JP2012229157A - Glass substrate for solar cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide method for producing a glass substrate for a solar cell which can improve surface quality and is excellent in devitrification resistance.SOLUTION: The glass substrate for a solar cell contains, by mass, 30 to 70% of SiO, 3 to 20% of AlO, 0 to 10% of BO, 0 to 10% of MgO, 0 to 10% of CaO, 0 to 25% of SrO, 0 to 25% of BaO, 0 to 10% of NaO, 0 to 10% of KO, and 0 to 8% of ZrOas a glass composition and is characterized in that the thermal expansion coefficient at 30 to 380°C is 50 to 95×10/°C.

Description

  The present invention relates to a glass substrate for a solar cell, and more particularly to a glass substrate for a solar cell suitable for a single crystal silicon solar cell, a polycrystalline silicon solar cell, an amorphous silicon solar cell, a thin film compound solar cell and the like. The “solar cell glass substrate” as used in the present invention includes both a solar cell cover glass and a solar cell substrate.

  A solar cell is a device that uses the photovoltaic effect to convert light energy directly into electric power. Currently, in addition to silicon solar cells, solar cells using various compound semiconductors and the like have been put into practical use. In general, a thin film compound solar cell has a structure in which an electrode layer, a photoelectric conversion layer, a buffer layer, and the like are formed on a glass substrate (base material). On the other hand, single crystal and polycrystalline silicon solar cells have a structure in which a silicon semiconductor is sandwiched between glass substrates through a resin or the like. In addition, these solar cells use a cover glass to protect the solar cell element. For example, in a thin film compound solar cell, a cover glass is applied after a resin such as ethylene vinyl acetate is applied on the solar cell element. It is pasted.

JP 11-298030 A JP 2000-91601 A

The following characteristics are required for a glass substrate for a solar cell.
(1) To have a coefficient of thermal expansion compatible with the peripheral member in order to prevent film peeling due to a difference in thermal expansion from the thin film compound formed on the glass substrate. (2) In the heat treatment process when forming the thin film compound, Since high-quality film can be formed by processing with, it must have high heat resistance to withstand such heat treatment. More specifically, the glass has a high strain point, which is an index of heat resistance. (3) No internal defects that adversely affect photoelectric conversion efficiency, especially no bubble defects. (4) The entire solar cell. To be low density to reduce the weight of

  In addition to the above required characteristics (1) to (4), the solar cell glass substrate is subjected to accurate patterning of electrodes and the like, and in order to prevent disconnection or short-circuiting of the electrodes or the like, (5) the surface of the glass substrate It is required that the shape is excellent, that is, the flatness of the glass substrate is excellent. Particularly, in recent years, the film thickness formed on the glass substrate tends to be thin, and the required quality for the flatness of the glass substrate has been increasing.

  The flatness of the glass substrate is determined by various factors, and a factor having the greatest influence is a method for forming the glass substrate.

  As a method for forming a glass substrate, there are various methods such as an overflow down draw method (also referred to as a fusion method), a float method, and a slot down draw method. Among them, the overflow downdraw method can obtain a glass substrate with good flatness without polishing the glass substrate. Therefore, it is considered that the overflow downdraw method is suitable as a method for forming a glass substrate for a solar cell that requires an excellent surface shape.

  On the other hand, the overflow down-draw method has a higher glass viscosity at the time of molding than other molding methods, so if the devitrification resistance of the glass is poor, devitrification will occur during molding and the glass substrate It becomes impossible to mold. Therefore, it is desirable that the glass substrate for solar cell has (6) a glass composition that is not easily devitrified.

  However, since conventional glass substrates for solar cells are difficult to obtain glass with good devitrification resistance, molding by the overflow downdraw method cannot be performed accurately, and surface quality is improved. I couldn't.

  Therefore, the present invention provides a technology for obtaining a glass substrate for a solar cell that can satisfy the above required characteristics (1) to (4), improve the surface quality, and has good devitrification resistance. As an objective.

The present inventors, as a result of extensive studies, the glass for a solar cell, the composition range of the glass, _SiO 2 30 to _70% by _{mass%, Al 2 O 3 3~20%} , B 2 O 3 0~10%, _{0~10% MgO, CaO 0~10%,} SrO 0~25%, BaO 0~25%, Na 2 O 0~10%, K 2 O 0~10%, and regulated to ZrO 2 0 to 8%, And it discovers that the said subject can be solved by setting the thermal expansion coefficient in 30-380 degreeC to 50-95x10 < ^-7 > / degreeC, and proposes as this invention. Here, “thermal expansion coefficient at 30 to 380 ° C.” refers to a value obtained by measuring an average thermal expansion coefficient at 30 to 380 ° C. using a dilatometer.

Since the glass substrate for solar cells of the present invention strictly regulates the glass composition range, the above required characteristics (1) to (4) can be satisfied. In particular, if the coefficient of thermal expansion at 30 to 380 ° C. is regulated to 50 to 95 × 10 ⁻⁷ / ° C., members such as thin film compounds formed on a glass substrate, metal, organic adhesive, and the coefficient of thermal expansion It becomes easy to align, and peeling of those members can be prevented.

In general, in the overflow down draw method, the devitrification resistance of the glass is required to be, for example, 1200 ° C. or lower in liquid phase temperature and 10 ^4.5 dPa · s or higher in liquid phase viscosity. Since the glass substrate for glass strictly regulates the glass composition range, it has good devitrification resistance, and achieves a liquidus temperature of 1200 ° C. or lower and a liquidus viscosity of 10 ^4.5 dPa · s or higher. can do. Therefore, a glass substrate having a good surface quality can be obtained. The present invention does not exclude a molding method other than the overflow downdraw method. Even if it is a molding method other than the overflow downdraw method, the better the devitrification resistance of the glass, the higher the production efficiency of the glass substrate. Therefore, the present invention is also effective in other molding methods (for example, the float method). It goes without saying that.

Secondly, a glass substrate for a solar cell of the present invention has a glass composition, characterized in that it contains ZrO ₂ .001 to 8% in mass%. As a result of diligent efforts, the present inventors have found an appropriate ZrO ₂ content that improves heat resistance while suppressing devitrification of the glass. If the content of ZrO ₂ is regulated as described above, the strain point can be increased and the viscosity necessary for performing the overflow downdraw method can be easily secured.

Thirdly, the glass substrate for a solar cell of the present invention has a glass composition, characterized the _B 2 _{O 3} in mass% to containing 0.1 to 8%. If the content of B ₂ O ₃ is regulated as described above, the meltability of the glass is improved and the devitrification resistance of the glass is further improved.

Fourth, the glass substrate for a solar cell of the present invention is characterized in that the value of Al ₂ O ₃ / BaO is 0.1 to _{2 in} terms of mole fraction.

Fifth, the glass substrate for solar cell of the present invention is characterized in that the Na ₂ O / K ₂ O value is 0 to 2 in terms of molar fraction.

Sixth, the glass substrate for a solar cell of the present invention is characterized by having a liquidus temperature of 1200 ° C. or lower and / or a liquidus viscosity of 10 ^4.5 dPa · s or higher. Here, “liquid phase viscosity” refers to pulverizing glass, passing through a standard sieve 30 mesh (500 μm), and putting the glass powder remaining on 50 mesh (300 μm) into a platinum boat and holding it in a temperature gradient furnace for 48 hours. Thus, the temperature at which crystals are deposited is measured. Further, “liquid phase viscosity” refers to a value obtained by measuring the viscosity of glass at the liquid phase temperature measured by the above method by a well-known platinum pulling method.

Seventh, the glass substrate for a solar cell of the present invention is characterized in that the density is 3.7 g / cm ³ or less.

  Eighth, the glass substrate for solar cells of the present invention is characterized in that the strain point is 590 ° C. or higher. Here, “strain point” refers to a value measured by a method based on ASTM C336-71.

Ninthly, the glass substrate for solar cells of the present invention is characterized in that the temperature at a high temperature viscosity of 10 ^2.5 dPa · s is 1650 ° C. or lower. Here, “temperature at a high temperature viscosity of 10 ^2.5 dPa · s” refers to a value measured by a platinum ball pulling method.

  10thly, the manufacturing method of the glass substrate for solar cells of this invention is a manufacturing method of said glass substrate for solar cells, Comprising: The shaping | molding method of a glass substrate is characterized by the overflow down draw method. If the overflow down draw method is employed, a glass substrate with excellent surface quality can be easily produced.

  The reason why the composition range is limited as described above will be described in detail below. In addition, the following% display points out the mass% except the case where there is especially limitation.

SiO ₂ is a glass network former, and its content is 30 to 70%, preferably 35 to 70%, more preferably 40 to 70%, still more preferably 45 to 70%, still more preferably 48 to 65. %, More preferably 50 to 60%, particularly preferably 52 to 58%, most preferably 55 to 58%. When the content of SiO ₂ exceeds 70%, it becomes difficult to melt and mold the glass, or the thermal expansion coefficient becomes too small to make it difficult to match the thermal expansion coefficient of the surrounding materials. On the other hand, when the content of SiO ₂ is less than 30%, the thermal expansion coefficient becomes too large, and the thermal shock resistance of the glass tends to be lowered or vitrification tends to be difficult.

Al ₂ O ₃ is a component that increases the strain point and Young's modulus of glass, and its content is 3 to 20%, preferably 5 to 18%, more preferably 6 to 15%, and still more preferably 7 to 13%. It is. When the content of Al ₂ O ₃ exceeds 20%, the devitrification resistance of the glass is deteriorated, the high-temperature viscosity is increased, and the meltability of the glass tends to be deteriorated. When the content of Al ₂ O ₃ is less than 3%, the thermal expansion coefficient increases, the thermal shock resistance of the glass tends to decrease, or the strain point of the glass tends to decrease. In the process, the glass substrate is easily cracked, and is likely to be thermally deformed, warped, or thermally contracted. In addition, from the viewpoint of improving the devitrification resistance of the glass, if the content of Al ₂ O ₃ is suppressed to 11% or less, further 10% or less, particularly 9.5% or less, the above effect can be enjoyed more accurately. Can do.

B ₂ O ₃ is a component that has the effect of improving the meltability of glass and suppressing devitrification related to ZrO ₂ , and its content is 0 to 10%, preferably 0.1 to 8%. More preferably, it is 0.5 to 5%. When the content of B ₂ O ₃ is more than 10%, the strain point and Young's modulus tend to be lowered, and the glass substrate is cracked during the heat treatment process when manufacturing the solar cell, or heat deformation and heat shrinkage are caused. Is likely to occur. Furthermore, from the viewpoint of increasing the strain point and Young's modulus of the glass, if the content of B ₂ O ₃ is reduced to 3% or less (preferably 2.5% or less, 2% or less), the above effect can be obtained more accurately. You can enjoy it.

  MgO is a component that increases the strain point of the glass and lowers the high temperature viscosity, and its content is 0 to 10%, more preferably 0 to 8%, still more preferably 0 to 5%, and most preferably 0 to 0%. 3%. When the content of MgO exceeds 10%, the thermal expansion coefficient tends to be too high, the density becomes high, or the devitrification resistance tends to deteriorate.

  CaO is a component that lowers the high-temperature viscosity without significantly reducing the strain point, and its content is 0 to 10%, more preferably 0 to 8%, still more preferably 0 to 5%, and most preferably 0. ~ 1%. When the content of CaO exceeds 10%, the thermal expansion coefficient tends to be too high, the density becomes high, and the devitrification resistance tends to deteriorate.

  SrO is a component that lowers the high temperature viscosity without deteriorating the devitrification resistance, and its content is 0 to 25%, preferably 0 to 20%, more preferably 0 to 17%, still more preferably 2. -15%, particularly preferably 5-13%, most preferably 7-13%. If the SrO content is more than 25%, the thermal expansion coefficient and density are too high, or the glass composition is not balanced and the devitrification resistance is deteriorated. Further, from the viewpoint of improving the devitrification resistance of the glass, when the SrO content is 11% or less, and further 10.5% or less, the above effect can be enjoyed more accurately.

  BaO is a component that reduces the high temperature viscosity without deteriorating devitrification resistance, and its content is 0 to 25% (preferably 0 to 20%, 0 to 17%, 2 to 17%, 5 to 5%, 16%, 7-15%, 9-14%, 11.5-14%). If the content of BaO is higher than 25%, the thermal expansion coefficient becomes too high, the density becomes high, the balance of the glass composition is lacking, and the devitrification resistance deteriorates conversely.

  The total amount of MgO + CaO + SrO + BaO is preferably 15 to 60%, more preferably 15 to 28%, still more preferably 17 to 26%, and particularly preferably 19 to 24%. When the total amount of MgO + CaO + SrO + BaO exceeds 60%, the density and thermal expansion coefficient of the glass tend to increase and the devitrification resistance also tends to deteriorate. On the other hand, if the total amount of MgO + CaO + SrO + BaO is less than 15%, the meltability of the glass deteriorates or the thermal expansion coefficient becomes too small.

  When SrO and BaO are introduced into the glass composition, the viscosity in the vicinity of the liquidus temperature does not decrease much compared to other alkaline earth metal oxides. Therefore, when a glass substrate is formed by the overflow down draw method, it is desirable to positively contain these components in order to obtain an appropriate liquid phase viscosity. Furthermore, from the viewpoint of improving the devitrification resistance and chemical durability of the glass, the value of (MgO + CaO) / (SrO + BaO) is 0 to 0.2 (preferably 0 to 0.1, 0 to 0) in terms of mass fraction. .05) is effective. In particular, from the above viewpoint, the value of SrO / BaO is 0.5 to 1.2 (preferably 0.4 to 1.2, 0.5 to 1.1, 0.6 to 1.0 by mass fraction). , 0.6 to 0.9, 0.6 to 0.8) is effective. If it is out of the set value range, the assumed effect cannot be fully enjoyed.

Na ₂ O is a component that reduces the high-temperature viscosity and adjusts the coefficient of thermal expansion, and its content is 0 to 10%, preferably 0 to 8%, more preferably 0 to 6%, and still more preferably 0. ~ 5%. When the content of Na ₂ O exceeds 10%, the strain point decreases or the thermal expansion coefficient becomes too high. In addition, the alkali component may diffuse into the thin film compound to cause warping of the substrate or deteriorate the quality of the film. On the other hand, in order to enjoy the effect of lowering the high temperature viscosity and the effect of adjusting the thermal expansion coefficient, it is preferable to contain Na ₂ O in an amount of 0.1% or more (preferably 0.5% or more, 1% or more). desirable.

K ₂ O is a component that decreases the high-temperature viscosity and adjusts the thermal expansion coefficient, and its content is 0 to 10%, preferably 0 to 8%, more preferably 0 to 6%. If the content of K ₂ O is more than 10%, the strain point is lowered or the thermal expansion coefficient is too high. In addition, the alkali component may diffuse into the thin film compound to cause warping of the substrate or deteriorate the quality of the film. On the other hand, in order to enjoy the effect of lowering the high temperature viscosity and the effect of adjusting the thermal expansion coefficient, K ₂ O is 0.1% or more (preferably 0.1% or more, 0.5% or more, 2% More than 3%) is desirable.

ZrO ₂ is a component that increases the strain point and Young's modulus. The content of ZrO ₂ is 0 to 8% (preferably 0.01 to 8%, 0.1 to 8%, 0.5 to 7%, 1 to 6%, 2 to 5%, 2.5 to 4) %). When the content of ZrO ₂ is more than 8%, the devitrification resistance is deteriorated and the liquid phase viscosity is lowered.

Moreover, the value of Al ₂ O ₃ / BaO is 0.1 to 2 (preferably 0.3 to ₂ , 0.5 to 1.5, 0.7 to 1.3, 0.8 to 0.8 by mole fraction. 1.1) is preferable because a high strain point can be achieved without deteriorating the devitrification resistance of the glass. When the molar fraction of Al ₂ O ₃ / BaO exceeds 2, devitrification resistance tends to deteriorate. When the molar fraction of Al ₂ O ₃ / BaO is smaller than 0.1, the devitrification resistance of the glass deteriorates and the strain point tends to decrease.

Furthermore, the effect of increasing the strain point while suppressing the devitrification resistance by setting the molar fraction of Al ₂ O ₃ / BaO in the range of 0.1 to ₂ is Na ₂ O / K. The value of ₂ O is adjusted to the range of 0 to 2 (preferably 0.3 to 1.5, 0.5 to 1.3, 0.7 to 1.1, 0.8 to 0.9). Therefore, it can be enjoyed more accurately. When the molar fraction of Na ₂ O / K ₂ O is small, the above effect due to the adjustment of the molar fraction of Al ₂ O ₃ / BaO is somewhat difficult to obtain, so the molar fraction of Na ₂ O / K ₂ O More preferably, the rate is 0.3 or more. On the other hand, when the molar fraction of Na ₂ O / K ₂ O exceeds 2, the strain point is lowered or the balance of the glass composition is lost, and devitrification is likely to occur.

From the viewpoint of keeping the strain point of the glass high and not increasing the thermal expansion coefficient too much, it is preferable to set the value of (Na ₂ O + K ₂ O) / (MgO + CaO + SrO + BaO) to 0 to 0.5 in terms of mass fraction. More preferably, it is set to 0.1 to 0.4, and more preferably 0.2 to 0.4. If the value of (Na ₂ O + K ₂ O) / (MgO + CaO + SrO + BaO) in terms of mass fraction is greater than 0.5, the above effects may not be enjoyed accurately.

Fe ₂ O ₃ is a component that affects the transmittance of the glass, and its content is 0 to 0.05%, preferably 1 ppm to 0.03%, more preferably 0.005 to 0.02%, Most preferably, it is 0.005 to 0.015%. When the content of Fe ₂ O ₃ increases, the transmittance in the visible region of the glass decreases too much, and the amount of sunlight irradiated to the solar cell element is reduced, and solarization is likely to occur. The photoelectric conversion efficiency of the solar cell tends to decrease. In addition, when the content of Fe ₂ O ₃ is reduced, a high-purity glass raw material must be used, leading to an increase in the manufacturing cost of the glass substrate. Further, when the content of Fe ₂ O ₃ is decreased, the transmittance in the ultraviolet region becomes too high, which may cause deterioration of the resin existing on the glass substrate and shorten the life of the solar cell.

In order to exhibit the effect of suppressing solarization of glass more effectively, the value of the mass ratio SnO ₂ / (Fe ₂ O ₃ + SnO ₂ ) is 0.9 or more, preferably 0.92 or more, 0.94 or more, 0 It may be restricted to 96 or more. When the value of the mass ratio SnO ₂ / (Fe ₂ O ₃ + SnO ₂ ) is less than 0.9, it is difficult to obtain a desired solarization suppressing effect, and the photoelectric conversion efficiency of the solar cell is likely to deteriorate over time.

TiO ₂ has an effect of suppressing solarization of glass, and is 0 to 10% (preferably 0 to 5%, more preferably 0 to 3%, still more preferably 0.001 to 1%, most preferably 0.005. Up to 0.1%). When the content of TiO ₂ increases, the devitrification resistance of the glass deteriorates or the glass is colored.

  ZnO is a component that increases the Young's modulus of glass or improves the meltability, and is 0 to 10% (preferably 0 to 5%, more preferably 0 to 3%, still more preferably 0 to 1%, most preferably. 0 to 0.5%). When the content of ZnO increases, the density and thermal expansion coefficient of the glass increase. Moreover, when the content of ZnO increases, the devitrification resistance and strain point of the glass tend to decrease.

As ₂ O ₃ acts as a glass refining agent, but if it is contained in a large amount in the glass composition, the glass is likely to be solarized, and the photoelectric conversion efficiency of the solar cell is likely to deteriorate over time. The amount is 0 to 1%, preferably 0 to 0.8%, more preferably 0 to 0.5%, still more preferably 0 to 0.3%, and most preferably not substantially contained. Further, if the glass composition does not substantially contain As ₂ O ₃ , it can satisfy recent environmental demands.

SnO ₂ acts as a glass refining agent and has an effect of suppressing solarization of the glass, and its content is 0.001 to 2%, preferably 0.005 to 1.5%, more preferably 0.00. It is 01 to 1%, More preferably, it is 0.05 to 0.5%, Most preferably, it is 0.05 to 0.3%. When the content of SnO ₂ increases, the devitrification resistance of the glass deteriorates. If the content of SnO ₂ is reduced, or it becomes poor effect of suppressing the solarization of the glass fining effect is reduced. It is also possible to use the raw material for the SnO ₂ as a main component as SnO ₂ introduction source, but no problem also contain from trace components contained in other raw materials.

Sb ₂ O ₃ is a component that acts as a glass refining agent, and is 0 to 2% (preferably 0 to 1.5%, more preferably 0 to 1%, still more preferably 0 to 0.5%, most preferably. 0 to 0.1%). When the content of Sb ₂ O ₃ increases, the density of the glass tends to increase.

  Halides such as Cl and F are components that act as glass refining agents, and are 0 to 1% (preferably 0 to 0.5%, more preferably 0 to 0.1%, still more preferably 0 to 0.0. 01%, most preferably 0 to 0.001%). When the content of Cl increases, the component volatilization from the glass melt increases, which may cause striae in the glass and may deteriorate the characteristics of the solar cell element.

Rare earth oxides such as Nb ₂ O ₅ and La ₂ O ₃ are components that increase the Young's modulus of glass. However, the rare earth oxide has a high cost of the raw material itself, and if it is contained in a large amount, the resistance to devitrification deteriorates. Therefore, the rare earth oxide content is desirably limited to 3% or less, 2% or less, 1% or less, particularly 0.5% or less.

  The glass for solar cells according to the present invention can contain up to 10% of various components other than the above components as long as the properties of the glass are not impaired.

In the glass composition range described above, it is naturally possible to select a preferable glass composition range by arbitrarily combining the preferable content ranges of the respective components, but among them, more preferable glass as a glass substrate for a solar cell. composition _{range, SiO 2 40~65%, Al 2} O 3 5~15%, B 2 O 3 0~5%, 0~8% MgO, CaO 0~8%, SrO 0~12.5%, BaO _{0~14%, Na 2 O 0~5%} , K 2 O 0~6%, a ZrO 2 0.01 to 4%. If the composition range of glass is regulated as described above, devitrification resistance can be improved, and suitable viscosity characteristics can be secured in molding by the overflow down draw method. Further, still more preferably in the range of _{SiO 2 50~60%, Al 2 O} 3 5~10%, B 2 O 3 0~5%, 0~5% MgO, CaO 0~5%, SrO 5~12.5% _{, BaO 9~14%, Na 2 O} 0~5%, K 2 O 3~6%, a ZrO 2 1 to 4%. If the glass composition range is regulated as described above, the devitrification resistance can be greatly improved, and a glass excellent in heat resistance can be obtained while securing suitable viscosity characteristics when forming by the overflow down draw method. Can do.

The glass substrate for solar cells of the present invention has a thermal expansion coefficient at 30 to 380 ° C. of 50 to 95 × 10 ⁻⁷ / ° C., preferably 50 to 90 × 10 ⁻⁷ / ° C., more preferably 55 to 55 ° C. 85 × 10 ⁻⁷ / ° C., more preferably 60 to 80 × 10 ⁻⁷ / ° C., particularly preferably 65 to less than 80 × 10 ⁻⁷ / ° C., and most preferably 65 to 75 × 10 ⁻⁷ / ° C. If the thermal expansion coefficient of the glass substrate is within the above range, the thermal expansion coefficient can be easily matched with a member such as a thin film compound, a metal, or an organic adhesive, and peeling from these members can be prevented.

  In the glass substrate for a solar cell of the present invention, the liquidus temperature is preferably 1200 ° C. or less, more preferably 1080 ° C. or less, further preferably 1050 ° C. or less, and most preferably 1000 ° C. or less. In general, the overflow downdraw method has a higher viscosity of glass during molding than other molding methods, so if the devitrification resistance of the glass is poor, devitrification will occur during molding. There is a risk that the substrate cannot be molded. Specifically, when the liquidus temperature is higher than 1200 ° C., it is difficult to apply the overflow downdraw method. Therefore, if the liquidus temperature is higher than 1200 ° C., unreasonable restrictions are imposed on the method for forming the glass substrate for solar cells, and there is a possibility that glass having a desired surface shape cannot be formed. The lower the liquidus temperature, the better the devitrification resistance of the glass. In general, the improvement of the properties of glass is achieved by reducing some properties, and tends to be in a so-called trade-off relationship with other properties. Here, considering the balance for satisfying various properties required for the glass, such as viscosity, density, and coefficient of thermal expansion, it is a guideline that the liquidus temperature of the glass is designed to be 850 ° C. or higher.

In the glass substrate for a solar cell of the present invention, the liquid phase viscosity is preferably 10 ^4.5 dPa · s or more, more preferably 10 ^5.0 dPa · s or more, further preferably 10 ^5.5 dPa · s or more. ^5.8 dPa · s or more is most preferable. In general, the overflow downdraw method has a higher viscosity of glass during molding than other molding methods, so if the devitrification resistance of the glass is poor, devitrification will occur during molding. There is a risk that the substrate cannot be molded. Specifically, when the liquid phase viscosity is less than 10 ^4.5 dPa · s, it becomes difficult to apply the overflow downdraw method. Therefore, if the liquid phase viscosity is less than 10 ^4.5 dPa · s, an unreasonable restriction is imposed on the method for forming the glass for solar cells, and there is a possibility that glass having a desired shape cannot be formed. Note that the higher the liquidus viscosity, the better the devitrification resistance of the glass. Here, considering the balance for satisfying various properties required for glass, such as viscosity, density, and coefficient of thermal expansion, the liquid phase viscosity of glass should be designed to be 10 ^6.5 dPa · s or less. Become.

In the glass substrate for a solar cell of the present invention, it is preferable that the density is 3.7 g / cm ³ or less, more preferably 3.0 g / cm ³ or less, if it is 2.9 g / cm ³ or less further preferable. The lower the density of the glass, the lighter the glass substrate can be, which can contribute to the weight reduction of the solar cell. When the density is larger than 3.7 g / cm ³ , it becomes difficult to contribute to the weight reduction of the solar cell.

  In the solar cell glass substrate of the present invention, the strain point, which is an index of heat resistance of the glass, is 500 ° C. or higher (more preferably 550 ° C. or higher, more preferably 600 ° C. or higher, particularly preferably 630 ° C. or higher). preferable. The higher the strain point, the higher the heat resistance of the glass, and the thermal deformation or warpage of the glass substrate in the film formation process (eg, thermal CVD process for forming a transparent electrode on the glass substrate) such as a thin film compound solar cell. Heat shrinkage is less likely to occur. In addition, since film formation at a high temperature is possible, film quality is improved, which can contribute to improvement in conversion efficiency of the solar cell.

In the glass substrate for a solar cell of the present invention, the temperature at a high temperature viscosity of 10 ^2.5 dPa · s is preferably 1650 ° C. or less, more preferably 1620 ° C. or less, and further preferably 1600 ° C. or less. The lower this temperature is, the faster the rising speed of bubbles present in the glass at the time of melting, so that it becomes easier to reduce bubbles and the bubble quality is improved. When the temperature at a high temperature viscosity of 10 ^2.5 dPa · s is higher than 1650 ° C., the rising speed of bubbles existing in the glass at the time of melting becomes slow, so that it becomes difficult to reduce bubbles and the bubble quality deteriorates. In addition, when the temperature at a high temperature viscosity of 10 ^2.5 dPa · s is higher than 1650 ° C., the durability of the furnace refractory also decreases, and as a result, the durability of the melting furnace and the like decreases, and the manufacturing cost of the glass substrate Soars.

In the glass substrate for solar cell of the present invention, the transmittance difference at a wavelength of 400 nm before and after the ultraviolet irradiation is within 2%, preferably within 1.5%, more preferably within 1%, and further preferably within 0.5%. . As the transmittance difference is smaller, the solarization of the glass can be suppressed, and the photoelectric conversion efficiency of the solar cell can be maintained over a long period. Here, “transmittance” refers to a value measured with a spectrophotometer using a glass substrate having a thickness of 0.7 mm. “Transmittance difference at a wavelength of 400 nm before and after irradiation with ultraviolet rays” means transmission at a wavelength of 400 nm when irradiated with ultraviolet rays having a wavelength of 185 nm (2.7 mW / cm ² ) and a wavelength of 254 nm (13 mW / cm ² ) for 12 hours. Refers to the amount that the rate has changed.

  In the glass substrate for a solar cell of the present invention, the transmittance at a wavelength of 400 nm to 1000 nm is preferably 90% or more. When the transmittance at a wavelength of 400 nm to 1000 nm is less than 90%, the photoelectric conversion efficiency of the solar cell tends to decrease.

In the glass substrate for a solar cell of the present invention, specific Young's modulus of the glass is preferably 25GPa / (g / cm ³⁾ or ^{more, 26GPa / (g / cm 3} ) or more preferably, 26.5GPa / (g / cm ³ ) or more is more preferable. As the specific Young's modulus of the glass is higher, the deflection of the glass substrate due to its own weight is reduced. As a result, when the glass substrate is housed in a cassette or the like, the clearance between the glass substrates can be narrowed and housed, so that the productivity of the solar cell is improved. As the Young's modulus, a value measured by a known resonance method is used.

  The glass substrate for a solar cell of the present invention preferably has a plate thickness of 3.0 mm or less, 2.0 mm or less, 1.5 mm or less, 0.7 mm or less, or 0.5 mm or less. The thinner the glass substrate, the lighter the glass substrate and the lighter the solar cell. In addition, plasma CVD methods and sputtering methods are generally employed in the manufacturing process of amorphous silicon solar cells. When a thin film is formed on a glass substrate in such a process, the thickness of the glass substrate is reduced. For example, when the thin film is formed, high-speed heating is possible, so that the manufacturing efficiency of the solar cell can be improved.

  The glass substrate for solar cell of the present invention preferably has an unpolished surface. The theoretical strength of glass is inherently very high, but breakage often occurs even at a stress much lower than the theoretical strength. This is because a small defect called Griffith flow occurs on the surface of the glass substrate in a post-molding process such as a polishing process. Therefore, if the surface of the glass substrate is not polished, the mechanical strength of the original glass substrate is difficult to be damaged, and the glass substrate is difficult to break. Further, if the surface of the glass substrate is unpolished, the polishing process can be omitted in the glass substrate manufacturing process, so that the manufacturing cost of the glass substrate can be reduced. In the glass substrate for solar cells of the present invention, if both surfaces of the glass substrate are unpolished, the glass substrate becomes more difficult to break. In particular, since the cover glass for solar cells is installed so as to face the sun, it is preferable to have an unpolished surface in order to improve characteristics such as impact resistance. Moreover, in the glass substrate for solar cells of this invention, in order to prevent the situation where it breaks from the cut surface of a glass substrate, you may give a chamfering process etc. to the cut surface of a glass substrate.

  In the glass substrate for solar cell of the present invention, the average surface roughness (Ra) of the glass substrate is preferably 20 mm or less, more preferably 10 mm or less, further preferably 7 mm or less, particularly preferably 4 mm or less. Most preferred is 2 mm or less. If the average surface roughness (Ra) is greater than 20 mm, it becomes difficult to accurately pattern electrodes and the like in the manufacturing process of the solar cell. As a result, the probability that the circuit electrode is disconnected or short-circuited increases. It becomes difficult to ensure the reliability of Here, “average surface roughness (Ra)” refers to a value measured by a method based on SEMI D7-94 “Measurement method of surface roughness of FPD glass substrate”.

  In the glass substrate for a solar cell of the present invention, the difference between the maximum plate thickness and the minimum plate thickness of the glass substrate is preferably 20 μm or less, and more preferably 10 μm or less. If the difference between the maximum thickness and the minimum thickness of the glass substrate is greater than 20 μm, it becomes difficult to accurately pattern electrodes, resulting in an increased probability of circuit electrodes being disconnected and short-circuited, and the reliability of solar cells. It becomes difficult to secure sex. Here, the “thickness difference between the maximum plate thickness and the minimum plate thickness” is the maximum plate of the glass substrate by scanning a laser from one side of the glass substrate in the plate thickness direction using a laser type thickness measuring device. The value obtained by subtracting the value of the minimum thickness from the value of the maximum thickness after measuring the thickness and the minimum thickness.

  In the glass substrate for a solar cell of the present invention, the undulation of the glass substrate is preferably 0.1 μm or less, more preferably 0.05 μm or less, further preferably less than 0.03 μm, and most preferably 0.01 μm or less. Furthermore, ideally, it is desirable that there is substantially no swell. If the waviness is larger than 0.1 μm, it becomes difficult to perform accurate patterning of the electrodes and the like. As a result, the probability that the circuit electrode is disconnected or shorted increases, and it becomes difficult to ensure the reliability of the solar cell. Here, “swell” is a value obtained by measuring WCA (filtered center line swell) described in JIS B-0610 using a stylus type surface shape measuring device, and this measurement is based on SEMI STD D15- 1296 "Measurement method of surface waviness of FPD glass substrate" Measured with a measurement cutoff of 0.8 to 8mm and a length of 300mm in the direction perpendicular to the drawing direction of the glass substrate. It is a thing.

  In the glass substrate for a solar cell of the present invention, the error with respect to the target plate thickness is preferably 10 μm or less, and more preferably 5 μm or less. If the error with respect to the target thickness of the glass substrate is larger than 10 μm, the patterning accuracy of the electrodes and the like is lowered, and it becomes difficult to stably manufacture high-quality solar cells under predetermined conditions. Here, the “error with respect to the target plate thickness” refers to the larger one of the absolute values of the values obtained by subtracting the maximum plate thickness or the minimum plate thickness obtained by the above method from the target plate thickness.

  The glass substrate for a solar cell of the present invention is prepared by charging a glass raw material prepared so as to have a desired glass composition into a continuous melting furnace, heating and melting the glass raw material at 1400 to 1600 ° C., clarifying it, and then supplying it to a molding apparatus Then, the molten glass can be formed into a plate shape and slowly cooled.

  Various methods can be adopted as a method for forming the glass substrate for a solar cell of the present invention. For example, various forming methods such as an overflow down draw method, a float method, a slot down method, a redraw method, a roll out method, a press method, and the like can be employed.

  It is preferable that the glass substrate for solar cells of the present invention is formed by an overflow down draw method. If the glass substrate is formed by the overflow down draw method, a glass substrate that is unpolished and has good surface quality can be produced. The reason for this is that, in the case of the overflow down draw method, the surface to be the surface of the glass substrate does not come into contact with the bowl-like refractory, and is molded in a free surface state. This is because it can be molded. Here, the overflow down draw method is a method in which molten glass is overflowed from both sides of a heat-resistant bowl-shaped structure, and the overflowed molten glass is stretched and formed downward while joining at the lower end of the bowl-shaped structure. It is a method of manufacturing. The structure and material of the bowl-shaped structure are not particularly limited as long as the dimensions and the surface quality of the glass substrate are in a desired state and the quality usable for the glass substrate can be realized. Moreover, in order to perform the downward extending | stretching shaping | molding, you may apply force with what kind of method with respect to a glass substrate. For example, a method may be employed in which a heat-resistant roll having a sufficiently large width is rotated and stretched in contact with the glass substrate, or a plurality of pairs of heat-resistant rolls are only near the end face of the glass substrate. You may employ | adopt the method of making it contact and extending | stretching. Since the glass for solar cells according to the present invention is excellent in devitrification resistance and has viscosity characteristics suitable for molding, the overflow downdraw method can be executed with high accuracy.

  Hereinafter, the present invention will be described based on examples.

  Tables 1-9 show Example No. of the present invention. 1 to 40, Comparative Example No. 1 of the present invention. 41 is shown.

  Each sample was produced as follows.

  First, various glass raw materials were prepared so as to have the compositions shown in Tables 1 to 9. These raw materials were melted at 1580 ° C. for 5.5 hours using a platinum pot. Thereafter, the molten glass was poured out on a carbon plate, formed into a plate shape, and subjected to various evaluations.

  For each sample thus prepared, density, thermal expansion coefficient, strain point, liquidus temperature, liquidus viscosity, and high temperature viscosity were measured.

  The density was measured by the well-known Archimedes method.

  The thermal expansion coefficient is obtained by measuring an average thermal expansion coefficient at 30 to 380 ° C. using a dilatometer.

  The strain point was measured by a method based on ASTM C336-71.

  The liquid phase temperature is measured by crushing glass, passing through a standard sieve 30 mesh (500 μm), putting the glass powder remaining on 50 mesh (300 μm) into a platinum boat, holding it in a temperature gradient furnace for 48 hours, The temperature at which precipitation occurs is measured. The liquid phase viscosity was measured by the well-known platinum pulling method for the viscosity of each glass at the liquid phase temperature.

A temperature corresponding to a high temperature viscosity of 10 ^2.5 dPa · s was measured by a well-known platinum ball pulling method.

  Young's modulus was measured by a resonance method.

As is apparent from Tables 1 to 8, sample No. 1 to 40 have a density of 2.81 to 3.60 g / cm ³ , a thermal expansion coefficient of 67 to 89 × 10 ⁻⁷ / ° C., a strain point of 603 to 698 ° C., a liquidus temperature of 950 to 1200 ° C., a liquid The phase viscosity was 10 ^4.5 to 10 ^6.4 , the temperature at a high temperature viscosity of 10 ^2.5 dPa · s was 1194 to 1650 ° C., and it had characteristics suitable as a glass substrate for solar cells. Moreover, since the liquidus temperature and the liquidus viscosity are the above values, a glass substrate can be produced by an overflow downdraw method, and a glass substrate with good surface quality can be obtained.

As apparent from Table 9, the sample No. No. 41 contained 12.0% by mass of Na ₂ O in the glass composition, so the strain point was as low as 510 ° C. and the heat resistance was poor.

  As explained above, the glass substrate for solar cells of the present invention is suitable as a cover glass for solar cells and a substrate for solar cells. Moreover, the glass substrate for solar cells of the present invention is suitable for single crystal silicon solar cells, polycrystalline silicon solar cells, amorphous silicon solar cells, thin film compound solar cells and the like.

The present inventors, as a result of extensive studies, the glass for a solar cell, the composition range of the glass, _SiO 2 30 to _70% by _{mass%, Al 2 O 3 3~20%} , B 2 O 3 0~10%, _{0~10% MgO, CaO 0~10%,} SrO 0~25%, BaO 0~25%, Na 2 O 0~10%, K 2 O 2 ~10%, was restricted to ZrO 2 0 to 8%, And it discovers that the said subject can be solved by setting the thermal expansion coefficient in 30-380 degreeC to 50-95x10 < ^-7 > / degreeC, and proposes as this invention. Here, “thermal expansion coefficient at 30 to 380 ° C.” refers to a value obtained by measuring an average thermal expansion coefficient at 30 to 380 ° C. using a dilatometer.

Secondly, a glass substrate for a solar cell of the present invention has a glass composition preferably contains ZrO ₂ 0.001 to 8% in mass%. As a result of diligent efforts, the present inventors have found an appropriate ZrO ₂ content that improves heat resistance while suppressing devitrification of the glass. If the content of ZrO ₂ is regulated as described above, the strain point can be increased and the viscosity necessary for performing the overflow downdraw method can be easily secured.

Thirdly, the glass substrate for a solar cell of the present invention has a glass composition, it is preferred that the _B 2 _{O 3} in mass% containing 0.1 to 8%. If the content of B ₂ O ₃ is regulated as described above, the meltability of the glass is improved and the devitrification resistance of the glass is further improved.

Fourthly, it is preferable that the glass substrate for solar cells of the present invention has a molar fraction of Al ₂ O ₃ / BaO of 0.1 to ₂ .

Fifth, a glass substrate for a solar cell of the present invention, it is preferable the value of _Na 2 O / _{K 2} O is 0 to 2 mole fraction.

Sixth, a glass substrate for a solar cell of the present invention, the liquidus temperature is preferably 1200 ° C. or less and / or liquidus viscosity of ¹⁰ 4.5 dPa · s or more. Here, “liquid phase viscosity” refers to pulverizing glass, passing through a standard sieve 30 mesh (500 μm), and putting the glass powder remaining on 50 mesh (300 μm) into a platinum boat and holding it in a temperature gradient furnace for 48 hours. Thus, the temperature at which crystals are deposited is measured. Further, “liquid phase viscosity” refers to a value obtained by measuring the viscosity of glass at the liquid phase temperature measured by the above method by a well-known platinum pulling method.

Seventh, the glass substrate for solar cell of the present invention preferably has a density of 3.7 g / cm ³ or less.

Eighth, the glass substrate for solar cell of the present invention preferably has a strain point of 590 ° C. or higher. Here, “strain point” refers to a value measured by a method based on ASTM C336-71.

Ninthly, the glass substrate for a solar cell of the present invention preferably has a temperature at a high temperature viscosity of 10 ^2.5 dPa · s of 1650 ° C. or lower. Here, “temperature at a high temperature viscosity of 10 ^2.5 dPa · s” refers to a value measured by a platinum ball pulling method.

10thly, it is preferable to use the glass substrate for solar cells of this invention for a thin film compound solar cell. The manufacturing method of the glass substrate for solar cells of this invention is a manufacturing method of said glass substrate for solar cells, Comprising: It is preferable that the shaping | molding method of a glass substrate is an overflow down draw method. If the overflow down draw method is employed, a glass substrate with excellent surface quality can be easily produced.

K ₂ O is a component that decreases the high-temperature viscosity and adjusts the thermal expansion coefficient, and its content is 2 to 10%, preferably 2 to 8%, more preferably 2 to 6%. If the content of K ₂ O is more than 10%, the strain point is lowered or the thermal expansion coefficient is too high. In addition, the alkali component may diffuse into the thin film compound to cause warping of the substrate or deteriorate the quality of the film. On the other hand, it is desirable to contain 2 % or more (preferably 3 % or more) of K ₂ O in order to enjoy the effect of reducing the high temperature viscosity and the effect of adjusting the thermal expansion coefficient.

In the glass composition range described above, it is naturally possible to select a preferable glass composition range by arbitrarily combining the preferable content ranges of the respective components, but among them, more preferable glass as a glass substrate for a solar cell. composition _{range, SiO 2 40~65%, Al 2} O 3 5~15%, B 2 O 3 0~5%, 0~8% MgO, CaO 0~8%, SrO 0~12.5%, BaO _{0~14%, Na 2 O 0~5%} , K 2 O 2 ~6%, a ZrO 2 0.01 to 4%. If the composition range of glass is regulated as described above, devitrification resistance can be improved, and suitable viscosity characteristics can be secured in molding by the overflow down draw method. Further, still more preferably in the range of _{SiO 2 50~60%, Al 2 O} 3 5~10%, B 2 O 3 0~5%, 0~5% MgO, CaO 0~5%, SrO 5~12.5% _{, BaO 9~14%, Na 2 O} 0~5%, K 2 O 3~6%, a ZrO 2 1 to 4%. If the glass composition range is regulated as described above, the devitrification resistance can be greatly improved, and a glass excellent in heat resistance can be obtained while securing suitable viscosity characteristics when forming by the overflow down draw method. Can do.

Tables 1-9 show Example No. of the present invention. 1 to 40, Comparative Example No. 1 of the present invention. 41 is shown. Sample No. Reference numerals 39 and 40 are reference examples.

Claims (10)

A glass composition, _SiO 2 30 to _70% by _{mass%, Al 2 O 3 3~20%} , B 2 O 3 0~10%, 0~10% MgO, CaO 0~10%, SrO 0~25%, BaO 0 to 25%, Na ₂ O 0 to 10%, K ₂ O 0 to 10%, ZrO ₂ 0 to 8%, and the thermal expansion coefficient at 30 to 380 ° C. is 50 to 95 × 10 ⁻⁷ / A glass substrate for solar cells, characterized in that it is at ° C. The glass substrate for solar cells according to claim 1, wherein the glass composition contains 0.01 to 8% of ZrO ₂ by mass%. As a glass composition, a glass substrate for a solar cell according to claim 1 or 2, characterized in that it contains _B 2 _{O 3} 0.1 to 8% by mass%. A glass substrate for a solar cell according to claim 1, wherein the value of _Al 2 _O 3 / BaO in a molar fraction of 0.1 to 2. The glass substrate for a solar cell according to any one of claims 1 to 4, wherein the Na ₂ O / K ₂ O value is 0 to 2 in terms of molar fraction. The glass substrate for a solar cell according to any one of claims 1 to 5, wherein a liquidus temperature is 1200 ° C or lower and / or a liquidus viscosity is 10 ^4.5 dPa · s or higher. The glass substrate for a solar cell according to claim 1, wherein the density is 3.7 g / cm ³ or less.   The glass substrate for a solar cell according to any one of claims 1 to 7, wherein the strain point is 590 ° C or higher. The glass substrate for solar cells according to any one of claims 1 to 8, wherein the temperature at a high temperature viscosity of 10 ^2.5 dPa · s is 1650 ° C or lower. It is a manufacturing method of the glass substrate for solar cells in any one of Claims 1-9,
A method for producing a glass substrate for a solar cell, wherein the glass substrate is formed by an overflow downdraw method.