CN105097962A - Solar cell anti-reflection film and preparation method thereof - Google Patents
Solar cell anti-reflection film and preparation method thereof Download PDFInfo
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- CN105097962A CN105097962A CN201510549529.3A CN201510549529A CN105097962A CN 105097962 A CN105097962 A CN 105097962A CN 201510549529 A CN201510549529 A CN 201510549529A CN 105097962 A CN105097962 A CN 105097962A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims abstract description 87
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 84
- 239000010703 silicon Substances 0.000 claims abstract description 84
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 80
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 67
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 40
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 39
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910000077 silane Inorganic materials 0.000 claims abstract description 38
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 31
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 25
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011261 inert gas Substances 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000151 deposition Methods 0.000 claims description 66
- 230000008021 deposition Effects 0.000 claims description 63
- 239000007789 gas Substances 0.000 claims description 48
- 230000003667 anti-reflective effect Effects 0.000 claims description 20
- 229910021529 ammonia Inorganic materials 0.000 claims description 19
- 150000004754 hydrosilicons Chemical class 0.000 claims description 19
- 150000004767 nitrides Chemical class 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 239000010408 film Substances 0.000 abstract description 56
- 230000000694 effects Effects 0.000 abstract description 8
- 239000010409 thin film Substances 0.000 abstract description 5
- 229910052990 silicon hydride Inorganic materials 0.000 abstract 1
- 239000006117 anti-reflective coating Substances 0.000 description 17
- 210000004027 cell Anatomy 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000008216 herbs Nutrition 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 210000002268 wool Anatomy 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
- H01L31/02—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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Sustainable Development (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
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Abstract
The invention relates to a solar cell anti-reflection film and a preparation method thereof. The solar cell anti-reflection film comprises a silicon oxynitride thin film layer, a nanometer titanium oxide layer, a silicon nitride layer, a silicon dioxide layer and an amorphous silicon layer which are sequentially stacked and deposited on the surface of a silicon wafer. The preparation method comprises the following steps of firstly, introducing the silicon wafer, a silicon hydride and nitrogen into a plasma enhanced chemical vapor deposition device to lead the silicon oxynitride thin film layer to be deposited on the surface of the silicon wafer; secondly, introducing nanometer titanium dioxide and an inert gas to deposit the nanometer titanium oxide layer; thirdly, introducing silane and an ammonia gas to deposit the silicon nitride layer; fourthly, introducing silicon dioxide to deposit the silicon dioxide layer; and finally, introducing the silane and a hydrogen to deposit the amorphous silicon layer. With the adoption of the multiple layers of thin films, an anti-reflection effect can be simultaneously played on multiple specific wavelengths; moreover, the thickness and the refractive indexes of the thin films can be controlled, so that a better anti-reflection effect can be simultaneously played on luminous energy of the multiple specific wavelengths; and the preparation method is moderate in condition and is easy to operate.
Description
Technical field
The present invention relates to technical field of new energies, be specifically related to solar battery antireflective film field, particularly relate to a kind of solar battery antireflective film and preparation method thereof.
Background technology
Along with the high speed development of human society, ecological deterioration and energy shortage have become whole world distinct issues the most.At present, more than 70% of global total energy consumption all from the energy that oil, natural gas, coal etc. are non-renewable.Utilize these non-renewable energy can cause many harm in a large number for a long time.Solar energy is a kind of ideal clean, reproducible new forms of energy, can alleviate energy shortage and environmental pollution.Solar cell is a kind of device solar radiant energy being directly converted to electric energy.Current crystal silicon solar batteries accounts for about 80% in world's solar cell yield, and crystal silicon solar batteries generating is exactly the sunlight utilizing solar cell to absorb 0.4 μm ~ 1.1 mum wavelengths, luminous energy is directly transformed into a kind of generation mode that electric energy exports.How to improve the conversion efficiency of crystal silicon solar batteries, one of them topmost measure is exactly coated with antireflection film on silicon chip, because light makes light loss up to more than 30% in the reflection of silicon chip surface, if plate suitable film at silicon face, utilize film interference principle that the reflection of light just can be made greatly to reduce, thus improve circuit photocurrent density and the photoelectric conversion efficiency of solar cell.As can be seen here, add plating one deck antireflective coating at silicon chip surface and seem extremely important.
CN104241402A discloses a kind of solar battery antireflective film and preparation method thereof; Wherein, antireflective coating forms by superposing the amorphous silicon layer of setting, the first silicon nitride film and the second silicon nitride film successively, makes by depositing three-layer thin-film successively on silicon chip of solar cell surface; The antireflective coating of this invention has passivation and antireflecting effect simultaneously, but equipment controllability is lower, and homogeneity of product is inadequate, not easily large-scale production.CN101989623A discloses a kind of solar battery antireflective film and preparation method thereof, and wherein, antireflective coating comprises the silicon nitride film being deposited on silicon chip and just showing, its mean refractive index is 2.1 ~ 2.3, and average reflectance is 1 ~ 10%; Its preparation method be by by silicon chip first time plated film, cooling and second time plated film step; The antireflective coating thickness of this invention is even and compactness is good, and thickness is controlled, but tack is poor, affects its reflection efficiency, and sedimentary condition is also stricter.
Summary of the invention
An object of the present invention is to provide one to have good reflection rate and refractive index, and good solar battery antireflective film of uniformity of film and preparation method thereof;
Two of object of the present invention is to provide a kind of mild condition, is easy to promotion and application and the preparation method of the solar energy antireflective coating of wide market.To achieve these goals, present invention employs following technical scheme:
First aspect, the invention provides a kind of solar battery antireflective film, comprises silicon oxynitride film layer, nanometer titanium dioxide layer, silicon nitride layer, silicon dioxide layer and amorphous silicon layer that superposition is successively deposited on silicon chip surface.
Preferably, the thickness of described silicon oxynitride film layer is 25 ~ 30nm, such as, can be 25nm, 25.5nm, 26nm, 26.5nm, 27nm, 27.5nm, 28nm, 28.5nm, 29nm, 29.5nm or 30nm; Refractive index is 2.15 ~ 2.36, such as, can be 2.15,2.16,2.17,2.18,2.19,2.2,2.21,2.22,2.23,2.24,2.25,2.26,2.27,2.28,2.29,2.3,2.31,2.32,2.33,2.34,2.35 or 2.36.
Preferably, the thickness of described nanometer titanium dioxide layer is 28 ~ 32nm, such as, can be 28nm, 28.5nm, 29nm, 29.5nm, 30nm, 30.5nm, 31nm, 31.5nm or 32nm; Refractive index is 2.1 ~ 2.2, such as, can be 2.1,2.11,2.12,2.13,2.14,2.15,2.16,2.17,2.18,2.19 or 2.2.
Preferably, the thickness of described silicon nitride layer is 35 ~ 42nm, such as, can be 35nm, 35.5nm, 36nm, 36.5nm, 37nm, 37.5nm, 38nm, 38.5nm, 39nm, 39.5nm, 40nm, 40.5nm, 41nm, 41.5nm or 42nm; Refractive index is 2.2 ~ 2.4, such as, can be 2.2,2.21,2.22,2.23,2.24,2.25,2.26,2.27,2.28,2.29,2.3,2.31,2.32,2.33,2.34,2.35,2.36,2.37,2.38,2.39 or 2.4.
The thickness of described silicon dioxide layer is 45 ~ 55nm, such as, can be 45nm, 46nm, 47nm, 48nm, 49nm, 50nm, 51nm, 52nm, 53nm, 54nm or 55nm; Refractive index is 1.4 ~ 1.55, such as, can be 1.4,1.41,1.42,1.43,1.44,1.45,1.46,1.47,1.48,1.49,1.5,1.51,1.52,1.53,1.54 or 1.55.
Preferably, in described silicon oxynitride film layer, the granularity of silicon oxynitride is 12 ~ 15.5nm, such as, can be 12nm, 12.2nm, 12.4nm, 12.6nm, 12.8nm, 13nm, 13.2nm, 13.4nm, 13.6nm, 13.8nm, 14nm, 14.2nm, 14.4nm, 14.6nm, 14.8nm, 15nm, 15.2nm, 15.4nm or 15.5nm.
Preferably, in described nanometer titanium dioxide layer, the granularity of nano titanium oxide is 8 ~ 12nm, such as, can be 8nm, 8.2nm, 8.4nm, 8.6nm, 8.8nm, 9nm, 9.2nm, 9.4nm, 9.6nm, 9.8nm, 10nm, 10.2nm, 10.4nm, 10.6nm, 10.8nm, 11nm, 11.2nm, 11.4nm, 11.6nm, 11.8nm or 12nm.
Preferably, in described silicon nitride layer, the granularity of silicon nitride is 10 ~ 15nm, such as, can be 10nm, 10.5nm, 11nm, 11.5nm, 12nm, 12.5nm, 13nm, 13.5nm, 14nm, 14.5nm or 15nm.
Preferably, in described silicon dioxide layer, the granularity of silicon dioxide is 20 ~ 25nm, such as, can be 20nm, 20.5nm, 21nm, 21.5nm, 22nm, 22.5nm, 23nm, 23.5nm, 24nm, 24.5nm or 25nm.
Preferably, the thicknesses of layers of described silicon oxynitride film layer, nanometer titanium dioxide layer, silicon nitride layer, silicon dioxide layer and amorphous silicon layer increases successively.
Well-known to those having ordinary skill in the art, antireflective coating is the retardation values utilizing light to produce in the reflection of antireflective coating upper and lower surface, two bundle reflecting interference are disappeared mutually, thus it is incident to weaken reflection increase, incident light is made to meet certain light path condition, thus reach antireflecting effect, therefore the present invention adopts plural layers, antireflecting effect can be played to multiple specific wavelength simultaneously, and film thickness of the present invention and refractive index controlled, make to play good anti-reflective effect to the luminous energy of multiple different wave length simultaneously.
Second aspect, the invention provides the preparation method of solar battery antireflective film as described in relation to the first aspect, comprises the steps:
(1) in plasma enhanced chemical vapor deposition equipment, pass into silicon chip, hydrosilicon and nitrogen, make the surface deposition silicon oxynitride film of described silicon chip;
(2) continue in plasma enhanced chemical vapor deposition equipment, pass into nano titanium oxide and inert gas, make nano titanium oxide be deposited on the surface of silicon oxynitride film layer;
(3) continue in plasma enhanced chemical vapor deposition equipment, pass into silane and ammonia, make nitride deposition on the surface of nanometer titanium dioxide layer;
(4) continue to pass into silicon dioxide in plasma enhanced chemical vapor deposition equipment, make silica deposit on the surface of silicon nitride layer;
(5) continue in plasma enhanced chemical vapor deposition equipment, pass into silane and hydrogen, make amorphous silicon layer be deposited on the surface of silicon dioxide layer.
Preferably, the flow-rate ratio of step (1) described silicon chip, hydrosilicon and nitrogen is 1:(1 ~ 4): (1 ~ 3) can be such as 1:1:1,1:2:1,1:3:1,1:4:1,1:1:2,1:1:3,1:2:2,1:2:3,1:3:2,1:3:3,1:4:2 or 1:4:3.
Preferably, the frequency of described plasma enhanced chemical vapor deposition equipment is 12 ~ 16MHz, such as, can be 12MHz, 12.5MHz, 13MHz, 13.5MHz, 14MHz, 14.5MHz, 15MHz, 15.5MHz or 16MHz; Gas pressure intensity is 20 ~ 80Pa, such as, can be 20Pa, 25Pa, 30Pa, 35Pa, 40Pa, 45Pa, 50Pa, 55Pa, 60Pa, 65Pa, 70Pa, 75Pa or 80Pa; Temperature is 100 ~ 300 DEG C, such as, can be 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C, 240 DEG C, 250 DEG C, 260 DEG C, 270 DEG C, 280 DEG C, 290 DEG C or 300 DEG C; Radio-frequency power is 3500 ~ 6000W, such as, can be 3500W, 3600W, 3700W, 3800W, 3900W, 4000W, 4100W, 4200W, 4300W, 4400W, 4500W, 4600W, 4700W, 4800W, 4900W, 5000W, 5100W, 5200W, 5300W, 5400W, 5500W, 5600W, 5700W, 5800W, 5900W or 6000W; Deposition power is 38 ~ 70W, such as, can be 38W, 39W, 40W, 41W, 42W, 43W, 44W, 45W, 46W, 47W, 48W, 49W, 50W, 51W, 52W, 53W, 54W, 55W, 56W, 57W, 58W, 59W, 60W, 61W, 62W, 63W, 64W, 65W, 66W, 67W, 68W, 69W or 70W.
Preferably, step (2) described inert gas is the mixture of any one or at least two kinds in neon, argon gas or helium.
Preferably, the flow-rate ratio of described nano titanium oxide and inert gas is 1:(10 ~ 25), can be such as 1:10,1:11,1:12,1:13,1:14,1:15,1:16,1:17,1:18,1:19,1:20,1:21,1:22,1:23,1:24 or 1:25.
Preferably, the frequency of described plasma enhanced chemical vapor deposition equipment is 10 ~ 13MHz, such as, can be 10MHz, 10.2MHz, 10.4MHz, 10.6MHz, 10.8MHz, 11MHz, 11.2MHz, 11.4MHz, 11.6MHz, 11.8MHz, 12MHz, 12.2MHz, 12.4MHz, 12.6MHz, 12.8MHz or 13MHz; Gas pressure intensity is 20 ~ 100Pa, such as, can be 20Pa, 25Pa, 30Pa, 35Pa, 40Pa, 45Pa, 50Pa, 55Pa, 60Pa, 65Pa, 70Pa, 75Pa, 80Pa, 85Pa, 90Pa, 95Pa or 100Pa; Temperature is 150 ~ 350 DEG C, such as, can be 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C, 240 DEG C, 250 DEG C, 260 DEG C, 270 DEG C, 280 DEG C, 290 DEG C, 300 DEG C, 310 DEG C, 320 DEG C, 330 DEG C, 340 DEG C or 350 DEG C; Radio-frequency power is 3500 ~ 6000W, such as, can be 3500W, 3600W, 3700W, 3800W, 3900W, 4000W, 4100W, 4200W, 4300W, 4400W, 4500W, 4600W, 4700W, 4800W, 4900W, 5000W, 5100W, 5200W, 5300W, 5400W, 5500W, 5600W, 5700W, 5800W, 5900W or 6000W; Deposition power is 50 ~ 80W, such as, can be 50W, 51W, 52W, 53W, 54W, 55W, 56W, 57W, 58W, 59W, 60W, 61W, 62W, 63W, 64W, 65W, 66W, 67W, 68W, 69W, 70W, 71W, 72W, 73W, 74W, 75W, 76W, 77W, 78W, 79W or 80W.
Preferably, the flow-rate ratio of step (3) described silane and ammonia is 1:(3 ~ 6), can be such as 1:3,1:3.5,1:4,1:4.5,1:5,1:5.5 or 1:6.
Preferably, the frequency of described plasma enhanced chemical vapor deposition equipment is 12 ~ 16MHz, such as, can be 12MHz, 12.5MHz, 13MHz, 13.5MHz, 14MHz, 14.5MHz, 15MHz, 15.5MHz or 16MHz; Gas pressure intensity is 100 ~ 300Pa, such as, can be 100Pa, 110Pa, 120Pa, 130Pa, 140Pa, 150Pa, 160Pa, 170Pa, 180Pa, 190Pa, 200Pa, 210Pa, 220Pa, 230Pa, 240Pa, 250Pa, 260Pa, 270Pa, 280Pa, 290Pa or 300Pa; Temperature is 100 ~ 300 DEG C, such as, can be 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C, 240 DEG C, 250 DEG C, 260 DEG C, 270 DEG C, 280 DEG C, 290 DEG C or 300 DEG C; Radio-frequency power is 3500 ~ 6000W, such as, can be 3500W, 3600W, 3700W, 3800W, 3900W, 4000W, 4100W, 4200W, 4300W, 4400W, 4500W, 4600W, 4700W, 4800W, 4900W, 5000W, 5100W, 5200W, 5300W, 5400W, 5500W, 5600W, 5700W, 5800W, 5900W or 6000W; Deposition power is 38 ~ 70W, such as, can be 38W, 39W, 40W, 41W, 42W, 43W, 44W, 45W, 46W, 47W, 48W, 49W, 50W, 51W, 52W, 53W, 54W, 55W, 56W, 57W, 58W, 59W, 60W, 61W, 62W, 63W, 64W, 65W, 66W, 67W, 68W, 69W or 70W.
Preferably, in step (4), the frequency of described plasma enhanced chemical vapor deposition equipment is 10 ~ 15MHz, such as, can be 10MHz, 10.5MHz, 11MHz, 11.5MHz, 12MHz, 12.5MHz, 13MHz, 13.5MHz, 14MHz, 14.5MHz or 15MHz; Gas pressure intensity is 20 ~ 100Pa, such as, can be 20Pa, 25Pa, 30Pa, 35Pa, 40Pa, 45Pa, 50Pa, 55Pa, 60Pa, 65Pa, 70Pa, 75Pa, 80Pa, 85Pa, 90Pa, 95Pa or 100Pa; Temperature is 300 ~ 500 DEG C, such as, can be 300 DEG C, 310 DEG C, 320 DEG C, 330 DEG C, 340 DEG C, 350 DEG C, 360 DEG C, 370 DEG C, 380 DEG C, 390 DEG C, 400 DEG C, 410 DEG C, 420 DEG C, 430 DEG C, 440 DEG C, 450 DEG C, 460 DEG C, 470 DEG C, 480 DEG C, 490 DEG C or 500 DEG C; Radio-frequency power is 3500 ~ 6000W, such as, can be 3500W, 3600W, 3700W, 3800W, 3900W, 4000W, 4100W, 4200W, 4300W, 4400W, 4500W, 4600W, 4700W, 4800W, 4900W, 5000W, 5100W, 5200W, 5300W, 5400W, 5500W, 5600W, 5700W, 5800W, 5900W or 6000W; Deposition power is 38 ~ 70W, such as, can be 38W, 39W, 40W, 41W, 42W, 43W, 44W, 45W, 46W, 47W, 48W, 49W, 50W, 51W, 52W, 53W, 54W, 55W, 56W, 57W, 58W, 59W, 60W, 61W, 62W, 63W, 64W, 65W, 66W, 67W, 68W, 69W or 70W.
Preferably, the flow-rate ratio of step (5) described silane and hydrogen is 1:(6 ~ 10), can be such as 1:6,1:6.5,1:7,1:7.5,1:8,1:8.5,1:9,1:9.5 or 1:10.
Preferably, the frequency of described plasma enhanced chemical vapor deposition equipment is 12 ~ 16MHz, such as, can be 12MHz, 12.5MHz, 13MHz, 13.5MHz, 14MHz, 14.5MHz, 15MHz, 15.5MHz or 16MHz; Gas pressure intensity is 100 ~ 300Pa, such as, can be 100Pa, 110Pa, 120Pa, 130Pa, 140Pa, 150Pa, 160Pa, 170Pa, 180Pa, 190Pa, 200Pa, 210Pa, 220Pa, 230Pa, 240Pa, 250Pa, 260Pa, 270Pa, 280Pa, 290Pa or 300Pa; Temperature is 100 ~ 300 DEG C, such as, can be 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C, 240 DEG C, 250 DEG C, 260 DEG C, 270 DEG C, 280 DEG C, 290 DEG C or 300 DEG C; Radio-frequency power is 3500 ~ 6000W, such as, can be 3500W, 3600W, 3700W, 3800W, 3900W, 4000W, 4100W, 4200W, 4300W, 4400W, 4500W, 4600W, 4700W, 4800W, 4900W, 5000W, 5100W, 5200W, 5300W, 5400W, 5500W, 5600W, 5700W, 5800W, 5900W or 6000W; Deposition power is 38 ~ 70W, such as, can be 38W, 39W, 40W, 41W, 42W, 43W, 44W, 45W, 46W, 47W, 48W, 49W, 50W, 51W, 52W, 53W, 54W, 55W, 56W, 57W, 58W, 59W, 60W, 61W, 62W, 63W, 64W, 65W, 66W, 67W, 68W, 69W or 70W.
Before carrying out plated film to the silicon chip of solar cell, need to anticipate silicon chip, specifically comprise silicon chip carried out cleaning corrosion making herbs into wool, prepare PN junction, PN junction that plasma etching removes silicon chip surrounding closes the step that phosphorosilicate glass is removed in cleaning.After carrying out above-mentioned process, plated film is carried out on the surface of silicon chip, the plasma enhanced chemical vapor deposition equipment that the present invention adopts is the gas ionization making containing film composed atom by microwave or radio frequency etc., there is high chemically active plasma being partially formed, thus be deposited as film on a silicon substrate, by realizing the accurate manipulation to deposited film thickness to the proportional control of gas flow.In addition, the present invention is normal ranges for the requirement of the frequency of equipment, pressure, temperature, radio-frequency power and deposition power, and condition is comparatively gentle, is easy to promotion and application.
Compared with prior art, the present invention at least possesses following beneficial effect:
Solar battery antireflective film of the present invention comprises silicon oxynitride film layer, nanometer titanium dioxide layer, silicon nitride layer, silicon dioxide layer and the amorphous silicon layer that superposition is successively deposited on silicon chip surface.The preparation method of solar energy antireflective coating of the present invention is included in plasma enhanced chemical vapor deposition equipment and passes into silicon chip, hydrosilicon and nitrogen and make silicon chip surface depositing silicon oxynitride silicon membrane layer, then nano titanium oxide and inert gas depositing nano titanium dioxide layer is passed into, then silane and ammonia deposited silicon nitride layer is passed into, then pass into silica deposit silicon dioxide layer, finally pass into the step of silane and hydrogen deposition of amorphous silicon layers.The present invention adopts plural layers, can play antireflecting effect to multiple specific wavelength simultaneously, and film thickness of the present invention and refractive index controlled, make to play good anti-reflective effect to the luminous energy of multiple different wave length simultaneously.In addition, the present invention makes the gas ionization containing film composed atom by microwave or radio frequency etc., there is high chemically active plasma being partially formed, thus be deposited as film on a silicon substrate, by realizing the accurate manipulation to deposited film thickness to the proportional control of gas flow.Preparation method itself is normal ranges for the requirement of the frequency of equipment, pressure, temperature, radio-frequency power and deposition power, and condition is comparatively gentle, is easy to promotion and application, wide market.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
The present embodiment adopts the antireflective coating preparing solar cell with the following method:
(1) in plasma enhanced chemical vapor deposition equipment, pass into silicon chip, hydrosilicon and nitrogen, make the surface deposition silicon oxynitride film of described silicon chip; The flow-rate ratio of described silicon chip, hydrosilicon and nitrogen is 1:1:1; The frequency of described plasma enhanced chemical vapor deposition equipment is 12MHz; Gas pressure intensity is 20Pa; Temperature is 100 DEG C; Radio-frequency power is 3500W; Deposition power is 38W;
(2) continue in plasma enhanced chemical vapor deposition equipment, pass into nano titanium oxide and inert gas, make nano titanium oxide be deposited on the surface of silicon oxynitride film layer; The flow-rate ratio of described nano titanium oxide and inert gas is 1:10; The frequency of described plasma enhanced chemical vapor deposition equipment is 10MHz; Gas pressure intensity is 20Pa; Temperature is 150 DEG C; Radio-frequency power is 3500W; Deposition power is 50W;
(3) continue in plasma enhanced chemical vapor deposition equipment, pass into silane and ammonia, make nitride deposition on the surface of nanometer titanium dioxide layer; The flow-rate ratio of described silane and ammonia is 1:3; The frequency of described plasma enhanced chemical vapor deposition equipment is 12MHz; Gas pressure intensity is 100Pa; Temperature is 100 DEG C; Radio-frequency power is 3500W; Deposition power is 38W;
(4) continue to pass into silicon dioxide in plasma enhanced chemical vapor deposition equipment, make silica deposit on the surface of silicon nitride layer; The frequency of described plasma enhanced chemical vapor deposition equipment is 10MHz; Gas pressure intensity is 20Pa; Temperature is 300 DEG C; Radio-frequency power is 3500W; Deposition power is 38W;
(5) continue in plasma enhanced chemical vapor deposition equipment, pass into silane and hydrogen, make amorphous silicon layer be deposited on the surface of silicon dioxide layer; The flow-rate ratio of described silane and hydrogen is 1:6; The frequency of described plasma enhanced chemical vapor deposition equipment is 12MHz; Gas pressure intensity is 100Pa; Temperature is 100 DEG C; Radio-frequency power is 3500W; Deposition power is 38W.
Embodiment 2
The present embodiment adopts the antireflective coating preparing solar cell with the following method:
(1) in plasma enhanced chemical vapor deposition equipment, pass into silicon chip, hydrosilicon and nitrogen, make the surface deposition silicon oxynitride film of described silicon chip; The flow-rate ratio of described silicon chip, hydrosilicon and nitrogen is 1:4:3; The frequency of described plasma enhanced chemical vapor deposition equipment is 16MHz; Gas pressure intensity is 80Pa; Temperature is 300 DEG C; Radio-frequency power is 6000W; Deposition power is 70W;
(2) continue in plasma enhanced chemical vapor deposition equipment, pass into nano titanium oxide and inert gas, make nano titanium oxide be deposited on the surface of silicon oxynitride film layer; The flow-rate ratio of described nano titanium oxide and inert gas is 1:25; The frequency of described plasma enhanced chemical vapor deposition equipment is 13MHz; Gas pressure intensity is 100Pa; Temperature is 350 DEG C; Radio-frequency power is 6000W; Deposition power is 80W;
(3) continue in plasma enhanced chemical vapor deposition equipment, pass into silane and ammonia, make nitride deposition on the surface of nanometer titanium dioxide layer; The flow-rate ratio of described silane and ammonia is 1:6; The frequency of described plasma enhanced chemical vapor deposition equipment is 16MHz; Gas pressure intensity is 300Pa; Temperature is 300 DEG C; Radio-frequency power is 6000W; Deposition power is 70W;
(4) continue to pass into silicon dioxide in plasma enhanced chemical vapor deposition equipment, make silica deposit on the surface of silicon nitride layer; The frequency of described plasma enhanced chemical vapor deposition equipment is 15MHz; Gas pressure intensity is 100Pa; Temperature is 500 DEG C; Radio-frequency power is 6000W; Deposition power is 70W;
(5) continue in plasma enhanced chemical vapor deposition equipment, pass into silane and hydrogen, make amorphous silicon layer be deposited on the surface of silicon dioxide layer; The flow-rate ratio of described silane and hydrogen is 1:10; The frequency of described plasma enhanced chemical vapor deposition equipment is 16MHz; Gas pressure intensity is 300Pa; Temperature is 300 DEG C; Radio-frequency power is 6000W; Deposition power is 70W.
Embodiment 3
The present embodiment adopts the antireflective coating preparing solar cell with the following method:
(1) in plasma enhanced chemical vapor deposition equipment, pass into silicon chip, hydrosilicon and nitrogen, make the surface deposition silicon oxynitride film of described silicon chip; The flow-rate ratio of described silicon chip, hydrosilicon and nitrogen is 1:2:1.5; The frequency of described plasma enhanced chemical vapor deposition equipment is 14MHz; Gas pressure intensity is 50Pa; Temperature is 200 DEG C; Radio-frequency power is 4250W; Deposition power is 54W;
(2) continue in plasma enhanced chemical vapor deposition equipment, pass into nano titanium oxide and inert gas, make nano titanium oxide be deposited on the surface of silicon oxynitride film layer; The flow-rate ratio of described nano titanium oxide and inert gas is 1:17.5; The frequency of described plasma enhanced chemical vapor deposition equipment is 11.5MHz; Gas pressure intensity is 60Pa; Temperature is 250 DEG C; Radio-frequency power is 4250W; Deposition power is 65W;
(3) continue in plasma enhanced chemical vapor deposition equipment, pass into silane and ammonia, make nitride deposition on the surface of nanometer titanium dioxide layer; The flow-rate ratio of described silane and ammonia is 1:4.5; The frequency of described plasma enhanced chemical vapor deposition equipment is 14MHz; Gas pressure intensity is 200Pa; Temperature is 200 DEG C; Radio-frequency power is 4250W; Deposition power is 54W;
(4) continue to pass into silicon dioxide in plasma enhanced chemical vapor deposition equipment, make silica deposit on the surface of silicon nitride layer; The frequency of described plasma enhanced chemical vapor deposition equipment is 22.5MHz; Gas pressure intensity is 60Pa; Temperature is 400 DEG C; Radio-frequency power is 4250W; Deposition power is 54W;
(5) continue in plasma enhanced chemical vapor deposition equipment, pass into silane and hydrogen, make amorphous silicon layer be deposited on the surface of silicon dioxide layer; The flow-rate ratio of described silane and hydrogen is 1:8; The frequency of described plasma enhanced chemical vapor deposition equipment is 14MHz; Gas pressure intensity is 200Pa; Temperature is 200 DEG C; Radio-frequency power is 4250W; Deposition power is 54W.
Embodiment 4
The present embodiment adopts the antireflective coating preparing solar cell with the following method:
(1) in plasma enhanced chemical vapor deposition equipment, pass into silicon chip, hydrosilicon and nitrogen, make the surface deposition silicon oxynitride film of described silicon chip; The flow-rate ratio of described silicon chip, hydrosilicon and nitrogen is 1:1:1; The frequency of described plasma enhanced chemical vapor deposition equipment is 13MHz; Gas pressure intensity is 30Pa; Temperature is 105 DEG C; Radio-frequency power is 3600W; Deposition power is 40W;
(2) continue in plasma enhanced chemical vapor deposition equipment, pass into nano titanium oxide and inert gas, make nano titanium oxide be deposited on the surface of silicon oxynitride film layer; The flow-rate ratio of described nano titanium oxide and inert gas is 1:20; The frequency of described plasma enhanced chemical vapor deposition equipment is 12MHz; Gas pressure intensity is 50Pa; Temperature is 200 DEG C; Radio-frequency power is 4000W; Deposition power is 50W;
(3) continue in plasma enhanced chemical vapor deposition equipment, pass into silane and ammonia, make nitride deposition on the surface of nanometer titanium dioxide layer; The flow-rate ratio of described silane and ammonia is 1:5; The frequency of described plasma enhanced chemical vapor deposition equipment is 15MHz; Gas pressure intensity is 150Pa; Temperature is 200 DEG C; Radio-frequency power is 4000W; Deposition power is 40W;
(4) continue to pass into silicon dioxide in plasma enhanced chemical vapor deposition equipment, make silica deposit on the surface of silicon nitride layer; The frequency of described plasma enhanced chemical vapor deposition equipment is 10MHz; Gas pressure intensity is 50Pa; Temperature is 300 DEG C; Radio-frequency power is 3500W; Deposition power is 42W;
(5) continue in plasma enhanced chemical vapor deposition equipment, pass into silane and hydrogen, make amorphous silicon layer be deposited on the surface of silicon dioxide layer; The flow-rate ratio of described silane and hydrogen is 1:8; The frequency of described plasma enhanced chemical vapor deposition equipment is 12MHz; Gas pressure intensity is 100Pa; Temperature is 100 DEG C; Radio-frequency power is 5000W; Deposition power is 40W.
Embodiment 5
The present embodiment adopts the antireflective coating preparing solar cell with the following method:
(1) in plasma enhanced chemical vapor deposition equipment, pass into silicon chip, hydrosilicon and nitrogen, make the surface deposition silicon oxynitride film of described silicon chip; The flow-rate ratio of described silicon chip, hydrosilicon and nitrogen is 1:2:3; The frequency of described plasma enhanced chemical vapor deposition equipment is 16MHz; Gas pressure intensity is 80Pa; Temperature is 280 DEG C; Radio-frequency power is 5500W; Deposition power is 58W;
(2) continue in plasma enhanced chemical vapor deposition equipment, pass into nano titanium oxide and inert gas, make nano titanium oxide be deposited on the surface of silicon oxynitride film layer; The flow-rate ratio of described nano titanium oxide and inert gas is 1:25; The frequency of described plasma enhanced chemical vapor deposition equipment is 11MHz; Gas pressure intensity is 60Pa; Temperature is 200 DEG C; Radio-frequency power is 4500W; Deposition power is 50W;
(3) continue in plasma enhanced chemical vapor deposition equipment, pass into silane and ammonia, make nitride deposition on the surface of nanometer titanium dioxide layer; The flow-rate ratio of described silane and ammonia is 1:5.5; The frequency of described plasma enhanced chemical vapor deposition equipment is 13MHz; Gas pressure intensity is 200Pa; Temperature is 200 DEG C; Radio-frequency power is 4500W; Deposition power is 60W;
(4) continue to pass into silicon dioxide in plasma enhanced chemical vapor deposition equipment, make silica deposit on the surface of silicon nitride layer; The frequency of described plasma enhanced chemical vapor deposition equipment is 10MHz; Gas pressure intensity is 60Pa; Temperature is 300 DEG C; Radio-frequency power is 4500W; Deposition power is 45W;
(5) continue in plasma enhanced chemical vapor deposition equipment, pass into silane and hydrogen, make amorphous silicon layer be deposited on the surface of silicon dioxide layer; The flow-rate ratio of described silane and hydrogen is 1:7.5; The frequency of described plasma enhanced chemical vapor deposition equipment is 15MHz; Gas pressure intensity is 300Pa; Temperature is 100 DEG C; Radio-frequency power is 5500W; Deposition power is 50W.
Comparative example 1
Disclosed in employing CN104241402A, the preparation method of solar battery antireflective film prepares the solar battery antireflective film described in this invention.
Comparative example 2
Disclosed in employing CN101989623A, the preparation method of solar battery antireflective film prepares the solar battery antireflective film described in this invention.
Comparative example 3
This comparative example adopts the antireflective coating preparing solar cell with the following method:
(1) in plasma enhanced chemical vapor deposition equipment, pass into silicon chip, hydrosilicon and nitrogen, make the surface deposition silicon oxynitride film of described silicon chip; The flow-rate ratio of described silicon chip, hydrosilicon and nitrogen is 1:2:3; The frequency of described plasma enhanced chemical vapor deposition equipment is 16MHz; Gas pressure intensity is 80Pa; Temperature is 280 DEG C; Radio-frequency power is 5500W; Deposition power is 58W;
(2) continue in plasma enhanced chemical vapor deposition equipment, pass into nano titanium oxide and inert gas, make nano titanium oxide be deposited on the surface of silicon oxynitride film layer; The flow-rate ratio of described nano titanium oxide and inert gas is 1:25; The frequency of described plasma enhanced chemical vapor deposition equipment is 11MHz; Gas pressure intensity is 60Pa; Temperature is 200 DEG C; Radio-frequency power is 4500W; Deposition power is 50W;
(3) continue in plasma enhanced chemical vapor deposition equipment, pass into silane and ammonia, make nitride deposition on the surface of nanometer titanium dioxide layer; The flow-rate ratio of described silane and ammonia is 1:5.5; The frequency of described plasma enhanced chemical vapor deposition equipment is 13MHz; Gas pressure intensity is 200Pa; Temperature is 200 DEG C; Radio-frequency power is 4500W; Deposition power is 60W.
Comparative example 4
This comparative example adopts the antireflective coating preparing solar cell with the following method:
(1) in plasma enhanced chemical vapor deposition equipment, pass into silicon chip, hydrosilicon and nitrogen, make the surface deposition silicon oxynitride film of described silicon chip; The flow-rate ratio of described silicon chip, hydrosilicon and nitrogen is 1:2:3; The frequency of described plasma enhanced chemical vapor deposition equipment is 16MHz; Gas pressure intensity is 80Pa; Temperature is 280 DEG C; Radio-frequency power is 5500W; Deposition power is 58W;
(2) continue in plasma enhanced chemical vapor deposition equipment, pass into silane and ammonia, make nitride deposition on the surface of nanometer titanium dioxide layer; The flow-rate ratio of described silane and ammonia is 1:5.5; The frequency of described plasma enhanced chemical vapor deposition equipment is 13MHz; Gas pressure intensity is 200Pa; Temperature is 200 DEG C; Radio-frequency power is 4500W; Deposition power is 60W;
(3) continue to pass into silicon dioxide in plasma enhanced chemical vapor deposition equipment, make silica deposit on the surface of silicon nitride layer; The frequency of described plasma enhanced chemical vapor deposition equipment is 10MHz; Gas pressure intensity is 60Pa; Temperature is 300 DEG C; Radio-frequency power is 4500W; Deposition power is 45W;
(4) continue in plasma enhanced chemical vapor deposition equipment, pass into silane and hydrogen, make amorphous silicon layer be deposited on the surface of silicon dioxide layer; The flow-rate ratio of described silane and hydrogen is 1:7.5; The frequency of described plasma enhanced chemical vapor deposition equipment is 15MHz; Gas pressure intensity is 300Pa; Temperature is 100 DEG C; Radio-frequency power is 5500W; Deposition power is 50W.
Performance test:
The SE400adv ellipsometer that refraction index test adopts SENTECH company to produce;
The PELAMBDA integration type reflectometer that reflectivity adopts PE company to produce;
Thickness evenness adopts the thickness extreme difference of on antireflection film 5 to evaluate the uniformity of its thickness, and extreme difference larger expression uniformity is poorer:
Extreme difference=maximum-minimum value.
The result of all tests is as shown in table 1, can find out, antireflective coating of the present invention is compared with comparative example, and its average reflectance significantly reduces, and refracting power effects is also better; And the uniformity extreme difference of film thickness only in 1 ~ 2nm fluctuation, illustrates that thickness evenness effect is very good.
Table 1 the performance test results
| Mean refractive index | Average reflectance (%) | Thickness evenness (nm) | |
| Embodiment 1 | 2.03 | 1.51 | 1 |
| Embodiment 2 | 2.21 | 3.22 | 2 |
| Embodiment 3 | 2.16 | 3.63 | 1 |
| Embodiment 4 | 2.24 | 9.04 | 2 |
| Embodiment 5 | 2.18 | 8.32 | 2 |
| Comparative example 1 | 2.06 | 21.6 | 8 |
| Comparative example 2 | 2.34 | 23.5 | 9 |
| Comparative example 3 | 2.21 | 20.9 | 6 |
| Comparative example 4 | 2.30 | 21.5 | 8 |
Applicant states, the present invention illustrates process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned processing step, does not namely mean that the present invention must rely on above-mentioned processing step and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of raw material selected by the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a solar battery antireflective film, is characterized in that, comprises silicon oxynitride film layer, nanometer titanium dioxide layer, silicon nitride layer, silicon dioxide layer and amorphous silicon layer that superposition is successively deposited on silicon chip surface.
2. solar battery antireflective film according to claim 1, is characterized in that, the thickness of described silicon oxynitride film layer is 25 ~ 30nm, and refractive index is 2.15 ~ 2.36;
Preferably, the thickness of described nanometer titanium dioxide layer is 28 ~ 32nm, and refractive index is 2.1 ~ 2.2;
Preferably, the thickness of described silicon nitride layer is 35 ~ 42nm, and refractive index is 2.2 ~ 2.4;
The thickness of described silicon dioxide layer is 45 ~ 55nm, and refractive index is 1.4 ~ 1.55.
3. solar battery antireflective film according to claim 1 and 2, is characterized in that, in described silicon oxynitride film layer, the granularity of silicon oxynitride is 12 ~ 15.5nm;
Preferably, in described nanometer titanium dioxide layer, the granularity of nano titanium oxide is 8 ~ 12nm;
Preferably, in described silicon nitride layer, the granularity of silicon nitride is 10 ~ 15nm;
Preferably, in described silicon dioxide layer, the granularity of silicon dioxide is 20 ~ 25nm.
4. according to the solar battery antireflective film one of claims 1 to 3 Suo Shu, it is characterized in that, the thicknesses of layers of described silicon oxynitride film layer, nanometer titanium dioxide layer, silicon nitride layer, silicon dioxide layer and amorphous silicon layer increases successively.
5., according to the preparation method of the solar battery antireflective film one of Claims 1 to 4 Suo Shu, it is characterized in that, comprise the steps:
(1) in plasma enhanced chemical vapor deposition equipment, pass into silicon chip, hydrosilicon and nitrogen, make the surface deposition silicon oxynitride film of described silicon chip;
(2) continue in plasma enhanced chemical vapor deposition equipment, pass into nano titanium oxide and inert gas, make nano titanium oxide be deposited on the surface of silicon oxynitride film layer;
(3) continue in plasma enhanced chemical vapor deposition equipment, pass into silane and ammonia, make nitride deposition on the surface of nanometer titanium dioxide layer;
(4) continue to pass into silicon dioxide in plasma enhanced chemical vapor deposition equipment, make silica deposit on the surface of silicon nitride layer;
(5) continue in plasma enhanced chemical vapor deposition equipment, pass into silane and hydrogen, make amorphous silicon layer be deposited on the surface of silicon dioxide layer.
6. preparation method according to claim 5, is characterized in that, the flow-rate ratio of step (1) described silicon chip, hydrosilicon and nitrogen is 1:(1 ~ 4): (1 ~ 3);
Preferably, the frequency of described plasma enhanced chemical vapor deposition equipment is 12 ~ 16MHz; Gas pressure intensity is 20 ~ 80Pa; Temperature is 100 ~ 300 DEG C; Radio-frequency power is 3500 ~ 6000W; Deposition power is 38 ~ 70W.
7. the preparation method according to claim 5 or 6, is characterized in that, step (2) described inert gas is the mixture of any one or at least two kinds in neon, argon gas or helium;
Preferably, the flow-rate ratio of described nano titanium oxide and inert gas is 1:(10 ~ 25);
Preferably, the frequency of described plasma enhanced chemical vapor deposition equipment is 10 ~ 13MHz; Gas pressure intensity is 20 ~ 100Pa; Temperature is 150 ~ 350 DEG C; Radio-frequency power is 3500 ~ 6000W; Deposition power is 50 ~ 80W.
8. according to the preparation method one of claim 5 ~ 7 Suo Shu, it is characterized in that, the flow-rate ratio of step (3) described silane and ammonia is 1:(3 ~ 6);
Preferably, the frequency of described plasma enhanced chemical vapor deposition equipment is 12 ~ 16MHz; Gas pressure intensity is 100 ~ 300Pa; Temperature is 100 ~ 300 DEG C; Radio-frequency power is 3500 ~ 6000W; Deposition power is 38 ~ 70W.
9. according to the preparation method one of claim 5 ~ 8 Suo Shu, it is characterized in that, in step (4), the frequency of described plasma enhanced chemical vapor deposition equipment is 10 ~ 15MHz; Gas pressure intensity is 20 ~ 100Pa; Temperature is 300 ~ 500 DEG C; Radio-frequency power is 3500 ~ 6000W; Deposition power is 38 ~ 70W.
10. according to the preparation method one of claim 5 ~ 9 Suo Shu, it is characterized in that, the flow-rate ratio of step (5) described silane and hydrogen is 1:(6 ~ 10);
Preferably, the frequency of described plasma enhanced chemical vapor deposition equipment is 12 ~ 16MHz; Gas pressure intensity is 100 ~ 300Pa; Temperature is 100 ~ 300 DEG C; Radio-frequency power is 3500 ~ 6000W; Deposition power is 38 ~ 70W.
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