CN104752551A - Cleaning method of solar silicon wafer - Google Patents
Cleaning method of solar silicon wafer Download PDFInfo
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- CN104752551A CN104752551A CN201310726922.6A CN201310726922A CN104752551A CN 104752551 A CN104752551 A CN 104752551A CN 201310726922 A CN201310726922 A CN 201310726922A CN 104752551 A CN104752551 A CN 104752551A
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- silicon wafers
- hydrogen peroxide
- solar silicon
- cleaning method
- solar
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 205
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 205
- 239000010703 silicon Substances 0.000 title claims abstract description 205
- 238000004140 cleaning Methods 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 title claims abstract description 121
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 138
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000005530 etching Methods 0.000 claims abstract description 56
- 229910001868 water Inorganic materials 0.000 claims abstract description 53
- 239000011259 mixed solution Substances 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 26
- 235000012431 wafers Nutrition 0.000 claims description 97
- 230000003647 oxidation Effects 0.000 claims description 38
- 238000007254 oxidation reaction Methods 0.000 claims description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims description 8
- 235000008216 herbs Nutrition 0.000 claims description 8
- 210000002268 wool Anatomy 0.000 claims description 8
- 230000000536 complexating effect Effects 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 7
- 238000013329 compounding Methods 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 229960002163 hydrogen peroxide Drugs 0.000 description 58
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 31
- 229910021417 amorphous silicon Inorganic materials 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000003643 water by type Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000003359 percent control normalization Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000004804 winding Methods 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1876—Particular processes or apparatus for batch treatment of the devices
-
- 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
- H01L21/02057—Cleaning during device manufacture
-
- 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
- H01L21/02096—Cleaning only mechanical cleaning
-
- 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
- H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
-
- 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
-
- 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 discloses a cleaning method of a solar silicon wafer. The method comprises the steps of performing RCA cleaning on the solar silicon wafer: precleaning the solar silicon wafer to oxidize the surface of the silicon wafer, and then performing etching treatment on the solar silicon wafer with an etching solution mixed by hydrogen peroxide, hydrofluoric acid and water. According to the cleaning method, the etching treatment is performed on the precleaned solar silicon wafer with the etching solution mixed by hydrogen peroxide, hydrofluoric acid and the water when the RCA cleaning is performed on the solar silicon wafer, and micro-etching on the surface of the silicon wafer is facilitated by utilizing interface chemistry change of a mixed solution of the silicon wafer, hydrogen peroxide, hydrofluoric acid and the water, so that metal pollution on the surface of the silicon wafer is reduced, compounding of a metal atom on the surface of the silicon wafer and a minority carrier in the silicon wafer is reduced, the service life of the minority carrier in the solar silicon wafer is prolonged, and the efficiency of a solar battery is improved.
Description
Technical field
The present invention relates to technical field of solar, particularly relate to a kind of cleaning method of solar silicon wafers.
Background technology
Along with the increase of solar cell system equalizing feature cost ratio, the conversion efficiency improving solar cell becomes particularly important.At present, solar cell staple market share is occupied by crystal silicon battery, and typical crystalline silicon high-efficiency technology has: selective emitter technology, back contacts high efficiency technical, metal piercing winding technique and the heterogeneous joint technology of crystal silicon/amorphous silicon etc.Wherein, the heterogeneous batteries technology of crystal silicon/amorphous silicon has low-temperature growth, low-temperature coefficient and efficient feature, is considered to the most competitive crystalline silicon high-efficiency technology.
The core point of the heterogeneous batteries of crystal silicon/amorphous silicon is the passivating technique on crystal silicon surface, its performance is directly related with interface cleaning method, and usually characterize with minority carrier life time, the metallic pollution of silicon chip surface is fewer, the minority carrier life time of silicon chip is longer, and the performance of the heterogeneous batteries of crystal silicon/amorphous silicon is better.
At present, conventional crystal silicon/amorphous silicon cleaning technique is generally RCA cleaning technique, namely first carries out the cleaning of removing impurities on surface of silicon chip to silicon chip, to remove the organic substance of silicon chip surface, particle and metallic element etc.; Then silicon chip is oxidized and complexing process, to remove the metallic atom of silicon chip surface; Finally utilize hydrofluoric acid solution, etching processing is carried out to silicon chip surface, to remove the oxide layer of silicon chip surface.But current existing silicon wafer cleaning method can not reach more efficient heterogeneous batteries demand, therefore, after how reducing cleaning, the metallic pollution of silicon chip surface has become the problem that those skilled in the art need solution badly.
Summary of the invention
Embodiments provide a kind of cleaning method of solar silicon wafers, in order to reduce the metallic pollution of silicon chip surface, thus improve the minority carrier life time of silicon chip.
The cleaning method of a kind of solar silicon wafers that the embodiment of the present invention provides, comprises and carries out RCA cleaning to solar silicon wafers, and wherein, described RCA cleaning comprises:
To solar silicon wafers carry out prerinse make silicon chip surface produce oxidation after, carry out etching processing; Wherein,
The mixed etching solution of hydrogen peroxide, hydrofluoric acid and water is adopted to carry out etching processing to solar silicon wafers.
The cleaning method of the above-mentioned solar silicon wafers that the embodiment of the present invention provides, when carrying out RCA cleaning to solar silicon wafers, adopt hydrogen peroxide, hydrofluoric acid and the mixed etching solution of water carry out etching processing to the solar silicon wafers after prerinse, utilize silicon chip and hydrogen peroxide, the surface chemistry change of the mixed solution of hydrofluoric acid and water, promote to carry out micro etch to silicon chip surface, thus reduce the metallic pollution of silicon chip surface, and then reduce the compound of the few son in the metallic atom of silicon chip surface and silicon chip, improve the life-span of few son in solar silicon wafers, thus improve the efficiency of solar cell.
Preferably, in order to improve the life-span of the few son of silicon chip further, in the above-mentioned cleaning method that the embodiment of the present invention provides, after described etching processing is carried out to solar silicon wafers, also comprise:
Oxidation processes is carried out to described solar silicon wafers;
The mixed etching solution of hydrogen peroxide, hydrofluoric acid and water is adopted to carry out etching processing to the solar silicon wafers after described oxidation processes.
Preferably, in order to improve the life-span of the few son of silicon chip further, in the above-mentioned cleaning method that the embodiment of the present invention provides, described oxidation processes and described etching processing alternately perform, and repeat 1-3 time.
Preferably, in order to reach good cleaning performance, in the above-mentioned cleaning method that the embodiment of the present invention provides, in the mixed solution of described hydrogen peroxide, hydrofluoric acid and water, concentration be 30% hydrogen peroxide, concentration be the hydrofluoric acid of 49% and the volume ratio of water be 0.1 ~ 1:1:20 ~ 500.
Preferably, in order to reach good cleaning performance, in the above-mentioned cleaning method that the embodiment of the present invention provides, the time adopting the mixed etching solution of hydrogen peroxide, hydrofluoric acid and water to carry out an etching processing to solar silicon wafers is 30 seconds to 5 minutes.
Preferably, in order to reach good cleaning performance, in the above-mentioned cleaning method that the embodiment of the present invention provides, oxidation processes being carried out to described solar silicon wafers, specifically comprises:
The aqueous solution of hydrogen peroxide is adopted to carry out oxidation processes to solar silicon wafers.
Preferably, in order to reach good cleaning performance, in the above-mentioned cleaning method that the embodiment of the present invention provides, in the aqueous solution of hydrogen peroxide, concentration is the hydrogen peroxide of 30% and the volume ratio of water is 0.1 ~ 10:20.
Preferably, in order to reach good cleaning performance, in the above-mentioned cleaning method that the embodiment of the present invention provides, the time adopting the aqueous solution of hydrogen peroxide to carry out once oxidation process to solar silicon wafers is 30 seconds to 5 minutes.
Preferably, in order to reach good cleaning performance, in the above-mentioned cleaning method that the embodiment of the present invention provides, described prerinse comprises:
Sulfuric acid and the mixed solution of hydrogen peroxide or the mixed solution of ammonium hydroxide, hydrogen peroxide and water is adopted to carry out removing the cleaning of impurities on surface of silicon chip to solar silicon wafers;
And/or adopt the mixed solution of hydrochloric acid, hydrogen peroxide and water to be oxidized and complexing process the solar silicon wafers after the cleaning of aforementioned removal impurities on surface of silicon chip.
Preferably, in the above-mentioned cleaning method that the embodiment of the present invention provides, before RCA cleaning is carried out to solar silicon wafers, also comprise:
Making herbs into wool process is carried out to described solar silicon wafers.
Accompanying drawing explanation
One of flow chart of the cleaning method of the solar silicon wafers that Fig. 1 provides for the embodiment of the present invention;
The flow chart two of the cleaning method of the solar silicon wafers that Fig. 2 provides for the embodiment of the present invention;
The flow chart three of the cleaning method of the solar silicon wafers that Fig. 3 provides for the embodiment of the present invention;
The structural representation of the rinse bath that Fig. 4 provides for the embodiment of the present invention;
The flow chart of the cleaning method of the solar silicon wafers that Fig. 5 provides for example one of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the embodiment of the cleaning method of the solar silicon wafers that the embodiment of the present invention provides is described in detail.
The cleaning method of a kind of solar silicon wafers that the embodiment of the present invention provides, comprises and carries out RCA cleaning to solar silicon wafers, and as shown in Figure 1, RCA cleaning specifically comprises the following steps:
S101, solar silicon wafers carried out to prerinse and make silicon chip surface produce oxidation;
Particularly, in RCA cleaning, carrying out prerinse to solar silicon wafers is to remove the organic contaminations of silicon chip surface, particle and part metals pollution etc., and in this process, silicon chip surface creates oxidation.In the specific implementation, carry out removing the cleaning of impurities on surface of silicon chip to solar silicon wafers can comprise:
Adopt sulfuric acid H
2sO
4and oxydol H
2o
2mixed solution or ammonium hydroxide NH
4oH, oxydol H
2o
2with water H
2the mixed solution of O carries out the cleaning of removing impurities on surface of silicon chip to solar silicon wafers;
And/or adopt the mixed solution of hydrochloric acid, hydrogen peroxide and water to be oxidized and complexing process the solar silicon wafers after the cleaning of aforementioned removal impurities on surface of silicon chip.
Particularly, H is adopted
2sO
4and H
2o
2mixed solution carry out removing the cleaning of impurities on surface of silicon chip, due to H to solar silicon wafers
2sO
4and H
2o
2mixed solution have very high oxidability, not only can be dissolved in after the metal pollutant oxidation being attached to silicon chip surface in this mixed solution, and the oxidation operation being attached to silicon chip surface can be become CO
2and H2O, thus the organic substance removing silicon chip surface stains and part metals is polluted.
Particularly, NH is adopted
4oH, H
2o
2and H
2the mixed solution of O carries out the cleaning of removing impurities on surface of silicon chip to solar silicon wafers, due to the oxidation of H2O2, the surface of silicon chip can generate one deck silicon oxide film layer (SiO2), makes the surfaces hydrophilic of silicon chip, thus make can by NH between the surface of silicon chip and particle
4oH, H
2o
2and H
2the mixed solution of O soaks into; Meanwhile, because the silicon oxide film layer of silicon chip surface and the Si of silicon chip surface are by NH
4oH corrodes, and the particle being attached to silicon chip surface therefore can be made to be easy to fall into NH
4oH, H
2o
2and H
2in the mixed solution of O, thus reach the object of the particle removing silicon chip surface.
Particularly, adopt the mixed solution of hydrochloric acid, hydrogen peroxide and water to be oxidized and complexing process the solar silicon wafers after the cleaning of aforementioned removal impurities on surface of silicon chip, be mainly used in the metal contamination such as sodium Na, iron Fe, magnesium Mg removing silicon chip surface.
S102, etching processing is carried out to the solar silicon wafers carried out after prerinse; Concrete employing hydrogen peroxide, hydrofluoric acid and the mixed etching solution of water carry out etching processing to solar silicon wafers.
Particularly in RCA cleaning, adopt H
2o
2, HF and H
2the mixed etching solution of O carries out etching processing to solar silicon wafers, utilizes silicon chip and H
2o
2, HF and H
2the surface chemistry change of the mixed solution of O, promotes to carry out micro etch to silicon chip surface, thus reduces the metallic pollution of silicon chip surface further.
The cleaning method of the above-mentioned solar silicon wafers that the embodiment of the present invention provides, when carrying out RCA cleaning to solar silicon wafers, adopt hydrogen peroxide, hydrofluoric acid and the mixed etching solution of water carry out etching processing to the solar silicon wafers after prerinse, utilize silicon chip and hydrogen peroxide, the surface chemistry change of the mixed solution of hydrofluoric acid and water, promote to carry out micro etch to silicon chip surface, thus reduce the metallic pollution of silicon chip surface, and then reduce the compound of the few son in the metallic atom of silicon chip surface and silicon chip, improve the life-span of few son in solar silicon wafers, thus improve the efficiency of solar cell.
Further, the above-mentioned cleaning method that the embodiment of the present invention provides, is applicable to clean monocrystalline silicon piece, is also applicable to clean polysilicon chip, does not limit at this.
Further, the above-mentioned cleaning method that the embodiment of the present invention provides, is applicable to clean N-type silicon chip, is also applicable to clean P-type silicon sheet, does not limit at this.
Preferably, in order to improve the life-span of the few son of silicon chip further, in the above-mentioned cleaning method that the embodiment of the present invention provides, after step S102 is to solar silicon wafers etching processing, as shown in Figure 2, also comprise:
S103, oxidation processes is carried out to solar silicon wafers;
Particularly, in the specific implementation, oxidation processes is carried out to solar silicon wafers, specifically can comprise:
Adopt oxydol H
2o
2the aqueous solution oxidation processes is carried out to solar silicon wafers.
Certainly, in the specific implementation, also nitric acid HNO can be adopted
3, hydrofluoric acid HF and water H
2o
2mixed solution oxidation processes is carried out to solar silicon wafers, do not limit at this.
S104, employing oxydol H
2o
2, hydrofluoric acid HF and water H
2the mixed etching solution of O carries out etching processing to solar silicon wafers.
Particularly, H is adopted
2o
2, HF and H
2the mixed solution of O carries out etching processing again to solar silicon wafers, utilizes silicon chip and H
2o
2, HF and H
2the surface chemistry change of the mixed solution of O, promotes to carry out micro etch to silicon chip surface, thus reduces the metallic pollution of silicon chip surface further.
Particularly, in the above-mentioned cleaning method that the embodiment of the present invention provides, after etching processing is carried out to solar silicon wafers, oxidation processes is carried out to solar silicon wafers, can Surface Creation one deck of silicon chip thin there is hydrophilic silicon oxide film, thus make silicon chip surface can by H
2o
2the aqueous solution soak into, and then etching processing is carried out to silicon chip, the surface chemistry between silicon chip and the aqueous solution of hydrogen peroxide is utilized to change, micro etch is carried out to what enter silicon chip, etch away the oxide layer of silicon chip surface, form hydrophobic surface, when the silicon oxide film of silicon chip surface is etched completely away, the silicon of silicon chip surface is almost no longer corroded, thus not only can reduce the metallic pollution of silicon chip surface, carried the life-span of few son of solar silicon wafers, the roughness of silicon chip surface can also be reduced, improve the passivation quality of silicon chip, and then improve the life-span of few son and the efficiency of solar cell of solar silicon wafers further.
Particularly, in the specific implementation, the above-mentioned cleaning method that provides of the embodiment of the present invention, as shown in Figure 3, step S103 oxidation processes and step S104 etching processing alternately perform, and repeat 1-3 time, through the alternately execution of oxidation and etching processing repeatedly, cleaning performance is better.
Preferably, in the above-mentioned cleaning method that the embodiment of the present invention provides, in the mixed solution of hydrogen peroxide, hydrofluoric acid and water, concentration be 30% hydrogen peroxide, concentration be that the hydrofluoric acid of 49% and the volume ratio of water control between 0.1 ~ 1:1:20 ~ 500, better to the etching effect of silicon chip.
Preferably, in the above-mentioned cleaning method that the embodiment of the present invention provides, in the mixed solution of hydrogen peroxide, hydrofluoric acid and water, concentration be 30% hydrogen peroxide, concentration to be the hydrofluoric acid of 49% and the volume ratio of water can be: 0.1:1:20,0.1:1:500,1:1:20,1:1:500,0.5:1:30 or 0.5:1:300.
Further, in the specific implementation, in the above-mentioned cleaning method that the embodiment of the present invention provides, the time controling adopting hydrogen peroxide, hydrofluoric acid and water mixed etching solution solar silicon wafers to be carried out to an etching processing was good between 30 seconds to 5 minutes.Preferably, in order to can fully react, the time controling of etching processing is more than 2 minutes.The temperature adopting the mixed etching solution of hydrogen peroxide, hydrofluoric acid and water to carry out etching processing to solar silicon wafers can be room temperature, does not limit at this.
Preferably, in the above-mentioned cleaning method that the embodiment of the present invention provides, in the aqueous solution of hydrogen peroxide, concentration is that the hydrogen peroxide of 30% and the volume ratio of water control between 0.1 ~ 10:20, better to the oxidation effectiveness of solar silicon wafers.
Preferably, in the above-mentioned cleaning method that the embodiment of the present invention provides, in the aqueous solution of hydrogen peroxide, to be the hydrogen peroxide of 30% and the volume ratio of water can be concentration: 0.1:20,0.5:20,1:20,2:20,5:20,8:20 or 10:20.
Further, in the specific implementation, in the above-mentioned cleaning method that the embodiment of the present invention provides, the time controling adopting the aqueous solution of hydrogen peroxide solar silicon wafers to be carried out to once oxidation process was good between 30 seconds to 5 minutes.Preferably, in order to can fully react, the time controling of oxidation processes is more than 2 minutes.Adopt the aqueous solution of hydrogen peroxide to solar silicon wafers carry out oxidation processes temperature for room temperature, can not limit at this.
Or, preferably, in the above-mentioned cleaning method that the embodiment of the present invention provides, in the mixed solution of nitric acid, hydrofluoric acid and water, concentration be 70% nitric acid, concentration be that the hydrofluoric acid of 49% and the volume ratio of water control between 0.1 ~ 5:1:20, better to the oxidation effectiveness of solar silicon wafers.
Further, in the specific implementation, in the above-mentioned cleaning method that the embodiment of the present invention provides, the time controling adopting the mixed solution of nitric acid, hydrofluoric acid and water solar silicon wafers to be carried out to once oxidation process is for 30 seconds to 5 minutes for good.Preferably, in order to can fully react, the time controling of oxidation processes is more than 2 minutes.The temperature adopting the mixed solution of nitric acid, hydrofluoric acid and water to carry out oxidation processes to solar silicon wafers can be room temperature, does not limit at this.
Preferably, in the above-mentioned cleaning method that the embodiment of the present invention provides, in the mixed solution of sulfuric acid and hydrogen peroxide, concentration be 98% sulfuric acid and concentration be that the volume ratio of the hydrogen peroxide of 30% controls between 2 ~ 5:1, better to the cleaning performance of solar silicon wafers.
Preferably, in the above-mentioned cleaning method that the embodiment of the present invention provides, the temperature of the mixed solution of sulfuric acid, hydrogen peroxide and water controls between 100 DEG C ~ 130 DEG C as good.
Or, preferably, in the above-mentioned cleaning method that the embodiment of the present invention provides, in the mixed solution of ammonium hydroxide, hydrogen peroxide and water, concentration is 29% is ammonium hydroxide, concentration is the hydrogen peroxide of 30% and the volume ratio of water controls between 0.5 ~ 1:1:5, better to the cleaning performance of solar silicon wafers.Best, concentration is 29% is ammonium hydroxide, concentration be the hydrogen peroxide of 30% and the volume ratio of water is 1:1:5.
Preferably, in the above-mentioned cleaning method that the embodiment of the present invention provides, in the mixed solution of hydrochloric acid, hydrogen peroxide and water, concentration be 37% hydrochloric acid, concentration be that the hydrogen peroxide of 30% and the volume ratio of water control between 0.5 ~ 2:1:6, better to the cleaning performance of solar silicon wafers.Best, concentration to be hydrochloric acid, the concentration of 37% the be hydrogen peroxide of 30% and the volume ratio of water are=1:1:6.
Further, in the above-mentioned cleaning method that the embodiment of the present invention provides, before RCA cleaning is carried out to solar silicon wafers, also comprise: making herbs into wool process is carried out to solar silicon wafers.Particularly, carrying out making herbs into wool process to solar silicon wafers mainly utilizes the chemical reaction of making herbs into wool solution and silicon chip to produce anisotropic etch at silicon chip surface, thus forming the matte of intensive micro-pyramid pyramid structure, making herbs into wool process belongs to prior art, does not describe in detail at this.
Further, in the above-mentioned cleaning method that the embodiment of the present invention provides, after RCA cleaning is carried out to solar silicon wafers, also comprise: using plasma strengthens the surface deposition one deck amorphous silicon membrane of chemical vapour deposition technique at solar silicon wafers, to maintain the cleanliness factor on solar silicon wafers surface.Particularly, using plasma strengthens chemical vapor deposition amorphous silicon membrane and belongs to prior art, does not describe in detail at this.
Particularly, in the specific implementation, the cleaning process of solar silicon wafers is generally carried out in a rinse bath device, and the structure of rinse bath device as shown in Figure 4, comprising: rinse bath 01 and be arranged in rinse bath 01 for placing the silicon chip flower basket 02 of silicon chip.
Below by a concrete example, the above-mentioned cleaning method that the embodiment of the present invention provides is described in detail.
Example one:
Particularly, n type single crystal silicon sheet after carrying out making herbs into wool process through the making herbs into wool solution of NaOH, sodium metasilicate, water and isopropyl alcohol is cleaned, and according to as shown in Figure 5 S501 remove impurities on surface of silicon chip cleaning, S502 oxidation and complexing process, S503 lose process, S504 oxidation processes, S505 etching processing order monocrystalline silicon piece is cleaned, specifically comprise the following steps:
(1), monocrystalline silicon piece is loaded in the silicon chip flower basket in rinse bath;
(2), the cleaning of removing impurities on surface of silicon chip is carried out to monocrystalline silicon piece;
Particularly, in the specific implementation:
30 liters of deionized waters are added in rinse bath;
When deionized water being heated to about 65 DEG C, start in rinse bath, add the ammonium hydroxide NH that 0.3 liter of concentration is 29%
4oH and 4 liter concentration is the oxydol H of 30%
2o
2and stir;
After about 10 minutes, adopt deionized water overflow about 6 minutes in rinse bath, the ammonium hydroxide and hydrogen peroxide that remain in monocrystalline silicon sheet surface are washed;
Solution in rinse bath is all discharged totally.
(3), monocrystalline silicon piece to be oxidized and complexing process;
16 liters of deionized waters are added in rinse bath;
When deionized water being heated to about 65 DEG C, start to add in rinse bath 3 liters of concentration be 37% hydrochloric acid HC to rise and 3 liters of concentration are the oxydol H of 30%
2o
2and stir;
After about 10 minutes, adopt deionized water overflow about 6 minutes in rinse bath, the hydrochloric acid and hydrogen peroxide that remain in monocrystalline silicon sheet surface are washed;
Solution in rinse bath is all discharged totally.
(4) etching processing is carried out to monocrystalline silicon piece;
Particularly, in the specific implementation: first, in rinse bath, add 15 liters of deionized waters, 0.5 liter of concentration be 49% hydrofluoric acid HF and 0.25 liter concentration be the oxydol H of 30%
2o
2and stir;
After about 2 minutes, adopt deionized water overflow about 1 minute in rinse bath, the hydrofluoric acid and hydrogen peroxide that remain in monocrystalline silicon sheet surface are washed;
Finally, the solution in rinse bath is all discharged totally.
(5) oxidation processes is carried out to monocrystalline silicon piece;
Particularly, in the specific implementation: first, in rinse bath, 20 liters of deionized waters are added and 2 liters of concentration are the oxydol H of 30%
2o
2and stir;
After about 2 minutes, adopt deionized water overflow about 6 minutes in rinse bath, the hydrogen peroxide remaining in monocrystalline silicon sheet surface is washed;
Finally, the solution in rinse bath is all discharged totally.
(6) etching processing is carried out to monocrystalline silicon piece;
Particularly, in the specific implementation: first, in rinse bath, add 15 liters of deionized waters, 0.5 liter of concentration be 49% hydrofluoric acid HF and 0.25 liter concentration be the oxydol H of 30%
2o
2and stir;
After about 2 minutes, adopt deionized water overflow about 1 minute in rinse bath, the hydrofluoric acid and hydrogen peroxide that remain in monocrystalline silicon sheet surface are washed;
Finally, the solution in rinse bath is all discharged totally.
(7) monocrystalline silicon piece is put into drier to dry.
Particularly in order to the cleaning performance of the cleaning method of the above-mentioned solar silicon wafers provided through the embodiment of the present invention is described, monocrystalline silicon piece after monocrystalline silicon piece after the cleaning of example one method and the existing cleaning method of employing being cleaned compares, particularly, existing cleaning method, comprise step (the 1)-step (3) of example one, after step (3), existing cleaning method adopts 15 liters of deionized waters and 0.5 liter of concentration to be that the mixed solution of the hydrofluoric acid HF of 49% carries out etching processing 2 minutes to monocrystalline silicon piece, then deionized water is adopted the hydrofluoric acid clean remaining in monocrystalline silicon sheet surface to be fallen, finally, monocrystalline silicon piece is put into drier to dry.
Further, in order to comparative example one and existing methodical cleaning performance, using plasma strengthens chemical vapour deposition technique, the film of 40nm amorphous silicon is deposited respectively on the surface of the monocrystalline silicon piece after the method and the cleaning of existing method of example one, then respectively minority carrier lifetime and battery efficiency test are done to the monocrystalline silicon piece after the cleaning of example one method and the monocrystalline silicon piece after existing method cleaning, test result is as shown in table 1a and table 1b, wherein, table 1a is the test result of the minority carrier life time of monocrystalline silicon piece, table 1b is the test result of the efficiency of the solar cell adopting above-mentioned monocrystalline silicon piece to make.
Table 1a
Table 1b
Test result as can be seen from table 1a, the monocrystalline silicon piece after the cleaning method provided through embodiment of the present invention cleaning, the life-span of few son of silicon chip is far longer than the minority carrier life time of the monocrystalline silicon piece after existing cleaning method cleaning; Test result as can be seen from table 1b, the monocrystalline silicon piece after the cleaning method cleaning that the embodiment of the present invention provides, the efficiency of battery is higher 0.2 percentage point than the mean value of the battery efficiency of the monocrystalline silicon piece after existing cleaning method cleaning.
To sum up test result is known, and the monocrystalline silicon piece after the cleaning method cleaning that the embodiment of the present invention provides, the life-span of few son of silicon chip is longer, and the efficiency of the solar cell adopting this monocrystalline silicon piece to make is higher.
The cleaning method of a kind of solar silicon wafers that the embodiment of the present invention provides, comprises and carries out RCA cleaning to solar silicon wafers, RCA cleaning comprise: to solar silicon wafers carry out prerinse make silicon chip surface produce oxidation after, carry out etching processing; Wherein, the mixed etching solution of hydrogen peroxide, hydrofluoric acid and water is adopted to carry out etching processing to solar silicon wafers.This cleaning method, when carrying out RCA cleaning to solar silicon wafers, the mixed etching solution of hydrogen peroxide, hydrofluoric acid and water is adopted to carry out etching processing to the solar silicon wafers after prerinse, the surface chemistry of the mixed solution of silicon chip and hydrogen peroxide, hydrofluoric acid and water is utilized to change, promote to carry out micro etch to silicon chip surface, thus reduce the metallic pollution of silicon chip surface, and then reduce the compound of the few son in the metallic atom of silicon chip surface and silicon chip, improve the life-span of few son in solar silicon wafers, thus improve the efficiency of solar cell.
Obviously, those skilled in the art can carry out various change and modification to the present invention and not depart from the spirit and scope of the present invention.Like this, if these amendments of the present invention and modification belong within the scope of the claims in the present invention and equivalent technologies thereof, then the present invention is also intended to comprise these change and modification.
Claims (10)
1. a cleaning method for solar silicon wafers, comprises and carries out RCA cleaning to solar silicon wafers, it is characterized in that, described RCA cleaning comprises:
To solar silicon wafers carry out prerinse make silicon chip surface produce oxidation after, carry out etching processing; Wherein,
The mixed etching solution of hydrogen peroxide, hydrofluoric acid and water is adopted to carry out etching processing to solar silicon wafers.
2. cleaning method as claimed in claim 1, is characterized in that, after carrying out described etching processing to solar silicon wafers, also comprise:
Oxidation processes is carried out to described solar silicon wafers;
The mixed etching solution of hydrogen peroxide, hydrofluoric acid and water is adopted to carry out etching processing to the solar silicon wafers after described oxidation processes.
3. cleaning method as claimed in claim 2, is characterized in that, described oxidation processes and described etching processing alternately perform, and repeat 1-3 time.
4. the cleaning method as described in any one of claim 1-3, is characterized in that, in the mixed solution of described hydrogen peroxide, hydrofluoric acid and water, concentration be 30% hydrogen peroxide, concentration be the hydrofluoric acid of 49% and the volume ratio of water be 0.1 ~ 1:1:20 ~ 500.
5. cleaning method as claimed in claim 2 or claim 3, is characterized in that, adopting the mixed etching solution of hydrogen peroxide, hydrofluoric acid and water to carry out an etching processing time to solar silicon wafers is 30 seconds to 5 minutes.
6. cleaning method as claimed in claim 2 or claim 3, is characterized in that, carry out oxidation processes, specifically comprise described solar silicon wafers:
The aqueous solution of hydrogen peroxide is adopted to carry out oxidation processes to solar silicon wafers.
7. cleaning method as claimed in claim 6, it is characterized in that, in the aqueous solution of hydrogen peroxide, concentration is the hydrogen peroxide of 30% and the volume ratio of water is 0.1 ~ 10:20.
8. cleaning method as claimed in claim 7, is characterized in that, the time adopting the aqueous solution of hydrogen peroxide to carry out once oxidation process to solar silicon wafers is 30 seconds to 5 minutes.
9. the cleaning method as described in any one of claim 1-3, is characterized in that, described prerinse comprises:
Sulfuric acid and the mixed solution of hydrogen peroxide or the mixed solution of ammonium hydroxide, hydrogen peroxide and water is adopted to carry out removing the cleaning of impurities on surface of silicon chip to solar silicon wafers;
And/or adopt the mixed solution of hydrochloric acid, hydrogen peroxide and water to be oxidized and complexing process the solar silicon wafers after the cleaning of aforementioned removal impurities on surface of silicon chip.
10. the cleaning method as described in any one of claim 1-3, is characterized in that, before carrying out RCA cleaning to solar silicon wafers, also comprises:
Making herbs into wool process is carried out to described solar silicon wafers.
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