CN103680673A - Light-facing side seed layer paste for SE (Selective Emitter) crystalline silicon solar cell, preparation method for light-facing side seed layer paste, SE crystalline silicon solar cell, and preparation method for SE crystalline silicon solar cell - Google Patents
Light-facing side seed layer paste for SE (Selective Emitter) crystalline silicon solar cell, preparation method for light-facing side seed layer paste, SE crystalline silicon solar cell, and preparation method for SE crystalline silicon solar cell Download PDFInfo
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Abstract
The invention relates to a light-facing side seed layer paste for a SE (Selective Emitter) crystalline silicon solar cell. The light-facing side seed layer paste is a mixture of 70-85 wt% metal functional powders, 2-10 wt% inorganic glass powders, and a 5-20 wt% organic carrier; the metal functional powders contain spherical nano antimony powders. The invention further provides a method adopting the seed layer paste for the preparation of the SE crystalline silicon solar cell, and the SE crystalline silicon solar cell prepared through the method. In the preparation method for the SE crystalline silicon solar cell provided by the invention, sintering is carried out after the double printing of the light-facing side seed layer paste and the traditional light-facing side silver conductive paste on the front surface of a silicon wafer, so as to well form a selective diffusion area below front silver electrode grid lines, and achieve firm adhesion of electrodes to a silicon matrix, high welding strength, small contact resistance of the electrodes, and more packing factors. Therefore, the SE crystalline silicon solar cell provided by the invention achieves an average photoelectric conversion efficiency of more than 17.3 percent, and the light-facing side electrode manufacturing costs are effectively reduced.
Description
Technical field
The present invention relates to area of solar cell, the SE crystal-silicon solar cell that is specifically related to a kind of SE crystal-silicon solar cell phototropic face Seed Layer slurry and preparation method thereof, a kind of SE crystal-silicon solar cell and is prepared by this preparation method.
Background technology
Solar energy is as a kind of green energy resource, inexhaustible, pollution-free with it, not be more and more subject to people's attention by the advantages such as region resource limitation.Crystal-silicon solar cell is simple with its technological process, and transformation efficiency is high, is convenient to the advantages such as large-scale production and develops rapidly, and such battery has occupied more than 80% share in current photovoltaic market.The manufacture method of existing crystal silicon solar energy battery phototropic face electrode is generally after printing aluminium paste and back silver paste, adopt silk screen printing front conductive silver slurry, then after crossing continuous tunnel furnace sintering, directly obtain positive silver electrode, short circuit current and the photoelectric conversion efficiency of the making performance appreciable impact battery of front electrode.
A technique of the commonplace employing of efficient solar battery is at present selective emitter (being called for short SE) battery structure, the method refers to form heavily diffusion under phototropic face metal electrode, and in other regions, form shallow diffusion, local so heavily diffusion can make electrode and silicon form good ohmic contact, increase the fill factor, curve factor of battery, and it is compound to reduce few son at shallow diffusion zone, improve the collection rate of photo-generated carrier.On producing, use at present realize preferably selectivity diffused emitter battery technology be direct printing mask layer method; this method feature is for passing through once heavily diffusion; then the region that adopts the organic wax covering protection of spraying need to print front electrode line; then silicon chip is adopted to nitration mixture corrosion, in not protected region, form the emitter region of shallow diffusion.The shortcoming that the method exists: the one, the equipment price of the organic wax of spraying is expensive, another is that border extension easily occurs in organic wax overlay area, and corrosion obtains shallow diffusion zone and reduces, thereby causes the reduction of battery efficiency, and, organic wax be cleaned also have certain difficulty completely.
Slurry doping method is the scheme of the easiest acquisition selective emitter solar battery, its conventional thought is the phosphorus source of mixing high concentration in silver paste, to be desirably in the process of sintering phosphorus, infiltrate in silicon to form heavy doping, still, in common sintering furnace, furnace atmosphere and extraneous circulation, phosphorus in slurry easily volatilizees and runs off when sintering, and, solid part major part or silver powder in silver paste, therefore, phosphorus is difficult to silicon chip substrate to reach the doping effect of expection in slurry.
Summary of the invention
Being difficult to of the invention solves that the preparation SE crystal-silicon solar cell that exists in prior art exists guarantee to adulterate preferably effect, cost is higher and battery efficiency is low technical problem, and a kind of new SE crystal-silicon solar cell phototropic face Seed Layer slurry and preparation method thereof, a kind of SE crystal-silicon solar cell and preparation method thereof are provided.
Therefore, the invention provides a kind of phototropic face Seed Layer slurry of SE crystal-silicon solar cell, described phototropic face Seed Layer slurry is the mixture that contains 70-85wt% metal function powder, 2-10wt% unorganic glass powder and 5-20wt% organic carrier; In described metal function powder, contain ball shaped nano antimony powder.
The present invention also provides the preparation method of the phototropic face Seed Layer slurry of described SE crystal-silicon solar cell, comprise unorganic glass powder is first scattered in organic carrier, then add metal function powder in batches, be ground to after slurry fineness is less than 5 μ m and obtain described SE crystal-silicon solar cell phototropic face Seed Layer slurry.
Further, the present invention also provides a kind of preparation method of SE crystal-silicon solar cell, comprise the following steps: first at silicon chip back side successively printed back conductive silver slurry and back field aluminum paste material, after oven dry, at front side of silicon wafer, print phototropic face Seed Layer slurry provided by the invention, after drying, adopt and align technique at Seed Layer slurry printed layers surface continuation printing phototropic face conductive silver slurry, enter continuous tunnel furnace sintering, obtain described SE crystalline silicon solar cell piece.
Finally, the invention provides a kind of SE crystal-silicon solar cell, described SE crystal-silicon solar cell is prepared by preparation method provided by the invention.
The phototropic face Seed Layer slurry of SE crystal-silicon solar cell provided by the invention, its function powder is mainly ball shaped nano antimony powder, due to the fusing point of the nano stibium powder fusing point lower than conventional antimony powder, more lower than the fusing point of aluminium powder, therefore in conventional solar cell sintering process, nano stibium powder can melting and is adhered on silicon substrate, and because it has larger specific area, therefore there is very strong sintering flowing activity, at sintering high temperature section antimony atoms, be easier to infiltrate silicon atom gap, or it is atom doped that thereby shape is replaced in silicon atom position, and antimony and phosphorus belong to the 5th major element, therefore this doping belongs to N-type doping, thereby can form selective emitter (SE) region.In addition, in phototropic face Seed Layer slurry provided by the invention, owing to not using or using on a small quantity argent, also reduced the cost of manufacture of cell piece front electrode.
In SE crystal-silicon solar cell preparation method provided by the invention, by by sintering after phototropic face Seed Layer slurry and the dual printing of traditional phototropic face conductive silver slurry and front side of silicon wafer, thereby can under positive silver electrode grid line, form well territory, selectively diffused regions, and electrode and silicon substrate adhesion-tight, weld strength is high, the contact resistance of electrode is little, and fill factor, curve factor is high, makes the average light photoelectric transformation efficiency of SE crystal-silicon solar cell provided by the invention surpass 17.3%.In addition, in the preparation method of SE crystal-silicon solar cell provided by the invention, do not need to adopt the needed equipment of direct printing mask method and mask material, only once sintered by twice printing, so technique simplifies greatly, cost is effectively reduced.
Embodiment
The invention provides a kind of phototropic face Seed Layer slurry of SE crystal-silicon solar cell, described phototropic face Seed Layer slurry is the mixture that contains 70-85wt% metal function powder, 2-10wt% unorganic glass powder and 5-20wt% organic carrier; In described metal function powder, contain ball shaped nano antimony powder.
The phototropic face Seed Layer slurry of SE crystal-silicon solar cell provided by the invention, its function powder is mainly ball shaped nano antimony powder, due to the fusing point of the nano stibium powder fusing point (conventional antimony powder fusing point is 631 ℃) lower than conventional antimony powder, more lower than the fusing point (aluminium powder fusing point is 660 ℃) of aluminium powder, therefore in current conventional solar cell sintering process, nano stibium powder can melting and is adhered on silicon substrate, and because it has larger specific area, therefore there is very strong sintering flowing activity, at sintering high temperature section antimony atoms, be easier to infiltrate silicon atom gap, or it is atom doped that thereby shape is replaced in silicon atom position, and antimony and phosphorus belong to the 5th major element, therefore this doping belongs to N-type doping, thereby can form selective emitter (SE) region.
In addition, in phototropic face Seed Layer slurry provided by the invention, owing to not using or using on a small quantity argent, also reduced the cost of manufacture of cell piece front electrode.
In the present invention, the particle diameter of the ball shaped nano antimony powder adopting in described metal function powder needs strict control; Particle diameter is too large, is not enough to form nano effect, and antimony doping effect is bad; And particle diameter is too little, may cause the melting point depression of antimony powder too many, when sintering, melting is run off, and cause the grid line shading-area forming to increase, and the processing cost of material also rises.Therefore, in the present invention, the middle particle diameter D of described ball shaped nano antimony powder
50 1be preferably 30 ~ 600nm, more preferably 50 ~ 250nm.The specific surface of described ball shaped nano antimony powder is preferably 3 ~ 8m
2/ g, more preferably 4 ~ 5.5 m
2/ g.
As a kind of preferred implementation of the present invention, in described metal function powder, also contain metal bismuth meal.The fusing point of bismuth metal (271 ℃) is lower than metallic antimony, and also belongs to the 5th major element, and itself can form N-type doping to silicon; And from metal phase diagram, antimony, bismuth can melt completely mutually, so can produce synergy to the doping of antimony adding of metal bismuth meal, impel antimony to shift to an earlier date melting, thereby have enough time to form doping to silicon.
As another kind of preferred implementation of the present invention, in described metal function powder, also contain metallic tin powder, glass putty add the ply adhesion that can increase between described phototropic face Seed Layer slurry and follow-up conventional phototropic face conductive silver slurry.
In the present invention, the bismuth meal and the glass putty that in described metal function powder, add are all preferably spherical powder particle, and its addition and particle size need be controlled; As bismuth meal or glass putty addition are too many, particle diameter is too little, may cause the fusing point of function powder too low, slurry is in sintering process, and the melting time is oversize and run off; In addition, as too many in bismuth meal, because the atomic volume diffusion coefficient larger than antimony, in silicon of bismuth is less than antimony, its doping effect, not as antimony powder end, can cause N-type doping effect bad.Therefore, more preferably in situation, the gross mass of described metal function powder of take is benchmark, and the addition of bismuth meal is 2 ~ 10wt%.The middle particle diameter D of described metal bismuth meal
50 2be 0.1 ~ 3.5 μ m, be preferably 0.3 ~ 2.5 μ m.
Similarly, the gross mass of described metal function powder of take is benchmark, and the addition of glass putty is 0.5 ~ 5wt%.The middle particle diameter D of described metallic tin powder
50 3be 0.1 ~ 3.5 μ m, be preferably 0.3 ~ 2.5 μ m.
In the present invention, for reducing the volume resistance of the seed grid line layer forming after described phototropic face Seed Layer slurry sintering, as a kind of preferred implementation of the present invention, described metal function powder also can contain a small amount of spherical micro aluminum powder, and the addition of silver powder can be 1 ~ 10wt%.Under preferable case, the middle particle diameter D of described spherical micro aluminum powder
50 4be 0.1 ~ 3.5 μ m, 0.3 ~ 2.5 μ m more preferably.The specific area of described spherical micro aluminum powder is 1 ~ 3.5m
2/ g, tap density is 4 ~ 7g/cm
3.
In the present invention, described unorganic glass powder, organic carrier can adopt various unorganic glass powder, the organic carrier of commonly using in electrode slurry in prior art, and the present invention is not particularly limited.
Under preferable case, described unorganic glass powder is Bi
2o
3-B
2o
3-SiO
2system glass dust, it specifically consists of: the Bi of 75 ~ 85wt%
2o
3, the B of 5 ~ 15wt%
2o
3, the SiO of 2 ~ 10wt%
2, the ZnO of 0.5 ~ 5wt%, the TiO of 0 ~ 2wt%
2.The middle particle diameter D of described unorganic glass powder
50 5be that 0.1 ~ 1 μ m, softening point (Ts) are 400 ~ 450 ℃.
In the present invention, described unorganic glass powder can directly adopt and be purchased product, also can oneself prepare, and preparation method is known to the skilled person.For example, the method of preparing described unorganic glass powder can be: the oxide powder that adopts V-Mixer that each is formed to glass dust mixes, proceed in corundum crucible and be placed in silicon carbide rod furnace, to in silicon carbide rod furnace, be warming up to 550 ℃, insulation 0.5h, be warming up to again 1250 ℃, insulation 2h, shrend is filtered and is obtained bead; Then pack this bead into ball grinder, in mass ratio zirconia ball: bead: deionized water=4:1:0.7,300 revs/min of tank speed, wet-milling 6.5h, filters post-drying, then the 0.5h that dry grinds, and during dry grinding, the mass ratio of zirconia ball and glass dust is 1:2.
Described organic carrier can directly adopt and be purchased product, also can oneself prepare, and preparation method is known to the skilled person.For example, the method of preparing described organic carrier can be: the various organic carrier usual component such as ethyl cellulose, lubricant, thixotropic agent are dissolved in the mixed solvent being comprised of two or more conventional organic solvents, at 50 ~ 80 ℃, stir it is fully dissolved, can obtain the organic carrier of transparent homogeneous.Wherein organic solvent can be selected from terpinol, dibutyl phthalate, butyl carbitol (DBP), turpentine oil, butyl carbitol acetate, butyl glycol ether, ethylene glycol ether acetate, lauryl alcohol ester.
The present invention also provides the preparation method of the phototropic face Seed Layer slurry of described SE crystal-silicon solar cell, comprise unorganic glass powder is first scattered in organic carrier, then add metal function powder in batches, be ground to after slurry fineness is less than 5 μ m and obtain described SE crystal-silicon solar cell phototropic face Seed Layer slurry.
Wherein, dispersion can adopt high speed dispersor to carry out.Under preferable case, the number of times in batches of described function powder is 2-3 time, stirs at every turn, then add next batch after adding; After all adding, high-speed stirred is even.Described grinding can adopt three-roll grinder to carry out, and is ground to slurry fineness and is less than 5 μ m.
The present invention also provides a kind of preparation method of SE crystal-silicon solar cell, comprise the following steps: first at silicon chip back side successively printed back conductive silver slurry and back field aluminum paste material, after oven dry, at front side of silicon wafer, print phototropic face Seed Layer slurry provided by the invention, after drying, adopt and align technique at Seed Layer slurry printed layers surface continuation printing phototropic face conductive silver slurry, enter continuous tunnel furnace sintering, obtain described SE crystalline silicon solar cell piece.
In SE crystal-silicon solar cell preparation method provided by the invention, by by sintering after phototropic face Seed Layer slurry and the dual printing of traditional phototropic face conductive silver slurry and front side of silicon wafer, thereby can under positive silver electrode grid line, form well territory, selectively diffused regions, and electrode and silicon substrate adhesion-tight, weld strength is high, the contact resistance of electrode is little, and fill factor, curve factor is high, makes the average light photoelectric transformation efficiency of SE crystal-silicon solar cell provided by the invention surpass 17.3%.
In addition, in the preparation method of SE crystal-silicon solar cell provided by the invention, do not need to adopt the needed equipment of direct printing mask method and mask material, only once sintered by twice printing, so technique simplifies greatly, cost is effectively reduced.
In the present invention, described back silver electrocondution slurry, back field aluminum paste material and phototropic face conductive silver slurry are the various conventional slurry that those skilled in the art commonly use, its printing process can directly adopt the conventional method for printing screen of those skilled in the art, the present invention is not particularly limited, and repeats no more herein., when printing phototropic face conductive silver slurry, need to guarantee that it aligns with the Seed Layer slurry printed layers of front side of silicon wafer with should be noted that.
Described silicon chip can be monocrystalline silicon piece or polysilicon chip, and the present invention is not particularly limited.
In the present invention, the method for printing Seed Layer slurry is preferably silk screen printing.Under preferable case, it is that 25 μ m, thickness are that the web plate of 3 μ m carries out that described silk screen printing can adopt 360 orders, live width, but is not limited to this.During silk screen printing, the printing consumption of Seed Layer slurry can suitably be selected according to the size of cell piece.Under preferable case, during printing Seed Layer slurry, printing wet-film thickness is 5 ~ 10 μ m, and the weight in wet base of printing is 25 ~ 55mg.
The consumption of printing phototropic face conductive silver slurry can suitably be selected according to actual phototropic face electrode height.Under preferable case, during printing phototropic face conductive silver slurry, printing wet-film thickness is 10 ~ 15 μ m.
According to preparation method provided by the invention, after printing slurry, silicon chip integral body can be sent into and in continuous tunnel furnace, carry out sintering.Under preferable case, during sintering, preheat temperature is 200 ~ 500 ℃, and peak temperature is 910 ~ 930 ℃.The whole time that crosses continuous tunnel furnace is 3 ~ 5min, and wherein under peak temperature, sintering time is 2 ~ 5s.
Finally, the invention provides a kind of SE crystal-silicon solar cell, described SE crystal-silicon solar cell is prepared by preparation method provided by the invention.
The SE crystal-silicon solar cell that adopts preparation method provided by the invention to prepare, phototropic face gate electrode line outward appearance is good, high with the weld strength of photovoltaic welding belt, good with silicon substrate adhesion property, and the fill factor, curve factor of battery has remarkable increase, average light photoelectric transformation efficiency surpasses 17.3%.
Below in conjunction with embodiment, the present invention is described further.In embodiment and comparative example, the raw material that adopts is all commercially available, and the present invention is not particularly limited.
Embodiment 1
(1) preparation of unorganic glass powder
Get the Bi of 83wt%
2o
3, 8wt% B
2o
3, 6wt% SiO
2, the ZnO of 2wt% is, the TiO of 1wt%
2, adopt V-Mixer to mix, pack in porcelain crucible, put into silicon carbide rod furnace, heat up and be preheating to 550 ℃, insulation 0.5h, be warming up to again 1250 ℃, melting 0.5h, shrend is filtered, pack the bead obtaining into ball grinder, control quality than zirconia ball: bead: deionized water=4:1:0.7,300 revs/min of tank speed, ball milling 7h, filtering drying, then the 1h that dry grinds, during dry grinding, the mass ratio of zirconia ball and bead is 1:2, obtains the unorganic glass powder of the present embodiment, tests wherein particle diameter D
50 5be 0.67 μ m, softening point (T
s) be 432 ℃.
(2) preparation of organic carrier
According to quality than lauryl alcohol ester: butyl carbitol: butyl carbitol acetate=70:20:10 is mixed, and obtains mixed solvent.Take carrier gross mass as benchmark, get 13wt% ethyl cellulose STD-100 (it is 100 that Tao Shi produces viscosity), 2.0wt% hexadecanol, 2.0wt% rilanit special, 83wt% mixed solvent, is heated to 75 ℃ it is fully dissolved, and stir, obtain the organic carrier of homogeneous.
(3) preparation of phototropic face Seed Layer slurry S1
The gross mass of metal function powder of take is benchmark, gets metal antimony powder (the middle particle diameter D of 92wt%
50 1be 120 ± 20nm, Beijing Deco Dao Jing Science and Technology Co., Ltd. produces, purity>=99.90%, subsequent embodiment unless stated otherwise, otherwise antimony powder parameter is identical with the present embodiment), 5wt% bismuth meal (middle particle diameter D
50 2be 1.20 ± 0.25 μ m, Shanghai Hong Rui Industry Co.,Ltd production purity>=99.90%, subsequent embodiment unless stated otherwise, otherwise bismuth meal parameter is identical with the present embodiment), the metallic tin powder of 3wt% (middle particle diameter D
50 3be 1.50 ± 0.30 μ m, paddy field, Shanghai material Science and Technology Ltd. produces, purity>=99.90%, subsequent embodiment unless stated otherwise, otherwise glass putty parameter is identical with the present embodiment), adopt V-Mixer to mix, obtain the metal function powder of the present embodiment.
The phototropic face Seed Layer slurry gross mass of take is benchmark, get the organic carrier that 15wt% is made by step (2), be placed in the stainless cylinder of steel of high speed dispersor, stir on one side, the unorganic glass powder that adds 5wt% step (1) to make on one side, stir, then divide and add 80wt% metal function powder for 3 times, add rear first stirring evenly to add again next time at every turn; After all adding, stir evenly at a high speed.Finally adopt three-roll grinder to be ground to slurry fineness and be less than 5 μ m, obtain the phototropic face Seed Layer slurry S1 of the present embodiment.
Embodiment 2
Adopt the step identical with embodiment 1 to prepare the phototropic face Seed Layer slurry S2 of the present embodiment, difference is:
In step (3), the component of metal function powder is: the metal antimony powder of 97.5wt%, 2wt% bismuth meal, the metallic tin powder of 0.5wt%;
By above-mentioned steps, obtain the phototropic face Seed Layer slurry S2 of the present embodiment.
Embodiment 3
Adopt the step identical with embodiment 1 to prepare the phototropic face Seed Layer slurry S3 of the present embodiment, difference is:
In step (3), the component of metal function powder is: the metal antimony powder of 85wt%, 10wt% bismuth meal, the metallic tin powder of 5wt%;
By above-mentioned steps, obtain the phototropic face Seed Layer slurry S3 of the present embodiment.
Embodiment 4
Adopt the step identical with embodiment 1 to prepare the phototropic face Seed Layer slurry S4 of the present embodiment, difference is:
In step (3), the component of metal function powder is: the metal antimony powder of 100wt%;
By above-mentioned steps, obtain the phototropic face Seed Layer slurry S4 of the present embodiment.
Embodiment 5
Adopt the step identical with embodiment 1 to prepare the phototropic face Seed Layer slurry S5 of the present embodiment, difference is:
In step (3), the component of metal function powder is: the metal antimony powder of 87wt%, 5wt% bismuth meal, the metallic tin powder of 3wt%, the spherical micro aluminum powder of 5wt% (particle diameter D in silver powder
50 4be 1.10 ± 0.25 μ m, specific area is 1.8 ± 0.5m
2/ g, tap density is 4.5 ± 1.0g/cm
3, adopt chemical reduction method to produce, Japanese DOWA company);
By above-mentioned steps, obtain the phototropic face Seed Layer slurry S5 of the present embodiment.
Embodiment 6
Adopt the step identical with embodiment 1 to prepare the phototropic face Seed Layer slurry S6 of the present embodiment, difference is:
In step (3), in metal function powder: the middle particle diameter D of metal antimony powder
50 1be 580 ± 20nm, particle diameter D in metal bismuth meal
50 2be 2.5 ± 0.2 μ m, the middle particle diameter D of metallic tin powder
50 3be 2.7 ± 0.3 μ m;
By above-mentioned steps, obtain the phototropic face Seed Layer slurry S6 of the present embodiment.
Embodiment 7
Adopt the step identical with embodiment 1 to prepare the phototropic face Seed Layer slurry S7 of the present embodiment, difference is:
In step (3), the consumption of metal function powder is 70wt%, and the consumption of unorganic glass powder is 10wt%, and the consumption of organic carrier is 20wt%;
By above-mentioned steps, obtain the phototropic face Seed Layer slurry S7 of the present embodiment.
Comparative example 1
Adopt the step identical with embodiment 1 to prepare the phototropic face Seed Layer slurry DS1 of this comparative example, difference is:
In step (3), adopt pure spherical micro aluminum powder (the particle diameter D in silver powder of equal quality percentage
50 4be 0.90 ± 0.15 μ m, specific area is 1.40 ± 0.25m
2/ g, tap density is 4.22 ± 0.50g/cm
3, adopt chemical reduction method to produce, Japanese DOWA company) and metal function powder in alternative embodiment 1;
By above-mentioned steps, obtain the phototropic face Seed Layer slurry DS1 of this comparative example.
Comparative example 2
Adopt the step identical with embodiment 1 to prepare the phototropic face Seed Layer slurry DS1 of this comparative example, difference is:
In step (2), get 8.7wt% ethyl cellulose STD-4 (Tao Shi produces, and viscosity is 4), 1.3wt% hexadecanol, 3wt% rilanit special, 87wt% mixed solvent, is heated to 75 ℃ it is fully dissolved, and stir, and obtains the organic carrier of homogeneous;
In step (3), get 85wt% fine silver powder (middle particle diameter D
50 4be 0.60 ± 0.25 μ m, specific area is 2.5 ± 0.6m
2/ g, tap density is 6.25 ± 1.00g/cm
3, adopt chemical reduction method to produce, Japanese SHOEI CHEMICAL INC), 5wt% unorganic glass powder, 10wt% organic carrier, is stirred with blender, then passes through milling processing, obtains the phototropic face electrocondution slurry DS2 of this comparative example.
Embodiment 8
Polysilicon chip specification: 156 * 156mm, before thickness is 200 μ m(corrosion), before printing, thickness is 180 μ m.First adopt the 200 object silk screen printing back silver slurry (PV505 of Du Pont, three eight sections, line systems, printing weight in wet base is 0.035 ~ 0.05g), 150 ℃ of oven dry, adopt again 280 object silk screen printing back field aluminum paste material (large standing grain 108C, printing weight in wet base is 1.40 ~ 1.6g), 150 ℃ of oven dry, drying time is 5 minutes.Then adopting 360 orders, live width is that 25 μ m, thickness are that the silk screen of 3 μ m is printed in phototropic face Seed Layer slurry S1 on the phototropic face of silicon chip, and printing wet-film thickness is that 6.0 ± 2.0 μ m printing weight in wet bases are 30 ~ 35mg, dries.Then adopt to align technique and on dry Seed Layer pulp layer, print commercially available phototropic face conductive silver slurry (70A of Du Pont), printing wet-film thickness is 10 ~ 15 μ m.Finally silicon chip integral body is sent in continuous tunnel furnace and dried sintering, preheat temperature is 200 ~ 500 ℃, and peak temperature is 925 ℃, and the whole time that crosses continuous tunnel furnace is 3 minutes and 48 seconds, and peak value sintering time is 4s, obtains the SE crystal-silicon solar cell of the present embodiment, is designated as S ' 1.
Embodiment 9-14
Adopt the step identical with embodiment 8 to prepare SE crystal-silicon solar cell S ' 2-S ' 7, difference is: adopt respectively phototropic face Seed Layer slurry S2-S7 to replace the S1 in embodiment 8.
Comparative example 3
Adopt the step identical with embodiment 8 to prepare SE crystal-silicon solar cell DS ' 1, difference is: adopt phototropic face Seed Layer slurry DS1 to replace the S1 in embodiment 8.
Comparative example 4
Polysilicon chip specification: 156 * 156mm, before thickness is 200 μ m(corrosion), before printing, thickness is 180 μ m.First adopt the 200 object silk screen printing back silver slurry (PV505 of Du Pont, three eight sections, line systems, printing weight in wet base is 0.035 ~ 0.05g), 150 ℃ of oven dry, adopt again 280 object silk screen printing back field aluminum paste material (large standing grain 108C, printing weight in wet base is 1.40 ~ 1.6g), 150 ℃ of oven dry, drying time is 5 minutes.Then adopting 360 orders, live width is that 30 μ m, thickness are that the silk screen of 5 μ m is printed in phototropic face electrocondution slurry DS2 on the phototropic face of silicon chip, and printing wet-film thickness is 20 ± 3 μ m, and printing weight in wet base is 145 ~ 170mg, oven dry.Then silicon chip integral body is sent in continuous tunnel furnace and dried sintering, preheat temperature is 200 ~ 400 ℃, and peak temperature is 910 ℃, and the whole time that crosses continuous tunnel furnace is 2 minutes and 20 seconds, and peak value sintering time is 1s, obtains the SE crystal-silicon solar cell of this comparative example, is designated as DS ' 2.
Performance test
The present invention adopts 200 batteries to test, and the data that record are averaged.
(1) surface appearance: adopt 3 ~ 5 times of magnifying glasses to observe the surface appearance of the phototropic face electrode of each SE crystal-silicon solar cell S ' 1-S ' 7 and DS ' 1-DS ' 2, if smooth surface, without plot point, without broken string, without hole phenomenon, be designated as OK, otherwise be designated as NG.
(2) weld strength: select victory footpath between fields, the Shanghai 2mm(wide) * 0.2mm(is thick) tin lead welding band, with Henkel X32-10I type scaling powder, soak post-drying, then at 330 ℃, electrode main grid line is carried out to manual welding.After cell piece is naturally cooling, use mountain degree SH-100 pull and push dynamometer, along 135 ° of directions, welding is peeled off to test, survey its average peeling force, unit is N/mm.
(3) with the adhesive strength of silicon chip: by tested slurry S1-S7 and the DS1-DS2 of the whole back of the body surface printing of silicon chip, cross after continuous tunnel furnace sintering, silicon chip after photovoltaic glass, EVA, printing slurry sintering, EVA and TPT are stacked in order, and carry out lamination, with wide rectangular of graduating with cutter 2cm, use mountain degree SH-100 pull and push dynamometer, along 135 ° of directions, it is carried out to tensile test, survey the average peeling force on its unit width, unit is N/mm.
(4) fill factor, curve factor and electricity conversion: adopt single flash operation simulation test instrument that each SE crystal-silicon solar cell S ' 1-S ' 7 and DS ' 1-DS ' 2 are tested and obtained.Test condition is standard test condition (STC): light intensity: 1000W/m
2; Spectrum: AM1.5; Temperature: 25 ℃.
Test result is as shown in table 1 below.
Table 1
From table 1, S ' 1-S ' 7 and DS ' 1-DS ' 2 test results relatively can be found out, the SE crystal-silicon solar cell that adopts phototropic face Seed Layer slurry of the present invention and battery preparation method to prepare, its phototropic face gate electrode line outward appearance is good, high with the weld strength of photovoltaic welding belt, good with silicon substrate adhesion property, especially the fill factor, curve factor of battery has remarkable increase, and average light photoelectric transformation efficiency surpasses 17.30%.In addition, in slurry, do not use or use on a small quantity argent, effectively reduced the cost of manufacture of phototropic face electrode, increased the competitiveness of crystal-silicon solar cell generating with tradition generating.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (16)
1. a phototropic face Seed Layer slurry for SE crystal-silicon solar cell, is characterized in that, described phototropic face Seed Layer slurry is the mixture that contains 70-85wt% metal function powder, 2-10wt% unorganic glass powder and 5-20wt% organic carrier; In described metal function powder, contain ball shaped nano antimony powder.
2. phototropic face Seed Layer slurry according to claim 1, is characterized in that, the middle particle diameter D of described ball shaped nano antimony powder
50 1be 30 ~ 600nm; Specific area is 3 ~ 8m
2/ g.
3. phototropic face Seed Layer slurry according to claim 2, is characterized in that, the middle particle diameter D of described ball shaped nano antimony powder
50 1be 50 ~ 250nm; Specific area is 4 ~ 5.5m
2/ g.
4. according to the phototropic face Seed Layer slurry described in claim 1-3 any one, it is characterized in that, in described metal function powder, also contain spherical metal bismuth meal; The gross mass of described metal function powder of take is benchmark, and the content of spherical metal bismuth meal is 2 ~ 10wt%.
5. phototropic face Seed Layer slurry according to claim 4, is characterized in that, the middle particle diameter D of described spherical metal bismuth meal
50 2be 0.1 ~ 3.5 μ m.
6. according to the phototropic face Seed Layer slurry described in claim 1-3 any one, it is characterized in that, in described metal function powder, also contain spherical metal glass putty; The gross mass of described metal function powder of take is benchmark, and the content of spherical metal glass putty is 0.5 ~ 5wt%.
7. phototropic face Seed Layer slurry according to claim 6, is characterized in that, the middle particle diameter D of described spherical metal glass putty
50 3be 0.1 ~ 3.5 μ m.
8. according to the phototropic face Seed Layer slurry described in claim 1-3 any one, it is characterized in that, in described metal function powder, also contain spherical micro aluminum powder; The gross mass of described metal function powder of take is benchmark, and the content of spherical micro aluminum powder is 1 ~ 10wt%.
9. phototropic face Seed Layer slurry according to claim 8, is characterized in that, the middle particle diameter D of described spherical micro aluminum powder
50 4be 0.1 ~ 3.5 μ m, specific area is 1 ~ 3.5m
2/ g, tap density is 4 ~ 7g/cm
3.
10. phototropic face Seed Layer slurry according to claim 1, is characterized in that, described unorganic glass powder is Bi
2o
3-B
2o
3-SiO
2system glass dust, it specifically consists of: the Bi of 75 ~ 85wt%
2o
3, the B of 5 ~ 15wt%
2o
3, the SiO of 2 ~ 10wt%
2, the ZnO of 0.5 ~ 5wt%, the TiO of 0 ~ 2wt%
2.
11. according to the phototropic face Seed Layer slurry described in claim 1 or 10, it is characterized in that the middle particle diameter D of described unorganic glass powder
50 5be that 0.1 ~ 1 μ m, softening point are 400 ~ 450 ℃.
The preparation method of the phototropic face Seed Layer slurry of 12. SE crystal-silicon solar cells claimed in claim 1, it is characterized in that, comprise unorganic glass powder is first scattered in organic carrier, then add metal function powder in batches, be ground to after slurry fineness is less than 5 μ m and obtain described SE crystal-silicon solar cell phototropic face Seed Layer slurry.
The preparation method of 13. 1 kinds of SE crystal-silicon solar cells, it is characterized in that, comprise the following steps: first at silicon chip back side successively printed back conductive silver slurry and back field aluminum paste material, after oven dry at the phototropic face Seed Layer slurry described in front side of silicon wafer printing claim 1-11 any one, after drying, adopt and align technique at Seed Layer slurry printed layers surface continuation printing phototropic face conductive silver slurry, enter continuous tunnel furnace sintering, obtain described SE crystalline silicon solar cell piece.
14. preparation methods according to claim 13, is characterized in that, the method for printing Seed Layer slurry is silk screen printing, and printing wet-film thickness is 5-10 μ m; The method of printing phototropic face conductive silver slurry is silk screen printing, and printing wet-film thickness is 10-15 μ m.
15. preparation methods according to claim 13, is characterized in that, preheat temperature during sintering is 200 ~ 500 ℃, and peak temperature is 910 ~ 930 ℃, and the whole time that crosses continuous tunnel furnace is 3 ~ 5min, and peak value sintering time is 2 ~ 5s.
16. 1 kinds of SE crystal-silicon solar cells, is characterized in that, described SE crystal-silicon solar cell is prepared by the preparation method described in claim 13-15 any one.
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