CN103559939A - Solar cell positive silver paste suitable for high-temperature sintering - Google Patents
Solar cell positive silver paste suitable for high-temperature sintering Download PDFInfo
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Abstract
The invention relates to solar cell positive silver paste suitable for high-temperature sintering. The paste comprises, by weight, 70-90% of silver powder, 1-3% of glass powder, 5-15% of solvent, 3-10% of organic binding agents and 0.01-2% of sintering accelerant, wherein the silver powder is of a spherical shape, the particle size of the silver powder is not larger than 5 micrometers, and the preference particle size of the silver powder is 1-3 micrometers. Compared with the prior art, an elementary substance containing rhodium or ruthenium or iridium or compounds containing rhodium or ruthenium or iridium serve as the sintering accelerant, the sintering accelerant can effectively restrain excessive sintering of the silver powder at a high temperature, crystalline of silver is prevented from being diffused to a junction area, generation of branch junctions is prevented, and the rate of finished products of battery pieces is increased. The sintering temperature of the paste is 800-900 DEG C, taking the 15 micrometers sintering thickness as an example, electric conductivity of the positive silver paste is 2m*omega/sq, the positive silver paste has excellent weldability, and adhesive force between a (2*2mm<2>) silver layer and a silicon substrate can reach more than 3N.
Description
Technical field
The present invention relates to a kind of silver slurry, be specifically related to a kind of solar cell positive silver paste that adapts to high temperature sintering.
Background technology
Sintering is one of important parameter of impact silver slurry performance.According to sintering temperature, silver-colored slurry can be divided into high-temperature sintered silver paste, intermediate sintering temperature silver slurry and low-temperature sintering silver slurry.Wherein, the sintering temperature of high-temperature sintered silver paste is 750-900 ℃ of left and right; And compare with middle temperature or low-temperature sintering silver slurry, the feature of high-temperature sintered silver paste is that soldering resistance and ageing resistance are outstanding.High-temperature sintered silver paste has important application on solar battery sheet; Compare with middle temperature or low-temperature sintering silver slurry, it can improve the welding sequence percent of pass in cell piece early stage and the useful life in later stage as its positive silver paste.At present, the peak firing temperature of solar cell positive silver paste is generally at 750-830 ℃.Higher sintering temperature is conducive to further improve production efficiency and the useful life of cell piece.Chinese patent literature 200810025430.3 discloses and a kind ofly can at 850～900 ℃, realize the high-viscosity solar cell front side silver paste of sintering, but contain too much glass dust in this silver slurry formula, be up to 10%, during high temperature sintering, glass dust easily penetrates emitter region, even can destroy P-N knot, cause sintering finished rate low.Chinese patent literature 200710171942.6 discloses a kind of hyperthermia drying wafer capacitance electrode silver plasm, in this silver slurry formula, the content of glass dust is lower, be only 1.2～2.3% left and right, this silver slurry has adopted the mixed liquor with high boiling terpinol and two sweet butanols ether as solvent simultaneously, the shortcoming that while having prevented low temperature drying, silver layer scratches, comes off, while having guaranteed hyperthermia drying solvent can evenly volatilize, non-foaming.Except attentional selection solvent and glass dust, how to prevent that in silver slurry, silver powder excessive sintering is at high temperature also a technical barrier of high-temperature sintered silver paste, be badly in need of solving.
Summary of the invention
The technical issues that need to address of the present invention are to provide a kind of solar cell positive silver paste that adapts to high temperature sintering, and this silver slurry can suppress the excessive sintering of silver powder under high temperature.
The technical issues that need to address of the present invention are achieved through the following technical solutions:
A kind of solar cell positive silver paste that adapts to high temperature sintering, its composition and percetage by weight thereof are: silver powder 70～90%, glass dust 1～3%, solvent 5～15%, organic binder bond 3～10% and sintering aids 0.01～2%, wherein silver powder is spherical, and its particle diameter is not more than 5 μ m.
Preferably, the composition of this slurry and percetage by weight thereof are: silver powder 75～90%, glass dust 1～2%, solvent 5～15%, organic binder bond 3～8% and sintering aids 0.01～2%.
Preferably, described silver powder particle diameter is 1～3 μ m.
Further preferably, described sintering aids is rhodium, ruthenium or iridium simple substance, or is rhodium-containing, ruthenium or iridic compound.
Still more preferably, described solvent is a kind of or any mixture in terpinol, butyl carbitol, butyl carbitol acetate, tributyl citrate and tributyl phosphate, and described organic binder bond is a kind of or any mixture in ethyl cellulose, CMC, nitrocellulose.
Still more preferably, described solvent is terpinol, and described organic binder bond is ethyl cellulose.
Still more preferably, in described solvent, alpha-terpineol content is not less than 80%.
Still more preferably, described glass dust is flint glass powder, lead-free glass powder or its mixture, and the softening temperature of described glass dust is 580～680 ℃, particle diameter <2 μ m.
Still more preferably, the composition of described flint glass powder and percetage by weight thereof are: lead oxide 60-85%, zinc oxide 1～10%, aluminium oxide 0.5～5%, boric acid 1～5%, silica 1～15%, calcium oxide 0～1%, zirconia 0～2% and titanium oxide 0～3%, and the percetage by weight sum of each component of glass dust is 100%.The softening point of this flint glass powder is 580～680 ℃.
Still more preferably, the composition of described lead-free glass powder and percetage by weight thereof are: bismuth oxide 50～60%, zinc oxide 10～30%, boric acid 3～5%, silica 5～9%, antimony oxide 0～15% and strontium oxide strontia 0～5%, and the percetage by weight sum of each component of glass dust is 100%.The softening point of this lead-free glass powder is 580～680 ℃.
Compared with prior art, advantage of the present invention and beneficial effect are:
1, adopted rhodium, ruthenium or iridium simple substance or rhodium-containing, ruthenium or iridic compound as sintering aids, this sintering aids can effectively suppress silver powder excessive sintering at high temperature occurs, stoped silver-colored crystalline solid to the diffusion in interface, prevented the generation of bypass knot, improved the rate of finished products of cell piece, the more important thing is, improved open circuit voltage and fill factor, curve factor, thereby improved transformation efficiency.
2, by reducing glass dust content, glass dust penetrating emitter region while having avoided high temperature sintering; Meanwhile, between electrode and matrix, form the glassy layer of thin layer, be also conducive to the tunneling effect of electric current, reduce string resistance, improve the photoelectric efficiency of battery.Although glass dust content is low in the more conventional silver slurry of glass dust content, owing to having adopted sintering aids, and sintering at high temperature, between electrode and silicon substrate, still can form good ohmic contact.
3, in formula, preferably high boiling solvent is used in conjunction with the glass dust that has the organic binder bond of high decomposition temperature and have a high sintering temperature, the softening of the decomposition of organic binder bond and glass dust make the volatilization of solvent in slurry, can evenly complete in the heat temperature raising process before sintering peak temperature reaches, prevented that silver layer from coming off and bubbling, guaranteed the effective adhesive that has between silver layer and silicon substrate.The sintering temperature of this slurry is 800～900 ℃, and the rear thickness of burning till of 15 μ m of take is example, and its conductance is <2m Ω/sq, has good solderability, silver layer (2 * 2mm
2) and silicon substrate between adhesive force can reach 3N more than.
Embodiment
Below in conjunction with embodiment, the specific embodiment of the present invention is described further.Following examples are only for technical scheme of the present invention is more clearly described, and can not limit the scope of the invention with this.
Embodiment 1～6
The present invention is a kind of solar cell positive silver paste that adapts to high temperature sintering, and in embodiment 1～6, the component of slurry and percetage by weight thereof are in Table 1.
In embodiment 1, silver powder is spherical, particle diameter <5 μ m; Sintering aids is rhodium simple substance; Described solvent is butyl carbitol or butyl carbitol acetate; Organic binder bond is ethyl cellulose, CMC or nitrocellulose; Glass dust is flint glass powder, and softening temperature is 580～680 ℃, particle diameter <2 μ m, and its composition and percetage by weight thereof are: lead oxide 60%, zinc oxide 10%, aluminium oxide 5%, boric acid 5%, silica 15%, zirconia 2% and titanium oxide 3%.
In embodiment 2, silver powder is spherical, and particle diameter is 1～3 μ m; Sintering aids is the compound of rhodium-containing, preferably oxide, chloride or the sulfide of rhodium; Described solvent is tributyl citrate or tributyl phosphate; Organic binder bond is ethyl cellulose, CMC and the nitrocellulose mixture of 40:30:30 by weight; Glass dust is flint glass powder, and softening temperature is 580～680 ℃, particle diameter <2 μ m, and its composition and percetage by weight thereof are: lead oxide 80%, zinc oxide 5%, aluminium oxide 0.5%, boric acid 1%, silica 12.5% and calcium oxide 1%.
In embodiment 3, silver powder is spherical, and particle diameter is 1～3 μ m; Sintering aids is iridium simple substance; Solvent is terpinol, butyl carbitol acetate and the tributyl phosphate mixture of 70:20:10 by weight; Organic binder bond is ethyl cellulose and the CMC mixture of 1:1 by weight; Glass dust is the mixture by weight 50:50 of lead-free glass powder and flint glass powder, the softening temperature of two kinds of glass dust is 580～680 ℃, particle diameter <2 μ m, wherein the composition of lead-free glass powder and percetage by weight thereof are: bismuth oxide 57%, zinc oxide 25%, boric acid 5%, silica 9% and strontium oxide strontia 4%, the composition of flint glass powder and percetage by weight thereof are: lead oxide 85%, zinc oxide 1%, aluminium oxide 4.5%, boric acid 3.5%, silica 1%, calcium oxide 0.8%, zirconia 1.7% and titanium oxide 2.5%.
In embodiment 4, silver powder is spherical, and particle diameter is 1～3 μ m; Sintering aids is the compound containing iridium, preferably oxide, chloride or the sulfide of iridium; Described solvent is terpinol, butyl carbitol and the tributyl citrate mixture of 80:10:10 by weight; Organic binder bond is CMC and the nitrocellulose mixture of 75:25 by weight; Glass dust is lead-free glass powder, and softening temperature is 580～680 ℃, particle diameter <2 μ m, and its composition and percetage by weight thereof are: bismuth oxide 57%, zinc oxide 25%, boric acid 5%, silica 9% and strontium oxide strontia 4%.
In embodiment 5, silver powder is spherical, and particle diameter is 1～3 μ m; Sintering aids is ruthenium simple substance; Solvent is terpinol, and wherein alpha-terpineol content is not less than 80%, all the other be β-, γ-and δ-terpinol; Organic binder bond is ethyl cellulose; Glass dust is lead-free glass powder, and softening temperature is 580～680 ℃, particle diameter <2 μ m, and its composition and percetage by weight thereof are: bismuth oxide 60%, zinc oxide 10%, boric acid 4%, silica 6%, antimony oxide 15% and strontium oxide strontia 5%.
In embodiment 6, silver powder is spherical, and particle diameter is 1～3 μ m; Sintering aids is the compound containing ruthenium, preferably oxide, chloride or the sulfide of ruthenium; Solvent is terpinol, and wherein alpha-terpineol content is not less than 80%, all the other be β-, γ-and δ-terpinol; Organic binder bond is ethyl cellulose; Glass dust is lead-free glass powder, and softening temperature is 580～680 ℃, particle diameter <2 μ m, and its composition and percetage by weight thereof are: bismuth oxide 50%, zinc oxide 30%, boric acid 3%, silica 5% and antimony oxide 12%.
Table 1:
The slurry of making according to above-mentioned formula, viscosity is 120～170Pas(25 ℃), under 25 ℃ of left and right ambient temperatures, print, after printing, at 120～150 ℃, dry 8～10 minutes to remove solvent, with the programming rate of 150 ℃/min, reach 800～900 ℃ subsequently, be incubated 0.1～2 minute, complete sintering process.Silverskin is silver gray, smooth, without coming off.The rear thickness of burning till of 15 μ m of take is example, and its conductance is <2m Ω/sq, has good solderability, silver layer (2 * 2mm
2) and silicon substrate between adhesive force can reach 3N more than; The electricity conversion (η) of the cell piece of test is on average more than 18%, and concrete numerical value is in Table 1.Above-mentioned each embodiment is further illustrating that foregoing of the present invention is made, but the scope that should not be construed as the above-mentioned theme of the present invention only limits to above-described embodiment.It should be pointed out that for those skilled in the art, not departing under the prerequisite of the technology of the present invention principle, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a solar cell positive silver paste that adapts to high temperature sintering, it is characterized in that: the composition of this slurry and percetage by weight thereof are: silver powder 70 ~ 90%, glass dust 1 ~ 3%, solvent 5 ~ 15%, organic binder bond 3 ~ 10% and sintering aids 0.01 ~ 2%, wherein silver powder is spherical, and its particle diameter is not more than 5 μ m.
2. solar cell positive silver paste according to claim 1, is characterized in that: the composition of this slurry and percetage by weight thereof are: silver powder 75 ~ 90%, glass dust 1 ~ 2%, solvent 5 ~ 15%, organic binder bond 3 ~ 8% and sintering aids 0.01 ~ 2%.
3. solar cell positive silver paste according to claim 2, is characterized in that: described silver powder particle diameter is 1 ~ 3 μ m.
4. according to the solar cell positive silver paste described in claims 1 to 3 any one, it is characterized in that: described sintering aids is rhodium, ruthenium or iridium simple substance, or be rhodium-containing, ruthenium or iridic compound.
5. solar cell positive silver paste according to claim 4, it is characterized in that: described solvent is a kind of or any mixture in terpinol, butyl carbitol, butyl carbitol acetate, tributyl citrate and tributyl phosphate, described organic binder bond is a kind of or any mixture in ethyl cellulose, CMC, nitrocellulose.
6. solar cell positive silver paste according to claim 5, is characterized in that: described solvent is terpinol, and described organic binder bond is ethyl cellulose.
7. solar cell positive silver paste according to claim 6, is characterized in that: in described solvent, alpha-terpineol content is not less than 80%.
8. solar cell positive silver paste according to claim 4, is characterized in that: described glass dust is flint glass powder, lead-free glass powder or its mixture, and the softening temperature of described glass dust is 580-680 ℃ particle diameter <2 μ m.
9. solar cell positive silver paste according to claim 8, it is characterized in that: the composition of described flint glass powder and percetage by weight thereof are: lead oxide 60 ~ 85%, zinc oxide 1 ~ 10%, aluminium oxide 0.5 ~ 5%, boric acid 1 ~ 5%, silica 1 ~ 15%, calcium oxide 0 ~ 1%, zirconia 0 ~ 2% and titanium oxide 0 ~ 3%, and the percetage by weight sum of each component of glass dust is 100%.
10. solar cell positive silver paste according to claim 8, it is characterized in that: the composition of described lead-free glass powder and percetage by weight thereof are: bismuth oxide 50 ~ 60%, zinc oxide 10 ~ 30%, boric acid 3 ~ 5%, silica 5 ~ 9%, antimony oxide 0 ~ 15% and strontium oxide strontia 0 ~ 5%, and the percetage by weight sum of each component of glass dust is 100%.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104157324A (en) * | 2014-07-30 | 2014-11-19 | 安徽状元郎电子科技有限公司 | Chlorite powder conductive silver paste and manufacturing method thereof |
| CN106887269A (en) * | 2017-02-20 | 2017-06-23 | 江苏瑞德新能源科技有限公司 | One kind adapts to low sintering solar cell positive silver paste and preparation method thereof |
| CN107230512A (en) * | 2017-05-31 | 2017-10-03 | 广西泰亿诺新能源有限公司 | A kind of welding conductive silver paste and Preparation method and use |
| CN107316674A (en) * | 2017-06-30 | 2017-11-03 | 北京市合众创能光电技术有限公司 | A kind of crystal silicon solar energy battery positive silver paste and preparation method thereof |
| CN109872829A (en) * | 2017-12-04 | 2019-06-11 | 北京市合众创能光电技术有限公司 | Back side silver paste |
| CN110021450A (en) * | 2019-04-17 | 2019-07-16 | 北京大学深圳研究生院 | A kind of lead-free glass powder being used to prepare silver paste of solar cells and its application |
| CN111292870A (en) * | 2020-03-09 | 2020-06-16 | 广东四维新材料有限公司 | High-temperature sintering conductive silver paste with lasting soldering resistance |
| CN111584645A (en) * | 2020-05-19 | 2020-08-25 | 江苏东鋆光伏科技有限公司 | High-efficiency solar cell and processing technology thereof |
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| CN104157324A (en) * | 2014-07-30 | 2014-11-19 | 安徽状元郎电子科技有限公司 | Chlorite powder conductive silver paste and manufacturing method thereof |
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| CN106887269A (en) * | 2017-02-20 | 2017-06-23 | 江苏瑞德新能源科技有限公司 | One kind adapts to low sintering solar cell positive silver paste and preparation method thereof |
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| CN107316674A (en) * | 2017-06-30 | 2017-11-03 | 北京市合众创能光电技术有限公司 | A kind of crystal silicon solar energy battery positive silver paste and preparation method thereof |
| CN109872829A (en) * | 2017-12-04 | 2019-06-11 | 北京市合众创能光电技术有限公司 | Back side silver paste |
| CN110021450A (en) * | 2019-04-17 | 2019-07-16 | 北京大学深圳研究生院 | A kind of lead-free glass powder being used to prepare silver paste of solar cells and its application |
| CN111292870A (en) * | 2020-03-09 | 2020-06-16 | 广东四维新材料有限公司 | High-temperature sintering conductive silver paste with lasting soldering resistance |
| CN111584645A (en) * | 2020-05-19 | 2020-08-25 | 江苏东鋆光伏科技有限公司 | High-efficiency solar cell and processing technology thereof |
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