CN102568648B - Conductive silver paste and preparation method thereof - Google Patents
Conductive silver paste and preparation method thereof Download PDFInfo
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- CN102568648B CN102568648B CN201110450403.2A CN201110450403A CN102568648B CN 102568648 B CN102568648 B CN 102568648B CN 201110450403 A CN201110450403 A CN 201110450403A CN 102568648 B CN102568648 B CN 102568648B
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- silver paste
- conductive silver
- compound
- zinc oxide
- indium compound
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Abstract
The invention discloses conductive silver paste, which comprises conventional conductive silver paste added with zinc oxide and indium compounds. The conductive silver paste has better viscosity coefficient, good mesh permeability after screening, optimal height-width ratio after printing, smaller serial resistance Rs after sintering, and can improve the conversion efficiency of a battery. The invention further discloses a preparation method of the conductive silver paste. The method comprises the following steps: adding zinc oxide and indium compounds according to the dosage in the conventional conductive silver paste; heating to 40-60 DEG C; and mixing uniformly to obtain the conductive silver paste. The preparation method has simple process, low investment in equipment, relatively lower cost of materials, high production rate and rapid volume production, and is appropriate for industrialized large scale production.
Description
Technical field
The invention belongs to technical field of solar cells, be specifically related to a kind of conductive silver paste and preparation method thereof.
Background technology
Solar cell is a kind of solid state device that utilizes semiconductor P-N junction photovoltaic effect transform light energy to be become to electric energy, have another name called photovoltaic device, mainly by mixing 5 valency element phosphors (Phosphors) and relying on the N type semiconductor of a large amount of electron conductions, and mix 3 valency element borons (Boron) and rely on the P type semiconductor of hole conduction to form, its interface is firm knot, is the significant components of crystal silicon solar batteries system.After be made as and reduce the whole battery surface of reflection and will cover one deck special anti-reflective film.Conventionally N type semiconductor surface is furnished with very thin metal grid lines, and another side is close to P type silicon, is conductive silver paste but make this metal grid lines important materials, and the design of conductive silver paste is to silk-screen, and sintering process and conversion efficiency have significant impact.The stock of single crystal silicon solar cell is that purity reaches 0.999999, the p type single crystal silicon of resistivity more than 10 Europe centimetre; comprise the parts such as p-n junction, electrode (front and back) and anti-reflective film; assembly is being subject to plane of illumination to add printing opacity cover plate (as quartz or ooze cerium glass) protection, prevents that battery is subject to the radiation damage of high energy electron and proton in the Van Allen belt of outer space.
Want towards efficient solar battery designer trends in conventional batteries structure at present, major part is that diffused sheet resistance is improved, increase front gate line quantity and reduce the directions such as grid line width, (>78 bar grid line under the condition of novel screen printing screens design, live width 50 μ m), when existing conductive silver paste technology exists silk screen printing, mesh permeability is not good, depth-width ratio not ideal enough (slightly print or subside), after sintering, series resistance Rs too high (not good with diffusion high square resistance matching), causes affecting battery conversion efficiency.
Summary of the invention
The object of the present invention is to provide a kind of conductive silver paste, this conductive silver paste has preferably viscosity coefficient (S.T.I.5 ~ 6), when silk-screen, mesh permeability is good, depth-width ratio (grid line height and the width ratio after printing, be the bigger the better) more excellent, after sintering, series resistance Rs is less, can promote the conversion efficiency of battery.
The present invention also aims to provide the preparation method of above-mentioned conductive silver paste, this preparation method's technique is simple, and equipment investment is few, and cost of material is relatively low, and productivity ratio is high, and volume production is fast applicable to large-scale industrialization and produces.
First object of the present invention is achieved by the following technical solution: a kind of conductive silver paste, comprise conductive silver paste, and in conductive silver paste, be also added with zinc oxide and contain indium compound.
Wherein conventional conductive silver paste of the present invention refers to the solar cell conductive silver paste conventionally adopting in commercially available conductive silver paste or this area, conventionally contain argent particulate, glass, resin, organic solvent (as dispersant, polymerizer etc.), and other additives etc.
Of the present invention is G containing indium compound
3b (Al (C
2h
5o
7)
3), it allocates acquisition by the following method, gets containing the raw material of element boron B, gallium Ga, indium In and thallium Tl and evenly mixes, and obtains product with compound G
3b represents, the raw material of aluminiferous metals particulate is evenly mixed with absolute ethyl alcohol, obtains product with compd A l (C
2h
5o
7)
3represent, by compound G
3b adds compd A l (C
2h
5o
7)
3in, after mixing, staticly settle, 300 ~ 600 ℃ of heating, make containing indium compound G
3b (Al (C
2h
5o
7)
3).
Wherein containing indium compound G
3b (Al (C
2h
5o
7)
3) design parameter as shown in Table 1 below, its preparation method is as follows: G
3b: according to the raw material that sequentially adds each component containing boron, gallium Ga, indium In and thallium Tl in component list 1, mix and prepare G
3b; Aluminiferous metals particulate and absolute ethyl alcohol are mixed to rear acquisition Al (C
2h
5o
7)
3, G3B is added to Al (C
2h
5o
7)
3, mix, staticly settle, after regulating temperature to be 300 ~ 600 ℃ of heating, make containing indium compound G
3b (Al (C
2h
5o
7)
3).
Table 1 G
3b (Al (C
2h
5o
7)
3) component list
Wherein of the present invention containing indium compound G
3b (Al (C
2h
5o
7)
3) middle compound G
3the weight percentage of B is preferably 10 ~ 30%, described Al (C
2h
5o
7)
3weight percentage be preferably 70 ~ 90%.
Zinc oxide of the present invention preferably accounts for 3 ~ 5% of conductive silver paste gross mass, and the described indium compound that contains preferably accounts for 1 ~ 3% of conductive silver paste gross mass.
Second object of the present invention is achieved by the following technical solution: the preparation method of above-mentioned conductive silver paste, and in conventional conductive silver paste, add zinc oxide and containing indium compound, be heated to 40 ~ 60 ℃ by above-mentioned consumption, mix and obtain conductive silver paste.
Heating of the present invention preferably adopts magnetic control agitating heating method.
Compared with prior art, tool of the present invention has the following advantages: the present invention utilizes zinc oxide and good physics and the chemical property of indium compound, has prepared the conductive silver paste with ladder degree, can promote the selective collection rate to charge carrier, reduces complex centre and forms; Effectively reduce sheet resistor, changed conductive silver paste viscosity and changed; The current viscosity STI of conductive silver paste, 5 ~ 6 better (STI is the ratio that silver is starched the viscosity numerical value obtaining in 1rpm and 10rpm), has increased silk-screen and sintering process window.
Embodiment
embodiment 1
The conductive silver paste that the present embodiment provides, comprise conventional conductive silver paste, in conventional conductive silver paste, also contain zinc oxide and contain indium compound, wherein the consumption of zinc oxide accounts for 3% of conventional conductive silver paste gross mass, consumption containing indium compound accounts for 3% of conductive silver paste gross mass, is G containing the molecular formula of indium compound
3b (Al (C
2h
5o
7)
3), it prepares by the following method: be about 1:3:3:3 with mol ratio and get the raw material containing element boron B, gallium Ga, indium In and thallium Tl, after evenly mixing, the product of acquisition is with compound G
3b represents, wherein boron, gallium Ga, indium In and thallium Tl can be simple substance form, also can be the forms such as compound or mixture (lower same), the product obtaining after the raw material of aluminiferous metals particulate is probably evenly mixed as 1:2 ~ 4 take mol ratio with absolute ethyl alcohol be with compd A l (C
2h
5o
7)
3represent compd A l (C
2h
5o
7)
3preparation process with reference to the preparation of method in document " Magnetic Behavior of Carbon-Metal Nanocomposites " (Solid State Phenomena (Volumes 168-169 (2011) pp349-352)) (lower with), by compound G
3b adds compd A l (C
2h
5o
7)
3in, after mixing, staticly settle, 300 ℃ of heating, make containing indium compound G
3b (Al (C
2h
5o
7)
3), wherein containing indium compound G
3b (Al (C
2h
5o
7)
3) middle compound G
3the weight percentage of B is 10%, described Al (C
2h
5o
7)
3weight percentage be 90%.
Above-mentioned conductive silver paste prepares by the following method: in conventional conductive silver paste, add zinc oxide and contain indium compound by above-mentioned consumption, magnetic control is heated with stirring to 60 ℃, mixes and obtains conductive silver paste.
The coefficient correlation of the conductive silver paste of making is as following table 2, as can be seen from Table 2: adding the zinc oxide of significant proportion and containing after indium compound, conductive silver paste solid content (S.C.) can be controlled in 85 ~ 90%, viscosity coefficient is in STI5 ~ 6, so condition can obtain lower sheet resistor after high temperature sintering (768 ℃ of@), even increase sintering time by approximately 25 seconds, also can be controlled in preferred range, so just can expand the process window (temperature of sintering, time tuning range increases), and general silver slurry was at the sheet resistor approximately 20 of 6 seconds; The sheet resistor of 25 seconds is about 50, and general cell front side silver paste peak temperature sintering process is for continuing 3 ~ 5 seconds, and string resistance is about 2.0 ~ 2.5 mohm.
The coefficient correlation of table 2 conductive silver paste
[0018] embodiment 2
The conductive silver paste that the present embodiment provides, comprise conventional conductive silver paste, in conventional conductive silver paste, also contain zinc oxide and contain indium compound, wherein the consumption of zinc oxide accounts for 5% of conventional conductive silver paste gross mass, consumption containing indium compound accounts for 1% of conductive silver paste gross mass, is wherein G containing the molecular formula of indium compound
3b (Al (C
2h
5o
7)
3), it allocates acquisition by the following method, is about 1:3:3:3 gets element boron B, gallium Ga, indium In and thallium Tl with mol ratio, mixes, and product is with compound G
3b represents, aluminum metal particulate and absolute ethyl alcohol are mixed, and the mol ratio of the two is probably 1:2 ~ 4, obtains product with compd A l (C
2h
5o
7)
3represent, by compound G
3b adds compd A l (C
2h
5o
7)
3in, after mixing, staticly settle, 600 ℃ of heating, make containing indium compound G
3b (Al (C
2h
5o
7)
3, its concrete preparation process can be consulted embodiment 1, wherein containing indium compound G
3b (Al (C
2h
5o
7)
3) middle compound G
3the weight percentage of B is 20%, compd A l (C
2h
5o
7)
3weight percentage be 80%.
Above-mentioned conductive silver paste prepares by the following method: in conventional conductive silver paste, add zinc oxide and containing indium compound, adopt magnetic control to be heated to 40 ℃ by above-mentioned consumption, mix and obtain conductive silver paste.
embodiment 3
The conductive silver paste that the present embodiment provides, comprise conventional conductive silver paste, in conventional conductive silver paste, also contain zinc oxide and contain indium compound, wherein the consumption of zinc oxide accounts for 4% of conventional conductive silver paste gross mass, consumption containing indium compound accounts for 2% of conductive silver paste gross mass, is wherein G containing the molecular formula of indium compound
3b (Al (C
2h
5o
7)
3), it prepares by the following method: be about 1:3:3:3 with mol ratio and get element boron B, gallium Ga, indium In and thallium Tl, mix, product is with compound G
3b represents, aluminum metal particulate and absolute ethyl alcohol are mixed, and the mol ratio of the two is probably 1:2 ~ 4, obtains product with compd A l (C
2h
5o
7)
3represent, by compound G
3b adds compd A l (C
2h
5o
7)
3in, after mixing, staticly settle, 450 ℃ of heating, make containing indium compound G
3b (Al (C
2h
5o
7)
3), its concrete preparation process can be consulted embodiment 1, wherein containing indium compound G
3b (Al (C
2h
5o
7)
3) middle compound G
3the weight percentage of B is 30%, compd A l (C
2h
5o
7)
3weight percentage be 70%.
Above-mentioned conductive silver paste prepares by the following method: in conventional conductive silver paste, add zinc oxide and containing indium compound, adopt magnetic control agitating heating method that conductive silver paste is heated to 50 ℃ by above-mentioned consumption, mix and obtain conductive silver paste.
The present invention will be described more than to enumerate specific embodiment.It is pointed out that above-described embodiment, only for the invention will be further described, does not represent protection scope of the present invention, nonessential modification and adjustment that other people prompting according to the present invention is made, still belong to protection scope of the present invention.
Claims (2)
1. a conductive silver paste, comprises conventional conductive silver paste, it is characterized in that: in conventional conductive silver paste, be also added with zinc oxide and contain indium compound, described is G containing indium compound
3b (Al (C
2h
5o
7)
3), it allocates acquisition by the following method, gets containing the raw material of element boron B, gallium Ga, indium In and thallium Tl and evenly mixes, and obtains product with compound G
3b represents, the raw material of aluminiferous metals particulate is evenly mixed with absolute ethyl alcohol, obtains product with compd A l (C
2h
5o
7)
3represent, by compound G
3b adds compd A l (C
2h
5o
7)
3in, after mixing, staticly settle, 300 ~ 600 ℃ of heating, make containing indium compound G
3b (Al (C
2h
5o
7)
3; Described containing indium compound G
3b (Al (C
2h
5o
7)
3middle compound G
3the weight percentage of B is 10 ~ 30%, compd A l (C
2h
5o
7)
3weight percentage be 70 ~ 90%.
2. conductive silver paste according to claim 1, is characterized in that: described zinc oxide accounts for 3 ~ 5% of conductive silver paste gross mass, and the described indium compound that contains accounts for 1 ~ 3% of conductive silver paste gross mass.
3. the preparation method of conductive silver paste claimed in claim 2, is characterized in that: in conventional conductive silver paste, add zinc oxide and containing indium compound, be heated to 40 ~ 60 ℃ by above-mentioned consumption, mix and obtain conductive silver paste.
4. the preparation method of conductive silver paste according to claim 3, is characterized in that: add thermal recovery magnetic control agitating heating method.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110450403.2A CN102568648B (en) | 2011-12-29 | 2011-12-29 | Conductive silver paste and preparation method thereof |
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|---|---|---|---|
| CN201110450403.2A CN102568648B (en) | 2011-12-29 | 2011-12-29 | Conductive silver paste and preparation method thereof |
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| CN102568648A CN102568648A (en) | 2012-07-11 |
| CN102568648B true CN102568648B (en) | 2014-06-18 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016205602A1 (en) * | 2015-06-19 | 2016-12-22 | Sun Chemical Corporation | A silver paste and its use in semiconductor devices |
| CN109364850A (en) * | 2018-11-19 | 2019-02-22 | 衡阳思迈科科技有限公司 | The production equipment of conductive silver paste |
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| CN101620939B (en) * | 2008-07-02 | 2011-09-28 | 比亚迪股份有限公司 | Semiconductor electrode, preparation method thereof and solar cell comprising semiconductor electrode |
| JP5236400B2 (en) * | 2008-09-04 | 2013-07-17 | 太陽ホールディングス株式会社 | Conductive paste and electrode using the same |
| CN102054882B (en) * | 2009-10-29 | 2012-07-18 | 上海宝银电子材料有限公司 | Conductive silver paste with grid electrode front of crystalline silicon solar cell and preparation method |
| CN102262940A (en) * | 2011-07-19 | 2011-11-30 | 彩虹集团公司 | Method for preparing rear silver slurry used for crystalline silicon solar battery |
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Address after: No. 69, C District, Leping Town Industrial Park, Sanshui, Foshan, Guangdong Patentee after: Guangdong Asahi Polytron Technologies Inc Address before: 528137 Qi Li No. 69, C District, Sanshui Industrial Park, Leping Town, Foshan City, Guangdong Patentee before: Guangdong Aiko Solar Energy Technology Co., Ltd. |