CN102568648A - Conductive silver paste and preparation method thereof - Google Patents
Conductive silver paste and preparation method thereof Download PDFInfo
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- CN102568648A CN102568648A CN2011104504032A CN201110450403A CN102568648A CN 102568648 A CN102568648 A CN 102568648A CN 2011104504032 A CN2011104504032 A CN 2011104504032A CN 201110450403 A CN201110450403 A CN 201110450403A CN 102568648 A CN102568648 A CN 102568648A
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- conductive silver
- silver paste
- 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 to become transform light energy 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, it is firm knot at the interface, is the significant components of crystal silicon solar batteries system.After be made as and reduce reflection entire cell surface and will cover the special anti-reflective film of one deck.Usually the 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 yet 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 remarkable influence.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 parts such as p-n junction, electrode (front and back) and anti-reflective film; Assembly is then receiving plane of illumination to add printing opacity cover plate (as quartzy or ooze cerium glass) protection, prevents that battery receives the radiation damage of high energy electron and proton in the Van Allen belt of outer space.
Desire towards the efficient solar battery designer trends in the conventional batteries structure at present; Most of is that the resistance of the side of diffusion is improved; Increase directions such as front gate line quantity and minimizing grid line width, (> 78 grid lines under the condition of novel screen printing screens design, live width 50 μ m); The mesh permeability was not good when there was silk screen printing in existing conductive silver paste technology; Depth-width ratio not ideal enough (slightly print or subside), series resistance Rs too high (not good with diffusion high square resistance matching) causes influencing battery conversion efficiency behind the sintering.
Summary of the invention
The object of the present invention is to provide a kind of conductive silver paste; This conductive silver paste has preferable viscosity coefficient (S.T.I.5 ~ 6); The mesh permeability is good during silk-screen, and printing back depth-width ratio (grid line height and the width ratio is the bigger the better) is more excellent; Series resistance Rs is less behind the sintering, 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 technology is simple, and equipment investment is few, and cost of material is relatively low, and productivity ratio is high, and volume production is applicable to large-scale industrialization production fast.
First purpose of the present invention realizes through following technical scheme: a kind of conductive silver paste, comprise conductive silver paste, and in conductive silver paste, also be added with zinc oxide and contain indium compound.
Conventional conductive silver paste wherein of the present invention refers to that the common solar cell that adopts is used conductive silver paste in commercially available conductive silver paste or this area; Usually contain argent particulate, glass, resin, organic solvent (like dispersant; And other additives etc. polymerizer etc.).
The indium compound that contains according to the invention is G
3B (Al (C
2H
5O
7)
3), it obtains through following method allotment, gets the raw material that contains element boron B, gallium Ga, indium In and thallium Tl and evenly mixes, and obtains product with compound G
3B representes, the raw material of aluminiferous metals particulate is evenly mixed with absolute ethyl alcohol, obtains product with compd A l (C
2H
5O
7)
3Expression is with compound G
3B adds compd A l (C
2H
5O
7)
3In, staticly settle behind the mixing, 300 ~ 600 ℃ of heating, process and contain indium compound G
3B (Al (C
2H
5O
7)
3).
Wherein contain indium compound G
3B (Al (C
2H
5O
7)
3) shown in concrete parameter such as the following table 1, its preparation method is following: G
3B: contain the raw material of boron, gallium Ga, indium In and thallium Tl according to adding each component in the component list 1 in regular turn, mixing prepares G
3B; With obtaining Al (C behind aluminiferous metals particulate and the absolute ethyl alcohol mixing
2H
5O
7)
3, G3B is added Al (C
2H
5O
7)
3, mix, staticly settle, regulate after temperature is 300 ~ 600 ℃ of heating, process and contain indium compound G
3B (Al (C
2H
5O
7)
3).
Table 1 G
3B (Al (C
2H
5O
7)
3) component list
The indium compound G that contains wherein according to the invention
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 according to the invention preferably accounts for 3 ~ 5% of conductive silver paste gross mass, and the said indium compound that contains preferably accounts for 1 ~ 3% of conductive silver paste gross mass.
Second purpose of the present invention realizes through following technical scheme: the preparation method of above-mentioned conductive silver paste, and in conventional conductive silver paste, add zinc oxide and contain indium compound by above-mentioned consumption, be heated to 40 ~ 60 ℃, mixing promptly obtains conductive silver paste.
Magnetic control agitating heating method is preferably adopted in heating according to the invention.
Compared with prior art, the present invention has following advantage: 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 the complex centre and forms; Effectively reduce sheet resistor, changed the conductive silver paste viscosity and changed; The present viscosity STI of conductive silver paste has increased silk-screen and sintering process window 5 ~ 6 preferable (STI starches the ratio of the viscosity numerical value that in 1rpm and 10rpm, obtains for silver).
Embodiment
Embodiment 1
The conductive silver paste that 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, and the consumption that contains indium compound accounts for 3% of conductive silver paste gross mass, and the molecular formula that contains indium compound is G
3B (Al (C
2H
5O
7)
3), it prepares through following method: be about 1:3:3:3 with mol ratio and get the raw material that contains element boron B, gallium Ga, indium In and thallium Tl, after evenly mixing, the product of acquisition is with compound G
3B representes; Wherein boron, gallium Ga, indium In and thallium Tl can be the simple substance form; Also can be forms such as compound or mixture (down with), probably be that the product of acquisition after evenly mix 1:2 ~ 4 is with compd A l (C with the raw material of aluminiferous metals particulate and absolute ethyl alcohol with mol ratio
2H
5O
7)
3Expression, compd A l (C
2H
5O
7)
3Prepared process with reference to the method preparation among document " Magnetic Behavior of Carbon-Metal Nanocomposites " (Solid State Phenomena (Volumes 168-169 (2011) pp349-352)) (down with), with compound G
3B adds compd A l (C
2H
5O
7)
3In, staticly settle behind the mixing, 300 ℃ of heating, process and contain indium compound G
3B (Al (C
2H
5O
7)
3), wherein contain 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 through 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 ℃, and mixing promptly obtains conductive silver paste.
The coefficient correlation of the conductive silver paste of processing such as following table 2; From table 2, can find out: at the zinc oxide that adds significant proportion and after containing indium compound, conductive silver paste solid content (S.C.) can be controlled in 85 ~ 90%, and viscosity coefficient is in STI5 ~ 6; So condition can obtain lower sheet resistor behind high temperature sintering (768 ℃); Even increase sintering time by about 25 seconds, and also can be controlled in the preferred range, so just can enlarge the process window (temperature of sintering; The time tuning range increases), and general silver slurry is at 6 seconds sheet resistor about 20; 25 seconds sheet resistor is about 50, and general cell front side silver paste peak temperature sintering process is for continuing 3 ~ 5 seconds, and the string resistance is about 2.0 ~ 2.5 mohm.
The coefficient correlation of table 2 conductive silver paste
Embodiment 2
The conductive silver paste that 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, and the consumption that contains indium compound accounts for 1% of conductive silver paste gross mass, and the molecular formula that wherein contains indium compound is G
3B (Al (C
2H
5O
7)
3), it obtains through following method allotment, and be about 1:3:3:3 with mol ratio and get element boron B, gallium Ga, indium In and thallium Tl, mixing, product is with compound G
3B representes that with aluminum metal particulate and absolute ethyl alcohol mixing, the mol ratio of the two probably is 1:2 ~ 4, obtains product with compd A l (C
2H
5O
7)
3Expression is with compound G
3B adds compd A l (C
2H
5O
7)
3In, staticly settle behind the mixing, 600 ℃ of heating, process and contain indium compound G
3B (Al (C
2H
5O
7)
3, it specifically prepares process can consult embodiment 1, wherein contains 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 through following method: in conventional conductive silver paste, add zinc oxide and contain indium compound by above-mentioned consumption, adopt magnetic control to be heated to 40 ℃, mixing promptly obtains conductive silver paste.
Embodiment 3
The conductive silver paste that 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, and the consumption that contains indium compound accounts for 2% of conductive silver paste gross mass, and the molecular formula that wherein contains indium compound is G
3B (Al (C
2H
5O
7)
3), it prepares through following method: is about 1:3:3:3 with mol ratio and gets element boron B, gallium Ga, indium In and thallium Tl, and mixing, product is with compound G
3B representes that with aluminum metal particulate and absolute ethyl alcohol mixing, the mol ratio of the two probably is 1:2 ~ 4, obtains product with compd A l (C
2H
5O
7)
3Expression is with compound G
3B adds compd A l (C
2H
5O
7)
3In, staticly settle behind the mixing, 450 ℃ of heating, process and contain indium compound G
3B (Al (C
2H
5O
7)
3), it specifically prepares process can consult embodiment 1, wherein contains 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 through following method: in conventional conductive silver paste, add zinc oxide and contain indium compound by above-mentioned consumption, adopt magnetic control agitating heating method that conductive silver paste is heated to 50 ℃, mixing promptly obtains conductive silver paste.
The present invention will be described more than to enumerate specific embodiment.It is pointed out that the foregoing description only is used for the present invention is described further, do 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 (6)
1. a conductive silver paste comprises conventional conductive silver paste, it is characterized in that: in conventional conductive silver paste, also be added with zinc oxide and contain indium compound.
2. conductive silver paste according to claim 1 is characterized in that: the said indium compound that contains is G
3B (Al (C
2H
5O
7)
3), it obtains through following method allotment, gets the raw material that contains element boron B, gallium Ga, indium In and thallium Tl and evenly mixes, and obtains product with compound G
3B representes, the raw material of aluminiferous metals particulate is evenly mixed with absolute ethyl alcohol, obtains product with compd A l (C
2H
5O
7)
3Expression is with compound G
3B adds compd A l (C
2H
5O
7)
3In, staticly settle behind the mixing, 300 ~ 600 ℃ of heating, process and contain indium compound G
3B (Al (C
2H
5O
7)
3).
3. conductive silver paste according to claim 2 is characterized in that: the said indium compound G that contains
3B (Al (C
2H
5O
7)
3) middle compound G
3The weight percentage of B is 10 ~ 30%, compd A l (C
2H
5O
7)
3Weight percentage be 70 ~ 90%.
4. according to claim 1 or 2 or 3 described conductive silver pastes, it is characterized in that: said zinc oxide accounts for 3 ~ 5% of conductive silver paste gross mass, and the said indium compound that contains accounts for 1 ~ 3% of conductive silver paste gross mass.
5. the preparation method of the described conductive silver paste of claim 4 is characterized in that: in conventional conductive silver paste, add zinc oxide and contain indium compound by above-mentioned consumption, be heated to 40 ~ 60 ℃, mixing promptly obtains conductive silver paste.
6. the preparation method of conductive silver paste according to claim 5 is characterized in that: add thermal recovery magnetic control agitating heating method.
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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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|---|---|---|---|
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| CN102568648B CN102568648B (en) | 2014-06-18 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107683532A (en) * | 2015-06-19 | 2018-02-09 | 太阳化学公司 | Silver paste and its application in the semiconductor device |
| 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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| CN101620939A (en) * | 2008-07-02 | 2010-01-06 | 比亚迪股份有限公司 | Semiconductor electrode, preparation method thereof and solar cell comprising semiconductor electrode |
| CN101667515A (en) * | 2008-09-04 | 2010-03-10 | 太阳油墨制造株式会社 | Conductive paste agent and electrode using the conductive paste agent |
| CN102054882A (en) * | 2009-10-29 | 2011-05-11 | 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 |
-
2011
- 2011-12-29 CN CN201110450403.2A patent/CN102568648B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101620939A (en) * | 2008-07-02 | 2010-01-06 | 比亚迪股份有限公司 | Semiconductor electrode, preparation method thereof and solar cell comprising semiconductor electrode |
| CN101667515A (en) * | 2008-09-04 | 2010-03-10 | 太阳油墨制造株式会社 | Conductive paste agent and electrode using the conductive paste agent |
| CN102054882A (en) * | 2009-10-29 | 2011-05-11 | 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107683532A (en) * | 2015-06-19 | 2018-02-09 | 太阳化学公司 | Silver paste and its application in the semiconductor device |
| 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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| Publication number | Publication date |
|---|---|
| CN102568648B (en) | 2014-06-18 |
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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. |
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