WO2019041455A1 - Glass powder used for fabricating photovoltaic cell electrode, paste composition comprising same, photovoltaic cell electrode, and photovoltaic cell - Google Patents

Glass powder used for fabricating photovoltaic cell electrode, paste composition comprising same, photovoltaic cell electrode, and photovoltaic cell Download PDF

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WO2019041455A1
WO2019041455A1 PCT/CN2017/105865 CN2017105865W WO2019041455A1 WO 2019041455 A1 WO2019041455 A1 WO 2019041455A1 CN 2017105865 W CN2017105865 W CN 2017105865W WO 2019041455 A1 WO2019041455 A1 WO 2019041455A1
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oxide
group
weight
glass frit
solar cell
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PCT/CN2017/105865
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French (fr)
Chinese (zh)
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崔永郁
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无锡帝科电子材料股份有限公司
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    • 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
    • C03C12/00—Powdered glass; Bead compositions
    • 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
    • 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
    • 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 the field of solar cell manufacturing technology, and in particular to a glass powder for preparing a solar cell electrode, a paste composition including the same, a solar cell electrode, and a solar cell.
  • Solar cells use the photovoltaic effect to convert the photons of sunlight into electricity through the p-n junction.
  • a front electrode and a rear electrode are respectively formed on upper and lower surfaces of a semiconductor wafer or substrate having a p-n junction. Then, the photoelectric effect of the p-n junction is induced by sunlight entering the semiconductor wafer, and electrons generated by the photoelectric effect of the p-n junction supply current to the outside through the electrode.
  • the composition for the electrode is placed on the wafer, patterned and baked to form an electrode of the solar cell.
  • the uppermost anti-reflective layer of the solar cell is a layer of silicon nitride.
  • the front electrode of the solar cell needs the glass frit component therein to etch away this layer of silicon nitride to conduct the current generated by the lower emitter.
  • the solar cells are connected to each other by a bonding tape to constitute a solar cell module.
  • the bismuth glass has a low melting point, is highly durable, and is easy to dissolve silver in a solid solution. It can be used for fluorescent display tube sealing applications (Japanese Patent Publication No. 10-029834A) and optical fiber material application (Japanese Patent Publication No. 2007-008802A) .
  • the glass powder having a composition of PbO-TeO 2 has high reactivity with silicon nitride.
  • the solar cell electrode manufactured by a typical lead-containing glass powder has insufficient adhesion to the ribbon, and the low adhesion between the electrode and the ribbon causes high series resistance and deterioration of conversion efficiency.
  • the invention aims to provide a glass powder for preparing solar cell electrodes, a paste composition comprising the same, a solar cell electrode and a solar cell, so as to solve the problem of insufficient adhesion between the solar cell electrode and the solder ribbon in the prior art.
  • the low adhesion between the electrode and the ribbon causes a technical problem of high series resistance and deterioration of conversion efficiency.
  • a glass frit for preparing a solar cell electrode contains sodium citrate pentahydrate and lead tetraoxide.
  • the glass frit contains 15% by weight to 85% by weight of sodium tellurite pentahydrate and 15% by weight to 85% by weight of lead tetraoxide.
  • the glass frit further comprises 0.1% by weight to 5% by weight of the Group I oxide; preferably, the Group I metal oxide is one selected from the group consisting of Li 2 O, Na 2 O and K 2 Okind or more.
  • the glass frit further contains 0.1% by weight to 5% by weight of the Group II oxide; preferably, the Group II oxide is one or more selected from the group consisting of MgO, CaO, SrO and BaO.
  • the glass frit further comprises 0.1% to 20% by weight of a transition metal oxide; preferably, the transition metal oxide is selected from the group consisting of titanium oxide, vanadium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide.
  • a transition metal oxide is selected from the group consisting of titanium oxide, vanadium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide.
  • zirconia, molybdenum oxide, cerium oxide, tungsten oxide, and zinc oxide preferably, the transition metal oxide is selected from the group consisting of titanium oxide, vanadium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide.
  • zirconia molybdenum oxide
  • cerium oxide cerium oxide
  • tungsten oxide and zinc oxide.
  • the glass frit further contains 1 wt% to 15 wt% of ZnO.
  • the glass frit further contains other oxides, and the other oxides are selected from one or more of the group consisting of phosphorus oxide, boron oxide, and silicon oxide.
  • the total amount of the Group I oxide, the Group II oxide, the transition metal oxide, and other oxides added to the glass powder is from 1 to 25% by weight.
  • the glass powder has an average particle diameter D50 of 0.1 to 10 ⁇ m.
  • a paste composition for preparing a solar cell electrode contains 60 to 95% by weight of conductive powder, 1.0 to 20% by weight of an organic vehicle, 0.1 to 5% by weight of the above glass powder, and the balance of additives.
  • the additive is one or more selected from the group consisting of a dispersant, a thixotropic agent, a plasticizer, a viscosity stabilizer, an antifoaming agent, a pigment, a UV stabilizer, an antioxidant, and a coupling agent.
  • the conductive powder is silver powder.
  • a solar cell electrode is provided.
  • the solar cell is prepared from the paste composition of any of the above.
  • a solar cell including an electrode is provided.
  • the electrode is the above-described solar cell electrode prepared from the paste composition of the present invention.
  • the glass powder of the invention contains lead tetraoxide-sodium citrate, which has a high eutectic point and can provide a certain space for controlling the reactivity of the glass powder and silicon nitride.
  • the Na compound of the composite compound in Na 2 TeO 3 can also form an Ag-Na ion complex, which can promote liquid phase sintering of Ag particles during sintering. Therefore, the lead trioxide-sodium citrate glass composition can provide stable reactivity with silicon nitride and provide an excellent and stable contact resistance of the solar cell.
  • the paste composition of the present invention can reduce the adverse effect of high surface resistance on the pn junction while reducing the contact resistance, thereby improving the efficiency of the solar cell and improving the performance of the electrode fabricated therefrom; the paste of the present invention
  • the solar cell electrodes prepared by the composition, and the solder have excellent bond strength and minimize series resistance (Rs), thereby providing high conversion efficiency.
  • FIG. 1 shows a schematic view of a solar cell fabricated using a paste composition in accordance with an embodiment of the present invention.
  • a glass frit for preparing a solar cell electrode is provided.
  • the glass frit contains sodium citrate pentahydrate and lead tetraoxide.
  • the glass powder of the invention contains lead tetraoxide-sodium citrate, which has a high eutectic point and can provide a certain space for controlling the reactivity of the glass powder and silicon nitride.
  • the Na compound of the composite compound in Na 2 TeO 3 can also form an Ag-Na ion complex, which can promote liquid phase sintering of Ag particles during sintering. Therefore, the lead trioxide-sodium citrate glass composition can provide stable reactivity with silicon nitride and provide an excellent and stable contact resistance of the solar cell.
  • the solar cell electrodes prepared using the paste composition of the present invention, and the solder have excellent bond strength and minimize series resistance (Rs), thereby providing high conversion efficiency.
  • the glass frit comprises 15% by weight to 85% by weight of sodium tellurite pentahydrate and 15% by weight to 85% by weight of lead tetraoxide.
  • Sodium citrate pentahydrate and lead pentoxide in this ratio range can optimize the properties of the glass powder.
  • the glass frit further comprises 0.1% by weight to 5% by weight of the Group I oxide; more preferably, the Group I metal oxide is selected from the group consisting of Li 2 O, Na 2 O and One or more of the groups consisting of K 2 O.
  • the Group I oxide can reduce the contact resistance.
  • the slurry containing the glass powder can be well combined with a standard substrate (such as alumina), and the structure is dense and possessed. Excellent resistance to electrical conductivity.
  • the glass powder further contains a Group II oxide, which can lower the viscosity of the slurry at a high temperature without lowering the strain point, preferably, the content of the Group II oxide. It is from 0.1% by weight to 5% by weight; when the content of the Group II metal oxide is sufficient, the content easily inhibits the diffusion of an alkali component, particularly Na 2 O.
  • the content of the Group II metal oxide is too large, the denitrification resistance is liable to be deteriorated, and the material cost is remarkably increased.
  • the content of the Group II metal oxide is too small, the viscosity at a high temperature is excessively increased.
  • MgO is a component that lowers the viscosity at a high temperature to improve meltability and formability. Further, MgO also has an excellent effect of preventing the glass sheet from being easily broken in an alkaline earth metal oxide. More preferably, the Group II oxide is one or more selected from the group consisting of MgO, CaO, SrO, and BaO.
  • the glass frit further comprises 0.1% to 20% by weight of a transition metal oxide; more preferably, the transition metal oxide is selected from the group consisting of TiO 2 , V 2 O 5 , MnO One or more of the group consisting of Fe 2 O 3 , CoO, NiO, CuO, ZrO, MoO 3 , RuO, WO 3 and ZnO. Further preferably, the glass frit further comprises from 1 wt% to 15 wt% of ZnO. In general, transition metal oxides have different effects on the glass composition.
  • tungsten oxide and molybdenum oxide are a component of the glass network that contributes to the formation of a glass network in addition to cerium oxide, helping to expand the vitrification range of the bismuth glass and stabilize the glass.
  • the glass frit further contains other oxides, and the other oxides are oxides other than lead trioxide, group I metal oxides, group II metal oxides, and transition metal oxides.
  • the other oxide is selected from one or more of the group consisting of phosphorus oxide, boron oxide and silicon oxide.
  • the total amount of the Group I oxide, the Group II oxide, the transition metal oxide and the other oxide added to the glass powder is from 1 to 25% by weight.
  • a paste composition for preparing a solar cell electrode contains 60 to 95% by weight of conductive powder, 1.0 to 20% by weight of an organic vehicle, 0.1 to 5% by weight of the above glass powder, and the balance of additives.
  • the additive is one or more selected from the group consisting of a dispersant, a thixotropic agent, a plasticizer, a viscosity stabilizer, an antifoaming agent, a pigment, a UV stabilizer, an antioxidant, and a coupling agent.
  • a solar cell electrode is provided.
  • the solar cell is prepared from the paste composition of any of the above.
  • a solar cell including an electrode is provided.
  • the electrode is the above-described solar cell electrode prepared from the paste composition of the present invention.
  • the solar cell electrode component comprises silver powder, sodium citrate-lead trioxide-based glass powder, and an organic vehicle. Now, the composition of the solar cell electrode of the present invention will be described in more detail.
  • a paste composition for preparing a solar cell electrode contains silver powder as a conductive powder.
  • the particle size of the silver powder can be on the order of nanometers or micrometers.
  • the silver powder may have a particle size of several tens to several hundreds of nanometers, or several to several tens of micrometers.
  • the silver powder may be a mixture of two or more silver powders having different particle sizes.
  • the silver powder may have a spherical shape, a flake or an amorphous shape.
  • the silver powder preferably has an average particle diameter (D50) of from about 0.1 ⁇ m to about 10 ⁇ m, more preferably an average particle diameter (D50) of from about 0.5 ⁇ m to about 5 ⁇ m.
  • the average particle diameter can be measured using an apparatus such as Mastersize 2000 (Malvern Co., Ltd.) after the conductive powder is dispersed by ultrasonic wave in isopropyl alcohol (IPA) at 25 ° C for 3 minutes. Within this average particle size range, the composition can provide low contact resistance and low line resistance.
  • the silver powder may be present in an amount from about 60% to about 95% by weight, based on the total weight of the composition. Within this range, the conductive powder can prevent deterioration of conversion efficiency due to an increase in electrical resistance. More preferably, the electrically conductive powder is present in an amount of from about 70% by weight to about 95% by weight.
  • the glass powder is used to enhance the adhesion between the conductive powder and the wafer or the substrate, and the contact resistance is reduced by forming the silver crystal grains in the emitter region by etching the anti-reflection layer and melting the silver powder during the sintering of the conductive paste. .
  • the glass frit softens and lowers the sintering temperature during the sintering process.
  • the solar cells are connected to each other by a bonding tape to constitute a solar cell module.
  • the low adhesive strength between the solar cell electrode and the ribbon may cause the battery to detach or lower the reliability.
  • sodium citrate-lead trioxide-based glass powder is used.
  • the sodium citrate-triodeta lead-based glass powder may comprise 15% by weight to 85% by weight of sodium sulfite pentahydrate and 15% by weight to 85% by weight of lead tetraoxide, preferably, glass powder Further comprising 0.1% by weight to 5% by weight of the Group I oxide; more preferably, the Group I metal oxide is one or more selected from the group consisting of Li 2 O, Na 2 O and K 2 O; Preferably, the glass frit further comprises 0.1% by weight to 5% by weight of the Group II oxide; more preferably, the Group II oxide is one or more selected from the group consisting of MgO, CaO, SrO and BaO Preferably, the glass frit further comprises 0.1% to 20% by weight of a transition metal oxide; more preferably, the transition metal oxide is selected from the group consisting of TiO 2 , V 2 O 5 , MnO, Fe 2 O 3 , CoO, NiO One or more of the group consisting of CuO, ZrO, MoO 3
  • the glass powder may also contain other oxides, and other oxides refer to oxides other than lead tetraoxide, group I metal oxides, group II metal oxides, and transition metal oxides; preferably, other oxides One or more of the group consisting of phosphorus oxide, boron oxide and silicon oxide are selected.
  • the total amount of the Group I oxide, the Group II oxide, the transition metal oxide, and other oxides added to the glass powder is from 1 to 25% by weight. Within this range, the glass powder can ensure excellent bond strength and excellent conversion efficiency.
  • the glass powder can be prepared by any typical method from sodium sulfite pentahydrate and lead tetraoxide.
  • sodium citrate pentahydrate and other oxides are mixed in a certain ratio.
  • Mixing can be carried out using a ball mill or a planetary mill.
  • the combined composition is melted at a temperature of from about 900 ° C to about 1400 ° C and then quenched to about 25 ° C.
  • the obtained material is pulverized using a disc grinder, a planetary mill or the like to provide a glass frit.
  • the glass powder may have an average particle diameter D50 of from about 0.1 ⁇ m to about 10 ⁇ m and an amount of from about 0.1% by weight to about 5% by weight based on the total amount of the composition.
  • the glass powder may have a spherical or amorphous shape.
  • the organic carrier imparts the appropriate viscosity and rheological properties required for the conductive paste printing process by mechanical mixing with the inorganic components in the solar cell electrodes.
  • the organic vehicle may be any typical organic vehicle used for the solar cell electrode composition, and may include a binder resin, a solvent, and the like.
  • the binder resin may be selected from an acrylate resin or a cellulose resin. Ethyl cellulose is usually used as the binder resin. Further, the binder resin may be selected from the group consisting of ethyl hydroxyethyl cellulose, nitrocellulose, a blend of ethyl cellulose and phenolic resin, alkyd resin, phenol, acrylate, xylene, polybutene, poly Ester, urea, melamine, vinyl acetate resin, wood rosin, polymethacrylate of alcohol, and the like.
  • the solvent may be selected, for example, from hexane, toluene, ethyl cellosolve, cyclohexanone, butyl cellosolve, butyl carbitol (digan) Alcohol monobutyl ether), dibutyl carbitol (diethylene glycol dibutyl ether), butyl carbitol acetate (monobutyl ether acetate), propylene glycol monomethyl ether, hexanediol, hydrazine Terpineol, methyl ethyl ketone, benzyl alcohol, ⁇ -butyrolactone, ethyl lactate, and combinations thereof.
  • the organic vehicle may be present in an amount from about 1% to about 20% by weight, based on the total weight of the composition. Within this range, the organic vehicle can provide sufficient adhesive strength and excellent printability to the composition.
  • the composition may further include typical additives as needed to enhance flow properties, processability and stability.
  • the additive may include, but is not limited to, a dispersant, a thixotropic agent, a plasticizer, a viscosity stabilizer, an antifoaming agent, a pigment, a UV stabilizer, an antioxidant, a coupling agent, and the like. These additives may be used singly or as a mixture thereof. These additives may be present in an amount of from about 0.1% to about 5% by weight of the composition, although the amount may be varied as desired.
  • the back electrode 210 and the front electrode 230 may be formed by printing a battery electrode composition on a wafer or substrate 100 including a p-layer 101 and an n-layer 102 serving as an emitter, and sintering.
  • a preliminary process for preparing a back electrode is carried out by printing a composition on the back side of a wafer and drying the printed composition at about 200 ° C to about 400 ° C for about 10 seconds to 60 seconds.
  • a preliminary process for preparing the front electrode can be performed by printing a paste on the front surface of the wafer and drying the printed composition.
  • the front electrode and the back electrode may be formed by sintering the wafer at about 400 ° C to about 950 ° C, preferably about 850 ° C to about 950 ° C for about 30 seconds to 50 seconds.
  • the oxides were mixed according to the composition shown in Table 1, and melted and sintered at 900 ° C to 1400 ° C to prepare a sodium citrate-triodeta-based glass powder having an average particle diameter (D50) of 2.0 ⁇ m. .
  • ethyl cellulose As an organic binder, 1.0% by weight of ethyl cellulose was sufficiently dissolved in 9.0% by weight of butyl carbitol at 60 ° C, and spherical silver powder having an average particle diameter of 1.5 ⁇ m including 2.05% by weight was added, 2.0 % by weight of the prepared sodium citrate and lead trioxide based glass powder and 0.5% by weight of the thixotropic agent Thixatrol ST into a binder solution, followed by grinding in a three-roll mill to prepare a solar cell electrode composition .
  • the electrode composition prepared as above was deposited by screen printing on a front surface of a single crystal silicon wafer in a predetermined pattern, followed by drying in an infrared drying oven. Then, the composition for preparing the back aluminum electrode was printed on the back surface of the wafer and dried in the same manner.
  • the cell sheet processed by the above procedure was fired in a belt firing furnace at 910 ° C for 40 seconds.
  • the solar energy efficiency tester PSS10, BERGER
  • the solar energy efficiency tester was used to measure the conversion efficiency (%) of the battery, the series resistance Rs (m ⁇ ), the open circuit voltage (Voc), and the like. Then, the electrode of the battery is welded to the ribbon with a solder using a soldering iron at 300 ° C to 400 ° C.
  • Examples 1 to 12 and Comparative Examples 1 to 16 were prepared in the same manner using the composition of the glass frit as shown in Table 1, and the physical properties were evaluated. It is to be noted that the examples and comparative examples in Table 1 are intended to highlight the features of one or more of the inventions, and are not intended to limit the scope of the invention, nor to illustrate that the comparative examples are outside the scope of the invention. Further, the inventive subject matter is not limited to the specific details described in the examples and the comparative examples.
  • the compositions prepared in Examples 1 to 12 using sodium sulfite pentahydrate and lead tetraoxide were used, and the composition of the composition was within the preferred range of the present invention, and the solar cell manufactured was used.
  • the electrode exhibits high bond strength and excellent conversion efficiency. While the compositions used in Comparative Examples 1 to 2 also contained sodium sulfite pentahydrate and lead pentoxide, the composition ratio was not in the most preferable range, although compared with other compositions using only PbO and TeO 2 . The effect is superior, and the conversion rate and tensile force of the solar cell electrode prepared therefrom are lower than those of the above embodiments.
  • Comparative Examples 3 to 5 used PbO and TeO 2 in place of sodium tellurite and Pb 3 O 4 in the present invention, showing very low tensile strength and efficiency. Even if one of PbO or TeO 2 was used in place of Comparative Examples 6 to 7 in place of sodium phthalocyanate pentahydrate or Pb 3 O 4 in the examples of the present invention, the prepared electrode also did not have good electrical properties. Comparative Examples 8 to 10 used TeO 2 , Na 2 O and PbO in place of sodium citrate and Pb 3 O 4 , and the prepared electrodes were inferior in performance. In Comparative Examples 11 to 16, although PbO, TeO 2 and Group I elements or Group II elements were contained, electrical properties and tensile strength were not good.

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Abstract

A glass powder used for fabricating a photovoltaic cell electrode, a paste composition comprising the same, a photovoltaic cell electrode, and a photovoltaic cell. The glass powder comprises sodium tellurite pentahydrate and lead tetraoxide. The glass powder comprises lead tetraoxide-sodium tellurite, having a high eutectic point, and being able to provide a certain space for controlling the reactivity of the glass powder and silicon nitride. The element Na in the composite compound Na2TeO3 may also form an Ag-Na ion complex, which may promote the liquid phase sintering of Ag particles during a sintering process. Therefore, the lead tetraoxide-sodium tellurite glass composition may provide a stable reactivity with silicon nitride such that a photovoltaic cell has excellent and stable contact resistance. A photovoltaic cell electrode prepared by applying the described paste composition, as well as a solder strip, have excellent adhesive strength and minimize series resistance (Rs), thus providing high conversion efficiency.

Description

用于制备太阳能电池电极的玻璃粉料、包括其的糊剂组合物、太阳能电池电极及太阳能电池Glass powder for preparing solar cell electrodes, paste composition including the same, solar cell electrode and solar cell 技术领域Technical field
本发明涉及太阳能电池制造技术领域，具体而言，涉及一种用于制备太阳能电池电极的玻璃粉料、包括其的糊剂组合物、太阳能电池电极及太阳能电池。The present invention relates to the field of solar cell manufacturing technology, and in particular to a glass powder for preparing a solar cell electrode, a paste composition including the same, a solar cell electrode, and a solar cell.
背景技术Background technique
太阳能电池通过p-n结利用光伏效应将太阳光的光子转换来产生电能。在太阳能电池中，前电极和后电极分别在具有p-n结的半导体晶片或基底的上下表面形成。然后，p-n结的光电效应由进入半导体晶片的太阳光诱导，进而由p-n结的光电效应产生的电子通过电极向外部提供电流。电极用组合物设置于晶片上，再经图案化和烘焙，形成太阳能电池的电极。Solar cells use the photovoltaic effect to convert the photons of sunlight into electricity through the p-n junction. In a solar cell, a front electrode and a rear electrode are respectively formed on upper and lower surfaces of a semiconductor wafer or substrate having a p-n junction. Then, the photoelectric effect of the p-n junction is induced by sunlight entering the semiconductor wafer, and electrons generated by the photoelectric effect of the p-n junction supply current to the outside through the electrode. The composition for the electrode is placed on the wafer, patterned and baked to form an electrode of the solar cell.
通过持续减小发射极厚度的方法来提高太阳能电池效率，反而有可能导致分流，这将使太阳能电池的性能变差。另外，太阳能电池已经逐渐增加面积以提高效率。然而，在这种情况下，可能存在由于太阳能电池的接触电阻的增加而导致的效率下降的问题。Increasing the efficiency of the solar cell by continuously reducing the thickness of the emitter may instead result in shunting, which will degrade the performance of the solar cell. In addition, solar cells have gradually increased in area to increase efficiency. However, in this case, there may be a problem of a drop in efficiency due to an increase in contact resistance of the solar cell.
太阳能电池最上面的抗反射层是一层氮化硅，太阳能电池的正面电极需要其中的玻璃粉组分刻蚀掉这层氮化硅，来导通下层发射极产生的电流。太阳能电池通过焊带彼此连接以构成太阳能电池组件。碲玻璃具有低熔点、高度耐用、容易将银溶解在固溶体中等特点，可用于荧光显示管密封应用的玻璃(日本专利公开号10-029834A)和光纤材料应用(日本专利公开No.2007-008802A)。但是碲玻璃与氧化硅具有极低的反应性，使其对氮化硅的刻蚀不充分。PbO可以降低玻璃的软化点，能够使玻璃粉组合物在低温下熔融。由于PbO可以和氮化硅形成低共晶点，具有PbO-TeO2组成的玻璃粉具有与氮化硅的高反应性。目前，典型含铅玻璃粉料在内的成份制造的太阳能电池电极与焊带的粘合力不足，电极和焊带之间的低粘附性会导致高的串联电阻和转换效率的劣化。The uppermost anti-reflective layer of the solar cell is a layer of silicon nitride. The front electrode of the solar cell needs the glass frit component therein to etch away this layer of silicon nitride to conduct the current generated by the lower emitter. The solar cells are connected to each other by a bonding tape to constitute a solar cell module. The bismuth glass has a low melting point, is highly durable, and is easy to dissolve silver in a solid solution. It can be used for fluorescent display tube sealing applications (Japanese Patent Publication No. 10-029834A) and optical fiber material application (Japanese Patent Publication No. 2007-008802A) . However, bismuth glass and silicon oxide have extremely low reactivity, which makes etching of silicon nitride insufficient. PbO can lower the softening point of the glass and can melt the glass frit composition at a low temperature. Since PbO can form a low eutectic point with silicon nitride, the glass powder having a composition of PbO-TeO 2 has high reactivity with silicon nitride. At present, the solar cell electrode manufactured by a typical lead-containing glass powder has insufficient adhesion to the ribbon, and the low adhesion between the electrode and the ribbon causes high series resistance and deterioration of conversion efficiency.
发明内容Summary of the invention
本发明旨在提供一种用于制备太阳能电池电极的玻璃粉料、包括其的糊剂组合物、太阳能电池电极及太阳能电池，以解决现有技术中太阳能电池电极与焊带的粘合力不足，电极和焊带之间的低粘附性会导致高的串联电阻和转换效率的劣化的技术问题。The invention aims to provide a glass powder for preparing solar cell electrodes, a paste composition comprising the same, a solar cell electrode and a solar cell, so as to solve the problem of insufficient adhesion between the solar cell electrode and the solder ribbon in the prior art. The low adhesion between the electrode and the ribbon causes a technical problem of high series resistance and deterioration of conversion efficiency.
为了实现上述目的，根据本发明的一个方面，提供了一种用于制备太阳能电池电极的玻璃粉料。该玻璃粉料包含五水合亚碲酸钠和四氧化三铅。In order to achieve the above object, according to an aspect of the invention, a glass frit for preparing a solar cell electrode is provided. The glass frit contains sodium citrate pentahydrate and lead tetraoxide.
进一步地，玻璃粉料包含15wt％至85wt％的五水合亚碲酸钠和15wt％至85wt％的四氧化三铅。 Further, the glass frit contains 15% by weight to 85% by weight of sodium tellurite pentahydrate and 15% by weight to 85% by weight of lead tetraoxide.
进一步地，玻璃粉料还包含0.1wt％至5wt％的第I族氧化物；优选的，第I族金属氧化物为选自由Li2O、Na2O和K2O组成的组中的一种或多种。Further, the glass frit further comprises 0.1% by weight to 5% by weight of the Group I oxide; preferably, the Group I metal oxide is one selected from the group consisting of Li 2 O, Na 2 O and K 2 O Kind or more.
进一步地，玻璃粉料还包含0.1wt％至5wt％的第II族氧化物；优选的，第II族氧化物为选自由MgO、CaO、SrO和BaO组成的组中的一种或多种。Further, the glass frit further contains 0.1% by weight to 5% by weight of the Group II oxide; preferably, the Group II oxide is one or more selected from the group consisting of MgO, CaO, SrO and BaO.
进一步地，玻璃粉料还包含0.1wt％至20wt％的过渡金属氧化物；优选的，过渡金属氧化物为选自由氧化钛、氧化钒、氧化锰、氧化铁、氧化钴、氧化镍、氧化铜、氧化锆、氧化钼、氧化钌、氧化钨和氧化锌组成的组中的一种或多种。Further, the glass frit further comprises 0.1% to 20% by weight of a transition metal oxide; preferably, the transition metal oxide is selected from the group consisting of titanium oxide, vanadium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide. One or more of the group consisting of zirconia, molybdenum oxide, cerium oxide, tungsten oxide, and zinc oxide.
进一步地，玻璃粉料还包含1wt％至15wt％的ZnO。Further, the glass frit further contains 1 wt% to 15 wt% of ZnO.
进一步地，玻璃粉料还包含其他氧化物，其他氧化物选自由氧化磷、氧化硼和氧化硅组成的组中的一种或多种。Further, the glass frit further contains other oxides, and the other oxides are selected from one or more of the group consisting of phosphorus oxide, boron oxide, and silicon oxide.
进一步地，第I族氧化物、第II族氧化物、过渡金属氧化物和其他氧化物的在玻璃粉料中的添加量总和为1～25wt％。Further, the total amount of the Group I oxide, the Group II oxide, the transition metal oxide, and other oxides added to the glass powder is from 1 to 25% by weight.
进一步地，玻璃粉料的平均粒径D50为0.1～10μm。Further, the glass powder has an average particle diameter D50 of 0.1 to 10 μm.
根据本发明的另一个方面，提供一种用于制备太阳能电池电极的糊剂组合物。该糊剂组合物包含60～95wt％的导电粉末、1.0～20wt％的有机载体、0.1～5wt％的上述玻璃粉料，以及余量的添加剂。According to another aspect of the present invention, a paste composition for preparing a solar cell electrode is provided. The paste composition contains 60 to 95% by weight of conductive powder, 1.0 to 20% by weight of an organic vehicle, 0.1 to 5% by weight of the above glass powder, and the balance of additives.
进一步地，添加剂为选自由分散剂、触变剂、增塑剂、粘度稳定剂、消泡剂、颜料、UV稳定剂、抗氧化剂和偶联剂组成的组中的一种或多种。Further, the additive is one or more selected from the group consisting of a dispersant, a thixotropic agent, a plasticizer, a viscosity stabilizer, an antifoaming agent, a pigment, a UV stabilizer, an antioxidant, and a coupling agent.
进一步地，导电粉末为银粉。Further, the conductive powder is silver powder.
根据本发明的再一个方面，提供一种太阳能电池电极。该太阳能电池由上述任一种的糊剂组合物制备而成。According to still another aspect of the present invention, a solar cell electrode is provided. The solar cell is prepared from the paste composition of any of the above.
根据本发明的又一方面，提供了一种太阳能电池，包括电极。该电极为上述由本发明的糊剂组合物制备而成的太阳能电池电极。According to still another aspect of the present invention, a solar cell including an electrode is provided. The electrode is the above-described solar cell electrode prepared from the paste composition of the present invention.
本发明的玻璃粉料含有四氧化三铅-亚碲酸钠，具有较高的共晶点，可以为控制玻璃粉与氮化硅的反应性提供一定的空间。Na2TeO3中的复合化合物Na元素也可以形成Ag-Na离子络合物，在烧结过程中可以促进Ag颗粒的液相烧结。因此，四氧化三铅-亚碲酸钠玻璃组合物可以提供与氮化硅的稳定的反应性，并使太阳能电池具有优异且稳定的接触电阻。本发明的糊剂组合物，其在降低接触电阻的同时，能够降低高表面电阻对p-n结的不利影响，从而提高太阳能电池效率，以及提高由其制造的电极的学性能；本发明的糊剂组合物制备的太阳能电池电极，和焊带有优异的粘合强度并且使串联电阻(Rs)最小化，从而提供高转换效率。The glass powder of the invention contains lead tetraoxide-sodium citrate, which has a high eutectic point and can provide a certain space for controlling the reactivity of the glass powder and silicon nitride. The Na compound of the composite compound in Na 2 TeO 3 can also form an Ag-Na ion complex, which can promote liquid phase sintering of Ag particles during sintering. Therefore, the lead trioxide-sodium citrate glass composition can provide stable reactivity with silicon nitride and provide an excellent and stable contact resistance of the solar cell. The paste composition of the present invention can reduce the adverse effect of high surface resistance on the pn junction while reducing the contact resistance, thereby improving the efficiency of the solar cell and improving the performance of the electrode fabricated therefrom; the paste of the present invention The solar cell electrodes prepared by the composition, and the solder have excellent bond strength and minimize series resistance (Rs), thereby providing high conversion efficiency.
附图说明 DRAWINGS
构成本申请的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：The accompanying drawings, which are incorporated in the claims of the claims In the drawing:
图1示出了根据本发明一实施方式中使用糊剂组合物制造的太阳能电池的示意图。1 shows a schematic view of a solar cell fabricated using a paste composition in accordance with an embodiment of the present invention.
具体实施方式Detailed ways
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将参考附图并结合实施例来详细说明本发明。It should be noted that the embodiments in the present application and the features in the embodiments may be combined with each other without conflict. The invention will be described in detail below with reference to the drawings in conjunction with the embodiments.
根据本发明一种典型的实施方式，提供一种用于制备太阳能电池电极的玻璃粉料。该玻璃粉料包含五水合亚碲酸钠和四氧化三铅。According to an exemplary embodiment of the present invention, a glass frit for preparing a solar cell electrode is provided. The glass frit contains sodium citrate pentahydrate and lead tetraoxide.
本发明的玻璃粉料含有四氧化三铅-亚碲酸钠，具有较高的共晶点，可以为控制玻璃粉与氮化硅的反应性提供一定的空间。Na2TeO3中的复合化合物Na元素也可以形成Ag-Na离子络合物，在烧结过程中可以促进Ag颗粒的液相烧结。因此，四氧化三铅-亚碲酸钠玻璃组合物可以提供与氮化硅的稳定的反应性，并使太阳能电池具有优异且稳定的接触电阻。应用本发明的糊剂组合物制备的太阳能电池电极，和焊带有优异的粘合强度并且使串联电阻(Rs)最小化，从而提供高转换效率。优选的，玻璃粉料包含15wt％至85wt％的五水合亚碲酸钠和15wt％至85wt％的四氧化三铅。五水合亚碲酸钠和四氧化三铅在此比例范围内，可以使玻璃粉料的性质达到优化的状态。The glass powder of the invention contains lead tetraoxide-sodium citrate, which has a high eutectic point and can provide a certain space for controlling the reactivity of the glass powder and silicon nitride. The Na compound of the composite compound in Na 2 TeO 3 can also form an Ag-Na ion complex, which can promote liquid phase sintering of Ag particles during sintering. Therefore, the lead trioxide-sodium citrate glass composition can provide stable reactivity with silicon nitride and provide an excellent and stable contact resistance of the solar cell. The solar cell electrodes prepared using the paste composition of the present invention, and the solder have excellent bond strength and minimize series resistance (Rs), thereby providing high conversion efficiency. Preferably, the glass frit comprises 15% by weight to 85% by weight of sodium tellurite pentahydrate and 15% by weight to 85% by weight of lead tetraoxide. Sodium citrate pentahydrate and lead pentoxide in this ratio range can optimize the properties of the glass powder.
为了改善玻璃粉料的性能，优选的，玻璃粉料还包含0.1wt％至5wt％的第I族氧化物；更优选的，第I族金属氧化物为选自由Li2O、Na2O和K2O组成的组中的一种或多种。第I族氧化物作为电子的提供者，有可以降低接触电阻的作用，在上述含量范围内，可以使得含该玻璃粉的浆料与标准基体(如氧化铝等)良好结合，结构密实，拥有优异耐电导电的性能。In order to improve the performance of the glass powder, preferably, the glass frit further comprises 0.1% by weight to 5% by weight of the Group I oxide; more preferably, the Group I metal oxide is selected from the group consisting of Li 2 O, Na 2 O and One or more of the groups consisting of K 2 O. As a supplier of electrons, the Group I oxide can reduce the contact resistance. In the above content range, the slurry containing the glass powder can be well combined with a standard substrate (such as alumina), and the structure is dense and possessed. Excellent resistance to electrical conductivity.
为了进一步改善玻璃粉料的性能，玻璃粉料还包含第II族氧化物，II族金属氧化物可以降低高温下的浆料的粘度而不降低应变点，优选的，第II族氧化物的含量为0.1wt％至5wt％；当II族金属氧化物的含量足够时，含量容易抑制碱成分，特别是Na2O的扩散。但是，当II族金属氧化物的含量过大时，耐脱氮性易于劣化，材料成本显着增加。另一方面，当的II族金属氧化物的含量太小时，高温下的粘度会过度增加。如MgO是降低高温下的粘度以提高熔融性和成形性的成分。此外，MgO还具有优异的防止玻璃板在碱土金属氧化物中容易破裂的效果。更优选的，第II族氧化物为选自由MgO、CaO、SrO和BaO组成的组中的一种或多种。In order to further improve the performance of the glass powder, the glass powder further contains a Group II oxide, which can lower the viscosity of the slurry at a high temperature without lowering the strain point, preferably, the content of the Group II oxide. It is from 0.1% by weight to 5% by weight; when the content of the Group II metal oxide is sufficient, the content easily inhibits the diffusion of an alkali component, particularly Na 2 O. However, when the content of the Group II metal oxide is too large, the denitrification resistance is liable to be deteriorated, and the material cost is remarkably increased. On the other hand, when the content of the Group II metal oxide is too small, the viscosity at a high temperature is excessively increased. For example, MgO is a component that lowers the viscosity at a high temperature to improve meltability and formability. Further, MgO also has an excellent effect of preventing the glass sheet from being easily broken in an alkaline earth metal oxide. More preferably, the Group II oxide is one or more selected from the group consisting of MgO, CaO, SrO, and BaO.
为了更进一步改善玻璃粉料的性能，优选的，玻璃粉料还包含0.1wt％至20wt％的过渡金属氧化物；更优选的，过渡金属氧化物为选自由TiO2、V2O5、MnO、Fe2O3、CoO、NiO、CuO、ZrO、MoO3、RuO、WO3和ZnO组成的组中的一种或多种。进一步优选的，玻璃粉料还包含1wt％至15wt％的ZnO。一般来说，过渡金属氧化物在玻璃组分上具有不同的作用。例如在碲玻璃中，氧化钨和氧化钼是除氧化碲外有助于形成玻璃网络的一种组分，有助于扩大碲化玻璃的玻璃化范围和稳定玻璃。 In order to further improve the performance of the glass powder, preferably, the glass frit further comprises 0.1% to 20% by weight of a transition metal oxide; more preferably, the transition metal oxide is selected from the group consisting of TiO 2 , V 2 O 5 , MnO One or more of the group consisting of Fe 2 O 3 , CoO, NiO, CuO, ZrO, MoO 3 , RuO, WO 3 and ZnO. Further preferably, the glass frit further comprises from 1 wt% to 15 wt% of ZnO. In general, transition metal oxides have different effects on the glass composition. For example, in bismuth glass, tungsten oxide and molybdenum oxide are a component of the glass network that contributes to the formation of a glass network in addition to cerium oxide, helping to expand the vitrification range of the bismuth glass and stabilize the glass.
根据本发明一种典型的实施方式，玻璃粉料还包含其他氧化物，其他氧化物是指除四氧化三铅、I族金属氧化物、II族金属氧化物和过渡金属氧化物之外氧化物；优选的，其他氧化物选自由氧化磷、氧化硼和氧化硅组成的组中的一种或多种。According to an exemplary embodiment of the present invention, the glass frit further contains other oxides, and the other oxides are oxides other than lead trioxide, group I metal oxides, group II metal oxides, and transition metal oxides. Preferably, the other oxide is selected from one or more of the group consisting of phosphorus oxide, boron oxide and silicon oxide.
优选的，第I族氧化物、第II族氧化物、过渡金属氧化物和其他氧化物的在玻璃粉料中的添加量总和为1～25wt％。Preferably, the total amount of the Group I oxide, the Group II oxide, the transition metal oxide and the other oxide added to the glass powder is from 1 to 25% by weight.
根据本发明一种典型的实施方式，提供一种用于制备太阳能电池电极的糊剂组合物。该糊剂组合物包含60～95wt％的导电粉末、1.0～20wt％的有机载体、0.1～5wt％的上述玻璃粉料，以及余量的添加剂。其中，添加剂为选自由分散剂、触变剂、增塑剂、粘度稳定剂、消泡剂、颜料、UV稳定剂、抗氧化剂和偶联剂组成的组中的一种或多种。According to an exemplary embodiment of the present invention, a paste composition for preparing a solar cell electrode is provided. The paste composition contains 60 to 95% by weight of conductive powder, 1.0 to 20% by weight of an organic vehicle, 0.1 to 5% by weight of the above glass powder, and the balance of additives. Wherein the additive is one or more selected from the group consisting of a dispersant, a thixotropic agent, a plasticizer, a viscosity stabilizer, an antifoaming agent, a pigment, a UV stabilizer, an antioxidant, and a coupling agent.
根据本发明一种典型的实施方式，提供了一种太阳能电池电极。该太阳能电池由上述任一种的糊剂组合物制备而成。According to an exemplary embodiment of the present invention, a solar cell electrode is provided. The solar cell is prepared from the paste composition of any of the above.
根据本发明一种典型的实施方式，提供了一种太阳能电池，包括电极。该电极为上述由本发明的糊剂组合物制备而成的太阳能电池电极。According to an exemplary embodiment of the present invention, a solar cell including an electrode is provided. The electrode is the above-described solar cell electrode prepared from the paste composition of the present invention.
根据本发明一种典型的实施方式，太阳能电池电极组分包括银粉、亚碲酸钠-四氧化三铅基玻璃粉料和有机载体。现在，将更详细地描述本发明的太阳能电池电极的组成。According to an exemplary embodiment of the present invention, the solar cell electrode component comprises silver powder, sodium citrate-lead trioxide-based glass powder, and an organic vehicle. Now, the composition of the solar cell electrode of the present invention will be described in more detail.
(A)银粉(A) Silver powder
根据本发明一种典型的实施方式，用于制备太阳能电池电极的糊剂组合物包含银粉作为导电粉末。银粉的粒度可以是纳米或微米级。例如，银粉可以具有几十至几百纳米，或几至几十微米的粒度。或者，银粉可以是具有不同粒径的两种或更多种银粉的混合物。According to an exemplary embodiment of the present invention, a paste composition for preparing a solar cell electrode contains silver powder as a conductive powder. The particle size of the silver powder can be on the order of nanometers or micrometers. For example, the silver powder may have a particle size of several tens to several hundreds of nanometers, or several to several tens of micrometers. Alternatively, the silver powder may be a mixture of two or more silver powders having different particle sizes.
银粉可以具有球形、薄片或无定形形状。The silver powder may have a spherical shape, a flake or an amorphous shape.
银粉优选具有约0.1μm至约10μm的平均粒径(D50)，更优选约0.5μm至约5μm的平均粒径(D50)。平均粒径可以使用仪器，如Mastersize 2000(Malvern Co.，Ltd。)在将导电粉末在25℃下通过超声波分散在异丙醇(IPA)中3分钟之后测量。在该平均粒径范围内，组合物可以提供低接触电阻和低线电阻。The silver powder preferably has an average particle diameter (D50) of from about 0.1 μm to about 10 μm, more preferably an average particle diameter (D50) of from about 0.5 μm to about 5 μm. The average particle diameter can be measured using an apparatus such as Mastersize 2000 (Malvern Co., Ltd.) after the conductive powder is dispersed by ultrasonic wave in isopropyl alcohol (IPA) at 25 ° C for 3 minutes. Within this average particle size range, the composition can provide low contact resistance and low line resistance.
基于组合物的总重量，银粉可以约60wt％至约95wt％的量存在。在该范围内，导电粉末可以防止由于电阻的增加而导致的转换效率的劣化。更佳情况下，导电粉末以约70wt％至约95wt％的量存在。The silver powder may be present in an amount from about 60% to about 95% by weight, based on the total weight of the composition. Within this range, the conductive powder can prevent deterioration of conversion efficiency due to an increase in electrical resistance. More preferably, the electrically conductive powder is present in an amount of from about 70% by weight to about 95% by weight.
(B)亚碲酸钠-四氧化三铅基玻璃粉料(B) sodium citrate-lead trioxide-based glass powder
玻璃粉料用于增强导电粉末与晶片或基板之间的粘附力，并且在导电浆料烧结过程中，通过蚀刻减反射层和熔化银粉而在发射极区域中形成银晶粒来降低接触电阻。此外，在烧结工艺期间，玻璃粉料软化并降低烧结温度。The glass powder is used to enhance the adhesion between the conductive powder and the wafer or the substrate, and the contact resistance is reduced by forming the silver crystal grains in the emitter region by etching the anti-reflection layer and melting the silver powder during the sintering of the conductive paste. . In addition, the glass frit softens and lowers the sintering temperature during the sintering process.
当为了提高太阳能电池效率而增加太阳能电池的面积时，可能存在太阳能电池的接触电 阻增加的问题。因此，需要最小化串联电阻(Rs)和对p-n结的影响。另外，随着使用具有不同表面电阻的各种晶片的适合烧结温度在宽范围内变化，玻璃粉料需要确保足够的热稳定性以耐受较大的烧结温度窗口。When the area of the solar cell is increased in order to increase the efficiency of the solar cell, there may be contact electricity of the solar cell. The problem of increased resistance. Therefore, it is necessary to minimize the series resistance (Rs) and the effect on the p-n junction. In addition, as the suitable sintering temperatures for various wafers having different surface resistances vary over a wide range, the glass frit needs to ensure sufficient thermal stability to withstand a large sintering temperature window.
太阳能电池通过焊带彼此连接以构成太阳能电池组件。在这种情况下，太阳能电池电极和焊带之间的低粘合强度有可能导致电池的脱离或降低可靠性。在本发明中，为了确保太阳能电池具有所需的电学和物理性质例如粘合强度，使用亚碲酸钠-四氧化三铅基玻璃粉料。The solar cells are connected to each other by a bonding tape to constitute a solar cell module. In this case, the low adhesive strength between the solar cell electrode and the ribbon may cause the battery to detach or lower the reliability. In the present invention, in order to ensure that the solar cell has desired electrical and physical properties such as adhesive strength, sodium citrate-lead trioxide-based glass powder is used.
在本发明中，亚碲酸钠-四氧化三铅基玻璃粉料可以包含15wt％至85wt％的五水合亚碲酸钠和15wt％至85wt％的四氧化三铅，优选的，玻璃粉料还包含0.1wt％至5wt％的第I族氧化物；更优选的，第I族金属氧化物为选自由Li2O、Na2O和K2O组成的组中的一种或多种；优选的，玻璃粉料还包含0.1wt％至5wt％的第II族氧化物；更优选的，第II族氧化物为选自由MgO、CaO、SrO和BaO组成的组中的一种或多种；优选的，玻璃粉料还包含0.1wt％至20wt％的过渡金属氧化物；更优选的，过渡金属氧化物为选自由TiO2、V2O5、MnO、Fe2O3、CoO、NiO、CuO、ZrO、MoO3、RuO、WO3和ZnO组成的组中的一种或多种；特别优选的，过渡金属氧化物为1wt％至15wt％的ZnO。另外，玻璃粉料还可以包含其他氧化物，其他氧化物是指除四氧化三铅、I族金属氧化物、II族金属氧化物和过渡金属氧化物之外氧化物；优选的，其他氧化物选自由氧化磷、氧化硼和氧化硅组成的组中的一种或多种。第I族氧化物、第II族氧化物、过渡金属氧化物和其他氧化物的在玻璃粉料中的添加量总和为1～25wt％。在该范围内，玻璃粉料可以确保优异的粘合强度和优异的转化效率。In the present invention, the sodium citrate-triodeta lead-based glass powder may comprise 15% by weight to 85% by weight of sodium sulfite pentahydrate and 15% by weight to 85% by weight of lead tetraoxide, preferably, glass powder Further comprising 0.1% by weight to 5% by weight of the Group I oxide; more preferably, the Group I metal oxide is one or more selected from the group consisting of Li 2 O, Na 2 O and K 2 O; Preferably, the glass frit further comprises 0.1% by weight to 5% by weight of the Group II oxide; more preferably, the Group II oxide is one or more selected from the group consisting of MgO, CaO, SrO and BaO Preferably, the glass frit further comprises 0.1% to 20% by weight of a transition metal oxide; more preferably, the transition metal oxide is selected from the group consisting of TiO 2 , V 2 O 5 , MnO, Fe 2 O 3 , CoO, NiO One or more of the group consisting of CuO, ZrO, MoO 3 , RuO, WO 3 and ZnO; particularly preferably, the transition metal oxide is from 1 wt% to 15 wt% of ZnO. In addition, the glass powder may also contain other oxides, and other oxides refer to oxides other than lead tetraoxide, group I metal oxides, group II metal oxides, and transition metal oxides; preferably, other oxides One or more of the group consisting of phosphorus oxide, boron oxide and silicon oxide are selected. The total amount of the Group I oxide, the Group II oxide, the transition metal oxide, and other oxides added to the glass powder is from 1 to 25% by weight. Within this range, the glass powder can ensure excellent bond strength and excellent conversion efficiency.
玻璃粉料可以由五水合亚碲酸钠和四氧化三铅等通过任何典型的方法制备。例如，五水合亚碲酸钠和其它氧化物以一定的比例混合。混合可以使用球磨机或行星式磨机进行。将混合的组合物在约900℃至约1400℃下熔融，然后骤冷至约25℃。使用盘磨机，行星式磨机等对所得材料进行粉碎，从而提供玻璃粉料。The glass powder can be prepared by any typical method from sodium sulfite pentahydrate and lead tetraoxide. For example, sodium citrate pentahydrate and other oxides are mixed in a certain ratio. Mixing can be carried out using a ball mill or a planetary mill. The combined composition is melted at a temperature of from about 900 ° C to about 1400 ° C and then quenched to about 25 ° C. The obtained material is pulverized using a disc grinder, a planetary mill or the like to provide a glass frit.
玻璃粉料的平均粒径D50可以约0.1μm至约10μm，并且占基于组合物的总量的约0.1wt％至约5wt％的量。玻璃粉料可以具有球形或无定形形状。The glass powder may have an average particle diameter D50 of from about 0.1 μm to about 10 μm and an amount of from about 0.1% by weight to about 5% by weight based on the total amount of the composition. The glass powder may have a spherical or amorphous shape.
(C)有机载体(C) organic carrier
通过与太阳能电池电极中的无机组分的机械混合，有机载体赋予导电浆料打印过程所需的适当的粘度和流变特性。The organic carrier imparts the appropriate viscosity and rheological properties required for the conductive paste printing process by mechanical mixing with the inorganic components in the solar cell electrodes.
有机载体可以是用于太阳能电池电极组合物的任何典型的有机载体，并且可以包括粘合剂树脂，溶剂等。The organic vehicle may be any typical organic vehicle used for the solar cell electrode composition, and may include a binder resin, a solvent, and the like.
粘合剂树脂可以选自丙烯酸酯树脂或纤维素树脂。通常使用乙基纤维素作为粘合剂树脂。此外，粘合剂树脂可以选自乙基羟乙基纤维素、硝化纤维素、乙基纤维素和酚醛树脂的共混物、醇酸树脂、苯酚、丙烯酸酯、二甲苯、聚丁烯、聚酯、脲、三聚氰胺、乙酸乙烯酯树脂、木松香、醇的聚甲基丙烯酸酯等。The binder resin may be selected from an acrylate resin or a cellulose resin. Ethyl cellulose is usually used as the binder resin. Further, the binder resin may be selected from the group consisting of ethyl hydroxyethyl cellulose, nitrocellulose, a blend of ethyl cellulose and phenolic resin, alkyd resin, phenol, acrylate, xylene, polybutene, poly Ester, urea, melamine, vinyl acetate resin, wood rosin, polymethacrylate of alcohol, and the like.
溶剂可以选自例如己烷、甲苯、乙基溶纤剂、环己酮、丁基溶纤剂、丁基卡必醇(二甘 醇单丁基醚)、二丁基卡必醇(二甘醇二丁基醚)、丁基卡必醇乙酸酯(单丁醚乙酸酯)、丙二醇单甲醚、己二醇、萜品醇、甲基乙基酮、苄醇、γ-丁内酯、乳酸乙酯及其组合。The solvent may be selected, for example, from hexane, toluene, ethyl cellosolve, cyclohexanone, butyl cellosolve, butyl carbitol (digan) Alcohol monobutyl ether), dibutyl carbitol (diethylene glycol dibutyl ether), butyl carbitol acetate (monobutyl ether acetate), propylene glycol monomethyl ether, hexanediol, hydrazine Terpineol, methyl ethyl ketone, benzyl alcohol, γ-butyrolactone, ethyl lactate, and combinations thereof.
基于组合物的总重量，有机载体可以约1wt％至约20wt％的量存在。在该范围内，有机载体可以为组合物提供足够的粘合强度和优异的可印刷性。The organic vehicle may be present in an amount from about 1% to about 20% by weight, based on the total weight of the composition. Within this range, the organic vehicle can provide sufficient adhesive strength and excellent printability to the composition.
(D)添加剂(D) Additives
根据需要，组合物可以进一步包括典型的添加剂，以增强流动性能，加工性能和稳定性。添加剂可以包括分散剂、触变剂、增塑剂、粘度稳定剂、消泡剂、颜料、UV稳定剂、抗氧化剂、偶联剂等，但不限于此。这些添加剂可以单独使用或作为其混合物使用。这些添加剂可以以组合物中约0.1wt％至约5wt％的量存在，但该量可根据需要改变。The composition may further include typical additives as needed to enhance flow properties, processability and stability. The additive may include, but is not limited to, a dispersant, a thixotropic agent, a plasticizer, a viscosity stabilizer, an antifoaming agent, a pigment, a UV stabilizer, an antioxidant, a coupling agent, and the like. These additives may be used singly or as a mixture thereof. These additives may be present in an amount of from about 0.1% to about 5% by weight of the composition, although the amount may be varied as desired.
根据本发明一种典型的实施方式，使用糊剂组合物制造的太阳能电池。如图1所示，背面电极210和正面电极230可以通过印刷电池电极组分于包括p层101和用作发射极的n层102的晶片或基板100上，并经过烧结来形成。例如，通过在晶片的背面上印刷组合物并在约200℃至约400℃下干燥所印刷的组合物约10秒至60秒，来进行用于制备背面电极的预备工艺。此外，可以通过在晶片的前表面上印刷浆料并干燥印刷的组合物来进行用于制备前电极的初步工艺。然后，可以通过在约400℃至约950℃，优选约850℃至约950℃下烧结晶片约30秒至50秒来形成正面电极和背面电极。According to an exemplary embodiment of the invention, a solar cell fabricated using a paste composition is used. As shown in FIG. 1, the back electrode 210 and the front electrode 230 may be formed by printing a battery electrode composition on a wafer or substrate 100 including a p-layer 101 and an n-layer 102 serving as an emitter, and sintering. For example, a preliminary process for preparing a back electrode is carried out by printing a composition on the back side of a wafer and drying the printed composition at about 200 ° C to about 400 ° C for about 10 seconds to 60 seconds. Further, a preliminary process for preparing the front electrode can be performed by printing a paste on the front surface of the wafer and drying the printed composition. Then, the front electrode and the back electrode may be formed by sintering the wafer at about 400 ° C to about 950 ° C, preferably about 850 ° C to about 950 ° C for about 30 seconds to 50 seconds.
接下来，本发明将通过参考实施例更详细地描述。然而，应当注意，这些实施例的提供仅用于说明本发明，不应以任何方式解释为限制本发明。Next, the present invention will be described in more detail by reference to examples. However, it should be noted that the examples are provided for illustrative purposes only and are not to be construed as limiting the invention in any way.
为了清楚的目的，省略了本领域技术人员清楚的详细描述。For the sake of clarity, a detailed description that is clear to those skilled in the art is omitted.
实施例及对比例Examples and comparative examples
根据表1所示的组成将氧化物混合，并在900℃～1400℃下进行熔融和烧结，从而制备平均粒径(D50)为2.0μm的亚碲酸钠-四氧化三铅基玻璃粉料。The oxides were mixed according to the composition shown in Table 1, and melted and sintered at 900 ° C to 1400 ° C to prepare a sodium citrate-triodeta-based glass powder having an average particle diameter (D50) of 2.0 μm. .
作为有机粘合剂，在60℃下将1.0重量％的乙基纤维素充分溶解在9.0重量％的丁基卡必醇中，并加入包括87.5重量％的平均粒径为1.5μm球形银粉，2.0重量％的所制备的亚碲酸钠和四氧化三铅基玻璃粉和0.5重量％的触变剂Thixatrol ST到粘合剂溶液中，随后在三辊机中研磨，从而制备太阳能电池电极组合物。As an organic binder, 1.0% by weight of ethyl cellulose was sufficiently dissolved in 9.0% by weight of butyl carbitol at 60 ° C, and spherical silver powder having an average particle diameter of 1.5 μm including 2.05% by weight was added, 2.0 % by weight of the prepared sodium citrate and lead trioxide based glass powder and 0.5% by weight of the thixotropic agent Thixatrol ST into a binder solution, followed by grinding in a three-roll mill to prepare a solar cell electrode composition .
将如上所制备的电极组合物通过丝网印刷，以预定图案沉积在单晶硅片的前表面上，随后在红外干燥炉中干燥。然后，将用于制备背铝电极的组合物印刷在晶片的背面上并以相同的方式干燥。将通过以上步骤处理的电池片在带式烧成炉中，于910℃下烧成40秒。使用太阳能效率测试仪(PSS10，BERGER)来测量电池的转换效率(％)，串联电阻Rs(mΩ)，开路电压(Voc)等。然后，使用烙铁在300℃至400℃下用焊剂将电池的电极与焊带焊接。然后，电池电极与焊带的的粘合强度(N/mm)使用张力测试仪在180°的剥离角和50mm/min的拉伸速率下测量。测量的转换效率和拉力测试显示于表1中。 The electrode composition prepared as above was deposited by screen printing on a front surface of a single crystal silicon wafer in a predetermined pattern, followed by drying in an infrared drying oven. Then, the composition for preparing the back aluminum electrode was printed on the back surface of the wafer and dried in the same manner. The cell sheet processed by the above procedure was fired in a belt firing furnace at 910 ° C for 40 seconds. The solar energy efficiency tester (PSS10, BERGER) was used to measure the conversion efficiency (%) of the battery, the series resistance Rs (mΩ), the open circuit voltage (Voc), and the like. Then, the electrode of the battery is welded to the ribbon with a solder using a soldering iron at 300 ° C to 400 ° C. Then, the adhesive strength (N/mm) of the battery electrode and the ribbon was measured using a tensile tester at a peel angle of 180° and a tensile rate of 50 mm/min. The measured conversion efficiencies and tensile tests are shown in Table 1.
实施例1～12和对比例1～16Examples 1 to 12 and Comparative Examples 1 to 16
实施例1～12和对比例1～16采用如表1所示的玻璃粉的组成，以相同的方式制备用于太阳能电池电极的组合物，并评价物理性能。需要表明的是表1中的实施例和对比例是为了突出一个或多个发明例的特点，而不是为限制本发明的范围，也不是说明对比例在本发明的范围之外。此外，发明主体并不局限于实施例和对比例中所描述的特定细节。Examples 1 to 12 and Comparative Examples 1 to 16 were prepared in the same manner using the composition of the glass frit as shown in Table 1, and the physical properties were evaluated. It is to be noted that the examples and comparative examples in Table 1 are intended to highlight the features of one or more of the inventions, and are not intended to limit the scope of the invention, nor to illustrate that the comparative examples are outside the scope of the invention. Further, the inventive subject matter is not limited to the specific details described in the examples and the comparative examples.
表1Table 1
Figure PCTCN2017105865-appb-000001
Figure PCTCN2017105865-appb-000001
如表1所示，使用实施例1～12中采用五水合亚碲酸钠和四氧化三铅等制备的组合物，且组合物的成份组成在本发明优选的范围内，而制造的太阳能电池电极，显示出较高的粘合强度以及优异的转换效率。而比较例1～2所采用的组合物虽然也含有五水合亚碲酸钠和四氧化三铅，但组分比例不在最优选的范围内，虽然对比其它只使用PbO和TeO2的组合物的效果较优，由其制备的太阳能电池电极的转化率和拉力较以上实施例都有所降低。比较例3～5采用PbO和TeO2替代本发明中的亚碲酸钠和Pb3O4，显示非常低的拉力及效率。即使如比较例6～7中采用PbO或TeO2中的一种相应地替代本发明实例中的五水合亚碲酸钠或Pb3O4，制备的电极同样没有良好的电性能。对比例8～10采用TeO2、Na2O和PbO替代亚碲酸钠和Pb3O4，制备的电极性能较差。比较例11～16虽然具有含有PbO，TeO2以及I族元素或II族元素，但电性能及拉力不好。 As shown in Table 1, the compositions prepared in Examples 1 to 12 using sodium sulfite pentahydrate and lead tetraoxide were used, and the composition of the composition was within the preferred range of the present invention, and the solar cell manufactured was used. The electrode exhibits high bond strength and excellent conversion efficiency. While the compositions used in Comparative Examples 1 to 2 also contained sodium sulfite pentahydrate and lead pentoxide, the composition ratio was not in the most preferable range, although compared with other compositions using only PbO and TeO 2 . The effect is superior, and the conversion rate and tensile force of the solar cell electrode prepared therefrom are lower than those of the above embodiments. Comparative Examples 3 to 5 used PbO and TeO 2 in place of sodium tellurite and Pb 3 O 4 in the present invention, showing very low tensile strength and efficiency. Even if one of PbO or TeO 2 was used in place of Comparative Examples 6 to 7 in place of sodium phthalocyanate pentahydrate or Pb 3 O 4 in the examples of the present invention, the prepared electrode also did not have good electrical properties. Comparative Examples 8 to 10 used TeO 2 , Na 2 O and PbO in place of sodium citrate and Pb 3 O 4 , and the prepared electrodes were inferior in performance. In Comparative Examples 11 to 16, although PbO, TeO 2 and Group I elements or Group II elements were contained, electrical properties and tensile strength were not good.
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。 The above description is only the preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes can be made to the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and scope of the present invention are intended to be included within the scope of the present invention.

Claims (14)

  1. 一种用于制备太阳能电池电极的玻璃粉料，其特征在于，所述玻璃粉料包含五水合亚碲酸钠和四氧化三铅。A glass frit for preparing a solar cell electrode, characterized in that the glass frit contains sodium citrate pentahydrate and lead trioxide.
  2. 根据权利要求1所述的玻璃粉料，其特征在于，所述玻璃粉料包含15wt％至85wt％的五水合亚碲酸钠和15wt％至85wt％的四氧化三铅。The glass frit according to claim 1, wherein the glass frit comprises 15% by weight to 85% by weight of sodium tellurite pentahydrate and 15% by weight to 85% by weight of lead tetraoxide.
  3. 根据权利要求2所述的玻璃粉料，其特征在于，所述玻璃粉料还包含0.1wt％至5wt％的第I族氧化物；优选的，所述第I族金属氧化物为选自由Li2O、Na2O和K2O组成的组中的一种或多种。The glass frit according to claim 2, wherein the glass frit further comprises 0.1% by weight to 5% by weight of the Group I oxide; preferably, the Group I metal oxide is selected from the group consisting of Li One or more of the group consisting of 2 O, Na 2 O, and K 2 O.
  4. 根据权利要求3所述的玻璃粉料，其特征在于，所述玻璃粉料还包含0.1wt％至5wt％的第II族氧化物；优选的，所述第II族氧化物为选自由MgO、CaO、SrO和BaO组成的组中的一种或多种。The glass frit according to claim 3, wherein the glass frit further comprises 0.1% by weight to 5% by weight of the Group II oxide; preferably, the Group II oxide is selected from the group consisting of MgO, One or more of the group consisting of CaO, SrO, and BaO.
  5. 根据权利要求2所述的玻璃粉料，其特征在于，所述玻璃粉料还包含0.1wt％至20wt％的过渡金属氧化物；优选的，所述过渡金属氧化物为选自由氧化钛、氧化钒、氧化锰、氧化铁、氧化钴、氧化镍、氧化铜、氧化锆、氧化钼、氧化钌、氧化钨和氧化锌组成的组中的一种或多种。The glass frit according to claim 2, wherein the glass frit further comprises 0.1% by weight to 20% by weight of a transition metal oxide; preferably, the transition metal oxide is selected from the group consisting of titanium oxide and oxidation One or more of the group consisting of vanadium, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, zirconium oxide, molybdenum oxide, cerium oxide, tungsten oxide, and zinc oxide.
  6. 根据权利要求5所述的玻璃粉料，其特征在于，所述玻璃粉料还包含1wt％至15wt％的ZnO。The glass frit according to claim 5, wherein the glass frit further comprises from 1 wt% to 15 wt% of ZnO.
  7. 根据权利要求2至6中任一项所述的玻璃粉料，其特征在于，所述玻璃粉料还包含其他氧化物，所述其他氧化物选自由氧化磷、氧化硼和氧化硅组成的组中的一种或多种。The glass frit according to any one of claims 2 to 6, wherein the glass frit further comprises other oxides selected from the group consisting of phosphorus oxide, boron oxide and silicon oxide. One or more of them.
  8. 根据权利要求7所述的玻璃粉料，其特征在于，第I族氧化物、第II族氧化物、过渡金属氧化物和其他氧化物的在所述玻璃粉料中的添加量总和为1～25wt％。The glass powder according to claim 7, wherein the total amount of the Group I oxide, the Group II oxide, the transition metal oxide and the other oxide added to the glass powder is 1 to 25wt%.
  9. 根据权利要求1至6中任一项所述的玻璃粉料，其特征在于，所述玻璃粉料的平均粒径D50为0.1～10μm。The glass frit according to any one of claims 1 to 6, wherein the glass frit has an average particle diameter D50 of 0.1 to 10 μm.
  10. 一种用于制备太阳能电池电极的糊剂组合物，其特征在于，包含60～95wt％的导电粉末、1.0～20wt％的有机载体、0.1～5wt％的如权利要求1至9中任一项所述玻璃粉料，以及余量的添加剂。A paste composition for preparing a solar cell electrode, comprising 60 to 95% by weight of an electrically conductive powder, 1.0 to 20% by weight of an organic vehicle, 0.1 to 5% by weight of any one of claims 1 to 9. The glass powder, and the balance of additives.
  11. 根据权利要求10所述的糊剂组合物，其特征在于，所述添加剂为选自由分散剂、触变剂、增塑剂、粘度稳定剂、消泡剂、颜料、UV稳定剂、抗氧化剂和偶联剂组成的组中的一种或多种。The paste composition according to claim 10, wherein the additive is selected from the group consisting of a dispersant, a thixotropic agent, a plasticizer, a viscosity stabilizer, an antifoaming agent, a pigment, a UV stabilizer, an antioxidant, and One or more of the group consisting of coupling agents.
  12. 根据权利要求10所述的糊剂组合物，其特征在于，所述导电粉末为银粉。The paste composition according to claim 10, wherein the conductive powder is silver powder.
  13. 一种太阳能电池电极，其特征在于，由权利要求10至12中任一项所述的糊剂组合物制备而成。 A solar cell electrode prepared by the paste composition according to any one of claims 10 to 12.
  14. 一种太阳能电池，包括电极，其特征在于，所述电极为如权利要求13所述的太阳能电池电极。 A solar cell comprising an electrode, characterized in that the electrode is a solar cell electrode according to claim 13.
PCT/CN2017/105865 2017-08-31 2017-10-12 Glass powder used for fabricating photovoltaic cell electrode, paste composition comprising same, photovoltaic cell electrode, and photovoltaic cell WO2019041455A1 (en)

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CN107879635B (en) * 2017-08-31 2021-05-04 无锡帝科电子材料股份有限公司 Glass frit for preparing solar cell electrode, paste composition comprising same, solar cell electrode and solar cell
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101828267A (en) * 2008-08-07 2010-09-08 京都一来电子化学股份有限公司 Conductive paste for formation of a solar cell element electrode, solar cell element, and manufacturing method for said solar cell element
EP2615613A2 (en) * 2012-01-16 2013-07-17 E. I. du Pont de Nemours and Company A solar cell back side electrode
EP2654087A1 (en) * 2012-04-17 2013-10-23 Heraeus Precious Metals North America Conshohocken LLC Tellurium inorganic reaction systems for conductive thick film paste for solar cell contacts
CN103959393A (en) * 2011-12-08 2014-07-30 第一毛织株式会社 Paste composition for solar cell electrode and electrode produced therefrom
CN106098138A (en) * 2015-04-27 2016-11-09 硕禾电子材料股份有限公司 Conductive paste and method for manufacturing solar cell using the same
CN107879635A (en) * 2017-08-31 2018-04-06 无锡帝科电子材料科技有限公司 For preparing glass powder including its paste composition, the electrode of solar battery and solar cell of electrode of solar battery

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100772501B1 (en) * 2005-06-30 2007-11-01 한국전자통신연구원 Tellurite glass composite, optical waveguide and optical amplifier using the same
KR101246686B1 (en) * 2010-03-19 2013-03-21 제일모직주식회사 Paste for forming electrode of solar cell and solar cell with the same
US9087937B2 (en) * 2012-05-10 2015-07-21 E I Du Pont De Nemours And Company Glass composition and its use in conductive silver paste
JP5690780B2 (en) * 2012-07-18 2015-03-25 株式会社ノリタケカンパニーリミテド Ag electrode forming paste composition, method for producing the same, and solar cell
KR20140022511A (en) * 2012-08-13 2014-02-25 제일모직주식회사 Electrode paste for solar cell, electrode prepared from the same and solar cell comprising the same
CN106328246A (en) * 2015-06-19 2017-01-11 江苏正能电子科技有限公司 Positive silver paste for crystalline silicon solar cell
CN106601335B (en) * 2016-12-30 2018-08-31 无锡帝科电子材料科技有限公司 It is used to prepare the paste composition, electrode of solar battery and solar cell of electrode of solar battery

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101828267A (en) * 2008-08-07 2010-09-08 京都一来电子化学股份有限公司 Conductive paste for formation of a solar cell element electrode, solar cell element, and manufacturing method for said solar cell element
CN103959393A (en) * 2011-12-08 2014-07-30 第一毛织株式会社 Paste composition for solar cell electrode and electrode produced therefrom
EP2615613A2 (en) * 2012-01-16 2013-07-17 E. I. du Pont de Nemours and Company A solar cell back side electrode
EP2654087A1 (en) * 2012-04-17 2013-10-23 Heraeus Precious Metals North America Conshohocken LLC Tellurium inorganic reaction systems for conductive thick film paste for solar cell contacts
CN106098138A (en) * 2015-04-27 2016-11-09 硕禾电子材料股份有限公司 Conductive paste and method for manufacturing solar cell using the same
CN107879635A (en) * 2017-08-31 2018-04-06 无锡帝科电子材料科技有限公司 For preparing glass powder including its paste composition, the electrode of solar battery and solar cell of electrode of solar battery

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