WO2011078629A2 - Glass frit, paste composition, and solar cell - Google Patents

Glass frit, paste composition, and solar cell Download PDF

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Publication number
WO2011078629A2
WO2011078629A2 PCT/KR2010/009336 KR2010009336W WO2011078629A2 WO 2011078629 A2 WO2011078629 A2 WO 2011078629A2 KR 2010009336 W KR2010009336 W KR 2010009336W WO 2011078629 A2 WO2011078629 A2 WO 2011078629A2
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WO
WIPO (PCT)
Prior art keywords
weight
glass frit
paste composition
group
solar cell
Prior art date
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Ceased
Application number
PCT/KR2010/009336
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French (fr)
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WO2011078629A3 (en
Inventor
Sang Gon Kim
Jin Gyeong Park
Jun Phil Eom
Soon Gil Kim
In Jae Lee
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LG Innotek Co Ltd
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LG Innotek Co Ltd
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Publication of WO2011078629A2 publication Critical patent/WO2011078629A2/en
Publication of WO2011078629A3 publication Critical patent/WO2011078629A3/en
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • H10F77/206—Electrodes for devices having potential barriers
    • H10F77/211—Electrodes for devices having potential barriers for photovoltaic cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. 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
    • 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
    • C03C8/10—Frit compositions, i.e. in a powdered or comminuted form containing lead
    • 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
    • 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
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/14—Photovoltaic cells having only PN homojunction potential barriers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/90—Structures for connecting between photovoltaic cells, e.g. interconnections or insulating spacers
    • H10F19/902—Structures for connecting between photovoltaic cells, e.g. interconnections or insulating spacers for series or parallel connection of photovoltaic cells
    • H10F19/906—Structures for connecting between photovoltaic cells, e.g. interconnections or insulating spacers for series or parallel connection of photovoltaic cells characterised by the materials of the structures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells

Definitions

  • the disclosure relates to glass frit, paste composition including the same, and a solar cell including an electrode formed by using the paste composition.
  • next generation clean energy has become more important due to the lack of fossil fuel.
  • next generation clean energy a solar cell is spotlighted as an energy source for solving the future energy problem because it rarely causes environmental pollution and has the semi-permanent life span and there exists infinite resources for the solar cell.
  • the solar cell may include front and back electrodes formed on a silicon substrate having N and P type semiconductors.
  • the disclosure provides glass frit capable of realizing high-efficiency solar cell and paste composition including the same, and the solar cell including a front electrode formed by using the paste composition.
  • glass frit constituting paste composition for a front electrode of a solar cell includes about 71.8 weight% to about 90 weight% of PbO, about 4.9 weight% to about 12 weight% of SiO 2, about 4.9 weight% to about 11 weight% of B 2 O 3 , about 0.5 weight% to about 5 weight% of ZnO, about 0.3 weight% to about 0.5 weight% of Fe 2 O 3 , about 0.2 weight% to about 0.5 weight% of Cr 2 O 3 , about 0.1 weight% to about 0.4 weight% of Co 2 O 3 or CoO, and about 0.3 weight% to about 0.5 weight% of MnO 2 .
  • the glass frit further comprises about 0.1 weight% to about 5 weight% of Al 2 O 3 .
  • the glass frit further comprises about 0.1 weight% to about 0.2 weight% of MgO.
  • the glass frit further comprises about 0.1 weight% to about 5 weight% of TiO 2 .
  • the glass frit comprises at least one selected from the group consisting of SrO, BaO, and ZrO.
  • the glass frit comprises less than about 5 weight% of at least one selected from the group consisting of SrO, BaO, and ZrO.
  • the glass frit further comprises at least one selected from the group consisting of AgO, Ag 2 O, and CaO.
  • a paste composition for a front electrode of a solar cell includes glass frit comprising about 71.8 weight% to about 90 weight% of PbO, about 4.9 weight% to about 12 weight% of SiO 2, about 4.9 weight% to about 11 weight% of B 2 O 3, about 0.5 weight% to about 5 weight% of ZnO, about 0.3 weight% to about 0.5 weight% of Fe 2 O 3 , about 0.2 weight% to about 0.5 weight% of Cr 2 O 3 , about 0.1 weight% to about 0.4 weight% of Co 2 O 3 or CoO, and about 0.3 weight% to about 0.5 weight% of MnO 2 , conductive powder, and an organic vehicle.
  • the paste composition includes about 1 weight% to about 10 weight% of the glass frit, about 60 weight% to about 90 weight% of the conductive powder, about 10 weight% to about 20 weight% of the organic vehicle, and about 1 weight% to about 10 weight% of a dispersing agent.
  • the organic vehicle includes a solvent and an organic binder.
  • the organic binder includes at least one selected from the group consisting of acrylate resin, ethylcellulous, nitrocellulous, a polymer of ethylcellulous and phenol resin, wood rosin, and polymethacrylate of alcohol.
  • the solvent includes at least one selected from the group consisting of butylcarbitolacetate, butylcarbitol, butylcellosolve, butylcellosolveacetate, propyleneglycolmonomethylether, dipropyleneglycolmonomethylether, propyleneglycolmonomethylpropionate, ethyletherpropionate, terpineol, propyleneglycolmonomethyletheracetate, dimethylamino formaldehyde, methylethylketone, gamma-butyrolactone, ethyllactate, and texanol.
  • the glass frit further includes about 0.1 weight% to about 5 weight% of Al 2 O 3 .
  • the glass frit further includes about 0.1 weight% to about 0.2 weight% of MgO.
  • the glass frit further includes about 0.1 weight% to about 5 weight% of TiO 2 .
  • the glass frit includes at least one selected from the group consisting of SrO, BaO, and ZrO.
  • the glass frit includes less than about 5 weight% of at least one selected from the group consisting of SrO, BaO, and ZrO.
  • the glass frit further includes at least one selected from the group consisting of AgO, Ag 2 O, and CaO.
  • the glass frit includes about 0.1 weight% to about 5 weight% of at least one selected from the group consisting of AgO, Ag 2 O, and CaO.
  • a solar cell comprising a front electrode formed by using the paste composition.
  • the efficiency of the solar cell can be increased.
  • FIG. 1 is a sectional view showing a solar cell
  • FIG. 2 is a photograph showing a front electrode manufactured using a paste composition according to the first embodiment.
  • FIG. 3 is a photograph showing the front electrode manufactured using the paste composition according to the first embodiment.
  • paste composition including the glass frit and used for a front electrode for a solar cell
  • solar cell including the front electrode manufactured using the paste composition according to the embodiment
  • the paste composition according to the embodiment may include conductive powder, an organic vehicle, glass frit, and additions, and the details thereof will be described in more detail.
  • the conductive powder includes silver (Ag), silver oxide, the alloy of Ag, the compound of Ag, or material capable of extracting Ag powder through a sintering process.
  • the conductive powder may include the single material or the mixture of at least two kinds of the above materials. However, preferably, the conductive powder may include silver powder.
  • the conductive powder may have various shapes such as a spherical shape or a flake shape.
  • the conductive powder may include the single material or the mixture of at least two materials.
  • the grain size of the Ag powder may be set by taking into consideration a desired sintering speed and an influence exerted on a process of forming an electrode.
  • the grain size of the Ag powder may be in the range of about 0.5um to about 4um. If the mean grain size of the Ag powder is less than 0.5, spaces among the conductive powders for receiving organic materials may be diminished, so distribution does not smoothly occur. If the mean grain size of the Ag powder exceeds 4, air gaps of conductive powders may be enlarged, so that the degree of compaction is degraded, and resistance is increased.
  • the purity of Ag powder may have various values to satisfy a condition generally required as an electrode.
  • the Ag powder may have the purity of about 90% or more, and preferably has the purity of about 95% or more.
  • about 60 weight% to about 90 weight% of conductive powders may be contained in the whole paste composition. If less than 60 weight% of the conductive powder is used, the resistance of the front electrode may be increased due to a small amount of conductive powder. If more than 90 weight% of the conductive powder is used, the viscosity is increased, so that the printing property of the paste is degraded, and the price of the paste may be increased.
  • the glass frit is mixed with the conductive powders to allow the conductive powders to be strongly bonded to a substrate in a sintering process.
  • the glass frit may be selected from the group consisting of PbO, SiO 2 , B 2 O 3 , ZnO, Fe 2 O 3 , Cr 2 O 3 , Co 2 O 3 (or CoO) and MnO 2 based-compositions.
  • the glass frit may additionally include Al 2 O 3 , MgO, TiO 2 , SrO, BaO, ZrO, AgO (or Ag 2 O), and CaO. If at least two compositions are contained in the glass frit, the compositions and the composition ratio may exert an influence on the contact property between the front electrode and the silicon substrate.
  • the glass frit includes various oxides.
  • the conventional glass frit includes restricted types of oxides.
  • the conventional glass frit mainly includes PbO and SiO 2 .
  • the glass frit includes about 71.8 weight% to about 90 weight% of PbO, about 4.9 weight% to about 12 weight% of SiO 2 , about 4.9 weight% to about 11 weight% of B 2 O 3 , about 0.5 weight% to about 5 weight% of ZnO, about 0.3 weight% to about 0.5 weight% of Fe 2 O 3 , about 0.2 weight% to about 0.5 weight% of Cr 2 O 3 , about 0.1 weight% to about 0.4 weight% of Co 2 O 3 (or CoO), and about 0.3 weight% to about 0.5 weight% of MnO 2 .
  • about 71.8 weight% to about 90 weight% of PbO, about 4.9 weight% to about 12 weight% of SiO 2 , and about 4.9 weight% to about 11 weight% of B 2 O 3 allow the paste composition to etch an anti-reflective layer (for example, SiN layer) to pass through the anti-reflective layer while adjusting an amount of Ag infiltrating into the silicon substrate. Accordingly, the contact characteristic between the front electrode formed by using the paste composition and the silicon substrate can be improved.
  • an anti-reflective layer for example, SiN layer
  • ZnO is added in order to improve the light absorption coefficient. As described above, about 0.5 weight% to about 5 weight% of ZnO may be contained. This range of the ZnO can minimize the variation in a glass transition temperature and a glass characteristic while improving efficiency.
  • Fe 2 O 3 , Cr 2 O 3 , Co 2 O 3 (or CoO), and MnO 2 is added in order to improve excitation voltage effect by reducing excitation voltage.
  • the excitation voltage means the minimum voltage to supply the minimum energy required to excite atoms or molecules in a ground state due to the collision of the atoms or the molecules.
  • Fe 2 O 3 , Cr 2 O 3 , Co 2 O 3 (or CoO), and MnO 2 is contained so that the excitation voltage can be reduced, thereby improving the efficiency of a solar cell.
  • the glass frit according to the embodiment may further contain Al 2 O 3 .
  • the Al 2 O 3 is contained to improve the contact effect between the glass frit and the conductive powder.
  • Al 2 O 3 occupies about 0.1 weight% to about 5 weight% based on the whole content of the glass frit. If less than 0.1 weight% of Al 2 O 3 is contained in the glass frit, the contact effect is not sufficiently represented. If more than 5 weight% of Al 2 O 3 is contained in the glass frit, the glass transition temperature may be raised, so that glass melting may be difficult.
  • the glass frit according to the embodiment may include SrO, BaO, or ZrO, so that light absorption efficiency can be improved, shunt resistance (Rsh) can be increased, and the series resistance can be lowered.
  • the electrical characteristics of the solar cell depend on the series resistance (Rs) and the shunt resistance (Rsh).
  • the composition of the interface of the front electrode and the fine structure of the front electrode determine the series resistance (Rs).
  • SrO, BaO or ZrO can improve the light absorption coefficient and is contained in the glass frit.
  • the series resistance (Rs) can be reduced, and the shunt resistance (Rsh) can be increased, so that the efficiency of the solar cell can be improved.
  • the glass frit may contain less than 5 weight% of SrO, BaO, or Zr.
  • the glass frit may contain 0.1 weight% to 5 weight% of SrO, BaO, or ZrO.
  • the glass frit according to the embodiment contains AgO or Ag 2 O so that the crystallization effects of silver can be improved. Accordingly, after metallization has been performed, silver is extracted, so that efficiency can be improved.
  • the glass frit may contain about 0.1 weight% to about 5 weight% of AgO or Ag 2 O.
  • the glass frit may contain about 1 weight% of AgO or Ag 2 O. In these composition ratio ranges, the crystallization of silver can be effectively achieved.
  • the glass frit further contains CaO, so that the glass transition temperature can be adjusted.
  • the glass frit may contain about 0.1 weight% to about 5 weight% of CaO.
  • the glass frit may contain about 2 weight% of CaO. In this range, the glass transition temperature can be effectively adjusted.
  • the glass frit does not contain an alkali-based compound such as Li 2 O, Na 2 O or K 2 O.
  • the alkali-based compound may cause Ag migration or color change.
  • the glass frit contains alkali-based compound so that the reliability can be improved.
  • Such the glass frit may occupy about 1 weight% to about 10 weight% based on the whole content of the paste composition. If less than 1 weight% of the glass frit is contained in the paste composition, a desired effect may not be obtained. If more than 10 weight% of the glass frit is contained in the paste composition, an anti-reflective layer may be excessively etched.
  • the front electrode When the front electrode is formed, the front electrode may include an organic vehicle together with the conductive powder and the glass frit such that the front electrode has the form of a paste to obtain the optimum characteristic.
  • the front electrode may include various organic vehicles.
  • the organic vehicle may include the mixture solution of a solvent and an organic binder.
  • the organic binder may include one selected from the group consisting of acrylate resin, ethylcellulous, nitrocellulous, a polymer of ethylcellulous and phenol resin, wood rosin, and polymethacrylate of alcohol.
  • the organic binder may include ethylcellulous.
  • the solvent may include one or at least two selected from the group consisting of butylcarbitolacetate, butylcarbitol, butylcellosolve, butylcellosolveacetate, propyleneglycolmonomethylether, dipropyleneglycolmonomethylether, propyleneglycolmonomethylpropionate, ethyletherpropionate, terpineol, propyleneglycolmonomethyletheracetate, dimethylamino formaldehyde, methylethylketone, gamma-butyrolactone, ethyllactate, and texanol.
  • the solvent may include butylcarbitolacetate.
  • the organic vehicle may be selected from the group consisting of a phosphoric dispersing agent, a thixotropic agent, a leveling agent, and an anti-foaming agent.
  • the thixotropic agent may include urea, amide, or urethane-based polymer/organic material, or may include inorganic silica.
  • the paste composition may include 10 weight% to 20 weight% of the organic vehicle may be contained.
  • the composition ratio range provides viscosity facilitating printing (e.g., screen printing) and prevents a paste from flowing down after the printing has been finished. Accordingly, the composition of the coated paste may represent a proper aspect ratio.
  • the paste composition for the front electrode according to the embodiment contains about 1 weight% to 10 weight% of other dispersing agents and thixotropic agents.
  • various types of dispersing agents and thixotropic agents may be used.
  • generally-known dispersing agents and thixotropic agents may be used.
  • the thixotropic agents may include urea, amide, or urethanebased polymer/organic material or may include inorganic-based silica.
  • the paste composition additionally includes additions if necessary.
  • the additions may include a sintering additive, a thickening agent, a stabilizer, or a surfactant.
  • materials constituting the glass frit are mixed with each other such that the materials have the above composition range.
  • the mixture is achieved by using a ball mill or a planetary mill.
  • the composition After drying the composition at a temperature of about 110°C, the composition is sintered at the temperature of about 900°C to 1300°C, and quenched at a temperature of 25°C which is a normal temperature.
  • the result is coarsely pulverized by a disk mill, and then finely pulverized by the planetary mill, thereby preparing the composition of the glass frit.
  • the grains of the glass frit may have various sizes.
  • the grains of the glass frit may have a mean size of about 0.1 nm to about 10 nm. If the mean size of the grains of the glass frit is in the above range, the paste may have proper viscosity. In addition, interfacial reaction can be prevented from being reduced.
  • About 1 weight% to about 10 weight% of the glass frit is preferably mixed with about 60 weight% to about 90 weight% of silver powder which is conductive powder.
  • the glass frit and the silver powder may be mixed and stirred by various mixing and stirring units capable of uniformly mixing and stirring the glass frit and the silver powder.
  • the organic vehicle serving as a binder is added to the mixture and stirred. This is necessary to prepare the mixture of the glass frit and the silver powder in the form of a paste.
  • the content of the organic vehicle is preferably in the range of about 10 weight% to about 20 weight%.
  • composition ratio range allows the paste composition to easily be screen-printed and have the proper viscosity.
  • composition ratio range prevents the paste composition from flowing down after the printing has been finished, so that a proper aspect ratio can be obtained.
  • About 1 weight% to about 10 weight% of dispersing agents and various additions are added to the result and mixed with the result by using the generally-known mixing and stirring units so that the uniform paste composition can be prepared.
  • a solvent is added to the paste composition having the mixture, and mixed with the paste composition.
  • the paste composition including the conductive powder, the glass frit, and the organic vehicle and used to form a front electrode may be prepared.
  • the solar cell includes a P type silicon substrate 10 provided at a front surface thereof with an N type semiconductor part 11, a front electrode 12 electrically connected to the N type semiconductor part 11, and a back electrode 13 electrically connected to the P type silicon substrate 10.
  • An anti-reflective layer 14 may be formed on a top surface of the N type semiconductor part 11 except for the front electrode 12.
  • the front electrode 12 may be connected to the N type semiconductor part 11 through the anti-reflective layer 14.
  • the silicon substrate 10 having the back electrode 13 is provided thereon with a BSF (Back Surface Field) 15.
  • a tabbing electrode is primarily printed. Thereafter, the tabbing electrode is dried at a temperature of about 190°C to about 210°C. Thereafter, the back electrode 13 is printed by using generally-known back surface paste composition including aluminum particles and dried at a temperature of about 190°C.
  • the paste composition according to the embodiment is printed on the front electrode 12 and dried under a condition the same as a condition in which the back electrode 12 is dried. Accordingly, the solar cell has been completely manufactured.
  • the front and rear electrodes 12 and 13 include metallic electrodes including silver and aluminum.
  • the electrode according to the embodiment may include various kinds of materials.
  • the silver electrode has superior conductivity and aluminum electrode has superior electrical conductivity and superior affinity with respect to the silicon substrate 10 so as to be smoothly bonded with the silicon substrate 10.
  • the front and rear electrodes 12 and 13 may be formed on the silicon substrate through generally-well known schemes.
  • the front and rear electrodes 12 and 13 may be formed on the silicon substrate through the screen-printing scheme.
  • the front electrode 12 is formed by screen-printing the paste for the front electrode according to the embodiment on a position, at which the front electrode 12 is formed, as described above and then performing an annealing process.
  • the back electrode 13 is subject to the annealing process, aluminum constituting the electrode is spread through the back surface of the substrate 10, so that the BSF 15 may be formed at the boundary surface between the rear electrode 13 and the silicon substrate 10.
  • the BSF 15 prevents carriers from moving to the back surface of the silicon substrate 10 and recombined. If the recombination of the carriers is prevented, the open voltage and the reliability are improved, so that the conversion efficiency of the solar cell can be improved.
  • the front and rear electrodes 12 and 13 may be formed by using a conventional photolithography process and a conventional metal deposition process in addition the screen-printing process. Therefore, the front and rear electrodes 12 and 13 according to the embodiment may be formed through various processes.
  • Embodiment 1 (SJ7)
  • About 77.9 weight% of PbO, about 11.6 weight% of SiO 2 , about 7.6 weight% of B 2 O 3 , about 0.4 weight% of Al 2 O 3 , about 1.2 weight% of ZnO, about 0.4 weight% of Fe 2 O 3 , about 0.4 weight% of Cr 2 O 3 , about 0.1 weight% of CoO, and about 0.4 weight% of MnO 2 are mixed with each other by using a ball mill and dried at a temperature of about 80°C. Then, the mixture is melted at a temperature of about 1000°C, and quenched at a normal temperature. The result is coarsely pulverized by using a disk mill, and finely pulverized by using a planetary mill. Accordingly, the glass frit having a mean grain size of about 3 um can be prepared.
  • Embodiment 2 (SJ22)
  • the solar cell according to the first and second embodiments has a superior characteristic.
  • the front electrode according to the first embodiment has a superior contact characteristic.
  • the front electrode according to the first embodiment is formed through the anti-reflective layer, so that metallization can be smoothly achieved.
  • any reference in this specification to one embodiment, an embodiment, example embodiment, etc. means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention.
  • the appearances of such phrases in various places in the specification are not necessarily all referring to the same embodiment.

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Photovoltaic Devices (AREA)
  • Conductive Materials (AREA)
  • Glass Compositions (AREA)

Abstract

Disclosed are glass frit, paste composition, and a solar cell. The glass frit contained in the paste composition for a front electrode of the solar cell includes about 71.8 weight% to about 90 weight% of PbO, about 4.9 weight% to about 12 weight% of SiO2, about 4.9 weight% to about 11 weight% of B2O3, about 0.5 weight% to about 5 weight% of ZnO, about 0.3 weight% to about 0.5 weight% of Fe2O3, about 0.2 weight% to about 0.5 weight% of Cr2O3, about 0.1 weight% to about 0.4 weight% of Co2O3 or CoO, and about 0.3 weight% to about 0.5 weight% of MnO2.

Description

GLASS FRIT, PASTE COMPOSITION, AND SOLAR CELL
The disclosure relates to glass frit, paste composition including the same, and a solar cell including an electrode formed by using the paste composition.
Recently, the development of next generation clean energy has become more important due to the lack of fossil fuel. Among the next generation clean energy, a solar cell is spotlighted as an energy source for solving the future energy problem because it rarely causes environmental pollution and has the semi-permanent life span and there exists infinite resources for the solar cell.
The solar cell may include front and back electrodes formed on a silicon substrate having N and P type semiconductors. After the paste composition for the front electrode has been formed on an anti-reflective layer, if heat is applied to the paste composition, the paste composition flows through the anti-reflective layer by the glass frit due to the punch through phenomenon so that the front electrode is electrically connected to the silicon substrate. Therefore, the glass frit has the important function for the paste composition. However, if the glass frit is not optimized, high efficiency cannot be achieved.
The disclosure provides glass frit capable of realizing high-efficiency solar cell and paste composition including the same, and the solar cell including a front electrode formed by using the paste composition.
According to the embodiment, glass frit constituting paste composition for a front electrode of a solar cell includes about 71.8 weight% to about 90 weight% of PbO, about 4.9 weight% to about 12 weight% of SiO2, about 4.9 weight% to about 11 weight% of B2O3, about 0.5 weight% to about 5 weight% of ZnO, about 0.3 weight% to about 0.5 weight% of Fe2O3, about 0.2 weight% to about 0.5 weight% of Cr2O3, about 0.1 weight% to about 0.4 weight% of Co2O3 or CoO, and about 0.3 weight% to about 0.5 weight% of MnO2.
The glass frit further comprises about 0.1 weight% to about 5 weight% of Al2O3.
The glass frit further comprises about 0.1 weight% to about 0.2 weight% of MgO.
The glass frit further comprises about 0.1 weight% to about 5 weight% of TiO2.
The glass frit comprises at least one selected from the group consisting of SrO, BaO, and ZrO.
The glass frit comprises less than about 5 weight% of at least one selected from the group consisting of SrO, BaO, and ZrO.
The glass frit further comprises at least one selected from the group consisting of AgO, Ag2O, and CaO.
The further comprises about 0.1 weight% to about 5 weight% of at least one selected from the group consisting of AgO, Ag2O, and CaO.
A paste composition for a front electrode of a solar cell includes glass frit comprising about 71.8 weight% to about 90 weight% of PbO, about 4.9 weight% to about 12 weight% of SiO2, about 4.9 weight% to about 11 weight% of B2O3, about 0.5 weight% to about 5 weight% of ZnO, about 0.3 weight% to about 0.5 weight% of Fe2O3, about 0.2 weight% to about 0.5 weight% of Cr2O3, about 0.1 weight% to about 0.4 weight% of Co2O3 or CoO, and about 0.3 weight% to about 0.5 weight% of MnO2, conductive powder, and an organic vehicle.
The paste composition includes about 1 weight% to about 10 weight% of the glass frit, about 60 weight% to about 90 weight% of the conductive powder, about 10 weight% to about 20 weight% of the organic vehicle, and about 1 weight% to about 10 weight% of a dispersing agent.
The organic vehicle includes a solvent and an organic binder. The organic binder includes at least one selected from the group consisting of acrylate resin, ethylcellulous, nitrocellulous, a polymer of ethylcellulous and phenol resin, wood rosin, and polymethacrylate of alcohol. The solvent includes at least one selected from the group consisting of butylcarbitolacetate, butylcarbitol, butylcellosolve, butylcellosolveacetate, propyleneglycolmonomethylether, dipropyleneglycolmonomethylether, propyleneglycolmonomethylpropionate, ethyletherpropionate, terpineol, propyleneglycolmonomethyletheracetate, dimethylamino formaldehyde, methylethylketone, gamma-butyrolactone, ethyllactate, and texanol.
The glass frit further includes about 0.1 weight% to about 5 weight% of Al2O3.
The glass frit further includes about 0.1 weight% to about 0.2 weight% of MgO.
The glass frit further includes about 0.1 weight% to about 5 weight% of TiO2.
The glass frit includes at least one selected from the group consisting of SrO, BaO, and ZrO.
The glass frit includes less than about 5 weight% of at least one selected from the group consisting of SrO, BaO, and ZrO.
The glass frit further includes at least one selected from the group consisting of AgO, Ag2O, and CaO.
The glass frit includes about 0.1 weight% to about 5 weight% of at least one selected from the group consisting of AgO, Ag2O, and CaO.
A solar cell comprising a front electrode formed by using the paste composition.
According to the embodiment, the efficiency of the solar cell can be increased.
FIG. 1 is a sectional view showing a solar cell;
FIG. 2 is a photograph showing a front electrode manufactured using a paste composition according to the first embodiment; and
FIG. 3 is a photograph showing the front electrode manufactured using the paste composition according to the first embodiment.
Hereinafter, glass frit, paste composition including the glass frit and used for a front electrode for a solar cell (hereinafter, referred to as paste composition), and the solar cell including the front electrode manufactured using the paste composition according to the embodiment will be described in detail.
The paste composition according to the embodiment may include conductive powder, an organic vehicle, glass frit, and additions, and the details thereof will be described in more detail.
(a) Conductive Powder
The conductive powder includes silver (Ag), silver oxide, the alloy of Ag, the compound of Ag, or material capable of extracting Ag powder through a sintering process. The conductive powder may include the single material or the mixture of at least two kinds of the above materials. However, preferably, the conductive powder may include silver powder.
The conductive powder may have various shapes such as a spherical shape or a flake shape. The conductive powder may include the single material or the mixture of at least two materials.
As the grain size of the Ag powder is increased, the sintering speed is lowered. Accordingly, the grain size of the Ag powder may be set by taking into consideration a desired sintering speed and an influence exerted on a process of forming an electrode. For example, the grain size of the Ag powder may be in the range of about 0.5um to about 4um. If the mean grain size of the Ag powder is less than 0.5, spaces among the conductive powders for receiving organic materials may be diminished, so distribution does not smoothly occur. If the mean grain size of the Ag powder exceeds 4, air gaps of conductive powders may be enlarged, so that the degree of compaction is degraded, and resistance is increased.
The purity of Ag powder may have various values to satisfy a condition generally required as an electrode. For example, the Ag powder may have the purity of about 90% or more, and preferably has the purity of about 95% or more.
In this case, about 60 weight% to about 90 weight% of conductive powders may be contained in the whole paste composition. If less than 60 weight% of the conductive powder is used, the resistance of the front electrode may be increased due to a small amount of conductive powder. If more than 90 weight% of the conductive powder is used, the viscosity is increased, so that the printing property of the paste is degraded, and the price of the paste may be increased.
(b) Glass Frit
The glass frit is mixed with the conductive powders to allow the conductive powders to be strongly bonded to a substrate in a sintering process.
The glass frit may be selected from the group consisting of PbO, SiO2, B2O3, ZnO, Fe2O3, Cr2O3, Co2O3 (or CoO) and MnO2 based-compositions. The glass frit may additionally include Al2O3, MgO, TiO2, SrO, BaO, ZrO, AgO (or Ag2O), and CaO. If at least two compositions are contained in the glass frit, the compositions and the composition ratio may exert an influence on the contact property between the front electrode and the silicon substrate. In this regard, according to the embodiment, the glass frit includes various oxides. In contrast, the conventional glass frit includes restricted types of oxides. The conventional glass frit mainly includes PbO and SiO2.
In this case, the glass frit includes about 71.8 weight% to about 90 weight% of PbO, about 4.9 weight% to about 12 weight% of SiO2, about 4.9 weight% to about 11 weight% of B2O3, about 0.5 weight% to about 5 weight% of ZnO, about 0.3 weight% to about 0.5 weight% of Fe2O3, about 0.2 weight% to about 0.5 weight% of Cr2O3, about 0.1 weight% to about 0.4 weight% of Co2O3 (or CoO), and about 0.3 weight% to about 0.5 weight% of MnO2.
In this case, about 71.8 weight% to about 90 weight% of PbO, about 4.9 weight% to about 12 weight% of SiO2, and about 4.9 weight% to about 11 weight% of B2O3 allow the paste composition to etch an anti-reflective layer (for example, SiN layer) to pass through the anti-reflective layer while adjusting an amount of Ag infiltrating into the silicon substrate. Accordingly, the contact characteristic between the front electrode formed by using the paste composition and the silicon substrate can be improved.
ZnO is added in order to improve the light absorption coefficient. As described above, about 0.5 weight% to about 5 weight% of ZnO may be contained. This range of the ZnO can minimize the variation in a glass transition temperature and a glass characteristic while improving efficiency.
Fe2O3, Cr2O3, Co2O3 (or CoO), and MnO2 is added in order to improve excitation voltage effect by reducing excitation voltage. The excitation voltage means the minimum voltage to supply the minimum energy required to excite atoms or molecules in a ground state due to the collision of the atoms or the molecules. As described above, according to the embodiment, Fe2O3, Cr2O3, Co2O3 (or CoO), and MnO2 is contained so that the excitation voltage can be reduced, thereby improving the efficiency of a solar cell.
In this case, about 0.3 weight% to about 0.5 weight% of Fe2O3, about 0.2 weight% to about 0.5 weight% of Cr2O3, about 0.1 weight% to about 0.4 weight% of Co2O3 or CoO, and about 0.3 weight% to about 0.5 weight% of MnO2 can be contained, and theses composition ratio ranges minimize the variation in glass transition temperature and characteristics while improving efficiency.
In addition, the glass frit according to the embodiment may further contain Al2O3. The Al2O3 is contained to improve the contact effect between the glass frit and the conductive powder. In this case, Al2O3 occupies about 0.1 weight% to about 5 weight% based on the whole content of the glass frit. If less than 0.1 weight% of Al2O3is contained in the glass frit, the contact effect is not sufficiently represented. If more than 5 weight% of Al2O3 is contained in the glass frit, the glass transition temperature may be raised, so that glass melting may be difficult.
The glass frit according to the embodiment may include SrO, BaO, or ZrO, so that light absorption efficiency can be improved, shunt resistance (Rsh) can be increased, and the series resistance can be lowered. In general, the electrical characteristics of the solar cell depend on the series resistance (Rs) and the shunt resistance (Rsh). The composition of the interface of the front electrode and the fine structure of the front electrode determine the series resistance (Rs). SrO, BaO or ZrO can improve the light absorption coefficient and is contained in the glass frit. In addition, the series resistance (Rs) can be reduced, and the shunt resistance (Rsh) can be increased, so that the efficiency of the solar cell can be improved.
The glass frit may contain less than 5 weight% of SrO, BaO, or Zr. For example, the glass frit may contain 0.1 weight% to 5 weight% of SrO, BaO, or ZrO.
In addition, the glass frit according to the embodiment contains AgO or Ag2O so that the crystallization effects of silver can be improved. Accordingly, after metallization has been performed, silver is extracted, so that efficiency can be improved. In this case, the glass frit may contain about 0.1 weight% to about 5 weight% of AgO or Ag2O. For example, the glass frit may contain about 1 weight% of AgO or Ag2O. In these composition ratio ranges, the crystallization of silver can be effectively achieved.
In addition, the glass frit further contains CaO, so that the glass transition temperature can be adjusted. The glass frit may contain about 0.1 weight% to about 5 weight% of CaO. For example, the glass frit may contain about 2 weight% of CaO. In this range, the glass transition temperature can be effectively adjusted.
The glass frit does not contain an alkali-based compound such as Li2O, Na2O or K2O. When the alkali-based compound is contained in the paste composition, the alkali-based compound may cause Ag migration or color change. In other words, the glass frit contains alkali-based compound so that the reliability can be improved.
Such the glass frit may occupy about 1 weight% to about 10 weight% based on the whole content of the paste composition. If less than 1 weight% of the glass frit is contained in the paste composition, a desired effect may not be obtained. If more than 10 weight% of the glass frit is contained in the paste composition, an anti-reflective layer may be excessively etched.
(c) Organic Vehicle
When the front electrode is formed, the front electrode may include an organic vehicle together with the conductive powder and the glass frit such that the front electrode has the form of a paste to obtain the optimum characteristic.
The front electrode may include various organic vehicles. The organic vehicle may include the mixture solution of a solvent and an organic binder.
The organic binder may include one selected from the group consisting of acrylate resin, ethylcellulous, nitrocellulous, a polymer of ethylcellulous and phenol resin, wood rosin, and polymethacrylate of alcohol. Preferably, the organic binder may include ethylcellulous.
The solvent may include one or at least two selected from the group consisting of butylcarbitolacetate, butylcarbitol, butylcellosolve, butylcellosolveacetate, propyleneglycolmonomethylether, dipropyleneglycolmonomethylether, propyleneglycolmonomethylpropionate, ethyletherpropionate, terpineol, propyleneglycolmonomethyletheracetate, dimethylamino formaldehyde, methylethylketone, gamma-butyrolactone, ethyllactate, and texanol. Preferably, the solvent may include butylcarbitolacetate.
The organic vehicle may be selected from the group consisting of a phosphoric dispersing agent, a thixotropic agent, a leveling agent, and an anti-foaming agent. The thixotropic agent may include urea, amide, or urethane-based polymer/organic material, or may include inorganic silica.
The paste composition may include 10 weight% to 20 weight% of the organic vehicle may be contained. The composition ratio range provides viscosity facilitating printing (e.g., screen printing) and prevents a paste from flowing down after the printing has been finished. Accordingly, the composition of the coated paste may represent a proper aspect ratio.
Preferably, the paste composition for the front electrode according to the embodiment contains about 1 weight% to 10 weight% of other dispersing agents and thixotropic agents. According to the embodiment, various types of dispersing agents and thixotropic agents may be used. In other words, generally-known dispersing agents and thixotropic agents may be used. The thixotropic agents may include urea, amide, or urethanebased polymer/organic material or may include inorganic-based silica.
In addition, the paste composition additionally includes additions if necessary. For example, the additions may include a sintering additive, a thickening agent, a stabilizer, or a surfactant.
Hereinafter, a method of preparing the glass frit and the paste composition including the same and a method of manufacturing a solar cell by using the paste composition according to the embodiment will be described.
Preparation of Glass Frit
Regarding the composition of the glass frit according to the embodiment, materials constituting the glass frit are mixed with each other such that the materials have the above composition range. In this case, the mixture is achieved by using a ball mill or a planetary mill.
After drying the composition at a temperature of about 110℃, the composition is sintered at the temperature of about 900℃ to 1300℃, and quenched at a temperature of 25℃ which is a normal temperature.
The result is coarsely pulverized by a disk mill, and then finely pulverized by the planetary mill, thereby preparing the composition of the glass frit.
The grains of the glass frit may have various sizes. Preferably, the grains of the glass frit may have a mean size of about 0.1 nm to about 10 nm. If the mean size of the grains of the glass frit is in the above range, the paste may have proper viscosity. In addition, interfacial reaction can be prevented from being reduced.
Preparation of Paste composition
About 1 weight% to about 10 weight% of the glass frit is preferably mixed with about 60 weight% to about 90 weight% of silver powder which is conductive powder. The glass frit and the silver powder may be mixed and stirred by various mixing and stirring units capable of uniformly mixing and stirring the glass frit and the silver powder.
The organic vehicle serving as a binder is added to the mixture and stirred. This is necessary to prepare the mixture of the glass frit and the silver powder in the form of a paste. In this case, the content of the organic vehicle is preferably in the range of about 10 weight% to about 20 weight%.
The composition ratio range allows the paste composition to easily be screen-printed and have the proper viscosity. In addition, the composition ratio range prevents the paste composition from flowing down after the printing has been finished, so that a proper aspect ratio can be obtained.
About 1 weight% to about 10 weight% of dispersing agents and various additions are added to the result and mixed with the result by using the generally-known mixing and stirring units so that the uniform paste composition can be prepared. A solvent is added to the paste composition having the mixture, and mixed with the paste composition.
Through the above process steps, the paste composition including the conductive powder, the glass frit, and the organic vehicle and used to form a front electrode may be prepared.
Manufacturing of Solar Cell
Referring to FIG. 1, the solar cell includes a P type silicon substrate 10 provided at a front surface thereof with an N type semiconductor part 11, a front electrode 12 electrically connected to the N type semiconductor part 11, and a back electrode 13 electrically connected to the P type silicon substrate 10. An anti-reflective layer 14 may be formed on a top surface of the N type semiconductor part 11 except for the front electrode 12. The front electrode 12 may be connected to the N type semiconductor part 11 through the anti-reflective layer 14. In addition, the silicon substrate 10 having the back electrode 13 is provided thereon with a BSF (Back Surface Field) 15.
In order to manufacture the solar cell, a tabbing electrode is primarily printed. Thereafter, the tabbing electrode is dried at a temperature of about 190℃ to about 210℃. Thereafter, the back electrode 13 is printed by using generally-known back surface paste composition including aluminum particles and dried at a temperature of about 190℃.
After the back electrode 13 has been dried and completed, the paste composition according to the embodiment is printed on the front electrode 12 and dried under a condition the same as a condition in which the back electrode 12 is dried. Accordingly, the solar cell has been completely manufactured.
The front and rear electrodes 12 and 13 include metallic electrodes including silver and aluminum. However, the electrode according to the embodiment may include various kinds of materials. The silver electrode has superior conductivity and aluminum electrode has superior electrical conductivity and superior affinity with respect to the silicon substrate 10 so as to be smoothly bonded with the silicon substrate 10.
The front and rear electrodes 12 and 13 may be formed on the silicon substrate through generally-well known schemes. Preferably, the front and rear electrodes 12 and 13 may be formed on the silicon substrate through the screen-printing scheme. In other words, the front electrode 12 is formed by screen-printing the paste for the front electrode according to the embodiment on a position, at which the front electrode 12 is formed, as described above and then performing an annealing process. When the back electrode 13 is subject to the annealing process, aluminum constituting the electrode is spread through the back surface of the substrate 10, so that the BSF 15 may be formed at the boundary surface between the rear electrode 13 and the silicon substrate 10. After the BSF 15 has been formed, the BSF 15 prevents carriers from moving to the back surface of the silicon substrate 10 and recombined. If the recombination of the carriers is prevented, the open voltage and the reliability are improved, so that the conversion efficiency of the solar cell can be improved.
The front and rear electrodes 12 and 13 may be formed by using a conventional photolithography process and a conventional metal deposition process in addition the screen-printing process. Therefore, the front and rear electrodes 12 and 13 according to the embodiment may be formed through various processes.
Hereinafter, embodiments of the disclosure will be described. The embodiments may have various modifications within the scope of the disclosure.
Embodiment 1 (SJ7)
Preparation of Glass Frit
About 77.9 weight% of PbO, about 11.6 weight% of SiO2, about 7.6 weight% of B2O3, about 0.4 weight% of Al2O3, about 1.2 weight% of ZnO, about 0.4 weight% of Fe2O3, about 0.4 weight% of Cr2O3, about 0.1 weight% of CoO, and about 0.4 weight% of MnO2 are mixed with each other by using a ball mill and dried at a temperature of about 80℃. Then, the mixture is melted at a temperature of about 1000℃, and quenched at a normal temperature. The result is coarsely pulverized by using a disk mill, and finely pulverized by using a planetary mill. Accordingly, the glass frit having a mean grain size of about 3 um can be prepared.
Preparation of Paste Composition
About 5 weight% of the glass frit, about 75 weight% of silver powder, and about 20 weight% of an organic vehicle are uniformly mixed with each other and stirred through a ball mill scheme, so that the paste composition has been prepared.
After forming a front electrode on a single silicon wafer cell using the paste composition, five-time tests are performed. The results of the average measurement efficiency obtained through the five-time tests are represented table 1.
Embodiment 2 (SJ22)
Preparation of Glass Frit
About 77.9 weight% of PbO, about 7.52 weight% of SiO2, about 4.525 weight% of B2O3, about 0.4 weight% of Al2O3, about 1.2 weight% of ZnO, 1 weight% of Ag2O, about 2 weight% of CaCO3, about 3 weight% of BaCO3, about 0.4 weight% of Fe2O3, about 0.4 weight% of Cr2O3, about 0.10 weight% of Co2O3, and about 0.4 weight% of MnO2 are mixed with each other by using a ball mill and dried at a temperature of about 80℃. Then, the mixture is melted at a temperature of about 1000℃, and quenched. The result is coarsely pulverized by using the disk mill, and finely pulverized by using the planetary mill. Accordingly, the glass frit having a mean grain size of about 3 um can be prepared.
Preparation of Paste Composition
About 5 weight% of the glass frit, about 75 weight% of silver powder, and about 20 weight% of an organic vehicle are uniformly mixed with each other and stirred through a ball mill scheme, so that the paste composition has been prepared.
After forming a front electrode on a single silicon wafer cell using the paste composition, five-time tests are performed. The results of the average measurement efficiency obtained through the five-time tests are represented table 1. The photograph of the front electrode manufactured by using the paste composition according to the first embodiment is shown in FIG. 2, and the photograph of the section of the front electrode manufactured by using the paste composition according to the first embodiment is shown in FIG. 3.
Table 1
실시예 1 실시예 2
Isc (A) 8.61 8.51
Poc (V) 0.624 0.627
Pmax (W) 4.09 4.19
Ipm (A) 8.03 7.96
Vpm (A) 0.51 0.53
Jsc (mA/cm2) 36.02 35.63
F.F(%) 0.762 0.785
Eff(%) 17.12 17.550
Rsh (Ohm) 19.93 13.79
Rs (Ohm) 0.0066 0.0125
C Area 238.95 238.95
Referring to FIG. 1, the solar cell according to the first and second embodiments has a superior characteristic. Referring to FIG. 2, the front electrode according to the first embodiment has a superior contact characteristic. Referring to FIG. 3, the front electrode according to the first embodiment is formed through the anti-reflective layer, so that metallization can be smoothly achieved.
Any reference in this specification to one embodiment, an embodiment, example embodiment, etc., means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. The appearances of such phrases in various places in the specification are not necessarily all referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with any embodiment, it is submitted that it is within the purview of one skilled in the art to effect such feature, structure, or characteristic in connection with other ones of the embodiments.
Although embodiments have been described with reference to a number of illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure. More particularly, various variations and modifications are possible in the component parts and/or arrangements of the subject combination arrangement within the scope of the disclosure, the drawings and the appended claims. In addition to variations and modifications in the component parts and/or arrangements, alternative uses will also be apparent to those skilled in the art.

Claims (19)

  1. Glass frit constituting paste composition for a front electrode of a solar cell, the glass frit comprising:
    about 71.8 weight% to about 90 weight% of PbO;
    about 4.9 weight% to about 12 weight% of SiO2;
    about 4.9 weight% to about 11 weight% of B2O3;
    about 0.5 weight% to about 5 weight% of ZnO;
    about 0.3 weight% to about 0.5 weight% of Fe2O3;
    about 0.2 weight% to about 0.5 weight% of Cr2O3;
    about 0.1 weight% to about 0.4 weight% of Co2O3 or CoO; and
    about 0.3 weight% to about 0.5 weight% of MnO2.
  2. The glass frit of claim 1, wherein the glass frit further comprises about 0.1 weight% to about 5 weight% of Al2O3.
  3. The glass frit of claim 1, wherein the glass frit further comprises about 0.1 weight% to about 0.2 weight% of MgO.
  4. The glass frit of claim 1, further comprising about 0.1 weight% to about 5 weight% of TiO2.
  5. The glass frit of claim 1, wherein the glass frit comprises at least one selected from the group consisting of SrO, BaO, and ZrO.
  6. The glass frit of claim 1, wherein the glass frit comprises less than about 5 weight% of at least one selected from the group consisting of SrO, BaO, and ZrO.
  7. The glass frit of claim 1, further comprising at least one selected from the group consisting of AgO, Ag2O, and CaO.
  8. The glass frit of claim 1, further comprising about 0.1 weight% to about 5 weight% of at least one selected from the group consisting of AgO, Ag2O, and CaO.
  9. A paste composition for a front electrode of a solar cell comprising:
    glass frit comprising about 71.8 weight% to about 90 weight% of PbO, about 4.9 weight% to about 12 weight% of SiO2, about 4.9 weight% to about 11 weight% of B2O3, about 0.5 weight% to about 5 weight% of ZnO, about 0.3 weight% to about 0.5 weight% of Fe2O3, about 0.2 weight% to about 0.5 weight% of Cr2O3, about 0.1 weight% to about 0.4 weight% of Co2O3 or CoO, and about 0.3 weight% to about 0.5 weight% of MnO2;
    conductive powder; and
    an organic vehicle.
  10. The paste composition of claim 9, wherein the paste composition includes about 1 weight% to about 10 weight% of the glass frit, about 60 weight% to about 90 weight% of the conductive powder, about 10 weight% to about 20 weight% of the organic vehicle, and about 1 weight% to about 10 weight% of a dispersing agent.
  11. The paste composition of claim 9, wherein the organic vehicle includes a solvent and an organic binder,
    wherein the organic binder includes at least one selected from the group consisting of acrylate resin, ethylcellulous, nitrocellulous, a polymer of ethylcellulous and phenol resin, wood rosin, and polymethacrylate of alcohol, and
    wherein the solvent includes at least one selected from the group consisting of butylcarbitolacetate, butylcarbitol, butylcellosolve, butylcellosolveacetate, propyleneglycolmonomethylether, dipropyleneglycolmonomethylether, propyleneglycolmonomethylpropionate, ethyletherpropionate, terpineol, propyleneglycolmonomethyletheracetate, dimethylamino formaldehyde, methylethylketone, gamma-butyrolactone, ethyllactate, and texanol.
  12. The paste composition of claim 9, wherein the glass frit further comprises about 0.1 weight% to about 5 weight% of Al2O3.
  13. The paste composition of claim 9, wherein the glass frit further comprises about 0.1 weight% to about 0.2 weight% of MgO.
  14. The paste composition of claim 9, wherein the glass frit further comprises about 0.1 weight% to about 5 weight% of TiO2.
  15. The paste composition of claim 9, wherein the glass frit includes at least one selected from the group consisting of SrO, BaO, and ZrO.
  16. The paste composition of claim 9, wherein the glass frit includes less than about 5 weight% of at least one selected from the group consisting of SrO, BaO, and ZrO.
  17. The paste composition of claim 9, wherein the glass frit further comprises at least one selected from the group consisting of AgO, Ag2O, and CaO.
  18. The paste composition of claim 9, wherein the glass frit includes about 0.1 weight% to about 5 weight% of at least one selected from the group consisting of AgO, Ag2O, and CaO.
  19. A solar cell comprising a front electrode formed by using the paste composition claimed according to claim 9.
PCT/KR2010/009336 2009-12-24 2010-12-24 Glass frit, paste composition, and solar cell Ceased WO2011078629A2 (en)

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TWI496755B (en) 2015-08-21

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