CN103000248B - A kind of solar cell positive silver paste powder material adapting to high square resistance shallow junction - Google Patents
A kind of solar cell positive silver paste powder material adapting to high square resistance shallow junction Download PDFInfo
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- CN103000248B CN103000248B CN201210446535.2A CN201210446535A CN103000248B CN 103000248 B CN103000248 B CN 103000248B CN 201210446535 A CN201210446535 A CN 201210446535A CN 103000248 B CN103000248 B CN 103000248B
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Abstract
The present invention relates to a kind of solar cell positive silver paste powder material adapting to high square resistance shallow junction.The composition of this powder material and percetage by weight thereof are: average grain diameter is thin silver powder 20-45%, glass dust 1-9%, the additive 0.1-3% of 2-5 μm raw Ag powder 50-75%, average grain diameter 0.5-2 μm; Wherein each component weight percentage sum is 100%, and glass dust and additive all have bimodal state domain size distribution.Compared with prior art, positive silver paste powder material of the present invention has carried out the optimization of powder grating, and glass dust and additive granularity suitable, effectively can fill the hole between thickness silver powder, sintering Hou Yin island size is less, is evenly distributed, can form good ohmic contact, outward appearance is good; And glass dust activity is suitable, P-N junction can not be punctured.The positive silver paste adopting this powder material to prepare is suitable for sintering on the silicon cell with shallow junction structures.
Description
Technical field
The present invention relates to a kind of electric slurry, be specifically related to a kind of solar cell positive silver paste powder material adapting to high square resistance shallow junction.
Background technology
Solar cell is a kind of semiconductor device that can convert solar energy into electrical energy.Along with the development of photovoltaic industry, high square resistance shallow junction is one of development trend becoming solar battery sheet gradually.The silicon solar cell of high square resistance shallow junction structures can reduce the minority carrier recombination speed of solar cell surface and improve short wave response, thus improves the electricity conversion of cell piece.The positive silver paste that the high square resistance shallow junction General Requirements realizing cell piece is used for making electrode of solar battery has high sintering temperature.Common silver slurry be used in there is shallow junction structures silicon cell on manyly when sintering can there is bypass junction phenomena, cause leakage current, and the contact resistance of electrode is large, can reduce the output characteristic of electric current, and then reduce the performance of battery.Therefore be necessary at the enterprising Row sum-equal matrix of the formula of positive silver paste, to adapt to the sintering requirement of the silicon cell with shallow junction structures.Because the solvent in positive silver paste, organic carrier and organic additive are substantially all removed in the low temperature drying stage of cell piece, therefore the sintering temperature of these components to positive silver paste does not have an impact substantially, and is mainly derived from silver powder, glass dust and inorganic additive to the factor that the sintering temperature of positive silver paste has an impact.Therefore, the solar cell positive silver paste powder material developing a kind of adaptation high square resistance shallow junction be made up of silver powder, glass dust and inorganic additive is very necessary.
At present, the silver powder of solar cell positive silver paste many employings single particle size is electric conductor, and its shortcoming is that the sintering activity of silver powder is single; If use Large stone silver powder, then after sintering, silverskin structure is fine and close not, and the contact resistance between electrode and silicon substrate is large; If use small particle diameter silver powder, then silver powder easily excessive curtain coating in sintering, and need high silver powder loading can reach the index of electrode conductivity, preparation cost is high.By contrast, use the electric conductor of mixture as positive silver paste of the silver powder of two particle diameters or many domain size distribution, if application number is the positive silver paste of mixture as electric conductor using the raw Ag powder of 0.1-1 μm of super fine silver powder, 1-3 μm thin silver powder and 3-6 μm a kind of disclosed in the Chinese patent of 201210030266.1, because the silver powder that wherein particle size is different has different sintering activities, therefore after this positive silver paste sintering, there is good electrode outward appearance.But, the basic optimization only carrying out powder grating from the angle of silver powder of positive silver paste powder material used at present; And in fact, glass dust and inorganic additive all affect the sintering of positive silver paste.
Summary of the invention
The technical issues that need to address of the present invention are to overcome the deficiencies in the prior art, provide a kind of solar cell positive silver paste powder material adapting to high square resistance shallow junction.
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 powder material adapting to high square resistance shallow junction, and its composition and percetage by weight thereof are: thin silver powder 20-45%, glass dust 1-9%, additive 0.1-3% that the raw Ag powder 50-75% that average grain diameter is 2-5 μm, average grain diameter are 0.5-2 μm; Wherein, the percetage by weight sum of each component is 100%.
In order to improve the compactness of the rear silverskin of sintering further, preferred technical scheme can be, above-mentioned thickness silver powder is spherical or class is spherical, tap density >5.5g/cm
3.This high tap density silver powder can closely be piled up, and ensures the conductivity of silverskin.
In order to avoid glass dust excessive curtain coating and cause the formation of block silver on a silicon substrate when high temperature sintering, this glass dust must have moderate softening temperature.Preferred technical scheme can be, the softening point of above-mentioned glass dust is 380-480 DEG C.
Preferred technical scheme can be that the composition of above-mentioned glass dust and percetage by weight thereof are further: lead oxide 65-85%, aluminium oxide 0.5-5%, silica 1-10%, zinc oxide 1-10%, magnesium oxide 1-10%; Wherein, each component weight percentage sum of glass dust is 100%.
In order to effectively realize the effective bonding of glass dust to above-mentioned thickness silver powder, preferred technical scheme can be further, above-mentioned glass dust has bimodal state domain size distribution, the thin glass dust weight that average grain diameter is less than 0.5 μm accounts for 10-35%, surplus to be average grain diameter the be coarse glass frit of 0.5-5 μm, the percetage by weight sum of coarse glass frit and thin glass dust is 100%.Therefore, coarse glass frit can be dispersed in the hole between above-mentioned crude aluminum silver powder, and thin glass dust can be dispersed in the hole between above-mentioned thin silver powder, therefore adopt the mixture of this thickness glass dust can effective bonding thickness silver powder, avoid the formation of block silver in high temperature sintering.
In order to promote the formation of ohmic contact between silverskin and silicon substrate, a small amount of additive can be used, with acceleration of sintering in this positive silver paste powder material.Preferred technical scheme can be, above-mentioned additive is one or more in copper, tin, zinc, nickel metal simple-substance.Silver particles can and add metal simple-substance between form alloy, penetrate antireflective coating after fusing, thus facilitate the diffusion of silver particles, formed ohmic contact, reduce series resistance.
Preferred technical scheme is further, above-mentioned additive has bimodal state domain size distribution, the weight of additive that average grain diameter is less than 0.5 μm accounts for 10-35%, and surplus to be average grain diameter the be additive of 0.5-5 μm, the percetage by weight sum of the additive of two kinds of different-grain diameters is 100%.This additive with bimodal state domain size distribution can fill the hole between thickness silver powder and thickness glass dust effectively, and make the process penetrating antireflective coating more even, the electrical property of the electrode of gained is more even.
Compared with prior art, advantage of the present invention and beneficial effect are: the solar cell positive silver paste powder material that the present invention adapts to high square resistance shallow junction adopts two kinds of different high jolt ramming silver powder collocation to use, sintering rear electrode compact structure, and outward appearance consistency is good; The activity of glass dust is suitable, can not puncturing of P-N junction be there is after penetrating antireflective coating and cause bypass junction phenomena, glass dust adopts two domain size distribution simultaneously, can bonding thickness silver powder effectively, the silver-colored island size formed in sintering cooling procedure is less, and be evenly distributed, therefore silverskin and silicon substrate can be made to produce good ohmic contact; Additive also can evenly and the ohmic contact effectively improved between silverskin and silicon substrate; In this powder material, the use amount of glass dust is few compared with the consumption of conventional positive silver paste glass dust, and can reach the adhesive force needed for commercial Application, therefore the resistance of the electrode of gained and grid line is little, and electricity conversion is high.This powder material is applicable to the positive silver paste for the preparation of sintering on the silicon cell with shallow junction structures.
Embodiment
Below in conjunction with embodiment, the specific embodiment of the present invention is described further.Following examples only for technical scheme of the present invention is clearly described, and can not limit the scope of the invention with this.
Embodiment 1
Adapt to a solar cell positive silver paste powder material for high square resistance shallow junction, its composition and percetage by weight thereof are: thin silver powder 45%, glass dust 4.9%, additive 0.1% that the raw Ag powder 50% that average grain diameter is 2-5 μm, average grain diameter are 0.5-2 μm.Wherein, thickness silver powder is spherical or class is spherical, tap density >5.5g/cm
3; The softening point of glass dust is 380-480 DEG C, and the composition of glass dust and percetage by weight thereof are: lead oxide 65%, aluminium oxide 5%, silica 10%, zinc oxide 10%, magnesium oxide 10%; Glass dust has bimodal state domain size distribution, and the thin glass dust weight that average grain diameter is less than 0.5 μm accounts for 10%, and average grain diameter is that the coarse glass frit of 0.5-5 μm accounts for 90%; Additive is tin simple substance, has bimodal state domain size distribution, and the weight of additive that average grain diameter is less than 0.5 μm accounts for 10%, and average grain diameter is that the additive of 0.5-5 μm accounts for 90%.
Embodiment 2
Adapt to a solar cell positive silver paste powder material for high square resistance shallow junction, its composition and percetage by weight thereof are: thin silver powder 20%, glass dust 2%, additive 3% that the raw Ag powder 75% that average grain diameter is 2-5 μm, average grain diameter are 0.5-2 μm.Wherein, thickness silver powder is spherical or class is spherical, tap density >5.5g/cm
3; The softening point of glass dust is 380-480 DEG C, and the composition of glass dust and percetage by weight thereof are: lead oxide 85%, aluminium oxide 5%, silica 1%, zinc oxide 4%, magnesium oxide 5%; Glass dust has bimodal state domain size distribution, and the thin glass dust weight that average grain diameter is less than 0.5 μm accounts for 35%, and average grain diameter is that the coarse glass frit of 0.5-5 μm accounts for 65%; Additive is copper simple substance, has bimodal state domain size distribution, and the weight of additive that average grain diameter is less than 0.5 μm accounts for 35%, and average grain diameter is that the additive of 0.5-5 μm accounts for 65%.
Embodiment 3
Adapt to a solar cell positive silver paste powder material for high square resistance shallow junction, its composition and percetage by weight thereof are: thin silver powder 27%, glass dust 9%, additive 2% that the raw Ag powder 62% that average grain diameter is 2-5 μm, average grain diameter are 0.5-2 μm.Wherein, thickness silver powder is spherical or class is spherical, tap density >5.5g/cm
3; The softening point of glass dust is 380-480 DEG C, and the composition of glass dust and percetage by weight thereof are: lead oxide 81%, aluminium oxide 2%, silica 9%, zinc oxide 1%, magnesium oxide 7%; Glass dust has bimodal state domain size distribution, and the thin glass dust weight that average grain diameter is less than 0.5 μm accounts for 15%, and average grain diameter is that the coarse glass frit of 0.5-5 μm accounts for 85%; Additive is nickel simple substance, has bimodal state domain size distribution, and the weight of additive that average grain diameter is less than 0.5 μm accounts for 20%, and average grain diameter is that the additive of 0.5-5 μm accounts for 80%.
Embodiment 4
Adapt to a solar cell positive silver paste powder material for high square resistance shallow junction, its composition and percetage by weight thereof are: thin silver powder 32%, glass dust 1%, additive 1% that the raw Ag powder 66% that average grain diameter is 2-5 μm, average grain diameter are 0.5-2 μm.Wherein, thickness silver powder is spherical or class is spherical, tap density >5.5g/cm
3; The softening point of glass dust is 380-480 DEG C, and the composition of glass dust and percetage by weight thereof are: lead oxide 85%, aluminium oxide 0.5%, silica 6%, zinc oxide 7.5%, magnesium oxide 1%; Glass dust has bimodal state domain size distribution, and the thin glass dust weight that average grain diameter is less than 0.5 μm accounts for 25%, and average grain diameter is that the coarse glass frit of 0.5-5 μm accounts for 75%; Additive be copper, zinc simple substance by weight the mixture of 1:1, have bimodal state domain size distribution, the weight of additive that average grain diameter is less than 0.5 μm accounts for 24%, and average grain diameter is that the additive of 0.5-5 μm accounts for 76%.
Above-mentioned each embodiment is further illustrating of making foregoing of the present invention, but the scope that should not be construed as the above-mentioned theme of the present invention is only limitted to above-described embodiment.It should be pointed out that for those skilled in the art, under the prerequisite not departing from 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 (5)
1. adapt to a solar cell positive silver paste powder material for high square resistance shallow junction, it is characterized in that: the composition of this powder material and percetage by weight thereof are: thin silver powder 20-45%, glass dust 1-9%, additive 0.1-3% that the raw Ag powder 50-75% that average grain diameter is 2-5 μm, average grain diameter are 0.5-2 μm; Wherein, the percetage by weight sum of each component is 100%; Described additive is one or more in copper, tin, zinc, nickel metal simple-substance; Described additive has bimodal state domain size distribution, and the weight of additive that average grain diameter is less than 0.5 μm accounts for 10-35%, and surplus to be average grain diameter the be additive of 0.5-5 μm, the percetage by weight sum of the additive of two kinds of different-grain diameters is 100%.
2. the solar cell positive silver paste powder material of adaptation high square resistance shallow junction according to claim 1, is characterized in that: described thickness silver powder is spherical or class is spherical, tap density >5.5g/cm
3.
3. the solar cell positive silver paste powder material of adaptation high square resistance shallow junction according to claim 1, is characterized in that: the softening point of described glass dust is 380-480 DEG C.
4. the solar cell positive silver paste powder material of adaptation high square resistance shallow junction according to claim 3, is characterized in that: the composition of described glass dust and percetage by weight thereof are: lead oxide 65-85%, aluminium oxide 0.5-5%, silica 1-10%, zinc oxide 1-10%, magnesium oxide 1-10%; Wherein, each component weight percentage sum of glass dust is 100%.
5. the solar cell positive silver paste powder material of the adaptation high square resistance shallow junction according to claim 3 or 4, it is characterized in that: described glass dust has bimodal state domain size distribution, the thin glass dust weight that average grain diameter is less than 0.5 μm accounts for 10-35%, surplus to be average grain diameter the be coarse glass frit of 0.5-5 μm, the percetage by weight sum of coarse glass frit and thin glass dust is 100%.
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| CN104668551B (en) * | 2015-01-28 | 2017-01-04 | 哈尔滨工业大学深圳研究生院 | A kind of bimodal distribution nano silver paste as thermal interfacial material and preparation method thereof |
| CN106816199B (en) * | 2017-01-23 | 2019-01-29 | 湖南省国银新材料有限公司 | A kind of high square resistance crystal silicon solar energy battery front electrode silver slurry and preparation method thereof |
| CN107658045B (en) * | 2017-08-30 | 2020-03-27 | 南通天盛新能源股份有限公司 | Back electrode silver paste for lead-free PERC battery and preparation method |
| EP3806111B1 (en) * | 2018-07-06 | 2024-03-13 | Senju Metal Industry Co., Ltd. | Electrically conductive paste and sintered body |
| CN110060794A (en) * | 2019-03-05 | 2019-07-26 | 苏州市贝特利高分子材料股份有限公司 | PERC silver paste based on granularity compounding |
| CN110061074B (en) * | 2019-03-05 | 2021-07-27 | 苏州市贝特利高分子材料股份有限公司 | PERC solar cell |
| CN113096846B (en) * | 2021-03-23 | 2023-03-28 | 华中科技大学 | P-type emitter ohmic contact silver electrode slurry |
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