CN114974649A - Solar cell electrode and forming method thereof - Google Patents
Solar cell electrode and forming method thereof Download PDFInfo
- Publication number
- CN114974649A CN114974649A CN202110211709.6A CN202110211709A CN114974649A CN 114974649 A CN114974649 A CN 114974649A CN 202110211709 A CN202110211709 A CN 202110211709A CN 114974649 A CN114974649 A CN 114974649A
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- Prior art keywords
- solar cell
- glass frit
- oxide
- cell electrode
- electrode
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-
- 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
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a solar cell electrode and a preparation method thereof, wherein the solar cell electrode comprises: a first electrode layer comprising a conductive powder and a first glass frit; and a second electrode layer formed on the first electrode layer, the second electrode layer including a conductive powder and a second glass frit which is different from the first glass frit and has a molar ratio of lead (Pb) oxide/(lead (Pb) oxide + copper (Cu) oxide) of more than 0.2 and 0.95 or less.
Description
Technical Field
The present invention relates to a solar cell electrode and a method for forming the same, and more particularly, to a solar cell electrode and a method for forming the same, in which the solar cell electrode has excellent efficiency and improved adhesion to a wafer or a bonding wire by improving open-circuit voltage characteristics.
Background
Solar cells generate electrical energy using the photovoltaic effect of p-n junctions that convert photons (photons) of sunlight into electricity. A solar cell has a front electrode and a back electrode formed on the upper and lower surfaces of a semiconductor wafer or a substrate constituting a p-n junction. The solar cell induces a photoelectric effect of p-n junction by sunlight incident on the semiconductor wafer, and a current flowing to the outside through the electrode is supplied by electrons generated thereby.
The electrode of such a solar cell can be formed in a predetermined pattern on the surface of the substrate by coating, patterning, and firing the electrode-forming composition. In order to manufacture a high efficiency solar cell, it is necessary to reduce factors that reduce the efficiency of the solar cell. The efficiency loss of the solar cell can be roughly classified into optical loss, recombination loss of electron and hole, and loss due to resistance components.
Disclosure of Invention
The present invention is directed to a solar cell electrode having improved open-circuit voltage characteristics by reducing recombination loss caused by etching an anti-reflective coating (ARC) layer during electrode firing.
Another object of the present invention is to provide a solar cell electrode having excellent conversion efficiency.
Another object of the present invention is to provide a solar cell electrode having improved adhesion to a wafer or a bonding wire, thereby improving reliability.
Another object of the present invention is to provide a method for forming the solar cell electrode.
1. According to an embodiment, a solar cell electrode is provided. The solar cell electrode may include: a first electrode layer comprising a conductive powder and a first glass frit; and a second electrode layer formed on the first electrode layer, the second electrode layer including a conductive powder and a second glass frit which is different from the first glass frit and has a molar ratio of lead (Pb) oxide/(lead (Pb) oxide + copper (Cu) oxide) of more than 0.2 and 0.95 or less.
2. In item 1 above, the second glass frit may comprise 15 to 75 mol percent lead (Pb) oxide.
3. In the above 1 or 2, the second glass frit may include 3 to 60 mol% of copper (Cu) oxide.
4. In any one of the above 1 to 3, the second glass frit may further include 1 or more elements selected from tellurium (T e), bismuth (Bi), lithium (Li), boron (B), phosphorus (P), germanium (Ge), gallium (Ga), cerium (Ce), iron (Fe), silicon (Si), zinc (Zn), tungsten (W), magnesium (Mg), cesium (Cs), strontium (Sr), molybdenum (Mo), titanium (Ti), tin (Sn), indium (In), vanadium (V), barium (Ba), nickel (Ni), sodium (Na), potassium (K), arsenic (As), cobalt (Co), zirconium (Zr), manganese (Mn), and aluminum (Al).
5. In any one of the above 1 to 4, the second glass frit may further include 1 or more of silicon (Si) oxide, titanium (Ti) oxide, and iron (Fe) oxide.
6. In any of the above 1 to 5, the second glass frit may further include 5 to 25 mol% of silicon (Si) oxide.
7. In any of the above 1 to 6, the second glass frit may further include 0.3 to 15 mol% of titanium (Ti) oxide.
8. In any one of the above 1 to 7, the above second glass frit may further include iron (Fe) oxide in an amount of 1 to 5 mol%.
9. In any one of the above 1 to 8, the second glass frit may further include 1 or more of boron (B) oxide, sodium (Na) oxide, aluminum (Al) oxide, tungsten (W) oxide, and molybdenum (Mo) oxide.
10. According to another embodiment, there is provided a solar cell electrode forming method of any one of the above 1 to 9. The method can comprise the following steps: the method for manufacturing the solar cell includes a step of applying a first composition for forming a solar cell electrode, the first composition including a conductive powder, a first glass frit, and an organic vehicle, to form a first electrode layer, a step of applying a second composition for forming a solar cell electrode, the second composition including a conductive powder, a second glass frit, and an organic vehicle, to form a second electrode layer, and a firing step.
11. In the above 10, the first solar cell electrode-forming composition or the second solar cell electrode-forming composition may further include 1 or more 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.
12. In the above 10 or 11, the first solar cell electrode-forming composition may include 60 to 95 wt% of the conductive powder, 0.1 to 20 wt% of the first glass frit, and 1 to 30 wt% of the organic vehicle, and the second solar cell electrode-forming composition may include 60 to 95 wt% of the conductive powder, 0.1 to 20 wt% of the second glass frit, and 1 to 30 wt% of the organic vehicle.
The present invention has the effect of providing a solar cell electrode and a method for forming the same, which improve open circuit voltage characteristics by controlling interfacial reactions generated during electrode firing, and have excellent conversion efficiency and improved adhesion.
Drawings
Fig. 1 schematically shows the structure of a solar cell according to an example of the present invention.
Detailed Description
In the present specification, the singular expressions include plural expressions unless the context clearly indicates otherwise.
The terms including or having in the present specification mean the presence of the features or structural elements described in the specification, and do not preclude the possibility of adding one or more other features or structural elements.
The terms first, second, etc. used in the present specification may be used to describe various structural elements, but the structural elements are not limited by the terms. The terminology is used for the purpose of distinguishing one structural element from other structural elements only.
In explaining the structural elements, the error range is to be interpreted as being included even if there is no additional explicit description.
"to" in "a to b" representing numerical value ranges in the present specification is defined as ≧ a and ≦ b.
Solar cell electrode
According to an embodiment, a solar cell electrode is provided. The solar cell electrode may include: a first electrode layer comprising a conductive powder and a first glass frit; and a second electrode layer formed on the first electrode layer, the second electrode layer including a conductive powder and a second glass frit which is different from the first glass frit and has a molar ratio of lead (Pb) oxide/(lead (Pb) oxide + copper (Cu) oxide) of more than 0.2 and 0.95 or less.
The conductive powder may include, for example, 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 having various shapes, for example, spherical, plate-like, or amorphous particles can be used.
The conductive powder may be a powder having a particle diameter of a nano size or a micro size, and for example, may be a conductive powder of a size of several tens or hundreds of nanometers or a conductive powder of a size of several to several tens of micrometers. In addition, as the conductive powder, 2 or more conductive powders with different sizes may be mixed and used.
Average particle diameter (D) of conductive powder 50 ) May be 0.1 to 10 μm, for example, may be 0.5 to 5 μm. Within the above range, the contact resistance and the series resistance may be reduced. The average particle diameter (D) can be measured using 1064LD model manufactured by CI LAS after conducting ultrasonic dispersion of conductive powder in isopropyl alcohol (IPA) at 25 ℃ for 3 minutes 50 )。
The glass frit is used for etching (etching) the antireflection film in a firing step of the electrode-forming composition, and melts the conductive powder to generate crystal particles of the conductive powder in the emitter region. The glass frit improves the adhesion between the conductive powder and the wafer, and softens during sintering to induce an effect of further lowering the sintering temperature.
The first glass frit included in the first electrode layer and the second glass frit included in the second electrode layer may be different. For example, the elements included in the first glass frit and the second glass frit may be different in kind or content.
The first glass frit may generally be a glass frit used in the preparation of electrodes for solar cells. For example, the first glass frit may include 1 or more elements selected from lead (Pb), tellurium (Te), bismuth (Bi), lithium (Li), boron (B), phosphorus (P), germanium (Ge), gallium (Ga), cerium (Ce), iron (Fe), silicon (Si), zinc (Zn), tungsten (W), magnesium (Mg), cesium (Cs), strontium (Sr), molybdenum (Mo), titanium (Ti), tin (Sn), indium (In), vanadium (V), barium (Ba), nickel (Ni), copper (Cu), sodium (Na), potassium (K), arsenic (As), cobalt (Co), zirconium (Zr), manganese (M n), and aluminum (Al).
According to an example, the first glass frit may comprise a Bi-Te-O type glass frit, a Pb-Bi-O type glass frit, a Pb-Te-Bi-O type glass frit, a Te-B-O type glass frit, a Te-Ag-O type glass frit, a Pb-Si-O type glass frit, a Bi-Si-O type glass frit, 1 or more selected from the group consisting of a Te-Zn-O glass frit, a Bi-Te-Li-Zn-O glass frit, a Pb-Te-Si-Na-W-O glass frit, a Bi-B-O glass frit, a Pb-B-O glass frit, a Bi-M O-O glass frit, a Mo-B-O glass frit and a Te-Si-O glass frit. In this case, there is an advantage that the balance of the electrical characteristics of the solar cell electrode is excellent.
The second glass frit is different from the first glass frit and includes lead (Pb) oxide and copper (Cu) oxide, and a molar ratio of lead (Pb) oxide/(lead (Pb) oxide + copper (Cu) oxide) may be greater than 0.2 and 0.95 or less. In this case, the open circuit voltage characteristics and the solar cell efficiency are improved by reducing recombination loss caused by etching the ARC layer during electrode firing, and the adhesion to the wafer-gate line interface or the gate line-bonding wire interface is also excellent. According to an example, the molar ratio of lead (Pb) oxide/(lead (Pb) oxide + copper (Cu) oxide) in the second glass frit may be 0.23 to 0.93, according to another example, 0.23 to 0.87, according to another example, 0.23 to 0.80, but is not limited thereto.
According to an example, the lead (Pb) oxide may include 15 to 75 mol% (e.g., 17 to 75 mol%, to cite another example, 17 to 70 mol%) based on the total molar amount of the second glass frit, and within the above range, the open circuit voltage characteristic and the solar cell efficiency may be improved by reducing recombination loss caused by etching the ARC layer during firing of the electrode, and the adhesion to the wafer-gate line interface or the gate line-wire bond interface may be excellent, but is not limited thereto.
According to an example, the copper (Cu) oxide may include 3 to 60 mol% (e.g., 5 to 60 mol%, to cite another example, 5 to 58 mol%) based on the total molar amount of the second glass frit, and within the above range, the open circuit voltage characteristic and the solar cell efficiency may be improved by reducing recombination loss caused by etching the ARC layer during firing of the electrode, and the adhesion to the wafer-gate line interface or the gate line-bonding wire interface may also be excellent, but is not limited thereto.
The second glass frit may include, In addition to the elements of lead (Pb) and copper (Cu), 1 or more elements selected from tellurium (Te), bismuth (Bi), lithium (Li), boron (B), phosphorus (P), germanium (Ge), gallium (Ga), cerium (Ce), iron (Fe), silicon (Si), zinc (Zn), tungsten (W), magnesium (Mg), cesium (Cs), strontium (Sr), molybdenum (Mo), titanium (Ti), tin (Sn), indium (In), vanadium (V), barium (Ba), nickel (Ni), sodium (Na), potassium (K), arsenic (As), cobalt (Co), zirconium (Zr), manganese (Mn), and aluminum (Al), for example.
According to an example, the second glass frit may also include silicon (Si) oxide. In this case, an adhesion improvement effect can be obtained. The silicon (Si) oxide may be included, for example, in an amount of 5 to 25 mol%, in another example, 5 to 20 mol%, and in another example, 6 to 15 mol%, based on the total molar amount of the second glass frit, and the adhesion improvement effect may be further excellent within the above range, but is not limited thereto.
According to another example, the second glass frit may also include titanium (Ti) oxide. In this case, an adhesion improvement effect can be obtained. The titanium (Ti) oxide may be included, for example, in an amount of 0.3 to 13 mol%, for another example, 0.3 to 11 mol%, for another example, 0.3 to 10 mol%, based on the total molar amount of the second glass frit, and the adhesion improvement effect may be further excellent within the above range, but is not limited thereto.
According to another example, the second glass frit may also include iron (Fe) oxide. In this case, an adhesion improvement effect can be obtained. The iron (Fe) oxide may be included, for example, in an amount of 1 to 5 mol%, for another example, 1.2 to 4 mol%, for another example, 1.2 to 3.6 mol%, based on the total molar amount of the second glass frit, and the adhesion improvement effect may be further excellent within the above range, but is not limited thereto.
According to another example, the second glass frit may also include boron (B) oxide. In this case, the glass can be easily produced, and can have an adhesion improving effect. The boron (B) oxide may be included, for example, in an amount of 0.1 to 20 mol%, and as another example, in an amount of 0.1 to 15 mol%, based on the total molar amount of the second glass frit, and within the above range, the glass may be easily prepared and may have an adhesion improving effect, but is not limited thereto.
According to another example, the second glass frit may also include sodium (Na) oxide. In this case, the resistance improvement effect can be obtained. The sodium (Na) oxide may be included, for example, in an amount of 1 to 8 mol%, or, in another example, in an amount of 1.5 to 6 mol%, or, in another example, in an amount of 1.5 to 5 mol%, based on the total molar amount of the second glass frit, and may have a resistance improvement effect within the above range, but is not limited thereto.
According to another example, the second glass frit may also include aluminum (Al) oxide. In this case, an adhesion improvement effect can be obtained. The aluminum (Al) oxide may be included, for example, in an amount of 0.1 to 2 mol% based on the total molar amount of the second glass frit, and may have an adhesion improvement effect within the above range, but is not limited thereto.
According to another example, the second glass frit may also include tungsten (W) oxide. In this case, an adhesion improvement effect can be obtained. The tungsten (W) oxide may be included, for example, in an amount of 0.1 to 5 mol%, for another example, 0.1 to 3.5 mol%, for another example, 0.1 to 3 mol%, based on the total molar amount of the second glass frit, and may have an adhesion improving effect within the above range, but is not limited thereto.
According to another example, the second glass frit may also include molybdenum (Mo) oxide. In this case, the open circuit voltage improvement effect can be obtained. The molybdenum (Mo) oxide may be included, for example, in an amount of 0.1 to 5 mol% based on the total molar amount of the second glass frit, and may have an open circuit voltage improvement effect within the above range, but is not limited thereto.
According to another example, the second glass frit may not include tellurium (Te) elements. In this case, the resistance improvement effect can be obtained.
The shape, size, etc. of the glass frit are not particularly limited. For example, the shape of the glass frit may be spherical or amorphous, respectively, and the average particle size (D) of the glass frit 50 ) May be 0.1 to 10 μm. The average particle size (D) can be measured using 1064LD model manufactured by CILAS corporation after 3 minutes of ultrasonic dispersion of the glass frit in isopropanol at 25 ℃ 50 )。
The glass frit may be prepared from the above-described elements and/or element oxides using conventional methods. For example, the above-mentioned elements and/or element oxides are mixed by a ball mill (ball mill) or a planetary mill (planetary mill), the mixed composition is melted at 800 to 1300 ℃, quenched (quenching) at 25 ℃, and the resultant is pulverized by a disc mill (d isk mill), a planetary mill, or the like.
Method for forming solar cell electrode
According to another embodiment, a method of forming the solar cell electrode is provided. The solar cell electrode forming method may include: the method for manufacturing the solar cell includes a step of applying a first composition for forming a solar cell electrode, the first composition including a conductive powder, a first glass frit, and an organic vehicle, to form a first electrode layer, a step of applying a second composition for forming a solar cell electrode, the second composition including a conductive powder, a second glass frit, and an organic vehicle, to form a second electrode layer, and a firing step.
The first solar cell electrode-forming composition may be prepared by mixing a conductive powder, a first glass frit, and an organic vehicle, and the second solar cell electrode-forming composition may be prepared by mixing a conductive powder, a second glass frit, and an organic vehicle. Since the conductive powder, the first glass frit, and the second glass frit have been described in detail, detailed description is omitted.
The amount of the conductive powder used is not particularly limited, and for example, the conductive powder may be included by 60 to 95 weight percent, for example, 70 to 90 weight percent, with respect to the total weight of the first or second solar cell electrode forming composition. Within the above range, the solar cell has excellent conversion efficiency and can be pasted smoothly.
The amount of the glass frit used is not particularly limited, and may be, for example, 0.1 to 20 wt%, for example, 0.1 to 10 wt%, based on the total weight of the first or second solar cell electrode forming composition. Within the above range, the solar cell efficiency can be improved by the excellent open circuit voltage, and the adhesive force improvement effect can be provided.
The composition for forming a solar cell electrode may include an organic vehicle for imparting viscosity and rheological characteristics suitable for printing to the composition by mechanical mixing with inorganic components of the composition. The organic vehicle may be generally the one used in the composition for forming the solar cell electrode, and may include a binder resin, a solvent, and the like.
As the binder resin, acrylic ester or cellulose resin can be used. According to an example, ethyl cellulose may be used as the binder resin. According to another example, ethyl hydroxyethyl cellulose, cellulose nitrate, a mixture of ethyl cellulose and a phenol resin, an alkyd resin, a phenol resin, an acrylate resin, a xylene resin, a polybutene resin, a polyester resin, a urea resin, a melamine resin, a vinyl acetate resin, wood rosin (rosin), or an alcohol polymethyl acrylate can be used as the binder resin.
Examples of the solvent include 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, terpineol (terpineol), methyl ethyl ketone, benzyl alcohol, γ -butyrolactone, ethyl lactate, and 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate (e.g., ester alcohol), which may be used alone or in combination.
The amount of the organic vehicle used is not particularly limited, and for example, the organic vehicle may be contained in an amount of 1 to 30 weight percent, for example, 3 to 25 weight percent, with respect to the total weight of the first or second solar cell electrode forming composition. Within the above range, sufficient adhesive strength and excellent printability can be ensured.
The composition for forming a solar cell electrode may further include 2 or more kinds of dispersing agents, thixotropic agents, plasticizers, viscosity stabilizers, antifoaming agents, pigments, ultraviolet stabilizers, antioxidants, coupling agents, and the like, alone or in combination, as necessary, in addition to the above components, in order to improve flow characteristics, process characteristics, and stability. These components may be contained in an amount of 0.1 to 5 weight percent with respect to the total weight of the first or second solar cell electrode-forming composition, but the content thereof may be changed as needed.
The solar cell electrode forming method may include, for example: a step of forming a first electrode layer by applying a first solar cell electrode-forming composition to the surface of a substrate in a predetermined pattern and then drying the composition; a step of forming a second electrode layer by applying a second composition for forming a solar cell electrode on the substrate on which the first electrode layer is formed, and then drying the composition; and firing the electrode patterns formed from the first and second solar cell electrode-forming compositions.
The composition for forming the solar cell electrode may be applied by, for example, screen printing, gravure offset printing, rotary screen printing, or a peeling method, but is not limited thereto.
The composition for forming a solar cell electrode may be dried, for example, at about 200 ℃ to about 400 ℃ for about 10 seconds to about 60 seconds, but is not limited thereto.
The firing process may be performed, for example, at about 400 to about 980 c (e.g., about 600 to about 950 c) for about 60 to about 210 seconds, but is not limited thereto.
Solar cell
According to another embodiment, a solar cell is provided comprising the solar cell electrode described above.
Fig. 1 schematically shows the structure of a solar cell 100 according to an example of the present invention.
Referring to fig. 1, a solar cell 100 may include: a substrate 10 including a p layer (or n layer) 11 and an n layer (or p layer) 12 as an emitter; a back electrode 21 and a front electrode 23. The rear electrode 21 or the front electrode 23 may include a first electrode layer formed on the substrate 10, which may include conductive powder and a first glass frit, and a second electrode layer formed on the first electrode layer, which may include conductive powder and a second glass frit.
The solar cell 100 can be prepared, for example, by printing a first solar cell electrode-forming composition on the front surface of the substrate 10, drying the composition to form a first electrode layer, printing a second solar cell electrode-forming composition, drying the composition to form a second electrode layer, performing a preliminary preparation step for the front electrode 23, printing an aluminum paste on the rear surface of the substrate 10, drying the aluminum paste, performing a preliminary preparation step for the rear electrode 21, and firing the aluminum paste.
The present invention will be described in further detail below with reference to examples. However, this is mentioned as a preferred example of the present invention, and it should not be construed that the present invention is limited thereto in any sense.
Examples
Preparation example 1
2 parts by weight of ethyl cellulose (STD4, Dow chemical) as a binder resin was sufficiently dissolved in 6.5 parts by weight of terpene alcohol (Nippon Terpine) as a solvent at 60 ℃ and then 90 parts by weight of spherical silver powder (4-8F, Dowa) having an average particle diameter of 2.0 μm and 1.0 μm of the layer 1 (1) of Table 1 having an average particle diameter of 1.0 μm were put in st layer) glass frit 1.5 parts by weight, and after uniformly mixing, the mixture was mixed and dispersed by a 3-roll kneader, thereby preparing a first composition for forming a solar cell electrode.
Preparation examples 2 to 11
A second solar cell electrode-forming composition was prepared by the same method as preparation example 1, except that glass frits a to J described in table 1 below were used, respectively.
[ TABLE 1 ]
(unit: mole percent)
Examples 1 to 8 and comparative examples 1 and 2
Texturing (texturing) the front of a wafer (a Boron doped (doting) p-type wafer), followed by POCl 3 An n + layer was formed, and after an aluminum paste was printed on the rear surface of a single crystal (mono crystalline) wafer on which silicon nitride (SiNx: H) was formed as an anti-reflection film, the wafer was dried at 300 ℃ for 30 seconds. Subsequently, the first solar cell electrode-forming composition according to preparation example 1 was screen-printed in front of the wafer, dried at 300 ℃ for 30 seconds to form a first electrode layer, and then a second solar cell electrode-forming composition according to any one of preparation examples 2 to 11 was screen-printed thereon, dried at 300 ℃ for 30 seconds to form a second electrode layer. The solar cell sheet formed through the above process was fired at 940 ℃ for 70 seconds using a belt firing furnace to prepare a solar cell sheet.
Evaluation example 1: electric characteristics
The solar cell sheets prepared in examples 1 to 8 and comparative examples 1 and 2 were measured for short-circuit current (Isc, unit: a), open-circuit voltage (Voc, unit: mV), series resistance (Rs, unit: Ω), fill factor (FF, unit:%) and conversion efficiency (eff., unit:%) using a solar cell efficiency measuring apparatus (Halm, Fortix tech), and the results thereof are shown in table 2 below.
Evaluation example 2: adhesion force
Flux (Flux) was applied to the second electrode layer of the solar cell chips prepared in examples 1 to 8 and comparative examples 1 and 2 (952S, Kester corporation), the bonding wire (62Sn/36Pb/2Ag, thickness 0.18mm, width 1.5mm) was adhered using an electric iron at a temperature of 360 ℃, then the end of the bonding wire was fixed at an angle of 180 degrees using a tester (Mocel H5K-T, Tinius Olsen corporation), pulled at a speed of 50mm/min, and the value thereof was measured, and the result thereof was shown in table 2 below.
[ TABLE 2 ]
As can be seen from table 2, the solar cells of examples 1 to 8 have higher open circuit voltages and superior conversion efficiencies as compared to the solar cells of comparative examples 1 and 2, and thus have superior adhesion.
So far, embodiments of the present invention have been mainly explained. Those skilled in the art to which the present invention pertains will appreciate that the present invention can be implemented in various forms without departing from the essential characteristics of the invention. The disclosed embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. The scope of the invention is indicated in the appended claims rather than in the foregoing description, and all differences within the equivalent scope will be construed as being included in the present invention.
Claims (12)
1. A solar cell electrode, comprising:
a first electrode layer comprising a conductive powder and a first glass frit; and
and a second electrode layer formed on the first electrode layer, the second electrode layer including a conductive powder and a second glass frit which is different from the first glass frit and has a molar ratio of lead (Pb) oxide/(lead (Pb) oxide + copper (Cu) oxide) of more than 0.2 and 0.95 or less.
2. The solar cell electrode of claim 1, wherein the second glass frit comprises 15 to 75 mole percent lead (Pb) oxide.
3. The solar cell electrode of claim 1, wherein the second glass frit comprises 3 to 60 mole percent copper (Cu) oxide.
4. The solar cell electrode according to claim 1, wherein the second glass frit further comprises 1 or more elements selected from tellurium (Te), bismuth (Bi), lithium (Li), boron (B), phosphorus (P), germanium (Ge), gallium (Ga), cerium (Ce), iron (Fe), silicon (Si), zinc (Zn), tungsten (W), magnesium (Mg), cesium (Cs), strontium (Sr), molybdenum (Mo), titanium (Ti), tin (Sn), indium (In), vanadium (V), barium (Ba), nickel (Ni), sodium (Na), potassium (K), arsenic (As), cobalt (Co), zirconium (Zr), manganese (Mn), and aluminum (Al).
5. The solar cell electrode according to claim 1, wherein the second glass frit further comprises at least one of silicon (Si) oxide, titanium (Ti) oxide, and iron (Fe) oxide.
6. The solar cell electrode of claim 1, wherein the second glass frit further comprises 5 to 25 mole percent silicon (Si) oxide.
7. The solar cell electrode of claim 1, wherein the second glass frit further comprises 0.3 to 13 mole percent titanium (Ti) oxide.
8. The solar cell electrode of claim 1, wherein the second glass frit further comprises 1 to 5 mole percent iron (Fe) oxide.
9. The solar cell electrode according to claim 1, wherein the second glass frit further comprises 1 or more of boron (B) oxide, sodium (Na) oxide, aluminum (Al) oxide, tungsten (W) oxide, and molybdenum (Mo) oxide.
10. A solar cell electrode forming method according to any one of claims 1 to 9, characterized by comprising:
a step of forming a first electrode layer by coating a first composition for forming a solar cell electrode, the composition comprising a conductive powder, a first glass frit, and an organic vehicle,
coating a second solar cell electrode-forming composition containing a conductive powder, a second glass frit, and an organic vehicle, forming a second electrode layer, and
and (5) a firing step.
11. The method of claim 10, wherein the first or second composition further comprises 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.
12. The solar cell electrode forming method according to claim 10,
the first solar cell electrode-forming composition includes 60 to 95 wt% of the conductive powder, 0.1 to 20 wt% of the first glass frit, and 1 to 30 wt% of the organic vehicle,
the second solar cell electrode-forming composition includes 60 to 95 wt% of the conductive powder, 0.1 to 20 wt% of the second glass frit, and 1 to 30 wt% of the organic vehicle.
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