WO2011046360A2 - Aluminum paste for back electrode of solar cell - Google Patents

Aluminum paste for back electrode of solar cell Download PDF

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Publication number
WO2011046360A2
WO2011046360A2 PCT/KR2010/006993 KR2010006993W WO2011046360A2 WO 2011046360 A2 WO2011046360 A2 WO 2011046360A2 KR 2010006993 W KR2010006993 W KR 2010006993W WO 2011046360 A2 WO2011046360 A2 WO 2011046360A2
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Prior art keywords
aluminum
aluminum paste
solar cell
aluminum powder
paste
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PCT/KR2010/006993
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French (fr)
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WO2011046360A3 (en
Inventor
Chang-Mo Lee
Seung-Yong Lee
Dae-Sung Lim
Hyung-Sub Choi
Seung-Kwon Hong
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Dongwoo Fine-Chem Co., Ltd.
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Priority to CN201080037313.4A priority Critical patent/CN102576578B/en
Publication of WO2011046360A2 publication Critical patent/WO2011046360A2/en
Publication of WO2011046360A3 publication Critical patent/WO2011046360A3/en

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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
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/056—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means the light-reflecting means being of the back surface reflector [BSR] type
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators

Definitions

  • the present invention relates to aluminum paste for a back electrode of a solar cell.
  • crystalline silicon solar cells use a P-type silicon substrate having a thickness of 180 ⁇ 220 ⁇ m.
  • An N-type impurity layer having a thickness of 0.2 ⁇ 0.6 ⁇ m is formed on the front surface of the P-type silicon substrate, and a SiNx layer for antireflection and a front electrode are sequentially formed on the N-type impurity layer.
  • an aluminum electrode is formed on the back surface of the P-type silicon substrate. This aluminum electrode is formed by applying aluminum paste using screen printing or the like, drying the applied aluminum paste and then two-stage-calcining the dried aluminum paste at low temperature (about 600°C) and at high temperature (800 ⁇ 950°C).
  • an Al-Si alloy layer is formed while aluminum diffuses into the P-type silicon substrate.
  • This Al-Si alloy layer forms a back surface field (BSF) layer preventing the recombination of electrons generated from a solar cell and improving the collection efficiency of carriers generated from the solar cell.
  • the efficiency of the solar cell is influenced by the thickness and uniformity of the BSF layer. That is, when the thickness of the BSF layer is decreased, the efficiency of the solar cell is decreased, and when the thickness thereof is increased, the efficiency thereof is increased.
  • the thickness of a silicon wafer has been recently decreased in order to reduce the cost of solar cells.
  • the silicon wafer warps due to the difference in the termal expansion coefficient between the silicon wafer and aluminum, and thus the silicon wafer cracks.
  • the thickness of an aluminum electrode that functions as a back electrode it is required to decrease the thickness of an aluminum electrode that functions as a back electrode, and this purpose can be accomplished by decreasing the amount of aluminum paste applied.
  • the thickness of the BSF layer which is a back electric field layer
  • aluminum bubbles or bumps are increasingly formed in an electrode layer during a calcination process.
  • the aluminum bubbles or bumps formed in the electrode layer decrease the flatness of the back surface of the silicon wafer, and stress is focused on these aluminum bubbles or bumps, thereby causing the solar cell to break during the solar cell manufacturing process or solar cell module manufacturing process.
  • Korean Patent Registration No. 10-0825580 discloses aluminum paste including aluminum powder having a particle size of 0.5 ⁇ 10 ⁇ m, an organic vehicle and a metal alkoxide
  • Korean Unexamined Patent Application Publication No. 10-2008-0068638 discloses aluminum paste including aluminum powder having a particle size of 2 ⁇ 20 ⁇ m, glass frit, an organic vehicle and a metal hydroxide
  • Korean Unexamined Patent Application Publication No. 10-2008-0057230 discloses aluminum paste including aluminum powder having a particle size of 2 ⁇ 20 ⁇ m, glass frit, an organic vehicle and a plasticizer
  • Korean Unexamined Patent Application Publication No. 10-2008-0104179 discloses aluminum paste including aluminum powder having a particle size of 4 ⁇ 10 ⁇ m, alkaline glass frit, boron ethoxide, titanium ethoxide, and fumed silica.
  • All of the aluminum pastes disclosed in the above patent documents include organic or inorganic additives in addition to aluminum powder, glass frit and an organic vehicle.
  • these additives are problematic because they exist as residues or include pores during a process of calcining aluminum paste, so that the resistance and uniformity of the aluminum paste is decreased, thereby badly influencing the efficiency of a solar cell.
  • the above aluminum pastes are problematic because aluminum powder has a maximum particle size of 10 ⁇ 20 ⁇ m, so that it is difficult for aluminum paste to uniformly come into contact with the textured back surface of a solar cell, with the result that aluminum bumps can be probably formed by pores formed therein.
  • an object of the present invention is to provide aluminum paste for a back electrode of a solar cell, which can prevent the warpage of a solar cell or minimize the formation of aluminum bubbles or bumps and the occurrence of yellow discoloration during a calcination process, which can greatly increase the values of short circuit current (Isc) and open circuit voltage (Voc), and which can remarkably improve the efficiency of a solar cell.
  • Isc short circuit current
  • Voc open circuit voltage
  • an aspect of the present invention provides aluminum paste for a back electrode of a solar cell, including: aluminum powder in which aluminum powder having an average particle size (D 50 ) of 4 ⁇ 6 ⁇ m and aluminum powder having an average particle size (D 50 ) of 2 ⁇ 4 ⁇ m are mixed in a ratio of 6:4 ⁇ 9.5:0.5 by weight.
  • Another aspect of the present invention provides a method of manufacturing a solar cell, including a process of forming a back electrode using the aluminum paste.
  • the warpage of a solar cell can be prevented and the formation of aluminum bubbles or bumps and the occurrence of yellow discoloration can be minimized during the calcination process, the values of short circuit current (Isc) and open circuit voltage (Voc) can be greatly increased, and the efficiency of a solar cell can be remarkably improved.
  • the “D 50 ” means an average particle size of aluminum powder.
  • the front and back surfaces of silicon solar cells are textured in order to enlarge the area that receives the solar light.
  • a monocrystalline silicon wafer is textured in the form of a pyramid, and the pyramid has a height of 2 ⁇ 15 ⁇ m and a width of 2 ⁇ 20 ⁇ m.
  • a polycrystalline silicon wafer is textured in the form of an irregular maze.
  • the textured silicon wafer is coated on the back surface thereof with aluminum paste by screen printing, gravure printing or offset printing, dried, and then calcined to form an aluminum electrode.
  • the present inventors found that when aluminum powder having a single particle size distribution is used, even if the particle size is small, the gap cannot be easily filled with the aluminum powder, and that when two or more kinds of aluminum powder having a different average particle size is used, the formation of the gap can be minimized.
  • the aluminum powder may be included in an amount of 65 ⁇ 75 wt%.
  • the amount of the aluminum powder included in the aluminum paste is below 65 wt%, there is a problem in that the aluminum layer printed after the calicination process becomes thin, so that a back surface field (BSF) layer is not sufficiently formed, thereby increasing the efficiency of a solar cell.
  • BSF back surface field
  • the amount of the aluminum powder included therein is greater than 75 wt%, there is a problem in that the printed aluminum layer becomes excessively thick, thereby causing the silicon wafer to warp.
  • the glass frit may be included in an amount of 0.01 ⁇ 5 wt%, preferably 0.05 ⁇ 3 wt%, more preferably 0.1 ⁇ 1 wt%.
  • the amount of the glass frit below 0.01 wt%, there is a problem in that the silicon wafer easily warp, and the adhesion between the aluminum paste and the silicon wafer decreases. Further, when the amount thereof greater than 5 wt%, there is a problem in that resistance becomes high, thus decreasing the efficiency of a solar cell.
  • the glass frit may be Bi 2 O 3 -SiO 2 -Al 2 O 3 -B 2 O 3 -SrO.
  • the glass frit may include, but is not limited to, 20 ⁇ 30 mol% of Bi 2 O 3 , 5 ⁇ 15 mol% of Al 2 O 3 , 25 ⁇ 35 mol% of SiO 2 , 1 ⁇ 10 mol% of SrO, and 20 ⁇ 40 mol% of B 2 O 3 .
  • the softening point of the glass frit is increased, so that the aluminum paste is not softened enough during the process of calcining a solar cell, with the result that the adhesion between the aluminum paste and the silicon wafer decreases, thereby decreasing the efficiency of the solar cell.
  • the glass frit includes an excessive amount of SrO, the softening point of the glass frit is excessively lowered, resulting in bumps in the aluminum electrode.
  • the glass frit used in the present invention may have a softening point of 400 ⁇ 600°C.
  • the softening point of the glass frit When the softening point of the glass frit is below 400°C, the thermal expansion coefficient of the glass frit is relatively increased, and thus the silicon wafer calcined during the solar cell manufacturing process easily warps. Further, when the softening point thereof is above 600°C, the glass frit does not sufficiently melt in the calcination process to such a degree that the adhesion is provided between the aluminum layer and the silicon wafer layer, thus deteriorating the adhesion therebetween.
  • the organic vehicle solution may be included in an amount of 20 ⁇ 34.90 wt% based on the total amount of the aluminum paste.
  • the amount of the organic vehicle solution is below 20 wt%, there is a problem in that the viscosity of the aluminum paste excessively increases, thus decreasing printability of the aluminum paste.
  • the amount thereof is greater than 34.90 wt%, there is a problem in that the content ratio of aluminum in the aluminum paste decreases, and thus it is difficult to form an aluminum layer having a sufficient thickness.
  • the organic vehicle solution is prepared by dissolving a polymer resin in an organic solvent, and, if necessary, may include a thixotropic agent, a wetting agent, an additive and the like.
  • the organic vehicle solution used in the present invention may include, based on the total amount thereof, 75 wt% or more of an organic solvent and 1 ⁇ 25 wt% of a polymer resin. Also, the organic vehicle solution may further include 5 wt% or less of a wetting agent and a thixotropic agent, and 1 ⁇ 10 wt% of an additive.
  • the organic solvent may have a boiling point of 150 ⁇ 300°C such that it is possible to prevent the aluminum paste from drying and to control the flowability of the aluminum paste.
  • Examples of commonly-used organic solvents may include glycol ethers, such as tripropyleneglycol methyl ether, dipropyleneglycol n-propyl ether, dipropyleneglycol n-butyl ether, tripropyleneglycol n-butyl ether, propyleneglycol phenyl ether, diethyleneglycol ethyl ether, diethyleneglycol n-butyl ether, diethyleneglycol hexyl ether, ethyleneglycol hexyl ether, triethyleneglycol methyl ether, triethyleneglycol ethyl ether, triethyleneglycol n-butyl ether, ethyleneglycol phenyl ether, terpineol, Texanol®, ethyleneglycol,
  • the polymer resin may include polyvinylpyrrolidone, polyvinylalcohol, polyethyleneglycol, ethylcellulose, rosin, a phenol resin, an acrylate resin, and the like.
  • the amount of the polymer may be 1 ⁇ 25 wt%, preferably, 5 ⁇ 25 wt%, based on the total amount of the organic vehicle solution.
  • the amount of the polymer resin is below 1 wt%, the printability and dispersion stability of the aluminum paste are deteriorated. Further, the amount thereof is above 25 wt%, the aluminum paste cannot be printed.
  • thixotropic agent and wetting agent thixotropic agents and wetting agents commonly used in the related field may be used without limitation.
  • the additive may be a dispersant or the like commonly used in the related field.
  • the dispersant commercially available surfactants may be used, and they may be used independently or in combination with each other.
  • the surfactants may include: nonionic surfactants, such as ethers including alkyl polyoxyethylene ether, alkylaryl polyoxyethylene ether, polyoxyethylene-polyoxypropylene copolymer and the like, ester-ethers including polyoxyethylene ether of glycerin ester, polyoxyethylene ether of sorbitan ester, polyoxyethylene ether of sorbitol ester and the like, esters including polyethylene glycol fatty acid ester, glycerin ester, sorbitan ester, propylene glycol ester, sugar ester, alkyl polyglucoside and the like, and nitrogen-containing surfactants including fatty acid alkanolamide, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine, amine oxide and the like; and polymeric surfact
  • Examples of commercially available surfactant products may include hypermer KD (manufactured by Uniqema Corp.), AKM 0531 (manufactured by NOF Corp.), KP (manufactured by Shinetsu Kagaku Kogyo Corp.), POLYFLOW (manufactured by Kyoei Kagaku Corp.), EFTOP (manufactured by Tokemu Products Corp.), Asahi guard, Surflon (manufactured by Asahi Glass Corp.), SOLSPERSE (manufactured by Geneka Corp.), EFKA (manufactured by EFKA Chemicals Co., Ltd.), PB 821 (manufactured by Ajinomoto Co., Inc.), BYK-184, BYK-185, BYK-2160, Anti-Terra U (manufactured by BYK Corp.), and the like.
  • the amount of the dispersant may be 1 ⁇ 10 wt%, preferably, 1 ⁇ 5 wt%, based on the total amount of the organic vehicle solution.
  • the aluminum paste according to the present invention can be easily prepared using a planar mixer which simultaneously rotates and revolves. That is, this aluminum paste can be prepared by putting the above-mentioned components into a planar mixer in the corresponding composition ratio and then stirring for the solids to be properly mixed and dispersed in an organic vehicle solution.
  • the aluminum paste prepared in this way has a viscosity of 20,000 ⁇ 200,000 cps at 5 rpm when its viscosity was measured at 25°C using a Brookfield HBDV-III Ultra Rheometer or a spindle CPE-52.
  • the aluminum paste may be prepared such that it has a viscosity of 40,000 ⁇ 100,000 cps.
  • the present invention provides a method of manufacturing a solar cell, including the step of forming a back electrode using the aluminum paste.
  • the solar cell manufactured in this way is advantageous in that it does not easily warp, and the minimum amount of aluminum bubbles or bumps are formed in the electrode layer, so that the values of short circuit current (Isc) and open circuit voltage (Voc) are greatly increased, and the efficiency thereof is remarkably improved.
  • Test Example Manufacturing a solar cell and testing characteristics thereof
  • a monocrystalline silicon wafer having a size of 156 X 156 mm and a thickness of 200 ⁇ m was surface-textured such that the height of a pyramid is about 4 ⁇ 6 ⁇ m, and then the N-side of the surface-textured silicon wafer was coated with SiNx. Subsequently, the silicon wafer was printed on the back surface thereof with bus bars and then dried, and then aluminum paste of each of Examples 1 to 5 and Comparative Examples 1 to 2 was applied thereon using a screen printing plate of 250 mesh such that the weight of the aluminum paste was 1.5 ⁇ 0.1 g and then dried. Further, the silicon wafer was printed on the front surface thereof with finger lines using silver paste and then dried.
  • the silicon wafer that had undergone the above processes was calcined in a continuous infrared furnace such that the temperature of a calcining zone was 720 ⁇ 900°C, thereby manufacturing a solar cell.
  • the front and back surface of the silicon wafer can be simultaneously calcined while passing through a belt furnace.
  • the belt furnace includes a burn-out zone of about 600°C and a firing zone of 800 ⁇ 950°C.
  • organic matter was removed from the aluminum paste and the silver paste, and then the aluminum paste and silver paste applied on the back surface and front surface of the silicon wafer were melted to form electrodes.
  • the degree of warpage of the manufactured solar cell was evaluated by matching four edges of the solar cell with the bottom and then measuring to what degree the central portion thereof had been lifted. Further, the occurrence of bumps and aluminum bubbles around an aluminum back electrode was observed with the naked eye, and the number thereof was counted. The results thereof are given in Table 2 below.
  • the efficiency of the manufactured solar cell was evaluated using an SCM-1000, which is an apparatus for evaluating the performance of solar cells, manufactured by FitTech Corporation. The results thereof are given in Table 3 below.
  • ⁇ Pmax maximum power of solar cell
  • the aluminum paste prepared in Example 1 was printed in amounts of 1.0 g, 1.2 g, 1.5 g, 1.8 g and 2.0g while changing printing conditions, and then the printed aluminum paste was analyzed in the same manner as the above-mentioned manner. The results thereof are given in Table 4 below.

Abstract

Disclosed herein is an aluminum paste for a back electrode of a solar cell, comprising: aluminum powder in which aluminum powder having an average particle size (D50) of 4 ~ 6 μm and aluminum powder having an average particle size (D50) of 2 ~ 4 μm are mixed in a ratio of 6:4 ~ 9.5:0.5 by weight. The aluminum paste is advantageous in that since the contact between aluminum paste and a silicon wafer textured using two or more kinds of aluminum powder having a different average particle size is improved, the warpage of a solar cell can be prevented or the formation of aluminum bubbles or bumps and the occurrence of yellow discoloration can be minimized during a calcination process, the values of short circuit current (Isc) and open circuit voltage (Voc) can be greatly increased, and the efficiency of a solar cell can be remarkably improved.

Description

ALUMINUM PASTE FOR BACK ELECTRODE OF SOLAR CELL
The present invention relates to aluminum paste for a back electrode of a solar cell.
Generally, crystalline silicon solar cells use a P-type silicon substrate having a thickness of 180 ~ 220μm. An N-type impurity layer having a thickness of 0.2 ~ 0.6μm is formed on the front surface of the P-type silicon substrate, and a SiNx layer for antireflection and a front electrode are sequentially formed on the N-type impurity layer. Further, an aluminum electrode is formed on the back surface of the P-type silicon substrate. This aluminum electrode is formed by applying aluminum paste using screen printing or the like, drying the applied aluminum paste and then two-stage-calcining the dried aluminum paste at low temperature (about 600℃) and at high temperature (800 ~ 950℃). In this calcination process, an Al-Si alloy layer is formed while aluminum diffuses into the P-type silicon substrate. This Al-Si alloy layer forms a back surface field (BSF) layer preventing the recombination of electrons generated from a solar cell and improving the collection efficiency of carriers generated from the solar cell. The efficiency of the solar cell is influenced by the thickness and uniformity of the BSF layer. That is, when the thickness of the BSF layer is decreased, the efficiency of the solar cell is decreased, and when the thickness thereof is increased, the efficiency thereof is increased.
Meanwhile, the thickness of a silicon wafer has been recently decreased in order to reduce the cost of solar cells. However, when the thickness of the silicon wafer is excessively decreased, the silicon wafer warps due to the difference in the termal expansion coefficient between the silicon wafer and aluminum, and thus the silicon wafer cracks.
In order to overcome the above problem, it is required to decrease the thickness of an aluminum electrode that functions as a back electrode, and this purpose can be accomplished by decreasing the amount of aluminum paste applied. However, when a smaller amount of aluminum paste is applied, the thickness of the BSF layer, which is a back electric field layer, is increased, so that the efficiency of the solar cell is deteriorated, and aluminum bubbles or bumps are increasingly formed in an electrode layer during a calcination process. In this case, the aluminum bubbles or bumps formed in the electrode layer decrease the flatness of the back surface of the silicon wafer, and stress is focused on these aluminum bubbles or bumps, thereby causing the solar cell to break during the solar cell manufacturing process or solar cell module manufacturing process.
In order to prevent the solar cell from warping and to form fewer aluminum bubbles during the calcination process, conventional technologies are proposed as follows. Korean Patent Registration No. 10-0825580 discloses aluminum paste including aluminum powder having a particle size of 0.5 ~ 10μm, an organic vehicle and a metal alkoxide; Korean Unexamined Patent Application Publication No. 10-2008-0068638 discloses aluminum paste including aluminum powder having a particle size of 2 ~ 20μm, glass frit, an organic vehicle and a metal hydroxide; Korean Unexamined Patent Application Publication No. 10-2008-0057230 discloses aluminum paste including aluminum powder having a particle size of 2 ~ 20μm, glass frit, an organic vehicle and a plasticizer; and Korean Unexamined Patent Application Publication No. 10-2008-0104179 discloses aluminum paste including aluminum powder having a particle size of 4 ~ 10μm, alkaline glass frit, boron ethoxide, titanium ethoxide, and fumed silica.
All of the aluminum pastes disclosed in the above patent documents include organic or inorganic additives in addition to aluminum powder, glass frit and an organic vehicle. However, these additives are problematic because they exist as residues or include pores during a process of calcining aluminum paste, so that the resistance and uniformity of the aluminum paste is decreased, thereby badly influencing the efficiency of a solar cell. Further, the above aluminum pastes are problematic because aluminum powder has a maximum particle size of 10 ~ 20μm, so that it is difficult for aluminum paste to uniformly come into contact with the textured back surface of a solar cell, with the result that aluminum bumps can be probably formed by pores formed therein.
Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide aluminum paste for a back electrode of a solar cell, which can prevent the warpage of a solar cell or minimize the formation of aluminum bubbles or bumps and the occurrence of yellow discoloration during a calcination process, which can greatly increase the values of short circuit current (Isc) and open circuit voltage (Voc), and which can remarkably improve the efficiency of a solar cell.
In order to accomplish the above object, an aspect of the present invention provides aluminum paste for a back electrode of a solar cell, including: aluminum powder in which aluminum powder having an average particle size (D50) of 4 ~ 6 μm and aluminum powder having an average particle size (D50) of 2 ~ 4 μm are mixed in a ratio of 6:4 ~ 9.5:0.5 by weight.
Another aspect of the present invention provides a method of manufacturing a solar cell, including a process of forming a back electrode using the aluminum paste.
According to the aluminum paste of the present invention, since the contact between aluminum paste and a silicon wafer textured using two or more kinds of aluminum powder having a different average particle size has improved, the warpage of a solar cell can be prevented and the formation of aluminum bubbles or bumps and the occurrence of yellow discoloration can be minimized during the calcination process, the values of short circuit current (Isc) and open circuit voltage (Voc) can be greatly increased, and the efficiency of a solar cell can be remarkably improved.
The present invention provides aluminum paste for a back electrode of a solar cell, including: aluminum powder in which aluminum powder of D50=4~6㎛ and aluminum powder of D50=2~4㎛ are mixed in a ratio of 6:4 ~ 9.5:0.5 by weight.
Here, the “D50” means an average particle size of aluminum powder.
Generally, the front and back surfaces of silicon solar cells are textured in order to enlarge the area that receives the solar light. Generally, a monocrystalline silicon wafer is textured in the form of a pyramid, and the pyramid has a height of 2 ~15 μm and a width of 2 ~ 20 μm. In contrast, a polycrystalline silicon wafer is textured in the form of an irregular maze. The textured silicon wafer is coated on the back surface thereof with aluminum paste by screen printing, gravure printing or offset printing, dried, and then calcined to form an aluminum electrode. In this process, when the size of aluminum particles is excessively large, aluminum paste does not easily come into contact with the silicon wafer, and thus a gap is formed between aluminum paste and the textured surface of the silicon wafer after being printed and dried. During the calcination process, the gab moves to the surface of an aluminum electrode through the aluminum paste layer, accompanied by the occurrence of aluminum bubbles and bumps.
However, the present inventors found that when aluminum powder having a single particle size distribution is used, even if the particle size is small, the gap cannot be easily filled with the aluminum powder, and that when two or more kinds of aluminum powder having a different average particle size is used, the formation of the gap can be minimized.
Therefore, the aluminum paste for a back electrode of a solar cell according to the present invention includes: aluminum powder in which aluminum powder of D500=4~6㎛ and aluminum powder of D50=2~4㎛ are mixed in a ratio of 6:4 ~ 9.5:0.5 by weight.
When aluminum paste is prepared using the aluminum powder having an average particle size distribution deviating from the above range, the aluminum paste cannot deeply infiltrate into the textured silicon wafer, and the porosity in the aluminum paste also increases. For this reason, a back surface field (BSF) layer cannot be uniformly formed on the silicon wafer, the resistance of an aluminum electrode does not become low, and the warpage of the silicon wafer cannot be prevented.
Conversely, when aluminum paste is prepared using aluminum powder having the average particle size distribution, the aluminum paste deeply infiltrates into the textured silicon wafer, and the porosity in the aluminum paste also decreases. For this reason, a back surface field (BSF) layer is uniformly formed on the silicon wafer, the resistance of an aluminum electrode becomes low, and the warpage of the silicon wafer is prevented. Therefore, when a solar cell is manufactured using the aluminum paste prepared using the aluminum powder, the value of the short-circuit current of the solar cell increases, and the efficiency thereof also increases. Further, the solar cell manufactured in this way is advantageous in that yellow discoloration occurring in the aluminum electrode after the calcination process can be prevented.
Further, the present invention provides aluminum paste for a back electrode of a solar cell, including, based on the total amount thereof: (a) 65 ~ 75 wt% of aluminum powder in which aluminum powder of D50=4~6㎛ and aluminum powder of D50=2~4㎛ are mixed in a ratio of 6:4 ~ 9.5:0.5 by weight; (b) 0.01 ~ 5 wt% of glass frit; and (c) 20 ~ 34.90 wt% of an organic vehicle solution.
In the aluminum paste of the present invention, the aluminum powder may be included in an amount of 65 ~ 75 wt%. When the amount of the aluminum powder included in the aluminum paste is below 65 wt%, there is a problem in that the aluminum layer printed after the calicination process becomes thin, so that a back surface field (BSF) layer is not sufficiently formed, thereby increasing the efficiency of a solar cell. Further, when the amount of the aluminum powder included therein is greater than 75 wt%, there is a problem in that the printed aluminum layer becomes excessively thick, thereby causing the silicon wafer to warp.
In the aluminum paste of the present invention, the glass frit may be included in an amount of 0.01 ~ 5 wt%, preferably 0.05 ~ 3 wt%, more preferably 0.1 ~ 1 wt%. When the amount of the glass frit below 0.01 wt%, there is a problem in that the silicon wafer easily warp, and the adhesion between the aluminum paste and the silicon wafer decreases. Further, when the amount thereof greater than 5 wt%, there is a problem in that resistance becomes high, thus decreasing the efficiency of a solar cell.
The glass frit may be Bi2O3-SiO2-Al2O3-B2O3-SrO. The glass frit may include, but is not limited to, 20 ~ 30 mol% of Bi2O3, 5 ~ 15 mol% of Al2O3, 25 ~ 35 mol% of SiO2, 1 ~ 10 mol% of SrO, and 20 ~ 40 mol% of B2O3.
In the glass frit, SrO is effectively used to lower the softening point of the glass frit. When the glass frit does not include SrO, the softening point of the glass frit is increased, so that the aluminum paste is not softened enough during the process of calcining a solar cell, with the result that the adhesion between the aluminum paste and the silicon wafer decreases, thereby decreasing the efficiency of the solar cell. However, when the glass frit includes an excessive amount of SrO, the softening point of the glass frit is excessively lowered, resulting in bumps in the aluminum electrode.
Further, the glass frit used in the present invention may have a softening point of 400 ~ 600℃. When the softening point of the glass frit is below 400℃, the thermal expansion coefficient of the glass frit is relatively increased, and thus the silicon wafer calcined during the solar cell manufacturing process easily warps. Further, when the softening point thereof is above 600℃, the glass frit does not sufficiently melt in the calcination process to such a degree that the adhesion is provided between the aluminum layer and the silicon wafer layer, thus deteriorating the adhesion therebetween.
In the aluminum paste of the present invention, the organic vehicle solution may be included in an amount of 20 ~ 34.90 wt% based on the total amount of the aluminum paste. When the amount of the organic vehicle solution is below 20 wt%, there is a problem in that the viscosity of the aluminum paste excessively increases, thus decreasing printability of the aluminum paste. Further, when the amount thereof is greater than 34.90 wt%, there is a problem in that the content ratio of aluminum in the aluminum paste decreases, and thus it is difficult to form an aluminum layer having a sufficient thickness.
The organic vehicle solution is prepared by dissolving a polymer resin in an organic solvent, and, if necessary, may include a thixotropic agent, a wetting agent, an additive and the like.
The organic vehicle solution used in the present invention may include, based on the total amount thereof, 75 wt% or more of an organic solvent and 1 ~ 25 wt% of a polymer resin. Also, the organic vehicle solution may further include 5 wt% or less of a wetting agent and a thixotropic agent, and 1 ~ 10 wt% of an additive.
The organic solvent may have a boiling point of 150 ~ 300℃ such that it is possible to prevent the aluminum paste from drying and to control the flowability of the aluminum paste. Examples of commonly-used organic solvents may include glycol ethers, such as tripropyleneglycol methyl ether, dipropyleneglycol n-propyl ether, dipropyleneglycol n-butyl ether, tripropyleneglycol n-butyl ether, propyleneglycol phenyl ether, diethyleneglycol ethyl ether, diethyleneglycol n-butyl ether, diethyleneglycol hexyl ether, ethyleneglycol hexyl ether, triethyleneglycol methyl ether, triethyleneglycol ethyl ether, triethyleneglycol n-butyl ether, ethyleneglycol phenyl ether, terpineol, Texanol®, ethyleneglycol, and the like.
Examples of the polymer resin may include polyvinylpyrrolidone, polyvinylalcohol, polyethyleneglycol, ethylcellulose, rosin, a phenol resin, an acrylate resin, and the like. The amount of the polymer may be 1 ~ 25 wt%, preferably, 5 ~ 25 wt%, based on the total amount of the organic vehicle solution. When the amount of the polymer resin is below 1 wt%, the printability and dispersion stability of the aluminum paste are deteriorated. Further, the amount thereof is above 25 wt%, the aluminum paste cannot be printed.
As the thixotropic agent and wetting agent, thixotropic agents and wetting agents commonly used in the related field may be used without limitation.
The additive may be a dispersant or the like commonly used in the related field. As the dispersant, commercially available surfactants may be used, and they may be used independently or in combination with each other. Examples of the surfactants may include: nonionic surfactants, such as ethers including alkyl polyoxyethylene ether, alkylaryl polyoxyethylene ether, polyoxyethylene-polyoxypropylene copolymer and the like, ester-ethers including polyoxyethylene ether of glycerin ester, polyoxyethylene ether of sorbitan ester, polyoxyethylene ether of sorbitol ester and the like, esters including polyethylene glycol fatty acid ester, glycerin ester, sorbitan ester, propylene glycol ester, sugar ester, alkyl polyglucoside and the like, and nitrogen-containing surfactants including fatty acid alkanolamide, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine, amine oxide and the like; and polymeric surfactants, such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, polyacrylic acid-maleic acid compolymers, poly-12-hydroxystearic acid and the like.
Examples of commercially available surfactant products may include hypermer KD (manufactured by Uniqema Corp.), AKM 0531 (manufactured by NOF Corp.), KP (manufactured by Shinetsu Kagaku Kogyo Corp.), POLYFLOW (manufactured by Kyoei Kagaku Corp.), EFTOP (manufactured by Tokemu Products Corp.), Asahi guard, Surflon (manufactured by Asahi Glass Corp.), SOLSPERSE (manufactured by Geneka Corp.), EFKA (manufactured by EFKA Chemicals Co., Ltd.), PB 821 (manufactured by Ajinomoto Co., Inc.), BYK-184, BYK-185, BYK-2160, Anti-Terra U (manufactured by BYK Corp.), and the like.
The amount of the dispersant may be 1 ~ 10 wt%, preferably, 1 ~ 5 wt%, based on the total amount of the organic vehicle solution.
The aluminum paste according to the present invention can be easily prepared using a planar mixer which simultaneously rotates and revolves. That is, this aluminum paste can be prepared by putting the above-mentioned components into a planar mixer in the corresponding composition ratio and then stirring for the solids to be properly mixed and dispersed in an organic vehicle solution. The aluminum paste prepared in this way has a viscosity of 20,000 ~ 200,000 cps at 5 rpm when its viscosity was measured at 25℃ using a Brookfield HBDV-III Ultra Rheometer or a spindle CPE-52. Preferably, the aluminum paste may be prepared such that it has a viscosity of 40,000 ~ 100,000 cps.
Further, the present invention provides a method of manufacturing a solar cell, including the step of forming a back electrode using the aluminum paste.
The solar cell manufactured in this way is advantageous in that it does not easily warp, and the minimum amount of aluminum bubbles or bumps are formed in the electrode layer, so that the values of short circuit current (Isc) and open circuit voltage (Voc) are greatly increased, and the efficiency thereof is remarkably improved.
Hereinafter, the present invention will be described in more detail with reference to the following Examples. However, the following Examples are set forth to illustrate the present invention, and the scope of the present invention is not limited thereto. The following Examples can be properly modified by those skilled in the art without departing from the scope of the invention.
Example 1: Preparation of aluminum paste
63 wt% of aluminum powder of D50=4~6㎛ and 7 wt% of aluminum powder of D50=2~4㎛ (4~6㎛ : 2~4㎛ = 9 : 1 (weight ratio), total amount of aluminum powder = 70 wt%), 0.5 wt% of glass frit having a composition ratio given in Table 1 below, and 29.5 wt% of an organic vehicle solution which is prepared by dissolving ethyl cellulose in glycol ether were sequentially mixed with each other to form a mixture, and then the mixture was stirred at a rotation speed of 1000 rpm for 3 minutes using a mixer which simultaneously rotates and revolves to prepare aluminum paste.
Table 1
Components Mol%
Al2O3 6.5%
SrO 5.5%
Bi2O3 26.0%
B2O3 30.0%
SiO2 32.0%
Total 100%
Tg (transition point) 453
Thermal expansion coefficient (10-7/℃ ) 77
Tdsp 507
Example 2: Preparation of aluminum paste
Aluminum paste was prepared in the same manner as in Example 1, except that 42 wt% of aluminum powder of D50=4~6㎛ and 28 wt% of aluminum powder of D50=2~4㎛ (4~6㎛ : 2~4㎛ = 6 : 4 (weight ratio), total amount of aluminum powder = 70 wt%) were added.
Example 3: Preparation of aluminum paste
Aluminum paste was prepared in the same manner as in Example 1, except that 66.5 wt% of aluminum powder of D50=4~6㎛ and 3.5 wt% of aluminum powder of D50=2~4㎛ (4~6㎛ : 2~4㎛ = 9.5 : 0.5 (weight ratio), total amount of aluminum powder = 70 wt%) were added.
Example 4: Preparation of aluminum paste
Aluminum paste was prepared in the same manner as in Example 1, except that 58.5 wt% of aluminum powder of D50=4~6㎛ and 6.5 wt% of aluminum powder of D50=2~4㎛ (4~6㎛ : 2~4㎛ = 9 : 1 (weight ratio), total amount of aluminum powder = 65 wt%) and 34.5 wt% of an organic vehicle solution were added.
Example 5: Preparation of aluminum paste
Aluminum paste was prepared in the same manner as in Example 1, except that 67.5 wt% of aluminum powder of D50=4~6㎛ and 7.5 wt% of aluminum powder of D50=2~4㎛ (4~6㎛ : 2~4㎛ = 9 : 1 (weight ratio), total amount of aluminum powder = 75 wt%) and 24.5 wt% of an organic vehicle solution were added.
Comparative Example 1: Preparation of aluminum paste
Aluminum paste was prepared in the same manner as in Example 1, except that 35 wt% of aluminum powder of D50=4~6㎛ and 35 wt% of aluminum powder of D50=2~4㎛ (4~6㎛ : 2~4㎛ = 5 : 5 (weight ratio), total amount of aluminum powder = 70 wt%) and 29.5 wt% of an organic vehicle solution were added.
Comparative Example 2: Preparation of aluminum paste
Aluminum paste was prepared in the same manner as in Example 1, except that 70 wt% of D50=2~4㎛ and 29.5 wt% of an organic vehicle solution were added.
Test Example: Manufacturing a solar cell and testing characteristics thereof
A monocrystalline silicon wafer having a size of 156 X 156 mm and a thickness of 200 μm was surface-textured such that the height of a pyramid is about 4 ~ 6 μm, and then the N-side of the surface-textured silicon wafer was coated with SiNx. Subsequently, the silicon wafer was printed on the back surface thereof with bus bars and then dried, and then aluminum paste of each of Examples 1 to 5 and Comparative Examples 1 to 2 was applied thereon using a screen printing plate of 250 mesh such that the weight of the aluminum paste was 1.5 ± 0.1 g and then dried. Further, the silicon wafer was printed on the front surface thereof with finger lines using silver paste and then dried.
Subsequently, the silicon wafer that had undergone the above processes was calcined in a continuous infrared furnace such that the temperature of a calcining zone was 720 ~ 900℃, thereby manufacturing a solar cell.
In the calcination process, the front and back surface of the silicon wafer can be simultaneously calcined while passing through a belt furnace. Here, the belt furnace includes a burn-out zone of about 600℃ and a firing zone of 800 ~ 950℃. In this belt furnace, organic matter was removed from the aluminum paste and the silver paste, and then the aluminum paste and silver paste applied on the back surface and front surface of the silicon wafer were melted to form electrodes.
The degree of warpage of the manufactured solar cell was evaluated by matching four edges of the solar cell with the bottom and then measuring to what degree the central portion thereof had been lifted. Further, the occurrence of bumps and aluminum bubbles around an aluminum back electrode was observed with the naked eye, and the number thereof was counted. The results thereof are given in Table 2 below.
The efficiency of the manufactured solar cell was evaluated using an SCM-1000, which is an apparatus for evaluating the performance of solar cells, manufactured by FitTech Corporation. The results thereof are given in Table 3 below.
Table 2
Exp. 1 Exp. 2 Exp. 3 Exp. 4 Exp. 5 Co. Exp. 1 Co. Exp. 2
D50=4~6㎛ : 2~4㎛(weight ratio) 9:1 6:4 9.5:0.5 9:1 9:1 5:5 Only D50= 2~4㎛
Al powder content 70 wt% 70 wt% 70 wt% 65 wt% 75 wt% 70 wt% 70 wt%
Warpage (mm) 0.2-0.3 0.3-0.5 0.1-0.2 0.2-0.3 0.5-0.8 1.5-2.0 2.5-3.0
Number of Bumps 0 1 0 1 - 2 0 1 - 2 10 - 12
Table 3
Exp. 1 Exp. 2 Exp. 3 Exp. 4 Exp. 5 Co. Exp. 1 Co. Exp. 2
Pmax (W) 4.2272 4.15587 4.24815 4.1705 4.25596 3.9002 3.7483
Efficiency (%) 17.691 17.392 17.778 17.453 17.811 16.322 15.687
FF(%) 79.342 78.329 79.194 78.42 79.561 74.73 72.116
Isc 8.5322 8.53653 8.53601 8.53601 8.53651 8.3981 8.3767
Voc 0.6244 0.62152 0.62843 0.62302 0.62667 0.6214 0.6205
Rs 0.00622 0.0074 0.00735 0.00754 0.00697 0.00816 0.00986
※ Pmax = maximum power of solar cell
Isc = short circuit current (A)
Voc = open circuit voltage (V)
Rs = Series Resistance
FF = Fill Factor
Example 6: Control of the printing amount of aluminum paste
The aluminum paste prepared in Example 1 was printed in amounts of 1.0 g, 1.2 g, 1.5 g, 1.8 g and 2.0g while changing printing conditions, and then the printed aluminum paste was analyzed in the same manner as the above-mentioned manner. The results thereof are given in Table 4 below.
Table 4
Printing amount 1.0g 1.2g 1.5g 1.8g 2g
Warpage (mm) 0.1 - 0.2 0.1 - 0.2 0.2 - 0.3 0.3 - 0.5 0.5 - 0.8
Number of Bumps 0 0 0 0 0
Pmax (W) 4.2154 4.22523 4.2272 4.23957 4.2663
Efficiency (%) 17.641 17.683 17.691 17.743 17.854
FF(%) 79.314 79.119 79.342 79.031 79.635
Isc 8.5102 8.53557 8.5322 8.53601 8.53575
Voc 0.6245 0.62565 0.6244 0.62845 0.6276
Rs 0.0063 0.0071 0.00622 0.00755 0.00703
It can be seen from Table 4 that the difference in the efficiency of a solar cell depending on the amount of the printed aluminum paste is not large, and thus sufficient soar cell efficiency can be obtained even when a small amount of aluminum paste is used compared to when about 2 g of aluminum paste, which is the amount of commercial use, is used.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

Claims (7)

  1. Aluminum paste for a back electrode of a solar cell, comprising aluminum powder in which aluminum powder having an average particle size (D50) of 4 ~ 6 μm and aluminum powder having an average particle size (D50) of 2 ~ 4 μm are mixed in a ratio of 6:4 ~ 9.5:0.5 by weight.
  2. The aluminum paste according to claim 1, further comprising glass frit and an organic vehicle solution.
  3. The aluminum paste according to claim 2, which comprises based on the total amount of the aluminum paste; 65 ~ 75 wt% of the aluminum powder; 0.01 ~ 5 wt% of the glass frit; and 20 ~ 34.90 wt% of the organic vehicle solution.
  4. The aluminum paste according to claim 3, wherein the glass frit has a softening point of 400 ~ 600℃.
  5. The aluminum paste according to claim 3, wherein the glass frit is Bi2O3-SiO2-Al2O3-B2O3-SrO.
  6. The aluminum paste according to claim 5, wherein the glass frit comprises 20 ~ 30 mol% of Bi2O3, 5 ~ 15 mol% of Al2O3, 25 ~ 35 mol% of SiO2, 1 ~ 10 mol% of SrO, and 20 ~ 40 mol% of B2O3.
  7. A method of manufacturing a solar cell, comprising a process of forming a back electrode using the aluminum paste of claim 1.
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CN102522142A (en) * 2011-12-28 2012-06-27 彩虹集团公司 Conducting paste for silicon solar cell and preparation method thereof
CN103489502A (en) * 2013-10-18 2014-01-01 南通天盛光伏科技有限公司 Back surface field aluminum paste applied to N type crystalline silicon solar cell and preparation method thereof
CN106448805A (en) * 2016-09-30 2017-02-22 江苏瑞德新能源科技有限公司 Solar aluminum conductor paste and preparation method thereof
US20170166759A1 (en) * 2015-12-15 2017-06-15 National Cheng Kung University Method of Fabricating High-Conductivity Thick-Film Aluminum Paste

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CN103811100A (en) * 2014-01-16 2014-05-21 北京林业大学 Silicon solar cell back-surface field forming aluminum paste and preparation method thereof
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CN102522142A (en) * 2011-12-28 2012-06-27 彩虹集团公司 Conducting paste for silicon solar cell and preparation method thereof
CN103489502A (en) * 2013-10-18 2014-01-01 南通天盛光伏科技有限公司 Back surface field aluminum paste applied to N type crystalline silicon solar cell and preparation method thereof
US20170166759A1 (en) * 2015-12-15 2017-06-15 National Cheng Kung University Method of Fabricating High-Conductivity Thick-Film Aluminum Paste
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