WO2009157727A2 - Conductive paste composition and method of preparing electrode using the same - Google Patents

Conductive paste composition and method of preparing electrode using the same Download PDF

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Publication number
WO2009157727A2
WO2009157727A2 PCT/KR2009/003444 KR2009003444W WO2009157727A2 WO 2009157727 A2 WO2009157727 A2 WO 2009157727A2 KR 2009003444 W KR2009003444 W KR 2009003444W WO 2009157727 A2 WO2009157727 A2 WO 2009157727A2
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WO
WIPO (PCT)
Prior art keywords
conductive paste
paste composition
electrode
composition
binder resin
Prior art date
Application number
PCT/KR2009/003444
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French (fr)
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WO2009157727A3 (en
Inventor
Hwa Joong Kim
Tae Hyun Jun
Ha Chul Song
Eun Kyoung Ryu
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Sscp Co., Ltd.
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Application filed by Sscp Co., Ltd. filed Critical Sscp Co., Ltd.
Priority to CN2009801240419A priority Critical patent/CN102077301A/en
Publication of WO2009157727A2 publication Critical patent/WO2009157727A2/en
Publication of WO2009157727A3 publication Critical patent/WO2009157727A3/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • 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
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
    • 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
    • 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
    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
    • 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
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
    • 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 conductive paste composition useful in preparing an electrode of a solar cell.
  • a solar cell has a p-type semiconductor-n-type semiconductor junction, and its basic structure is the same as that of a diode.
  • the incident light absorbed by the solar cell creates negatively charged electrons and positively charged holes created by the removal electrons which function to generate electric power.
  • a semiconductor may be an n-type semiconductor attracting negatively charged electrons or a p-type semiconductor attracting positively charged holes.
  • the negative charges generated in the semiconductor are attracted toward the n- type semiconductor, and the positive charges, toward the p-type semiconductor. These charges are collected at the respective electrodes, and when a wire is connected to the electrodes, an electrical circuit is formed and an electric current is generated.
  • a crystalline silicon solar cell is generally classified into a single crystal silicon solar cell and a polycrystalline silicon solar cell, and typically contains a p-n homojunction.
  • a single crystal has a high purity and a low crystal defect density, and is capable of achieving a high cell conversion efficiency, although it is expensive. Meanwhile, a relatively inexpensive polycrystalline material is used when the conversion efficiency is high enough for commercialization and provides a low cost solar cell.
  • a single crystal silicon solar cell is known to exhibit a conversion efficiency of about 24% in the absence of a collector and a conversion efficiency of 28% or more hi the presence of a collector, while a polycrystalline silicon solar cell shows a conversion efficiency of about 18%.
  • the theoretically achievable efficiencies of the single crystal and the polycrystalline material are about 35% and 19%, respectively.
  • the electrode paste composition used in the fabrication of the electrode of a conventional solar cell is problematic because the aspect ratio may greatly change during the course of heat-drying the printed electrode paste at 150 to 250 °C for 1 to 2 min and heat-treating at 750 ° C for tens of sec, which reduces the light-receiving region, leading to deteriorated cell conversion efficiency.
  • a conductive paste composition which is capable of preventing the deformation of the printed film during drying and heat-treating. It is another object of the present invention to provide a method for preparing an electrode using the conductive paste composition.
  • a conductive paste composition comprising a binder resin, a diluent, a conductive metal material, glass frit, and an inorganic thixotrophic agent.
  • a method for preparing an electrode using the conductive paste composition which comprises the steps of: printing the conductive paste composition on a substrate; drying the printed conductive paste thus obtained; and heat-treating the dried conductive paste.
  • a solar cell comprising the electrode prepared in the above method as a surface electrode.
  • FIG. 1 shows a schematic view of a solar cell.
  • the conductive paste composition according to the present invention comprises a binder resin, a diluent, a conductive metal material, glass frit, and an inorganic thixotrophic agent.
  • the composition comprises 1 to 10 wt% of the binder resin, 5 to 25 wt% of the diluent, 60 to 90 wt% of the conductive metal material, 1 to 10 wt% of the glass frit, and 0.1 to 5 wt% of the inorganic thixotrophic agent.
  • the composition of the present invention may further comprise 0.1 to 5 parts by weight of a dispersant based on the total weight of the composition.
  • the binder resin is a cellulose-based compound having a viscosity of 5 to 500 cps (5 wt% solvent in an 8:2 mixture of toluene and ethanol), or an acrylic resin-based compound having a molecular weight of 5,000 to 50,000.
  • the binder resin may be selected from the group consisting of a cellulose-based compound such as cellulose acetate, cellulose acetate butyrate, ethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxypropylmethyl cellulose and hydroxyethylmethyl cellulose, an acrylic compound such as polyacrylamide, polymethacrylate, polymethylmethacrylate and polyethylmethacrylate, a vinylic compound such as polyvinylbutyral, polyvinylacetate and polyvinylalcohol, and a mixture thereof.
  • a cellulose-based compound such as cellulose acetate, cellulose acetate butyrate, ethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxypropylmethyl cellulose and hydroxyethylmethyl cellulose
  • an acrylic compound such as polyacrylamide, polymethacrylate, polymethylmethacrylate and polyeth
  • the diluent used in the composition according to the present invention may be selected from the group consisting of ⁇ -terpineol, texanol, dioctyl phthalate, dibutyl phthalate, cyclohexane, hexane, toluene, benzylalcohol, dioxane, diethyleneglycol, ethyleneglycol monobutyl ether, ethyleneglycol monobutyl ether acetate, diethyleneglycol monobutyl ether, diethyleneglycol monobutyl ether acetate, and a mixture thereof.
  • the inorganic thixotrophic agent used in the composition is bentonite or silica and is preferably Aerosil (available from DEGUSSA, Germany).
  • composition according to the present invention containing 0.1 to 5 wt% of the inorganic thixotrophic agent changes in aspect ratio are small before and after a heat-treating process, thereby preventing the deformation of the io printed film upon preparing of an electrode.
  • the conductive metal material used in the present invention may include a silver powder, a copper powder, a nickel powder, or an aluminum powder.
  • the silver powder is prefered. Below, the conductive metal material exemplified by silver powder is described for convenience.
  • the shape of the silver powder may include at least one selected from the group consisting of a spherical shape, an acicular shape, a planar shape, and an amorphous shape.
  • the average particle size of the silver powder may be 0.5 to 5 ⁇ m in consideration of ease of pasting and of density thereof upon heat-treating.
  • the silver powder may be contained in an amount of 60 to 90 wt% in
  • the conductive paste composition in consideration of the thickness and line resistance of the electrode formed upon printing.
  • the glass frit used in the present invention may have an average particle size of 0.5 to 5 ⁇ m, and the component thereof may include at least one selected from the group consisting of 43 to 91 wt% of PbO, 21 wt% or less of SiO 2 , 25
  • the glass frit may have a glass softening temperature of 320 to 520 0 C and a coefficient of thermal expansion of 62 to 110 x 10 "7 /°C .
  • the amount of glass frit may be set to 1 to 10 wt% based on the total weight of the conductive paste
  • the amount of glass frit is smaller than 1 wt%, incomplete heat- treating occurs, undesirably increasing electric resistivity. In contrast, if the amount thereof is greater than 10 wt%, the glass component is excessively increased in the heat-treated silver powder body, undesirably increasing electric resistivity.
  • composition according to the present invention may further include an additive typically known in the art, as necessary.
  • the additive may include at least one selected from the group consisting of a photosensitizer, a polymerization inhibitor, a defoaming agent, a leveling agent and an organic thixotrophic agent.
  • the conductive paste composition according to the present invention may be employed for preparing a surface electrode of a solar cell.
  • a method of preparing an electrode using the inventive conductive paste composition comprises the steps of: printing the conductive paste composition on a substrate; drying the printed conductive paste thus obtained; and heat-treating the dried conductive paste.
  • the electrode according to the present invention may have a thickness of 10 to 40 ⁇ in.
  • the electrode paste printed (or patterned) using the inventive conductive paste composition may be dried at a temperature of 150 to 250 ° C for ones of min, and then heat-treated at a temperature of 700 to 900 ° C for ones of sec.
  • the conductive paste composition according to the present invention may be printed on the substrate using any printing process selected from the group consisting of screen printing, gravure offset printing, rotary screen printing, and lift off printing.
  • the electrode prepared using the inventive conductive paste composition can be usefully employed as the surface electrode of the solar cell.
  • FIG. 1 schematically shows the solar cell.
  • the silicon substrate may include polycrystalline silicon or single crystal silicon.
  • a p-n junction is formed in the vicinity of a light-receiving surface.
  • the substrate In the formation of the p-n junction, the substrate may be a p-type and the light-receiving surface side may be an n-type due to diffusion, or conversely the substrate may be an n-type and the light- receiving surface side may be a p-type.
  • an anti-reflective layer is formed on the light-receiving surface through chemical vapor deposition (CVD).
  • the anti-reflective layer may be formed of titanium oxide, silicon dioxide, or silicon nitride. Particularly useful is silicon nitride because of its high device stability.
  • the anti-reflective layer may be used as a passivation layer.
  • the thickness of the anti-reflective layer may be about 50 to 100 nm.
  • a back electrode formed on the backside of the silicon substrate is prepared by applying a conductive metal material such as aluminum and then drying it.
  • the conductive paste according to the present invention may be utilized to form the surface electrode on the surface of the anti-reflective layer.
  • the pattern of the surface electrode is formed and then dried, after which the surface electrode and the back electrode are simultaneously heat-treated.
  • Examples of the shape of the pattern of the surface electrode may include parallel lines and lattices.
  • the solar cell fabricated using the composition according to the present invention may have an additional element for improving cell performance.
  • a welding layer may be formed on the surface of the surface electrode.
  • the surface electrode formed using the conductive paste according to the present invention has an aspect ratio (height/width) of 0.3 or more. Hence, when such a surface electrode is included in the solar cell, the solar cell can increase its light-receiving area to 93% or above.
  • the conductive paste according to the present invention is heat-treated, line resistance is reduced, so that electromotive force generated by light incidence can be efficiently used as current.
  • ethylcellulose Ethocel Std 100, available from DOW CHEMICAL 5 USA
  • Texanol available from EASTMAN
  • DOP dioctyl phthalate
  • the viscosity was measured at a shear rate of 10 s "1 using a viscometer (RVl, available from HAKKE) and a Ti 35 spindle. Furthermore, the viscosity was measured at a shear rate of each of 1 s “1 and 10 s "1 , and then, a viscosity ratio represented by viscosity measured at 1 s ' Vviscosity measured at 10 s "1 , called the thixo index, was determined.
  • Printability for a width of 100 ⁇ m was confirmed using a 325 mesh screen. Printing was performed at a squeegee rate of 40 cm/min using a screen printer, thereafter drying at 150 0 C was performed. Subsequently, heat-treating was performed in a heat-treating furnace (available from SIEREATHERM) at a maximum of 750 0 C , the printed shape was observed, and an aspect ratio (AJR) was determined. Upon heat-treating, the extent of the deformation of the film could be seen by comparing changes in aspect ratio before and after the heat- treating process.
  • the conductive paste of Examples 1 to 7 had small changes in aspect ratio before and after the heat-treating process, thus reducing the deformation of the printed film.
  • the composition of the comparative examples had large changes in aspect ratio, thus increasing the deformation of the printed film.
  • both the aspect ratio (0.313) before the heat-treating process and the aspect ratio (0.284) after the heat-treating process were improved.
  • the aspect ratio was improved in this way, the light-receiving area was increased and line resistance was reduced.
  • the present invention provides a conductive paste composition and a method of preparing an electrode using the same.
  • the conductive paste composition for preparing an electrode can prevent the deformation of the printed film upon heat-drying and heat-treating after printing thereof. Therefore, when a surface electrode formed using the inventive conductive paste composition according to the present invention is included in a solar cell, the solar cell can have an enlarged light- receiving area and high photoelectric conversion efficiency.

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Abstract

The present invention relates to a conductive paste composition comprising a binder resin, a diluent, a conductive metal material, glass frit, and an inorganic thixotrophic agent, which is useful for preparing an electrode of a solar cell and it prevents the the deformation of an electrode after a heat-treating process, thereby increasing a light-receiving region and photoelectric conversion efficiency.

Description

CONDUCTIVE PASTE COMPOSITION AND METHOD OF PREPARING
ELECTRODE USINGTHE SAME
FIELD OF THE INVENTION
The present invention relates to a conductive paste composition useful in preparing an electrode of a solar cell.
BACKGROUND OF THE INVENTION
A solar cell has a p-type semiconductor-n-type semiconductor junction, and its basic structure is the same as that of a diode.
When light enters the solar cell, the incident light absorbed by the solar cell creates negatively charged electrons and positively charged holes created by the removal electrons which function to generate electric power.
A semiconductor may be an n-type semiconductor attracting negatively charged electrons or a p-type semiconductor attracting positively charged holes. The negative charges generated in the semiconductor are attracted toward the n- type semiconductor, and the positive charges, toward the p-type semiconductor. These charges are collected at the respective electrodes, and when a wire is connected to the electrodes, an electrical circuit is formed and an electric current is generated.
A crystalline silicon solar cell is generally classified into a single crystal silicon solar cell and a polycrystalline silicon solar cell, and typically contains a p-n homojunction. A single crystal has a high purity and a low crystal defect density, and is capable of achieving a high cell conversion efficiency, although it is expensive. Meanwhile, a relatively inexpensive polycrystalline material is used when the conversion efficiency is high enough for commercialization and provides a low cost solar cell. A single crystal silicon solar cell is known to exhibit a conversion efficiency of about 24% in the absence of a collector and a conversion efficiency of 28% or more hi the presence of a collector, while a polycrystalline silicon solar cell shows a conversion efficiency of about 18%. Accidentally, the theoretically achievable efficiencies of the single crystal and the polycrystalline material are about 35% and 19%, respectively.
However, the electrode paste composition used in the fabrication of the electrode of a conventional solar cell is problematic because the aspect ratio may greatly change during the course of heat-drying the printed electrode paste at 150 to 250 °C for 1 to 2 min and heat-treating at 750 °C for tens of sec, which reduces the light-receiving region, leading to deteriorated cell conversion efficiency.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a conductive paste composition, which is capable of preventing the deformation of the printed film during drying and heat-treating. It is another object of the present invention to provide a method for preparing an electrode using the conductive paste composition.
It is a further object of the present invention to provide a solar cell comprising the electrode prepared by the method.
In accordance with an aspect of the present invention, there is provided a conductive paste composition comprising a binder resin, a diluent, a conductive metal material, glass frit, and an inorganic thixotrophic agent.
In accordance with another aspect of the present invention, there is provided a method for preparing an electrode using the conductive paste composition, which comprises the steps of: printing the conductive paste composition on a substrate; drying the printed conductive paste thus obtained; and heat-treating the dried conductive paste.
In accordance with a further aspect of the present invention, there is provided a solar cell comprising the electrode prepared in the above method as a surface electrode. BRIEF DESCRIPTION OF THE DRAWING
The above and other objects and features of the present invention will become apparent from the following description of the invention, when taken in conjunction with the accompanying FIG. 1 which shows a schematic view of a solar cell.
DETAILED DESCRIPTION OFTHE INVENTION
Hereinafter, a detailed description of the present invention will be given.
The conductive paste composition according to the present invention comprises a binder resin, a diluent, a conductive metal material, glass frit, and an inorganic thixotrophic agent.
According to an embodiment of the present invention, the composition comprises 1 to 10 wt% of the binder resin, 5 to 25 wt% of the diluent, 60 to 90 wt% of the conductive metal material, 1 to 10 wt% of the glass frit, and 0.1 to 5 wt% of the inorganic thixotrophic agent. The composition of the present invention may further comprise 0.1 to 5 parts by weight of a dispersant based on the total weight of the composition. In the conductive paste composition according to the present invention, the binder resin is a cellulose-based compound having a viscosity of 5 to 500 cps (5 wt% solvent in an 8:2 mixture of toluene and ethanol), or an acrylic resin-based compound having a molecular weight of 5,000 to 50,000.
Specifically, the binder resin may be selected from the group consisting of a cellulose-based compound such as cellulose acetate, cellulose acetate butyrate, ethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxypropylmethyl cellulose and hydroxyethylmethyl cellulose, an acrylic compound such as polyacrylamide, polymethacrylate, polymethylmethacrylate and polyethylmethacrylate, a vinylic compound such as polyvinylbutyral, polyvinylacetate and polyvinylalcohol, and a mixture thereof.
The diluent used in the composition according to the present invention may be selected from the group consisting of α-terpineol, texanol, dioctyl phthalate, dibutyl phthalate, cyclohexane, hexane, toluene, benzylalcohol, dioxane, diethyleneglycol, ethyleneglycol monobutyl ether, ethyleneglycol monobutyl ether acetate, diethyleneglycol monobutyl ether, diethyleneglycol monobutyl ether acetate, and a mixture thereof.
5 The inorganic thixotrophic agent used in the composition is bentonite or silica and is preferably Aerosil (available from DEGUSSA, Germany).
The composition according to the present invention containing 0.1 to 5 wt% of the inorganic thixotrophic agent changes in aspect ratio are small before and after a heat-treating process, thereby preventing the deformation of the io printed film upon preparing of an electrode.
The conductive metal material used in the present invention may include a silver powder, a copper powder, a nickel powder, or an aluminum powder. The silver powder is prefered. Below, the conductive metal material exemplified by silver powder is described for convenience.
15 The shape of the silver powder may include at least one selected from the group consisting of a spherical shape, an acicular shape, a planar shape, and an amorphous shape. The average particle size of the silver powder may be 0.5 to 5 βm in consideration of ease of pasting and of density thereof upon heat-treating. Furthermore, the silver powder may be contained in an amount of 60 to 90 wt% in
20 the conductive paste composition in consideration of the thickness and line resistance of the electrode formed upon printing.
The glass frit used in the present invention may have an average particle size of 0.5 to 5 μm, and the component thereof may include at least one selected from the group consisting of 43 to 91 wt% of PbO, 21 wt% or less of SiO2, 25
25. wt% or less of B2O3+Bi2O3, 7 wt% or less of Al2O3, 20 wt% or less of ZnO, 15 wt% or less of Na2O+K2O+Li2O, and 15 wt% or less of BaO+CaO+MgO+SrO. The glass frit may have a glass softening temperature of 320 to 5200C and a coefficient of thermal expansion of 62 to 110 x 10"7/°C . The amount of glass frit may be set to 1 to 10 wt% based on the total weight of the conductive paste
30 composition. If the amount of glass frit is smaller than 1 wt%, incomplete heat- treating occurs, undesirably increasing electric resistivity. In contrast, if the amount thereof is greater than 10 wt%, the glass component is excessively increased in the heat-treated silver powder body, undesirably increasing electric resistivity.
The composition according to the present invention may further include an additive typically known in the art, as necessary. For example, the additive may include at least one selected from the group consisting of a photosensitizer, a polymerization inhibitor, a defoaming agent, a leveling agent and an organic thixotrophic agent.
The conductive paste composition according to the present invention may be employed for preparing a surface electrode of a solar cell. A method of preparing an electrode using the inventive conductive paste composition comprises the steps of: printing the conductive paste composition on a substrate; drying the printed conductive paste thus obtained; and heat-treating the dried conductive paste.
The electrode according to the present invention may have a thickness of 10 to 40 μin.
The electrode paste printed (or patterned) using the inventive conductive paste composition may be dried at a temperature of 150 to 250 °C for ones of min, and then heat-treated at a temperature of 700 to 900 °C for ones of sec.
The conductive paste composition according to the present invention may be printed on the substrate using any printing process selected from the group consisting of screen printing, gravure offset printing, rotary screen printing, and lift off printing.
The electrode prepared using the inventive conductive paste composition can be usefully employed as the surface electrode of the solar cell. FIG. 1 schematically shows the solar cell. The silicon substrate may include polycrystalline silicon or single crystal silicon. In order to generate electromotive force in response to light incidence, a p-n junction is formed in the vicinity of a light-receiving surface. In the formation of the p-n junction, the substrate may be a p-type and the light-receiving surface side may be an n-type due to diffusion, or conversely the substrate may be an n-type and the light- receiving surface side may be a p-type.
In order to prevent the reflection of light from the light-receiving surface of the solar cell and increase light-receiving efficiency, an anti-reflective layer is formed on the light-receiving surface through chemical vapor deposition (CVD). The anti-reflective layer may be formed of titanium oxide, silicon dioxide, or silicon nitride. Particularly useful is silicon nitride because of its high device stability. The anti-reflective layer may be used as a passivation layer. The thickness of the anti-reflective layer may be about 50 to 100 nm. Also, a back electrode formed on the backside of the silicon substrate is prepared by applying a conductive metal material such as aluminum and then drying it. The conductive paste according to the present invention may be utilized to form the surface electrode on the surface of the anti-reflective layer. The pattern of the surface electrode is formed and then dried, after which the surface electrode and the back electrode are simultaneously heat-treated. Examples of the shape of the pattern of the surface electrode may include parallel lines and lattices.
The solar cell fabricated using the composition according to the present invention may have an additional element for improving cell performance. For example, to increase reliability in terms of cell performance, a welding layer may be formed on the surface of the surface electrode.
The surface electrode formed using the conductive paste according to the present invention has an aspect ratio (height/width) of 0.3 or more. Hence, when such a surface electrode is included in the solar cell, the solar cell can increase its light-receiving area to 93% or above. In the case where the conductive paste according to the present invention is heat-treated, line resistance is reduced, so that electromotive force generated by light incidence can be efficiently used as current. The following Examples are intended to further illustrate the present invention without limiting its scope.
Preparation of Binder Resin Mixture
PREPARATIVE EXAMPLE 1
In a 1 I flask, 10 g of ethylcellulose (EC) (Ethocel Std 100, available from DOW CHEMICAL5 USA) was homogeniged with a mixture of 85 g of Texanol (available from EASTMAN) and 5 g of dioctyl phthalate (DOP) at 85 °C for 1 hour, to obtain a binder resin mixture.
PREPARATIVE EXAMPLE 2
In a 1 t flask, 20 g of EC (Ethocel Std 45, available from DOW CHEMICAL, USA) was homogeniged with a mixture of 75 g of Texanol (available from EASTMAN) and 5 g of DOP at 850C for 1 hour, to obtain a binder resin mixture.
Preparation of Conductive Paste Composition
EXAMPLE 1
15 g of the binder resin mixture obtained in Preparative Example 1 (containing 1.5 g of the binder resin and 13.5 g of Texanol and DOP), 1 g of a dispersant (BYK 110, available from BYK CHEMI), and 5 g of glass frit (having an average particle size of 1 μm) were dispersed using a three roll-mill, the resulting material was mixed with 78.5 g of silver powder (having a spherical shape and an average particle size of 1 μm) and 0.5 g of an inorganic thixotrophic agent (Aerosil-200, available from DEGUSSA), and then dispersed using a three roll-mill. The mixture thus obtained was subjected to depressurization and defoaming, to obtain a conductive paste, which was filtered using a 325 SUS mesh filter, and the paste's properties were evaluated.
EXAMPLE 2
15 g of the binder resin mixture obtained in Preparative Example 1 (containing 1.5 g of the binder resin and 13.5 g of Texanol and DOP), 1 g of a dispersant (BYK 110, available from BYK CHEMI), and 5 g of glass frit (having an average particle size of 1 μm) were dispersed using a three roll-mill, the resulting material was mixed with 78 g of silver powder (having a spherical shape and an average particle size of 1 μm) and 1 g of an inorganic thixotrophic agent (Aerosil-200, available from DEGUSSA), and then dispersed using a three roll- mill. The mixture thus obtained was subjected to depressurization and defoaming, to obtain a conductive paste, which was filtered using a 325 SUS mesh filter, and the paste's properties were evaluated.
EXAMPLE 3
15 g of the binder resin mixture obtained in Preparative Example 2
(containing 3 g of the binder resin and 12 g of Texanol and DOP), 1 g of a dispersant (BYK 110, available from BYK CHEMI), and 5 g of glass frit (having an average particle size of 1 μm) were dispersed using a three roll-mill, the resulting material was mixed with 78 g of silver powder (having a spherical shape and an average particle size of 1 μm) and 1 g of an inorganic thixotrophic agent (Aerosil-200, available from DEGUSSA), and then dispersed using a three roll- mill. The mixture thus obtained was subjected to depressurization and defoaming, to obtain a conductive paste, which was filtered using a 325 SUS mesh filter, and the paste's properties were evaluated.
EXAMPLE 4
13 g of the binder resin mixture obtained in Preparative Example 1 (containing 1.3 g of the binder resin and 11.7 g of Texanol and DOP), 1 g of a dispersant (BYK 110, available from BYK CHEMI), and 5 g of glass frit (having an average particle size of 1 μm) were dispersed using a three roll-mill, the resulting material was mixed with 80 g of silver powder (having a spherical shape and an average particle size of 1 μm) and 1 g of an inorganic tliixotrophic agent (Aerosil-200, available from DEGUSSA), and then dispersed using a three roll- mill. The mixture thus obtained was subjected to depressurization and defoaming, to obtain a conductive paste, which was filtered using a 325 SUS mesh filter, and the paste's properties were evaluated. EXAMPLE 5
11 g of the binder resin mixture obtained in Preparative Example 1 (containing 1.1 g of the binder resin and 9.9 g of Texanol and DOP), 1 g of a dispersant (BYK 110, available from BYK CHEMI), and 5 g of glass frit (having an average particle size of 1 μm) were dispersed using a three roll-mill, the resulting material was mixed with 82 g of silver powder (having a spherical shape and an average particle size of 1 μm) and 1 g of an inorganic thixotrophic agent (Aerosil-200, available from DEGUSSA), and then dispersed using a three roll- mill. The mixture thus obtained was subjected to depressurization and defoaming, to obtain a conductive paste, which was filtered using a 325 SUS mesh filter, and the paste's properties were evaluated.
EXAMPLE 6
15 g of the binder resin mixture obtained in Preparative Example 1 (containing 1.5 g of the binder resin and 13.5 g of Texanol and DOP), 1 g of a dispersant (BYK 110, available from BYK CHEMI), and 5 g of glass frit (having an average particle size of 1 μm) were dispersed using a three roll-mill, the resulting material was mixed with 38 g of silver powder (having a spherical shape and an average particle size of 1 μm), 40 g of silver powder (having a flake shape and an average particle size of 3 μm) and 1 g of an inorganic thixotrophic agent (Aerosil-200, available from DEGUSSA), and then dispersed using a three roll- mill. The mixture thus obtained was subjected to depressurization and defoaming, to obtain a conductive paste, which was filtered using a 325 SUS mesh filter, and the paste's properties were evaluated.
EXAMPLE 7
15 g of the binder resin mixture obtained in Preparative Example 1 (containing 1.5 g of the binder resin and 13.5 g of Texanol and DOP), 1 g of a dispersant (BYK 110, available from BYK CHEMI), and 5 g of glass frit (having an average particle size of 1 μm) were dispersed using a three roll-mill, the resulting material was mixed with 78 g of silver powder (having a spherical shape and an average particle size of 2 μm) and 1 g of an inorganic thixotrophic agent (Aerosil-200, available from DEGUSSA), and then dispersed using a three roll- mill. The mixture thus obtained was subjected to depressurization and defoaming, to obtain a conductive paste, which was filtered using a 325 SUS mesh filter, and the paste's properties were evaluated.
COMPARATIVE EXAMPLE 1
15 g of the binder resin mixture obtained in Preparative Example 1 (containing 1.5 g of the binder resin and 13.5 g of Texanol and DOP), 1 g of a dispersant (BYK 110, available from BYK CHEMI), and 5 g of glass frit (having an average particle size of 1 μm) were dispersed using a three roll-mill, the resulting material was mixed with 79 g of silver powder (having a spherical shape and an average particle size of 1 μm) and then dispersed using a three roll-mill. The mixture thus obtained was subjected to depressurization and defoaming, to obtain a conductive paste, which was filtered using a 325 SUS mesh filter, and the paste's properties were evaluated.
COMPARATIVE EXAMPLE 2
15 g of the binder resin mixture obtained in Preparative Example 1 (containing 1.5 g of the binder resin and 13.5 g of Texanol and DOP), 1 g of a dispersant (BYK 110, available from BYK CHEMI), and 5 g of glass frit (having an average particle size of 1 μm) were dispersed using a three roll-mill, the resulting material was mixed with 39 g of silver powder (having a spherical shape and an average particle size of 1 μm) and 40 g of silver powder (having a flake shape and an average particle size of 3 μm) and then dispersed using a three roll- mill. The mixture thus obtained was subjected to depressurization and defoaming, to obtain a conductive paste, which was filtered using a 325 SUS mesh filter, and the paste's properties were evaluated.
COMPARATIVE EXAMPLE 3
15 g of the binder resin mixture obtained in Preparative Example 1
(containing 1.5 g of the binder resin and 13.5 g of Texanol and DOP), 1 g of a dispersant (BYK 110, available from BYK CHEMI), and 5 g of glass frit (having an average particle size of 1 μm) were dispersed using a three roll-mill, the resulting material was mixed with 78 g of silver powder (having a spherical shape and an average particle size of 1 μm) and 1 g of an organic thixotrophic agent (BYK 410, available from BYK CHEMI) and then dispersed using a three roll- mill. The mixture thus obtained was subjected to depressurization and defoaming, to obtain a conductive paste, which was filtered using a 325 SUS mesh filter, and the paste's properties were evaluated.
Evaluation of Properties
The properties of the conductive pastes prepared in Examples 1 to 7 and Comparative Examples 1 to 3 were evaluated as follows. The results are shown in Table 1.
(1) Viscosity & Thixo Index (T.I.)
The viscosity was measured at a shear rate of 10 s"1 using a viscometer (RVl, available from HAKKE) and a Ti 35 spindle. Furthermore, the viscosity was measured at a shear rate of each of 1 s"1 and 10 s"1, and then, a viscosity ratio represented by viscosity measured at 1 s'Vviscosity measured at 10 s"1, called the thixo index, was determined.
(2) Aspect Ratio
Printability for a width of 100 μm was confirmed using a 325 mesh screen. Printing was performed at a squeegee rate of 40 cm/min using a screen printer, thereafter drying at 1500C was performed. Subsequently, heat-treating was performed in a heat-treating furnace (available from SIEREATHERM) at a maximum of 7500C , the printed shape was observed, and an aspect ratio (AJR) was determined. Upon heat-treating, the extent of the deformation of the film could be seen by comparing changes in aspect ratio before and after the heat- treating process.
(3) Measurement of Resistance
The line width and thickness of lines 100 μm wide were measured, and resistance was measured using a multi-meter (available from FLUKE), thus calculating resistivity (= resistance x line width x thickness / length).
<Table 1>
Figure imgf000013_0001
As shown in Table 1, the conductive paste of Examples 1 to 7 had small changes in aspect ratio before and after the heat-treating process, thus reducing the deformation of the printed film. However, the composition of the comparative examples had large changes in aspect ratio, thus increasing the deformation of the printed film.
In Examples 1 to 7, as the amount of inorganic thixotropliic agent was increased, the aspect ratio could be seen to increase. This indicates that an effect of preventing deformation of the printed film upon heat-treating becomes superior. Also, as the amount of silver powder was increased, it could be seen that resistance was improved and the aspect ratio was increased.
In particular, in the conductive composition of Example 5, both the aspect ratio (0.313) before the heat-treating process and the aspect ratio (0.284) after the heat-treating process were improved. When the aspect ratio was improved in this way, the light-receiving area was increased and line resistance was reduced.
As described in above, the present invention provides a conductive paste composition and a method of preparing an electrode using the same. According to the present invention, the conductive paste composition for preparing an electrode can prevent the deformation of the printed film upon heat-drying and heat-treating after printing thereof. Therefore, when a surface electrode formed using the inventive conductive paste composition according to the present invention is included in a solar cell, the solar cell can have an enlarged light- receiving area and high photoelectric conversion efficiency.
While the invention has been described with respect to the above specific embodiments, it should be recognized that various modifications and changes may be made to the invention by those skilled in the art which also fall within the scope of the invention as defined by the appended claims.

Claims

WHAT IS CLAIMED IS:
1. A conductive paste composition comprising a binder resin, a diluent, a conductive metal material, glass frit, and an inorganic thixotrophic agent.
2. The conductive paste composition of claim 1, wherein the conductive paste composition comprises 1 to 10 wt% of the binder resin, 5 to 25 wt% of the diluent, 60 to 90 wt% of the conductive metal material, 1 to 10 wt% of the glass frit, and 0.1 to 5 wt% of the inorganic thixotrophic agent.
3. The conductive paste composition of claim 1, wherein the composition further comprises 0.1 to 5 parts by weight of a dispersant based on the total weight of the composition.
4. The conductive paste composition of claim 1, wherein the binder resin is a cellulose-based compound having a viscosity of 5 to 500 cps (5 wt% solvent in an 8:2 mixture of toluene and ethanol), or an acrylic resin-based compound having a molecular weight of 5,000 to 50,000.
5. The conductive paste composition of claim 1, wherein the diluent is selected from the group consisting of α-terpineol, texanol, dioctyl phthalate, dibutyl phthalate, cyclohexane, hexane, toluene, benzylalcohol, dioxane, diethyleneglycol, ethyleneglycol monobutyl ether, ethyleneglycol monobutyl ether acetate, diethyleneglycol monobutyl ether, diethyleneglycol monobutyl ether acetate, and a mixture thereof.
6. The conductive paste composition of claim 1, wherein the inorganic thixotrophic agent is bentonite or silica.
7. The conductive paste composition of claim 1, wherein the conductive metal material is a silver powder having an average particle size of 0.5 to 5 μm.
8. The conductive paste composition of claim 1, wherein the composition further comprises at least one additive selected from the group consisting of a photosensitizer, a polymerization inhibitor, a defoaming agent, a leveling agent, and an organic thixotrophic agent.
9. A method of preparing an electrode, which comprises the steps of: printing the conductive paste composition on a substrate; drying the printed conductive paste thus obtained; and heat-treating the dried conductive paste.
10. The method of claim 9, wherein the electrode has a thickness of 10 to 40 μm.
11. The method of claim 9, wherein the printed electrode paste is heat-treated at a temperature of 700 to 900 °C .
12. The method of claim 9, wherein the conductive paste composition is printed on the substrate by screen printing, gravure offset printing, rotary screen printing, or lift off printing.
13. The method of claim 9, wherein the electrode is a surface electrode of a solar cell.
14. A solar cell comprising the electrode prepared by the method of claim 9 as a surface electrode.
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