CN103811100A - Silicon solar cell back-surface field forming aluminum paste and preparation method thereof - Google Patents
Silicon solar cell back-surface field forming aluminum paste and preparation method thereof Download PDFInfo
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- CN103811100A CN103811100A CN201410020146.2A CN201410020146A CN103811100A CN 103811100 A CN103811100 A CN 103811100A CN 201410020146 A CN201410020146 A CN 201410020146A CN 103811100 A CN103811100 A CN 103811100A
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Abstract
The invention discloses silicon solar cell back-surface field forming aluminum paste and a preparation method thereof. The silicon solar cell back-surface field forming aluminum paste comprises, by mass, 70-75 parts of aluminum powder, 0.5-3.0 parts of inorganic adhesives, and 20-25 parts of organic carriers, wherein the inorganic adhesives comprise glass powder; the silicon solar cell back-surface field forming aluminum paste further comprises 10-30 wt.% of inorganic oxide or anaerobic ceramic micro powder, and 1.0-10wt.% of organic acid is added to the organic carriers. The organic carriers, the inorganic adhesives and the aluminum powder are proportionally put into a stirring machine to be continuously stirred for 2 hours to form a uniform system, and then ground by a three-roll grinder into the paste, wherein the viscosity of the paste is controlled to be 20-30 pa.s. According to the silicon solar cell back-surface field forming aluminum paste and the preparation method thereof, the problem of large deformation of thin silicon wafers during a sintering process of aluminum paste in a back-surface field is solved.
Description
Technical field
The present invention relates to a kind of solar cell field of new, relate in particular to a kind of crystal silicon solar batteries back surface field and form with aluminium paste and preparation method thereof.
Background technology
Along with the continuous consumption of fossil energy and the destruction to earth environment of causing thus, find clean energy resource, become one of key issue of human kind sustainable development; Solar energy is the source of inexhaustible clean energy.At present, solar cell (photovoltaic) is through the lasting exploitation of more than 50 years, obtained the development of advancing by leaps and bounds, and become the main path that obtains energy from the sun, it is applied from space technology, military project to civilian, affects its a large amount of key factors that use and remains cost of electricity-generating.
Use in solar cell current, crystal silicon solar batteries accounts for more than 90%, and silicon chip still accounts for the more than 50% of total cost in crystal silicon solar pond, the silicon wafer thickness using in present stage suitability for industrialized production is all more than 200 μ m, constantly reduce the thickness of silicon chip, the use that reduces silicon is still one of striving direction reducing cost of electricity-generating.
In the production of current crystal silicon solar batteries, from lateral thinkings such as cost efficiencys, all adopt the back up aluminium paste at P type crystal silicon solar batteries sheet, form aluminium back surface field through oversintering.Increase carrier lifetime, reduce compound.Thereby realize good contact and improve transformation efficiency.The basic production technique of crystal silicon solar batteries is as follows:
To purchasing the polysilicon chip of the standard (156mm × 156mm) of coming, thickness is 200 ± 5 μ m, forms matte through acid, caustic corrosion, and thickness reduces to 160 ± 5 μ m; Carry out phosphorus with pocl3 and be diffused in the positive N-type emitter that forms, produce P/N knot; Use again PECVD (plasma gas-phase deposit), form SiNx anti-reflection layer in front; On this polysilicon chip, first stamp back silver slurry, dry.Stamp again back surface field and form with aluminium paste oven dry, then stamp front silver electrode paste in front, form complete monolithic solar cell through high temperature sintering.
In prior art, the relevant aluminium paste (by aluminium powder+organic carrier+inorganic adhesive) that crystal silicon solar batteries is produced, a lot of patents are all gone out both at home and abroad, as CN102142467A, CN102169739A, CN101425545A, US2007/0079868Al, U.S2008/0302411Al, JP2010-251389, JP2005-317898, JP2009-129600 etc.
Above-mentioned prior art is described is to be all applied to thick silicon chip (> 200 μ aluminium paste m) cannot solve the large problem (> 2mm) of sintering warpage amount that thin silicon sheet is relevant.
Summary of the invention
The object of this invention is to provide a kind of crystal silicon solar batteries back surface field that can reduce thin silicon sheet deflection in back field aluminum paste sintering process forms with aluminium paste and preparation method thereof.
The object of the invention is to be achieved through the following technical solutions:
Crystal silicon solar batteries back surface field formation aluminium paste of the present invention, comprise the aluminium powder of 70～75 mass parts, the inorganic adhesive of 0.5～3.0 mass parts, the organic carrier of 20～25 mass parts, described inorganic adhesive comprises glass dust, also comprise inorganic oxide or anaerobic ceramic, in described organic carrier, add organic acid.
Above-mentioned crystal silicon solar batteries back surface field of the present invention forms the preparation method with aluminium paste, described organic carrier, inorganic adhesive and aluminium powder are dropped in mixer to uniform stirring 2 hours in proportion, then the slurry being ground to through three-roll grinder, its viscosity is controlled at 20～30pa.s.
As seen from the above technical solution provided by the invention, the crystal silicon solar batteries back surface field that the embodiment of the present invention provides forms with aluminium paste and preparation method thereof, because inorganic adhesive is except glass dust, also comprise inorganic oxide or anaerobic ceramic, in organic carrier, add organic acid, solved thin silicon sheet and in back field aluminum paste sintering process, produced moderate finite deformation amount problem.
Embodiment
To be described in further detail the embodiment of the present invention below.
Crystal silicon solar batteries back surface field formation aluminium paste of the present invention, its preferably embodiment be:
Comprise the aluminium powder of 70～75 mass parts, the inorganic adhesive of 0.5～3.0 mass parts, the organic carrier of 20～25 mass parts, described inorganic adhesive comprises glass dust, also comprises inorganic oxide or anaerobic ceramic, in described organic carrier, adds organic acid.
Described inorganic oxide or inorganic ceramic micro mist account for 10～30wt%(mass percent of described inorganic adhesive gross mass).
In described organic carrier, add the organic acid of 1.0～10wt%.
Described aluminium powder average grain diameter is that 4.5 μ m to 7.5 μ m, maximum particle diameter are less than or equal to 20 μ m.
The average grain diameter of described glass dust, inorganic oxide and anaerobic ceramic powder is less than or equal to 1.5 μ m, maximum particle diameter is less than or equal to 5.0 μ m.
It is as follows that described organic carrier does not add component before organic acid:
The ethyl cellulose of 10wt% and the DBE of 90wt%, described DBE comprises succinic acid two formicesters, glutaric acid two formicesters of 15wt% and hexanedioic acid two formicesters of 85wt% of 5wt%.
Above-mentioned crystal silicon solar batteries back surface field of the present invention forms the preparation method with aluminium paste, its preferably embodiment be:
Described organic carrier, inorganic adhesive and aluminium powder are dropped in mixer to uniform stirring 2 hours in proportion, then the slurry being ground to through three-roll grinder, its viscosity is controlled at 20～30pa.s.
The preparation method of described organic carrier is: described ethyl cellulose and inorganic acid are joined in described DBE under 80 ℃ of environment to uniform stirring 2 hours.
The average grain diameter of described slip is less than or equal to 10 μ m.
Crystal silicon solar batteries back surface field formation aluminium paste of the present invention, the basic recipe of aluminium paste comprises: crystal silicon solar batteries back surface field forms with in aluminium paste gross mass, the aluminium powder of 70-75wt%.The inorganic binder of 0.5-3.0wt%, the organic carrier of 20-25wt% adds the organic acid of 1.0-10.0 in organic carrier, adds inorganic oxide or the anaerobic ceramic of 10-30wt% in inorganic binder.
Inorganic binder is that glass dust adds inorganic oxide or anaerobic ceramic powder, and glass dust consists of Bi-Si-B-Zn glass.Softening point is again between 400 ℃-500 ℃.Use on record melting, shrend, ball milling method preparation, inorganic oxide comprises: SiO
2, MgO, ZnO, TiO
2, Al
2o
3in one or more composition, the anaerobic ceramic powder of interpolation comprises: SIN
x, SiC, the one in AlN, the amount of adding is in above-mentioned scope time, could and organic carrier in inorganic acid coordinate and control deflection, addition is few, aluminium film sintering degree is higher, rete is densification too, silicon chip deflection is large; In addition situation how, affect the formation of sintering and P+ layer (back surface field), reduce the transformation efficiency of crystal silicon solar batteries.
In organic carrier, add the organic acid of 1.0～10.0wt%, comprise laurate, stearic acid, terephthalic acid (TPA), malonic acid, use wherein one or more combination, addition is lower than institute's how, sintering silicon chip deflection is bigger than normal, addition exceedes practical range, affects the formation of back surface field (P+ layer) after sintering, thereby reduces the transformation efficiency of crystal silicon solar batteries.
Organic carrier comprises ethyl cellulose N20010wt%, inorganic acid 1.0～10.0wt%, DBE (succinic acid two formicesters 5%, dimethyl glutarate 1.5%, hexanedioic acid two formicesters 85%) 80～89%, in DBE, to add ethyl cellulose and organic acid to add thermal agitation 2hr in 80 ℃ be homogeneous solution in gradation.Be organic carrier of the present invention.
Aluminium powder is the ball aluminum powder that nitrogen atomization method is produced, and active aluminium content is greater than 98%, and aluminium content is greater than 99.8%, Fe, Ti impurity is less than 10ppm.
Crystal silicon solar batteries back surface field of the present invention forms the preparation method with aluminium paste, under proportionally stirring, add aluminium powder and inorganic adhesive in organic carrier, continue 2hr and stir formation homogeneous system, guarantee fully to infiltrate between organic carrier and inorganic material the homogeneous mixture that stirring is obtained.Grind rolling 3～5 times through three rollers again, control the fineness≤10 μ m of aluminium paste, viscosity is at 20～30pa.s.
Enumerate preferred embodiment below in order to understand the present invention, but scope of the present invention is not limited to following embodiment.It is 156mm × 156mm polysilicon chip that embodiment tests silicon chip used, and through cleaning, making herbs into wool, diffusion, after the operations such as PECVD, silicon wafer thickness is that 160 ± 5 μ m, German Asy automatic press, meshcount are 290 orders, and printing weight is every 1.2～1.3g.Bake out temperature is 250 ℃, 3 minutes.Dispatch sintering furnace, belt speed 250inch/ minute, 825 ℃～830 ℃ of peak temperatures, back silver slurry uses the PV505 of Du Pont, and front side silver paste uses the PV17F of Du Pont.
Embodiment mono-:
Organic carrier
The under agitation gradation of the stearic acid of the ethyl cellulose of 10wt% weight and 3wt% is joined in the DBE solvent of 87wt%, stir 2hr in 80 ℃ of temperature, form even carrier.DBE solvent specifically consist of dimethyl succinate 5wt%, dimethyl glutarate 15wt%, hexanedioic acid dimethyl ester 85%.
Inorganic adhesive
Glass dust is lead-free glass powder, and it is composed as follows: Bi
2o
375wt%, SiO
25%, Al
2o
31.5%, Zn2.5%, B
2o
316.5%.Above-mentioned AP level (analyzing pure) oxide is mixed in proportion, put into platinum crucible in insulation in 1300 ℃/60 minutes, then through shrend, ball milling becomes unorganic glass powder, with unorganic glass powder 80wt%.SiO
2powder 20%, composition inorganic adhesive.
Aluminium powder
Aluminium powder active aluminium content > 98%, aluminium content >=99.8%, Ti, Fe impurity content≤10ppm, average grain diameter is 5.52 μ m, aluminium powder prepared by the nitrogen protection atomization of maximum particle diameter Dmax≤20 μ m.
The preparation of aluminium paste
Aluminium powder 75wt%, inorganic adhesive 3%, organic carrier 22% stirs 2hr and forms homogeneous mixture at≤50 ℃, then grinds formation fineness≤10 μ m, the aluminium paste of viscosity 20～30pa.s 3～5 times through three-roll grinder.
Comparative example one:
Except inorganic adhesive, other component of aluminium paste and preparation method are identical with embodiment mono-, and inorganic adhesive is glass described in embodiment mono-, does not add inorganic oxide or anaerobic ceramic powder.
Comparative example two:
Except organic carrier, other composition of aluminium paste and preparation method are identical with embodiment mono-, the present embodiment organic carrier N20010wt%, and DBE90wt% composition, does not add inorganic acid.
Embodiment bis-:
The present embodiment organic carrier, aluminium powder and aluminium paste preparation method are identical with embodiment mono-.Inorganic adhesive is mutually for glass adds SiNx micro mist.
Embodiment tri-:
The present embodiment, inorganic adhesive, aluminium paste composition and preparation method are identical with embodiment mono-, and organic carrier consists of: ethyl cellulose N20010wt%, terephthalic acid (TPA) 3wt%, DBE87wt% production method is identical.
Comparative example three:
Commercially available aluminium paste GF-Al-2974
Test result:
Table one, aluminium paste composition parameter
Viscosity is VT-04E viscosimeter, 25 ℃, 60rpm.1# rotor measurement result, and fineness adopts Tianjin QXD type scraper plate fineness scale.
The battery performance that table two burns till and aluminium film surface situation
The substrate of test use is 156mm × 156mm polysilicon chip, and thickness is 160 ± 5 μ m.Emitter sheet resistance is 90; The positive PV-17F of the Du Pont slurry that adopts of electrode, back silver slurry is PV505, sintering furnace is Dispatch standard sintered stove.Belt speed is 250inch/min.Peak temperature is 825 ℃/1～2 second.
The aluminium paste that specific embodiments of the invention obtain can reach following effect:
Use 156mm × 156mm polysilicon chip, silicon wafer thickness is 160 ± 5 μ m.Adopt the PV505 of Du Pont silver slurry at silicon chip back side, the positive 17F of Du Pont positive silver paste, the Dispatch sintering furnace of using.Belt speed 250inch/min, peak temperature 825 ℃/1～2 second.Take commercially available GTF-Al-2974 slurry as reference, deflection > 3mm after this slurry sintering, transformation efficiency is 17.45%.Use slurry deflection≤1mm of the present invention, transformation efficiency >=17.45%.It is more than the average data of 10 sample substrate.Solve thin silicon sheet and in back field aluminum paste sintering process, produced moderate finite deformation amount problem.
The above; only for preferably embodiment of the present invention, but protection scope of the present invention is not limited to this, is anyly familiar with in technical scope that those skilled in the art disclose in the present invention; the variation that can expect easily or replacement, within all should being encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection range of claims.
Claims (9)
1. a crystal silicon solar batteries back surface field formation aluminium paste, comprise the aluminium powder of 70～75 mass parts, the inorganic adhesive of 0.5～3.0 mass parts, the organic carrier of 20～25 mass parts, it is characterized in that, described inorganic adhesive comprises glass dust, also comprise inorganic oxide or anaerobic ceramic, in described organic carrier, add organic acid.
2. crystal silicon solar batteries back surface field formation aluminium paste according to claim 1, is characterized in that, described inorganic oxide or inorganic ceramic micro mist account for 10～30wt% of described inorganic adhesive gross mass.
3. crystal silicon solar batteries back surface field formation aluminium paste according to claim 2, is characterized in that, adds the organic acid of 1.0～10wt% in described organic carrier.
4. crystal silicon solar batteries back surface field formation aluminium paste according to claim 3, is characterized in that, described aluminium powder average grain diameter is that 4.5 μ m to 7.5 μ m, maximum particle diameter are less than or equal to 20 μ m.
5. crystal silicon solar batteries back surface field formation aluminium paste according to claim 4, is characterized in that, the average grain diameter of described glass dust, inorganic oxide and anaerobic ceramic powder is less than or equal to 1.5 μ m, maximum particle diameter is less than or equal to 5.0 μ m.
6. crystal silicon solar batteries back surface field formation aluminium paste according to claim 5, is characterized in that, it is as follows that described organic carrier does not add component before organic acid:
The ethyl cellulose of 10wt% and the DBE of 90wt%, described DBE comprises succinic acid two formicesters, glutaric acid two formicesters of 15wt% and hexanedioic acid two formicesters of 85wt% of 5wt%.
7. the crystal silicon solar batteries back surface field described in claim 1 to 6 any one forms the preparation method with aluminium paste, it is characterized in that, described organic carrier, inorganic adhesive and aluminium powder are dropped in mixer to uniform stirring 2 hours in proportion, the slurry being ground to through three-roll grinder again, its viscosity is controlled at 20～30pa.s.
8. crystal silicon solar batteries back surface field according to claim 7 forms the preparation method with aluminium paste, it is characterized in that, the preparation method of described organic carrier is: described ethyl cellulose and inorganic acid are joined in described DBE under 80 ℃ of environment to uniform stirring 2 hours.
9. crystal silicon solar batteries back surface field according to claim 8 forms the preparation method with aluminium paste, it is characterized in that, the average grain diameter of described slip is less than or equal to 10 μ m.
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