CN109545880A - A kind of monocrystalline silicon base class inverted pyramid suede structure back passivating solar battery and preparation method thereof - Google Patents
A kind of monocrystalline silicon base class inverted pyramid suede structure back passivating solar battery and preparation method thereof Download PDFInfo
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- CN109545880A CN109545880A CN201910054804.2A CN201910054804A CN109545880A CN 109545880 A CN109545880 A CN 109545880A CN 201910054804 A CN201910054804 A CN 201910054804A CN 109545880 A CN109545880 A CN 109545880A
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- inverted pyramid
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- 229910021421 monocrystalline silicon Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 71
- 239000010703 silicon Substances 0.000 claims abstract description 71
- 239000000758 substrate Substances 0.000 claims abstract description 45
- 238000002161 passivation Methods 0.000 claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003376 silicon Chemical class 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 238000000151 deposition Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 30
- 239000002585 base Substances 0.000 claims description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 24
- 229910004205 SiNX Inorganic materials 0.000 claims description 23
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 15
- 229910021426 porous silicon Inorganic materials 0.000 claims description 13
- 238000000231 atomic layer deposition Methods 0.000 claims description 12
- 238000009792 diffusion process Methods 0.000 claims description 10
- 238000005530 etching Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 7
- 238000005516 engineering process Methods 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000007650 screen-printing Methods 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 235000009421 Myristica fragrans Nutrition 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 238000003486 chemical etching Methods 0.000 claims description 4
- 239000001115 mace Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- MNWRORMXBIWXCI-UHFFFAOYSA-N tetrakis(dimethylamido)titanium Chemical compound CN(C)[Ti](N(C)C)(N(C)C)N(C)C MNWRORMXBIWXCI-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- -1 that is Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 claims 1
- 230000003595 spectral effect Effects 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 description 15
- 238000003475 lamination Methods 0.000 description 6
- 230000005611 electricity Effects 0.000 description 4
- 230000003667 anti-reflective effect Effects 0.000 description 3
- 238000005234 chemical deposition Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- SBEQWOXEGHQIMW-UHFFFAOYSA-N silicon Chemical compound [Si].[Si] SBEQWOXEGHQIMW-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940095676 wafer product Drugs 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
- H01L31/04—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
-
- 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
- H01L31/02—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
-
- 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
- H01L31/02—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
- 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
-
- 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
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
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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
- 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
-
- 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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1868—Passivation
-
- 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
- Y02E10/547—Monocrystalline silicon PV cells
-
- 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
A kind of monocrystalline silicon base class inverted pyramid suede structure back passivating solar battery, belong to technical field of solar batteries, the battery includes monocrystal silicon substrate, and the front surface of monocrystal silicon substrate uses silicon substrate class inverted pyramid structure emitter, and the back surface of monocrystal silicon substrate is using back passivating structure；The silicon substrate class inverted pyramid structure emitter is made of silicon class inverted pyramid structure and 2 layers of passivation dielectric film；The invention further relates to the preparation methods of monocrystalline silicon base class inverted pyramid structure back passivating solar battery.The present invention is to optimize battery in the spectral response of short-wave band and long-wave band, realize excellent spectral response of the silica-based solar cell on entire wave band (300-1100nm), the final raising for realizing efficiency of solar cell, in 156 × 156 mm of N-shaped standard solar cell size2On realize 22.09% photoelectric conversion efficiency.
Description
Technical field
The present invention relates to a kind of solar battery, especially a kind of monocrystalline silicon base class inverted pyramid suede structure back passivation is too
Positive electricity pond further relates to the preparation method of above-mentioned monocrystalline silicon base class inverted pyramid suede structure back passivating solar battery.
Background technique
The eternal theme for being solar cell research and producing is improved efficiency, and the essence for improving efficiency of solar cell is to be promoted
The spectral response performance of device.The existing large area crystal silicon solar battery commercially produced is due to front surface residual reflection and back table
Face recombination losses still have the space being substantially improved in the short-wave band and long-wave band spectral response of spectrum.Therefore, too to business crystal silicon
The substitution that the front and rear surfaces in positive electricity pond carry out advanced technology is unavoidable.
Traditional single crystal silicon solar cell technical solution is: using monocrystalline silicon as substrate, front etching pyramid structure, and pyramid
Upper covering PECVD-SiNx(x is positive number) passivation film, front, the back side are led to using the positive silver of silk-screen printing, aluminium paste and back electrode
Oversintering technique realizes front ohmic contact and Al-BSF, the disadvantage is that battery device is in short-wave band (300-450 nm) and long wave
The spectral response of section (900-1100 nm) is not high, and there are also the spaces further promoted, and main cause is positive pyramid structure
Antireflective ability it is general, cause the external quantum efficiency in short-wave band not high；Back side Al-BSF recombination-rate surface is larger, causes
Battery is lower in the external quantum efficiency of long-wave band.
Summary of the invention
The technical problem to be solved by the present invention is in view of the deficiencies of the prior art, provide a kind of optimization battery in short-wave band
With the spectral response of long-wave band, the monocrystalline silicon base class inverted pyramid suede structure back passivation sun electricity of efficiency of solar cell is improved
Pond.
There is provided above-mentioned monocrystalline silicon base class inverted pyramid suede structures for another technical problem to be solved by this invention
Carry on the back the preparation method of passivating solar battery.
The technical problem to be solved by the present invention is to what is realized by technical solution below.The present invention is a kind of monocrystalline
Silicon substrate class inverted pyramid suede structure carries on the back passivating solar battery, which includes monocrystal silicon substrate, the front surface of monocrystal silicon substrate
Using silicon substrate class inverted pyramid structure emitter, the back surface of monocrystal silicon substrate is using back passivating structure；The silicon substrate class is fallen golden
Word tower structure emitter is made of silicon class inverted pyramid structure and 2 layers of passivation dielectric film.
The technical problems to be solved by the invention can also be further realized by technical solution below, for above
The monocrystalline silicon base class inverted pyramid suede structure carries on the back passivating solar battery, and the silicon class inverted pyramid structure is by { 111 } crystalline substance
8 faces of face race form.
The technical problems to be solved by the invention can also be further realized by technical solution below, for above
The monocrystalline silicon base class inverted pyramid suede structure carries on the back passivating solar battery, the silicon class inverted pyramid structure upper opening side length
2 μm -3 μm, preferably 2.7 μm, inclined-plane and bottom surface angle are 52 ° -58 °, preferably 54.7 °, and depth is 1 μm -3 μm, preferably 2 μm.
The technical problems to be solved by the invention can also be further realized by technical solution below, for above
The monocrystalline silicon base class inverted pyramid suede structure carries on the back passivating solar battery, and in 2 layers of passivation dielectric film: internal layer passivation is situated between
Plasma membrane is the SiO of PECVD deposition2Film, with a thickness of 9.5nm -10.5nm, preferably 10 nm, outer layer passivation dielectric film is PECVD
The SiN of depositionx(x is positive number, similarly hereinafter) film, with a thickness of 66nm -74nm, preferably 70 nm.
The technical problems to be solved by the invention can also be further realized by technical solution below, for above
The monocrystalline silicon base class inverted pyramid suede structure carries on the back passivating solar battery, and the back passivating structure uses TiO2/SiNxLamination
Passivation.
The technical problems to be solved by the invention can also be further realized by technical solution below, for above
The monocrystalline silicon base class inverted pyramid suede structure carries on the back passivating solar battery, and the back passivating structure is by 2 layers of passivation dielectric film
Composition, internal layer passivation dielectric film are the TiO of ALD deposition2Film, with a thickness of 3nm -8nm, preferably 5 nm；Outer layer passivation dielectric film
For the SiN of PECVD depositionxFilm, with a thickness of 240nm -260nm, preferably 250 nm.
The technical problems to be solved by the invention can also be further realized by technical solution below, and the present invention is also
The preparation method of above-described monocrystalline silicon base class inverted pyramid suede structure back passivating solar battery is disclosed, step is such as
Under:
(1) silicon wafer prepares: making substrate using the cutting of N-shaped face, solar-grade Cz silicon wafer, it is clear that silicon wafer is carried out RCA standard technology
It washes, obtains monocrystal silicon substrate；
(2) prepared by porous silicon: by HF, AgNO3、H2O2In the mixed liquor of composition, using MACE, that is, metal Assisted Chemical Etching Process side
Method etches Porous Silicon structures in monocrystal silicon substrate front surface, and etch period 55 seconds -65 seconds, then use HNO3Solution is by remaining silver
It cleans up；In mixed liquor: the concentration of HF is 1.95M -2.05M, AgNO3Concentration be 0.0045M -0.0055M, H2O2's
Concentration is 1.02M -1.08M；
(3) HF/HNO of the porous silicon wafer at 6 DEG C -9 DEG C will acid modification: be had3In=1:3 (vol) mixed acid solution, etching
The nano aperture structure of bottom by the porous silicon removal of one layer of surface, while being carried out " reaming " by 85s -95s.
(4) prepared by class inverted pyramid structure: the silicon wafer after " reaming " is put into 76 DEG C -84 DEG C of NaOH solution, into
Row anisotropic etching, the class inverted pyramid structure being evenly distributed；
(5) p+Emitter preparation: the silicon wafer with class inverted pyramid structure is put into quartz diffusion tube, at 900 DEG C -980 DEG C
Under conditions of, the min of 40 min -52 is spread using the method for trimethylborate thermal diffusion, silicon substrate class is formed in silicon chip surface and falls
Pyramid structure p+ emitter；
(6) back surface is handled: in monocrystal silicon substrate back surface after the polishing of alkali technique, with ALD Atomic layer deposition method, in silicon
Piece back surface deposits overlayer passivation film TiO2/SiNx, depositing temperature is 430 DEG C -470 DEG C, 58 minutes -64 points of sedimentation time
Clock, TiO2Sedimentary origin is TDMAT, SiNxSedimentary origin is NH4And SiH4；
(7) front surface is handled: after positive phosphorosilicate glass is removed with 4.5% -6.5% dilute HF solution, being continued with PECVDization
Deposition method is learned, deposits overlayer passivation film SiO in front side of silicon wafer2 /SiNx, depositing temperature is 430 DEG C -470 DEG C, when deposition
Between 58 minutes -64 minutes；
(8) back surface is open: in depositing Ti O2 /SiNxBack surface after overlayer passivation film, by the way of laser windowing,
Linear opening is formed on stack membrane, exposes monocrystal silicon substrate；
(9) finished product: by silk-screen printing technique, positive silver electrode, back electrode and back side aluminium paste are printed, using sintering, shape
At front, back surface ohmic contacts and Al-BSF to get.
The technical problems to be solved by the invention can also be further realized by technical solution below, for above
The preparation method of the described monocrystalline silicon base class inverted pyramid suede structure back passivating solar battery, in the mixed liquor of step (2): HF
Concentration be 2M, AgNO3Concentration be 0.005M, H2O2Concentration be 1.06M；It will be put with porous silicon wafer in step (4)
Into carrying out anisotropic etching in 80 DEG C of NaOH solutions；In step (5): under conditions of 950 DEG C, using trimethylborate heat
The method of diffusion spreads 50 min, forms the silicon substrate class p of falling inverted pyramid structure in silicon chip surface+Emitter；Step (6) and (7)
In: depositing temperature is 450 DEG C, sedimentation time minute 60 minutes.
The technical problems to be solved by the invention can also be further realized by technical solution below, for above
The preparation method of the monocrystalline silicon base class inverted pyramid suede structure back passivating solar battery, step (8) back surface opening
Method is: back surface after deposit, using the laser of wavelength 532nm pulse width 10ps, in TiO2 /SiNxOverlayer passivation film
The upper linear opening for forming the 50 μm wide 1mm period.
The technical problems to be solved by the invention can also be further realized by technical solution below, for above
The preparation method of the described monocrystalline silicon base class inverted pyramid suede structure back passivating solar battery, in step (6), back surface
ALD—TiO2Film replaces ALD deposition, thickness 6nm with thermal oxidation process；In step (7), front surface PECVD-SiO2Film,
Replace PECVD deposition, thickness 8nm -10nm with thermal oxidation process.
Monocrystalline silicon base class inverted pyramid structure of the present invention carries on the back passivating solar battery for silicon class inverted pyramid structure and back surface
Passivation combines, and can provide complementary spectral response in short-wave band and long-wave band, it means that a kind of very effective reality
Existing solar cell device spectral response excellent in all band.In the present invention, cell backside uses ALD-TiO2/PECVD—
SiNxLamination carries on the back passivating structure: positive silicon substrate class inverted pyramid suede structure has shortwave antireflective energy more better than tradition
Power, better emitter recombination losses inhibit；TiO2/ SiNx lamination back passivating structure makes battery have higher interior back reflection rate
And lower recombination-rate surface；Due to the optimization of the above battery structure, make this novel silicon substrate class inverted pyramid flannelette
Structure back passivating solar battery realizes excellent spectral response in all band, in N-shaped standard solar cell size 156 × 156
mm2On realize 22.09% photoelectric conversion efficiency.
Compared with prior art, the present invention is to optimize battery in the spectral response of short-wave band and long-wave band, realizes silicon substrate too
Excellent spectral response of the positive electricity pond on entire wave band (300-1100nm), the final raising for realizing efficiency of solar cell, simultaneously
It ensure that the excellent photoelectric properties of positive (shortwave) and the back side (long wave).
Detailed description of the invention
Fig. 1 is silicon class inverted pyramid structure scanning electron microscope (SEM) photograph in the present invention；
Fig. 2 is silicon class inverted pyramid structure scanning electron microscope enlarged drawing in the present invention；
Fig. 3 is the scanning electron microscope (SEM) photograph in the present invention before the modification of silicon class inverted pyramid structure acid；
Fig. 4 is the scanning electron microscope (SEM) photograph in the present invention after the modification of silicon class inverted pyramid structure acid；
Fig. 5 is solar battery structure schematic diagram of the present invention；
Fig. 6 is the spectral response advantage figure of solar cell of the present invention compared with traditional positive pyramid solar cell；
Fig. 7 is I-V and P-V output characteristics figure of solar cell of the present invention.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, right below in conjunction with attached drawing of the present invention
Technical solution in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is a part of the invention
Embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making wound
Every other embodiment obtained under the premise of the property made labour, shall fall within the protection scope of the present invention.
Referring to Fig.1-4, a kind of silicon substrate class inverted pyramid suede structure carries on the back passivating solar battery, including N-shaped monocrystal silicon substrate
1, the back passivating structure of 1 back surface of class inverted pyramid structure emitter 5 and the monocrystal silicon substrate of the monocrystalline silicon front surface；
The silicon silicon substrate class inverted pyramid suede structure emitter 5 is by class inverted pyramid suede structure and 2 layers of passivation dielectric film PECVD-
SiO2/SiNx(x is positive number, similarly hereinafter) is constituted；The class inverted pyramid suede structure is made of 8 faces of { 111 } family of crystal planes, and
Common inverted pyramid is made of 4 faces of { 111 } family of crystal planes；Class inverted pyramid suede structure upper opening side length is 2.7 μm or so,
Inclined-plane and bottom surface angle are 54.7 °, and depth is 2 μm or so；2 layers of passivation dielectric film, internal layer passivation dielectric film are heavy for PECVD
Long-pending SiO2Film 2, with a thickness of 10 nm or so, outer layer passivation dielectric film is the SiN of PECVD depositionxFilm 3, with a thickness of 70 nm
Left and right；
The back passivating structure is made of 2 layers of passivation dielectric film, and internal layer passivation dielectric film is the TiO of ALD deposition2Film 8, thickness
For 5 nm or so；Outer layer passivation dielectric film is the SiN of PECVD depositionxFilm 7, with a thickness of 250 nm or so.
A kind of preparation method of monocrystalline silicon base class inverted pyramid suede structure back passivating solar battery, its step are as follows: first
RCA standard cleaning is carried out to N-shaped monocrystalline silicon piece；In HF (2 M)/AgNO3(0.0005 M)/H2O2In (1.06 M) mixed liquor, adopt
With MACE(metal Assisted Chemical Etching Process) technology, etch nanoporous silicon structure；In 6-9 DEG C of HF/HNO3=1:3 (vol) is mixed
It closes in acid solution, removes porous silicon, while " reaming " is carried out to the nano aperture structure of bottom；Silicon wafer Jing Guo " reaming " is put
Into in 80 DEG C of NaOH solutions, anisotropic etching, the silicon substrate class inverted pyramid suede structure being evenly distributed are carried out；By band
There is the silicon wafer of class inverted pyramid structure to be put into quartz diffusion tube, under conditions of 950 DEG C, using trimethylborate thermal diffusion
Method spreads 50 min, forms silicon substrate class inverted pyramid suede structure p+ emitter；Then using alkali technique to cell backside into
Row polishing forms overlayer passivation film PECVD-SiO using PECVD chemical deposition technique2/SiNx；It is removed with 5% dilute HF solution
Pyrex deposit overlayer passivation film PECVD-SiO in front using PECVD chemical deposition technique2/SiNx；Cell backside
Laser windowing, using the laser of 10 ps of wavelength 532nm pulse width, the shape that opens a window is threadiness, window size be it is 40 μm wide,
Every 1 mm；Silk-screen printing front silver electrode 4, back electrode and back side aluminium paste 6 form front, back side Europe finally using sintering
Nurse contact and Al-BSF.
Specific embodiments of the present invention are as follows: using N-shaped (100) face, 156 × 156 mm2Size (counterfeit square), the sun
The Cz silicon wafer of grade, 190 ± 10 μm of silicon wafer thickness, resistivity ~ 3 Ω cm.
Preparation process is as follows:
The cleaning of silicon wafer RCA standard technology；
Porous silicon preparation, in HF (2 M)/AgNO3(0.0005 M)/H2O2In (1.06 M) mixed liquor, using MACE(metal
Assisted Chemical Etching Process) in silicon chip surface etching nanoporous silicon structure, 6 min of etch period, then use HNO3Solution is by remnants'
Silver cleans up；
Acid modification, in 6-9 DEG C of HF/HNO3In=1:3 (vol) mixed acid solution, 1 min 30s is etched, by one layer of surface
Porous silicon removal, while the nano aperture structure of bottom is subjected to " reaming "；
The preparation of silicon substrate class inverted pyramid suede structure, the silicon wafer Jing Guo " reaming " is put into 80 DEG C of NaOH solution, is carried out
Anisotropic etching, the class inverted pyramid structure being evenly distributed；
Silicon wafer with silicon substrate class inverted pyramid suede structure is put into quartz diffusion tube, under conditions of 950 DEG C, is adopted
50 min are spread with the method for trimethylborate thermal diffusion, form silicon substrate class inverted pyramid suede structure p in silicon chip surface+Transmitting
Pole；
Alkali technique polished back face, with atomic layer deposition (ALD) technology in silicon wafer back surface depositing Ti O2Then passivation layer covers
One layer of PECVD-SiN of lidxFilm；ALD deposition source is TDMAT, and TDMAT is four (dimethylamino) titaniums, and depositing temperature is 150 DEG C, is sunk
10 circulations of product, about 5nm；PECVD depositing temperature is 450 DEG C, 60 min of sedimentation time, and SiNx sedimentary origin is NH4And SiH4；
Pyrex cleaning after being removed with 5% dilute HF solution, continues to use PECVD chemical deposition, heavy in front side of silicon wafer
Product overlayer passivation film SiO2/SiNx, depositing temperature is 450 DEG C, 60 min of sedimentation time；
Using the laser of 10 ps of wavelength 532nm pulse width, overleaf TiO2/SiNxIt is formed on the blunt film of lamination 50 μm wide by 1
The linear opening in mm period；
By silk-screen printing technique, positive silver electrode, back electrode and back side aluminium paste are printed, using sintering, is formed just
Face, back surface ohmic contacts.
Technical solution of the present invention bring the utility model has the advantages that
Battery front side light trapping structure uses silicon substrate class inverted pyramid, and cell backside uses ALD-TiO2/PECVD—SiNxLamination
Carry on the back passivating structure: positive silicon substrate class inverted pyramid suede structure has than traditional better shortwave antireflective ability, preferably
Emitter recombination losses inhibit；TiO2/SiNxLamination back passivating structure makes battery have higher interior back reflection rate and lower
Recombination-rate surface makes this novel silicon substrate class inverted pyramid suede structure back passivation due to the optimization of the above battery structure
Solar cell realizes excellent spectral response in all band, and photoelectric conversion efficiency reaches 22.09%.
Claims (10)
1. a kind of monocrystalline silicon base class inverted pyramid suede structure carries on the back passivating solar battery, it is characterised in that: the battery includes monocrystalline
Silicon base, the front surface of monocrystal silicon substrate use silicon substrate class inverted pyramid structure emitter, and the back surface of monocrystal silicon substrate uses
Carry on the back passivating structure；The silicon substrate class inverted pyramid structure emitter is made of silicon class inverted pyramid structure and 2 layers of passivation dielectric film.
2. monocrystalline silicon base class inverted pyramid suede structure according to claim 1 carries on the back passivating solar battery, it is characterised in that:
The silicon class inverted pyramid structure is made of 8 faces of { 111 } family of crystal planes.
3. monocrystalline silicon base class inverted pyramid suede structure according to claim 1 or 2 carries on the back passivating solar battery, feature exists
In: described 2 μm -3 μm of silicon class inverted pyramid structure upper opening side length, preferably 2.7 μm, inclined-plane and bottom surface angle are 52 ° -58 °,
It is preferred that 54.7 °, depth is 1 μm -3 μm, preferably 2 μm.
4. monocrystalline silicon base class inverted pyramid suede structure according to claim 1 carries on the back passivating solar battery, it is characterised in that:
In 2 layers of passivation dielectric film: internal layer passivation dielectric film is the SiO of PECVD deposition2Film, with a thickness of 9.5nm -10.5nm,
It is preferred that 10 nm, outer layer passivation dielectric film is the SiN of PECVD depositionx(x is positive number, similarly hereinafter) film, with a thickness of 66nm -74nm,
It is preferred that 70 nm.
5. monocrystalline silicon base class inverted pyramid suede structure according to claim 1 carries on the back passivating solar battery, it is characterised in that:
The back passivating structure uses TiO2/SiNxOverlayer passivation.
6. monocrystalline silicon base class inverted pyramid suede structure carries on the back passivating solar battery according to claim 1 or 5, feature exists
In: the back passivating structure is made of 2 layers of passivation dielectric film, and internal layer passivation dielectric film is the TiO of ALD deposition2Film, with a thickness of
3nm -8nm, preferably 5 nm；Outer layer passivation dielectric film is the SiN of PECVD depositionxFilm, with a thickness of 240nm -260nm, preferably
250 nm。
7. a kind of preparation method of monocrystalline silicon base class inverted pyramid suede structure back passivating solar battery, it is characterised in that: it is walked
It is rapid as follows:
(1) silicon wafer prepares: making substrate using the cutting of N-shaped face, solar-grade Cz silicon wafer, it is clear that silicon wafer is carried out RCA standard technology
It washes, obtains monocrystal silicon substrate；
(2) prepared by porous silicon: by HF, AgNO3、H2O2In the mixed liquor of composition, using MACE, that is, metal Assisted Chemical Etching Process side
Method etches Porous Silicon structures in monocrystal silicon substrate front surface, and etch period 55 seconds -65 seconds, then use HNO3Solution is by remaining silver
It cleans up；In mixed liquor: the concentration of HF is 1.95M -2.05M, AgNO3Concentration be 0.0045M -0.0055M, H2O2's
Concentration is 1.02M -1.08M；
(3) HF/HNO of the porous silicon wafer at 6 DEG C -9 DEG C will acid modification: be had3In=1:3 (vol) mixed acid solution, etching
The nano aperture structure of bottom by the porous silicon removal of one layer of surface, while being carried out " reaming " by 85s -95s；
(4) prepared by class inverted pyramid structure: the silicon wafer after " reaming " being put into 76 DEG C -84 DEG C of NaOH solution, is carried out each
Anisotropy etching, the class inverted pyramid structure being evenly distributed；
(5) p+Emitter preparation: the silicon wafer with class inverted pyramid structure is put into quartz diffusion tube, at 900 DEG C -980 DEG C
Under conditions of, 40min -52min is spread using the method for trimethylborate thermal diffusion, forms silicon substrate class gold in silicon chip surface
Word tower structure p+Emitter；
(6) back surface is handled: in monocrystal silicon substrate back surface after the polishing of alkali technique, with ALD Atomic layer deposition method, in silicon
Piece back surface deposits overlayer passivation film TiO2/SiNx, depositing temperature is 430 DEG C -470 DEG C, 58 minutes -64 points of sedimentation time
Clock, TiO2Sedimentary origin is TDMAT, SiNxSedimentary origin is NH4And SiH4；
(7) front surface is handled: after positive phosphorosilicate glass is removed with 4.5% -6.5% dilute HF solution, being continued with PECVDization
Deposition method is learned, deposits overlayer passivation film SiO in front side of silicon wafer2 /SiNx, depositing temperature is 430 DEG C -470 DEG C, when deposition
Between 58 minutes -64 minutes；
(8) back surface is open: in depositing Ti O2 /SiNxBack surface after overlayer passivation film, by the way of laser windowing, folded
Linear opening is formed on tunic, exposes monocrystal silicon substrate；
(9) finished product: by silk-screen printing technique, positive silver electrode, back electrode and back side aluminium paste are printed, using sintering, shape
At front, back surface ohmic contacts and Al-BSF to get.
8. the preparation method of monocrystalline silicon base class inverted pyramid suede structure back passivating solar battery according to claim 7,
It is characterized by: in the mixed liquor of step (2): the concentration of HF is 2M, AgNO3 Concentration be 0.005M, H2O2Concentration be
1.06M；It will be put into 80 DEG C of NaOH solution with porous silicon wafer in step (4) and carry out anisotropic etching；Step (5)
In: under conditions of 950 DEG C, 50min is spread using the method for trimethylborate thermal diffusion, silicon substrate class is formed in silicon chip surface and falls
Pyramid structure p+Emitter；In step (6) and (7): depositing temperature is 450 DEG C, sedimentation time minute 60 minutes.
9. the preparation method of monocrystalline silicon base class inverted pyramid suede structure back passivating solar battery according to claim 7,
It is characterized by: the method for step (8) back surface opening is: back surface after deposit, using wavelength 532nm pulse width
The laser of 10ps, in TiO2 /SiNxThe linear opening in 50 μm wide 1mm period is formed on overlayer passivation film.
10. the preparation method of monocrystalline silicon base class inverted pyramid suede structure back passivating solar battery according to claim 7,
It is characterized by: in step (6), back surface ALD-TiO2Film replaces ALD deposition with thermal oxidation process；In step (7), just
Surface PECVD-SiO2Film replaces PECVD deposition with thermal oxidation process.
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| CN111864013A (en) * | 2020-07-16 | 2020-10-30 | 江苏海洋大学 | Dry-wet mixed preparation method of monocrystal silicon-based inverted pyramid suede |
| CN115020503A (en) * | 2021-08-04 | 2022-09-06 | 上海晶科绿能企业管理有限公司 | Solar cell, preparation method thereof and photovoltaic module |
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