CN109853036A - A kind of etching method of Buddha's warrior attendant wire cutting polysilicon chip - Google Patents
A kind of etching method of Buddha's warrior attendant wire cutting polysilicon chip Download PDFInfo
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- CN109853036A CN109853036A CN201910164295.9A CN201910164295A CN109853036A CN 109853036 A CN109853036 A CN 109853036A CN 201910164295 A CN201910164295 A CN 201910164295A CN 109853036 A CN109853036 A CN 109853036A
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- buddha
- polysilicon chip
- wire cutting
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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
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Abstract
The invention discloses a kind of etching method of Buddha's warrior attendant wire cutting polysilicon chip, the further perfect technique that black silicon is prepared using wet etching selects Fe when preparing black silicon2+Ion, rather than the noble metals such as gold used in conventional wet etch process, platinum or silver, preparation cost are substantially reduced；Use Fe2+Compared to using the noble metals such as gold, platinum or silver that will not cause serious environmental pollution；The black silicon reflectivity of preparation is low, and performance is stablized；This method provides a new route to improve crystal silicon solar energy battery efficiency and reducing production cost, has good economic benefits.
Description
Technical field
The present invention relates to solar cell material technical fields, and in particular to a kind of making herbs into wool of Buddha's warrior attendant wire cutting polysilicon chip
Method.
Background technique
The traditional energies such as coal, petroleum, natural gas not only have it is non-renewable, long-time service also result in serious ring
Border pollution problem, moment threaten the health of the mankind.Therefore, renewable energy has been to be concerned by more and more people, solar energy conduct
Important green energy resource becomes one of research hotspot in recent years, wherein crystal silicon battery is currently the only depth industrialization again
A kind of solar battery.
Currently, the cost of electricity-generating of crystal silicon battery is still higher than traditional coal power generation, in order to reduce its cost of electricity-generating, need into one
Step optimizes its production technology, reduces production cost and make great efforts to improve its photoelectric efficiency.Improve crystal silicon battery photoelectric conversion efficiency
There are many methods, but the factors such as considering cost, efficiency, can be used for realizing the technique of large-scale production and few.
Silicon wafer used in conventional crystalline silicon cell piece mainly uses free abrasive cutting method to prepare, the letter though this method operates
Singly, conveniently, but more serious problem of environmental pollution can be brought when waste mortar is cut in processing, meanwhile, this method was implemented
Silicon loss in journey is big and cutting speed is slower.In order to further decrease silicon wafer cutting cost, introduces fixed abrasive diamond wire and cut
It cuts, though this method compensates for the defects of free abrasive cutting method cutting speed is slow, mortar processing is difficult, silicon loss is high, gold
The polysilicon chip surface damage layer of rigid wire cutting is shallower, this will lead to later period silicon wafer and is difficult to reduce reflection by conventional etching method
Rate.
The principle of the polycrystalline silicon texturing technology of industrialization is to etch silicon substrate by acid solution to be formed on its surface
The suede structure of micron order worm hole shape, silicon wafer average reflectance are reduced to 23% or so by 40% or so, and reflectivity is still very
Greatly, in order to further increase the efficiency of polycrystal silicon cell, need to be further reduced the reflectivity on its surface.
In order to solve the problems, such as the making herbs into wool of silicon wafer cut by diamond wire while reducing polysilicon chip reflectivity, researcher draws
Into black silicon technology.So-called black silicon is exactly to prepare one layer of nanometer-scale texture extremely low with high light absorptive, reflectivity in silicon chip surface
Structure.In the prior art, mainly there are two kinds of dry and wet about the preparation method of black silicon.Dry method is mainly that plasma is carved
Erosion, uses fluoro-gas to corrode at low pressure to silicon chip surface, and that there are production efficiencys is low for this method, equipment cost is high
The disadvantages of.And wet etching is mainly corroded under metallic catalyst assistance, this method is simple with apparatus, operates
It reacted under easy, at low cost, room temperature, be easy to implement the features such as large-scale production, therefore this method becomes black silicon technology in recent years
The research hotspot in field.But this kind of method is also perfectly not, and in practical application, there is also some defects, such as production process
In need to add noble metal, the addition one side of such as metal ion of gold, platinum, silver, noble metal increases production cost, another party
Face also brings along problem of environmental pollution.
Therefore, noble metal can be substituted by finding one kind, while the method that can guarantee black silicon making herbs into wool quality again, it will be brought aobvious
The economic benefit of work.
Summary of the invention
It is an object of the invention to solve deficiency in the prior art, a kind of making herbs into wool of Buddha's warrior attendant wire cutting polysilicon chip is provided
Method provides a new technical support to improve crystal silicon solar energy battery efficiency and reducing production cost, further complete
It has been apt to prepare the technique of black silicon using wet etching, it is with good economic efficiency.
The technical solution of the present invention is as follows: providing a kind of etching method of Buddha's warrior attendant wire cutting polysilicon chip, comprising the following steps:
(1) Buddha's warrior attendant wire cutting polysilicon chip is placed in containing H2O2With prerinse is carried out in the aqueous solution of ethyl alcohol；
(2) by aqueous solution of the silicon wafer merging containing 2~8wt%HF, 5~10min is stood, by the SiO of silicon chip surface2It is molten
Solution, solution temperature are 15~50 DEG C；
(3) it prepares and contains Fe2+、H2O2With the aqueous solution of HF；
(4) by the solution prepared through step 1 treated silicon wafer merging step 3, nanometer is obtained on polysilicon chip surface
The black silicon flannelette of grade；
(5) will through step 4, treated that polysilicon chip is placed in hydrochloric acid solution, remove the Fe of silicon chip surface2+Ion；
(6) deionized water cleaning silicon chip is used, then by silicon wafer blow-drying.
Further, H in the step 12O2Concentration is 2~10wt%, and concentration of alcohol is 5~10wt%, aqueous temperature
It is 40~70 DEG C, scavenging period is 1~5min.
Further, in the solution that step 3 is prepared, Fe2+、H2O2Concentration with HF be respectively 0.05~1mol/L, 1~
3mol/L and 2~8mol/L.
Further, reaction solution temperature is 20~50 DEG C in step 4,1~5min of reaction time.
Further, the concentration of hydrochloric acid is 2~5mol/L in step 5, and solution temperature is 20~40 DEG C.
Further, in the solution that step 3 is prepared, Fe2+Source includes ferrous sulfate, frerrous chloride, ferrous acetate, carbonic acid
Ferrous iron, ferrous nitrate, potassium ferrocyanide and ferrous sulfide.
The invention has the benefit that
(1) present invention selects Fe when preparing black silicon2+Ion, rather than gold used in conventional wet etch process, platinum or
The noble metals such as silver, preparation cost are substantially reduced；
(2) compared to problem of environmental pollution brought by the noble metals such as gold, platinum or silver is used, Fe is used2+It not will cause tight
The environmental pollution of weight；
(3) conventional wet etch process generallys use concentrated nitric acid removal silicon chip surface noble metal, and the present invention only needs to use
Low-concentration hcl removes silicon chip surface iron ion, and preparation method is more simple；
(4) the black silicon that through the invention prepared by published method, reflectivity is low, and performance is stablized.
Detailed description of the invention
Fig. 1 is black silicon sample figure prepared by the embodiment of the present invention 1；
Fig. 2 is black silicon reflectivity map prepared by the embodiment of the present invention 1.
Specific embodiment
Following embodiment further illustrates the contents of the present invention, but should not be construed as limiting the invention.Without departing substantially from
In the case where essence of the present invention, to modification made by the method for the present invention, step or condition and replaces, belong to model of the invention
It encloses.
Involved correlated response principle is as follows in the embodiment of the present invention:
Fe is selected when preparing black silicon process2+Ion, it is main in the process to occur to react as shown in formula (1) and (2), and OH has
There is 2.72eV oxidation potential, there is stronger oxidisability, understand reaction shown in generating polynomial (3) later, silica exists in hydrofluoric acid
In the case of, it can then reaction shown in generating polynomial (4).
Fe2++H2O2→Fe3++·OH+OHˉ (1)
Fe3++H2O2→Fe2++·OH+H+ (2)
Si+4·OH→SiO2+2H2O (3)
SiO2+6HF→H2SiF6+H2O (4)
Embodiment 1:
(1) Buddha's warrior attendant wire cutting polysilicon chip is placed in containing H2O2With prerinse is carried out in the aqueous solution of ethyl alcohol, wherein H2O2It is dense
Degree is 5wt%, and concentration of alcohol 8wt%, aqueous temperature is 60 DEG C, scavenging period 3min；
(2) silicon wafer is placed in the aqueous solution containing 5wt%HF, 8min is stood, by the SiO of silicon chip surface2Dissolution, solution temperature
Degree is 30 DEG C；
(3) it prepares and contains Fe2+、H2O2With the aqueous solution of HF, three's concentration is respectively 0.5mol/L, 2mol/L and 6mol/L；
(4) by the solution prepared through the processed silicon wafer merging step 3 of step 2, solution temperature is 40 DEG C, the time
3min obtains the black silicon flannelette of nanoscale on polysilicon chip surface；
(5) it by through step 4, treated that polysilicon chip is placed in the aqueous hydrochloric acid solution of 4mol/L, 30 DEG C of solution temperature, goes
Except silicon chip surface Fe2+Ion；
(6) deionized water cleaning silicon chip is used, then by silicon wafer blow-drying.
Embodiment 2:
(1) Buddha's warrior attendant wire cutting polysilicon chip is placed in containing H2O2With prerinse is carried out in ethanol water, wherein H2O2Concentration
For 2wt%, concentration of alcohol 5wt%, aqueous temperature is 40 DEG C, scavenging period 1min；
(2) silicon wafer is placed in the aqueous solution containing 2wt%HF, 5min is stood, by the SiO of silicon chip surface2Dissolution, solution temperature
Degree is 15 DEG C；
(3) it prepares and contains Fe2+、H2O2With the aqueous solution of HF, three's concentration is respectively 0.05mol/L, 1mol/L and 2mol/L；
(4) by the solution prepared through the processed silicon wafer merging step 3 of step 2, solution temperature is 20 DEG C, the time
1min obtains the black silicon flannelette of nanoscale on polysilicon chip surface；
(5) will through step 4, treated that polysilicon chip is placed in 2mol/L aqueous hydrochloric acid solution, 20 DEG C of solution temperature, removal
Silicon chip surface Fe2+Ion；
(6) deionized water cleaning silicon chip is used, then by silicon wafer blow-drying.
Embodiment 3:
(1) Buddha's warrior attendant wire cutting polysilicon chip is placed in containing H2O2With prerinse is carried out in ethanol water, wherein H2O2Concentration
For 10wt%, concentration of alcohol 10wt%, aqueous temperature is 70 DEG C, scavenging period 5min；
(2) silicon wafer is placed in the aqueous solution containing 8wt%HF, 10min is stood, by the SiO of silicon chip surface2Dissolution, solution
Temperature is 50 DEG C；
(3) it prepares and contains Fe2+、H2O2With the aqueous solution of HF, three's concentration is respectively 1mol/L, 3mol/L and 8mol/L；
(4) by the solution prepared through the processed silicon wafer merging step 3 of step 2, solution temperature is 50 DEG C, the time
5min obtains the black silicon flannelette of nanoscale on polysilicon chip surface；
(5) will through step 4, treated that polysilicon chip is placed in 5mol/L aqueous hydrochloric acid solution, 40 DEG C of solution temperature, removal
Silicon chip surface Fe2+Ion；
(6) deionized water cleaning silicon chip is used, then by silicon wafer blow-drying.
Embodiment 4:
(1) Buddha's warrior attendant wire cutting polysilicon chip is placed in containing H2O2With prerinse is carried out in ethanol water, wherein H2O2Concentration
For 2wt%, concentration of alcohol 10wt%, aqueous temperature is 40 DEG C, scavenging period 2min；
(2) silicon wafer is placed in the aqueous solution containing 8wt%HF, 5min is stood, by the SiO of silicon chip surface2Dissolution, solution temperature
Degree is 50 DEG C；
(3) it prepares and contains Fe2+、H2O2With the aqueous solution of HF, three's concentration is respectively 0.1mol/L, 2mol/L and 8mol/L；
(4) by the solution prepared through the processed silicon wafer merging step 3 of step 2, solution temperature is 20 DEG C, the time
5min obtains the black silicon flannelette of nanoscale on polysilicon chip surface；
(5) will through step 4, treated that polysilicon chip is placed in 2mol/L aqueous hydrochloric acid solution, 40 DEG C of solution temperature, removal
Silicon chip surface Fe2+Ion；
(6) deionized water cleaning silicon chip is used, then by silicon wafer blow-drying.
Basic principles and main features and advantage of the invention have been shown and described above.But the foregoing is merely this hairs
Bright specific embodiment, technical characteristic of the invention are not limited thereto, and any those skilled in the art is not departing from this hair
The other embodiments obtained under bright technical solution should all cover within the scope of the patent of the present invention.
Claims (6)
1. a kind of etching method of Buddha's warrior attendant wire cutting polysilicon chip, which is characterized in that specifically includes the following steps:
(1) Buddha's warrior attendant wire cutting polysilicon chip is placed in containing H2O2With prerinse is carried out in the aqueous solution of ethyl alcohol；
(2) by aqueous solution of the silicon wafer merging containing 2~8wt%HF, 5~10min is stood, by the SiO of silicon chip surface2Dissolution, solution
Temperature is 15~50 DEG C；
(3) it prepares and contains Fe2+、H2O2With the aqueous solution of HF；
(4) by the solution prepared through step 1 treated silicon wafer merging step 3, it is black that nanoscale is obtained on polysilicon chip surface
Silicon flannelette；
(5) will through step 4, treated that polysilicon chip is placed in hydrochloric acid solution, remove silicon chip surface Fe2+Ion；
(6) deionized water cleaning silicon chip is used, then by silicon wafer blow-drying.
2. a kind of etching method of Buddha's warrior attendant wire cutting polysilicon chip as described in claim 1, which is characterized in that the step 1
Middle H2O2Concentration be 2~10wt%, concentration of alcohol be 5~10wt%, aqueous temperature be 40~70 DEG C, scavenging period be 1~
5min。
3. a kind of etching method of Buddha's warrior attendant wire cutting polysilicon chip as described in claim 1, which is characterized in that step 3 is prepared
Solution in, Fe2+、H2O2Concentration with HF is respectively 0.05~1mol/L, 1~3mol/L and 2~8mol/L.
4. a kind of etching method of Buddha's warrior attendant wire cutting polysilicon chip as described in claim 1, which is characterized in that anti-in step 4
Answering solution temperature is 20~50 DEG C, 1~5min of reaction time.
5. a kind of etching method of Buddha's warrior attendant wire cutting polysilicon chip as described in claim 1, which is characterized in that salt in step 5
The concentration of acid is 2~5mol/L, and solution temperature is 20~40 DEG C.
6. a kind of etching method of Buddha's warrior attendant wire cutting polysilicon chip as described in claim 1, which is characterized in that step 3 is prepared
Solution in, Fe2+Source include ferrous sulfate, frerrous chloride, ferrous acetate, ferrous carbonate, ferrous nitrate, potassium ferrocyanide
And ferrous sulfide.
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| CN201910164295.9A CN109853036A (en) | 2019-03-05 | 2019-03-05 | A kind of etching method of Buddha's warrior attendant wire cutting polysilicon chip |
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Citations (5)
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|---|---|---|---|---|
| WO2011152973A1 (en) * | 2010-06-01 | 2011-12-08 | Asia Union Electronic Chemical Corporation | Texturing of multi-crystalline silicon substrates |
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| CN105154982A (en) * | 2015-07-08 | 2015-12-16 | 中国科学院宁波材料技术与工程研究所 | Polycrystalline black silicon texturization treatment fluid, polysilicon chip texturization method applying treatment fluid, and polycrystalline black silicon texturization product |
| CN106935669A (en) * | 2017-05-23 | 2017-07-07 | 江苏福吉食品有限公司 | A kind of etching method of the diamond wire section black silicon of polycrystalline |
| CN108281508A (en) * | 2018-01-25 | 2018-07-13 | 浙江大学 | The preparation method of low surface reflectivity Buddha's warrior attendant wire cutting polysilicon chip matte |
-
2019
- 2019-03-05 CN CN201910164295.9A patent/CN109853036A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011152973A1 (en) * | 2010-06-01 | 2011-12-08 | Asia Union Electronic Chemical Corporation | Texturing of multi-crystalline silicon substrates |
| CN104393114A (en) * | 2014-11-17 | 2015-03-04 | 中国电子科技集团公司第四十八研究所 | Preparation method of polycrystalline black silicon of micro-nano composite suede structure |
| CN105154982A (en) * | 2015-07-08 | 2015-12-16 | 中国科学院宁波材料技术与工程研究所 | Polycrystalline black silicon texturization treatment fluid, polysilicon chip texturization method applying treatment fluid, and polycrystalline black silicon texturization product |
| CN106935669A (en) * | 2017-05-23 | 2017-07-07 | 江苏福吉食品有限公司 | A kind of etching method of the diamond wire section black silicon of polycrystalline |
| CN108281508A (en) * | 2018-01-25 | 2018-07-13 | 浙江大学 | The preparation method of low surface reflectivity Buddha's warrior attendant wire cutting polysilicon chip matte |
Non-Patent Citations (1)
| Title |
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| 张倩等主编: "《普通高等院校环境科学与工程类系列规划教材 水环境化学》", 30 June 2018, 中国建材工业出版社 * |
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