WO2010098297A1 - 電極形成用ガラス組成物および電極形成材料 - Google Patents
電極形成用ガラス組成物および電極形成材料 Download PDFInfo
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- WO2010098297A1 WO2010098297A1 PCT/JP2010/052672 JP2010052672W WO2010098297A1 WO 2010098297 A1 WO2010098297 A1 WO 2010098297A1 JP 2010052672 W JP2010052672 W JP 2010052672W WO 2010098297 A1 WO2010098297 A1 WO 2010098297A1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/14—Silica-free oxide glass compositions containing boron
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/14—Silica-free oxide glass compositions containing boron
- C03C3/145—Silica-free oxide glass compositions containing boron containing aluminium or beryllium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/14—Silica-free oxide glass compositions containing boron
- C03C3/15—Silica-free oxide glass compositions containing boron containing rare earths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/14—Compositions for glass with special properties for electro-conductive glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/08—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances quartz; glass; glass wool; slag wool; vitreous enamels
- H01B3/087—Chemical composition of glass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- the present invention relates to a glass composition for electrode formation and an electrode forming material, and in particular, a back electrode of a silicon solar cell (including a single crystal silicon solar cell, a polycrystalline silicon solar cell, a microcrystalline silicon solar cell, an amorphous silicon solar cell, etc.). It is related with the glass composition for electrode formation suitable for formation of electrode, and an electrode formation material.
- a silicon solar cell including a single crystal silicon solar cell, a polycrystalline silicon solar cell, a microcrystalline silicon solar cell, an amorphous silicon solar cell, etc.
- a silicon solar cell includes a silicon semiconductor substrate, a light-receiving surface electrode, a back electrode, an antireflection film, and the like.
- a grid-shaped light-receiving surface electrode is formed on the light-receiving surface side of the silicon semiconductor substrate.
- a back electrode is formed on the back side.
- the light receiving surface electrode is generally an Ag electrode and the back surface electrode is generally an Al electrode.
- the back electrode is usually formed by a thick film method.
- an electrode forming material is screen-printed on a silicon semiconductor substrate so as to have a desired electrode pattern, and this is fired for a short time at a maximum temperature of 660 to 900 ° C.
- This is a method of forming a back electrode on a silicon semiconductor substrate by diffusing Al into the silicon semiconductor substrate for 3 minutes and holding at the maximum temperature for 10 to 30 seconds).
- the electrode forming material used for forming the back electrode contains Al powder, glass powder, vehicle and the like. When this electrode forming material is baked, the Al powder reacts with Si of the silicon semiconductor substrate to form an Al—Si alloy layer at the interface between the back electrode and the silicon semiconductor substrate, and the Al—Si alloy layer and the silicon semiconductor substrate.
- a p + electrolytic layer (also referred to as a Back Surf Field layer or a BSF layer) is formed at the interface.
- the glass powder contained in the electrode forming material promotes the reaction between Al powder and Si, and has a function of forming a p + electrolytic layer at the interface between the Al—Si alloy layer and the silicon semiconductor substrate to impart a BSF effect.
- the silicon semiconductor substrate thinner. If the silicon semiconductor substrate is made thin, the back surface side where the back electrode is formed on the silicon semiconductor substrate becomes concave after firing of the electrode forming material due to the difference in thermal expansion coefficient between Al and the silicon semiconductor substrate. It tends to occur. If the coating amount of the electrode forming material is reduced and the back electrode is made thin, the warp of the silicon semiconductor substrate can be suppressed. However, if the coating amount of the electrode forming material is reduced, blister or Al Aggregation tends to occur.
- the present invention provides a glass composition for electrode formation and an electrode forming material that are less likely to cause blister and Al agglomeration and that are suitable for forming an Al—Si alloy layer and a p + electrolytic layer. It is a technical problem to reduce the manufacturing cost of a silicon solar cell while improving the characteristics such as photoelectric conversion efficiency of the solar cell.
- the present inventor solved the above technical problem by using Bi 2 O 3 —B 2 O 3 —ZnO-based glass and introducing a predetermined amount of alkaline earth metal oxide into the glass composition.
- the present invention is found and proposed as the present invention. That is, the electrode-forming glass composition of the present invention has a glass composition expressed in terms of mass% in terms of the following oxide, Bi 2 O 3 60 to 90%, B 2 O 3 2 to 25%, ZnO 0 to 25%. MgO + CaO + SrO + BaO (total amount of MgO, CaO, SrO, BaO) 0.01-20%, SiO 2 0-25%.
- Bi 2 O 3 and B 2 O 3 are introduced as the main components of the glass, the reaction between the Al powder and Si is facilitated while the reaction between the Al powder and Si is facilitated, and blister and Al aggregation are suppressed. can do.
- Bi 2 O 3 —B 2 O 3 glass it becomes easier to form a p + electrolytic layer than lead borate glass, so that it is easy to enjoy the BSF effect and photoelectric conversion of the silicon solar cell. Efficiency can be increased.
- MgO + CaO + SrO + BaO is introduced in a predetermined range or more, aggregation of blisters or Al can be suppressed, and if the content of MgO + CaO + SrO + BaO is regulated to a predetermined range or less, it becomes easy to prevent a situation where it is difficult to enjoy the BSF effect. If the content of ZnO is restricted to a predetermined range or less, blister and Al aggregation can be suppressed.
- the content of SiO 2 is regulated to a predetermined range or less, a situation in which the softening point of the glass is unreasonably increased or a thermal stability of the glass is lowered, and a situation in which the glass is devitrified when the electrode forming material is fired is prevented. It becomes easy to do.
- the content of Bi 2 O 3 , B 2 O 3 , ZnO, MgO + CaO + SrO + BaO, SiO 2 is regulated within a predetermined range, the manufacturing cost of the silicon solar cell is improved while improving the photoelectric conversion efficiency and the like of the silicon solar cell. Can be reduced.
- the electrode-forming glass composition of the present invention is characterized in that the ZnO content is 7.9% or less. If the content of ZnO is restricted to 7.9% or less, it becomes easy to suppress the aggregation of blisters and Al.
- the glass composition for electrode formation of the present invention is characterized in that the content of ZnO is less than the content of B 2 O 3 . If it does in this way, it will become easy to suppress aggregation of a blister or Al.
- the electrode-forming glass composition of the present invention is characterized in that the CaO content is 0.1 to 20%. If CaO is introduced in a predetermined range or more, blister or Al aggregation can be remarkably suppressed, and if the CaO content is regulated to a predetermined range or less, it becomes easy to prevent a situation where it is difficult to enjoy the BSF effect.
- the glass composition for electrode formation of the present invention is characterized in that the content of BaO is 0.1 to 20%.
- the content of BaO is restricted to a predetermined range or less, it becomes easy to prevent a situation in which it is difficult to enjoy the BSF effect.
- the electrode-forming glass composition of the present invention is characterized in that the content of SiO 2 is less than 3%. If it does in this way, it will become easy to prevent the situation where the softening point of glass raises unjustly, or the thermal stability of glass falls, and the situation where glass devitrifies at the time of baking of electrode formation material.
- the electrode forming material of the present invention is characterized in that it contains a glass powder made of the above-mentioned electrode forming glass composition, a metal powder, and a vehicle. If it does in this way, an electrode pattern can be formed by a thick film method, and the production efficiency of a silicon solar cell can be improved.
- vehicle generally refers to a resin in which an organic solvent is dissolved. However, in the present invention, the resin does not contain a high-viscosity organic solvent (for example, isotridecyl alcohol or the like). The aspect comprised only with a higher alcohol) is included.
- the electrode forming material of the present invention wherein the average particle diameter D 50 of the glass powder is less than 5 [mu] m.
- the “average particle diameter D 50 ” refers to a value measured by the laser diffraction method. In the volume-based cumulative particle size distribution curve measured by the laser diffraction method, the accumulated amount is accumulated from the smaller particle. The particle diameter is 50%.
- the electrode forming material of the present invention is characterized in that the softening point of the glass powder is 500 ° C. or less. In this way, the back electrode can be formed at a low temperature.
- the “softening point” refers to a value measured with a macro-type differential thermal analysis (DTA) apparatus, DTA starts measurement from room temperature, and the rate of temperature rise is 10 ° C./min.
- mold DTA apparatus points out the temperature (Ts) of the 4th bending point shown in FIG.
- the electrode forming material of the present invention is characterized in that the crystallization temperature of the glass powder is 600 ° C. or higher. If it does in this way, the thermal stability of glass will improve and it will become difficult to devitrify glass at the time of baking of an electrode formation material, As a result, the mechanical strength of a back surface electrode will become difficult to fall.
- the “crystallization temperature” refers to the peak temperature measured with a macro DTA apparatus, DTA starts measurement from room temperature, and the rate of temperature rise is 10 ° C./min.
- the electrode forming material of the present invention is characterized in that the glass powder content is 0.2 to 10% by mass. This makes it easier to enjoy the BSF effect by forming the p + electrolytic layer at the interface between the Al—Si alloy layer and the silicon semiconductor substrate.
- the electrode forming material of the present invention is characterized in that the metal powder contains Ag, Al, Au, Cu, Pd, Pt and one or more of these alloys. These metal powders have good compatibility with the glass powder according to the present invention, and have a property that the glass is difficult to foam during firing of the electrode forming material.
- the electrode forming material of the present invention is characterized in that the metal powder is Al.
- the electrode forming material of the present invention is used for an electrode of a silicon solar cell.
- the electrode forming material of the present invention is used for a back electrode of a silicon solar cell.
- Bi 2 O 3 is a component that forms a skeleton of glass, and when it is contained as a main component, it is a component that has an effect of suppressing aggregation of blisters and Al, and is a component that lowers the softening point of glass.
- the content thereof is 60 to 90%, preferably 67 to 86%, more preferably 69 to 86%, still more preferably 75 to 82.5%.
- the softening point of the glass becomes too high, and it becomes difficult to form the back electrode at a low temperature.
- the content of Bi 2 O 3 is increased, the thermal stability of the glass is lowered, the glass is easily devitrified when the electrode forming material is fired, and the mechanical strength of the back electrode is easily lowered.
- B 2 O 3 is a component that forms a glass skeleton.
- B 2 O 3 is a component that provides an effect of suppressing aggregation of blisters and Al.
- B 2 O 3 is a component that increases the thermal stability of the glass and a component that lowers the softening point of the glass.
- the content of B 2 O 3 is 2 to 25%, preferably 3 to 14.5%, more preferably 4 to 13%, and particularly preferably 6 to 10.5%.
- the content of B 2 O 3 decreases, the reaction between Al powder and Si tends to be non-uniform, the amount of Al—Si alloy generated locally increases, and blisters and Al agglomeration tend to occur.
- ZnO is a component that increases the thermal stability of the glass and lowers the softening point of the glass without increasing the thermal expansion coefficient of the glass. Its content is 0 to 25%, preferably 1 It is ⁇ 16%, more preferably 1.5 to 12%, still more preferably 2 to 7.9%, particularly preferably 3 to 7%.
- the ZnO content is reduced, the thermal stability of the glass is lowered, the glass is easily devitrified when the electrode forming material is fired, and the mechanical strength of the back electrode is easily lowered.
- the ZnO content increases, the reaction between the Al powder and Si tends to be non-uniform, the amount of Al—Si alloy produced locally increases, and blisters and Al agglomeration tend to occur.
- the content of ZnO is preferably smaller than the content of B 2 O 3.
- the content of ZnO is decreased with respect to the content of B 2 O 3 , there is a tendency that blisters and Al aggregation hardly occur.
- MgO + CaO + SrO + BaO is a component that suppresses aggregation of blisters and Al, and its content is preferably 0.01 to 20%, 0.1 to 20%, 1 to 15%, particularly preferably 3 to 10%.
- the content of MgO + CaO + SrO + BaO decreases, the reaction between Al powder and Si tends to be non-uniform, the amount of Al—Si alloy produced locally increases, and blisters and Al agglomeration tend to occur.
- the content of MgO + CaO + SrO + BaO increases, it becomes difficult to form a p + electrolytic layer, so that it becomes difficult to enjoy the BSF effect, and the photoelectric conversion efficiency of the silicon solar cell tends to be lowered.
- content of MgO + CaO + SrO + BaO increases, the component balance of a glass composition will be impaired and a crystal
- MgO is a component that suppresses the aggregation of blisters and Al, and its content is preferably 0 to 5%, 0.1 to 3%, particularly preferably 0 to 1%.
- the content of MgO increases, it becomes difficult to form a p + electrolytic layer, so that it becomes difficult to enjoy the BSF effect, and the photoelectric conversion efficiency of the silicon solar cell is likely to decrease.
- CaO is a component having a high effect of suppressing aggregation of blisters and Al, and the content thereof is 0 to 20%, 0.01 to 10%, 0.1 to 8%, 0.5 to 5%, particularly 1 ⁇ 4% is preferred.
- the content of CaO increases, it becomes difficult to form a p + electrolytic layer, so that it becomes difficult to enjoy the BSF effect, and the photoelectric conversion efficiency of the silicon solar cell is likely to decrease.
- SrO is a component that suppresses the aggregation of blisters and Al, and is a component that enhances the thermal stability of the glass, and its content is preferably 0 to 15%, 0 to 10%, particularly preferably 0 to 5%.
- the content of SrO increases, it becomes difficult to form the p + electrolytic layer, so that it becomes difficult to enjoy the BSF effect, and the photoelectric conversion efficiency of the silicon solar cell is likely to decrease.
- the content of SrO increases, the component balance of the glass composition is impaired, and conversely, crystals easily precipitate on the glass.
- BaO is a component that suppresses the aggregation of blisters and Al, and is a component that remarkably increases the thermal stability of glass, and its content is 0 to 20%, 0.01 to 15%, 0.1 to 12%, 1 to 10%, particularly 3 to 9% are preferable.
- the content of BaO decreases, the reaction between the Al powder and Si tends to be non-uniform, the amount of Al—Si alloy produced locally increases, and blisters and Al agglomeration tend to occur.
- the content of BaO is excessively large, it becomes difficult to form the p + electrolytic layer, so that it is difficult to enjoy the BSF effect, and the photoelectric conversion efficiency of the silicon solar cell is likely to be lowered.
- the content of BaO increases, the component balance of the glass composition is impaired, and conversely, crystals easily precipitate on the glass.
- SiO 2 is a component that enhances the water resistance of the glass, but has the effect of significantly increasing the softening point of the glass, so its content is 25% or less, preferably 8.5% or less, more preferably 5%. Hereinafter, it is more preferably 3% or less, particularly preferably less than 1%. When the content of SiO 2 increases, the softening point of the glass becomes too high, and it becomes difficult to form the back electrode at a low temperature.
- the glass composition for electrode formation of the present invention can contain, for example, the following components up to 20%, preferably up to 10%.
- CuO + Fe 2 O 3 (total amount of CuO and Fe 2 O 3 ) is a component that increases the thermal stability of the glass, and its content is 0 to 15%, 0.1 to 10%, particularly 1 to 10%. Is preferred.
- the content of CuO + Fe 2 O 3 is more than 15%, it is impaired balance of components a glass composition, thermal stability of the glass on the contrary tends to decrease. It is necessary to add a large amount of Bi 2 O 3 to the glass composition in order to enjoy the BSF effect accurately while suppressing the aggregation of blisters and Al. If the content of Bi 2 O 3 is increased, The glass tends to be devitrified during the firing of the electrode forming material, and the mechanical strength of the back electrode is likely to be reduced due to the devitrification.
- the Bi 2 O 3 content when the Bi 2 O 3 content is 75% or more, the tendency becomes remarkable. Therefore, if an appropriate amount of CuO + Fe 2 O 3 is added to the glass composition, devitrification of the glass can be suppressed even if the Bi 2 O 3 content is 75% or more.
- the CuO content is preferably 0 to 15%, 0.1 to 10%, particularly 1 to 5%.
- the content of Fe 2 O 3 is preferably 0 to 10%, 0.05 to 5%, particularly preferably 0.2 to 3%.
- the CuO content is preferably larger than the BaO content. If it does in this way, aggregation of blister and Al can be controlled effectively.
- Li 2 O, Na 2 O, K 2 O and Cs 2 O are components that lower the softening point of the glass, but since they have an action of promoting devitrification of the glass when melted, the content of these components is Each is preferably 2% or less.
- Sb 2 O 3 is a component that enhances the thermal stability of the glass, and its content is preferably 0 to 7%, particularly preferably 0.1 to 3%.
- the content of Sb 2 O 3 is too large, is impaired balance of components a glass composition, the thermal stability of the glass tends to decrease conversely.
- the use of Sb 2 O 3 may be restricted from an environmental point of view. In such a case, it is preferable that Sb 2 O 3 is not substantially contained.
- “substantially does not contain Sb 2 O 3 ” refers to a case where the content of Sb 2 O 3 in the glass composition is 1000 ppm or less.
- Nd 2 O 3 is a component that enhances the thermal stability of the glass, and its content is preferably 0 to 10%, 0 to 5%, particularly preferably 0.1 to 3%. If a predetermined amount of Nd 2 O 3 is added to the glass composition, the glass network of Bi 2 O 3 —B 2 O 3 glass is stabilized, and Bi 2 O 3 (bismite), Bi 2 O 3 and B are used during firing. 2 O 3, such as 2Bi 2 O 3 ⁇ B 2 O 3 or 12Bi 2 O 3 ⁇ B 2 O 3 is formed in the crystal is less likely to precipitate. However, if the content of Nd 2 O 3 is too large, is impaired balance of components a glass composition, crystals are liable to precipitate in glass to the contrary.
- WO 3 is a component that enhances the thermal stability of the glass, and its content is preferably 0 to 5%, particularly preferably 0 to 2%. When the content of WO 3 is too large, is impaired balance of components a glass composition, the thermal stability of the glass tends to decrease conversely.
- In 2 O 3 + Ga 2 O 3 (total amount of In 2 O 3 and Ga 2 O 3 ) is a component that increases the thermal stability of the glass, and its content is 0 to 5%, 0 to 3%, In particular, 0 to 1% is preferable.
- the contents of In 2 O 3 and Ga 2 O 3 are each preferably 0 to 2%.
- P 2 O 5 is a component that suppresses the devitrification of the glass at the time of melting. However, if the content is large, the glass is easily phase-separated at the time of melting, and an Al—Si alloy layer and a p + electrolytic layer are uniformly formed. It becomes difficult to do. Therefore, the content of P 2 O 5 is preferably 1% or less.
- MoO 3 + La 2 O 3 + Y 2 O 3 + CeO 2 (total amount of MoO 3 , La 2 O 3 , Y 2 O 3 , CeO 2 ) has an effect of suppressing the phase separation of the glass at the time of melting.
- the content of MoO 3 + La 2 O 3 + Y 2 O 3 + CeO 2 is preferably 3% or less.
- the contents of MoO 3 , La 2 O 3 , Y 2 O 3 and CeO 2 are each preferably 0 to 2%.
- the bismuth-based glass composition of the present invention does not exclude the inclusion of PbO, but it is preferable that it does not substantially contain PbO from the environmental viewpoint. Moreover, since PbO tends to cause aggregation of blisters and Al, it is preferable that PbO does not substantially contain PbO when used for forming the back electrode of the silicon solar battery.
- substantially does not contain PbO refers to a case where the content of PbO in the glass composition is 1000 ppm or less.
- the electrode forming material of the present invention includes glass powder made of the above electrode forming glass composition, metal powder, and vehicle.
- Glass powder is a component that promotes the reaction between Al powder and Si, forms a p + electrolytic layer at the interface between the Al—Si alloy layer and the silicon semiconductor substrate, and imparts a BSF effect.
- the metal powder is a main component for forming the electrode and a component for ensuring conductivity.
- the vehicle is a component for making a paste, and a component for imparting a viscosity suitable for printing.
- the average particle diameter D 50 of the glass powder less than 5 [mu] m, 4 [mu] m or less, 3 [mu] m or less, 2 [mu] m or less, 1 [mu] m or less, in particular less than 1 [mu] m is preferred.
- the average particle diameter D 50 of the glass powder is 5 ⁇ m or more, due to the surface area of the glass powder is reduced, it becomes difficult to promote the reaction of the Al powder and Si, it is difficult to enjoy the BSF effect.
- the average particle diameter D 50 of the glass powder is 5 ⁇ m or more, the softening point of the glass powder is increased, the temperature range is increased required to form the electrode.
- the average particle diameter D 50 of the glass powder is 5 ⁇ m or more, it becomes difficult to form a fine electrode pattern, the photoelectric conversion efficiency of the silicon solar cells tends to decrease.
- the lower limit of the average particle diameter D 50 of the glass powder is not particularly limited, the average particle diameter D 50 of the glass powder is too small, the handling property and material yield of the glass powder tends to decrease. In view of such situation, the average particle diameter D 50 of the glass powder is preferably at least 0.1 [mu] m.
- the obtained glass powder is classified by air, or (2)
- the glass film is coarsely pulverized with a ball mill or the like and then wet pulverized with a bead mill or the like. it can be produced glass powder having a D 50.
- the maximum particle diameter Dmax of the glass powder is preferably 25 ⁇ m or less, 20 ⁇ m or less, 15 ⁇ m or less, 10 ⁇ m or less, particularly preferably less than 10 ⁇ m.
- the “average particle diameter D max ” refers to a value measured by the laser diffraction method. In the volume-based cumulative particle size distribution curve measured by the laser diffraction method, the accumulated amount is accumulated from the smaller particle. The particle diameter is 99%.
- the density of the glass powder is preferably 7.0 g / cm 3 or less, 6.5 g / cm 3 or less, particularly 6.2 g / cm 3 or less. According to the inventor's investigation, the greater the volume of the glass powder, the more reactive the Al powder and Si. Therefore, the smaller the density of the glass powder is, the more the reactivity of the Al powder and Si is improved in terms of unit weight of the glass powder, so that the BSF effect can be easily enjoyed.
- the softening point of the glass powder is preferably 500 ° C. or less, particularly preferably 480 ° C. or less.
- the softening point of the glass powder is higher than 500 ° C., the temperature range necessary for forming the electrode increases, and the production efficiency of the silicon solar cell decreases.
- the softening point of glass powder is preferably 400 ° C. or higher.
- the crystallization temperature of the glass powder is preferably 600 ° C. or higher, 620 ° C. or higher, particularly 650 ° C. or higher.
- the crystallization temperature of the glass powder is lower than 600 ° C., the thermal stability of the glass is lowered, the glass is easily devitrified when the electrode forming material is fired, and the mechanical strength of the back electrode is easily lowered. Further, when the glass is completely devitrified, it becomes difficult to promote the reaction between the Al powder and Si, and it is difficult to enjoy the BSF effect.
- the glass powder content is preferably 0.2 to 10% by mass, 0.5 to 6% by mass, 0.7 to 4% by mass, and particularly preferably 1 to 3% by mass.
- the glass powder content is less than 0.2% by mass, the reaction between the Al powder and Si becomes non-uniform, the amount of Al-Si alloy produced locally increases, and blisters and Al agglomeration tend to occur. In addition, the mechanical strength of the back electrode tends to decrease.
- the content of the glass powder is more than 10% by mass, the glass tends to segregate after the electrode forming material is fired, the conductivity of the back electrode is lowered, and the photoelectric conversion efficiency of the silicon solar cell may be lowered. is there.
- the content of the glass powder and the content of the metal powder are 0.3: 99.7 to 13:87, 1.5: 98.5 to 7:93 in mass ratios for the same reason as described above. 1.8: 98.2 to 4:96 are preferred.
- the content of the glass powder and the content of the metal powder are 1:99 to 10:90, 2:98 to 6:94, particularly 2. 5: 97.5 to 5:95 are preferred.
- the glass powder content decreases, the reaction between the Al powder and Si becomes non-uniform, the amount of Al-Si alloy produced locally increases, and blisters and Al agglomeration are likely to occur.
- the mechanical strength of the electrode tends to decrease.
- the content of the glass powder increases, the glass tends to segregate after the electrode forming material is baked, and the conductivity of the back electrode is lowered, which may reduce the photoelectric conversion efficiency of the silicon solar cell.
- the content of the metal powder is preferably 50 to 97% by mass, 65 to 95% by mass, particularly 70 to 92% by mass.
- content of metal powder is less than 50 mass%, the electroconductivity of a back surface electrode will fall and the photoelectric conversion efficiency of a silicon solar cell will fall easily.
- the content of the metal powder is more than 97% by mass, the content of the glass powder or the vehicle must be relatively lowered, and it becomes difficult to form the p + electrolytic layer.
- the metal powder is preferably one or more of Ag, Al, Au, Cu, Pd, Pt and alloys thereof, and Al is particularly preferable from the viewpoint of enjoying the BSF effect.
- These metal powders have good electrical conductivity and good compatibility with the glass powder according to the present invention. Therefore, when these metal powders are used, the glass is less likely to be devitrified when the electrode forming material is fired, and the glass is less likely to foam. Further, in order to form a fine electrode pattern, the mean particle diameter D 50 of the metal powder is 5 ⁇ m or less, 3 [mu] m or less, 2 [mu] m or less, especially 1 ⁇ m or less.
- the content of the vehicle is preferably 5 to 50% by mass, particularly 10 to 30% by mass.
- the content of the vehicle is less than 5% by mass, it becomes difficult to form a paste and it is difficult to form an electrode by the thick film method.
- the content of the vehicle is more than 50% by mass, the film thickness and film width are likely to fluctuate before and after the electrode forming material is fired, and as a result, it is difficult to form a desired electrode pattern.
- a vehicle generally refers to a resin in which a resin is dissolved in an organic solvent.
- a resin acrylic acid ester (acrylic resin), ethyl cellulose, polyethylene glycol derivative, nitrocellulose, polymethylstyrene, polyethylene carbonate, methacrylic acid ester and the like can be used.
- acrylic acid ester, nitrocellulose, and ethylcellulose are preferable because of their good thermal decomposability.
- Organic solvents include N, N′-dimethylformamide (DMF), ⁇ -terpineol, higher alcohol, ⁇ -butyllactone ( ⁇ -BL), tetralin, butyl carbitol acetate, ethyl acetate, isoamyl acetate, diethylene glycol monoethyl ether , Diethylene glycol monoethyl ether acetate, benzyl alcohol, toluene, 3-methoxy-3-methylbutanol, water, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl Ether, tripropylene glycol monobutyl ether, propylene carbonate, dimethyl sulfoxide (DMSO) N- methyl-2-pyrrolidone and the like can be used.
- DMSO dimethyl sulfoxide
- DMSO dimethyl s
- the electrode-forming material of the present invention has ceramic filler powder such as cordierite for adjusting the thermal expansion coefficient, oxide powder such as NiO for adjusting the surface resistance of the electrode, and paste characteristics.
- ceramic filler powder such as cordierite for adjusting the thermal expansion coefficient
- oxide powder such as NiO for adjusting the surface resistance of the electrode
- paste characteristics In order to adjust, a surfactant, a thickener, a plasticizer, a surface treatment agent, a pigment or the like may be included to adjust the color tone.
- the electrode forming material (electrode forming glass composition) of the present invention is suitable for forming not only the back electrode but also the light receiving surface electrode.
- a phenomenon in which the electrode forming material penetrates the antireflection film at the time of firing is used, and this phenomenon electrically connects the light-receiving surface electrode and the semiconductor layer. This phenomenon is generally called fire-through.
- fire-through it is not necessary to etch the antireflection film when forming the light receiving surface electrode, and it is not necessary to etch the antireflection film and align the electrode pattern, which dramatically increases the production efficiency of silicon solar cells. To improve.
- the degree to which the electrode-forming material penetrates the antireflection film (hereinafter referred to as fire-through property) varies depending on the composition of the electrode-forming material and the firing conditions, and is particularly affected by the glass composition of the glass powder. Moreover, the photoelectric conversion efficiency of a silicon solar cell correlates with the fire-through property of the electrode forming material. If the fire-through property is insufficient, these characteristics are deteriorated and the basic performance of the silicon solar cell is deteriorated. Since the electrode forming material of the present invention regulates the glass composition range of the glass powder to a predetermined range, it has good fire-through properties and is suitable for forming a light-receiving surface electrode. When the electrode forming material of the present invention is used for forming a light-receiving surface electrode, the metal powder is preferably Ag powder, and the content and the like of Ag powder are as described above.
- the light receiving surface electrode and the back electrode may be formed separately, or the light receiving surface electrode and the back electrode may be formed simultaneously. If the light-receiving surface electrode and the back electrode are formed at the same time, the number of firings can be reduced, so that the production efficiency of the silicon solar cell is improved.
- the electrode forming material of the present invention is used for both the light receiving surface electrode and the back surface electrode, it becomes easy to form the light receiving surface electrode and the back surface electrode simultaneously.
- Tables 1 to 4 show examples of the present invention (sample Nos. 1 to 20) and comparative examples (samples No. 21 and 22).
- Sample No. 21 and 22 exemplify conventional glass compositions for electrode formation.
- Each sample was prepared as follows. First, glass raw materials such as various oxides and carbonates were prepared so as to have the glass composition shown in the table, and after preparing a glass batch, the glass batch was put in a platinum crucible and 1 to 1 at 1000 to 1100 ° C. Melted for 2 hours. Next, a part of the molten glass was poured out into a stainless steel mold as a sample for measuring the thermal expansion coefficient of the push rod (TMA). Molding the other of the molten glass into a film with a water-cooled roller, the obtained glass film was pulverized by a ball mill, after passed through the mesh 250 mesh sieve, and air classification, the average particle diameter D 50 of 1 A glass powder of 5 ⁇ m was obtained.
- TMA thermal expansion coefficient of the push rod
- the obtained glass sample was measured for thermal expansion coefficient ⁇ , softening point and thermal stability.
- the thermal expansion coefficient ⁇ is a value measured with a TMA apparatus, and is a value measured within a temperature range of 30 to 300 ° C.
- Softening point is a value measured with a macro DTA apparatus.
- the measurement temperature range of the macro type DTA was from room temperature to 650 ° C., and the rate of temperature increase was 10 ° C./min.
- the thermal stability was evaluated as “ ⁇ ” when the crystallization temperature was 600 ° C. or higher, and “X” when the crystallization temperature was lower than 600 ° C.
- the crystallization temperature is a value measured with a macro type DTA apparatus.
- the measurement temperature range of the macro type DTA is room temperature to 650 ° C., and the rate of temperature rise is 10 ° C./min.
- the surface resistance of the p + electrolytic layer is the sample no. Based on the surface resistance value of the p + electrolytic layer produced by No. 22, the case where the surface resistance value is lower than “ ⁇ ” is evaluated, and the case where the surface resistance value is higher than “X” is evaluated. In addition, it becomes easy to enjoy a BSF effect, so that the surface resistance value of a p + electrolytic layer is low.
- Appearance was evaluated by visually observing the surface of the back electrode and observing the number of blisters and Al aggregates.
- the case where the number of blisters and Al aggregates was 5 or less was designated as “ ⁇ ”
- the case where the number was 5 to 10 was designated as “ ⁇ ”
- the case where the number was 11 or more was designated as “x”.
- the warpage was evaluated by measuring the surface on the light receiving surface side of the silicon semiconductor substrate with a contact-type surface roughness meter. In the central part of the silicon semiconductor, measurement was performed at an interval of 30 mm, and a case where the difference between the lowest part and the uppermost part was less than 20 ⁇ m was designated as “ ⁇ ”, and a case where the difference was 20 ⁇ m or more was designated as “X”.
- sample no. Nos. 1 to 20 had a low coefficient of thermal expansion and a softening point, and the evaluation of thermal stability was good. Furthermore, sample no. For Nos. 1 to 20, the evaluation of the surface resistance, appearance and warpage of the p + electrolytic layer was good. On the other hand, sample No. No. 21 had poor evaluation of the surface resistance and appearance of the p + electrolytic layer. Sample No. In No. 22, the surface resistance of the p + electrolytic layer was inferior, and the appearance was poorly evaluated.
- the fire-through property was evaluated as follows. Each electrode-forming material is linearly screen-printed on a SiN film (thickness: 200 nm) formed on a silicon semiconductor substrate so as to have a length of 200 mm and a width of 100 ⁇ m, dried, and then dried in an electric furnace at 700 ° C. for 1 minute. Baked. Next, the fired silicon semiconductor substrate was immersed in an aqueous hydrochloric acid solution (10 wt% concentration) and subjected to ultrasonic waves for 12 hours to etch each sample. The etched silicon semiconductor substrate was observed with an optical microscope (100 times) to evaluate fire-through properties.
- ⁇ indicates that the linear electrode pattern was formed on the silicon semiconductor substrate through the SiN film, and the linear electrode pattern was generally formed on the silicon semiconductor substrate.
- An evaluation was given as “ ⁇ ” when there was a non-existing portion and the electrical connection with the silicon semiconductor substrate was partially broken, and “X” when it was not penetrating the SiN film.
- sample no. 1 to 20 were evaluated as “ ⁇ ”, and the fire-through property was good. Therefore, sample no. Nos. 1 to 20 are considered suitable for formation of the light-receiving surface electrode of the silicon solar cell.
- sample No. No. 21 was an evaluation of “ ⁇ ”, and the fire-through property was poor.
- Sample No. No. 22 was an evaluation of “x”, and the fire-through property was poor.
- the electrode-forming glass composition and electrode-forming material of the present invention can be suitably used for forming a silicon solar cell electrode, particularly a silicon solar cell back electrode, as described above. Furthermore, the electrode-forming glass composition and electrode-forming material of the present invention can be applied to ceramic electronic parts such as ceramic capacitors and optical parts such as photodiodes.
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Abstract
Description
Claims (15)
- ガラス組成として、下記酸化物換算の質量%表示で、Bi2O3 60~90%、B2O3 2~25%、ZnO 0~25%、MgO+CaO+SrO+BaO 0.1~20%、SiO2 0~25%含有することを特徴とする電極形成用ガラス組成物。
- ZnOの含有量が7.9%以下であることを特徴とする請求項1に記載の電極形成用ガラス組成物。
- ZnOの含有量がB2O3の含有量より少ないことを特徴とする請求項1または2に記載の電極形成用ガラス組成物。
- CaOの含有量が0.1~20%であることを特徴とする請求項1~3のいずれかに記載の電極形成用ガラス組成物。
- BaOの含有量が0.1~20%であることを特徴とする請求項1~4のいずれかに記載の電極形成用ガラス組成物。
- SiO2の含有量が3%未満であることを特徴とする請求項1~5のいずれかに記載の電極形成用ガラス組成物。
- 請求項1~6のいずれかに記載の電極形成用ガラス組成物からなるガラス粉末と、金属粉末と、ビークルとを含むことを特徴とする電極形成材料。
- ガラス粉末の平均粒子径D50が5μm未満であることを特徴とする請求項7に記載の電極形成材料。
- ガラス粉末の軟化点が500℃以下であることを特徴とする請求項7または8に記載の電極形成材料。
- ガラス粉末の結晶化温度が600℃以上であることを特徴とする請求項7~9のいずれかに記載の電極形成材料。
- ガラス粉末の含有量が0.2~10質量%であることを特徴とする請求項7~10のいずれかに記載の電極形成材料。
- 金属粉末がAg、Al、Au、Cu、Pd、Ptおよびこれらの合金の一種または二種以上を含むことを特徴とする請求項7~11のいずれかに記載の電極形成材料。
- 金属粉末がAlであることを特徴とする請求項7~12のいずれかに記載の電極形成材料。
- シリコン太陽電池の電極に用いることを特徴とする請求項7~13のいずれかに記載の電極形成材料。
- シリコン太陽電池の裏面電極に用いることを特徴とする請求項7~14のいずれかに記載の電極形成材料。
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US13/202,626 US20110303883A1 (en) | 2009-02-24 | 2010-02-23 | Glass composition for electrode formation and electrode formation material |
CN2010800079579A CN102317227A (zh) | 2009-02-24 | 2010-02-23 | 电极形成用玻璃组合物和电极形成材料 |
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US (1) | US20110303883A1 (ja) |
JP (1) | JP5532512B2 (ja) |
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WO (1) | WO2010098297A1 (ja) |
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JP2010222238A (ja) | 2010-10-07 |
CN102317227A (zh) | 2012-01-11 |
US20110303883A1 (en) | 2011-12-15 |
JP5532512B2 (ja) | 2014-06-25 |
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