CN102751384A - Surface texturing method of crystalline silicon - Google Patents
Surface texturing method of crystalline silicon Download PDFInfo
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- CN102751384A CN102751384A CN2012102335335A CN201210233533A CN102751384A CN 102751384 A CN102751384 A CN 102751384A CN 2012102335335 A CN2012102335335 A CN 2012102335335A CN 201210233533 A CN201210233533 A CN 201210233533A CN 102751384 A CN102751384 A CN 102751384A
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- crystalline silicon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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 relates to a surface texturing method of crystalline silicon. A KOH aqueous solution used frequently in the texturing process of a crystalline silicon wafer in conventional micro-electronic industry and photovoltaic industry is replaced by a tetraethyl ammonium hydroxide (TEAOH) aqueous solution which serves as a corrosive liquid, wherein under the texturing process condition that the concentration of the corrosive liquid is 4-8wt%, the corrosive temperature is 70-77 DEG C, and the corrosive temperature of 36-40 minutes, excellent anisotropic corrosion is realized, and influence of alkali metal ions on related subsequent operations in the industry is eliminated. The texturing process provided by the invention has high corrosion rate, good anisotropic corrosion effect, good surface uniformity and low cost, can be compatible with micro-electronic and photovoltaic technologies well, and is an ideal surface texturing process of crystalline silicon.
Description
Technical field
The present invention relates to microelectronics and photovoltaic technology field, particularly used for solar batteries crystal silicon chip surface texture technology in the photovoltaic technology.
Background technology
Surface of crystalline silicon texture generally realizes in alkaline aqueous solution; At present, in microelectronics and photovoltaic cell industry, to surface of crystalline silicon texture; Most widely used etchant solution is the mixture of KOH (or NaOH), water and isopropyl alcohol (IPA); The concentration of corrosive agent, etching time, corrosion temperature play decisive influence to the pattern and the surface reflectivity of silicon chip surface, for example, when KOH concentration greater than 25%, corrosion temperature is during greater than 80 ℃; What obtain is an even curface, main reduction processing with the affected layer and the silicon chip that remove silicon chip surface; When NaOH concentration less than 5%, temperature is used in the preparation of surface of crystalline silicon pyramid matte between 70～80 ℃ the time, this is to have utilized solution under this concentration and the temperature conditions to the anisotropic etch characteristic of silicon.But the KOH of this routine adds the mixed liquor caustic solution of isopropyl alcohol many shortcomings are arranged; Pollute and problem such as the isopropyl alcohol cost is too high and more hard to manage like potassium ion; Particularly potassium ion pollutes, and this brings very large adverse effect can for microelectronic component and photovoltaic cell.Simultaneously the temperature spot of the boiling point of isopropyl alcohol and process for etching is approaching, be unfavorable for technology effectively carry out and to the control of cost.
Summary of the invention
To the existing in prior technology defective, the object of the present invention is to provide a kind of and microelectronics, the compatible better surface of crystalline silicon texture technology of photovoltaic industry, realize that simultaneously corrosion rate is high, anisotropic etch is effective and the corrosion surface good uniformity.
The objective of the invention is to be achieved through following technical scheme:
A kind of surface of crystalline silicon texture method is characterized in that, adopt concentration be the tetraethyl ammonium hydroxide TEAOH aqueous solution of 4 ~ 8wt.% as corrosive agent, said method comprising the steps of:
The preparation of A, corrosive liquid
With resistivity>deionized water of 18MW and the tetraethyl ammonium hydroxide that concentration is 25wt.% be raw material, compound concentration is that the tetraethyl ammonium hydroxide aqueous solution of 4 ~ 8wt.% is as corrosive liquid;
The thermostat water bath of B, use band magnetic stirring apparatus is as the texture device; The above-mentioned corrosive liquid for preparing is put into beaker; Heat temperature raising to 70 ~ 77 ℃ are put into corrosive liquid with the monocrystalline silicon piece after the surface preparation and were corroded 36 ~ 40 minutes, in the corrosion process; Even through stirring magneton maintenance corrosive liquid temperature constant and concentration, the monocrystalline silicon piece that etches is used washed with de-ionized water.
Said surface preparation is meant, earlier monocrystalline silicon piece is carried out degrease in acetone and handles, and adopts the NaOH aqueous solution of 20wt.% under 75 ℃ of conditions, to corrode 10min then, removes the affected layer of silicon chip surface.
The present invention proposes a kind of new surface of crystalline silicon texture technology; Adopt the tetraethyl ammonium hydroxide TEAOH aqueous solution as corrosive liquid; Have excellent anisotropic etch characteristic, and can realize that corrosion rate is high, anisotropic etch is effective, the effect of corrosion surface good uniformity, this technology does not contain photovoltaic cell and the harmful alkali metal ion of microelectronic component simultaneously; Compatible better with microelectric technique, photovoltaic technology, be a kind of desirable surface of crystalline silicon texture technology.
Description of drawings
Fig. 1 is for the matte of the monocrystalline silicon piece texture that adopts the present invention's preparation and traditional KOH corrosive liquid preparation and do not have the hemispherical reflectance of the silicon chip of suede structure to compare;
Fig. 2 adopts the SEM figure of the monocrystalline silicon suede of the present invention's preparation and the suede structure that traditional KOH corrosive liquid prepares to compare;
Fig. 3 be the photovoltaic property I-V curve chart of the monocrystalline silicon piece that has matte of two kinds of different surfaces texture prepared when being used for amorphous silicon/crystalline silicon heterojunction solar cell relatively.
Embodiment
Provide specific embodiment of the present invention below
1, being tetraethyl ammonium hydroxide (TEAOH) and 95 milliliters of resistivity of 25wt.% with 5 gram concentration>deionized water of 18MW joins in the beaker and fully mixes, and is mixed with the corrosive liquid that concentration is 5 wt.%;
2, select the N type CZ monocrystalline silicon piece in single-sided polishing (100) crystal orientation for use, the silicon chip diameter is 4 inches, and resistivity is 1Wcm.At first monocrystalline silicon piece is carried out degrease in acetone and handle, then adopt 20wt.%NaOH solution under 75 ℃ of conditions, to corrode 10min,, with deionized water silicon chip surface is rinsed well then to remove the affected layer of silicon chip surface.
3, be 72 ℃ through regulating the setting of thermostat water bath control panel temperature required, temperature error is ± 1 ℃, and by the ring heater heat temperature raising, and stirring obtains stable experimental temperature.Observe solution temperature in the beaker with thermometer, consistent when solution temperature with temperature in the water-bath, and when reaching design temperature, monocrystalline silicon piece is put into solution.In corrosion process, constantly stir with the magnetic stirrer magneton, make solution keep temperature, concentration even.Etching time is 38 minutes, at last the silicon chip that etches is washed with deionization, just obtains the prepared sample that suede structure is arranged.
4, as a comparison, adopt traditional KOH corrosive liquid that identical monocrystalline silicon piece is carried out surperficial texture and handle, the concentration of KOH corrosive liquid is: KOH, 1.4wt.%; Isopropyl alcohol (IPA), 8 wt.%; Deionized water, 90.6 wt.%.Corrosion temperature is 80 ± 1 ℃, and etching time is 20 minutes.
5, measure surface reflectivity and the surface topography that the present invention and conventional method prepare sample respectively and observe, means of testing is respectively ultraviolet-uisible spectrophotometer and field emission electron flying-spot microscope (SEM).
6, to the monocrystalline silicon suede structure of above-mentioned two kinds of technologies making, be respectively applied for the preparation of amorphous silicon (P)/crystalline silicon (N) heterojunction solar battery, compare the cell photovoltaic performance difference under two kinds of different surfaces texture conditions.
Visible by Fig. 2 sem photograph (SEM), adopt the silicon chip surface pyramid of the present invention surface texture method preparation to arrange in order, and size is less, the reflectivity that this helps reducing silicon chip surface reaches desirable texture effect.Visible by Fig. 1 hemispherical reflectance; Adopt the silicon wafer suede of prepared of the present invention; Its average surface reflectance is about 10%; Be superior to 15% of traditional KOH corrosive liquid technology, also reduce much than the smooth silicon chip surface reflectivity that does not have surperficial texture, this performance improvement for photovoltaic cell has positive effect.
Table 1 is used for the photoelectric properties comparison of the amorphous silicon/crystalline silicon heterojunction solar cell (a-Si/c-Si) of same structure, the preparation of identical preparation process condition for the present invention surperficial texture method that proposes and the suede structure that traditional KOH etching process obtains; Visible by data in the table; What adopt the present invention's proposition is the prepared surface of crystalline silicon suede structure of surperficial texture technology of corrosive agent with TEAOH; When being used for the heterojunction battery, its short-circuit current density J
SC3 mA/cm have been improved than traditional handicraft
2More than, improve ratio and reach 12%, and open circuit voltage V
OCThen maintain an equal level with fill factor, curve factor FF, thereby the raising of photoelectric conversion efficiency is had positive facilitation with it.Fig. 3 is the illumination I-V curve chart of two batteries.
Two kinds of technologies of table 1 obtain the performance comparison that suede structure is used for the different joint solar cell of amorphous silicon/crystalline silicon
| ? | V OC(mV) | J SC(mA/cm 2) | FF | h(%) |
| TEAOH (corrosion) | 551 | 31.6 | 0.733 | 12.76 |
| KOH (corrosion) | 553 | 28.3 | 0.728 | 11.39 |
The above only is preferred embodiment of the present invention, is not the present invention is done any pro forma restriction.Though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention.Any those of ordinary skill in the art; Do not breaking away under the technical scheme scope situation of the present invention; All the method for above-mentioned announcement capable of using and technology contents are made many possible changes and modification to technical scheme of the present invention, or are revised as the equivalent embodiment of equivalent variations.Therefore, every content that does not break away from technical scheme of the present invention, according to technical spirit of the present invention to any simple modification that above embodiment did, be equal to replacement, equivalence changes and modify, all still belong in the scope that technical scheme of the present invention protects.
Claims (3)
1. a surface of crystalline silicon texture method is characterized in that, adopt concentration be the tetraethyl ammonium hydroxide aqueous solution of 4 ~ 8wt.% as corrosive agent, said method comprising the steps of:
The preparation of A, corrosive liquid
With resistivity>deionized water of 18MW and the tetraethyl ammonium hydroxide that concentration is 25wt.% be raw material, compound concentration is that the tetraethyl ammonium hydroxide aqueous solution of 4 ~ 8wt.% is as corrosive liquid;
The thermostat water bath of B, use band magnetic stirring apparatus is as the texture device; The above-mentioned corrosive liquid for preparing is put into beaker; Heat temperature raising to 70 ~ 77 ℃ are put into corrosive liquid with the monocrystalline silicon piece after the surface preparation and are corroded, in the corrosion process; Even through stirring magneton maintenance corrosive liquid temperature constant and concentration, the monocrystalline silicon piece that etches is used washed with de-ionized water.
2. a kind of surface of crystalline silicon texture method according to claim 1; It is characterized in that said surface preparation is meant, earlier monocrystalline silicon piece is carried out degrease in acetone and handles; Adopt the NaOH aqueous solution of 20wt.% under 75 ℃ of conditions, to corrode 10min then, remove the affected layer of silicon chip surface.
3. a kind of surface of crystalline silicon texture method according to claim 1 is characterized in that etching time is 36 ~ 40 minutes.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104835867A (en) * | 2015-03-23 | 2015-08-12 | 中建材浚鑫科技股份有限公司 | Novel silicon slice cleaning process single face acid corrosion texturing method |
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| US20100319735A1 (en) * | 2008-02-15 | 2010-12-23 | Lion Corporation | Cleaning composition and method for cleaning substrate for electronic device |
| CN102169818A (en) * | 2009-12-17 | 2011-08-31 | 罗门哈斯电子材料有限公司 | Improved method of texturing semiconductor substrates |
| WO2011154875A1 (en) * | 2010-06-09 | 2011-12-15 | Basf Se | Aqueous alkaline etching and cleaning composition and method for treating the surface of silicon substrates |
| CN102484060A (en) * | 2009-08-20 | 2012-05-30 | 瑞纳有限责任公司 | Method for etching of silicon surfaces |
| CN102479698A (en) * | 2010-11-24 | 2012-05-30 | 气体产品与化学公司 | Compositions and methods for texturing of silicon wafers |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20100319735A1 (en) * | 2008-02-15 | 2010-12-23 | Lion Corporation | Cleaning composition and method for cleaning substrate for electronic device |
| CN102484060A (en) * | 2009-08-20 | 2012-05-30 | 瑞纳有限责任公司 | Method for etching of silicon surfaces |
| CN102169818A (en) * | 2009-12-17 | 2011-08-31 | 罗门哈斯电子材料有限公司 | Improved method of texturing semiconductor substrates |
| WO2011154875A1 (en) * | 2010-06-09 | 2011-12-15 | Basf Se | Aqueous alkaline etching and cleaning composition and method for treating the surface of silicon substrates |
| CN102479698A (en) * | 2010-11-24 | 2012-05-30 | 气体产品与化学公司 | Compositions and methods for texturing of silicon wafers |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104835867A (en) * | 2015-03-23 | 2015-08-12 | 中建材浚鑫科技股份有限公司 | Novel silicon slice cleaning process single face acid corrosion texturing method |
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