CN102306681A - Quasi-monocrystalline silicon etching method - Google Patents
Quasi-monocrystalline silicon etching method Download PDFInfo
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- CN102306681A CN102306681A CN201110265315A CN201110265315A CN102306681A CN 102306681 A CN102306681 A CN 102306681A CN 201110265315 A CN201110265315 A CN 201110265315A CN 201110265315 A CN201110265315 A CN 201110265315A CN 102306681 A CN102306681 A CN 102306681A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to the solar energy cell production technology method field, concretely relating to a quasi-monocrystalline silicon etching method which comprises an alkaline etching operation on a quasi-monocrystalline silicon which mainly is (100) crystal grain and an acid etching operation on the quasi-monocrystalline silicon. Compared with simple acid etching, according to the invention, photoelectric conversion efficiency of a quasi-monocrystalline cell is obviously raised, a shiny phenomenon of part etching face caused by adopting simple alkaline etching can be obviously eliminated, and a whole process can be accurately adjusted according to an area the (100) crystal grain occupies. The quasi-monocrystalline silicon etching method has the characteristics of a fully controllable processing process, a good integral etching effect, qualified appearance and simple technology, and is suitable for quasi-monocrystalline silicon large scale production.
Description
Technical field
The present invention relates to the production technology method field of solar cell, be specifically related to a kind of etching method of quasi-monocrystalline silicon sheet.
Background technology
Making herbs into wool is that preparation has the silicon chip surface processing method that reduces the light reflection, with surface-texturing, utilizes the sunken light action on surface to improve absorbing of light, is to make the requisite operation of high performance solar batteries.
In the manufacture craft of silicon solar cell, monocrystalline silicon piece generally adopts the alkali making herbs into wool method of anisotropic to form the pyramid matte at silicon chip surface, makes incident ray repeatedly reflect, and has improved the absorption of light greatly, reaches the purpose that improves conversion efficiency.It is local that alkali etching method technology becomes, and is applicable to the scale of mass production of monocrystalline silicon piece.
Polysilicon chip exists a large amount of crystal boundaries and defective, compare the monocrystalline silicon piece conversion efficiency and will hang down 1.5-2%, but polysilicon chip compares monocrystalline silicon piece and has tangible cost advantage, and the ratio that in solar cell market, occupies in recent years is increasing.Polysilicon chip can't adopt the alkali etching method because the orientation of each crystal grain differs, and the sour process for etching of general use forms certain etch pit matte on the surface in the production, can play texturing effect preferably.
Monocrystalline silicon and polysilicon exist remarkable advantages and inferior position, are a kind of methods that can monocrystalline, polycrystalline advantage be combined with the accurate single crystal technology of polycrystalline casting ingot method production.Begun volume production quasi-monocrystalline silicon sheet successively at present.The quasi-monocrystalline silicon sheet of present volume production, main body have (100) crystal face to constitute, and the crystal grain in other crystal orientation of growing at random of part is arranged simultaneously.
For such silicon chip, if use the advantage that sour making herbs into wool can't the big crystal grain of fine performance merely; And if simple employing alkali making herbs into wool can't be satisfied the appearance requirement of commercially producing assembly.Combine the existing reported method of soda acid process for etching to carry out sour process for etching earlier at present and carry out the alkali process for etching again for employing; This process controllability in actual production is had relatively high expectations; The easy part of silicon chip surface is shinny; Through behind the PECVD plated film tangible outward appearance aberration is arranged, accurate mono-crystal component outward appearance after the encapsulation and present polycrystalline assembly appearance color difference are bigger.
Summary of the invention
The invention provides a kind of etching method of quasi-monocrystalline silicon sheet, in conjunction with the technological advantage of soda acid making herbs into wool, the technical process simple controllable, after the making herbs into wool effect, battery conversion efficiency is high, be packaged into behind the assembly outward appearance qualified, meet the appearance requirement that assembly is sold.
For realizing above-mentioned purpose, the technical scheme that the present invention adopted is:
A kind of etching method of quasi-monocrystalline silicon sheet comprises that elder generation to being master's quasi-monocrystalline silicon sheet employing alkali making herbs into wool operation with (100) crystal grain, adopts sour making herbs into wool operation again.Wherein, (100) crystal grain is that crystal grain diameter is 100nm.
Further be provided with as such scheme, in the said alkali making herbs into wool operation, the aqueous slkali of being selected for use is NaOH (NaOH) or KOH (potassium hydroxide) solution, and its mass fraction is 1%-3%.
The volume fraction of isopropyl alcohol is 3%-15% in the said aqueous slkali.
Temperature during said aqueous slkali making herbs into wool is 70 ℃-85 ℃.
The corrosion depth of the quasi-monocrystalline silicon sheet after the said alkali making herbs into wool operation is 1 μ m-10 μ m.
In the said sour making herbs into wool operation, the acid solution of being selected for use is HF (hydrofluoric acid) and HNO
3(nitric acid) mixed acid solution, volume fraction are 60%-80%.
Said HF and HNO
3In the mixed acid solution, HF and HNO
3Between volume ratio be 1:2-4.
Temperature during said acid solution making herbs into wool is 3 ℃-10 ℃.
The said alkali making herbs into wool operation of process earlier is after the corrosion depth of the quasi-monocrystalline silicon sheet after the peracid making herbs into wool operation is 2 μ m-20 μ m.
Advantage of the present invention: combine the technological advantage of alkali making herbs into wool and sour making herbs into wool, light utilization is high after the making herbs into wool, and reflectivity is low, and the outward appearance aberration is little.Adopted alkali making herbs into wool on original (100) crystal grain, to form pyramid matte preferably earlier, but non-(100) crystal grain then is burnishing surface, the matte difference in appearance is bigger between the two; Adopt sour process for etching to come this difference in appearance of balance again; Pyramid to forming on (100) crystal grain carries out a spot of corrosion; But the whole high light line utilance of alkali process for etching, the characteristic of antiradar reflectivity of still keeping; Burnishing surface to after non-(100) crystal grain alkali making herbs into wool then forms etch pit with acid solution, and is consistent with the reflectivity of matte after the polycrystalline of the routine acid making herbs into wool.Calculate making herbs into wool again, silicon chip outward appearance high conformity after adopting alkali making herbs into wool.Sour making herbs into wool earlier is the technology of alkali making herbs into wool again, because the alkali making herbs into wool process after the sour making herbs into wool causes the outward appearance aberration bigger to the polishing action of non-(100) crystal grain, adopts the present invention then effectively to avoid the bigger shortcoming of plug-in aberration of quasi-monocrystalline silicon sheet after the making herbs into wool.Adopt accurate monocrystalline process for etching process simple controllable of the present invention, can according to adjustment alkali making herbs into wool of the size of (100) crystal grain coupling and sour making herbs into wool corrosion depth, under the prerequisite that guarantees suitable outward appearance, obtain optimum light utilization.Outward appearance was consistent with conventional polycrystalline assembly outward appearance after the accurate single crystal battery sheet that adopts the present invention to make was packaged into assembly, effectively satisfied the appearance requirement of assembly commercial distribution.
Embodiment
Below in conjunction with specific embodiment the present invention is further described.
Embodiment 1
The silicon chip that experiment is adopted is 156 * 156 the accurate single crystal battery silicon chip of P type, and (100) chip area accounts for whole silicon wafer area >=50%.
Alkali making herbs into wool: select KOH solution, mass fraction is 1.5%, in aqueous slkali, adds isopropyl alcohol, and volume fraction is 5%, wound S929-B making herbs into wool additive when adding in addition, and volume fraction is 0.5%; Solution temperature is 78 ℃, and the control making herbs into wool time makes that silicon chip single face corrosion depth is 3.5 μ m-4 μ m.
Acid making herbs into wool: the silicon chip that will pass through after the alkali making herbs into wool is put into acid solution, and acid solution is HF and HNO
3Mixed acid solution, HF and HNO
3Total volume fraction be 60%, wherein HF and HNO
3Volume ratio is 1:3.2, and the making herbs into wool temperature is 8 ℃, makes that through time control silicon chip single face corrosion depth is 2.5 μ m-3 μ m.
Through the silicon chip that above process for etching obtains, the average reflectance of (100) crystal grain is 11%-13%, and the reflectivity of other crystal grain is 16%-21%, and whole reflectivity is 13%-16%, surveys reflectivity institute and uses the R9000-2DMA of instrument as Ideaoptics company.
The average conversion efficiency of final accurate single crystal battery sheet is 17.4%-17.7%, and battery sheet outward appearance is qualified, does not have tangible aberration, and accurate single crystal battery chip module encapsulation back is consistent with polycrystalline assembly outward appearance, meets the requirements of the customers.
Embodiment 2
The silicon chip that experiment is adopted is 156 * 156 the accurate single crystal battery silicon chip of P type, and (100) chip area accounts for whole silicon wafer area >=70%.
Alkali making herbs into wool: select KOH solution, mass fraction is 1.2%, in aqueous slkali, adds isopropyl alcohol, and volume fraction is 15%, wound S929-B making herbs into wool additive when adding in addition, and volume fraction is 0.5%; Solution temperature is 85 ℃, and the control making herbs into wool time makes that silicon chip single face corrosion depth is 3.5 μ m-4.5 μ m.
Acid making herbs into wool: the silicon chip that will pass through after the alkali making herbs into wool is put into acid solution, and acid solution is HF and HNO
3Mixed acid solution, HF and HNO
3Total volume fraction be 80%, wherein HF and HNO
3Volume ratio is 1:3, and the making herbs into wool temperature is 10 ℃, makes that through time control silicon chip single face corrosion depth is 1.5 μ m-2.5 μ m.
Through the silicon chip that above process for etching obtains, the average reflectance of (100) crystal grain is 10%-12%, and the reflectivity of other crystal grain is 16%-21%, and whole reflectivity is 12%-15%, surveys reflectivity institute and uses the R9000-2DMA of instrument as Ideaoptics company.
The average conversion efficiency of final accurate single crystal battery sheet is 17.6%-18%, and battery sheet outward appearance is qualified, does not have tangible aberration, and accurate single crystal battery chip module encapsulation back is consistent with conventional polycrystalline assembly outward appearance, meets the requirements of the customers.
Embodiment 3
The silicon chip that experiment is adopted is 156 * 156 the accurate single crystal battery silicon chip of P type, and (100) chip area accounts for whole silicon wafer area >=80%.
Alkali making herbs into wool: select KOH solution, mass fraction is 2%, in aqueous slkali, adds isopropyl alcohol, and volume fraction is 3%, wound S929-B making herbs into wool additive when adding in addition, and volume fraction is 0.5%; Solution temperature is 75 ℃, and the control making herbs into wool time makes that silicon chip single face corrosion depth is 4 μ m-5 μ m.
Acid making herbs into wool: the silicon chip that will pass through after the alkali making herbs into wool is put into acid solution, and acid solution is HF and HNO
3Mixed acid solution, HF and HNO
3Total volume fraction be 70%, wherein HF and HNO
3Volume ratio is 1:2; The making herbs into wool temperature is 3 ℃, makes that through time control silicon chip single face corrosion depth is 1.5 μ m-2 μ m.
Through the silicon chip that above process for etching obtains, the average reflectance of (100) crystal grain is 11%-12%, and the reflectivity of other crystal grain is 16%-21%, and whole reflectivity is 12%-15%, surveys reflectivity institute and uses the R9000-2DMA of instrument as Ideaoptics company.
The average conversion efficiency of final accurate single crystal battery sheet is 17.7%-18.2%, and battery sheet outward appearance is qualified, does not have tangible aberration, and accurate single crystal battery chip module encapsulation back is consistent with conventional polycrystalline assembly outward appearance, meets the requirements of the customers.
The foregoing description only is used to the inventive concept of the present invention of explaining, but not to the qualification of rights protection of the present invention, allly utilizes this design that the present invention is carried out the change of unsubstantiality, all should fall into protection scope of the present invention.
Claims (9)
1. the etching method of a quasi-monocrystalline silicon sheet is characterized in that: comprise that elder generation to being master's quasi-monocrystalline silicon sheet employing alkali making herbs into wool operation with (100) crystal grain, adopts sour making herbs into wool operation again.
2. the etching method of a kind of quasi-monocrystalline silicon sheet as claimed in claim 1 is characterized in that: in the said alkali making herbs into wool operation, the aqueous slkali of being selected for use is NaOH or KOH solution, and its mass fraction is 1%-3%.
3. the etching method of a kind of quasi-monocrystalline silicon sheet as claimed in claim 2 is characterized in that: the volume fraction of isopropyl alcohol is 3%-15% in the said aqueous slkali.
4. the etching method of a kind of quasi-monocrystalline silicon sheet as claimed in claim 3 is characterized in that: the temperature during said aqueous slkali making herbs into wool is 70 ℃-85 ℃.
5. the etching method of a kind of quasi-monocrystalline silicon sheet as claimed in claim 4 is characterized in that: the corrosion depth of the quasi-monocrystalline silicon sheet after the said alkali making herbs into wool operation is 1 μ m-10 μ m.
6. the etching method of a kind of quasi-monocrystalline silicon sheet as claimed in claim 1 is characterized in that: in the said sour making herbs into wool operation, the acid solution of being selected for use is HF and HNO
3Mixed acid solution, volume fraction are 60%-80%.
7. the etching method of a kind of quasi-monocrystalline silicon sheet as claimed in claim 6 is characterized in that: said HF and HNO
3In the mixed acid solution, HF and HNO
3Between volume ratio be 1:2-4.
8. the etching method of a kind of quasi-monocrystalline silicon sheet as claimed in claim 7 is characterized in that: the temperature during said acid solution making herbs into wool is 3 ℃-10 ℃.
9. like the etching method of claim 1 or 5 or 8 described a kind of quasi-monocrystalline silicon sheets, it is characterized in that: the said alkali making herbs into wool operation of process earlier is after the corrosion depth of the quasi-monocrystalline silicon sheet after the peracid making herbs into wool operation is 2 μ m-20 μ m.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618938A (en) * | 2012-04-21 | 2012-08-01 | 湖南红太阳光电科技有限公司 | Method for preparing pseudo single crystal silicon chip suede |
| CN102738303A (en) * | 2012-06-20 | 2012-10-17 | 常州天合光能有限公司 | Method for manufacturing single-crystal-like solar cell |
| CN103165753A (en) * | 2013-03-22 | 2013-06-19 | 浙江正泰太阳能科技有限公司 | Preparation method for pseudo-single crystal silicon solar cell |
| CN103258918A (en) * | 2013-05-31 | 2013-08-21 | 英利集团有限公司 | Silicon wafer texturing method, solar battery piece and manufacturing method of solar battery piece |
| CN111883617A (en) * | 2020-08-03 | 2020-11-03 | 山西潞安太阳能科技有限责任公司 | Production process of quasi-single crystal battery piece |
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| CN101634027A (en) * | 2009-08-26 | 2010-01-27 | 北京市太阳能研究所有限公司 | Method for preparing monocrystal silicon textured surface |
| CN101851756A (en) * | 2010-06-08 | 2010-10-06 | 常州时创能源科技有限公司 | Additive of alkali wool making solution for monocrystalline silicon pieces and using method |
| CN101935884A (en) * | 2009-07-02 | 2011-01-05 | 比亚迪股份有限公司 | Method for preparing textured polycrystalline silicon wafer |
| CN102034900A (en) * | 2010-10-27 | 2011-04-27 | 晶澳太阳能有限公司 | Texture etching method for quasi-monocrystalline silicon wafer |
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| CN101935884A (en) * | 2009-07-02 | 2011-01-05 | 比亚迪股份有限公司 | Method for preparing textured polycrystalline silicon wafer |
| CN101634027A (en) * | 2009-08-26 | 2010-01-27 | 北京市太阳能研究所有限公司 | Method for preparing monocrystal silicon textured surface |
| CN101851756A (en) * | 2010-06-08 | 2010-10-06 | 常州时创能源科技有限公司 | Additive of alkali wool making solution for monocrystalline silicon pieces and using method |
| CN102034900A (en) * | 2010-10-27 | 2011-04-27 | 晶澳太阳能有限公司 | Texture etching method for quasi-monocrystalline silicon wafer |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618938A (en) * | 2012-04-21 | 2012-08-01 | 湖南红太阳光电科技有限公司 | Method for preparing pseudo single crystal silicon chip suede |
| CN102738303A (en) * | 2012-06-20 | 2012-10-17 | 常州天合光能有限公司 | Method for manufacturing single-crystal-like solar cell |
| CN103165753A (en) * | 2013-03-22 | 2013-06-19 | 浙江正泰太阳能科技有限公司 | Preparation method for pseudo-single crystal silicon solar cell |
| CN103165753B (en) * | 2013-03-22 | 2015-11-11 | 浙江正泰太阳能科技有限公司 | A kind of preparation method of quasi-monocrystalline silicon solar cell |
| CN103258918A (en) * | 2013-05-31 | 2013-08-21 | 英利集团有限公司 | Silicon wafer texturing method, solar battery piece and manufacturing method of solar battery piece |
| CN111883617A (en) * | 2020-08-03 | 2020-11-03 | 山西潞安太阳能科技有限责任公司 | Production process of quasi-single crystal battery piece |
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Application publication date: 20120104 |