CN109148262A - A kind of cleaning method of the black silicon wafer of solar energy polycrystal - Google Patents
A kind of cleaning method of the black silicon wafer of solar energy polycrystal Download PDFInfo
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- CN109148262A CN109148262A CN201810813246.9A CN201810813246A CN109148262A CN 109148262 A CN109148262 A CN 109148262A CN 201810813246 A CN201810813246 A CN 201810813246A CN 109148262 A CN109148262 A CN 109148262A
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- 229910021418 black silicon Inorganic materials 0.000 title claims abstract description 124
- 238000004140 cleaning Methods 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 64
- 230000008569 process Effects 0.000 claims abstract description 26
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000005554 pickling Methods 0.000 claims abstract description 7
- 238000009792 diffusion process Methods 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 235000012431 wafers Nutrition 0.000 claims description 94
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 40
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 38
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000012545 processing Methods 0.000 claims description 12
- 238000010129 solution processing Methods 0.000 claims description 9
- 235000008216 herbs Nutrition 0.000 claims description 5
- 210000002268 wool Anatomy 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims description 2
- 238000002310 reflectometry Methods 0.000 abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 5
- 230000003749 cleanliness Effects 0.000 abstract description 2
- 239000003518 caustics Substances 0.000 abstract 1
- 238000005201 scrubbing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 39
- 230000002000 scavenging effect Effects 0.000 description 15
- 239000012535 impurity Substances 0.000 description 13
- 238000012546 transfer Methods 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000428 dust Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
-
- 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 present invention relates to the black silicon wafer fields of solar energy polycrystal, disclose a kind of cleaning method of black silicon wafer of solar energy polycrystal.The cleaning method includes once washing, alkali cleaning, once rinsing, mixing pickling and secondary rinsing, the cleaning of the black silicon wafer for the wet process preparation that the present invention is oxidized or pollutes suitable for through a long time placement or transport rear surface.This cleaning method can guarantee that the black silicon wafer reflectivity changes in cleaning front and back are no more than 2%, and can obtain higher short circuit current.Silicon chip surface cleanliness after cleaning improves, and is conducive to the progress of the techniques such as subsequent diffusion, plated film.Caustic scrubbing step in the cleaning method simultaneously, can the flannelette to black silicon wafer modified again, to obtain higher open-circuit voltage and fill factor, obtain the cell piece of higher conversion efficiency.
Description
Technical field
The present invention relates to the black silicon wafer field of solar energy polycrystal more particularly to a kind of cleaning sides of the black silicon wafer of solar energy polycrystal
Method.
Background technique
The black silicon wafer of polycrystalline has relatively low reflectivity, is the mainstream of the following polycrystalline cell piece, but expensive dry method is set
The standby and wet processing with environmental protection pressure, so that some enterprises can only hang back to the technology of preparing of black silicon.Again because of tradition
Additive diamond wire efficiency is relatively low, so, replacing former silicon wafer with the black silicon wafer after making herbs into wool is to improve polycrystalline cell piece transfer efficiency
Effective way.
Currently, the preparation method of black silicon mainly has reactive ion etching method and metal assistant chemical solution etches method, battery
No matter factory buys a kind of that black silicon wafer, can all there are problems that standing time and haulage time, in this process black silicon wafer
It is oxidized easily and pollutes.Black silicon wafer needs to carry out a step cleaning process before entering diffusion, just can ensure that its transfer efficiency, together
When reduce the pollution problem of cell piece to the greatest extent.
Black silicon wafer after placing and transport for a long time, surface is oxidized easily and pollutes, so needing to carry out before diffusion
One step cleaning process.The cleaning method of current black silicon wafer is mainly that mix acid liquor is used to carry out clearly by different cleaning equipments
It washes.This cleaning method can not remove black after placement or transport although the metal impurities of black silicon chip surface can be removed
The promotion of the damage of the flannelette of silicon wafer, the transfer efficiency of the black silicon wafer after cleaning is unobvious.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of cleaning methods of the black silicon wafer of solar energy polycrystal.This is clear
Washing method is specific to the black silicon chip design for being contaminated or aoxidizing by long-time placement or during transportation surface.This
The surface cleanliness of black silicon wafer can be improved in the cleaning method of invention, reduces the pollution ratio of black silicon wafer, and to the flannelette of black silicon wafer
Carry out certain modification.The open-circuit voltage and fill factor of black silicon wafer can be improved by the cleaning method, improve solar energy polycrystal
The transfer efficiency of black silicon wafer.
The specific technical proposal of the invention is: a kind of cleaning method of the black silicon wafer of solar energy polycrystal, comprising the following steps:
(1) primary washing: at normal temperature, the surface of black silicon wafer is washed with water into 10-60s；
(2) alkali cleaning: will be 0.5-5wt% potassium hydroxide solution processing 10- with concentration through step (1) treated black silicon wafer
100s, the temperature of potassium hydroxide solution are 20-30 DEG C, with reaction carry out add potassium hydroxide solution；
(3) primary rinsing: at normal temperature, will treated that black silicon wafer washes with water 10-60s through step (2)；
(4) mix pickling: by be 6-20wt% with concentration through step (3) treated black silicon wafer hydrochloric acid solution, concentration 1-
Mixed acid solution made of the hydrofluoric acid solution and water of 7wt% handles 10-100s, hydrochloric acid solution, hydrofluoric acid in mixed acid solution
The volume ratio of solution and water be 3-10:1-6:2-14, temperature be 20-30 DEG C, with reaction carry out add mixed acid solution；
(5) secondary rinsing: finally, at normal temperature, will through step (4), treated that black silicon wafer washes with water 10-60s, in 50-
30-60s is dried under conditions of 100 DEG C, then enters back into post-order process.
For the present invention by cleaning black silicon wafer with water, aqueous slkali and mixed acid solution, treatment temperature as mild as a dove, makes black silicon wafer
Surface it is cleaner, be conducive to the progress of the techniques such as subsequent diffusion, plated film, while the pollution problem of cell piece can be reduced.Alkali cleaning
Can the flannelette to black silicon wafer modified again, and clean front and back reflectivity changes be no more than 2%, to improve the short of black silicon wafer
Road electric current, open-circuit voltage and fill factor.Pickling can remove the metal impurities and silicon oxide layer of black silicon chip surface.The present invention uses
The mixed acid solution of hydrochloric acid solution and hydrofluoric acid solution cleans black silicon wafer, and Pt can be complexed in the chloride ion in hydrochloric acid solution2+、Au3+、
Ag+、Cd2+、Hg2+、Cu+Equal metal ions, can effectively remove the metal impurities of black silicon chip surface.Hydrofluoric acid solution can remove black silicon
The very thin silicon oxide layer that piece is formed in storage or transportational process on surface.The scavenging period for adjusting water can wash away black silicon wafer table
The impurity in face and remaining acid, aqueous slkali.Adjust acid, the concentration of aqueous slkali and scavenging period with obtain higher open-circuit voltage and
Fill factor finally obtains the cell piece with high conversion efficiency.
Cleaning method through the invention, the pollution ratio of black silicon wafer are reduced to original 1/9th, and black silicon wafer turns
Change improved efficiency 0.1%.The transfer efficiency of the black silicon wafer of common polycrystalline is lower in currently available technology, and the black silicon of polycrystalline
Bottleneck period has also been arrived in the development of piece, and transfer efficiency hardly results in promotion.After the surface of black silicon wafer is oxidized or pollutes, transfer efficiency
It can be declined, influence the performance of solar energy polycrystal cell piece.Currently, a cleaning method can be by black silicon not yet both at home and abroad
Piece surface impurity is cleared and can guarantee that the transformation efficiency of the black silicon wafer after cleaning reaches the level before being contaminated.The present inventor passes through
The reagent concentration and scavenging period during black Wafer Cleaning are adjusted, while removing the impurity and oxide layer of de-black silicon chip surface
Improve the transfer efficiency of black silicon wafer.Although literally 0.1% promotion is smaller, led in solar energy polycrystalline silicon
Domain, the promotion of transfer efficiency 0.1% are also very difficult.
Cleaning process of the invention, it is not very big for seeming with the difference of similar product making herbs into wool in the prior art cleaning, but
It is in the black silicon wafer field of solar energy polycrystal, common cleaning agent is just so several, has been difficult to have in the selection of cleaning agent at present
It breaks through, and the difference of the performance after black Wafer Cleaning mostlys come from the adjustment of different detergent concentrations, proportion and scavenging period.
For a certain performance after black Wafer Cleaning, it can be obtained preferably perhaps by the test of simple limited times
Performance, but the comprehensive performance of the black silicon wafer of solar energy polycrystal after cleaning to be made integrally to get a promotion, but there is no imagination ground that
It is simple.For example, in the process of cleaning, perhaps pollution ratio can be reduced to by the concentration or dosage for increasing a certain cleaning agent
Close to zero, but but will affect the surface reflectivity and short circuit current of black silicon wafer simultaneously, and at present for, people can not also be from
A set of more apparent rule is summed up in a large number of experiments of this complexity.This is also can be black by polycrystalline there is presently no one
Impurities on surface of silicon chip is cleared and can guarantee that the transformation efficiency of the black silicon wafer after cleaning reaches contaminated preceding horizontal cleaning method
Reason.
Preferably, the black silicon wafer extremely spreads surface quilt in preceding through a long time placement or transportational process after cleaning for making herbs into wool
Pollute or be oxidized wet process preparation black silicon wafer.
Cleaning method of the invention is specific to after making herbs into wool cleaning to before spreading in through a long time placement or transportational process
Surface is contaminated or the black silicon wafer of wet process preparation that is oxidized and designs.Cleaning step of the invention is also to exist according to black silicon wafer
By long-time place or during transportation surface generate impurity the characteristics of and design.
Preferably, the concentration of potassium hydroxide solution is 1-4wt% in the step (2).Potassium hydroxide solution can wash away
The greasy dirt of black silicon chip surface, and the flannelette of black silicon wafer is modified again.After the excessive concentration of potassium hydroxide will lead to cleaning
The changing value of the surface reflectivity of black silicon wafer is greater than 2%, reduces the short circuit current of black silicon wafer.By adjusting potassium hydroxide solution
Concentration and scavenging period can control reflectivity, open-circuit voltage and the fill factor of the black silicon wafer in cleaning front and back.
Preferably, the additional amount of potassium hydroxide solution is that 100 black silicon wafers of every processing add 20- in the step (2)
50ml.With the progress in reaction time, the concentration of alkali can decline in solution, so needing to add lye.
Preferably, the additional amount of mixed acid solution is that 100 black silicon wafers of every processing add 100- in the step (4)
200ml hydrochloric acid solution and 40-100ml hydrofluoric acid solution.With the progress in reaction time, sour concentration can decline in solution, institute
To need to add hydrochloric acid and hydrofluoric acid, hydrochloric acid solution and hydrofluoric acid solution are molten according to hydrochloric acid solution in former mixed solution and hydrofluoric acid
The volume ratio of liquid is added.
Preferably, the step (1), (3), the water in (5) are at least one of deionized water, ultrapure water.
Preferably, the time that water cleans in the step (1) is 30-60s, potassium hydroxide solution processing in step (2)
Time be 40-60s, the time of water cleaning is 40-60s in step (3), in step (4) time of mixed acid solution processing be
40-60s, the time of water cleaning is 40-60s in step (5).
Water scavenging period is preferably 30-60s in the step of cleaning method of the invention (1), and scavenging period is too short, will lead to
The punching of the impurity such as the dust of black silicon chip surface is attached to not wash clean.The processing time of potassium hydroxide solution is preferably in step (2)
40-60s, scavenging period is too short, and the greasy dirt of black silicon chip surface does not wash clean clearly, handles overlong time, will lead to black silicon chip surface
Reflectivity increase.Water cleaning in step (3) is mainly washed away through step (2) treated the black remaining alkali of silicon chip surface
Liquid does not wash clean clearly if washing time is too short.The scavenging period of mixed acid solution is preferably 40-60s in step (4), when cleaning
Between it is too short, the removal of the metal impurities and silicon oxide layer of black silicon chip surface is not clean, and scavenging period is too long to will affect turning for black silicon wafer
Change efficiency.Water scavenging period is preferably 40-60s in step (5), and scavenging period is too short, will lead to the remaining acid of black silicon chip surface
Liquid removal is not clean.
It is compared with the prior art, the beneficial effects of the present invention are: black silicon wafer is passed through water, aqueous slkali and mixed acid by the present invention
The cleaning of solution, surface is cleaner, is conducive to the progress of the techniques such as subsequent diffusion, plated film.Alkali cleaning can be to the suede of black silicon wafer
Face is modified again, and clean front and back reflectivity changes be no more than 2%, thus obtain higher short circuit current, open-circuit voltage and
Fill factor.
Specific embodiment
The present invention will be further described with reference to the examples below.Related device, connection structure in the present invention
And method, if being device well known in the art, connection structure and method without refering in particular to.
Embodiment 1
A kind of cleaning method of the black silicon wafer of solar energy polycrystal, comprising the following steps:
(1) primary washing: under room temperature, black silicon chip surface 30s is cleaned with deionized water, this walks black silicon chip surface dust capable of washing etc.
Impurity.
(2) alkali cleaning: the black silicon wafer after deionized water is cleaned handles 40s with the potassium hydroxide solution that concentration is 1wt%,
The temperature of potassium hydroxide solution is 20 DEG C, and with the progress in reaction time, 100 black silicon wafers of every processing add 30mL potassium hydroxide
Solution.This step process can the structure to black silicon chip surface modified again, this process will control variation before and after reflectivity and not surpass
2% is crossed, its short circuit current otherwise can be reduced.
(3) it primary rinsing: at normal temperature, will be carried out clearly by the black silicon wafer of potassium hydroxide solution processing with deionized water
It washes, scavenging period 40s cleans remaining potassium hydroxide solution.
(4) mix pickling: again by deionized water clean black silicon wafer, with concentration be 6wt% hydrochloric acid solution 30L, concentration
Mixed solution made of hydrofluoric acid solution 10L and 140L deionized water for 1wt% handles 40s, and temperature is 20 DEG C.With reaction
The progress of time, 100 black silicon wafers of every processing add 100mL hydrochloric acid solution and 40ml hydrofluoric acid solution.Hydrochloric acid and hydrofluoric acid
Mixed solution can remove remaining lye and foreign metal ion.
(5) it secondary rinsing: finally, at normal temperature, being cleaned the remaining acid solution of black silicon chip surface using deionized water, cleans
Time is 40s, and dries 40s under the conditions of 50 DEG C, then enters back into post-order process.
Embodiment 2:
A kind of cleaning method of the black silicon wafer of solar energy polycrystal, comprising the following steps:
(1) primary washing: under room temperature, black silicon chip surface 50s is cleaned with deionized water, this walks black silicon chip surface dust capable of washing etc.
Impurity.
(2) alkali cleaning: the black silicon wafer after deionized water is cleaned handles 50s with the potassium hydroxide solution that concentration is 2wt%,
The temperature of potassium hydroxide solution is 25 DEG C, and with the progress in reaction time, 100 black silicon wafers of every processing add 40mL potassium hydroxide
Solution.This step process can the structure to black silicon chip surface modified again, this process will control variation before and after reflectivity and not surpass
2% is crossed, its short circuit current otherwise can be reduced.
(3) it primary rinsing: at normal temperature, will be carried out clearly by the black silicon wafer of potassium hydroxide solution processing with deionized water
It washes, scavenging period 50s cleans remaining potassium hydroxide solution.
(4) mix pickling: again by deionized water clean black silicon wafer, with concentration be 18wt% hydrochloric acid solution 90L, concentration
Mixed solution made of hydrofluoric acid solution 30L and 60L deionized water for 3.3wt% handles 50s, and temperature is 25 DEG C.With anti-
Progress between seasonable, 100 black silicon wafers of every processing add 150mL hydrochloric acid solution and 60ml hydrofluoric acid solution.Hydrochloric acid and hydrofluoric acid
Mixed solution can remove remaining lye and foreign metal ion.
(5) it secondary rinsing: finally, at normal temperature, being cleaned the remaining acid solution of black silicon chip surface using deionized water, cleans
Time is 50s, and dries 50s under the conditions of 75 DEG C, then enters back into post-order process.
Embodiment 3:
A kind of cleaning method of the black silicon wafer of solar energy polycrystal, comprising the following steps:
(1) primary washing: under room temperature, black silicon chip surface 50s is cleaned with deionized water, this walks black silicon chip surface dust capable of washing etc.
Impurity.
(2) alkali cleaning: the black silicon wafer after deionized water is cleaned handles 50s with the potassium hydroxide solution that concentration is 4wt%,
The temperature of potassium hydroxide solution is 30 DEG C, and with the progress in reaction time, 100 black silicon wafers of every processing add 50mL potassium hydroxide
Solution.This step process can the structure to black silicon chip surface modified again, this process will control variation before and after reflectivity and not surpass
2% is crossed, its short circuit current otherwise can be reduced.
(3) it primary rinsing: at normal temperature, will be carried out clearly by the black silicon wafer of potassium hydroxide solution processing with deionized water
It washes, scavenging period 60s cleans remaining potassium hydroxide solution.
(4) pickling is mixed: the black silicon wafer for again cleaning deionized water, the hydrochloric acid solution 100L, dense for being 20wt% with concentration
Degree is that mixed solution made of hydrofluoric acid solution 60L and the 20L deionized water of 6.7wt% handles 50s, and temperature is 30 DEG C.With
The progress in reaction time, 100 black silicon wafers of every processing add 200mL hydrochloric acid solution and 100ml hydrofluoric acid solution.Hydrochloric acid and hydrogen fluorine
The mixed solution of acid can remove remaining lye and foreign metal ion.
(5) it secondary rinsing: finally, at normal temperature, being cleaned the remaining acid solution of black silicon chip surface using deionized water, cleans
Time is 60s, and dries 60s under the conditions of 100 DEG C, then enters back into post-order process.
Performance evaluation
Black silicon wafer is divided into sisters' piece before cleaning, Examples 1 to 3 and contrast groups (not cleaning) are different in addition to cleaning process, other
Cell piece process conditions processed all ensure that the same.The following table 1 gives the electrical ginseng that Examples 1 to 3 and contrast groups (not cleaning) measure
Number.The following table 2 gives Examples 1 to 3 and contrast groups (not cleaning) after silk-screen printing, the damage ratio of the cell piece detected
Example.
Table 1
| Uoc(V) | Isc(A) | Rs(mΩ) | Rsh(Ω) | FF (%) | NCell (%) | |
| Embodiment 1 | 0.6390 | 9.1799 | 2.41 | 314.32 | 79.30 | 18.93 |
| Embodiment 2 | 0.6399 | 9.1900 | 2.32 | 375.44 | 79.32 | 18.98 |
| Embodiment 3 | 0.6410 | 9.1630 | 2.42 | 323.44 | 79.30 | 18.95 |
| Contrast groups | 0.6385 | 9.1700 | 2.22 | 380.44 | 79.23 | 18.88 |
Table 2
| Pollution ratio | |
| Embodiment 1 | 0.15% |
| Embodiment 2 | 0.1% |
| Embodiment 3 | 0.1% |
| Contrast groups | 0.9% |
Wherein, Uoc is open-circuit voltage, and Isc is short circuit current, and Rs is series resistance, and Rsh is parallel resistance, and FF is fill factor,
Ncell is the transfer efficiency of cell piece.Contrast groups are with Examples 1 to 3 using identical evaluation parameter.Compared with contrast groups,
Embodiment 1, the open-circuit voltage of embodiment 2 and embodiment 3, short circuit current and fill factor all improve, in embodiment 3
The concentration of alkali cleaning step alkali is 2 times of embodiment 2, and alkali cleaning temperature is also higher.The reflectivity of black silicon wafer increases after embodiment 3 is cleaned
2%, it can decrease so the short circuit current of embodiment 3 and embodiment 2 compare, and reflectivity only increases in embodiment 2
1%, so the transfer efficiency of treated the black silicon wafer of embodiment 3 is relatively low.Dirt in terms of pollution ratio data, in Examples 1 to 3
Dye ratio has and significantly reduces, and embodiment 2 and embodiment 3 can ensure that minimum pollution ratio substantially.So comprehensive conversion
Efficiency and pollution ratio, it is final to determine that embodiment 2 is most preferred embodiment, and the transfer efficiency of black silicon wafer and unwashed contrast groups
Compared to improving 0.1%.Although literally 0.1% promotion is smaller, in solar energy polycrystalline silicon field, conversion
The promotion of efficiency 0.1% has been very big improves.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way, it is all according to the present invention
Technical spirit any simple modification, change and equivalent structure transformation to the above embodiments, still fall within skill of the present invention
The protection scope of art scheme.
Claims (7)
1. a kind of cleaning method of the black silicon wafer of solar energy polycrystal, which comprises the following steps:
(1) primary washing: at normal temperature, the surface of black silicon wafer is washed with water into 10-60s；
(2) alkali cleaning: will be 0.5-5wt% potassium hydroxide solution processing 10- with concentration through step (1) treated black silicon wafer
100s, the temperature of potassium hydroxide solution are 20-30 DEG C, with reaction carry out add potassium hydroxide solution；
(3) primary rinsing: at normal temperature, will treated that black silicon wafer washes with water 10-60s through step (2)；
(4) mix pickling: by be 6-20wt% with concentration through step (3) treated black silicon wafer hydrochloric acid solution, concentration 1-
Mixed acid solution made of the hydrofluoric acid solution and water of 7wt% handles 10-100s, and hydrochloric acid solution, hydrofluoric acid are molten in mixed acid solution
The volume ratio of liquid and water be 3-10:1-6:2-14, temperature be 20-30 DEG C, with reaction carry out add mixed acid solution；
(5) secondary rinsing: finally, at normal temperature, will through step (4), treated that black silicon wafer washes with water 10-60s, in 50-
30-60s is dried under conditions of 100 DEG C, then enters back into post-order process.
2. a kind of cleaning method of the black silicon wafer of solar energy polycrystal as described in claim 1, which is characterized in that the black silicon wafer is
The black silicon for the wet process preparation that surface is contaminated or is oxidized into through a long time placement before diffusion or transportational process after making herbs into wool is cleaned
Piece.
3. a kind of cleaning method of the black silicon wafer of solar energy polycrystal as described in claim 1, which is characterized in that the step (2)
The concentration of middle potassium hydroxide solution is 1-4wt%.
4. a kind of cleaning method of the black silicon wafer of solar energy polycrystal as described in claim 1, which is characterized in that the step (2)
The additional amount of middle potassium hydroxide solution is that 100 black silicon wafers of every processing add 20-50ml potassium hydroxide solution.
5. a kind of cleaning method of the black silicon wafer of solar energy polycrystal as described in claim 1, which is characterized in that the step (4)
The additional amount of middle mixed acid solution is that 100 black silicon wafers of every processing add 100-200ml hydrochloric acid solution and 40-100ml hydrofluoric acid
Solution.
6. a kind of cleaning method of the black silicon wafer of solar energy polycrystal as described in claim 1, which is characterized in that the step (1),
(3), the water in (5) is at least one of deionized water, ultrapure water.
7. a kind of cleaning method of the black silicon wafer of solar energy polycrystal as described in claim 1, which is characterized in that the step (1)
The time of middle water cleaning is 30-60s, and the time of potassium hydroxide solution processing is 40-60s in step (2), and water is clear in step (3)
The time washed is 40-60s, and the time of mixed acid solution processing is 40-60s in step (4), the time of water cleaning in step (5)
For 30-60s.
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