JP5733811B2 - Manufacturing method of glass substrate for solar cell - Google Patents

Manufacturing method of glass substrate for solar cell Download PDF

Info

Publication number
JP5733811B2
JP5733811B2 JP2008323012A JP2008323012A JP5733811B2 JP 5733811 B2 JP5733811 B2 JP 5733811B2 JP 2008323012 A JP2008323012 A JP 2008323012A JP 2008323012 A JP2008323012 A JP 2008323012A JP 5733811 B2 JP5733811 B2 JP 5733811B2
Authority
JP
Japan
Prior art keywords
glass
glass substrate
solar cell
cao
mgo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
JP2008323012A
Other languages
Japanese (ja)
Other versions
JP2010143790A (en
Inventor
寛典 高瀬
寛典 高瀬
Original Assignee
日本電気硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Priority to JP2008323012A priority Critical patent/JP5733811B2/en
Publication of JP2010143790A publication Critical patent/JP2010143790A/en
Application granted granted Critical
Publication of JP5733811B2 publication Critical patent/JP5733811B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00Technologies relating to the processing of minerals
    • Y02P40/50Glass production, e.g. reusing waste heat during processing or shaping

Description

  The present invention relates to a method for producing a solar cell glass substrate, and more specifically to a method for producing a solar cell glass substrate capable of recycling waste glass.

  In recent years, the demand for solar cells has increased from an environmental point of view, and single crystal silicon, polycrystalline silicon, or amorphous silicon solar cells are mainly used for household power generation, commercial power generation, and the like. As other solar cells, chalcopyrite thin film polycrystalline solar cells, CdTe solar cells, dye-sensitized solar cells, organic thin film solar cells and the like have been developed, and these are also being put into practical use.

A solar cell generally has a structure in which an electrode film, a light absorption layer, and an electrode film are provided on a substrate surface, and a protective cover glass is provided thereon. Since the electrode film and the light absorption layer are formed by a heat treatment process, the solar cell substrate is required to have heat resistance. For this reason, a glass substrate is used as a solar cell substrate.
International Publication No. 08/098968 Pamphlet

  In recent years, recycling of resources has been promoted from an environmental viewpoint, and glass products are no exception. However, looking at the glass products as a whole, the recycling rate is not high and it is difficult to say that they meet environmental requirements. Therefore, it is necessary to promote recycling of waste glass generated from glass products.

  Further, in the process of manufacturing a glass product, a considerable amount of waste glass is generated. However, from an environmental viewpoint, it is highly necessary to recycle the waste glass and reduce it to a glass product.

  In view of the above circumstances, the present invention has developed a method for manufacturing a glass substrate for a solar cell that can efficiently recycle waste glass, raises the recycling rate of glass products, and satisfies recent environmental demands as a technical problem. To do.

As a result of intensive studies, the present inventors have found that the above technical problems can be solved by using a waste glass as a part of a glass raw material and producing a glass substrate for a solar cell with this glass raw material. It is what we propose. That method of manufacturing a glass substrate for a solar cell of the present invention has a glass composition, in mass%, SiO 2 50~75%, Al 2 O 3 7.4 ~18%, Na 2 O 0.5~20% The glass raw material is prepared so as to contain 0 to 1.8% of ZrO 2 , waste glass is used as a part of the glass raw material, and the obtained glass raw material is melted in a glass melting kiln. It is characterized by molding.

As for the manufacturing method of the glass substrate for solar cells of this invention, it is preferable that content of the waste glass in a glass raw material is 1-90 mass%.

Method of manufacturing a glass substrate for a solar cell of the present invention has a glass composition, in weight percent terms of oxide, SiO 2 50~75%, Al 2 O 3 7.4 ~18%, B 2 O 3 0~ 12%, MgO 0-10%, CaO 0-20%, SrO 0-15%, BaO 0-15%, RO (MgO + CaO + SrO + BaO: Total amount of MgO, CaO, SrO and BaO) 5-25%, Na 2 O It is preferable to prepare the glass raw material so as to contain 0.5 to 20%, K 2 O 0 to 15%, and ZrO 2 0 to 1.8%.

Method of manufacturing a glass substrate for a solar cell of the present invention has a glass composition, in weight percent terms of oxide, As 2 O 3 + Sb 2 O 3 + SnO 2 + SO 3 (As 2 O 3, Sb 2 O 3, SnO It is preferable to prepare the glass raw material so as to contain 0.05 to 5% of the total amount of 2 and SO 3 .

In the method for producing a glass substrate for a solar cell of the present invention, it is preferable to prepare the glass raw material so that the liquid phase viscosity is 10 4.0 dPa · s or more. Here, the “liquid phase viscosity” is a value obtained by measuring the viscosity of the glass at the liquid phase temperature by a platinum ball pulling method. “Liquid phase temperature” is obtained by crushing glass, passing through a standard sieve 30 mesh (a sieve opening of 500 μm), and putting the glass powder remaining at 50 mesh (a sieve opening of 300 μm) into a platinum boat, and putting it in a temperature gradient furnace. This is a value obtained by measuring the temperature at which crystals are deposited while maintaining the time.

In the method for producing a glass substrate for a solar cell of the present invention, it is preferable to prepare a glass raw material so that the strain point is 560 ° C. or higher. Here, the “strain point” refers to a value measured based on the method of ASTM C336-71. If it does in this way, the situation where a glass substrate changes in a heat treatment process can be prevented.

As for the manufacturing method of the glass substrate for solar cells of this invention, it is preferable that the glass composition of waste glass is either of following (1)-(8).
(1) in weight percent terms of oxide, SiO 2 65~75%, Al 2 O 3 0.5~5%, MgO 1~6%, CaO 2~12%, Na 2 O 10~15%, K 2 O 0-4%, SO 3 0-1%, Fe 2 O 3 0-1% contained,
(2) mass% terms of oxide, SiO 2 65~75%, Al 2 O 3 0.5~5%, 0~4% MgO, CaO 6~14%, Na 2 O 10~15%, K 2 O 0-4%, SO 3 0-1%, Fe 2 O 3 0-1% contained,
(3) mass% terms of oxide, SiO 2 65~75%, Al 2 O 3 0.5~5%, B 2 O 3 0~20%, 0~5% MgO, CaO 0~10% BaO 0-5%, Na 2 O 0-20%, K 2 O 0-10%, Sb 2 O 3 0-1%, TiO 2 0-5%, Fe 2 O 3 0-1%,
(4) mass% terms of oxide, SiO 2 50~75%, Al 2 O 3 0~30%, B 2 O 3 0~30%, 0~10% MgO, CaO 0~30%, Na 2 O 0~15%, K 2 O 0~15%, ZrO 2 0~30%, 0~5% ZnO, TiO 2 0~5%, Fe 2 O 3 0~1%, SO 3 0~1% Containing,
(5) weight percent terms of oxide, SiO 2 55~65%, Al 2 O 3 1~3%, 0~1% MgO, CaO 0~2%, SrO 8~12%, BaO 5~12 %, ZrO 2 0~3%, Na 2 O 6~9%, K 2 O 7~12%, 0~1% ZnO, CeO 2 0~1%, TiO 2 0~1%, Fe 2 O 3 0 ~1%, Sb 2 O 3 0~1 %, NiO 0~0.02%, CoO 0~0.003% containing,
(6) Mass% in terms of the following oxides: SiO 2 50-60%, Al 2 O 3 1-6%, MgO 0-3%, CaO 1-5%, SrO 0-3%, BaO 0-2 %, PbO 20-25%, Na 2 O 4-8%, K 2 O 6-10%, Sb 2 O 3 0-1%, Fe 2 O 3 0-1%,
(7) Mass% in terms of the following oxides: SiO 2 50 to 70%, Al 2 O 3 0 to 8%, MgO 0 to 8%, CaO 0 to 12%, SrO 0 to 14%, BaO 0 to 14 %, ZrO 2 0-10%, Na 2 O 0.5-5%, K 2 O 1-10%, Fe 2 O 3 0-1%, SO 3 0-1%,
(8) mass% terms of oxide, SiO 2 55~75%, Al 2 O 3 2~20%, B 2 O 3 1~12%, 0~10% MgO, CaO 0~10%, SrO 0~10%, BaO 0~15%, 0~1 % ZnO, As 2 O 3 0~2%, Sb 2 O 3 0~2%, SnO 2 0~1%, Fe 2 O 3 0~1% Contains.

In the method for producing a solar cell glass substrate of the present invention, it is preferable to use waste glass of CRT glass as a part of the glass raw material.

As for the manufacturing method of the glass substrate for solar cells of this invention, it is preferable to shape | mold a glass substrate by the float glass process. In this way, a large glass substrate can be stably manufactured, and as a result, the manufacturing cost of the glass substrate can be reduced.

The solar cell glass substrate according to the present invention is preferably produced by any of the methods described above.

The glass substrate for a solar cell according to the present invention has a strain point of 560 ° C. or higher and is preferably used for a chalcopyrite thin film polycrystalline solar cell or a dye-sensitized solar cell. The “chalcopyrite thin film polycrystalline solar cell” refers to a solar cell using a compound of the IB-IIIB-VIB group, CuInSe 2 : CIS system, Cu (In, Ga) Se 2 : CIGS system, Cu ( In, Ga) (Se, S): refers to a solar cell having a light absorption layer such as CIGSS.

The cover glass for a solar cell according to the present invention is prepared by preparing a glass raw material so as to contain 0.5 to 20% by mass of Na 2 O as a glass composition, and using waste glass as part of the glass raw material. After melting in a glass melting furnace, it is preferable to form a cover glass.

  In the manufacturing method of the glass substrate for solar cells of this invention, content of the waste glass in a glass raw material is 1-90 mass%, 10-85 mass%, Especially 30-75 mass% is preferable. When the content of waste glass decreases, it becomes difficult to promote recycling of waste glass. On the other hand, when the content of waste glass increases, it becomes difficult to adjust the glass composition, and it becomes difficult to introduce carbonates, nitrates, sulfates, fining agents, etc. that generate gas at the time of melting into the glass raw material. As a result, defects such as reduced homogeneity of the molten glass and difficulty in defoaming easily occur. Note that a non-homogeneous glass substrate is likely to be distorted by heat treatment, which may cause cracks and the like. Further, when the bubbles are exposed on the glass substrate surface, it is difficult to form the electrode film uniformly. In addition, in the manufacturing method of the glass substrate for solar cells of this invention, the particle size of waste glass is 10 mm or less, Especially 5 mm or less is preferable. When the particle size of the waste glass increases, the homogeneity of the glass tends to decrease.

The method of manufacturing a glass substrate for a solar cell of the present invention, a glass substrate, a glass composition, in weight percent terms of oxide, SiO 2 50~75%, Al 2 O 3 7.4 ~18%, B 2 O 3 0-12%, MgO 0-10%, CaO 0-20%, SrO 0-15%, BaO 0-15%, RO (MgO + CaO + SrO + BaO) 5-25%, Na 2 O 0.5-20%, K 2 O 0~15%, preferably contains ZrO 2 from 0 to 1.8%.

  The reason for limiting the glass composition of the glass substrate as described above in the method for producing a glass substrate for solar cell of the present invention will be described below.

SiO 2, together with a component for forming a glass network, or to enhance the strain point, the content thereof is 50% to 75%, good Mashiku is 50-60%. When the content of SiO 2 decreases, the high temperature viscosity becomes too low, the liquid phase viscosity tends to decrease, and the recycling of waste glass becomes difficult to promote. On the other hand, when the content of SiO 2 increases, the high-temperature viscosity becomes too high, and the meltability and moldability tend to decrease.

B 2 O 3 is a component that acts as a flux and lowers the high temperature viscosity to improve the meltability and moldability, and its content is 0 to 12%, preferably 0 to 8%. When the content of B 2 O 3 increases, the high temperature viscosity becomes too low, the liquid phase viscosity tends to decrease, and the strain point tends to decrease.

Al 2 O 3 is a component that increases the strain point, and its content is 7.4 to 18%, preferably 7.4 to 15%. When the content of Al 2 O 3 decreases, it becomes difficult to promote recycling of waste glass. On the other hand, when the content of Al 2 O 3 increases, the high-temperature viscosity becomes too high, and the meltability and moldability tend to decrease.

  MgO is a component that lowers the high-temperature viscosity and improves meltability and moldability, and its content is 0 to 10%, preferably 1 to 8%. When the content of MgO decreases, it becomes difficult to promote recycling of waste glass such as window glass. On the other hand, when the content of MgO increases, the strain point tends to increase, but the high-temperature viscosity becomes too low, and the glass is liable to devitrify, so the liquidus temperature rises and the liquidus viscosity decreases. It becomes easy.

  CaO is a component that increases the meltability and moldability by reducing the high-temperature viscosity, and its content is 0 to 20%, preferably 2 to 10%. When the content of CaO decreases, it becomes difficult to promote recycling of waste glass such as window glass, bottle glass, and funnel glass for CRT. On the other hand, as the CaO content increases, the strain point tends to increase, but the high-temperature viscosity becomes too low, and the glass tends to devitrify, so the liquidus temperature rises and the liquidus viscosity decreases. It becomes easy.

  SrO is a component that lowers the high-temperature viscosity and improves meltability and moldability, and its content is 0 to 15%, preferably 2 to 12%. When the SrO content increases, the strain point tends to increase, but the high-temperature viscosity becomes too low, and the glass tends to devitrify, so the liquidus temperature rises and the liquidus viscosity tends to decrease. . On the other hand, when the content of SrO decreases, it becomes difficult to promote recycling of waste glass such as CRT panel glass.

  BaO is a component that increases the meltability and moldability by lowering the high-temperature viscosity, and its content is 0 to 15%, preferably 2 to 12%. When the content of BaO decreases, it becomes difficult to promote recycling of waste glass such as CRT panel glass. On the other hand, when the content of BaO increases, the strain point tends to increase, but the high-temperature viscosity becomes too low and the glass tends to devitrify, so that the liquidus temperature rises and the liquidus viscosity decreases. It becomes easy.

RO (MgO + CaO + SrO + BaO) is a component that lowers the temperature and melting temperature at 10 4.0 dPa · s, and its content is 5 to 25%, preferably 10 to 25%, more preferably 17 to 25%. When the content of RO (MgO + CaO + SrO + BaO) decreases, the strain point tends to decrease, and the temperature and melting temperature at a high temperature viscosity of 10 4.0 dPa · s tend to increase. On the other hand, when the content of RO (MgO + CaO + SrO + BaO) increases, the glass tends to devitrify and it becomes difficult to form the glass substrate.

ZrO 2 is a component that increases the strain point, and its content is 0 to 1.8 %. When the content of ZrO 2 increases, the high-temperature viscosity becomes too high, and the meltability and moldability tend to decrease.

Na 2 O is a component that significantly lowers the high-temperature viscosity and improves the meltability and moldability, and its content is 0.5 to 20%, preferably 0.5 to 8%. When the content of Na 2 O decreases, it becomes difficult to promote recycling of waste glass such as window glass, bottle glass, CRT panel glass, CRT funnel glass, and PDP glass substrate. On the other hand, when the content of Na 2 O increases, the high temperature viscosity becomes too low, the liquid phase viscosity tends to decrease, and the strain point tends to decrease.

K 2 O is a component that greatly lowers the high-temperature viscosity and improves meltability and moldability, and its content is 0 to 15%, preferably 0 to 13%. When the content of K 2 O decreases, it becomes difficult to promote recycling of waste glass such as CRT panel glass, CRT funnel glass, and PDP glass substrate. On the other hand, when the content of K 2 O increases, the high temperature viscosity tends to decrease, the liquid phase viscosity tends to decrease, and the strain point tends to decrease.

As 2 O 3 , Sb 2 O 3 , SnO 2 , and SO 3 are fining agents and are components that homogenize the glass by gas release, and the content of As 2 O 3 + Sb 2 O 3 + SnO 2 + SO 3 is 0.05 to 5%, preferably 0.1 to 1.0%. When the content of As 2 O 3 + Sb 2 O 3 + SnO 2 + SO 3 decreases, the clarification effect becomes poor and it becomes difficult to defoam, and it is difficult to homogenize the glass. On the other hand, if the content of As 2 O 3 + Sb 2 O 3 + SnO 2 + SO 3 increases, gas is generated too much, and a foam layer is generated on the surface of the molten glass being melted, making it difficult to heat the glass homogeneously. The foam resulting from the foam layer is likely to flow into the product.

In addition to the above components, other components (for example, Fe 2 O 3 , TiO 2 , CeO 2 , NiO, CoO) can be added to the glass composition up to 20%. The NiO content is preferably 15 ppm to 20%.

In the method for producing a glass substrate for a solar cell of the present invention, the liquid phase viscosity is 10 4.0 dPa · s or more, 10 4.4 dPa · s or more, 10 4.8 dPa · s or more, particularly 10 5.0 dPa. -It is preferable to prepare a glass raw material so that it may become more than s. When the liquidus viscosity is less than 10 4.0 dPa · s, crystal glass is easily precipitated, to decrease the production efficiency of the glass substrate at the time of molding. When there is much content of the waste glass in a glass raw material, since it becomes easy to devitrify glass at the time of shaping | molding, it is highly necessary to control liquid phase viscosity to the said range.

In the manufacturing method of the glass substrate for solar cells of this invention, it is preferable to prepare a glass raw material so that a strain point may be 560 degreeC or more, 570 degreeC or more, especially 580 degreeC or more. When the strain point is lower than 560 ° C., the glass substrate tends to be thermally deformed in a high-temperature heat treatment process.

In the manufacturing method of the glass substrate for solar cells of this invention, it is preferable to prepare a glass raw material so that a thermal expansion coefficient may be 75-95 * 10 < -7 > / degreeC, especially 80-90 * 10 < -7 > / degreeC. . In this way, the thermal expansion coefficient of the glass substrate matches the thermal expansion coefficient of the light absorbing layer such as CIS, and the oxide semiconductor porous film such as titanium oxide, and the residual stress between the materials can be reduced. As a result, peeling of these materials can be prevented. Here, “thermal expansion coefficient” refers to an average value of linear thermal expansion coefficient in a temperature range of 30 to 380 ° C. with a dilatometer using a cylinder having a diameter of 5.0 mm and a length of 20 mm as a measurement sample.

The method of manufacturing a glass substrate for a solar cell of the present invention, 10 4.0 dPa · Temperature in s is 1200 ° C. or less, 1170 ° C. or less, in particular so as to be 1150 ° C. or less, it is preferable to formulate a glass raw material. If it does in this way, it will become easy to shape | mold a glass substrate by the float method, the overflow downdraw method, the rollout method, etc. When the temperature at 10 4.0 dPa · s is higher than 1200 ° C., the molten glass is easily deteriorated due to component volatilization at the time of molding, and the molding temperature becomes high, resulting in an increased load on the molding apparatus. The life of the molding apparatus is shortened and the production cost of the glass substrate is increased. On the other hand, if the temperature at 10 4.0 dPa · s is too low, the strain point tends to decrease, so the temperature at 10 4.0 dPa · s is preferably 1050 ° C. or higher. Here, “temperature at 10 4.0 dPa · s” refers to a value measured by a platinum ball pulling method.

Currently, various glass products are distributed in the market. From the environmental point of view, there is a high need to recycle waste glass generated from glass products. In particular, window glass, bottle glass, glass for fluorescent lamps, glass fiber, CRT panel glass, CRT funnel glass, glass substrates for PDP, glass substrates for LCD, etc. have a large distribution volume, and it is highly necessary to recycle waste glass. . These glass compositions vary somewhat depending on the manufacturer, but are generally as shown below.
(1) window glass, in weight percent terms of oxide, SiO 2 65~75%, Al 2 O 3 0.5~5%, MgO 1~6%, CaO 2~12%, Na 2 O 10 ~15%, K 2 O 0~4% , SO 3 0~1%, Fe 2 O 3 0~1% containing,
(2) bottles glass, by mass% terms of oxide, SiO 2 65~75%, Al 2 O 3 0.5~5%, 0~4% MgO, CaO 6~14%, Na 2 O 10 ~15%, K 2 O 0~4% , SO 3 0~1%, Fe 2 O 3 0~1% containing,
(3) glass for fluorescent lamps, in mass% terms of oxide, SiO 2 65~75%, Al 2 O 3 0.5~5%, B 2 O 3 0~20%, MgO 0~5% , CaO 0-10%, BaO 0-5%, Na 2 O 0-20%, K 2 O 0-10%, Sb 2 O 3 0-1%, TiO 2 0-5%, Fe 2 O 3 0 Containing 1%,
(4) Glass fiber, in mass% terms of oxide, SiO 2 50~75%, Al 2 O 3 0~30%, B 2 O 3 0~30%, 0~10% MgO, CaO 0~ 30%, Na 2 O 0~15% , K 2 O 0~15%, ZrO 2 0~30%, 0~5% ZnO, TiO 2 0~5%, Fe 2 O 3 0~1%, SO 3 0 to 1% content,
(5) CRT panel glass, in weight percent terms of oxide, SiO 2 55~65%, Al 2 O 3 1~3%, 0~1% MgO, CaO 0~2%, SrO 8~12% BaO 5-12%, ZrO 2 0-3%, Na 2 O 6-9%, K 2 O 7-12%, ZnO 0-1%, CeO 2 0-1%, TiO 2 0-1%, Fe 2 O 3 0 to 1%, Sb 2 O 3 0 to 1%, NiO 0 to 0.02%, CoO 0 to 0.003% contained,
(6) CRT funnel glass, in weight% terms of oxide, SiO 2 50~60%, Al 2 O 3 1~6%, 0~3% MgO, CaO 1~5%, SrO 0~3% BaO 0-2%, PbO 20-25%, Na 2 O 4-8%, K 2 O 6-10%, Sb 2 O 3 0-1%, Fe 2 O 3 0-1%,
(7) The glass substrate for PDP is mass% in terms of the following oxides: SiO 2 50 to 70%, Al 2 O 3 0 to 8%, MgO 0 to 8%, CaO 0 to 12%, SrO 0 to 14 %, BaO 0-14%, ZrO 2 0-10%, Na 2 O 0.5-5%, K 2 O 1-10%, Fe 2 O 3 0-1%, SO 3 0-1%,
(8) a glass substrate for LCD, by mass% terms of oxide, SiO 2 55~75%, Al 2 O 3 2~20%, B 2 O 3 1~12%, 0~10% MgO, CaO 0~10%, SrO 0~10%, BaO 0~15%, 0~1% ZnO, As 2 O 3 0~2%, Sb 2 O 3 0~2%, SnO 2 0~1%, Fe 2 O 3 0 to 1% contained.

  In the method for producing a glass substrate for a solar cell of the present invention, it is preferable to use waste glass of CRT glass (CRT panel glass, CRT funnel glass) as a part of the raw material. It is required to dismantle used CRT TVs, sort them into different types of materials, etc., and reuse as many materials as possible as resources. The Japan Home Appliances Association has developed a recycling plant, and home appliance manufacturers Various companies have proposed various dismantling means. In particular, CRT glass occupies a large volume in the components of CRT televisions, and it is highly necessary to separate this and recycle it as a glass raw material. Therefore, when the glass substrate for solar cells is produced using waste glass of CRT glass as a part of the raw material, the above requirement can be satisfied accurately.

In the method for manufacturing a glass substrate for a solar cell of the present invention, as a forming method, a float method, a slot down draw method, an overflow down draw method, a redraw method, a roll out method, or the like can be used. In particular, the float method can produce a large glass substrate at low cost. In the case of the float process, it is preferable not to add As 2 O 3 or Sb 2 O 3 as a fining agent in the glass composition. In this way, it is possible to As 2 O 3, Sb 2 O 3 is reduced in the float bath, to prevent the foreign metal substance is precipitated.

The glass substrate for solar cells according to the present invention is manufactured by any of the methods described above. Here, the technical characteristics (a suitable glass composition, glass characteristics, etc.) of the glass substrate for solar cells of the present invention are as described above, and the description thereof is omitted here.

The glass substrate for a solar cell according to the present invention has a strain point of 560 ° C. or higher and is preferably used for a chalcopyrite thin film polycrystalline solar cell. In the chalcopyrite thin film polycrystalline solar cell, an electrode (for example, Mo) is first formed on a glass substrate by sputtering or the like, and then a precursor of a light absorption layer is prepared by sputtering or vapor deposition. Then, a light absorption layer is formed by heat treatment. Subsequently, a buffer layer (for example, CdS) is formed by a chemical deposition method or the like, and a window layer (for example, ZnO) and a transparent conductive film (for example, ITO) are formed by a sputtering method or the like. When the light absorption layer is formed, if the heat treatment temperature is increased, the reconfiguration of particles by thermal diffusion can be promoted. In addition to the effect of promoting the recycling of waste glass, the glass substrate for solar cell of the present invention has a strain point of 560 ° C. or higher, so that the glass substrate is not easily deformed even when heat-treated at a high temperature. The absorption layer can be stably formed, and as a result, the characteristics of the chalcopyrite thin film polycrystalline solar cell can be enhanced.

The glass substrate for a solar cell according to the present invention has a strain point of 560 ° C. or higher and is preferably used for a dye-sensitized solar cell. In a dye-sensitized solar cell, a transparent conductive film (for example, ITO, FTO, ATO) is first formed on a glass substrate by a sputtering method, and then oxide semiconductor fine particles are applied on the glass substrate and heat-treated. An oxide semiconductor porous film is formed. Here, the heat treatment temperature for forming the oxide semiconductor porous film may exceed 600 ° C. in some cases. Next, a dye is adsorbed on the oxide semiconductor porous film. Subsequently, a cell is manufactured using a glass substrate on which an oxide semiconductor porous film is formed and a glass substrate on which a transparent conductive film is formed, and the inside of the cell is filled with an electrolyte solution containing a redox pair such as iodine redox. In addition to the effect of promoting the recycling of waste glass, the glass substrate for solar cells of the present invention has a strain point of 560 ° C. or higher. The oxide semiconductor porous film can be stably formed, and as a result, the characteristics of the dye-sensitized solar cell can be improved.

The glass substrate for a solar cell according to the present invention preferably has a plate thickness of 4 mm or less, 3 mm or less, particularly preferably less than 2 mm. As the plate thickness of the glass substrate is smaller, the solar cell can be made thinner and lighter.

The method for producing a cover glass for a solar cell according to the present invention is characterized in that waste glass is used as part of a glass raw material, the glass raw material is melted in a glass melting furnace, and then formed into a cover glass. The glass substrate for a solar cell of the present invention may be used not only for a substrate used on a side where light does not enter but also for a substrate (cover glass) on a side where light enters. When used for a substrate on which light is incident, 0.1 to 5% of TiO 2 may be added to the glass composition in order to prevent ultraviolet coloring. In order to increase the mechanical strength, the surface of the glass substrate may be subjected to a strengthening process (physical strengthening or chemical strengthening). The technical characteristics (glass composition, official characteristics, etc.) of the glass substrate for solar cells according to the present invention can be similarly provided by the cover glass for solar cells according to the present invention. Is omitted.

  Hereinafter, the present invention will be described based on examples. The present invention is not limited to these examples.

  Table 1 shows the glass composition of waste glass, Table 2 shows examples (sample Nos. 1 to 7) of the present invention, and Table 3 shows comparative examples (samples No. 8 and 9) of the present invention. .

  Each sample described in Tables 2 and 3 was prepared as follows. Each waste glass grind | pulverized to the magnitude | size of 5 mm or less was prepared, waste glass and an oxide raw material were mixed, and the glass raw material was produced so that it might become a glass composition of Tables 2 and 3. Next, the glass raw material was melted in a continuous melting furnace, and the obtained molten glass was formed on a glass substrate. Subsequently, the obtained glass substrate was cut into a size of 200 mm square to obtain each sample.

Obtained for each sample was evaluated strain point, liquidus temperature, liquidus viscosity, temperature at 10 4.0 dPa · s, homogeneity.

  The strain point is a value measured by the method described in ASTM C336-71.

  The liquid phase temperature is obtained by crushing glass, passing through a standard sieve 30 mesh (a sieve opening of 500 μm), putting the glass powder remaining at 50 mesh (a sieve opening of 300 μm) in a platinum boat, and keeping it in a temperature gradient furnace for 24 hours The value at which the temperature at which crystals precipitate is measured.

  The liquid phase viscosity is a value obtained by measuring the viscosity of glass at the liquid phase temperature by a platinum ball pulling method.

The temperature at 10 4.0 dPa · s is a value measured by a platinum ball pulling method.

  The homogeneity was evaluated by observing the transmitted light at an optical path length of 40 mm by cutting each sample into 10 mm × 40 mm. Those with very good homogeneity were evaluated with “「 ”, good with“ ◯ ”, and bad with“ × ”.

As apparent from Table 2, the sample No. Nos. 1 to 7 have a recycling rate of waste glass of 10% or more, a strain point of 535 ° C. or more, a liquidus temperature of 1080 ° C. or less, and a liquidus viscosity of 10 4.4 dPa · s or more. It was good.

  On the other hand, as apparent from Table 3, the sample No. In No. 8, since the recycling rate of waste glass was 100%, the evaluation of homogeneity was poor. Sample No. In No. 9, the recycling rate of waste glass is 0%, which does not meet recent environmental requirements.

The glass substrate for solar cell according to the present invention is not limited to chalcopyrite thin film polycrystalline solar cells and dye-sensitized solar cells, but also silicon solar cells (single crystal silicon solar cells, polycrystalline silicon solar cells, microcrystalline silicon solar cells). Battery, amorphous silicon solar cell), CdTe solar cell, and organic thin film solar cell.

Claims (10)

  1. As a glass composition, in mass%, SiO 2 50~75%, Al 2 O 3 7.4 ~18%, Na 2 O 0.5~20%, to contain ZrO 2 0 to 1.8%, A method for producing a glass substrate for a solar cell, comprising preparing a glass raw material, using waste glass as a part of the glass raw material, melting the obtained glass raw material in a glass melting furnace, and then forming the glass substrate. .
  2.   Content of the waste glass in a glass raw material is 1-90 mass%, The manufacturing method of the glass substrate for solar cells of Claim 1 characterized by the above-mentioned.
  3. As a glass composition, in weight percent terms of oxide, SiO 2 50~75%, Al 2 O 3 7.4 ~18%, B 2 O 3 0~12%, 0~10% MgO, CaO 0~20 %, SrO 0-15%, BaO 0-15%, RO (MgO + CaO + SrO + BaO) 5-25%, Na 2 O 0.5-20%, K 2 O 0-15%, ZrO 2 0-1.8%. The method for producing a glass substrate for a solar cell according to claim 1 or 2, wherein a glass raw material is prepared so as to contain.
  4. The glass raw material is prepared so as to contain 0.05 to 5% of As 2 O 3 + Sb 2 O 3 + SnO 2 + SO 3 as a glass composition in mass% in terms of the following oxides. The manufacturing method of the glass substrate for solar cells in any one of -3.
  5. The method for producing a glass substrate for a solar cell according to any one of claims 1 to 4, wherein the glass raw material is prepared so that the liquid phase viscosity is 10 4.0 dPa · s or more.
  6.   The method for producing a glass substrate for a solar cell according to any one of claims 1 to 5, wherein the glass raw material is prepared so that the strain point is 560 ° C or higher.
  7. The method for producing a glass substrate for a solar cell according to any one of claims 1 to 6, wherein the glass composition of the waste glass is any one of the following (1) to (8).
    (1) in weight percent terms of oxide, SiO 2 65~75%, Al 2 O 3 0.5~5%, MgO 1~6%, CaO 2~12%, Na 2 O 10~15%, K 2 O 0-4%, SO 3 0-1%, Fe 2 O 3 0-1% contained,
    (2) mass% terms of oxide, SiO 2 65~75%, Al 2 O 3 0.5~5%, 0~4% MgO, CaO 6~14%, Na 2 O 10~15%, K 2 O 0-4%, SO 3 0-1%, Fe 2 O 3 0-1% contained,
    (3) mass% terms of oxide, SiO 2 65~75%, Al 2 O 3 0.5~5%, B 2 O 3 0~20%, 0~5% MgO, CaO 0~10% BaO 0-5%, Na 2 O 0-20%, K 2 O 0-10%, Sb 2 O 3 0-1%, TiO 2 0-5%, Fe 2 O 3 0-1%,
    (4) mass% terms of oxide, SiO 2 50~75%, Al 2 O 3 0~30%, B 2 O 3 0~30%, 0~10% MgO, CaO 0~30%, Na 2 O 0~15%, K 2 O 0~15%, ZrO 2 0~30%, 0~5% ZnO, TiO 2 0~5%, Fe 2 O 3 0~1%, SO 3 0~1% Containing,
    (5) weight percent terms of oxide, SiO 2 55~65%, Al 2 O 3 1~3%, 0~1% MgO, CaO 0~2%, SrO 8~12%, BaO 5~12 %, ZrO 2 0~3%, Na 2 O 6~9%, K 2 O 7~12%, 0~1% ZnO, CeO 2 0~1%, TiO 2 0~1%, Fe 2 O 3 0 ~1%, Sb 2 O 3 0~1 %, NiO 0~0.02%, CoO 0~0.003% containing,
    (6) Mass% in terms of the following oxides: SiO 2 50-60%, Al 2 O 3 1-6%, MgO 0-3%, CaO 1-5%, SrO 0-3%, BaO 0-2 %, PbO 20-25%, Na 2 O 4-8%, K 2 O 6-10%, Sb 2 O 3 0-1%, Fe 2 O 3 0-1%,
    (7) Mass% in terms of the following oxides: SiO 2 50 to 70%, Al 2 O 3 0 to 8%, MgO 0 to 8%, CaO 0 to 12%, SrO 0 to 14%, BaO 0 to 14 %, ZrO 2 0-10%, Na 2 O 0.5-5%, K 2 O 1-10%, Fe 2 O 3 0-1%, SO 3 0-1%,
    (8) mass% terms of oxide, SiO 2 55~75%, Al 2 O 3 2~20%, B 2 O 3 1~12%, 0~10% MgO, CaO 0~10%, SrO 0~10%, BaO 0~15%, 0~1 % ZnO, As 2 O 3 0~2%, Sb 2 O 3 0~2%, SnO 2 0~1%, Fe 2 O 3 0~1% Contains.
  8.   The method for producing a glass substrate for a solar cell according to any one of claims 1 to 7, wherein waste glass of PDP glass is used as part of the glass raw material.
  9.   The method for producing a glass substrate for a solar cell according to any one of claims 1 to 8, wherein the particle size of the waste glass is 10 mm or less.
  10.   A glass substrate is shape | molded by the float glass process, The manufacturing method of the glass substrate for solar cells in any one of Claims 1-9 characterized by the above-mentioned.
JP2008323012A 2008-12-19 2008-12-19 Manufacturing method of glass substrate for solar cell Active JP5733811B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2008323012A JP5733811B2 (en) 2008-12-19 2008-12-19 Manufacturing method of glass substrate for solar cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2008323012A JP5733811B2 (en) 2008-12-19 2008-12-19 Manufacturing method of glass substrate for solar cell

Publications (2)

Publication Number Publication Date
JP2010143790A JP2010143790A (en) 2010-07-01
JP5733811B2 true JP5733811B2 (en) 2015-06-10

Family

ID=42564607

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2008323012A Active JP5733811B2 (en) 2008-12-19 2008-12-19 Manufacturing method of glass substrate for solar cell

Country Status (1)

Country Link
JP (1) JP5733811B2 (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012106875A (en) * 2010-11-15 2012-06-07 Recycle One Inc Method for melting crushed glass, molten glass, and glass material
JP5748453B2 (en) * 2010-11-15 2015-07-15 株式会社レノバ Method for heating ground glass containing arsenic, method for preventing arsenic elution from ground glass, and glass material
TW201245080A (en) * 2011-03-17 2012-11-16 Asahi Glass Co Ltd Glass for chemical strengthening
JP6410108B2 (en) * 2011-07-19 2018-10-24 日本電気硝子株式会社 Glass substrate
JP5850392B2 (en) * 2011-09-20 2016-02-03 日本電気硝子株式会社 Glass plate
JPWO2014024850A1 (en) * 2012-08-06 2016-07-25 旭硝子株式会社 Glass substrate for Cu-In-Ga-Se solar cell and solar cell using the same
JP6128128B2 (en) * 2012-09-10 2017-05-17 旭硝子株式会社 Glass substrate for solar cell and solar cell using the same
JP5797222B2 (en) * 2012-10-02 2015-10-21 AvanStrate株式会社 Glass substrate manufacturing method and manufacturing apparatus
JP6090705B2 (en) * 2012-11-09 2017-03-08 日本電気硝子株式会社 Glass plate for thin film solar cell
JP6172445B2 (en) * 2013-03-08 2017-08-02 日本電気硝子株式会社 cover glass
JP2016117627A (en) * 2014-12-24 2016-06-30 日本電気硝子株式会社 Production method of glass fiber
GB201505091D0 (en) 2015-03-26 2015-05-06 Pilkington Group Ltd Glass

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4320823B2 (en) * 1998-02-27 2009-08-26 旭硝子株式会社 Substrate glass composition
JP5105571B2 (en) * 2003-10-10 2012-12-26 日本電気硝子株式会社 Method for producing alkali-free glass
JP2005213132A (en) * 2004-02-02 2005-08-11 Nippon Electric Glass Co Ltd Method for manufacturing glass substrate for plasma display panel and glass substrate for plasma display panel
DE102004011218B4 (en) * 2004-03-04 2006-01-19 Schott Ag X-ray opaque glass, process for its preparation and its use
JP5808069B2 (en) * 2007-02-16 2015-11-10 日本電気硝子株式会社 Glass substrate for solar cell
JP2008280189A (en) * 2007-05-08 2008-11-20 Nippon Electric Glass Co Ltd Glass substrate for solar cell, and method of manufacturing the same
JP2008305711A (en) * 2007-06-08 2008-12-18 Nippon Electric Glass Co Ltd Manufacturing method of glass substrate for plasma display panel and glass substrate for plasma display panel

Also Published As

Publication number Publication date
JP2010143790A (en) 2010-07-01

Similar Documents

Publication Publication Date Title
JP6202353B2 (en) Alkali-free glass
JP5594444B2 (en) Tempered glass substrate and manufacturing method thereof
JP6417531B2 (en) Glass with intermediate thermal expansion coefficient
JP5578343B2 (en) Glass film fixed body
JP5556947B2 (en) Tempered glass and method for producing the same
EP2683665B1 (en) Substrate for a photovoltaic cell
US10173919B2 (en) Fusion formable sodium free glass
JP5150126B2 (en) Aluminoborosilicate glass free of alkali metals and use thereof
JP5826935B2 (en) Fusion moldable, alkali free intermediate thermal expansion glass
CN1673140B (en) Glass for display substrate
US9530910B2 (en) Fusion formable silica and sodium containing glasses
DE69916683T2 (en) Glass substrate for screens
JP5589252B2 (en) Tempered glass substrate
US8835335B2 (en) Alkali-free glass
JP5557168B2 (en) Method for producing tempered glass substrate and tempered glass substrate
KR101493764B1 (en) Tempered glass plate
CN103201228B (en) Non-alkali glass
CN103068758B (en) Alkali-free glass
JP5339173B2 (en) Tempered glass substrate, glass and method for producing tempered glass substrate
JP2013014516A (en) Method for manufacturing tempered glass, and method for manufacturing glass for reinforcement
JP5875133B2 (en) Tempered glass substrate
JP5413562B2 (en) Sealing material
US9637408B2 (en) Fusion formable sodium containing glass
US6680266B1 (en) Alkaline-earth aluminoborosilicate glass and the uses thereof
US20120199203A1 (en) Glass sheet for cu-in-ga-se solar cells, and solar cells using same

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20111108

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20130123

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20130128

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20130321

A02 Decision of refusal

Free format text: JAPANESE INTERMEDIATE CODE: A02

Effective date: 20131125

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20131227

A911 Transfer of reconsideration by examiner before appeal (zenchi)

Free format text: JAPANESE INTERMEDIATE CODE: A911

Effective date: 20140127

A912 Removal of reconsideration by examiner before appeal (zenchi)

Free format text: JAPANESE INTERMEDIATE CODE: A912

Effective date: 20140320

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20141030

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20150318

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20150410

R150 Certificate of patent or registration of utility model

Ref document number: 5733811

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150