1%, particularly preferably less than 0 to 0.1%.

Ａｓ２Ｏ３は、清澄剤として作用する成分であるが、フロート法でガラス板を成形する場合、ガラスを着色させる成分であり、また環境的負荷が懸念される成分である。よって、Ａｓ２Ｏ３の含有量は０〜１％、特に０〜０．１％未満が好ましい。 As 2 O 3 is a component that acts as a fining agent. However, when a glass plate is formed by the float process, it is a component that colors the glass and is a component that is concerned about the environmental burden. Therefore, the content of As 2 O 3 is preferably 0 to 1%, particularly preferably less than 0 to 0.1%.

ＳｎＯ２は、清澄剤として作用する成分であるが、耐失透性を低下させる成分である。但し、ダウンドロー法による成形ではＳｎＯ２を清澄剤とすることが好ましい。よって、ＳｎＯ２の含有量は０〜１％、特に０〜０．３％未満が好ましい。 SnO 2 is a component that acts as a fining agent, but is a component that reduces devitrification resistance. However, it is preferable to use SnO 2 as a clarifier in molding by the downdraw method. Therefore, the SnO 2 content is preferably 0 to 1%, particularly preferably less than 0 to 0.3%.

上記成分以外にも、溶解性、清澄性、成形性を高めるために、Ｆ、ＣｅＯ２を各々１％、好ましくは０．５％まで添加してもよい。また、化学的耐久性を高めるために、Ｎｂ２Ｏ５、ＨｆＯ２、Ｔａ２Ｏ５、Ｙ２Ｏ３、Ｌａ２Ｏ３を各々３％、好ましくは１％まで添加してもよい。更に、色調の調整のために、上記以外の希土類酸化物、遷移金属酸化物を合量で２％、好ましくは１％まで添加してもよい。 In addition to the above components, F and CeO 2 may be added to 1%, preferably 0.5%, respectively, in order to improve solubility, clarity, and moldability. Further, in order to increase chemical durability, Nb 2 O 5 , HfO 2 , Ta 2 O 5 , Y 2 O 3 , and La 2 O 3 may each be added to 3%, preferably up to 1%. Furthermore, in order to adjust the color tone, a rare earth oxide and a transition metal oxide other than those described above may be added in a total amount of 2%, preferably 1%.

本発明の太陽電池用ガラス板は、以下の特性を有することが好ましい。   The solar cell glass plate of the present invention preferably has the following characteristics.

熱膨張係数は８０×１０−７〜１１０×１０−７／℃が好ましい。熱膨張係数の好適な下限範囲は８３×１０−７／℃以上、８５×１０−７／℃以上、９０×１０−７／℃以上、特に９５×１０−７／℃以上であり、好適な上限範囲は１０５×１０−７／℃以下、１０３×１０−７／℃以下、１００×１０−７／℃以下、特に９５×１０−７／℃以下である。このようにすれば、ＣＩＧＳ系太陽電池の電極膜、ＣＩＧＳ膜等の周辺部材の熱膨張係数に整合させ易くなる。なお、熱膨張係数が高過ぎると、耐熱衝撃性が低下し易くなり、結果として、成膜工程でガラス板に割れが発生し易くなる。 The thermal expansion coefficient is preferably 80 × 10 −7 to 110 × 10 −7 / ° C. The preferred lower limit range of the coefficient of thermal expansion is 83 × 10 −7 / ° C. or higher, 85 × 10 −7 / ° C. or higher, 90 × 10 −7 / ° C. or higher, particularly 95 × 10 −7 / ° C. or higher. The upper limit ranges are 105 × 10 −7 / ° C. or lower, 103 × 10 −7 / ° C. or lower, 100 × 10 −7 / ° C. or lower, particularly 95 × 10 −7 / ° C. or lower. If it does in this way, it will become easy to match with the thermal expansion coefficient of peripheral members, such as an electrode film of a CIGS type solar cell, and a CIGS film. If the thermal expansion coefficient is too high, the thermal shock resistance tends to decrease, and as a result, the glass plate is likely to be cracked in the film forming process.

密度は２．７５ｇ／ｃｍ３以下、２．６ｇ／ｃｍ３以下、２．５５ｇ／ｃｍ３以下、特に２．５０ｇ／ｃｍ３以下が好ましい。このようにすれば、太陽電池の支持部材のコストを低廉化し易くなる。なお、「密度」は、周知のアルキメデス法で測定可能である。 Density 2.75 g / cm 3 or less, 2.6 g / cm 3 or less, 2.55 g / cm 3 or less, particularly preferably 2.50 g / cm 3 or less. If it does in this way, it will become easy to reduce the cost of the support member of a solar cell. The “density” can be measured by a known Archimedes method.

歪点は４７５℃〜５７０℃が好ましい。歪点の好適な下限範囲は５１０℃超、５１５℃以上、５２０℃以上、特に５２５℃以上であり、好適な上限範囲は５６０℃以下、５５０℃以下、５４０℃以下、５３５℃以下、特に５３０℃以下である。このようにすれば、ＣＩＧＳ膜の成膜温度を低下させた場合に、アルカリイオンの拡散を適正化し易くなる。また膜構成成分の拡散が抑制されるため、バンドギャップの最適化が達成し易くなる。結果として、太陽電池の光電変換効率を十分に高めることが可能になる。   The strain point is preferably 475 ° C to 570 ° C. The preferred lower limit range of the strain point is over 510 ° C, 515 ° C or more, 520 ° C or more, particularly 525 ° C or more, and the preferred upper limit range is 560 ° C or less, 550 ° C or less, 540 ° C or less, 535 ° C or less, particularly 530 ° C. It is below ℃. In this way, when the film formation temperature of the CIGS film is lowered, it becomes easy to optimize the diffusion of alkali ions. In addition, since the diffusion of the film constituents is suppressed, the band gap can be easily optimized. As a result, the photoelectric conversion efficiency of the solar cell can be sufficiently increased.

１０４．０ｄＰａ・ｓにおける温度は１２３０℃以下、１２００℃以下、１１８０℃以下、特に１１５０℃以下が好ましい。このようにすれば、低温でガラス板を成形し易くなる。 The temperature at 10 4.0 dPa · s is preferably 1230 ° C. or lower, 1200 ° C. or lower, 1180 ° C. or lower, particularly 1150 ° C. or lower. If it does in this way, it will become easy to shape | mold a glass plate at low temperature.

１０２．５ｄＰａ・ｓにおける温度は１６００℃以下、１５５０℃以下、特に１５００℃以下が好ましい。このようにすれば、低温でガラス原料を溶解し易くなる。 The temperature at 10 2.5 dPa · s is preferably 1600 ° C. or lower, 1550 ° C. or lower, and particularly preferably 1500 ° C. or lower. If it does in this way, it will become easy to melt | dissolve a glass raw material at low temperature.

液相温度は１２００℃以下、１１００℃以下、１０５０℃以下、特に１０００℃以下が好ましい。液相温度が高くなると、成形時にガラスが失透し易くなり、成形性が低下し易くなる。   The liquidus temperature is preferably 1200 ° C. or lower, 1100 ° C. or lower, 1050 ° C. or lower, particularly 1000 ° C. or lower. When the liquidus temperature becomes high, the glass tends to be devitrified at the time of molding, and the moldability tends to be lowered.

液相粘度は１０３．７ｄＰａ・ｓ以上、１０４．０ｄＰａ・ｓ以上、１０４．３ｄＰａ・ｓ以上、１０４．５ｄＰａ・ｓ以上、１０４．７ｄＰａ・ｓ以上、特に１０５．０ｄＰa・以上が好ましい。液相粘度が低くなると、成形時にガラスが失透し易くなり、成形性が低下し易くなる。 The liquid phase viscosity is 10 3.7 dPa · s or more, 10 4.0 dPa · s or more, 10 4.3 dPa · s or more, 10 4.5 dPa · s or more, particularly 10 4.7 dPa · s or more, 10 5.0 dPa · or more is preferable. When the liquid phase viscosity is low, the glass is easily devitrified during molding, and the moldability is likely to be lowered.

ナトリウム溶出量は０．３ｍｇ以下が好ましい。ナトリウム溶出量の好適な上限範囲は０．２５ｍｇ以下、０．２０ｍｇ以下、特に０．１５ｍｇ以下である。このようにすれば、大気中の水分や炭酸ガスとガラス中のアルカリ成分との反応性が低下するため、ガラス表面に形成されるアルカリ塩の偏析を抑制することができる。結果として、ＣＩＧＳ膜等の太陽電池膜の均質性や耐剥離性が改善されて、太陽電池の光電変換効率を十分に高めることが可能になる。   The amount of sodium elution is preferably 0.3 mg or less. The preferable upper limit range of the amount of sodium elution is 0.25 mg or less, 0.20 mg or less, particularly 0.15 mg or less. In this way, the reactivity between the moisture and carbon dioxide in the atmosphere and the alkali component in the glass decreases, so that segregation of the alkali salt formed on the glass surface can be suppressed. As a result, the homogeneity and peel resistance of the solar cell film such as the CIGS film are improved, and the photoelectric conversion efficiency of the solar cell can be sufficiently increased.

本発明の太陽電池用ガラス板は、上記のガラス組成範囲になるように、調合済みのガラスバッチを連続溶融炉に投入し、加熱溶融した後、得られた溶融ガラスを脱泡した上で、成形装置に供給し、板状に成形、徐冷することにより、作製することができる。   The glass plate for a solar cell of the present invention is charged with the prepared glass batch in a continuous melting furnace so as to be in the above glass composition range, heated and melted, and after defoaming the obtained molten glass, It can be manufactured by supplying to a molding device, molding into a plate shape, and slow cooling.

ガラス板の成形方法としては、フロート法、スロットダウンドロー法、オーバーフローダウンドロー法、リドロー法等を例示し得るが、大量のガラス板を安価に作製したい場合、フロート法を採択することが好ましい。   Examples of the glass plate forming method include a float method, a slot down draw method, an overflow down draw method, a redraw method, and the like. However, when a large number of glass plates are desired to be manufactured at a low cost, it is preferable to adopt the float method.

本発明の太陽電池用ガラス板は、製造コストの観点から、イオン交換処理が行われていないことが好ましい。つまりイオン交換による表面圧縮応力層を有していないことが好ましい。このようにすれば、イオン交換処理が不要になるため、ガラス板の製造コストを低廉化し易くなる。また表面圧縮応力層の不存在により、ガラス板の切断加工、端面加工等の加工処理の効率も向上する。なお、成膜温度が高い場合、表面圧縮応力層が消失する虞があり、化学強化処理を行う実益が乏しくなる。   It is preferable that the ion exchange process is not performed for the glass plate for solar cells of this invention from a viewpoint of manufacturing cost. That is, it is preferable not to have a surface compressive stress layer by ion exchange. In this way, the ion exchange process is not necessary, and the manufacturing cost of the glass plate can be easily reduced. Further, due to the absence of the surface compressive stress layer, the efficiency of processing such as cutting and end face processing of the glass plate is improved. In addition, when the film forming temperature is high, the surface compressive stress layer may be lost, and the actual benefit of performing the chemical strengthening process becomes poor.

本発明の太陽電池用ガラスは、光電変換効率の観点から、イオン交換処理が行われていることが好ましい。つまりイオン交換による表面圧縮応力層を有することが好ましい。このようにすれば、イオン交換によりガラス表面のナトリウム濃度が減少するため、ガラス表面のナトリウム濃度が過剰である場合に、ＣＩＧＳ系太陽電池の光電変換効率を改善することができる（逆に言えば、ガラス表面のナトリウム濃度が過剰でない場合は、イオン交換による表面圧縮応力層を形成しないことが好ましい）。また、イオン交換によりガラス表面のナトリウム濃度を低減すると、太陽電池カバーガラスに用いる場合に、太陽電池モジュールに高電圧が印加された際に発生するＰＩＤ現象を緩和することができる。   The glass for solar cells of the present invention is preferably subjected to ion exchange treatment from the viewpoint of photoelectric conversion efficiency. That is, it is preferable to have a surface compressive stress layer by ion exchange. In this way, since the sodium concentration on the glass surface is reduced by ion exchange, when the sodium concentration on the glass surface is excessive, the photoelectric conversion efficiency of the CIGS solar cell can be improved (in other words, When the sodium concentration on the glass surface is not excessive, it is preferable not to form a surface compressive stress layer by ion exchange). Further, when the sodium concentration on the glass surface is reduced by ion exchange, the PID phenomenon that occurs when a high voltage is applied to the solar cell module can be mitigated when used for a solar cell cover glass.

圧縮応力層の圧縮応力値は２００ＭＰａ以上、３００ＭＰａ以上、４００ＭＰａ以上、６００ＭＰａ以上、特に８００ＭＰａ以上が好ましい。一方、ガラス表面に極端に大きな圧縮応力が形成されると、ガラス板に内在する引っ張り応力が極端に高くなり、ガラス板が自己破壊する虞がある。またイオン交換処理の前後でガラス板の寸法変化が大きくなる虞がある。よって、圧縮応力層の圧縮応力値は１２００ＭＰａ以下が好ましい。   The compressive stress value of the compressive stress layer is preferably 200 MPa or more, 300 MPa or more, 400 MPa or more, 600 MPa or more, and particularly preferably 800 MPa or more. On the other hand, when an extremely large compressive stress is formed on the glass surface, the tensile stress inherent in the glass plate becomes extremely high, and the glass plate may be self-destructed. Moreover, there is a possibility that the dimensional change of the glass plate becomes large before and after the ion exchange treatment. Therefore, the compressive stress value of the compressive stress layer is preferably 1200 MPa or less.

圧縮応力層の応力深さは１μｍ以上、５μｍ以上、１０μｍ以上、特に２０μｍ以上が好ましい。圧縮応力層の応力深さが大きい程、ガラス板に深い傷が付いても、ガラス板が割れ難くなると共に、機械的強度のばらつきが小さくなる。また、圧縮応力層の応力深さが大き過ぎると、ガラス板に内在する引っ張り応力が極端に高くなり、ガラス板が自己破壊する虞がある。更にガラス板の切断加工、端面加工等の加工処理の効率が低下し易くなる。よって、圧縮応力層の応力深さは６０μｍ以下が好ましい。   The stress depth of the compressive stress layer is preferably 1 μm or more, 5 μm or more, 10 μm or more, particularly 20 μm or more. The greater the stress depth of the compressive stress layer, the more difficult the glass plate is to be cracked and the less the variation in mechanical strength even if the glass plate is deeply damaged. Moreover, if the stress depth of the compressive stress layer is too large, the tensile stress inherent in the glass plate becomes extremely high, and the glass plate may be self-destructed. Further, the efficiency of processing such as cutting and end face processing of the glass plate is likely to decrease. Therefore, the stress depth of the compressive stress layer is preferably 60 μm or less.

以下、実施例に基づいて、本発明を詳細に説明する。なお、以下の実施例は単なる例示である。本発明は、以下の実施例に何ら限定されない。   Hereinafter, based on an Example, this invention is demonstrated in detail. The following examples are merely illustrative. The present invention is not limited to the following examples.

表１〜３は、本発明の実施例（試料Ｎｏ．１〜５７）及び比較例（試料Ｎｏ．５８）を示している。なお、試料Ｎｏ．５８は、特許文献２の試料Ｎｏ．２に相当している。   Tables 1 to 3 show examples (sample Nos. 1 to 57) and comparative examples (sample No. 58) of the present invention. Sample No. 58 is the sample No. 5 of Patent Document 2. It corresponds to 2.

次のようにして、試料Ｎｏ．１〜５８を作製した。まず表中のガラス組成になるように調合したガラスバッチを白金坩堝に入れて、１５５０℃の電気炉内で２時間溶融した。次に、得られた溶融ガラスをカーボン板上に流し出して、平板形状に成形した後、徐冷した。その後、各測定に応じて、所定の加工を行った。得られた各試料について、熱膨張係数α、密度ｄ、歪点Ｐｓ、徐冷点Ｔａ、軟化点Ｔｓ、１０４．０ｄＰａ・ｓにおける温度、１０３．０ｄＰａ・ｓにおける温度、１０２．５ｄＰａ・ｓにおける温度、液相温度ＴＬ、液相粘度ｌｏｇηＴＬ、ナトリウム溶出量、圧縮応力層の圧縮応力値ＣＳ、圧縮応力層の応力深さＤＯＬを評価した。これらの結果を表１〜３に示す。 Sample no. 1-58 were produced. First, a glass batch prepared so as to have the glass composition shown in the table was placed in a platinum crucible and melted in an electric furnace at 1550 ° C. for 2 hours. Next, the obtained molten glass was poured out on a carbon plate, formed into a flat plate shape, and then gradually cooled. Thereafter, predetermined processing was performed according to each measurement. For each sample obtained, the thermal expansion coefficient alpha, density d, strain point Ps, the annealing point Ta, the temperature at the softening point Ts, 10 4.0 dPa · s, the temperature at 10 3.0 dPa · s, 10 2 The temperature at 0.5 dPa · s, the liquidus temperature TL, the liquidus viscosity logη TL , the sodium elution amount, the compressive stress value CS of the compressive stress layer, and the stress depth DOL of the compressive stress layer were evaluated. These results are shown in Tables 1-3.

熱膨張係数αは、ディラトメーターにより３０〜３８０℃における平均熱膨張係数を測定した値である。なお、測定試料として、直径５．０ｍｍ、長さ２０ｍｍの円柱試料を用いた。   The thermal expansion coefficient α is a value obtained by measuring an average thermal expansion coefficient at 30 to 380 ° C. using a dilatometer. A cylindrical sample having a diameter of 5.0 mm and a length of 20 mm was used as a measurement sample.

密度ｄは、公知のアルキメデス法で測定した値である。   The density d is a value measured by a known Archimedes method.

歪点Ｐｓ、徐冷点Ｔａ、軟化点Ｔｓは、ＡＳＴＭ Ｃ３３６−７１に基づいて測定した値である。   The strain point Ps, the annealing point Ta, and the softening point Ts are values measured based on ASTM C336-71.

１０４．０ｄＰａ・ｓにおける温度、１０３．０ｄＰａ・ｓにおける温度及び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。なお、１０４．０ｄＰａ・ｓにおける温度は、成形温度に相当しており、１０２．５ｄＰａ・ｓにおける温度は、溶融温度に相当している。 The temperature at 10 4.0 dPa · s, the temperature at 10 3.0 dPa · s, and the temperature at 10 2.5 dPa · s are values measured by a platinum ball pulling method. The temperature at 10 4.0 dPa · s corresponds to the molding temperature, and the temperature at 10 2.5 dPa · s corresponds to the melting temperature.

液相温度ＴＬは、標準篩３０メッシュ（５００μｍ）を通過し、５０メッシュ（３００μｍ）に残るガラス粉末を白金ボートに入れた後、この白金ボートを温度勾配炉中に２４時間保持して、結晶が析出する温度を測定した値である。液相粘度ｌｏｇηＴＬは、液相温度ＴＬにおけるガラスの粘度を白金球引き上げ法で測定した値である。なお、液相温度が低い程、また液相粘度が高い程、耐失透性が向上し、成形時にガラス中に失透結晶が析出し難くなり、結果として、ガラス板を安価に作製し易くなる。 The liquid phase temperature TL passes through a standard sieve 30 mesh (500 μm), and after the glass powder remaining in 50 mesh (300 μm) is placed in a platinum boat, the platinum boat is held in a temperature gradient furnace for 24 hours to obtain a crystal It is the value which measured the temperature which deposits. The liquid phase viscosity logη TL is a value obtained by measuring the viscosity of the glass at the liquid phase temperature TL by a platinum ball pulling method. In addition, the lower the liquidus temperature and the higher the liquidus viscosity, the better the devitrification resistance, and it becomes difficult for the devitrified crystals to precipitate in the glass during molding. As a result, it is easy to produce a glass plate at a low cost. Become.

ナトリウムの溶出量は、ＪＩＳ Ｒ３５０２に記載の方法により測定した値であり、溶液中のＮａ２Ｏ濃度を原子吸光分析装置で測定し、そのＮａ２Ｏ濃度からナトリウムの溶出量を計算したものである。なお、ナトリウムの溶出量は、耐候性や耐水性の目安になる。ナトリウムの溶出量が多い場合、大気中の水分や炭酸ガスとガラス板のガラス成分が反応し易く、アルカリ塩がガラス表面に析出し易いと言える。 The elution amount of sodium is a value measured by the method described in JIS R3502, and the Na 2 O concentration in the solution is measured with an atomic absorption analyzer, and the elution amount of sodium is calculated from the Na 2 O concentration. is there. The elution amount of sodium is a measure of weather resistance and water resistance. When the amount of sodium elution is large, it can be said that moisture or carbon dioxide in the atmosphere easily reacts with the glass component of the glass plate, and the alkali salt easily precipitates on the glass surface.

次にようにして圧縮応力層の圧縮応力値ＣＳと圧縮応力層の応力深さＤＯＬを測定した。まず各試料の両表面に光学研磨を施した後、４３０℃のＫＮＯ３溶融塩中に４時間浸漬することにより、イオン交換処理を行った。次に、得られた試料の表面を洗浄した。続いて、表面応力計（株式会社東芝製ＦＳＭ−６０００）を用いて観察される干渉縞の本数とその間隔から圧縮応力層の圧縮応力値ＣＳと圧縮応力層の応力深さＤＯＬを算出した。算出に当たり、各試料の屈折率を１．５０、光学弾性定数を２９．５［（ｎｍ／ｃｍ）／ＭＰａ］とした。 Next, the compressive stress value CS of the compressive stress layer and the stress depth DOL of the compressive stress layer were measured as follows. First, both surfaces of each sample were subjected to optical polishing, and then ion exchange treatment was performed by immersing in KNO 3 molten salt at 430 ° C. for 4 hours. Next, the surface of the obtained sample was washed. Subsequently, the compressive stress value CS of the compressive stress layer and the stress depth DOL of the compressive stress layer were calculated from the number of interference fringes observed using a surface stress meter (FSM-6000 manufactured by Toshiba Corporation) and the interval therebetween. In the calculation, the refractive index of each sample was set to 1.50, and the optical elastic constant was set to 29.5 [(nm / cm) / MPa].

表１〜３から明らかなように、試料Ｎｏ．１〜５７は、ガラス組成が所定範囲に規制されているため、歪点が４７８〜５６８℃であり、ＣＩＧＳ膜の成膜温度を低下させた場合、アルカリイオンの拡散を適正化し易くなるものと考えられる。また、試料Ｎｏ．１〜５７は、熱膨張係数が８１×１０−７〜１０３×１０−７／℃であるため、ＣＩＧＳ系太陽電池の電極膜、ＣＩＧＳ膜の熱膨張係数に整合させ易い。更に、試料Ｎｏ．１〜５７は、１０４．０ｄＰａ・ｓにおける温度が１２２７℃以下、液相粘度が１０３．６ｄＰａ・ｓ以上であるため、ガラス板の生産性に優れている。また、ナトリウム溶出量が０．０４２〜０．２９ｍｇであるため、アルカリ塩がガラス表面に析出し難い。更に、圧縮応力層の圧縮応力値が２６０〜９５５ＭＰａ、圧縮応力層の応力深さが９〜３０μｍであるため、機械的強度が高いものと考えられる。 As is apparent from Tables 1 to 3, sample No. Nos. 1 to 57 have a strain point of 478 to 568 ° C. because the glass composition is regulated within a predetermined range. When the film formation temperature of the CIGS film is lowered, it becomes easy to optimize the diffusion of alkali ions. Conceivable. Sample No. Since 1 to 57 have a thermal expansion coefficient of 81 × 10 −7 to 103 × 10 −7 / ° C., it is easy to match the thermal expansion coefficient of the electrode film and CIGS film of the CIGS solar cell. Furthermore, sample no. Nos. 1 to 57 have excellent glass plate productivity because the temperature at 10 4.0 dPa · s is 1227 ° C. or lower and the liquid phase viscosity is 10 3.6 dPa · s or higher. Moreover, since the sodium elution amount is 0.042 to 0.29 mg, the alkali salt hardly deposits on the glass surface. Furthermore, since the compressive stress value of the compressive stress layer is 260 to 955 MPa and the stress depth of the compressive stress layer is 9 to 30 μm, it is considered that the mechanical strength is high.

一方、試料Ｎｏ．５８は、歪点が高過ぎるため、ＣＩＧＳ膜中の深さ方向のバンドギャップ構造を最適化し難いものと考えられる。また、試料Ｎｏ．５８は、Ｎａ２Ｏの含有量が少なく、質量比Ｎａ２Ｏ／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）が低過ぎるため、ＣＩＧＳ膜へのナトリウムイオンの拡散量が少なく、高品位のＣＩＧＳ膜を形成し難いものと考えられる。 On the other hand, sample No. No. 58 is considered to be difficult to optimize the band gap structure in the depth direction in the CIGS film because the strain point is too high. Sample No. No. 58 has a low Na 2 O content and a mass ratio of Na 2 O / (MgO + CaO + SrO + BaO + Li 2 O + Na 2 O + K 2 O) is too low, so that the diffusion amount of sodium ions into the CIGS film is small, and a high-quality CIGS film is formed. It is considered difficult to form.

Claims (23)

ガラス組成として、質量％で、ＳｉＯ２ ５０〜８０％、Ａｌ２Ｏ３ ０〜３０％、Ｂ２Ｏ３ ０〜２０％、ＭｇＯ ０〜２０％、ＣａＯ ０〜２０％、Ｎａ２Ｏ ４．４〜３０％、Ｋ２Ｏ ０〜２０％、ＺｒＯ２ ０〜５％を含有することを特徴とする太陽電池用ガラス板。 As a glass composition, in mass%, SiO 2 50~80%, Al 2 O 3 0~30%, B 2 O 3 0~20%, 0~20% MgO, CaO 0~20%, Na 2 O 4. 4~30%, K 2 O 0~20% , a glass plate for a solar cell, characterized by containing ZrO 2 0 to 5%. 質量比Ｎａ２Ｏ／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）が０．３〜１．０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。 2. The glass plate for a solar cell according to claim 1, wherein the mass ratio Na 2 O / (MgO + CaO + SrO + BaO + Li 2 O + Na 2 O + K 2 O) is 0.3 to 1.0. ガラス組成として、質量％で、ＳｉＯ２ ５０〜８０％、Ａｌ２Ｏ３ ５〜１８％、Ｂ２Ｏ３ ０〜４％、ＭｇＯ ０〜３．４％、ＣａＯ ０〜２％未満、ＭｇＯ＋ＣａＯ ２〜５．４％、Ｌｉ２Ｏ ０〜２％、Ｎａ２Ｏ ４．６〜３０％、Ｋ２Ｏ ０〜４％未満、ＺｒＯ２ ０〜３％、ＳｉＯ２＋Ａｌ２Ｏ３＋ＭｇＯ＋ＣａＯ＋Ｎａ２Ｏ＋Ｋ２Ｏ ９０％以上を含有することを特徴とする請求項１又は２に記載の太陽電池用ガラス板。 As a glass composition, in mass%, SiO 2 50~80%, Al 2 O 3 5~18%, B 2 O 3 0~4%, MgO 0~3.4%, CaO less than 0~2%, MgO + CaO 2 ˜5.4%, Li 2 O 0-2%, Na 2 O 4.6-30%, K 2 O 0-4%, ZrO 2 0-3%, SiO 2 + Al 2 O 3 + MgO + CaO + Na 2 O + K 2 O The glass plate for solar cells of Claim 1 or 2 containing 90% or more. ガラス組成として、質量％で、ＳｉＯ２ ５０〜８０％、Ａｌ２Ｏ３ ０〜３０％、Ｂ２Ｏ３ ０〜３．５％、ＭｇＯ ３．４超〜２０％、ＣａＯ １．０超〜２０％、Ｎａ２Ｏ ５．５〜２３％、Ｋ２Ｏ １．４〜２０％、ＺｒＯ２ ０〜１．９％を含有し、質量比Ｎａ２Ｏ／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）が０．４７〜０．７９であることを特徴とする請求項１又は２に記載の太陽電池用ガラス板。 As a glass composition, in mass%, SiO 2 50~80%, Al 2 O 3 0~30%, B 2 O 3 0~3.5%, MgO 3.4 super to 20%, CaO 1.0 ultra- 20%, Na 2 O 5.5~23% , K 2 O 1.4~20%, containing ZrO 2 from 0 to 1.9%, the weight ratio Na 2 O / (MgO + CaO + SrO + BaO + Li 2 O + Na 2 O + K 2 O) The glass plate for solar cell according to claim 1 or 2, wherein is from 0.47 to 0.79. ガラス組成として、質量％で、ＳｉＯ２ ５０〜８０％、Ａｌ２Ｏ３ ３〜３０％、Ｂ２Ｏ３ ０〜１．５％未満、ＭｇＯ ３．４超〜２０％、ＣａＯ １．０超〜２０％、Ｎａ２Ｏ ４．４〜２３％、Ｋ２Ｏ ０．５〜２０％、ＺｒＯ２ ０〜１．９％を含有し、質量比Ｎａ２Ｏ／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）が０．４６〜０．８２であることを特徴とする請求項１又は２に記載の太陽電池用ガラス板。 As a glass composition, in mass%, SiO 2 50~80%, Al 2 O 3 3~30%, B 2 O 3 less than 0 to 1.5%, MgO 3.4 super to 20%, CaO 1.0 than ~20%, Na 2 O 4.4~23% , K 2 O 0.5~20%, containing ZrO 2 from 0 to 1.9%, the weight ratio Na 2 O / (MgO + CaO + SrO + BaO + Li 2 O + Na 2 O + K 2 O ) Is 0.46 to 0.82, The glass plate for a solar cell according to claim 1 or 2. ガラス組成として、質量％で、ＳｉＯ２ ５０〜８０％、Ａｌ２Ｏ３ １０〜３０％、Ｂ２Ｏ３ ０〜１０％、ＭｇＯ ３．３超〜２０％、ＣａＯ ０〜２０％、Ｎａ２Ｏ １１．５超〜３０％、Ｋ２Ｏ ０〜１．５％、ＺｒＯ２ ０〜３％未満を含有することを特徴とする請求項１又は２に記載の太陽電池用ガラス板。 As a glass composition, in mass%, SiO 2 50~80%, Al 2 O 3 10~30%, B 2 O 3 0~10%, MgO 3.3 super ~20%, CaO 0~20%, Na 2 O 11.5 super ~30%, K 2 O 0~1.5% , a glass plate for a solar cell according to claim 1 or 2, characterized in that it contains ZrO 2 less than 0-3%. ガラス組成として、質量％で、ＳｉＯ２ ５０〜８０％、Ａｌ２Ｏ３ ４．７超〜３０％、Ｂ２Ｏ３ ０〜３．５％、ＭｇＯ ４．０超〜２０％、ＣａＯ ０．３〜２０％、Ｎａ２Ｏ ４．９〜２３％、Ｋ２Ｏ １．４〜２０％、ＺｒＯ２ ０〜１．９％を含有し、質量比Ｎａ２Ｏ／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）が０．４６〜０．８０であることを特徴とする請求項１又は２に記載の太陽電池用ガラス板。 As a glass composition, in mass%, SiO 2 50~80%, Al 2 O 3 4.7 super ~30%, B 2 O 3 0~3.5 %, MgO 4.0 super to 20%, CaO 0. It contains 3 to 20%, Na 2 O 4.9 to 23%, K 2 O 1.4 to 20%, ZrO 2 0 to 1.9%, and a mass ratio of Na 2 O / (MgO + CaO + SrO + BaO + Li 2 O + Na 2 O + K 2). O) is 0.46-0.80, The glass plate for solar cells of Claim 1 or 2 characterized by the above-mentioned. ガラス組成として、質量％で、ＳｉＯ２ ５０〜８０％、Ａｌ２Ｏ３ ２．５〜３０％、Ｂ２Ｏ３ ０〜２０％、ＭｇＯ ３．１〜２０％、ＣａＯ １．０超〜２０％、Ｎａ２Ｏ ４．４〜２３％、Ｋ２Ｏ １〜２０％、ＺｒＯ２ ０〜１．９％を含有し、質量比Ｎａ２Ｏ／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）が０．４６〜０．８１であることを特徴とする請求項１又は２に記載の太陽電池用ガラス板。 As a glass composition, in mass%, SiO 2 50~80%, Al 2 O 3 2.5~30%, B 2 O 3 0~20%, MgO 3.1~20%, CaO 1.0 Ultra 20 %, Na 2 O 4.4-23%, K 2 O 1-20%, ZrO 2 0-1.9%, and a mass ratio of Na 2 O / (MgO + CaO + SrO + BaO + Li 2 O + Na 2 O + K 2 O) is 0. It is 46-0.81, The glass plate for solar cells of Claim 1 or 2 characterized by the above-mentioned. ガラス組成として、質量％で、ＳｉＯ２ ５０〜８０％、Ａｌ２Ｏ３ ３〜３０％、Ｂ２Ｏ３ ０〜３％、ＭｇＯ ３．２〜５．１％、ＣａＯ １．０超〜２０％、Ｎａ２Ｏ ６〜２３％、Ｋ２Ｏ ２〜２０％、ＺｒＯ２ ０〜５％未満を含有し、質量比Ｎａ２Ｏ／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）が０．４９〜０．７８であることを特徴とする請求項１又は２に記載の太陽電池用ガラス板。 As a glass composition, in mass%, SiO 2 50~80%, Al 2 O 3 3~30%, B 2 O 3 0~3%, MgO 3.2~5.1%, CaO 1.0 Ultra 20 %, Na 2 O 6-23%, K 2 O 2-20%, ZrO 2 less than 0-5%, and a mass ratio of Na 2 O / (MgO + CaO + SrO + BaO + Li 2 O + Na 2 O + K 2 O) is 0.49-0 The glass plate for a solar cell according to claim 1, wherein the glass plate is for solar cells. 歪点が５６０℃以下であることを特徴とする請求項１〜９の何れか一項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 9, wherein the strain point is 560 ° C or lower. ナトリウム溶出量が０．３ｍｇ以下であることを特徴とする請求項１〜１０の何れか一項に記載の太陽電池用ガラス板。   The amount of sodium elution is 0.3 mg or less, The glass plate for solar cells as described in any one of Claims 1-10 characterized by the above-mentioned. 熱膨張係数が８０〜１１０×１０−７／℃であることを特徴とする請求項１〜１１の何れか一項に記載の太陽電池用ガラス板。 The thermal expansion coefficient is 80 to 110 × 10 −7 / ° C., The solar cell glass plate according to claim 1. １０４．０ｄＰａ・ｓにおける温度が１２００℃未満であることを特徴とする請求項１〜１２の何れか一項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 12, wherein the temperature at 10 4.0 dPa · s is less than 1200 ° C. １０２．５ｄＰａ・ｓにおける温度が１６００℃未満であることを特徴とする請求項１〜１３の何れか一項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 13, wherein the temperature at 10 2.5 dPa · s is less than 1600 ° C. 液相粘度が１０３．７ｄＰａ・ｓ以上であることを特徴とする請求項１〜１４の何れか一項に記載の太陽電池用ガラス板。 Liquid phase viscosity is 10 3.7 dPa * s or more, The glass plate for solar cells as described in any one of Claims 1-14 characterized by the above-mentioned. イオン交換による表面圧縮応力層を有していないことを特徴とする請求項１〜１５の何れか一項に記載の太陽電池用ガラス板。   It has no surface compressive-stress layer by ion exchange, The glass plate for solar cells as described in any one of Claims 1-15 characterized by the above-mentioned. イオン交換による表面圧縮応力層を有していることを特徴とする請求項１〜１５の何れか一項に記載の太陽電池用ガラス板。   It has a surface compressive-stress layer by ion exchange, The glass plate for solar cells as described in any one of Claims 1-15 characterized by the above-mentioned. 圧縮応力層の圧縮応力値が２００〜１２００ＭＰａ、圧縮応力層の厚みが５〜６０μｍであることを特徴とする請求項１７に記載の太陽電池用ガラス板。   18. The solar cell glass plate according to claim 17, wherein the compressive stress layer has a compressive stress value of 200 to 1200 MPa, and the compressive stress layer has a thickness of 5 to 60 μm. カルコパイライト太陽電池の基材に用いることを特徴とする請求項１〜１８の何れか一項に記載の太陽電池用ガラス板。   It uses for the base material of a chalcopyrite solar cell, The glass plate for solar cells as described in any one of Claims 1-18 characterized by the above-mentioned. 薄膜太陽電池又は色素増感太陽電池の基材に用いることを特徴とする請求項１〜１８の何れか一項に記載の太陽電池用ガラス板。   It uses for the base material of a thin film solar cell or a dye-sensitized solar cell, The glass plate for solar cells as described in any one of Claims 1-18 characterized by the above-mentioned. 太陽電池のカバーガラスに用いることを特徴とする請求項１〜１８の何れか一項に記載の太陽電池用ガラス板。   It uses for the cover glass of a solar cell, The glass plate for solar cells as described in any one of Claims 1-18 characterized by the above-mentioned. ガラス組成として、質量％で、ＳｉＯ２ ５０〜８０％、Ａｌ２Ｏ３ ４．７超〜３０％、Ｂ２Ｏ３ ０〜１．５％未満、ＭｇＯ ３．４超〜２０％、ＣａＯ １．０超〜２０％、Ｎａ２Ｏ ５．６〜２３％、Ｋ２Ｏ １．４〜２０％、ＺｒＯ２ ０〜１．９％、ＺｎＯ ０〜５％を含有し、質量比Ｎａ２Ｏ／（Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ＋ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）が０．４９〜０．８０であることを特徴とするガラス板。 As a glass composition, in mass%, SiO 2 50~80%, Al 2 O 3 4.7 super ~30%, B 2 O 3 less than 0 to 1.5%, MgO 3.4 super to 20%, CaO 1 More than 0.0 to 20%, Na 2 O 5.6 to 23%, K 2 O 1.4 to 20%, ZrO 2 0 to 1.9%, ZnO 0 to 5%, and mass ratio Na 2 O / glass plate (Li 2 O + Na 2 O + K 2 O + MgO + CaO + SrO + BaO) is characterized in that it is a .49 to .80. ガラス組成として、質量％で、ＳｉＯ２ ５０〜８０％、Ａｌ２Ｏ３ ０〜３０％、Ｂ２Ｏ３ ０〜２０％、ＭｇＯ ０〜２０％、ＣａＯ ０〜２０％、Ｎａ２Ｏ ４．４〜３０％、Ｋ２Ｏ ０〜２０％、ＺｒＯ２ ０〜５％を含有することを特徴とするガラス。 As a glass composition, in mass%, SiO 2 50~80%, Al 2 O 3 0~30%, B 2 O 3 0~20%, 0~20% MgO, CaO 0~20%, Na 2 O 4. 4~30%, K 2 O 0~20% , glass, characterized in that it contains ZrO 2 0 to 5%.
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