CN110164586B - Organic system for fine line high aspect ratio screen printing pastes - Google Patents
Organic system for fine line high aspect ratio screen printing pastes Download PDFInfo
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- CN110164586B CN110164586B CN201910321257.XA CN201910321257A CN110164586B CN 110164586 B CN110164586 B CN 110164586B CN 201910321257 A CN201910321257 A CN 201910321257A CN 110164586 B CN110164586 B CN 110164586B
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- H01—ELECTRIC ELEMENTS
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- 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
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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
- H01B1/20—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
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- H—ELECTRICITY
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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Abstract
The invention adopts vinyl chloride-vinyl acetate copolymer as a resin system, provides an organic system for screen printing slurry with fine lines and high aspect ratio, and the preparation method comprises the steps of uniformly mixing vinyl chloride-vinyl acetate copolymer with a curing agent, a plasticizer, a leveling agent, a dispersing agent, a thixotropic agent and a solvent, heating and stirring for 0.5-4 hours at 30-90 ℃ to form a uniform and stable mixture, namely the prepared organic system. The conductive paste prepared by the organic system disclosed by the invention has good screen dropping property and excellent plasticity, can be suitable for 430/13 screen printing plates with screen knots with openings of 28 mu m at the lowest, can be suitable for non-screen printing plates with openings of 22 mu m at the lowest, and is excellent in printing property, and printed lines have higher aspect ratio.
Description
Technical Field
The invention relates to the technical field of manufacturing of conductive silver paste for screen printing, in particular to a silicon solar cell, and particularly relates to an organic system for screen printing paste with fine lines and high aspect ratio.
Technical Field
The screen printing process is an important process in the production process of the silicon solar cell, and each electrode is prepared by printing the conductive paste on a silicon wafer by using the screen printing process and sintering the conductive paste. Since screen printing is a line operation, it is required that the paste used maintain stable viscosity, good screen-off property and moldability in continuous and long-term printing.
The conversion rate is the most critical index for evaluating the solar cell, the higher the conversion rate is, the better the conversion rate is, and in various schemes for improving the slurry and the conversion rate, the method for reducing the line width, improving the line height, namely, improving the aspect ratio (electrode thickness/electrode line width) of the line to reduce the series resistance of the cell and improve the short-circuit current is the mainstream. More specifically say, when the lines width of printing reduces, can increase the photic area of battery piece, the high promotion of lines simultaneously can reduce the string of resistance of battery piece, guarantees that the electric current effectively flows to promote the conversion efficiency of battery piece.
In response to the above requirements, manufacturers of solar cells are continuously reducing the width of the fine grid when printing the cell from 35 μm opening to 28 μm, and then to 24 μm opening. With the reduction of the opening of the printing screen, the requirement on the sizing agent is higher and higher. The thinner opening requires the slurry to have good screen dropping performance, otherwise, the screen blocking phenomenon can occur, and the normal production is influenced; the slurry is required to keep a certain viscosity under high-speed printing shearing, and the excessively low viscosity can cause the diffusion phenomenon of the printed line edge to influence the conversion rate; the paste is required to have good plasticity to ensure that the printed lines have enough height, so that the series resistance of the paste is reduced to improve the short-circuit current; meanwhile, the paste is required to have certain leveling property, so that the upper surface of the paste can be automatically leveled after printing is finished, and the phenomenon of fluctuation can not occur, so that the performance of the paste is ensured.
The current conductive paste can not fully meet the requirements, mainly a paste organic system has certain defects, and a large amount of paste uses cellulose systems of different series and different viscosities, so that the viscosity, the shaping property and the lower net property of the paste can not be perfectly balanced. In addition, in the prior art, the vinyl chloride-vinyl acetate copolymer is generally used in halogen low-temperature curing type silver paste, the use process of the silver paste is low-temperature baking curing at 150 ℃, the use process of the crystalline silicon solar silver paste is high-temperature sintering at 780 ℃, the two silver pastes are essentially different, and the low-temperature curing silver paste cannot be used in solar cell production.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a conductive paste organic system suitable for screen printing with fine lines and high aspect ratio by adopting vinyl chloride-vinyl acetate copolymer as a resin system. The conductive paste prepared by the organic system disclosed by the invention has good screen dropping property and excellent plasticity, can be suitable for 430/13 screen printing plates with screen knots with openings of 28 mu m at the lowest, can be suitable for non-screen printing plates with openings of 22 mu m at the lowest, and is excellent in printing property, and printed lines have higher aspect ratio.
The technical scheme of the invention is as follows:
an organic system for fine line high aspect ratio screen printing paste, which consists of the following raw materials in percentage by weight:
0.5 to 3 percent of curing agent
10 to 25 percent of plasticizer
0.1-5% of vinyl chloride-vinyl acetate copolymer
0.1-2% of thixotropic agent
0.1 to 5 percent of dispersant
0.1 to 5 percent of flatting agent
The balance being solvent.
The sum of the amounts of the raw materials of the organic system is 100%.
Preferably, the organic system consists of the following raw materials in percentage by weight:
1 to 2 percent of curing agent
18 to 22 percent of plasticizer
2-4% of vinyl chloride-vinyl acetate copolymer
0.2 to 0.8 percent of thixotropic agent
1 to 3 percent of dispersant
4 to 5 percent of flatting agent
The balance being solvent.
Preferably, the curing agent is one or more of aliphatic amine curing agent, aromatic amine curing agent and amidoamine curing agent; more preferably, the curing agent is one or more of SBN-70D, MF-B60X, MF-K60X, E402-90T, E405-80T, AE700-100, A201H and TPA-B80X.
Preferably, the leveling agent is an organic silicon type leveling agent and/or an acrylate type leveling agent. More preferably, the leveling agent is one or more of BYK-378, BYK-349, BYK-333, BYK-354, BYK-3521, BYK-371, BYK-3520, TEGO-425, TEGO-500 TEGO-440 TEGO-450, DC29, DC51, DC57 and the like
Preferably, the plasticizer is one or more of polyol ester plasticizer, phosphate ester plasticizer, phthalate ester plasticizer and fatty acid ester plasticizer.
Preferably, the thixotropic agent is one or more of hydrogenated castor oil, polyamide modified hydrogenated castor oil, polyamide wax slurry, polyethylene wax slurry, fumed silica and bentonite.
Preferably, the dispersant is a nonionic surfactant; more preferably one or more of tween 20, tween 80, sorbitan ester, alkylphenol polyoxyethylene ether and fatty amine polyoxyethylene ether.
Preferably, the vinyl chloride-vinyl acetate copolymer is one or more of fat-soluble binary vinyl chloride-vinyl acetate copolymer, ternary carboxyl modified vinyl chloride-vinyl acetate copolymer and ternary hydroxyl modified vinyl chloride-vinyl acetate copolymer; more preferably, the vinyl chloride-vinyl acetate copolymer resin is selected from one or more of MLC-20, MLC-14-40, MLC-14-55, YSZ-744, (M) VAM, VMA, VMC, MAVD, MVAH and MVOH.
Preferably, the vinyl acetate content of the vinyl chloride-vinyl acetate copolymer is 1-40, the K value is 30-50, and the average molecular weight is 15000-60000. More preferably, the vinyl acetate content of the vinyl chloride-vinyl acetate copolymer is 15-18, the K value is 32-36, and the average molecular weight is 13000-18000.
Preferably, the solvent is one or more of 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, diethylene glycol butyl ether acetate, dimethyl adipate, terpineol, kerosene, mixed dibasic ester DBE and isophorone, and preferably 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate and dimethyl adipate.
In the technical scheme, the preparation method of the organic system comprises the steps of uniformly mixing the vinyl chloride-vinyl acetate copolymer, the curing agent, the plasticizer, the flatting agent, the dispersing agent, the thixotropic agent and the solvent, and stirring for 0.5-4 hours at the temperature of 30-90 ℃ to obtain the organic system.
The invention discloses an application of the organic system for the screen printing paste with the fine lines and the high aspect ratio in the preparation of the solar cell front silver paste; for example, the solar cell front silver paste can comprise the following raw materials in percentage by weight:
85-91% of silver powder
1.5 to 3.5 percent of glass powder
7-11.5% of an organic system.
Mixing an organic system for fine line high aspect ratio screen printing paste with glass powder to obtain glass paste; and then adding silver powder into the glass paste to obtain the positive silver paste for the solar cell.
According to the invention, the viscosity of the positive silver paste for the solar cell prepared by an organic system of the screen printing paste with the fine line and the high aspect ratio is 270-320 Pa.s, and the fineness is less than 5 mu m.
The specific steps of preparing the solar cell front silver paste by the organic system for the fine line high aspect ratio silk-screen printing paste can be as follows:
(1) preparation of organic systems
Uniformly mixing vinyl chloride-vinyl acetate copolymer with a curing agent, a plasticizer, a leveling agent, a dispersing agent, a thixotropic agent and a solvent, heating and stirring for 0.5-4 hours at the temperature of 30-90 ℃ to form a uniform and stable mixture, namely a prepared organic system;
(2) preparation of glass paste
Taking the organic system prepared in the step (1), adding a certain amount of glass powder into the organic system, fully stirring, and dispersing by using a three-roller machine until the fineness is less than 5 mu m, wherein the paste is pasty, namely the prepared glass paste;
(3) preparation of silver paste
And (3) adding a certain amount of silver powder into the glass paste obtained in the step (2), fully mixing, dispersing to a fineness of less than 5 micrometers by using a three-roll machine to obtain the thin-line high-aspect-ratio screen printing paste for the solar cell, standing for 24 hours, and performing a viscosity test to obtain the paste with a viscosity of 270-320 Pa.s.
The beneficial technical effects of the invention are as follows:
the conventional crystalline silicon solar front silver has the problem that the viscosity, the plasticity and the off-network property are not balanced, and when the viscosity of the slurry is higher and the plasticity is better, the off-network property of the slurry is not good, so that the situations of virtual printing, gourd knots and the like are easy to occur; if the viscosity of the slurry is reduced and the lower net property of the slurry is improved, the poor shaping property of the slurry can be caused, the line height is not enough, the line width is increased, the short-circuit current of the battery piece is too low, the conversion rate is low and the like.
In the low-temperature curing silver halide paste, the vinyl chloride-vinyl acetate resin is commonly added as a component for reducing the resistance and improving the curing effect, but the use of the vinyl chloride-vinyl acetate resin in the front silver paste of the crystalline silicon solar cell has never been reported. The vinyl chloride-vinyl acetate copolymer prepared by the method has good screening performance, can recover well after being sheared, can ensure the plasticity of the sizing agent and have a certain lubricating effect, can improve the screening performance of the sizing agent, and can ensure the smoothness of the upper surface of the sizing agent after being printed. Compared with the prior art, the grid line printed by the conductive paste prepared by the organic system disclosed by the invention has good plasticity, the height-width ratio of the sintered silver line is improved, the collapse of the sintered silver line is reduced, the occupied light receiving area is further reduced, and the conversion efficiency of the cell is improved.
Drawings
FIG. 1 is a diagram of an embodiment printed line;
fig. 2 is a comparative example printed line.
Detailed Description
The present invention will be described in detail with reference to examples.
In this example, the curing agent was produced by Asahi Kasei corporation, the leveling agent was produced by Bick Germany, and the vinyl chloride-vinyl acetate copolymer was produced by Pangao chemical Co. The organic system based on the vinyl chloride-vinyl acetate copolymer disclosed by the invention has high cohesiveness and shaping characteristics, can maintain line width, prevents lines from diffusing and collapsing, has good application performance in high-precision crystalline silicon solar front silver paste, and can realize high-precision printing due to good shaping and printing characteristics of the solar front silver paste prepared by using the vinyl chloride-vinyl acetate copolymer.
The front silver paste of the embodiment and the comparative proportion is printed on the passivation layer on the front surface of the solar cell silicon wafer to form a main grid and a fine grid through a screen printing process, the main grid and the fine grid are sintered in an infrared tunnel sintering process after being dried at 300 ℃, and the sintering peak temperature is 780 ℃, the time is 3s when being higher than 700 ℃, and the time is 7s when being higher than 600 ℃. And volatilizing the solvent in the slurry in a drying stage, decomposing and burning out other organic matters at a high-temperature stage, melting and hardening the glass powder and the silver powder in the slurry, burning through the passivation layer, forming good ohmic contact with the PN junction of the silicon wafer, and finally preparing and forming the solar cell.
Example 1
An organic system for fine line high aspect ratio screen printing pastes, the preparation method comprising the steps of:
according to parts by weight, 3 parts of VMA vinyl chloride-vinyl acetate copolymer (vinyl acetate content of vinyl chloride-vinyl acetate copolymer is 17, K value is 32-34, average molecular weight is 15000), 1.5 parts of SBN-70D curing agent, 20 parts of dibutyl phthalate, 5 parts of BYK-378 leveling agent, 0.5 part of polyamide wax, 2 parts of Tween 80, 45 parts of 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate and 23 parts of dimethyl adipate are mixed, heated and stirred for 30min at 60 ℃ to prepare a uniform and transparent solution, namely an organic system.
Comparative example 1
The preparation method of the conductive paste using the conventional ethyl cellulose resin comprises the following steps:
according to parts by weight, 3 parts of ethyl cellulose N200, 1.5 parts of SBN-70D curing agent, 20 parts of dibutyl phthalate, 5 parts of BYK-378 flatting agent, 0.5 part of polyamide wax, 2 parts of Tween 80, 45 parts of 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate and 23 parts of dimethyl adipate are mixed and heated and stirred for 30min at the temperature of 60 ℃ to prepare a uniform and transparent solution, namely an organic system is prepared.
Preparing the solar cell front silver paste:
(1) preparation of glass paste
According to the parts by weight, 1 part of glass powder with D50 of 1.0 mu m and Tg point of 300 ℃ is uniformly dispersed on a dispersion machine together with 4.26 parts of organic system prepared in the embodiment or the comparative example, and then the mixture is rolled on a three-roller machine to the fineness of below 5 mu m to prepare glass slurry;
(2) preparation of silver paste
Taking 88 parts of silver powder with D50 of 1.8 mu m and tap density of 5.7g/ml and 12 parts of glass slurry prepared in the step (1) according to parts by weight, uniformly dispersing on a dispersion machine, and then rolling on a three-roller machine until the fineness is below 5um to obtain the fine line high aspect ratio silk-screen printing slurry for the solar cell; the prepared silver paste is placed for 24h and then subjected to viscosity test, and the performance data of the final silver paste is shown in table 1.
And (3) testing:
performing rheological test on silver paste prepared by the organic systems in the embodiment 1 and the comparative example 1 on a rheometer (anti-paar/MCR 102, 25 ℃), performing conventional screen printing on a screen printing machine to manufacture a solar cell, performing electrical performance test on the manufactured cell on an I/V tester, and observing the grid line condition of the cell under a laser microscope; meanwhile, the comparison of the existing commercially available silver paste is given; the test data are shown in table 1.
TABLE 1 Performance data
As can be seen from the data in the above table, the difference between the example 1 and the comparative example 1 is only the resin used, and the formulation of the present invention can improve the plasticity of the slurry, so that the slurry has a more three-dimensional and full line, specifically, the short circuit current in the example 1 is significantly higher than that in the comparative example, and the open voltage of the slurry is also slightly higher, so that the final conversion rate is significantly higher than that in the comparative example. 3D scanning is carried out on the fine grid through a laser electron microscope, and the fact that lines of the embodiment are obviously fuller, the line height is higher, the upper surface of the lines is smoother, the line type is better is found, and the figure 1 and the comparative figure 2 are shown.
The conductive paste prepared by the invention has good screen-off performance and excellent plasticity, and when the conductive paste is printed on a conventional screen printing plate with screen knots of 430-13-28 mu m, the screen-off performance is good, no broken line exists, the upper edge of a line is flat, and the line shape is good. Good printing can be realized when the printing is carried out on a 400-16-22 mu m non-mesh-junction screen printing plate, no broken grids exist, the line shape is good, but the comparative example cannot pass through the mesh under the limit printing condition, the fine grids of the battery piece are seriously printed, and the EL broken grids are more.
Claims (3)
1. An organic system for fine line high aspect ratio screen printing paste, characterized in that the organic system is composed of the following raw materials by weight percent:
1.5 percent of curing agent
20 percent of plasticizer
Vinyl chloride-vinyl acetate copolymer 3%
0.5 percent of thixotropic agent
2 percent of dispersant
5 percent of flatting agent
The balance being solvent
The vinyl chloride-vinyl acetate copolymer resin is one or more of fat-soluble binary vinyl chloride-vinyl acetate copolymer resin, ternary carboxyl modified vinyl chloride-vinyl acetate copolymer resin and ternary hydroxyl modified vinyl chloride-vinyl acetate copolymer resin; the plasticizer is one or more of polyol ester plasticizer, phosphate plasticizer, phthalate plasticizer and fatty acid ester plasticizer; the thixotropic agent is one or more of hydrogenated castor oil, polyamide modified hydrogenated castor oil, polyamide wax slurry, polyethylene wax slurry, fumed silica and bentonite; the dispersing agent is a nonionic surfactant; the solvent is one or more of 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, diethylene glycol butyl ether acetate, dimethyl adipate, terpineol, kerosene, mixed dibasic ester DBE and isophorone.
2. An organic system for fine line high aspect ratio screen printing pastes according to claim 1, characterised in that the curing agent is one or more of aliphatic amine curing agents, aromatic amine curing agents, amidoamine curing agents; the leveling agent is an organic silicon type leveling agent and/or an acrylate type leveling agent.
3. An organic system for fine line high aspect ratio screen printing pastes according to claim 1, characterized in that the vinyl acetate content of the vinyl chloride-vinyl acetate resin is 1 to 40, the K-value is 30 to 50 and the average molecular weight is 15000 to 60000.
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| CN113571228A (en) * | 2021-07-02 | 2021-10-29 | 浙江晶科新材料有限公司 | Front conductive silver paste for crystalline silicon solar cell and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106887270A (en) * | 2017-03-16 | 2017-06-23 | 无锡晶睿光电新材料有限公司 | A kind of depth-width ratio solar energy front side silver paste high and preparation method thereof |
| CN107240436A (en) * | 2017-06-30 | 2017-10-10 | 北京市合众创能光电技术有限公司 | A kind of PERC crystal silicon solar energy batteries positive silver paste and preparation method thereof |
| CN109509568A (en) * | 2017-12-29 | 2019-03-22 | 太原氦舶新材料有限责任公司 | A kind of high-performance conductive silver paste |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106887270A (en) * | 2017-03-16 | 2017-06-23 | 无锡晶睿光电新材料有限公司 | A kind of depth-width ratio solar energy front side silver paste high and preparation method thereof |
| CN107240436A (en) * | 2017-06-30 | 2017-10-10 | 北京市合众创能光电技术有限公司 | A kind of PERC crystal silicon solar energy batteries positive silver paste and preparation method thereof |
| CN109509568A (en) * | 2017-12-29 | 2019-03-22 | 太原氦舶新材料有限责任公司 | A kind of high-performance conductive silver paste |
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