CN113380439A - Composition for forming solar cell electrode and solar cell electrode formed therefrom - Google Patents

Composition for forming solar cell electrode and solar cell electrode formed therefrom Download PDF

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Publication number
CN113380439A
CN113380439A CN202110232672.5A CN202110232672A CN113380439A CN 113380439 A CN113380439 A CN 113380439A CN 202110232672 A CN202110232672 A CN 202110232672A CN 113380439 A CN113380439 A CN 113380439A
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oxide
solar cell
glass powder
mole percent
composition
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辜贤珍
金君浩
朴光源
张东珍
许伦旼
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Changzhou Fusion New Material Co Ltd
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Changzhou Fusion New Material Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
    • C03C3/072—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron
    • C03C3/074—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/14—Compositions for glass with special properties for electro-conductive glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • 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
    • 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
    • C03C8/22—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions containing two or more distinct frits having different 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
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • 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
    • 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
    • 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
    • H01L31/022441—Electrode arrangements specially adapted for back-contact solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—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 characterised by their semiconductor bodies
    • H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/0328—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032
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Abstract

Disclosed are a composition for forming a solar cell electrode and a solar cell electrode formed therefrom. The composition for forming the solar cell electrode comprises conductive powder, glass powder and an organic carrier, wherein the glass powder comprises more than one of specified first glass powder, second glass powder and third glass powder.

Description

Composition for forming solar cell electrode and solar cell electrode formed therefrom
Technical Field
The present invention relates to a composition for forming a solar cell electrode and a solar cell electrode formed therefrom, and more particularly, to a composition for forming a solar cell electrode and a solar cell electrode formed therefrom, which can improve contact resistance to realize excellent conversion efficiency and adhesive strength.
Background
Solar cells utilize the photoelectric effect of a p-n junction to convert solar photons (photons) into electricity to produce electrical energy. In a solar cell, front and rear electrodes are formed on upper and lower surfaces of a semiconductor wafer or substrate having a p-n junction, respectively. In a solar cell, a photoelectric effect of a p-n junction is caused by sunlight incident on a semiconductor wafer, and a plurality of electrons generated by the photoelectric effect supply a current flowing to the outside through an electrode. The electrode of the solar cell may be formed on the surface of the wafer by coating, patterning, and baking the electrode paste composition.
Recently, the thickness of the emitter (emitter) is continuously reduced to improve the efficiency of the solar cell, thereby inducing a shunt (shading) phenomenon that reduces the performance of the solar cell. Also, increasing the area of the solar cell gradually in order to improve the efficiency of the solar cell increases the contact resistance of the solar cell, thereby decreasing the efficiency of the solar cell.
Furthermore, since cells (cells) constituting a solar cell are connected to each other by a ribbon to form a module, if the adhesion between an electrode and the ribbon is poor, there is a possibility that the durability of the module is lowered, the series resistance is large, and the conversion efficiency is lowered.
Disclosure of Invention
Problems to be solved
The present invention aims to provide a composition for forming a solar cell electrode, which has excellent conversion efficiency and adhesive strength by improving contact resistance.
Another object of the present invention is to provide a solar cell electrode formed of the above composition.
Means for solving the problems
1. According to an embodiment, a composition for forming a solar cell electrode is provided. The composition comprises conductive powder, glass powder and an organic carrier.
The glass powder comprises more than one of first glass powder, second glass powder and third glass powder,
the above-mentioned first glass frit is a bismuth-tellurium-lithium-calcium-silicon-oxide (Bi-Te-Li-Ca-Si-O) based glass frit which does not contain lead (Pb), in which the total mole percentage of bismuth (Bi), tellurium (Te) and lithium (Li) is 40 to 95 mole percentage, the mole ratio of calcium (Ca) to silicon (Si) is 1: 0.005 to 1: 220,
the second glass frit is a tellurium (Te) -free lead-boron-zinc-calcium-silicon-oxide (Pb-B-Zn-Ca-Si-O) glass frit in which the total mole percentage of lead (Pb), boron (B) and zinc (Zn) or the total mole percentage of lead (Pb) and boron (B) is 25 to 95 mole percent, the mole ratio of calcium (Ca) to silicon (Si) is 1: 0.05 to 1: 250,
the third glass powder is bismuth-boron-zinc-calcium-silicon-oxide (Bi-B-Zn-Ca-Si-O) glass powder containing no tellurium (Te), wherein the total mole percentage of bismuth (Bi), boron (B) and zinc (Zn) in the third glass powder is 25 to 95 mole percentage, and the mole ratio of calcium (Ca) to silicon (Si) is 1: 0.05 to 1: 250.
2. In the above 1, the first glass frit may include:
0.1 to 60 mole percent bismuth (Bi) oxide;
15 to 70 mole percent tellurium (Te) oxide;
0.1 to 35 mole percent lithium (Li) oxide;
0.1 to 15 mole percent calcium (Ca) oxide; and
0.1 to 30 mole percent silicon (Si) oxide.
3. In the above 1 or 2, the second glass frit may include:
0.1 to 80 mole percent lead (Pb) oxide;
0.1 to 40 mole percent boron (B) oxide;
0.1 to 60 mole percent of zinc (Zn) oxide;
0.1 to 15 mole percent calcium (Ca) oxide; and
0.1 to 30 mole percent silicon (Si) oxide.
4. In any one of the above 1 to 3, the above third glass powder may contain:
0.1 to 80 mole percent bismuth (Bi) oxide;
0.1 to 50 mole percent boron (B) oxide;
0.1 to 70 mole percent of zinc (Zn) oxide;
0.1 to 15 mole percent calcium (Ca) oxide; and
0.1 to 30 mole percent silicon (Si) oxide.
5. In any one of the above 1 to 4, the first glass frit may further include one or more elements selected from zinc (Zn), sodium (Na), phosphorus (P), germanium (Ge), gallium (Ga), silver (Ag), iron (Fe), tungsten (W), magnesium (Mg), molybdenum (Mo), niobium (Nb), strontium (Sr), titanium (Ti), tin (Sn), indium (In), vanadium (V), barium (Ba), nickel (Ni), copper (Cu), potassium (K), selenium (Se), arsenic (As), cobalt (Co), zirconium (Zr), manganese (Mn), aluminum (Al), thallium (T1), tantalum (Ta), cesium (Cs), cerium (Ce), and boron (B),
the second glass frit may further include one or more elements selected from the group consisting of lithium (Li), sodium (Na), phosphorus (P), germanium (Ge), gallium (Ga), silver (Ag), iron (Fe), tungsten (W), magnesium (Mg), molybdenum (Mo), niobium (Nb), strontium (Sr), titanium (Ti), tin (Sn), indium (In), vanadium (V), barium (Ba), nickel (Ni), copper (Cu), potassium (K), arsenic (As), selenium (Se), cobalt (Co), zirconium (Zr), manganese (Mn), aluminum (Al), thallium (T1), tantalum (Ta), cesium (Cs) and cerium (Ce),
the third glass powder may further include one or more elements selected from lead (Pb), lithium (Li), sodium (Na), phosphorus (P), germanium (Ge), gallium (Ga), silver (Ag), iron (Fe), tungsten (W), magnesium (Mg), molybdenum (Mo), niobium (Nb), strontium (Sr), titanium (Ti), tin (Sn), indium (In), vanadium (V), barium (Ba), nickel (Ni), copper (Cu), potassium (K), selenium (Se), arsenic (As), cobalt (Co), zirconium (Zr), manganese (Mn), aluminum (Al), thallium (T1), tantalum (Ta), cesium (Cs), and cerium (Ce).
6. In any one of the above 1 to 5, the first glass frit, the second glass frit, or the third glass frit may further include aluminum (Al) oxide in an amount of more than 0 mol% and not more than 5 mol%.
7. In any one of the above 1 to 6, the above third glass powder may not contain lead (Pb) element.
8. In any one of the above 1 to 7, the composition for forming a solar cell electrode may further include one or more of a dispersant, a thixotropic agent, a plasticizer, a viscosity stabilizer, an anti-foaming agent, a pigment, an ultraviolet stabilizer, an antioxidant, and a coupling agent.
9. In any one of the above 1 to 8, the above composition for forming a solar cell electrode may comprise:
60 to 95 weight percent of the above conductive powder;
0.1 to 20 weight percent of the glass powder; and
1 to 30 weight percent of the above organic vehicle.
10. According to another embodiment, a solar cell electrode is provided. The above electrode may be formed of the composition of any one of 1 to 9 above.
ADVANTAGEOUS EFFECTS OF INVENTION
The invention has the following effects: provided are a composition for forming a solar cell electrode, which achieves excellent conversion efficiency and adhesive strength by improving contact resistance, and a solar cell electrode formed therefrom.
Drawings
Fig. 1 is a diagram schematically showing a solar cell according to an example of the present invention.
Detailed Description
In this specification, the singular expressions include the plural expressions, unless the context clearly dictates otherwise.
In the present specification, the terms "including" or "having" and the like mean that there are the features or structural elements described in the specification, and the possibility of adding one or more other features or structural elements is not previously excluded.
The terms "first" and "second", etc. used in the present specification may be used to describe various structural elements, but the structural elements should not be limited to these terms. These terms are only intended to distinguish one structural element from another.
In explaining the components, the components are to be interpreted as including an error range even if not explicitly described.
In the present specification, "to" in "a to b" representing a numerical range is defined as ≧ a and ≦ b.
Composition for forming solar cell electrode
According to one embodiment, a composition for forming a solar cell electrode includes a conductive powder, a glass frit, and an organic vehicle, and the glass frit may include one or more of a first glass frit, a second glass frit, and a third glass frit.
Hereinafter, the respective components of the composition for forming the solar cell electrode will be described in more detail.
Conductive powder
The conductive powder may include one or more metal powders of silver (Ag), gold (Au), platinum (Pt), palladium (Pd), aluminum (Al), and nickel (Ni), but is not limited thereto. According to an example, the conductive powder may include silver powder.
The particle shape of the conductive powder is not particularly limited, and particles of various shapes such as spherical particles, plate-like particles, or amorphous particles may be used.
The conductive powder may be a powder having a nano-scale or micro-scale particle size, and for example, may be a conductive powder of a size of tens of nanometers to hundreds of nanometers, or a conductive powder of a size of several micrometers to tens of micrometers. Further, two or more kinds of conductive powders having different sizes may be mixed and used as the conductive powder.
Average particle diameter (D) of conductive powder50) May be 0.1 μm to 10 μm, for example, may be 0.5 μm to 5 μm. Within the above range, the contact resistance and the series resistance can be reduced. The average particle diameter (D) may be measured using a 1064LD model manufactured by CILAS corporation after ultrasonically dispersing conductive powder in isopropyl alcohol (IPA) at a temperature of 25 ℃ for 3 minutes50)。
The amount of the conductive powder used is not particularly limited, but for example, 60 to 95 weight percent (e.g., 70 to 90 weight percent) of the conductive powder may be included based on the total weight of the composition for forming the solar cell electrode. Within the above range, the solar cell has excellent conversion efficiency and can smoothly realize gelatinization.
Glass powder
The glass frit is used to etch (etching) the anti-reflection film in a baking process of the composition for forming the solar cell electrode and to melt the conductive powder to generate grains of the conductive powder in the emitter region. Also, the glass frit has an effect of improving adhesion between the conductive powder and the wafer, and softening at the time of sintering to further reduce the baking temperature.
The glass frit may include one or more of first glass frit, second glass frit, and third glass frit.
The first glass frit may be a bismuth-tellurium-lithium-calcium-silicon-oxide (Bi-Te-Li-Ca-Si-O) type glass frit that does not contain lead (Pb), and in the first glass frit, the total mole percentage of bismuth (Bi), tellurium (Te), and lithium (Li) may be 40 to 95 mole percentage, and the mole ratio of calcium (Ca) to silicon (Si) may be 1: 0.005 to 1: 220. In this case, contact resistance is improved, and excellent adhesive strength can be obtained. For example, the total mole percentage of bismuth (Bi), tellurium (Te), and lithium (Li) in the first glass frit may be 40 to 90 mole%, and in still another example, may be 45 to 90 mole%, and in yet another example, may be 50 to 80 mole%, but is not limited thereto. For example, in the first glass frit, the molar ratio of calcium (Ca) to silicon (Si) may be 1: 0.005 to 1: 150, and in yet another example, may be 1: 0.05 to 1: 100, and in yet another example, may be 1: 0.1 to 1: 15, but is not limited thereto.
According to an example, the first glass frit may include 0.1 to 60 mole percent bismuth oxide. Within the above range, contact resistance is improved, and excellent adhesive strength can be obtained. For example, the first glass frit may include 0.1 mol% to 40 mol% of bismuth oxide, and in yet another example, may include 0.1 mol% to 25 mol%, and in yet another example, may include 0.1 mol% to 10 mol%, but is not limited thereto.
According to an example, the first glass frit may include 15 to 70 mol% of tellurium oxide. Within the above range, contact resistance is improved, and excellent adhesive strength can be obtained. For example, the first glass frit may include 15 mol% to 60 mol% of tellurium oxide, and in another example, may include 20 mol% to 60 mol%, and in another example, may include 30 mol% to 60 mol%, but is not limited thereto.
According to an example, the first glass frit may include 0.1 to 35 mol% of lithium oxide. Within the above range, contact resistance is improved, and excellent adhesive strength can be obtained. For example, the first glass frit may include 2 mol% to 30 mol% of lithium oxide, and as another example, may include 5 mol% to 30 mol%, and as another example, may include 8 mol% to 25 mol%, but is not limited thereto.
According to an example, the first glass frit may comprise 0.1 to 15 mole percent calcium oxide. Within the above range, contact resistance is improved, and excellent adhesive strength can be obtained. For example, the first glass frit may include 0.1 mol% to 10 mol% of calcium oxide, but is not limited thereto.
According to an example, the first glass frit may include 0.1 to 30 mole percent silicon oxide. Within the above range, contact resistance is improved, and excellent adhesive strength can be obtained. For example, the first glass frit may include 0.1 mol% to 20 mol% of silicon oxide, such as 0.1 mol% to 15 mol%, and such as 0.1 mol% to 10 mol%, but is not limited thereto.
According to an example, the first glass frit may further include one or more elements of zinc (Zn), sodium (Na), phosphorus (P), germanium (Ge), gallium (Ga), silver (Ag), iron (Fe), tungsten (W), magnesium (Mg), molybdenum (Mo), niobium (Nb), strontium (Sr), titanium (Ti), tin (Sn), indium (In), vanadium (V), barium (Ba), nickel (Ni), copper (Cu), potassium (K), selenium (Se), arsenic (As), cobalt (Co), zirconium (Zr), manganese (Mn), aluminum (Al), thallium (T1), tantalum (Ta), cesium (Cs), cerium (Ce), and boron (B). For example, the first glass frit may further include aluminum oxide of more than 0 mol% and 5 mol% or less (e.g., 0.1 mol% to 5 mol%, such as 0.1 mol% to 3 mol%, as still another example), in which case, when applied to a passivation layer including an aluminum oxide layer, it may have an effect of preventing the glass frit from excessively etching the aluminum oxide layer, but is not limited thereto.
The second glass frit may be a tellurium (Te) -free lead-boron-zinc-calcium-silicon-oxide (Pb-B-Zn-Ca-Si-O) type glass frit, in which the total mole percentage of lead (Pb), boron (B), and zinc (Zn) or the total mole percentage of lead (Pb) and boron (B) may be 25 mole percent to 95 mole percent, and the mole ratio of calcium (Ca) to silicon (Si) may be 1: 0.05 to 1: 250. In this case, contact resistance is improved, and excellent adhesive strength can be obtained. For example, the total mole percentage of the lead (Pb) and the boron (B) in the second glass frit may be 25 mole percent to 90 mole percent, such as still another example, 30 mole percent to 90 mole percent, such as another example, 40 mole percent to 90 mole percent, but is not limited thereto. For example, in the second glass frit, the molar ratio of calcium (Ca) to silicon (Si) may be 1: 0.05 to 1: 230, as still another example, 1: 0.3 to 1: 200, and as another example, 1: 1.5 to 1: 100, but is not limited thereto.
According to an example, the second glass frit may include 0.1 to 80 mole percent of lead oxide. Within the above range, contact resistance is improved, and excellent adhesive strength can be obtained. For example, the second glass frit may include 5 mol% to 70 mol% of lead oxide, and in still another example, 20 mol% to 70 mol%, and in yet another example, 40 mol% to 70 mol%, but is not limited thereto.
According to an example, the second glass frit may include 0.1 to 40 mole percent of boron oxide. Within the above range, contact resistance is improved, and excellent adhesive strength can be obtained. For example, the second glass frit may include 0.1 mol% to 30 mol% of boron oxide, and in still another example, may include 0.1 mol% to 25 mol%, and in yet another example, may include 0.3 mol% to 22 mol%, but is not limited thereto.
According to an example, the second glass frit can comprise 0.1 to 60 mole percent zinc oxide. Within the above range, contact resistance is improved, and excellent adhesive strength can be obtained. For example, the second glass frit may include 0.5 mol% to 50 mol% of zinc oxide, and as another example, may include 5 mol% to 40 mol%, but is not limited thereto.
According to an example, the second glass frit may comprise 0.1 to 15 mole percent calcium oxide. Within the above range, contact resistance is improved, and excellent adhesive strength can be obtained. For example, the second glass frit may include 0.1 mol% to 10 mol% of calcium oxide, and in still another example, may include 0.1 mol% to 8 mol%, and in yet another example, may include 0.2 mol% to 6 mol%, but is not limited thereto.
According to an example, the second glass frit may include 0.1 to 30 mole percent silicon oxide. Within the above range, contact resistance is improved, and excellent adhesive strength can be obtained. For example, the second glass frit may include 0.1 mol% to 20 mol% of silicon oxide, such as 0.1 mol% to 15 mol%, and such as 1 mol% to 15 mol%, but is not limited thereto.
According to an example, the second glass frit may further include one or more elements of lithium (Li), sodium (Na), phosphorus (P), germanium (Ge), gallium (Ga), silver (Ag), iron (Fe), tungsten (W), magnesium (Mg), molybdenum (Mo), niobium (Nb), strontium (Sr), titanium (Ti), tin (Sn), indium (In), vanadium (V), barium (Ba), nickel (Ni), copper (Cu), potassium (K), arsenic (As), selenium (Se), cobalt (Co), zirconium (Zr), manganese (Mn), aluminum (Al), thallium (T1), tantalum (Ta), cesium (Cs), and cerium (Ce). For example, the second glass frit may further include aluminum oxide in an amount greater than 0 mol% and equal to or less than 5 mol% (e.g., 0.1 mol% to 5 mol%, such as 0.1 mol% to 3 mol%, as yet another example), and in this case, when applied to a passivation layer including an aluminum oxide layer, may have an effect of preventing the glass frit from excessively etching the aluminum oxide layer, but is not limited thereto.
The third glass frit may be a bismuth-boron-zinc-calcium-silicon-oxide (Bi-B-Zn-Ca-Si-O) based glass frit which does not contain tellurium (Te), and in the third glass frit, the total mole percentage of bismuth (Bi), boron (B), and zinc (Zn) may be 25 mole percent to 95 mole percent, and the mole ratio of calcium (Ca) to silicon (Si) may be 1: 0.05 to 1: 250. In this case, contact resistance is improved, and excellent adhesive strength can be obtained. For example, in the third glass frit, the total mole percentage of bismuth (Bi), boron (B), and zinc (Zn) may be 25 mole percent to 90 mole percent, such as 30 mole percent to 90 mole percent, and such as 40 mole percent to 90 mole percent, for another example, but is not limited thereto. For example, in the third glass frit, the molar ratio of calcium (Ca) to silicon (Si) may be 1: 0.05 to 1: 230, as still another example, 1: 0.3 to 1: 200, and as another example, 1: 0.5 to 1: 100, but is not limited thereto.
According to an example, the third glass frit may include 0.1 to 80 mole percent bismuth oxide. Within the above range, contact resistance is improved, and excellent adhesive strength can be obtained. For example, the third glass powder may include 5 mol% to 65 mol% of bismuth oxide, and as yet another example, may include 10 mol% to 50 mol%, and as yet another example, may include 15 mol% to 50 mol%, but is not limited thereto.
According to an example, the third glass frit may include 0.1 to 50 mole percent of boron oxide. Within the above range, contact resistance is improved, and excellent adhesive strength can be obtained. For example, the third glass frit may include 4 mol% to 45 mol% of boron oxide, such as 5 mol% to 45 mol%, such as 10 mol% to 40 mol%, but is not limited thereto.
According to an example, the third glass frit can comprise 0.1 mole percent to 70 mole percent zinc oxide. Within the above range, contact resistance is improved, and excellent adhesive strength can be obtained. For example, the third glass frit may include 1 mol% to 65 mol% of zinc oxide, and in still another example, may include 5 mol% to 60 mol%, and in yet another example, may include 10 mol% to 60 mol%, but is not limited thereto.
According to an example, the third glass frit may comprise 0.1 to 15 mole percent calcium oxide. Within the above range, contact resistance is improved, and excellent adhesive strength can be obtained. For example, the third glass powder may contain 0.1 to 12 mol% of calcium oxide, but is not limited thereto.
According to an example, the third glass frit may include 0.1 to 30 mole percent silicon oxide. Within the above range, contact resistance is improved, and excellent adhesive strength can be obtained. For example, the third glass powder may include 0.1 mol% to 20 mol% of silicon oxide, as another example, 0.1 mol% to 15 mol%, and as another example, 1 mol% to 15 mol%, but is not limited thereto.
According to an example, the third glass frit may further include one or more elements of lead (Pb), lithium (Li), sodium (Na), phosphorus (P), germanium (Ge), gallium (Ga), silver (Ag), iron (Fe), tungsten (W), magnesium (Mg), molybdenum (Mo), niobium (Nb), strontium (Sr), titanium (Ti), tin (Sn), indium (In), vanadium (V), barium (Ba), nickel (Ni), copper (Cu), potassium (K), selenium (Se), arsenic (As), cobalt (Co), zirconium (Zr), manganese (Mn), aluminum (Al), thallium (Tl), tantalum (Ta), cesium (Cs), and cerium (Ce). For example, the third glass powder may further include aluminum oxide in an amount greater than 0 mol% and equal to or less than 5 mol% (e.g., 0.1 mol% to 5 mol%, such as 0.1 mol% to 3 mol%, as yet another example), in which case, when applied to a passivation layer including an aluminum oxide layer, it may have an effect of preventing the glass powder from excessively etching the aluminum oxide layer, but is not limited thereto.
According to an example, the third glass frit may not include lead element, in which case, it may have an effect of strongly etching the passivation layer.
The shape, size, and the like of the glass frit are not particularly limited. For example, the shape of the glass frit may be spherical or amorphous particle shape, and the average particle diameter (D) of the glass frit50) May be 0.1 μm to 10 μm. The average particle diameter (D) can be measured using a 1064LD model manufactured by CILAS corporation after ultrasonically dispersing glass frit in isopropyl alcohol (IPA) at a temperature of 25 ℃ for 3 minutes50)。
The glass frit can be prepared from the above elements and/or element oxides using a conventional method. For example, the glass powder is obtained by mixing the above elements and/or element oxides using a ball mill (ball mill), a planetary mill (planetary mill), or the like, then melting the mixed composition at a temperature of 800 ℃ to 1300 ℃, further quenching (quenching) at a temperature of 25 ℃, and then pulverizing the resultant product using a disk mill (disk mill), a planetary mill, or the like.
The amount of the glass frit used is not particularly limited, but, for example, the glass frit may be included in an amount of 0.1 to 20 weight percent (e.g., 0.1 to 10 weight percent) based on the total weight of the composition for forming the solar cell electrode. Within the above range, the stability of the p-n junction at various sheet resistances can be ensured, the resistance can be minimized, and the efficiency of the solar cell can be finally improved.
Organic vehicle
The organic vehicle imparts viscosity and rheological properties suitable for printing to the composition by mechanical mixing with the inorganic components of the composition used to form the solar cell electrode.
The organic vehicle may be an organic vehicle generally used for a composition for forming a solar cell electrode, and may include a binder resin, a solvent, and the like.
As the binder resin, an acrylate resin, a cellulose resin, or the like can be used. For example, ethyl cellulose may be used as the binder resin. As another example, ethyl hydroxyethyl cellulose, nitrocellulose, a mixture of ethyl cellulose and a phenol resin, an alkyd resin, a phenol resin, an acrylate resin, a xylene resin, a polybutylene resin, a polyester resin, a urea resin, a melamine resin, a vinyl acetate resin, wood rosin (rosin), polymethacrylate, or the like can be used as the binder resin.
The solvent may be used alone or in combination with, for example, hexane, toluene, ethyl cellosolve, cyclohexanone, butyl cellosolve, butyl carbitol (diethylene glycol monobutyl ether), dibutyl carbitol (diethylene glycol dibutyl ether), butyl carbitol acetate (diethylene glycol monobutyl ether acetate), propylene glycol monomethyl ether, hexylene glycol, rosin alcohol (Terpineol), methyl ethyl ketone, benzyl alcohol, γ -butyrolactone, ethyl lactate, or 2, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate (for example, dodecanol (Texanol)), or the like.
The amount of the organic vehicle used is not particularly limited, but for example, the organic vehicle may be included in an amount of 1 to 30 weight percent (e.g., 3 to 20 weight percent) based on the total weight of the composition for forming the solar cell electrode. Within the above range, sufficient adhesive strength and excellent printability can be ensured.
Additive agent
In order to improve flow characteristics, process characteristics, and stability, the composition for forming a solar cell electrode may further include a dispersant, a thixotropic agent, a plasticizer, a viscosity stabilizer, an anti-foaming agent, a pigment, an ultraviolet stabilizer, an antioxidant, a coupling agent, etc. in addition to the above components, and the above additives may be included singly or in an amount of 2 or more. The additive may be included in an amount of 0.1 to 5 weight percent based on the total weight of the composition for forming the solar cell electrode, but the content thereof may be changed as needed.
Solar cell electrode and solar cell comprising same
According to another embodiment, there are provided a solar cell electrode formed of the above composition for forming a solar cell electrode and a solar cell including the same. Fig. 1 is a diagram schematically showing the structure of a solar cell 100 according to an example of the present invention.
Referring to fig. 1, a composition for forming a solar cell electrode may be printed and baked on a wafer or substrate 10 including a p-type layer (or n-type layer) 11 and an n-type layer (or p-type layer) 12 as an emitter, thereby forming a rear electrode 21 and a front electrode 23. For example, the preliminary preparation step for preparing the rear electrode may be performed by printing a composition for forming the solar cell electrode on the rear surface of the wafer, followed by drying at a temperature of 200 to 400 ℃ for 10 to 60 seconds. Also, a preliminary preparation step for preparing a front electrode may be performed by drying after printing a composition for forming a solar cell electrode on the front surface of the wafer. Thereafter, the front and rear electrodes may be formed by performing a baking process of baking at a temperature of 400 to 950 ℃, for example, 600 to 900 ℃ for 30 to 210 seconds.
Hereinafter, a composition for forming an electrode of a solar cell according to an embodiment of the present invention will be described in further detail with reference to examples. This is merely a preferred illustration of the invention and should not be construed as limiting the invention in any way.
Examples
Example 1
2 parts by weight of ethyl cellulose (STD4, Dow chemical Co., Ltd.) as a binder resin was sufficiently dissolved in 6.5 parts by weight of Butyl Carbitol (Butyl Carbitol) at 60 ℃, 90 parts by weight of spherical silver powder (4-8F, Dow high tech Co., Ltd.) having an average particle diameter of 2.0 μm and 1.5 parts by weight of glass powder A shown in Table 1 below having an average particle diameter of 1.0 μm were added and uniformly mixed, and then mixed and dispersed in a 3-roll kneader, thereby preparing a composition for a solar cell electrode.
Examples 2 to 5 and comparative examples 1 to 7
Compositions for forming electrodes of solar cells were prepared in the same manner as in example 1, except that glass frits B to L in table 1 below were used instead of glass frit a.
Evaluation example 1: electric characteristics
After texturing (texturing) of the front surface of a wafer (monocrystalline wafer) with Boron (Boron) doped p-type wafer, a wafer (following monocrystalline wafer) was treated with triclosanPhosphating (POCl)3) Form n+Layer of n+Silicon nitride (SiNx: H) as an antireflection film) was formed on the rear surface thereof, and then dried at a temperature of 300 c for 30 seconds. Thereafter, the compositions for forming solar cell electrodes prepared in examples and comparative examples were screen-printed on the front surface of the wafer, and were allowed to dry at a temperature of 300 ℃ for 30 seconds. The cell formed through the above process was baked at a temperature of 940 ℃ for 70 seconds using a belt baking oven, thereby preparing a solar cell. The series resistance (Rs, unit: Ω) and the conversion efficiency (eff, unit:%) of the solar cell prepared in the above manner were measured using a solar cell efficiency testing apparatus (Halm, ford technologies), and the results thereof are shown in the following table 2.
Evaluation example 2: adhesion (Unit: N)
After applying Flux (Flux) on the electrode layer of the above-prepared solar cell (952S, Kester corporation) and adhering a tape (62Sn/36Pb/2Ag, thickness of 0.18mm, width of 1.5mm) at a temperature of 360 ℃ using an electric iron, the end of the tape was fixed at an angle of 180 ° and stretched at a speed of 50mm/min, and its value was measured using a tensioner (Mocel H5K-T, zenith Olsen, inc.) and the result thereof is shown in the following table 2.
Figure BDA0002957221840000121
Figure BDA0002957221840000131
As can be confirmed from table 2 above, the solar cells formed from the compositions for forming solar cell electrodes of examples 1 to 5 including the first glass frit, the second glass frit, or the third glass frit of the present invention have improved contact resistance, and thus excellent conversion efficiency and adhesion, as compared to comparative examples 1 to 7, which are not the same.
The present invention has been described above centering on a plurality of embodiments. It will be understood by those skilled in the art that the present invention may be embodied in various forms without departing from the essential characteristics thereof. Accordingly, the disclosed embodiments are to be considered in all respects as illustrative and not restrictive. The scope of the invention is shown only in the claims of the invention rather than in the above description, and all differences within the equivalent scope to the present invention should be construed as being included in the present invention.
Figure BDA0002957221840000141

Claims (10)

1. A composition for forming an electrode of a solar cell, characterized in that,
comprises conductive powder, glass powder and an organic carrier,
the glass powder comprises more than one of first glass powder, second glass powder and third glass powder,
the first glass powder is bismuth-tellurium-lithium-calcium-silicon-oxide glass powder without lead, the total mole percentage of bismuth, tellurium and lithium in the first glass powder is 40 to 95, and the mole ratio of calcium to silicon is 1: 0.005 to 1: 220,
the second glass powder is tellurium-free lead-boron-zinc-calcium-silicon-oxide glass powder, the total mole percentage of lead, boron and zinc or the total mole percentage of lead and boron in the second glass powder is 25 to 95, the mole ratio of calcium to silicon is 1: 0.05 to 1: 250,
the third glass powder is bismuth-boron-zinc-calcium-silicon-oxide glass powder without tellurium, the total mole percentage of bismuth, boron and zinc in the third glass powder is 25 to 95, the mole ratio of calcium to silicon is 1: 0.05 to 1: 250.
2. the composition for forming a solar cell electrode according to claim 1, wherein the first glass frit comprises:
0.1 to 60 mole percent bismuth oxide;
15 to 70 mole percent of tellurium oxide;
0.1 to 35 mole percent lithium oxide;
0.1 to 15 mole percent calcium oxide; and
0.1 to 30 mole percent silicon oxide.
3. The composition for forming a solar cell electrode according to claim 1, wherein the second glass frit comprises:
0.1 to 80 mole percent of lead oxide;
0.1 to 40 mole percent of boron oxide;
0.1 to 60 mole percent zinc oxide;
0.1 to 15 mole percent calcium oxide; and
0.1 to 30 mole percent silicon oxide.
4. The composition for forming a solar cell electrode according to claim 1, wherein the third glass powder comprises:
0.1 to 80 mole percent bismuth oxide;
0.1 to 50 mole percent of a boron oxide;
0.1 to 70 mole percent zinc oxide;
0.1 to 15 mole percent calcium oxide; and
0.1 to 30 mole percent silicon oxide.
5. The composition for forming a solar cell electrode according to claim 1,
the first glass powder further contains at least one element selected from zinc, sodium, phosphorus, germanium, calcium, silver, iron, tungsten, magnesium, molybdenum, niobium, strontium, titanium, tin, indium, vanadium, barium, nickel, copper, potassium, selenium, arsenic, cobalt, zirconium, manganese, aluminum, thallium, tantalum, cesium, cerium and boron,
the second glass powder also contains more than one element of lithium, sodium, phosphorus, germanium, calcium, silver, iron, tungsten, magnesium, molybdenum, niobium, strontium, titanium, tin, indium, vanadium, barium, nickel, copper, potassium, arsenic, selenium, cobalt, zirconium, manganese, aluminum, thallium, tantalum, cesium and cerium,
the third glass powder further contains one or more elements selected from the group consisting of lead, lithium, sodium, phosphorus, germanium, calcium, silver, iron, tungsten, magnesium, molybdenum, niobium, strontium, titanium, tin, indium, vanadium, barium, nickel, copper, potassium, selenium, arsenic, cobalt, zirconium, manganese, aluminum, thallium, tantalum, cesium, and cerium.
6. The composition for forming a solar cell electrode according to claim 1, wherein the first glass frit, the second glass frit, or the third glass frit further comprises aluminum oxide in an amount of more than 0 mol% and 5 mol% or less.
7. The composition for forming a solar cell electrode according to claim 1, wherein the third glass frit does not contain lead element.
8. The composition for forming a solar cell electrode according to claim 1, further comprising at least one of a dispersant, a thixotropic agent, a plasticizer, a viscosity stabilizer, an antifoaming agent, a pigment, an ultraviolet stabilizer, an antioxidant, and a coupling agent.
9. The composition for forming an electrode of a solar cell according to claim 1, wherein the composition for forming an electrode of a solar cell comprises:
60 to 95 weight percent of the above conductive powder;
0.1 to 20 weight percent of the glass powder; and
1 to 30 weight percent of the above organic vehicle.
10. A solar cell electrode formed from the composition of any one of claims 1 to 9.
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