CN109087965A - A kind of crystal silicon solar energy battery of passivating back and preparation method thereof - Google Patents
A kind of crystal silicon solar energy battery of passivating back and preparation method thereof Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 83
- 239000010703 silicon Substances 0.000 title claims abstract description 83
- 239000013078 crystal Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 28
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910021419 crystalline silicon Inorganic materials 0.000 claims abstract description 25
- 238000002161 passivation Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 229910004205 SiNX Inorganic materials 0.000 claims abstract description 8
- 230000005540 biological transmission Effects 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 3
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 3
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 68
- 239000010410 layer Substances 0.000 claims description 43
- 229910052757 nitrogen Inorganic materials 0.000 claims description 34
- 238000009792 diffusion process Methods 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 19
- 229910052709 silver Inorganic materials 0.000 claims description 19
- 239000004332 silver Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N hydrofluoric acid Substances F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 17
- 210000002268 wool Anatomy 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 14
- 239000004411 aluminium Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 14
- 235000008216 herbs Nutrition 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000010453 quartz Substances 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 5
- 238000004518 low pressure chemical vapour deposition Methods 0.000 claims description 5
- 239000011241 protective layer Substances 0.000 claims description 5
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 230000003667 anti-reflective effect Effects 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 238000001312 dry etching Methods 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 239000004519 grease Substances 0.000 claims description 3
- 239000008236 heating water Substances 0.000 claims description 3
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 3
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 claims description 3
- 238000005477 sputtering target Methods 0.000 claims description 3
- 230000006641 stabilisation Effects 0.000 claims description 3
- 238000011105 stabilization Methods 0.000 claims description 3
- 239000013077 target material Substances 0.000 claims description 3
- 238000002207 thermal evaporation Methods 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000006701 autoxidation reaction Methods 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 16
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 abstract description 7
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 abstract description 7
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 12
- 239000010408 film Substances 0.000 description 8
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910004806 Na2 SiO3.9H2 O Inorganic materials 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 1
- 238000006388 chemical passivation reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 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
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/049—Protective back sheets
-
- 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
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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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0304—Inorganic materials including, apart from doping materials or other impurities, only AIIIBV compounds
- H01L31/03044—Inorganic materials including, apart from doping materials or other impurities, only AIIIBV compounds comprising a nitride compounds, e.g. GaN
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- H—ELECTRICITY
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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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1876—Particular processes or apparatus for batch treatment of the devices
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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
- Y02E10/544—Solar cells from Group III-V materials
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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
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses crystal silicon solar energy batteries of a kind of passivating back and preparation method thereof, using molybdenum oxide as p-type crystalline silicon passivation layer and hole transmission layer, have following structure: Ag/SiNx/n‑c‑Si/p‑c‑Si/SiO2/MoO3/ Al/Ag, wherein x=0.9~1.2, n-c-Si are the N-shaped crystalline silicon of phosphorus doping.The present invention replaces aluminium oxide as the passivating back material of p-type crystal silicon cell using molybdenum oxide, the compound of cell backside can not only be significantly reduced, it can also be used as the hole transmission layer of p-type crystal silicon cell simultaneously, therefore, need laser opening unlike PERC battery in the actual production technique of battery to guarantee the transmission of carrier, this just reached can reduce crystalline silicon the back side it is compound, again while avoiding laser opening bring and negatively affect.
Description
Technical field
The invention belongs to area of solar cell, and in particular to the crystal silicon solar energy battery of passivating back and its preparation side
Method.
Background technique
In solar cells, the separation of photo-generated carrier, transport and collect very crucial to the raising of battery overall performance.
Reduce photo-generated carrier crystalline silicon (c-Si) in vivo and surface it is compound to raising carrier collection efficiency it is most important, especially
It is when the thickness of the minority diffusion length of silicon wafer and silicon wafer quite or be more than silicon wafer thickness when, silicon chip surface it is compound to battery
The influence of characteristic is compound more much bigger than in vivo, and therefore, surface passivation is the key that crystal silicon solar energy battery design and optimization.Mesh
Before, using silicon nitride film as the positive anti-reflection layer of p-type crystal silicon cell and passivation layer, in addition to that can be hung with saturated surface
Key reduces outside interfacial state, and silicon nitride also by the positive charge of itself, reduces the minority carrier density in the positive emission layer of battery, to drop
Low recombination-rate surface.As the positive passivation effect of crystal silicon cell and contact performance are constantly optimized and are improved,
The compound common concern for having caused photovoltaic industry circle of the back surface of battery.In the crystal silicon cell of traditional silk-screened
In, although Al-BSF effect can reduce minority carrier density, reduction is compound, but still can not imitate with using the passivation of dielectric layer bring
Fruit compares favourably.
Aluminium oxide possesses the negative electrical charge opposite with silicon nitride, in addition to can be passivated back surface defect, reduce interface state density,
Play the role of except chemical passivation, also there is field-effect passivation effect, to significantly reduce answering for the p-type crystal silicon cell back side
It closes.Passivation emitter rear-face contact (PERC) crystal silicon cell possesses the passivation structure on back of comparatively perfect, has begun gradually
Move towards industrialization.Currently, the peak efficiencies world record of volume production monocrystalline silicon and polysilicon PERC battery is 22.61% He respectively
21.25%.Compared to other high-efficiency battery technologies, PERC battery has apparent cost advantage, is next-generation high-efficiency solar electricity
The most powerful competitor in pond.
Relative to conventional batteries, PERC technology mainly increases back passivation and two process procedures of laser opening at present.?
In the production process of practical PERC battery, laser opening is carried out to cell backside first, then prints silver in hole inner region
Slurry, prints aluminium paste on other regions, and finally sintering forms back side silver electrode and Al-BSF.During the sintering process, silver paste is to sharp
Silicon substrate in light aperture carries out ablation, increases complex centre, reduces minority carrier life time, to influence battery efficiency.Meanwhile
Stress caused by backside laser ablation and uneven Al-BSF, so that cell piece generates crack and the probability of crackle increases
Add.In addition, since aperture limits the transmission path of carrier, offset from perpendicular to contact surface shortest path and congestion exist
Opening increases the loss of fill factor.
Summary of the invention
In order to solve the problems, such as above-mentioned the deficiencies in the prior art and, the invention proposes a kind of crystal of passivating back
Silicon solar cell and preparation method thereof, can reduce that the back side is compound, does not need laser opening again.
The technical solution adopted by the present invention is that such: a kind of crystal silicon solar energy battery of passivating back, feature exist
In: using molybdenum oxide as p-type crystalline silicon passivation layer and hole transmission layer, there is following structure: Ag/SiNx/n-c-Si/p-c-
Si/SiO2/MoO3/ Al/Ag, wherein x=0.9~1.2, n-c-Si are the N-shaped crystalline silicon of phosphorus doping.
Another technical solution of the invention is such that a kind of preparation side of the crystal silicon solar energy battery of passivating back
Method, comprising the following steps:
1) cleaning and making herbs into wool: taking resistivity is 0.5~1.5 Ω .cm, with a thickness of 180 μm, having a size of 4 × 4cm2Monocrystalline
Silicon wafer is successively immersed acetone, in ethanol solution and using ultrasonic cleaning 10min by silicon wafer first, removal surface grease stain and
Dirt；Then water bath processing 20min at a temperature of in the sodium hydroxide solution that concentration is 30% at 80 DEG C, removes surface damage
Layer；Finally, corroding 120s at normal temperature in solution in nitric/hydrofluoric/glacial acetic acid solution (volume ratio 3:3:1), to table
Face carries out chemical polishing, obtains flat surface, then uses deionized water repeated flushing 3 times or more, and with being dried with nitrogen；
2) back side grown silicon nitride: being respectively nitrogen source and silicon source with electron level ammonia and silane, using high pure nitrogen as carrier gas,
Using Low Pressure Chemical Vapor Deposition silicon chip back side growth thickness be 80~100nm silicon nitride protective layer；
3) front surface making herbs into wool: making herbs into wool is carried out to silicon wafer front surface using conventional alkali systems, using mass fraction 1~2%
The Na of NaOH, mass fraction 2.5~5.0%2SiO3.9H2O, the solution system of the isopropanol of volume fraction 5~10%, 80~
Heating water bath and 20~30min of ultrasonic treatment, are then rinsed with deionized water, are dried with nitrogen at 85 DEG C；
4) diffusion furnace: being warming up to 850~900 DEG C of diffusion temperature by front surface phosphorus diffusion in advance, is passed through nitrogen and is driven away boiler tube
Interior residual gas；Silicon wafer after surface wool manufacturing is put into quartz boat, flat-temperature zone is pushed into, preheats 5min under nitrogen protection；It takes
Source nitrogen flow is 80~120sccm, and oxygen flow is 50~90sccm, closes after 5~10min and takes source nitrogen and oxygen valve
Door；The heating power supply for closing diffusion furnace, allows quartz boat cooled to room temperature, takes out silicon wafer；Diffusion terminate after, using etc. from
Daughter dry etching removes the n-layer of silicon chip edge, is then placed in 5~12% hydrofluoric acid solution of mass fraction, soaks at room temperature
Steep 30~90s；Finally, being rinsed with deionized water, it is dried with nitrogen；
5) front surface grows SiNxPassivation layer and anti-reflective layer: using plasma enhances chemical vapour deposition technique, and radio frequency is
The base vacuum of 13.56MHz, deposition chamber are better than 1 × 10-3Pa, radio frequency power density are 0.5~1.0W/cm2, with electron level
Ammonia and silane are respectively nitrogen source and silicon source, and the flow-rate ratio of ammonia and silane is 1:2~6, and operating air pressure is 100~200Pa, raw
Long temperature is 200~300 DEG C, in the SiN that silicon wafer front surface growth thickness is 80~100nmxFilm；
6) back side thermal oxide growth silica: the nature of the hydrofluoric acid removal silicon wafer back surface of volume fraction 1% is utilized
Oxide layer is rinsed with deionized water, is dried with nitrogen；Then high-temperature quick oxidizing process is used, grows a thickness in silicon wafer back surface
Degree is the silica tunnel layer of 1.2~1.5nm；
7) back side thermal evaporation growth molybdenum oxide and metallic aluminium: the vacuum degree of evaporation coating cavity is better than 1 × 10-4Pa is adjusted
Heated current is saved, so that molybdenum oxide evaporation rate is 0.05nm/s, baffle is opened after rate stabilization, starts to be deposited；Work as thickness
When reaching 3nm, baffle is closed, closes heated current；Then, under the conditions of not vacuum breaker, heated current is adjusted, so that metallic aluminium
Evaporation rate is the aluminium that 3nm is deposited in 0.1nm/s；
8) silver electrode: the silver electrode that the front and rear surfaces of silicon wafer are 500nm using magnetron sputtering method growth thickness, preceding table is grown
Face utilizes grid line mask plate, forms silver grating line electrode, and rear surface is completely formed silver electrode；Sputtering target material is metallic silver, sputtering chamber
The base vacuum of body is better than 1 × 10-3Pa, working gas are argon gas, and operating air pressure 1.0Pa, sputter temperature is room temperature, sputter function
Rate is 1~3W/cm2；
9) it making annealing treatment: being made annealing treatment at 750~850 DEG C of temperature and nitrogen atmosphere, the time is 5~10min, from
And obtain required crystal silicon solar energy battery.
Molybdenum oxide (MoO3) with silicon heterogenous interface there is lesser Valence-band Offsets, simultaneous oxidation molybdenum and tungsten oxide (WO3)、
Vanadium oxide (V2O5) etc. materials equally there is very high work function.In addition, molybdenum oxide is preferable to the passivation effect of surface of crystalline silicon,
And the contact resistance of molybdenum oxide and silicon is also smaller, therefore molybdenum oxide can be used as the hole transport of crystal silicon solar energy battery
Layer.In the present invention, replace aluminium oxide as the passivating back material of p-type crystal silicon cell using molybdenum oxide, it not only can be big
Width reduces the compound of cell backside, while can also be used as the hole transmission layer of p-type crystal silicon cell, therefore, in battery
Laser opening is needed unlike PERC battery to guarantee the transmission of carrier in actual production technique, this, which has just reached, to drop
The back side of low crystalline silicon is compound, avoids the negative effect of laser opening bring simultaneously again.
In view of in the technical process of heat treatment and the metallization of crystal silicon cell, molybdenum oxide becomes the passivation effect of silicon
Difference will lead to the open-circuit voltage (V of batteryOC) and fill factor (FF) attenuating, in the present invention, between molybdenum oxide and crystalline silicon
It is inserted into one layer of ultra-thin silica (SiO2) it is used as tunneled holes layer, this guarantees the high-temperature technology mistakes in crystal silicon cell
The passivation effect of Cheng Zhong, the silicon back side are unaffected.
Crystal silicon solar energy battery usually requires to carry out making herbs into wool processing to two-sided unpolished silicon wafer front surface, to reduce too
Sunlight is in the reflection of silicon chip surface, while the back surface of silicon wafer generally also has the effect of making herbs into wool, this carrys out conventional crystalline silion cell
Saying influences very little.However, making herbs into wool significantly increases the specific area of back surface for the battery of passivating back, back is increased
The recombination velocity in face.Therefore, back surface polishing can not only reduce surface recombination velocity (S.R.V.), but also flat surface makes subsequent growth
Film more evenly.The chemical stability of silicon nitride film is very good, handles other than hydrofluoric acid, other bronsted lowry acids and bases bronsted lowries and silicon nitride
Hardly chemically react.For this purpose, this patent grows one layer before carrying out making herbs into wool to front surface, in the back surface of silicon wafer
Then silicon nitride protective layer removes again.
In order to reduce the resistance of Electrochromic Molybdenum Oxide Coatings, under the premise of not reducing the passivation effect of molybdenum oxide, Electrochromic Molybdenum Oxide Coatings
Thickness be selected as 3nm.The resistance for for amplitude peak reducing molybdenum oxide, increases one layer of ultra-thin metallic aluminium (Al), aluminium with
Molybdenum oxide can react during subsequent battery high-temperature, form aluminium oxide in interface, increase the oxygen in molybdenum oxide
Vacancy concentration, to increase the electric conductivity of molybdenum oxide.Meanwhile it being damaged to reduce metal aluminium film to the optics of silicon chip back side
It loses, the thickness of aluminium is selected as 3nm.
Detailed description of the invention
It is described in further detail below in conjunction with attached drawing and embodiments of the present invention
Fig. 1 is battery structure schematic diagram of the invention；
Fig. 2 is battery preparation flow figure of the invention.
Specific embodiment
Crystal silicon solar energy battery described in the present embodiment, using molybdenum oxide as p-type crystalline silicon passivation layer and hole transport
Layer has following structure: front surface A g electrode 1, SiNxLayer (80nm) 2, n-c-Si layer 3, p-c-Si layer 4, SiO2Layer (1.2~
1.5nm)5、MoO3Layer (3nm) 6, Al layers of (3nm) 7, back side Ag electrode 8, wherein x=0.9~1.2, n-c-Si are the n of phosphorus doping
Type crystalline silicon.
The preparation process of battery is as follows:
1) cleaning and making herbs into wool
Experiment is the monocrystalline silicon piece of Buddha's warrior attendant wire cutting with silicon wafer, and resistivity is 0.5~1.5 Ω .cm, with a thickness of 180 μm, ruler
Very little is 4 × 4cm2.Silicon wafer is successively immersed to acetone, in ethanol solution and using ultrasonic cleaning 10min first, removes surface
Grease stain and dirt；Secondly, concentration be 30% sodium hydroxide solution at 80 DEG C at a temperature of water bath processing 20min, remove table
Surface damage layer；Finally, corroding at normal temperature in solution in nitric/hydrofluoric/glacial acetic acid solution (volume ratio 3:3:1)
120s carries out chemical polishing to surface, obtains flat surface, then uses deionized water repeated flushing 3 times or more, and blown with nitrogen
It is dry.
2) back side LPCVD method grown silicon nitride
Silicon nitride (the Si grown using low-pressure chemical vapor deposition (LPCVD)3N4) film have compact structure, growth speed
The features such as rate is fast, uniformity is good, is typically used as passivation layer, can stop the diffusion of impurity and moisture well.With electron level ammonia
Gas and silane are respectively nitrogen source and silicon source, are 80~100nm silicon nitride in silicon chip back side growth thickness using high pure nitrogen as carrier gas
Protective layer.The base vacuum of reaction chamber is better than 0.1Pa, and operating air pressure is 100~130Pa, and growth temperature is 800~850 DEG C, ammonia
The flow-rate ratio of gas and silane is 4~8:1.
3) front surface making herbs into wool
Making herbs into wool is carried out to silicon wafer front surface using conventional alkali systems, obtains the sunken optical surface of pyramid structure.In order to have
The size of the control of effect ground reaction speed and flannelette, adds a certain amount of IPA (isopropanol) as sustained release agent and complexing agent.Using
NaOH (1~2%, mass fraction), Na2SiO3.9H2O (2.5~5.0%, mass fraction), IPA (5~10%, volume fraction)
Solution system, at 80~85 DEG C heating water bath and be ultrasonically treated 20~30min, then rinsed with deionized water, nitrogen is blown
It is dry.
4) front surface phosphorus diffusion
It is spread using conventional phosphorus oxychloride as liquid source, impurity is brought into diffusion furnace by nitrogen carrying method and is realized
Diffusion.Firstly, diffusion furnace to be warming up to 850~900 DEG C of diffusion temperature in advance, it is passed through nitrogen (500~1000sccm), drives away furnace
Residual gas in pipe；Secondly, the silicon wafer after surface wool manufacturing is put into quartz boat, be pushed into flat-temperature zone, nitrogen (500~
1000sccm) protection is lower preheats 5min；Third, take source nitrogen flow be 80~120sccm, oxygen flow be 50~90sccm, 5
It is closed after~10min and takes source nitrogen and oxygen valve；4th, the heating power supply of diffusion furnace is closed, quartz boat is allowed to naturally cool to
Room temperature takes out silicon wafer.After diffusion furnace temperature drops to 450 DEG C, quartz boat is pulled to fire door position, allow sample in air from
It is so cooling.
After diffusion terminates, using plasma dry etching removes the n-layer of silicon chip edge, prevents edge from being formed short
Road.Then, be put into hydrofluoric acid solution (5~12%, mass fraction) and impregnate 30~90s at room temperature, removal silicon chip surface due to
Phosphorous silica (PSG) caused by diffusion technique, while having also been removed the silicon nitride protective layer of silicon chip back side.Finally, spending
Ionized water rinses, and is dried with nitrogen.
5) front surface PECVD grows SiNxPassivation layer and anti-reflective layer
SiN is deposited using plasma enhanced chemical vapor deposition (PECVD) methodxWhen film, generated in plasma
A large amount of hydrogen atoms there is excellent body passivation effect, therefore SiNxFilm has surface passivation and the body passivation effect of high quality
And excellent reflection preventing ability.The radio frequency of PECVD is 13.56MHz, and the base vacuum of deposition chamber is better than 1 × 10-3Pa is penetrated
Frequency power density is 0.5~1.0W/cm2, it is respectively nitrogen source and silicon source, the flow of ammonia and silane with electron level ammonia and silane
Than for 1:2~6, operating air pressure is 100~200Pa, and growth temperature is 200~300 DEG C, in the SiN of silicon wafer front surface growthxIt is thin
Film thickness is 80~100nm.
6) back side thermal oxide growth silica
Using the natural oxidizing layer of diluted hydrofluoric acid (1%, volume fraction) removal silicon wafer back surface, rushed with deionized water
It washes, is dried with nitrogen.Then high-temperature quick oxidizing process is utilized, grows two that a layer thickness is 1.2~1.5nm in silicon wafer back surface
Silica tunnel layer.
Tube type vacuum furnace is rapidly heated to 700 DEG C, heating rate is 20~50 DEG C/min, silicon wafer is packed into quartz boat,
It is pushed into flat-temperature zone, is passed through oxygen (500~1500sccm), oxidization time 90s is then shut off heating power supply, simultaneously closes off oxygen
Air valve.After furnace temperature drops to 450 DEG C, quartz boat is pulled to fire door position, allows sample natural cooling in air.
7) back side thermal evaporation growth molybdenum oxide and metallic aluminium
The vacuum degree of evaporation coating cavity is better than 1 × 10-4Pa adjusts heated current, so that molybdenum oxide evaporation rate is
0.05nm/s opens baffle after rate stabilization, starts to be deposited.When thickness reaches 3nm, baffle is closed, closes heated current.
Then, under the conditions of not vacuum breaker, heated current is adjusted, so that metallic aluminium evaporation rate is that 3nm is deposited in 0.1nm/s
Aluminium.
8) silver electrode is grown
The silver electrode that the front and rear surfaces of silicon wafer are 500nm using magnetron sputtering method growth thickness, front surface are covered using grid line
Diaphragm plate, forms silver grating line electrode, and rear surface is completely formed silver electrode.Sputtering target material is metallic silver, the base vacuum of sputter chamber
Better than 1 × 10-3Pa, working gas are argon gas, and operating air pressure 1.0Pa, sputter temperature is room temperature, and sputtering power is 1~3W/
cm2。
9) it makes annealing treatment
In order to make metallic silver and the n-type area of silicon wafer of silicon wafer front surface form good Ohmic contact and silicon chip back side
Aluminium and molybdenum oxide in interface form aluminium oxide, increase the electric conductivity of molybdenum oxide, battery is needed in 750~850 DEG C of temperature
It is made annealing treatment under degree and nitrogen atmosphere, the time is 5~10min.
Claims (2)
1. a kind of crystal silicon solar energy battery of passivating back, it is characterised in that: using molybdenum oxide as p-type crystalline silicon passivation layer and
Hole transmission layer has following structure: Ag/SiNx/n-c-Si/p-c-Si/SiO2/MoO3/ Al/Ag, wherein x=0.9~
1.2, n-c-Si be the N-shaped crystalline silicon of phosphorus doping.
2. a kind of preparation method of crystal silicon solar energy battery described in claim 1, it is characterised in that: the following steps are included:
1) cleaning and making herbs into wool: taking resistivity is 0.5~1.5 Ω .cm, with a thickness of 180 μm, having a size of 4 × 4cm2Monocrystalline silicon piece,
Silicon wafer is successively immersed to acetone, in ethanol solution and using ultrasonic cleaning 10min first, removes surface grease stain and dirt；
Then water bath processing 20min at a temperature of in the sodium hydroxide solution that concentration is 30% at 80 DEG C, removes surface damage layer；Most
Afterwards, corrode 120s at normal temperature in solution in nitric/hydrofluoric/glacial acetic acid solution (volume ratio 3:3:1), surface is carried out
Chemical polishing obtains flat surface, then uses deionized water repeated flushing 3 times or more, and with being dried with nitrogen；
2) back side grown silicon nitride: being respectively nitrogen source and silicon source with electron level ammonia and silane, using high pure nitrogen as carrier gas, utilizes
Low Pressure Chemical Vapor Deposition is 80~100nm silicon nitride protective layer in silicon chip back side growth thickness；
3) front surface making herbs into wool: carrying out making herbs into wool to silicon wafer front surface using conventional alkali systems, using the NaOH of mass fraction 1~2%,
The Na of mass fraction 2.5~5.0%2SiO3.9H2O, the solution system of the isopropanol of volume fraction 5~10%, at 80~85 DEG C
Lower heating water bath is simultaneously ultrasonically treated 20~30min, is then rinsed, is dried with nitrogen with deionized water；
4) diffusion furnace: being warming up to 850~900 DEG C of diffusion temperature by front surface phosphorus diffusion in advance, is passed through nitrogen and is driven away in boiler tube
Residual gas；Silicon wafer after surface wool manufacturing is put into quartz boat, flat-temperature zone is pushed into, preheats 5min under nitrogen protection；Take source nitrogen
Throughput is 80~120sccm, and oxygen flow is 50~90sccm, closes after 5~10min and takes source nitrogen and oxygen valve；It closes
The heating power supply for closing diffusion furnace, allows quartz boat cooled to room temperature, takes out silicon wafer；After diffusion terminates, using plasma
Dry etching removes the n-layer of silicon chip edge, is then placed in 5~12% hydrofluoric acid solution of mass fraction, impregnates 30 at room temperature
~90s；Finally, being rinsed with deionized water, it is dried with nitrogen；
5) front surface grows SiNxPassivation layer and anti-reflective layer: using plasma enhances chemical vapour deposition technique, and radio frequency is
The base vacuum of 13.56MHz, deposition chamber are better than 1 × 10-3Pa, radio frequency power density are 0.5~1.0W/cm2, with electron level
Ammonia and silane are respectively nitrogen source and silicon source, and the flow-rate ratio of ammonia and silane is 1:2~6, and operating air pressure is 100~200Pa, raw
Long temperature is 200~300 DEG C, in the SiN that silicon wafer front surface growth thickness is 80~100nmxFilm；
6) back side thermal oxide growth silica: the autoxidation of the hydrofluoric acid removal silicon wafer back surface of volume fraction 1% is utilized
Layer, is rinsed with deionized water, is dried with nitrogen；Then high-temperature quick oxidizing process is used, growing a layer thickness in silicon wafer back surface is
The silica tunnel layer of 1.2~1.5nm；
7) back side thermal evaporation growth molybdenum oxide and metallic aluminium: the vacuum degree of evaporation coating cavity is better than 1 × 10-4Pa is adjusted and is added
Thermocurrent opens baffle after rate stabilization, starts to be deposited so that molybdenum oxide evaporation rate is 0.05nm/s；When thickness reaches
When 3nm, baffle is closed, closes heated current；Then, under the conditions of not vacuum breaker, heated current is adjusted, so that metal aluminum evaporation
Rate is the aluminium that 3nm is deposited in 0.1nm/s；
8) silver electrode: the silver electrode that the front and rear surfaces of silicon wafer are 500nm using magnetron sputtering method growth thickness, front surface benefit are grown
With grid line mask plate, silver grating line electrode is formed, rear surface is completely formed silver electrode；Sputtering target material is metallic silver, sputter chamber
Base vacuum is better than 1 × 10-3Pa, working gas are argon gas, and operating air pressure 1.0Pa, sputter temperature is room temperature, and sputtering power is
1~3W/cm2；
9) it making annealing treatment: being made annealing treatment at 750~850 DEG C of temperature and nitrogen atmosphere, the time is 5~10min, thus
To required crystal silicon solar energy battery.
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| CN113130669A (en) * | 2021-04-20 | 2021-07-16 | 浙江师范大学 | Silicon oxide passivation contact silicon solar cell with controllable pinhole size and density |
| CN113130669B (en) * | 2021-04-20 | 2022-02-15 | 浙江师范大学 | Silicon oxide passivation contact silicon solar cell with controllable pinhole size and density |
| CN117133834A (en) * | 2023-10-25 | 2023-11-28 | 金阳(泉州)新能源科技有限公司 | Short-process preparation method and application of combined passivation back contact battery |
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