CN107623054A - A kind of process for etching based on silicon wafer cut by diamond wire - Google Patents
A kind of process for etching based on silicon wafer cut by diamond wire Download PDFInfo
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- CN107623054A CN107623054A CN201710848456.7A CN201710848456A CN107623054A CN 107623054 A CN107623054 A CN 107623054A CN 201710848456 A CN201710848456 A CN 201710848456A CN 107623054 A CN107623054 A CN 107623054A
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- silicon chip
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- alkali lye
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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
A kind of process for etching based on silicon wafer cut by diamond wire provided by the invention, suitable for the monocrystalline silicon piece and polysilicon chip of Buddha's warrior attendant wire cutting.Chemical deposition is adopted first and deposits Ag nano-particles in silicon chip surface, and HF, H are then used under the catalytic action of Ag nano-particles2O2、H2O mixed solutions carry out corrosion making herbs into wool to silicon chip, finally do further expanding treatment with NaOH solution, obtain the silicon chip with micro nano structure matte.Uniform by the silicon wafer suede of the PROCESS FOR TREATMENT, no to cut trace, silicon chip surface reduces to the reflectivity of light, and sunken light effect is good, is advantageous to improve the energy conversion efficiency of day sun energy battery.Moreover, this method technique is simple, cost is low, it is adapted to industrialized production.
Description
Technical field
The present invention relates to a kind of process for etching based on silicon wafer cut by diamond wire, belongs to crystal silicon solar energy battery making herbs into wool neck
Domain, more particularly to a kind of making herbs into wool technical field of the silicon chip based on Buddha's warrior attendant wire cutting.
Background technology
The process for etching of silicon chip can reduce the reflection of incident sunshine on battery smooth surface, be to improve solar cell light
One of effective means of photoelectric transformation efficiency.Process for etching possesses different schemes according to the type of crystalline silicon, wherein monocrystalline silicon because
Its crystal orientation aligned orderly, the corrosion rate of each crystal orientation is different in aqueous slkali, using this feature frequently with alkali lye making herbs into wool, most
The matte with pyramid structure is obtained eventually；The crystal orientation of polysilicon is more random, without rule, typically using sour making herbs into wool, i.e., it is each to
Same sex heterogeneity is corroded, and obtains the matte in concavo-convex gully.
In addition, crystalline silicon hardness is high, plasticity is poor, brittle and be also easy to produce micro-crack, therefore machining property is poor.In silicon
In piece manufacturing process, higher is required to cutting technique, Buddha's warrior attendant wire cutting technology can overcome lacking for silicon chip machining property difference
Point, cutting, therefore be widely used in the cutting processing of crystalline silicon well is realized to silicon chip.But to the making herbs into wool of polysilicon chip,
Buddha's warrior attendant line cutting technology can produce a series of problems, can form cutting line when being mainly reflected in cutting on silicon chip, and these are cut
Cut is difficult to eliminate when using conventional acid corrosion method used making herbs into wool, so that the silicon chip reflectivity after making herbs into wool can not meet to give birth to
Production requires.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of process for etching based on silicon wafer cut by diamond wire, is applied to
The polysilicon and monocrystalline silicon of Buddha's warrior attendant wire cutting, silicon chip surface can be removed due to cutting line caused by Buddha's warrior attendant wire cutting, and
Silicon chip surface making herbs into wool, reflectivity of the silicon chip surface to sunshine is reduced, improve utilization rate of the crystal silicon cell to sunshine.
To reach above technical purpose, a kind of process for etching based on silicon wafer cut by diamond wire comprises the following steps：
Step 1：Go to damage layer process, cleaned silicon chip is immersed in alkali lye, removes the surface cutting damage of silicon chip, then will
Silicon chip is cleaned with deionized water, removes the alkali lye of remained on surface；
Step 2：Ag nano particles are deposited, above-mentioned silicon chip is placed in AgNO3With in HF mixed solution silicon chip surface deposition on
One layer of Ag nano particle, subsequent silicon chip are cleaned with deionized water, remove the AgNO of remained on surface3And HF；
Step 3：HF、H2O2Mixed solution corrodes making herbs into wool：Above-mentioned silicon chip is placed in HF, H2O2In the mixed solution of deionized water
Corrosion making herbs into wool is carried out, then cleans silicon chip with purified water, removes HF, H of remained on surface2O2；
Step 4：The Ag nano particles of residual are removed, above-mentioned silicon chip is placed in NH4OH and H2O2Mixed solution in remove residual
Ag nano particles, then silicon chip is cleaned with purified water, removes [Ag (the NH of remained on surface3)2]+、NH4OH、H2O2；
Step 5：Alkali lye expanding treatment, above-mentioned sample is placed in alkali lye and carries out expanding treatment.It is then that silicon chip purified water is clear
Wash, remove the alkali lye of remained on surface, dried up under last condition of nitrogen gas；
Further, the silicon wafer cut by diamond wire is one kind of monocrystalline silicon and polysilicon.
Further, alkali lye described in step 1 is KOH solution, one kind in NaOH solution, mass concentration is 10%~
20%, 80 DEG C~90 DEG C of reaction temperature, the reaction time is 1min~5min.
Further, AgNO described in step 23Solution solubility 1mmol/L~5mmol/L, the HF solubility 4mol/L, sink
Accumulated temperature degree is room temperature, and sedimentation time is 30s~50s.
Further, HF, H described in step 32O2Mixed solution with deionized water is H2O2Solubility 0.3mol/L~
0.5mol/L, HF solubility 2mol/L, corrosion temperature are room temperature, and etching time is 40s~60s.
Further, NH described in step 44OH and H2O2Mixed solution be：NH4OH and H2O2Molar concentration rate 2:1,
H2O2Concentration is 0.5mol/L~3mol/L.Dissolving Ag reaction temperatures are room temperature, 10~30min of reaction time.
Further, alkali lye described in step 5 is KOH solution, one kind in NaOH solution, mass concentration is 1%~
2%, treatment temperature is room temperature, and processing time is 10min~30min.
It is heavy using chemistry based on a kind of described above, process for etching based on silicon wafer cut by diamond wire provided by the invention
Area method then uses HF, H in silicon chip surface deposited metal Ag nano-particles under the catalytic action of Ag nano-particles2O2、H2O is mixed
Close solution and corrosion making herbs into wool is carried out to silicon chip, finally do further expanding treatment with NaOH solution, preparation has micro nano structure
The silicon chip of matte.The silicon wafer suede prepared by the technique is uniform, and no cutting trace, silicon chip surface reflectivity reduces, and falls into light efficiency
Fruit is good, so as to which the solar cell for ensureing to obtain has higher conversion efficiency.Moreover, this method technique is simple, cost is low, fit
Close industrialized production.
Embodiment
The present invention is described in detail with reference to embodiment：
Embodiment 1
A kind of process for etching based on silicon wafer cut by diamond wire, using the polysilicon chip after Buddha's warrior attendant wire cutting as raw material pass through with
Lower step process is in silicon chip surface making herbs into wool：
I) silicon chip after Buddha's warrior attendant wire cutting is used successively ethanol and acetone are cleaned by ultrasonic 5min, removal surface irregularities.Then use
25% NaOH solution, under the conditions of 85 DEG C, immersion treatment 1min.Deionized water cleaning silicon chip surface then is used, removes residual
NaOH alkali lye；
II) at room temperature, above-mentioned silicon chip is soaked in the solution containing 2mmol/LAgNO3 and 4mol/LHF, handles 50s.Then
With deionized water cleaning silicon chip surface, the AgNO of remained on surface is removed3And HF；
III) at room temperature, above-mentioned silicon chip is soaked in containing 1.5mol/LHF and 0.3mol/LH2O2Solution in, corrode 50s, with
Purified water cleaning silicon chip surface is used afterwards, removes HF, H of remained on surface2O2；
IV) at room temperature, above-mentioned silicon chip is soaked in the NH containing 2mol/L4OH and 1mol/L H2O2Handled in mixed solution
20min, the Ag nano particles of residual are removed, then clean silicon chip with purified water, remove [Ag (the NH of remained on surface3)2]+、
NH4OH、H2O2；
V) at room temperature, above-mentioned silicon chip is placed in the NaOH solution of mass fraction 2%, immersion treatment 20min.Subsequent deionization
Water cleaning silicon chip surface, remove the NaOH of remained on surface.Dried up under last condition of nitrogen gas.The product of gained be process for etching into
Product.
Embodiment 2
A kind of process for etching based on silicon wafer cut by diamond wire, using the monocrystalline silicon piece after Buddha's warrior attendant wire cutting as raw material pass through with
Lower step process is in silicon chip surface making herbs into wool：
I) silicon chip after Buddha's warrior attendant wire cutting is used successively ethanol and acetone are cleaned by ultrasonic 5min, removal surface irregularities.Then use
25% KOH solution, under the conditions of 85 DEG C, immersion treatment 1min.Deionized water cleaning silicon chip surface then is used, removes residual
NaOH alkali lye；
II) at room temperature, above-mentioned silicon chip is immersed in the solution containing 2mmol/LAgNO3 and 4mol/LHF, handles 50s.Then
With deionized water cleaning silicon chip surface, the AgNO of remained on surface is removed3And HF；
III) at room temperature, above-mentioned silicon chip is immersed in containing 1.5mol/L HF and 0.3mol/L H2O2Solution in, corrode 50s,
Purified water cleaning silicon chip surface then is used, removes HF, H of remained on surface2O2；
IV) at room temperature, above-mentioned silicon chip is immersed in the NH containing 2mol/L4OH and 1mol/L H2O2In mixed solution, processing
20min, the Ag nano particles of residual are removed, then clean silicon chip with purified water, remove [Ag (the NH of remained on surface3)2]+、
NH4OH、H2O2；
V) at room temperature, above-mentioned silicon chip is placed in the KOH solution of mass fraction 1%, immersion treatment 20min.Subsequent deionized water
Cleaning silicon chip surface, remove the KOH of remained on surface.Dried up under last condition of nitrogen gas.The product of gained is process for etching finished product.
For comparative experiments result, comparison of design example 1 and comparative example 2, solar-electricity is prepared into resulting making herbs into wool finished product
Pond, carry out battery efficiency test.Wherein comparative example 1：Polysilicon cutting sheet in embodiment 1 is traditionally subjected to sour making herbs into wool
Processing；Comparative example 2：Monocrystalline silicon cutting sheet traditionally carries out alkali making herbs into wool processing in embodiment 2.Test result such as following table institute
Show：
Conversion efficiency of solar cell prepared by the embodiment silicon chip of table 1
The data from table 1, using the new technology in embodiment by silicon chip surface making herbs into wool, it is subsequently assembled into solar-electricity
Pond, the suitable battery conversion efficiency of traditional handicraft can be reached, it was demonstrated that the process for etching can be very good to be applied to diamond wire
Cut silicon chip.
Corrosion making herbs into wool process in embodiment can be explained with following electrochemical equations：
Cathode reaction occurs on Ag particles：H2O2+2H+→2H2O+2h+
2H++2e-→H2↑
Anode reaction occurs on Si matrixes：Si+4h++4HF→SiF4+4H+
SiF4+2HF→H2SiF6
Overall reaction：Si+H2O2+6HF→2H2O+H2SiF6+H2↑
Reaction equation shows：Ag plays catalytic action during making herbs into wool is corroded, and HF starts from Ag particles to Si etching
Neighboring area, and progressively develop to bottom, form straight and deep macropore.Have additionally, due to HF and the H2O2 aqueous solution to Si
Slow corrasion, a large amount of micropores for being less than 2nm can be formed in the silicon substrate surface of macropore hole wall and no Ag.Therefore, invent
Middle step 5 adds the step of step alkali lye reaming, it is intended that allowing HF and H2O2Corrode the micropore size formed later and become big,
Further improve the quality of matte.
The present invention is described in detail above-described embodiment, but present disclosure is not limited to above example, right
In industry personnel, in the case of the basic thought of the present invention is not departed from, any change done to technical solution of the present invention is all
In claims of the present invention limited range.
Claims (7)
1. a kind of process for etching based on silicon wafer cut by diamond wire, its essential characteristic is that the process for etching comprises the following steps：
Step 1：Go to damage layer process, cleaned silicon chip is immersed in alkali lye, removes the surface cutting damage of silicon chip, then will
Silicon chip is cleaned with deionized water, removes the alkali lye of remained on surface；
Step 2：Ag nano particles are deposited, above-mentioned silicon chip is placed in AgNO3With in HF mixed solution silicon chip surface deposition on one
Layer Ag nano particles, subsequent silicon chip are cleaned with deionized water, remove the AgNO of remained on surface3And HF；
Step 3：HF、H2O2Mixed solution corrodes making herbs into wool：Above-mentioned silicon chip is placed in HF, H2O2Enter with the mixed solution of deionized water
Row corrosion making herbs into wool, silicon chip is then cleaned, remove HF, H of remained on surface with purified water2O2；
Step 4：The Ag nano particles of residual are removed, above-mentioned silicon chip is placed in NH4OH and H2O2Mixed solution in remove residual
Ag nano particles, then silicon chip is cleaned with purified water, removes [Ag (the NH of remained on surface3)2]+、NH4OH、H2O2；
Step 5：Alkali lye expanding treatment, above-mentioned sample is placed in alkali lye and carries out expanding treatment.It is then that silicon chip purified water is clear
Wash, remove the alkali lye of remained on surface, dried up under last condition of nitrogen gas.
2. according to described in claim 1, it is characterised in that silicon wafer cut by diamond wire is one kind of monocrystalline silicon or polysilicon.
3. according to described in claim 1, it is characterised in that alkali lye described in step 1 is one kind in KOH solution, NaOH solution,
Mass concentration is 10%~20%, and 80 DEG C~90 DEG C of reaction temperature, the reaction time is 1min~5min.
4. according to described in claim 1, it is characterised in that AgNO described in step 23Solution solubility 1mmol/L~5mmol/L, institute
HF solubility 4mol/L are stated, depositing temperature is room temperature, and sedimentation time is 30s~50s.
5. according to described in claim 1, it is characterised in that HF, H described in step 32O2Mixed solution with deionized water is H2O2
Solubility 0.3mol/L~0.5mol/L, HF solubility 2mol/L, corrosion temperature are room temperature, and etching time is 40s~60s.
6. according to described in claim 1, it is characterised in that NH described in step 44OH and H2O2Mixed solution be：NH4OH and
H2O2Molar concentration rate 2:1, H2O2Concentration is 0.5mol/L~3mol/L.Dissolving Ag reaction temperatures are room temperature, the reaction time 10
~30min.
7. according to described in claim 1, it is characterised in that alkali lye described in step 5 is one kind in KOH solution, NaOH solution,
Mass concentration is 1%~2%, and treatment temperature is room temperature, and processing time is 10min~30min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108447943A (en) * | 2018-03-23 | 2018-08-24 | 浙江师范大学 | Simple and effective store method after a kind of Wafer Cleaning |
| CN108807569A (en) * | 2018-06-20 | 2018-11-13 | 通威太阳能（合肥）有限公司 | Preparation method of surface micron/nano composite structure of single crystal battery piece |
| CN108847432A (en) * | 2018-06-22 | 2018-11-20 | 东方日升（洛阳）新能源有限公司 | A kind of process for etching for polysilicon diamond wire slice |
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| CN103456804A (en) * | 2013-09-24 | 2013-12-18 | 上海大学 | Method for forming inverted-pyramid porous surface nanometer texture on polycrystalline silicon and method for manufacturing short-wave reinforcing solar cell |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108447943A (en) * | 2018-03-23 | 2018-08-24 | 浙江师范大学 | Simple and effective store method after a kind of Wafer Cleaning |
| CN108807569A (en) * | 2018-06-20 | 2018-11-13 | 通威太阳能（合肥）有限公司 | Preparation method of surface micron/nano composite structure of single crystal battery piece |
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| CN108847432A (en) * | 2018-06-22 | 2018-11-20 | 东方日升（洛阳）新能源有限公司 | A kind of process for etching for polysilicon diamond wire slice |
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Address after: Hangzhou City, Zhejiang province 311201 block Bridge Economic Development Zone Xiaoshan Hung Hing Road No. 358 Applicant after: Zhejiang green yup Polytron Technologies Inc Address before: Hangzhou City, Zhejiang province 311201 block Bridge Economic Development Zone Xiaoshan Hung Hing Road No. 358 Applicant before: Green energy technology (Hangzhou) Co., Ltd. |
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Application publication date: 20180123 |