CN109360869A - A kind of low cost black silicon solar cell production method - Google Patents
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- 229910021418 black silicon Inorganic materials 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 43
- 239000010703 silicon Substances 0.000 claims abstract description 42
- 238000002161 passivation Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000000151 deposition Methods 0.000 claims abstract description 22
- 238000005530 etching Methods 0.000 claims abstract description 12
- 229910004205 SiNX Inorganic materials 0.000 claims abstract description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052796 boron Inorganic materials 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 8
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 4
- 239000002019 doping agent Substances 0.000 claims abstract description 4
- 239000011521 glass Substances 0.000 claims abstract description 4
- 238000005245 sintering Methods 0.000 claims abstract description 4
- 238000009966 trimming Methods 0.000 claims abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 4
- 238000009792 diffusion process Methods 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 9
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 5
- 235000008216 herbs Nutrition 0.000 claims description 5
- 210000002268 wool Anatomy 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract 1
- 230000003667 anti-reflective effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000002310 reflectometry Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005247 gettering Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- SBEQWOXEGHQIMW-UHFFFAOYSA-N silicon Chemical compound [Si].[Si] SBEQWOXEGHQIMW-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
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- 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
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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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
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- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
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- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/068—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1864—Annealing
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- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1868—Passivation
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Abstract
The invention discloses a kind of inexpensive black silicon solar cell production methods, are related to crystal silicon solar batteries production, comprising: carry out surface clean and wet-method etching to silicon wafer；Using boron source, high temperature dopant is carried out to silicon wafer, makes P-N junction；The silicon boron glass of silicon chip surface, and etching trimming are removed in acid solution, aqueous slkali；ALD deposition method depositing Al is used in front side of silicon wafer2O3Layer realizes the upper surface passivation of black silicon；In Al2O3PECVD deposition method SiN is used on layerXAntireflection layer；In the backside deposition SiO of silicon wafer2And SiNxOverlayer passivation layer realizes the back surface passivation of black silicon；Laser slotting is carried out on silicon chip back side passivation layer；Screen-printed conductive Ag slurry and Al slurry, make metal electrode；High temperature sintering forms black silicon solar cell.The present invention solves the problems, such as the contradiction between anti-reflection effect and its bring surface passivation, is suitble to industrialization.
Description
Technical field
The present invention relates to crystal silicon solar batteries production technical fields, more particularly to a kind of inexpensive black silicon solar electricity
Pond production method.
Background technique
The storage of silicon on earth is abundant, is easily purified, high temperature resistant, natural oxide easy to form, partly leads with good
Body interfacial dielectric layer, therefore crystalline silicon is largely used for semiconductor integrated circuit field, is also widely applied in the opto-electronic device.
Because forbidden bandwidth is big, crystalline silicon is unable to the light wave that absorbing wavelength is greater than 1100nm, when the wavelength of incident light is greater than
When 1100nm, silicon detector will substantially reduce the absorptivity and response rate of light.In order to solve the problems, such as the high reflectance of silicon, technology
Personnel's method has invented making herbs into wool method and antireflection embrane method.Making herbs into wool method: in silicon chip surface KOH(or NaOH) and alcohol mixeding liquid wet process
Preparation, surface texture is in pyramid, but etching method requires the crystal orientation of crystal silicon material, and reflectivity is with incidence
Angle change is violent.Antireflection embrane method: silicon face one layer of anti-reflective film (SiO, ZnO, TiO or Si3N4) of preparation, and anti-reflective film
Film thickness is related with the rate of lambda1-wavelength and anti-reflective film, this just determines that anti-reflective film can only play the anti-of limited spectral range
Reflex, and it is also restricted to incident light angle.
Reducing surface reflectivity is the key that improve crystal silicon battery efficiency, late 1990s, Harvard University's object
Reason laboratory professor ultrashort wave, high intensity laser pulse scan common silicon wafer, after the scanning of 500 subpulses, with the naked eye
Silicon wafer is seen in black, this substance is named as black silicon by researcher.A kind of black silicon silicon face very low as reflectivity
Or silica-base film, there is peculiar photoelectric property, near ultraviolet-near infrared band light (0.25-2.5um) almost all is absorbed
Characteristic.In 2008, start to promote RIE technology in China as the equipment manufacturer of representative using Korean company.Some lines Battery Plant
Family also carried out small lot assessment, since higher process costs and component power income are undesirable, the technology to the technology
Success could not finally be promoted.Nearly 2 years, the expection that diamond wire microtomy is imported based on silicon wafer producer and battery, component skill
The fast development of art, the black silicon technology of RIE progress into the visual field of those skilled in the art again, meanwhile, domestic RIE equipment also promotes
Technology development, but the synthesis cost performance of RIE equipment restricts the large-scale promotion of the technology always.Another can be extensive
The black silicon technology of industrialization is the black silicon technology of wet process.Early in 2006, German Stutzmann group proposed metal catalytic
The concept of chemical attack simultaneously conducts a preliminary study in laboratory；Until 2009, National Renewable Energy laboratory
(NREL) doctor Branz proposes the black silicon preparation method of full liquid phase, and the black silicon technology of wet process is advanced again towards industrialization direction
One step.But they fail to resolve black silicon face passivation problem always, so that the black silicon technology of wet process rests on always laboratory
Stage.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of inexpensive black silicon solar cell production method, including
Following steps:
S1, the substrate used mix gallium silicon substrate for N-type, carry out surface clean and wet-method etching to silicon wafer；
S2, P-N junction is made to silicon wafer progress high temperature dopant using boron source；
S3, the silicon boron glass that silicon chip surface is removed in acid solution, aqueous slkali, and etching trimming；
S4, ALD deposition method depositing Al is used in front side of silicon wafer2O3Layer realizes the upper surface passivation of black silicon；
S5, in Al2O3PECVD deposition method SiN is used on layerXAntireflection layer；
S6, PECVD deposition method SiO is used at the back side of silicon wafer2And SiNXOverlayer passivation layer realizes that the back surface of black silicon is blunt
Change；
S7, laser slotting is carried out on silicon chip back side passivation layer；
S8, Screen-printed conductive Ag slurry and Al slurry, make metal electrode；
S9, high temperature sintering form black silicon solar cell.
Technical effect: the present invention by the optimization of nano-micro structure and later process matching, solve anti-reflection effect with
Contradiction between its bring surface passivation problem, develops a kind of process for stabilizing process of suitable industrialization, is conducive to control
Cost improves net profit.
The technical solution that the present invention further limits is:
A kind of preceding inexpensive black silicon solar cell production method, step S1, using n type single crystal silicon piece as substrate,
Resistivity control uses existing metal ion catalysis lithographic technique in 1-5ohmcm, making herbs into wool technology.
A kind of preceding inexpensive black silicon solar cell production method, step S2 use liquid boron source for diffusion source,
Temperature is 890-950 DEG C, diffusion time 15-30min；Diffusion cooling uses O2It anneals, O2Flow is 3000-
10000sccm, annealing temperature are 600-750 DEG C, and the time controls in 20-40min, diffused sheet resistance 60-150ohm/sq.
A kind of preceding inexpensive black silicon solar cell production method, step S4, the Al of deposition2O3The thickness of passivation layer
Degree is 5-55nm.
A kind of preceding inexpensive black silicon solar cell production method, step S5, the SiN of depositionXAntireflection layer
With a thickness of 30-95nm, refractive index is in 1.9-2.3.
A kind of preceding inexpensive black silicon solar cell production method, step S6, SiO2And SiNXOverlayer passivation layer,
SiO2Layer refractive index is 2.4-2.7, with a thickness of 2-10mm, SiNXLayer refractive index is 1.9-2.4, with a thickness of 70-85nm.
A kind of preceding inexpensive black silicon solar cell production method, step S7, laser slotting figure is linear array
Or lattice array, the etching width of linear array are 10-70 μm, spacing 0.05-2.5mm, the spot diameter of lattice array is 10-70 μm,
Spacing is 0.1-3mm.
The beneficial effects of the present invention are:
(1) present invention in spread when increase cooling annealing steps so that diffusion after boron atom and silicon atom arrangement it is more neat,
The silicon key of suspension is passivated simultaneously, there is better gettering effect, open-circuit voltage promotes 2-3mV, and short circuit current increases 30-
50mA greatly improves cell piece efficiency；
(2) Al is increased in silicon wafer upper surface in the present invention2O3Passivation layer solves the problems, such as black silicon face passivation, makes black silicon
The recombination rate of battery surface is reduced to 50cm/sec or less；
(3) silicon wafer back surface uses SiO in the present invention2And SiNXOverlayer passivation film, not only increases passivation effect, reduces back
The recombination rate on surface, while back internal reflection being made to increase to 85% from 50%, the absorbability to the long glistening light of waves is improved, is silicon wafer
It is further thinning to provide technology guarantee；
(4) the method for the present invention simple possible, cost is relatively low, easy to spread.
Specific embodiment
A kind of inexpensive black silicon solar cell production method provided in this embodiment, comprising the following steps:
S1, the substrate used mix gallium silicon substrate for N-type, carry out surface clean and wet-method etching to silicon wafer；
S2, P-N junction is made to silicon wafer progress high temperature dopant using boron source；
S3, the silicon boron glass that silicon chip surface is removed in acid solution, aqueous slkali, and etching trimming；
S4, ALD deposition method depositing Al is used in front side of silicon wafer2O3Layer realizes the upper surface passivation of black silicon；
S5, in Al2O3PECVD deposition method SiN is used on layerXAntireflection layer；
S6, PECVD deposition method SiO is used at the back side of silicon wafer2And SiNXOverlayer passivation layer realizes that the back surface of black silicon is blunt
Change；
S7, laser slotting is carried out on silicon chip back side passivation layer；
S8, Screen-printed conductive Ag slurry and Al slurry, make metal electrode；
S9, high temperature sintering form black silicon solar cell.
Step S1, using n type single crystal silicon piece as substrate, resistivity control is in 1-5ohmcm, and making herbs into wool technology is using existing
Metal ion catalysis lithographic technique.
Step S2 uses liquid boron source for diffusion source, and temperature is 890-950 DEG C, diffusion time 15-30min；Diffusion drop
Temperature uses O2It anneals, O2Flow is 3000-10000sccm, and annealing temperature is 600-750 DEG C, and the time controls in 20-
40min, diffused sheet resistance 60-150ohm/sq.
Step S4, the Al of deposition2O3Passivation layer with a thickness of 5-55nm.
Step S5, the SiN of depositionXAntireflection layer with a thickness of 30-95nm, refractive index is in 1.9-2.3.
Step S6, SiO2And SiNXOverlayer passivation layer, SiO2Layer refractive index is 2.4-2.7, with a thickness of 2-10mm, SiNXLayer
Refractive index is 1.9-2.4, with a thickness of 70-85nm.
Step S7, laser slotting figure are linear array or lattice array, and the etching width of linear array is 10-70 μm, and spacing is
0.05-2.5mm, the spot diameter of lattice array are 10-70 μm, spacing 0.1-3mm.
The present invention solves anti-reflection effect and its bring table by the optimization of nano-micro structure and later process matching
Contradiction between the problem of passivation of face develops a kind of process for stabilizing process of suitable industrialization, is conducive to control cost, improve only
Income.
In addition to the implementation, the present invention can also have other embodiments.It is all to use equivalent substitution or equivalent transformation shape
At technical solution, fall within the scope of protection required by the present invention.
Claims (7)
1. a kind of low cost black silicon solar cell production method, which comprises the following steps:
S1, the substrate used mix gallium silicon substrate for N-type, carry out surface clean and wet-method etching to silicon wafer；
S2, P-N junction is made to silicon wafer progress high temperature dopant using boron source；
S3, the silicon boron glass that silicon chip surface is removed in acid solution, aqueous slkali, and etching trimming；
S4, ALD deposition method depositing Al is used in front side of silicon wafer2O3Layer realizes the upper surface passivation of black silicon；
S5, in Al2O3PECVD deposition method SiN is used on layerxAntireflection layer；
S6, PECVD deposition method SiO is used at the back side of silicon wafer2And SiNxOverlayer passivation layer realizes that the back surface of black silicon is blunt
Change；
S7, laser slotting is carried out on silicon chip back side passivation layer；
S8, Screen-printed conductive Ag slurry and Al slurry, make metal electrode；
S9, high temperature sintering form black silicon solar cell.
2. a kind of inexpensive black silicon solar cell production method according to claim 1, it is characterised in that: the step
S1, using n type single crystal silicon piece as substrate, resistivity control is urged in 1-5ohmcm, making herbs into wool technology using existing metal ion
Change lithographic technique.
3. a kind of inexpensive black silicon solar cell production method according to claim 1, it is characterised in that: the step
S2 uses liquid boron source for diffusion source, and temperature is 890-950 DEG C, diffusion time 15-30min；Diffusion cooling uses O2It carries out
Annealing, O2Flow is 3000-10000sccm, and annealing temperature is 600-750 DEG C, and the time controls in 20-40min, and diffused sheet resistance is
60-150ohm/sq。
4. a kind of inexpensive black silicon solar cell production method according to claim 1, it is characterised in that: the step
S4, the Al of deposition2O3Passivation layer with a thickness of 5-55nm.
5. a kind of inexpensive black silicon solar cell production method according to claim 1, it is characterised in that: the step
S5, the SiN of depositionxAntireflection layer with a thickness of 30-95nm, refractive index is in 1.9-2.3.
6. a kind of inexpensive black silicon solar cell production method according to claim 1, it is characterised in that: the step
S6, SiO2And SiNxOverlayer passivation layer, SiO2Layer refractive index is 2.4-2.7, with a thickness of 2-10mm, SiNxLayer refractive index is 1.9-
2.4, with a thickness of 70-85nm.
7. a kind of inexpensive black silicon solar cell production method according to claim 1, it is characterised in that: the step
S7, laser slotting figure are linear array or lattice array, and the etching width of linear array is 10-70 μm, spacing 0.05-2.5mm, point
The spot diameter of array is 10-70 μm, spacing 0.1-3mm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110581183A (en) * | 2019-08-29 | 2019-12-17 | 江苏顺风新能源科技有限公司 | Pure black component single crystal PERC battery and preparation process thereof |
| CN111129218A (en) * | 2019-12-20 | 2020-05-08 | 浙江爱旭太阳能科技有限公司 | Method for producing a solar cell and solar cell |
| WO2020252827A1 (en) * | 2019-06-19 | 2020-12-24 | 南通天盛新能源股份有限公司 | Method for fabricating p-type crystalline silicon back electrode |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2012256713A (en) * | 2011-06-09 | 2012-12-27 | Shin Etsu Chem Co Ltd | Manufacturing method of solar cell |
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| CN110581183A (en) * | 2019-08-29 | 2019-12-17 | 江苏顺风新能源科技有限公司 | Pure black component single crystal PERC battery and preparation process thereof |
| CN111129218A (en) * | 2019-12-20 | 2020-05-08 | 浙江爱旭太阳能科技有限公司 | Method for producing a solar cell and solar cell |
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