CN103730347B - Recycled silicon wafer texturing method - Google Patents
Recycled silicon wafer texturing method Download PDFInfo
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- CN103730347B CN103730347B CN201410024937.2A CN201410024937A CN103730347B CN 103730347 B CN103730347 B CN 103730347B CN 201410024937 A CN201410024937 A CN 201410024937A CN 103730347 B CN103730347 B CN 103730347B
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- silicon chip
- etching
- etching method
- recycling
- liquid
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 81
- 239000010703 silicon Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 239000002253 acid Substances 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000005530 etching Methods 0.000 claims description 39
- 238000004064 recycling Methods 0.000 claims description 35
- 210000002268 wool Anatomy 0.000 claims description 19
- 238000005516 engineering process Methods 0.000 claims description 17
- 235000008216 herbs Nutrition 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 abstract description 4
- 238000001039 wet etching Methods 0.000 abstract description 4
- 235000012431 wafers Nutrition 0.000 abstract 5
- 239000000126 substance Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000008155 medical solution Substances 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 239000012634 fragment Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000003749 cleanliness Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 provides a recycled silicon wafer texturing method. The method comprises the following steps of S10, emptying chemical liquid in the top tank of the process tank of a texturing device or a wet-etching device; S20, subjecting recycled silicon wafers to passing through the top tank of the process tank and then entering a alkaline washing tank for alkaline washing; S30, enabling the alkaline-washed recycled silicon wafer to enter an acid tank. The recycled silicon wafer texturing method effectively solves the problem that recycled silicon wafer in the prior art are prone to flashing and thinning.
Description
Technical field
The present invention relates to battery manufacturing process technical field, in particular to a kind of etching method recycling silicon chip.
Background technology
Fig. 1 shows the manufacturing process schematic diagram of cell piece of the prior art, as shown in figure 1, the manufacture stream of cell piece
Journey mainly includes making herbs into wool, diffusion, wet etching, pecvd (plasma enhanced chemical vapor deposition method), printing-sintering and survey
Examination packaging and other steps.The effect of above-mentioned steps is specific as follows:
Making herbs into wool: making herbs into wool is carried out to silicon chip surface by the mixed solution of nitric acid and hydrofluoric acid；Cause when removing silicon chip cutting
Surface damage layer；Form rugged surface and substantial amounts of hole in silicon chip surface, increase the sensitive surface on cell piece surface
Long-pending, reduce reflectivity, thus improving the conversion efficiency of solar cell.
Diffusion a: laminar sublayer is spread on p-substrate silicon, defines one layer of p-n junction.
Wet etching: silicon chip is performed etching by the mixed solution of nitric acid and hydrofluoric acid；Etching silicon wafer edge p-n junction,
Cell piece is avoided to leak electricity；Polishing cell backside, plays mirror effect so that sunlight is reflected back inside silicon chip, repeatedly utilizes.
Pecvd: make energy source using low temperature plasma, sample is placed on the electrode of glow discharge under low pressure, utilize
Glow discharge (or separately plus heater) makes sample be warmed up to predetermined temperature, then passes to appropriate reacting gas, and gas is through one
Sequence of chemical reaction and plasma reaction, form solid film in sample surfaces.
Printing-sintering: serigraphy is can not to pass through ink, picture and text portion using the closing of forme non-graphic part silk screen hole
Sub-wire mesh is penetrating to be printed through the principle of ink.By silk screen tensioning and be securely fixed on screen frame, using hand
Work or photochemical method, produce the areas that can pass through ink on silk screen and mesh closing can not pass through ink
Non-graphic part.During printing, ink is put in forme side, is applied with ink position on screen printing forme for the sdueegee (scraper)
Certain pressure, moves to the other end of silk screen simultaneously.In this process, ink leads to from the silk screen of areas under the extruding of scraper
Leak in hole to stock, thus completing one-step print.
Making herbs into wool, diffusion, wet etching, pecvd and print each operation all have defective work produce, above-mentioned unqualified
Product referred to as recycle silicon chip, and above-mentioned recycling silicon chip needs to be processed again.Fig. 2 shows the etching method recycling silicon chip
Schematic flow sheet.As shown in Fig. 2 recycling the etching method of silicon chip to include step: load；Recycling silicon chip is made to pass sequentially through
(it is contained within hno to texturing slot3Mixing liquid with hf), (it is contained within for alkaline bath (it is contained within koh liquid) and acid tank
The mixing liquid of hcl and hf)；Heated-air drying.It is additionally provided with di water (deionized water) to wash after texturing slot, alkaline bath and acid tank
Groove.
Recycle silicon chip it may appear that different degrees of paillette after one or many making herbs into wool process, and part paillette
Lattice is obvious, easily causes assembly flower piece.The recycling of silicon chip can increase the paillette of cell piece, flower piece quantity, reduces into
The appearance ratings of product cell piece are processed, and increase production cost.Additionally, recycling the ratio that silicon chip becomes relatively thin, fragile.The two of silicon chip
Secondary recycling processing method can make cell piece conversion efficiency low, and unqualified ratio is high.
Content of the invention
The present invention is intended to provide a kind of etching method recycling silicon chip, to solve to recycle silicon chip easily to go out in prior art
Existing paillette and thinning problem.
To achieve these goals, according to an aspect of the invention, it is provided a kind of recycle silicon chip etching method,
Comprise the following steps: step s10: by the liquid emptying in the inverted draw cut of etching device or the technology groove of wet-method etching equipment；Step
S20: make recycling silicon chip enter alkaline bath after the inverted draw cut of technology groove and carry out alkali cleaning；Step s30: make the recycling after alkali cleaning
Silicon chip enters acid tank.
Further, it is provided with the upper roller being oppositely arranged and bottom roller, in step s10, liquid in the inverted draw cut of technology groove
Cleaning upper roller and bottom roller after emptying, to remove the liquid of residual on upper roller and bottom roller.
Further, in step s20, the making herbs into wool of recycling silicon chip is made to face down through upper roller and bottom roller.
Further, also include water-washing step between step s20 and step s30 and after step s30.
Further, the inverted draw cut of technology groove is built-in with hno3Mixed solution with hf.
Further, alkaline bath is built-in with koh solution.
Further, the acid tank of etching device is built-in with the mixed solution of hcl and hf；The acid tank of wet-method etching equipment is built-in
There is hf solution.
Application technical scheme, by the liquid row in the inverted draw cut of etching device or the technology groove of wet-method etching equipment
Sky, is so recycled silicon chip when the inverted draw cut of technology groove, is only reacted with the liquid of residual, or do not reacted with liquid, but
It is directly entered alkaline bath and acid tank.So can farthest retain the pile effects of silicon chip first time making herbs into wool and the thickness of silicon chip
Degree, can be effectively reduced the consumption of acid, reduce fragment rate, lift conversion efficiency, improve product qualified rate and reduce battery
The paillette of piece, reducing increases component facade flower piece because of battery paillette.
Brief description
The Figure of description constituting the part of the application is used for providing a further understanding of the present invention, and the present invention shows
Meaning property embodiment and its illustrate for explaining the present invention, does not constitute inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows the manufacturing process schematic diagram of cell piece of the prior art；
Fig. 2 shows the schematic flow sheet of the etching method recycling silicon chip of the prior art；And
Fig. 3 shows the schematic flow sheet of the embodiment of the etching method of the recycling silicon chip according to the present invention.
Specific embodiment
It should be noted that in the case of not conflicting, the embodiment in the application and the feature in embodiment can phases
Mutually combine.To describe the present invention below with reference to the accompanying drawings and in conjunction with the embodiments in detail.
For the silicon chip that recycles mentioned in background technology, paillette and thinning problem easily occur, inventor has carried out one
Find easily to occur after the experimental verification of series paillette and thinning the reason as follows:
Silicon chip, when texturing slot, carries out making herbs into wool by the mixed solution of nitric acid and hydrofluoric acid to silicon chip surface.Above-mentioned work
The purpose of skill is 1) remove the surface damage layer causing during silicon chip cutting.2) form rugged surface and big in silicon chip surface
The hole of amount, increases the light-receiving area on cell piece surface, reduces reflectivity, thus improving the conversion efficiency of solar cell.And again
Etching method using silicon chip identical with silicon chip first time etching method it is also desirable to through texturing slot, the liquid meeting of such the inside
Damage matte, namely make the rugged surface (matte) of silicon chip gradually become smooth, and then make silicon chip easily become class
Paillette like mirror effect.Additionally, many secondary responses, so meeting can be carried out in the matte of silicon chip through texturing slot again or repeatedly
Reduce the thickness of silicon chip, and then thinning problem easily occurs.
For above-mentioned reason, present applicant proposes a kind of effective solution.As shown in figure 3, recycling the system of silicon chip
The preferred embodiment of velvet figures method comprises the following steps:
Step s10: by the medicine in the inverted draw cut (texturing slot or etching groove) of etching device or the technology groove of wet-method etching equipment
Liquid empties；
Step s20: make recycling silicon chip enter alkaline bath after texturing slot and carry out alkali cleaning, alkali cleaning is used for removing pn-junction；
Step s30: make the recycling silicon chip after alkali cleaning enter acid tank.
Apply in this preferred embodiment, it is possible to use etching device or wet-method etching equipment carry out recycling the system of silicon chip
Suede.Technology groove includes inverted draw cut and kerve, and kerve stores liquid, the liquid in inverted draw cut and silicon chip directly contact.Originally it is being preferable to carry out
In mode, by the liquid emptying in the inverted draw cut of technology groove, so recycle silicon chip when texturing slot, only anti-with the liquid of residual
Should, or do not react with liquid, but it is directly entered alkaline bath and acid tank.So can farthest retain silicon chip for the first time
The pile effects of making herbs into wool and the thickness of silicon chip, can be effectively reduced the consumption of acid, reduce fragment rate, lift conversion efficiency, carry
High product qualified rate and the paillette reducing cell piece, reducing increases component facade flower piece because of battery paillette.
When preferably, using etching device, in acid tank, need proportioning finite concentration hf, hcl admixing medical solutions, wherein hcl measures
Concentration than high point of the prior art, reason is the metal impurities that hcl can remove silicon chip surface, and hf can purify silicon
Piece cleanliness factor.
It is provided with the upper roller being oppositely arranged and bottom roller, in step s10, liquid cleans upper roller after discharging in texturing slot
And bottom roller, to remove the liquid of residual on upper roller and bottom roller.Can be using clear after the liquid in texturing slot is discharged
Water cleaning upper roller and bottom roller be not so that have liquid completely on upper roller and bottom roller.
Or, in step s10, liquid need not clean upper roller and bottom roller after discharging, and upper roller and bottom roller have
There is the liquid of residual.So, manufacture when recycling silicon chip, some recycle silicon chips through out-of-date can will be residual on upper roller and bottom roller
The liquid staying carries away, and so also can make not having completely liquid on upper roller and bottom roller.
For the ease of follow-up diffusion technique, in step s20, the making herbs into wool of recycling silicon chip is made to face down through upper roller
And bottom roller.Additionally, through experimental verification, when the liquid of residual is had on upper roller and bottom roller, recycling the system of silicon chip
Matte, upward after alkaline bath and acid tank, finds there is rolling wheel stamp on the making herbs into wool face recycle silicon chip.So, impact recycles silicon
Beautiful appearance after piece plated film, causes surface unqualified.Main cause is that have hf, hno on roller3Mixing medicine, silicon chip and rolling
The place corrosion of wheel contact is too high, forms rolling wheel stamp.And when the liquid of residual is had on upper roller and bottom roller, recycle silicon
The making herbs into wool of piece faces down after alkaline bath and acid tank, the making herbs into wool face of recycling silicon chip does not have rolling wheel stamp, main cause is silicon
The area that piece is contacted with bottom roller increases, and the area of whole silicon chip all can touch roller, participates in liquid and reacts than more uniform.
Further illustrate beneficial effects of the present invention with reference to specific embodiment.
Embodiment one
Texturing slot (hf, hno etching device3Admixing medical solutions groove) inverted draw cut liquid flows back to kerve it is ensured that in texturing slot
Upper roller and bottom roller on hf, hno of having not a particle of3Admixing medical solutions.After proportioning certain density koh, hf, hcl, wherein
, in 12-15, the electrical conductivity of acid tank is in 650-690 for the electrical conductivity of koh groove.After recycling silicon chip to be directly over alkaline bath and acid tank,
Recycle silicon chip surface clean, dark line is normal, the matte after the brightness of piece and normally former silicon wafer wool making is similar, diffused sheet resistance
Uniformity poor 5.1%, the efficiency of cell piece is 17.31%, and unqualified ratio is 4.8%.
Embodiment two
The concentration of change alkali groove, the electrical conductivity improving alkali groove is 18, the texturing slot (mixing of hf, hno3 of etching device
Dipper) inverted draw cut liquid flows back to kerve it is ensured that there being the mixing medicine of some hf, hno3 on upper roller in texturing slot and bottom roller
Liquid.Recycling silicon wafer wool making to face up, it is directly over alkali groove, after acid tank, finds that some recycle the making herbs into wool face of silicon chips still
There is rolling wheel stamp, reason is that silicon chip local corrosion is too high, be not the porous silicon that silicon chip participates in chemical reaction in technique and generates.
According to the experiment condition of embodiment two, the etching device speed of service is set as the cell piece effect that 2.1 tracking recycle
Rate, data is as follows:
Other specification setting is constant, and the change equipment speed of service is 1.8, follows the tracks of the cell piece efficiency recycling, data is such as
Under:
Wherein, uoc refer to the voltage of cell piece, isc refer to electric current, rser refer to series connection, rsh refer to parallel connection, ff refer to filling,
Ncell refers to transformation efficiency, irev1 refers to electric leakage, count refers to piece number.
Embodiment three
Technology groove (hf, hno etching device3Admixing medical solutions groove) inverted draw cut liquid flows back to kerve it is ensured that in technology groove
Upper roller and bottom roller on have some hf, hno3Admixing medical solutions, alkali groove, acid tank concentration proportioning are same as embodiment two.Profit again
Faced down with silicon wafer wool making, be directly over alkali groove, after acid tank, the making herbs into wool face recycling silicon chip does not have rolling wheel stamp, main cause
It is that the area that contacts with bottom roller of silicon chip increases that (area of whole silicon chip all can touch roller, participates in liquid reaction more equal
Even.A certain amount of hf, hno are carried on bottom roller3Admixing medical solutions, can cleaning silicon wafer surface to a certain extent cleanliness factor.
Identical with the conductance of acid tank in alkaline bath, under the premise of equipment speed of service identical, the recycling of prior art
Technique is counted with the recycling artistic face piece of the application, and fragment rate statistics and assembly flower piece statistics are as follows:
Wherein, during experiment, the equipment speed of service is 2.0m/min, and alkali groove electrical conductivity is 15ms, and acid tank electrical conductivity is
660ms.Automatic liquid supply amount hno3 is 25/45ml, and hf is 25/92ml.Prior art recycling texturing slot parameter be
Speed 2.5m/min, temperature is 10 °.
| Contrast experiment | Surface proportion | Fragment rate | Assembly flower piece |
| Prior art | 2.2% | 3.95% | 65% |
| The application | 2.7% | 1.67% | 16.5% |
Wherein, a general block assembly is to be together in series by 60 cell pieces, and surface proportion refers to have in a block assembly
The shinny cell piece of 39 lattices.
Contrasted by small lot batch manufacture, the battery of the recycling technique of prior art and the recycling technique productions of the application
Piece parameter is as follows:
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, made any repair
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (7)
1. a kind of etching method recycling silicon chip is it is characterised in that comprise the following steps:
Step s10: by the liquid emptying in the inverted draw cut of etching device or the technology groove of wet-method etching equipment；
Step s20: make recycling silicon chip enter alkaline bath after the inverted draw cut of described technology groove and carry out alkali cleaning；
Step s30: make the described recycling silicon chip after alkali cleaning enter acid tank.
2. etching method according to claim 1 it is characterised in that be provided with the inverted draw cut of described technology groove is oppositely arranged
Upper roller and bottom roller, in described step s10, clean described upper roller and described bottom roller, to go after described liquid emptying
Described liquid except residual on described upper roller and described bottom roller.
3. etching method according to claim 2 is it is characterised in that in described step s20, make described recycling silicon chip
Making herbs into wool face down through described upper roller and described bottom roller.
4. etching method according to claim 1 is it is characterised in that between described step s20 and step s30 and described
Water-washing step is also included after step s30.
5. etching method according to claim 1 is it is characterised in that the inverted draw cut of described technology groove is built-in with hno3With hf's
Mixed solution.
6. etching method according to claim 1 is it is characterised in that described alkaline bath is built-in with koh solution.
7. etching method according to claim 1 is it is characterised in that the acid tank of described etching device is built-in with hcl and hf
Mixed solution；The acid tank of described wet-method etching equipment is built-in with hf solution.
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| CN201410024937.2A CN103730347B (en) | 2014-01-10 | 2014-01-10 | Recycled silicon wafer texturing method |
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| CN201410024937.2A CN103730347B (en) | 2014-01-10 | 2014-01-10 | Recycled silicon wafer texturing method |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4062102A (en) * | 1975-12-31 | 1977-12-13 | Silicon Material, Inc. | Process for manufacturing a solar cell from a reject semiconductor wafer |
| CN102496569A (en) * | 2011-12-31 | 2012-06-13 | 英利集团有限公司 | Texturing method of monocrystal N type solar cell slice |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011515872A (en) * | 2008-03-25 | 2011-05-19 | アプライド マテリアルズ インコーポレイテッド | Surface cleaning and uneven formation process of crystalline solar cell |
| US20110079250A1 (en) * | 2009-10-01 | 2011-04-07 | Mt Systems, Inc. | Post-texturing cleaning method for photovoltaic silicon substrates |
| CN102214726B (en) * | 2010-04-01 | 2013-03-06 | 索日新能源股份有限公司 | Method for treating flocking on surface of solar silicon slice |
| CN201796935U (en) * | 2010-09-29 | 2011-04-13 | 常州天合光能有限公司 | Single surface etching equipment through corrosive acid |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4062102A (en) * | 1975-12-31 | 1977-12-13 | Silicon Material, Inc. | Process for manufacturing a solar cell from a reject semiconductor wafer |
| CN102496569A (en) * | 2011-12-31 | 2012-06-13 | 英利集团有限公司 | Texturing method of monocrystal N type solar cell slice |
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