CN105047767A - Texturizing method of silicon wafer - Google Patents
Texturizing method of silicon wafer Download PDFInfo
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- CN105047767A CN105047767A CN201510571969.9A CN201510571969A CN105047767A CN 105047767 A CN105047767 A CN 105047767A CN 201510571969 A CN201510571969 A CN 201510571969A CN 105047767 A CN105047767 A CN 105047767A
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 94
- 239000010703 silicon Substances 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 74
- 238000005530 etching Methods 0.000 claims abstract description 50
- 239000000243 solution Substances 0.000 claims abstract description 27
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 22
- 239000010432 diamond Substances 0.000 claims abstract description 22
- 239000012670 alkaline solution Substances 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 66
- 238000004140 cleaning Methods 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229910021426 porous silicon Inorganic materials 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000006056 electrooxidation reaction Methods 0.000 abstract description 4
- 238000011282 treatment Methods 0.000 abstract description 4
- 238000005457 optimization Methods 0.000 abstract description 3
- 239000007888 film coating Substances 0.000 abstract 1
- 238000009501 film coating Methods 0.000 abstract 1
- 210000002268 wool Anatomy 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 235000008216 herbs Nutrition 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000005520 cutting process Methods 0.000 description 14
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 11
- 229920005591 polysilicon Polymers 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 5
- 238000001020 plasma etching Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- ZLMJMSJWJFRBEC-OUBTZVSYSA-N potassium-40 Chemical compound [40K] ZLMJMSJWJFRBEC-OUBTZVSYSA-N 0.000 description 3
- 238000002310 reflectometry Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/08—Etching
- C30B33/10—Etching in solutions or melts
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Weting (AREA)
Abstract
The invention provides a texturizing method of a silicon wafer. The method includes the following steps that: A) a silicon wafer cut by a diamond line is etched through an etchant solution; B) the etched silicon wafer is arranged in an electrolyte, and is energized, so that the silicon wafer can be treated; and C) the treated silicon wafer is subjected to alkaline etching through adopting an alkaline solution. Compared with the prior art, and according to the texturizing method of the invention, a porous silicon structure is formed on the surface of the silicon wafer through an electrochemical corrosion method, and structure optimization treatment is performed on the silicon wafer through the alkaline solution subsequently, and as a result, an ideal texturized surface structure can be obtained. The texturizing method of the invention has the advantages of simplicity, high stability and high practicability. With the texturizing method adopted, problems existing in the texturizing of the silicon wafer cut by the diamond line can be solved, and the uniformity of subsequent film coating can be improved, and the yield of products can be improved, and the conversion efficiency of batteries can be improved.
Description
Technical field
The invention belongs to technical field of solar batteries, particularly relate to a kind of etching method of silicon chip.
Background technology
Diamond wire cutting technique is also referred to as concretion abrasive cutting technique, and it utilizes plating or resin bonded method that diamond abrasive is attached to steel wire surface, diamond wire is directly acted on silicon rod or the generation grinding of silicon ingot surface, reaches the effect of cutting.Compare with conventional slurry cutting technique, it is fast that diamond wire cutting has speed, and production capacity is high, the features such as cutting accuracy is high, and spillage of material is low, but silicon chip surface stria is clearly, it is very low that the line of silicon chip splits density, and conventional wet-method etching cannot form effective matte.
After diamond wire cutting polysilicon chip uses the making herbs into wool of conventional wet lay making herbs into wool mode, silicon chip surface is brighter, and reflectivity is greater than 30%.And optical loss is one of significant obstacle hindering efficiency of solar cell to improve, the diamond wire cutting polysilicon chip efficiency made so final is seriously on the low side.Therefore, need to adopt suitable method to solve the making herbs into wool problem of diamond wire cutting polysilicon chip.
Wherein, reactive ion etching RIE (ReactiveIonEtching) goes for diamond wire cutting polycrystalline silicon texturing, although RIE effectively can reduce the reflectivity of silicon chip and improve battery efficiency, but equipment investment cost is very high, and need to introduce extra chemical cleaning flow process, increase unconventional special process gas.
Application number is that the Chinese patent of CN201110112185.1 proposes a kind of etching method, by H
2sO
4or H
3pO
4-HF-HNO
3acid corrosion making herbs into wool is carried out in mixed acid solution; Application number is that the Chinese patent of CN201310049552.7 proposes a kind of sour making herbs into wool additive and using method thereof; Although change making herbs into wool formula by such as above-mentioned two kinds of patents and increase the scheme that making herbs into wool additive improves diamond wire cutting polysilicon chip and have report more, but true effect is unknown, do not have the special solution being applicable to diamond wire cutting polysilicon chip or making herbs into wool additive can be for sale at least at present on the market.
Application number is that the Chinese patent of CN201410842630.3 proposes a kind of making herbs into wool preprocess method, the method first carries out the preliminary treatment of expansion phosphorus under 850 DEG C ~ 900 DEG C high temperature, to form the N-type heavily doped layer that one deck square resistance is 40 ~ 100ohm/Sq, obtain making herbs into wool preliminary treatment silicon chip, then conventional making herbs into wool process is being carried out, follow-up when preparing battery, also need again through High temperature diffusion to form emitter.The drawback of the method needs to form making herbs into wool pretreated sheet through High temperature diffusion, but high temperature can cause polysilicon chip body life time to reduce, and need extra increase diffusion furnace high-energy equipment, and cost performance is not good.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is the etching method providing a kind of silicon chip, and the method is simple and cost is lower.
The invention provides a kind of etching method of silicon chip, comprise the following steps:
A) the silicon chip etchant solution that diamond wire cuts is etched;
B) the silicon chip placement after etching is energized in the electrolytic solution, processes;
C) the silicon chip alkaline solution after process is carried out alkaline etch.
Preferably, also comprise:
D) the silicon chip acid solution after alkaline etch is cleaned.
Preferably, described acid solution is the mixed solution of hydrofluoric acid and hydrochloric acid; In described acid solution, the concentration of hydrofluoric acid is 10 ~ 30mol/L; In described acid solution, the concentration of hydrochloric acid is 0.5 ~ 12mol/L.
Preferably, the time of described cleaning is 1 ~ 20min; The temperature of cleaning is 20 DEG C ~ 60 DEG C.
Preferably, the time of described etching is 1 ~ 20min; The temperature of described etching is 6 DEG C ~ 12 DEG C.
Preferably, the current density of described energising is 1 ~ 10mA/cm
2; The time of described energising is 5 ~ 60min.
Preferably, described electrolyte is the aqueous solution of hydrofluoric acid and alcoholic solvent.
Preferably, in described electrolyte, the concentration of hydrofluoric acid is 1 ~ 30mol/L; In described electrolyte, the concentration of alcohols solvent is 0.1 ~ 16mol/L.
Preferably, described alkaline solution is the aqueous solution of alkali metal hydroxide; The concentration of described alkali metal hydroxide is 0.005 ~ 0.05mol/L.
Preferably, the time of described alkaline etch is 1 ~ 5min; The temperature of alkaline etch is 20 DEG C ~ 40 DEG C.
The invention provides a kind of etching method of silicon chip, comprise the following steps: A) the silicon chip etchant solution that diamond wire cuts is etched; B) the silicon chip placement after etching is energized in the electrolytic solution, processes; C) the silicon chip alkaline solution after process is carried out alkaline etch.Compared with prior art, the present invention forms Porous Silicon structures by the method for electrochemical corrosion at silicon chip surface, and carry out structure optimization process by follow-up alkaline solution and obtain desirable suede structure, simple and the good stability of this technique, both solved the silicon wafer wool making problem of diamond wire cutting, and also improved the uniformity of follow-up plated film simultaneously, improve the yield of product, improve battery conversion efficiency, there is good practicality.
Experiment shows, its surface reflectivity of silicon chip after the making herbs into wool adopting etching method of the present invention to obtain can be down to 5%, and plated film back reflection rate can be down to 1%.
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention 1 double flute electrochemical treatments schematic diagram;
Fig. 2 is the electron scanning micrograph of the silicon chip after the embodiment of the present invention 1 energising process;
Fig. 3 is the photo of the scanning electron microscopy of silicon chip after the embodiment of the present invention 1 alkaline etch.
Embodiment
Below in conjunction with the accompanying drawing of the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of etching method of silicon chip, comprise the following steps: A) the silicon chip etchant solution that diamond wire cuts is etched; B) the silicon chip placement after etching is energized in the electrolytic solution, processes; C) the silicon chip alkaline solution after process is carried out alkaline etch.
Wherein, the restriction that the present invention is not special to the source of all raw materials, for commercially available.
The silicon chip etchant solution that diamond wire cuts is etched; Wherein said silicon chip is silicon chip well known to those skilled in the art, there is no special restriction, is preferably polysilicon chip in the present invention; Described etchant solution is etchant solution well known to those skilled in the art, is preferably the mixed solution of hydrofluoric acid and nitric acid in the present invention; The concentration of described hydrofluoric acid is preferably 1 ~ 5mol/L, is more preferably 1 ~ 4mol/L, then is preferably 2 ~ 3mol/L; The solubility of described nitric acid is preferably 3 ~ 15mol/L, is more preferably 4 ~ 12mol/L, then is preferably 6 ~ 10mol/L; The temperature of described etching is preferably 6 DEG C ~ 12 DEG C, is more preferably 7 DEG C ~ 10 DEG C, then is preferably 7 DEG C ~ 9 DEG C; The time of described etching is preferably 1 ~ 20min, is more preferably 4 ~ 15min, then is preferably 4 ~ 10min.
After etching, preferably clean with water, more preferably adopt deionized water to clean; The temperature of described cleaning is preferably 20 DEG C ~ 80 DEG C, is more preferably 20 DEG C ~ 60 DEG C, then is preferably 20 DEG C ~ 40 DEG C; The time of described cleaning is preferably 1 ~ 20min, is more preferably 4 ~ 15min, then is preferably 4 ~ 10min.
After cleaning, then place and be energized in the electrolytic solution, process.Wherein, described electrolyte is preferably the aqueous solution of hydrofluoric acid and alcoholic solvent; The concentration of described hydrofluoric acid is preferably 1 ~ 30mol/L, is more preferably 1 ~ 25mol/L, then is preferably 3 ~ 20mol/L, most preferably is 5 ~ 15mol/L; The concentration of described alcoholic solvent is preferably 0.5 ~ 16mol/L, is more preferably 1 ~ 13mol/L, then is preferably 3 ~ 10mol/L, most preferably is 5 ~ 10mol/L; The kind of described alcoholic solvent is alcoholic solvent well known to those skilled in the art, there is no special restriction, is preferably ethanol and/or propyl alcohol, is more preferably ethanol or propyl alcohol in the present invention; For avoiding other foreign ions on the impact of silicon chip, the described aqueous solution is preferably deionized water solution; The current density of described energising is preferably 1 ~ 10mA/cm
2, be more preferably 2 ~ 8mA/cm
2, then be preferably 3 ~ 7mA/cm
2; The time of described energising is preferably 5 ~ 60min, is more preferably 10 ~ 50min, then is preferably 20 ~ 40min, most preferably is 25 ~ 35min.
In the present invention, the place of carrying out processing that is energized is preferably electrolysis tank, namely carries out energising process to silicon chip in a cell; Described electrolysis tank can be single groove structure, also can be dual-slot structure and there is no special restriction; The electrode of described electrolysis tank is preferably copper electrode or platinum electrode.Namely utilize electrolysis tank to process silicon chip inserts silicon chip on the fixed mount in the middle of electrolysis tank, electrolysis tank is divided into two separate " half grooves " by silicon chip, realize conducting by silicon substrate between half groove, just the silicon chip surface of negative electrode is become to the anode of electrochemical reaction, generate Porous Silicon structures.
Electrochemical etching is in the mixed solution of hydrofluoric acid and alcohols solvent, applies to obtain porous silicon lower than the current density of electropolishing to silicon chip.The porous silicon that electrochemical etching method is formed has aperture little (most I reach several nanometer), pore size distribution is more regular, porous layer depth is comparatively large and can be easy to the advantage that controls as required, the roughness of the porous silicon layer upper surface formed still keeps the same with substrate substantially with lattice structure, and this is conducive to carrying out other processes at porous layer and not affecting performance.
After energising process, preferably clean with water, more preferably adopt deionized water to clean; The temperature of described cleaning is preferably 20 DEG C ~ 80 DEG C, is more preferably 20 DEG C ~ 60 DEG C, then is preferably 20 DEG C ~ 40 DEG C; The time of described cleaning is preferably 1 ~ 20min, is more preferably 4 ~ 15min, then is preferably 4 ~ 10min.
And then carry out alkaline etch with alkaline solution.Described alkaline solution is preferably the aqueous solution of alkali metal hydroxide, is more preferably the aqueous solution of NaOH and/or potassium hydroxide, then is preferably the aqueous solution of potassium hydroxide; In described alkaline solution, the concentration of alkali metal hydroxide is preferably 0.005 ~ 0.05mol/L, is more preferably 0.01 ~ 0.05mol/L, then is preferably 0.02 ~ 0.05mol/L; The temperature of described alkaline etch is preferably 20 DEG C ~ 40 DEG C, is more preferably 30 DEG C ~ 40 DEG C; The time of described alkaline etch is preferably 1 ~ 5min, is more preferably 3 ~ 5min.
Electrolytic cell equipment is used to apply electric current to silicon chip surface, under electrochemical corrosion effect, silicon chip forms uniform Porous Silicon structures in the face of the surface of negative pole, again the silicon chip with Porous Silicon structures is placed in alkaline solution and carries out micro-nano compound matte structural modifications etching, finally obtain desirable suede structure.
After alkaline etch, preferably clean with water, more preferably adopt deionized water to clean; The temperature of described cleaning is preferably 20 DEG C ~ 80 DEG C, is more preferably 20 DEG C ~ 60 DEG C, then is preferably 20 DEG C ~ 40 DEG C; The time of described cleaning is preferably 1 ~ 20min, is more preferably 4 ~ 15min, then is preferably 4 ~ 10min.
After water cleaning, preferably clean with acid solution again.Described acid solution is preferably the mixed solution of hydrofluoric acid and hydrochloric acid; In described acid solution, the concentration of hydrofluoric acid is preferably 10 ~ 30mol/L, is more preferably 20 ~ 30mol/L, then is preferably 25 ~ 30mol/L; In described acid solution, the concentration of hydrochloric acid is preferably 0.5 ~ 12mol/L, is more preferably 3 ~ 12mol/L, then is preferably 5 ~ 12mol/L, most preferably is 8 ~ 12mol/L; The temperature of described acid solution cleaning is preferably 20 DEG C ~ 60 DEG C, is more preferably 20 DEG C ~ 40 DEG C, then is preferably 20 DEG C ~ 30 DEG C; The time of described acid solution cleaning is preferably 1 ~ 20min, is more preferably 5 ~ 20min, then is preferably 10 ~ 20min, most preferably be 15 ~ 20min.Through acid solution cleaning, the harmful substances such as the metal ion of silicon chip surface, organic substance can be removed.
After acid solution cleans, preferably also comprise and cleaning with water, more preferably adopt deionized water to clean; The temperature of described cleaning is preferably 20 DEG C ~ 80 DEG C, is more preferably 20 DEG C ~ 60 DEG C, then is preferably 20 DEG C ~ 40 DEG C; The time of described cleaning is preferably 1 ~ 20min, is more preferably 4 ~ 15min, then is preferably 4 ~ 10min.
The present invention forms Porous Silicon structures by the method for electrochemical corrosion at silicon chip surface, and carry out structure optimization process by follow-up alkaline solution and obtain desirable suede structure, simple and the good stability of this technique, both the silicon wafer wool making problem of diamond wire cutting had been solved, also improve the uniformity of follow-up plated film simultaneously, improve the yield of product, improve battery conversion efficiency, there is good practicality.
In order to further illustrate the present invention, be described in detail below in conjunction with the etching method of embodiment to a kind of silicon chip provided by the invention.
Reagent used in following examples is commercially available.
Embodiment 1
The mixed solution that the polysilicon chip that diamond wire cuts puts into hydrofluoric acid and nitric acid etches by 1.1, wherein, in mixed solution, the concentration of hydrofluoric acid is 2mol/L, the concentration of nitric acid is 6mol/L, the temperature of etching is 8 DEG C, the time of etching is 6min, puts into deionized water 25 DEG C cleaning 5min, obtain the silicon chip after etching after having etched.
Silicon chip after the etching obtained in 1.1 is put into the middle fixed head of dual bath apparatus by 1.2, and as shown in Figure 1, wherein 1 is fixed body to its structural representation, and 2 is sealing ring, and 3 is platinum electrode, and 4 is silicon chip, and 5 is electrolyte; Electrolyte is the mixed solution of hydrofluoric acid, ethanol and water, and the concentration of hydrofluoric acid is 10mol/L, and the concentration of ethanol is 5mol/L, applies 5mA/cm
2constant current, energising process 30min, then puts into deionized water 25 DEG C cleaning 5min, is energized the silicon chip after process.
1.3 the silicon chip after the energising process obtained in 1.2 is put into concentration is 0.05mol/L potassium hydroxide solution, and 40 DEG C of etching 5min, then put into deionized water 25 DEG C cleaning 5min, obtain the silicon chip of alkaline etch.
1.4 mixed solutions silicon chip of the alkaline etch obtained in 1.3 being put into hydrofluoric acid and hydrochloric acid carry out 25 DEG C and clean 20min, the concentration of hydrofluoric acid is 30mol/L, and the concentration of hydrochloric acid is 12mol/L, and then puts into deionized water 25 DEG C cleaning 5min, dry up, obtain the silicon chip after making herbs into wool.
Scanning electron microscopy is utilized to analyze the silicon chip after the alkaline etch obtained in the silicon chip and 1.3 after the energising process obtained in 1.2, obtain the photo of its scanning electron microscopy, as shown in Figure 2 and Figure 3, wherein Fig. 2 is the electron scanning micrograph of silicon chip after energising process, and Fig. 3 is the photo of the scanning electron microscopy of silicon chip after alkaline etch.
Analyze (method of testing of employing is the method that those skilled in the art commonly use) the silicon chip after making herbs into wool, test result is in table 1.As shown in Table 1, adopt the silicon chip after the inventive method making herbs into wool can increase substantially light utilization efficiency and finally improve the photoelectric conversion efficiency of cell piece, compared with the silicon chip of making herbs into wool after mortar cuts, absolute efficiency improves 0.6%, also has the power ascension of about 4W at assembly end.
Silicon chip the performance test results after the making herbs into wool that table 1 embodiment 1 obtains
Embodiment 2
The mixed solution that the polysilicon chip that diamond wire cuts puts into hydrofluoric acid and nitric acid etches by 2.1, wherein, in mixed solution, the concentration of hydrofluoric acid is 1mol/L, the concentration of nitric acid is 6mol/L, the temperature of etching is 6 DEG C, the time of etching is 10min, puts into deionized water 25 DEG C cleaning 5min, obtain the silicon chip after etching after having etched.
Silicon chip after the etching obtained in 2.1 is put into the middle fixed head of dual bath apparatus by 2.2, and electrolyte is the mixed solution of hydrofluoric acid, ethanol and water, and the concentration of hydrofluoric acid is 15mol/L, and the concentration of ethanol is 3mol/L, applies 1mA/cm
2constant current, energising process 50min, then puts into deionized water 25 DEG C cleaning 5min, is energized the silicon chip after process.
2.3 the silicon chip after the energising process obtained in 2.2 is put into concentration is 0.005mol/L potassium hydroxide solution, and 40 DEG C of etching 5min, then put into deionized water 25 DEG C cleaning 5min, obtain the silicon chip of alkaline etch.
2.4 mixed solutions silicon chip of the alkaline etch obtained in 2.3 being put into hydrofluoric acid and hydrochloric acid carry out 40 DEG C and clean 20min, the concentration of hydrofluoric acid is 20mol/L, and the concentration of hydrochloric acid is 10mol/L, and then puts into deionized water 25 DEG C cleaning 5min, dry up, obtain the silicon chip after making herbs into wool.
Performance test is carried out to the silicon chip after the making herbs into wool obtained in embodiment 2, obtains the results are shown in Table 2.
Silicon chip the performance test results after the making herbs into wool obtained in table 2 embodiment 2
Embodiment 3
The mixed solution that the polysilicon chip that diamond wire cuts puts into hydrofluoric acid and nitric acid etches by 3.1, wherein, in mixed solution, the concentration of hydrofluoric acid is 5mol/L, the concentration of nitric acid is 3mol/L, the temperature of etching is 7 DEG C, the time of etching is 10min, puts into deionized water 25 DEG C cleaning 5min, obtain the silicon chip after etching after having etched.
Silicon chip after the etching obtained in 3.1 is put into the middle fixed head of dual bath apparatus by 3.2, and electrolyte is the mixed solution of hydrofluoric acid, ethanol and water, and the concentration of hydrofluoric acid is 30mol/L, and the concentration of ethanol is 0.5mol/L, applies 5mA/cm
2constant current, energising process 10min, then puts into deionized water 25 DEG C cleaning 5min, is energized the silicon chip after process.
3.3 the silicon chip after the energising process obtained in 3.2 is put into concentration is 0.02mol/L potassium hydroxide solution, and 40 DEG C of etching 5min, then put into deionized water 25 DEG C cleaning 5min, obtain the silicon chip of alkaline etch.
3.4 mixed solutions silicon chip of the alkaline etch obtained in 3.3 being put into hydrofluoric acid and hydrochloric acid carry out 25 DEG C and clean 20min, the concentration of hydrofluoric acid is 10mol/L, and the concentration of hydrochloric acid is 5mol/L, and then puts into deionized water 25 DEG C cleaning 5min, dry up, obtain the silicon chip after making herbs into wool.
Performance test is carried out to the silicon chip after the making herbs into wool obtained in embodiment 3, obtains the results are shown in Table 3.
Silicon chip the performance test results after the making herbs into wool obtained in table 3 embodiment 3
Claims (10)
1. an etching method for silicon chip, is characterized in that, comprises the following steps:
A) the silicon chip etchant solution that diamond wire cuts is etched;
B) the silicon chip placement after etching is energized in the electrolytic solution, processes;
C) the silicon chip alkaline solution after process is carried out alkaline etch.
2. etching method according to claim 1, is characterized in that, also comprises:
D) the silicon chip acid solution after alkaline etch is cleaned.
3. etching method according to claim 2, is characterized in that, described acid solution is the mixed solution of hydrofluoric acid and hydrochloric acid; In described acid solution, the concentration of hydrofluoric acid is 10 ~ 30mol/L; In described acid solution, the concentration of hydrochloric acid is 0.5 ~ 12mol/L.
4. etching method according to claim 2, is characterized in that, the time of described cleaning is 1 ~ 20min; The temperature of cleaning is 20 DEG C ~ 60 DEG C.
5. etching method according to claim 1, is characterized in that, the time of described etching is 1 ~ 20min; The temperature of described etching is 6 DEG C ~ 12 DEG C.
6. etching method according to claim 1, is characterized in that, the current density of described energising is 1 ~ 10mA/cm
2; The time of described energising is 5 ~ 60min.
7. etching method according to claim 1, is characterized in that, described electrolyte is the aqueous solution of hydrofluoric acid and alcoholic solvent.
8. etching method according to claim 7, is characterized in that, in described electrolyte, the concentration of hydrofluoric acid is 1 ~ 30mol/L; In described electrolyte, the concentration of alcohols solvent is 0.1 ~ 16mol/L.
9. etching method according to claim 1, is characterized in that, described alkaline solution is the aqueous solution of alkali metal hydroxide; The concentration of described alkali metal hydroxide is 0.005 ~ 0.05mol/L.
10. etching method according to claim 1, is characterized in that, the time of described alkaline etch is 1 ~ 5min; The temperature of alkaline etch is 20 DEG C ~ 40 DEG C.
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| CN108400200A (en) * | 2018-02-13 | 2018-08-14 | 南通苏民新能源科技有限公司 | A kind of black silicon process for etching recycling electrolyte solution |
| CN109461791A (en) * | 2018-10-24 | 2019-03-12 | 盐城阿特斯协鑫阳光电力科技有限公司 | The etching method of monocrystalline silicon piece |
| CN112899789A (en) * | 2021-01-19 | 2021-06-04 | 西安交通大学 | Texturing method for pretreating surface of monocrystalline silicon wafer by electrochemical method |
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