CN104465814A - Super-small suede solar cell combined with zinc oxide nanostructure and preparation method thereof - Google Patents
Super-small suede solar cell combined with zinc oxide nanostructure and preparation method thereof Download PDFInfo
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- CN104465814A CN104465814A CN201410776650.5A CN201410776650A CN104465814A CN 104465814 A CN104465814 A CN 104465814A CN 201410776650 A CN201410776650 A CN 201410776650A CN 104465814 A CN104465814 A CN 104465814A
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- zinc oxide
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- solar cell
- small suede
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 70
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 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
- 238000002161 passivation Methods 0.000 claims abstract description 33
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004332 silver Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 36
- 239000000758 substrate Substances 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 16
- 238000009792 diffusion process Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 9
- 238000001039 wet etching Methods 0.000 claims description 9
- 238000005229 chemical vapour deposition Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 238000007650 screen-printing Methods 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 6
- 238000004513 sizing Methods 0.000 claims description 6
- 230000007797 corrosion Effects 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 5
- 238000001312 dry etching Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 238000001020 plasma etching Methods 0.000 claims description 4
- 238000004549 pulsed laser deposition Methods 0.000 claims description 4
- 239000012808 vapor phase Substances 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 230000007547 defect Effects 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000003475 lamination Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 2
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 238000004070 electrodeposition Methods 0.000 claims description 2
- 238000000608 laser ablation Methods 0.000 claims description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 2
- 229920005591 polysilicon Polymers 0.000 claims description 2
- 238000001338 self-assembly Methods 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 239000002073 nanorod Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 description 31
- 230000008901 benefit Effects 0.000 description 6
- 239000002800 charge carrier Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006701 autoxidation reaction Methods 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000002310 reflectometry Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000010792 warming Methods 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
- H01L31/0236—Special surface textures
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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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
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
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- 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
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Abstract
The invention discloses a super-small suede solar cell combined with a zinc oxide nanostructure and a preparation method of the super-small suede solar cell combined with the zinc oxide nanostructure. The solar cell comprises a silicon wafer, a PN junction, the zinc oxide nanostructure, a passivation layer, silver paste and aluminum paste, wherein the surface of the silicon wafer is provided with super-small suede; the PN junction is formed at the position, close to the nanometer super-small suede structure, of the silicon wafer; the zinc oxide nanostructure grows in the surface and gaps of the super-small suede; the passivation layer is arranged on the side, provided with the super-small suede, of the silicon wafer; the silver paste is arranged on the side, provided with the super-small suede, of the silicon wafer to form a front electrode of the solar cell; the aluminum paste is arranged on the side, not provided with the super-small suede, of the silicon wafer to form a back electrode of the solar cell. According to the super-small suede solar cell, through combination with zinc oxide nanorods, absorption of photons at a short waveband can be further enhanced. Besides, since the gaps of the silicon-based micro-nano structure are filled with zinc oxide, on one hand, the electrode contact area is effectively increased, and good electrode contact is formed; on the other hand, transverse carrier transportation of the super-small suede cell can be enhanced, and meanwhile a certain passivation effect is achieved. The efficiency of the silicon-based nanostructure solar cell is effectively improved.
Description
Technical field
The invention belongs to high-efficiency crystal silicon technical field of solar cells, particularly relate to a kind of efficient enhancement mode extra small suede solar cell in conjunction with transparent conductive zinc oxide nanostructure and preparation method thereof.
Background technology
In recent years, the environmental problem of energy scarcity problem and global warming is day by day serious, and the mankind are unprecedentedly eager to clean regenerative resource demand.Photovoltaic solar is a kind of important regenerative resource, have the energy extensively, region restriction less and the many advantages such as safe and reliable.
The solar cell of existing market application is based on crystal silicon cell, but the high bottleneck remaining restriction theCourse of PV Industry of cost, therefore how to raise the efficiency to reduce costs the focus becoming solar cell research.
Due to reasons such as spectral losses, the theoretical limit efficiency of crystal silicon battery is about 30%.And the crystal silicon battery average efficiency of industrialization is at present about 17%.The main cause causing the actual efficiency of battery and theoretical efficiency to there is gap comprises: optical loss, recombination losses and electrode contact etc.And wherein optical loss account for greatly.
In order to reduce optical loss, improve battery efficiency, people have prepared multiple light trapping structure.Include porous silicon, pyramid matte and nano thread structure etc., these structures can reduce reflected incident light on the one hand, add the light path of light in cell body on the other hand, strengthen the absorption to light.For silicon nanostructure solar cell, what generally adopt at present is the method for wet etching grown silicon post, its have cost low, make simple feature.But because coarse surface increases surface area, this kind of battery also exists the problems such as the large and electrode contact performance of surface recombination is not good.
The research of zinc oxide (ZnO) nanostructure in recent years becomes focus, and zinc oxide is a kind of Novel direct tape splicing gap semiconductor material, and under room temperature, energy gap is 3.37eV.Nano structure of zinc oxide is semi-conducting material and piezoelectric, the new property such as quantum confinement, small-size effect is there is at nanoscale, after suitable doping, it shows good low-resistance characteristic and photopermeability, has unique piezoelectricity photoelectric characteristic simultaneously.If be applied on silicon nanostructure solar cell, may be conducive to improving battery charge carrier horizontal transport and light absorption etc., strengthen extra small suede solar cell performance.
The present invention proposes one in conjunction with nano structure of zinc oxide extra small suede solar cell and preparation method thereof; existing sunken optical property well can overcome again self electrode contact performance not good carrier collection inefficiency drawback; simultaneously can the preparation of low-coat scale, there is very large market application foreground.
Summary of the invention
(1) technical problem that will solve
For this reason, embodiments of the invention propose one in conjunction with nano structure of zinc oxide extra small suede solar cell and preparation method thereof, zinc oxide nano rod growth has been carried out to existing silica-based micro-nano structure, realize surface gaps uniform filling to cover, can effectively increase electrode contact area, reduce series resistance, and effectively can improve charge carrier transportation ability raising short circuit current simultaneously, thus improve battery efficiency.
(2) technical scheme
According to an aspect of the present invention, the embodiment of the present invention proposes one in conjunction with nano structure of zinc oxide extra small suede solar cell, and this solar cell comprises: surface has the silicon chip of extra small suede; PN junction is formed near nanometer extra small suede structure place at silicon chip; Grow the nano structure of zinc oxide in extra small suede surface and gap; There is at silicon chip the passivation layer of extra small suede side; There is the silver paste of extra small suede side, to form electrode before solar cell at silicon chip; And there is no the aluminum slurry of extra small suede side at silicon chip, to form the back electrode of solar cell.
In such scheme, described extra small suede is silicon chip surface because corroding the suede structure with certain distribution sinking and formed, and its degree of depth is 0.1 ~ 10 μm, and diameter is that tens nanometer arrives hundreds of nanometer.
In such scheme, described PN junction depth is tens to hundreds of nanometer.
In such scheme, described nano structure of zinc oxide comprises linear and clavate, and diameter is 1 ~ 500nm, and length is 0.01 ~ 10 μm.
In such scheme, described passivation layer thickness is 1 ~ 1000nm, and passivation material is individual layer or the lamination of silica, silicon nitride or aluminium oxide.
According to an aspect of the present invention, the embodiment of the present invention also proposed a kind of preparation method in conjunction with nano structure of zinc oxide extra small suede solar cell, comprises the following steps: a) cleaning silicon chip; B) wet etching or dry etching formation nanometer extra small suede structure are carried out to silicon chip surface; C) clean, removal impurity defect and surface metal remain; D) spread, form PN junction at silicon backing wafer near nanometer extra small suede structure place; E) carve the diffusion zone that edge is removed on limit, the PSG of silicon chip surface is removed in cleaning; F) in nanometer extra small suede, ZnO transparent conductive inculating crystal layer is prepared; G) nano structure of zinc oxide is prepared in ZnO transparent conductive seed crystal surface; H) at silicon chip, there is extra small suede side and prepare passivation layer; I) electrode before silicon chip has the making of extra small suede side, does not have extra small suede side to make back electrode at silicon chip, has finally sintered battery preparation.
In such scheme, step a) described in silicon chip be monocrystalline or polysilicon chip, doping type is P type or N-type.Step a) described in cleaning, be silicon chip is put into concentrated acid mixed solution to boil, then insert HF solution, finally use washed with de-ionized water, nitrogen dries up.
In such scheme, step b) described in wet etching be chemical corrosion method.Step b) described in dry etching be reactive ion etching (RIE).Step b) described in nanometer extra small suede be size at 1 ~ 500nm, length is at the anti-reflection matte layer of the nanostructure of 0.1 ~ 10 μm.
In such scheme, step c) described in cleaning comprise and silicon chip is placed in nitric acid cleans, the time is 1 ~ 10 hour, then puts into HF solution, then uses washed with de-ionized water.
In such scheme, steps d) described in be diffused as N-shaped or p-type diffusion, P type substrate is adopted to the N-shaped diffusion at least comprising the diffusion of phosphorus source, N-type substrate is adopted to the p-type diffusion at least comprising the diffusion of boron source or aluminium and advance.Steps d) described in PN junction depth be 1 ~ 1000nm.
In such scheme, step e) described in the PSG of removal silicon chip surface solution used be acids mixed solution.
In such scheme, step f) described in prepare ZnO transparent conductive inculating crystal layer in silicon nanometer extra small suede and cover one deck zinc oxide coverlay in gap, the method for preparation comprises spin-coating method, ALD method or pulsed laser deposition (PLD) method.
In such scheme, step g) described in prepare nano structure of zinc oxide adopt hydro thermal method, vapor phase method, liquid phase method, template or chemical reaction self-assembly method, wherein, vapor phase method comprises physical vaporous deposition (PVD), chemical vapour deposition technique (CVD), metal organic chemical vapor deposition (MOCVD), plasma reinforced chemical vapour deposition (PECVD) or laser ablation method (LPA), and liquid phase method comprises hydro thermal method, electrochemical deposition method or solvent-thermal method.
In such scheme, step h) described in passivation layer of preparing adopt oxide passivation layer, silicon nitride passivation, aluminium oxide passivation and overlayer passivation, preparation method is dry-oxygen oxidation, wet-oxygen oxidation, PECVD deposition or ALD growth.Step h) described in passivation layer thickness be 1 ~ 1000nm.
In such scheme, step I) described in making before electrode adopt screen printing sizing agent and sinter, or plated metal the mode of annealing have been come, and slurry or metal select Ag; Step I) described in making back electrode adopt screen printing sizing agent sintering, or plated metal the mode of annealing have been come, and the metal of slurry or deposition is distinguished to some extent with the difference of substrate: for p-type substrate, adopts Al slurry or plated metal Al; For n-type substrate, adopt Ag slurry or plated metal Ag, so that good ohmic contact can be formed with substrate.
In such scheme, step I) described in sintering adopt chain-type sintering furnace or pipe type sintering furnace, to form ohmic contact.
(3) beneficial effect
The present invention compared with prior art has following obvious advantage and beneficial effect:
1, extra small suede is compared with traditional surface of crystalline silicon and conventional matte, can effectively reduce battery surface reflectivity, and have good light trapping effect, improves absorbing visible ray and infrared band light;
2, increase zinc oxide nano rod at extra small suede battery surface, matte and electrode contact area can be increased on the one hand and improve contact performance and reduce series resistance; Effectively can also increase charge carrier lateral transport ability on the other hand, strengthen the collection to charge carrier, also there is certain passivation simultaneously, thus improve the short circuit current of battery.
Following practical advantage is had compared with other techniques in prepared by technique:
1, the present invention adopt etch particularly wet etching legal system for extra small suede, be applicable to large-scale production, can be mutually compatible with existing production technology;
2, the present invention adopts chemical method growth of zinc oxide nano linear array, can reduce cost, is applicable to the large-scale production of industry;
3, the battery of preparation adopts silica-base material and zinc oxide, and these raw material ratio are more sufficient, and cost is lower, and silicon process technology is quite ripe, are conducive to applying of large-scale production.
In sum, the present invention is a kind of new and effective extra small suede solar battery structure and preparation method thereof.On the basis of existing extra small suede battery, the good characteristic combining nano structure of zinc oxide of novelty is applied to extra small suede solar battery structure surface, to improve the conversion efficiency of crystal silicon solar batteries, reduce the production cost of solar cell, and can be compatible with existing solar cell preparation technology well, thus move towards practical, the creation of value.The present invention has above-mentioned many advantages and practical value, has large improvement technically, and creates handy and practical effect, thus is more suitable for practicality.
Above-mentioned explanation is only the general introduction of technical solution of the present invention, in order to better understand technological means of the present invention, and can be implemented according to the content of specification, coordinates accompanying drawing to be described in detail as follows below with preferred embodiment of the present invention.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage will become obvious and easy understand from the following description of the accompanying drawings of embodiments, wherein:
Fig. 1 is the preparation method's flow chart in conjunction with nano structure of zinc oxide extra small suede solar cell of the embodiment of the present invention;
Fig. 2 to Fig. 7 is the schematic diagram of each production phase of extra small suede battery of the embodiment of the present invention.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly understand, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.
The embodiment of the present invention proposes one in conjunction with nano structure of zinc oxide extra small suede solar cell, and described solar cell comprises: surface has the silicon chip of extra small suede; PN junction is formed near nanometer extra small suede structure place at silicon chip; Grow the nano structure of zinc oxide in extra small suede surface and gap; There is at silicon chip the passivation layer of extra small suede side; There is the silver paste of extra small suede side, to form electrode before solar cell at silicon chip; And there is no the aluminum slurry of extra small suede side at silicon chip, to form the back electrode of solar cell.
Wherein, described extra small suede is silicon chip surface because corroding the suede structure with certain distribution sinking and formed, and its degree of depth is 0.1 ~ 10 μm, and diameter is that tens nanometer arrives hundreds of nanometer.Described PN junction depth is tens to hundreds of nanometer.Described nano structure of zinc oxide comprises linear and clavate, and diameter is 1 ~ 500nm, and length is 0.01 ~ 10 μm.Described passivation layer thickness is 1 ~ 1000nm, and passivation material is individual layer or the lamination of silica, silicon nitride or aluminium oxide.
The introducing of extra small suede of the present invention effectively can reduce the reflectivity of battery surface.And on the basis at existing extra small suede battery, propose the preparation method of innovation, matte increases nano structure of zinc oxide as packed layer and conducting shell, to improve the many drawbacks of existing extra small suede battery.On the one hand by electrode contact area can be increased to extra small suede calking, effectively improve the problem of extra small suede battery electrode loose contact.On the other hand, zinc oxide nano rod interconnects and forms horizontal conduction, increases and effectively can reduce the compound of charge carrier on surface to the collection efficiency of charge carrier simultaneously.Add photogenerated current, thus improve the conversion efficiency of crystal silicon solar batteries, reduce the production cost of solar cell, and can be compatible with existing solar cell preparation technology well.
Show according to an embodiment of the invention in conjunction with the flow chart of the preparation method of nano structure of zinc oxide extra small suede solar cell with reference to figure 1, Fig. 1, specifically comprise the following steps:
Step 101, first cleans silicon substrate 201.Wherein silicon substrate can be p-type silicon chip, also can n-type silicon chip, as shown in Figure 2.Preferably, adopt p-type silicon chip, p-type silicon chip is adopted H
2sO
4and H
2o
2mixed solution boil 30 minutes, then insert HF solution 1 minute, finally use washed with de-ionized water.
Step 102, carries out corrosion to the surface of silicon substrate 201 and forms nanometer extra small suede structure, as shown in Figure 3.Wherein, corrosion formation extra small suede can be wet etching also can be dry etching.Preferably, the method for wet etching is adopted.
Such as in a particular embodiment, HF/AgNO is adopted
3solution corrodes silicon chip surface, and the time of corrosion is 30 minutes, forms nanometer extra small suede structure.Matte diameter is 20 ~ 200nm, and length is 0.2 ~ 2 μm.
Step 103, cleans the silicon substrate of structure described in Fig. 3, and removal impurity defect and surface metal remain.Preferably, the cleaning in step 103 is cleaned for silicon chip is placed in nitric acid, and the time is 1 ~ 2 hour, then puts into HF solution 1 minute, then uses washed with de-ionized water;
Step 104, spreads the silicon substrate 201 with extra small suede, forms PN junction 202, as shown in Figure 4 in silicon substrate 201 near nanometer extra small suede structure place.
In embodiments of the present invention, can phosphorous diffusion source be adopted to P type substrate, comprise liquid source and Solid Source; Can boron diffusion source be adopted to N-type substrate, comprise liquid source and Solid Source.Preferably, be diffused as on p-type silicon substrate, with phosphorus oxychloride expansion for loose source described in.By step 104, the PN junction depth of formation is 200 ~ 600nm.
Step 105, after having spread, adopt solar cell etching machine, remove the diffusion zone of edge, then the HF solution of dilution (volume ratio of HF and deionized water is 1: 20) is used to soak the PSG that 180 seconds remove silicon chip 201 surface, again through the flushing of deionized water, dry with drier.
Step 106, developing zinc oxide electrically conducting transparent inculating crystal layer 203 on the silicon substrate 202 with extra small suede side, as shown in Figure 5, carries out field effect passivation and grows Seed Layer as zinc oxide nano rod.
Step 107, as shown in Figure 6, prepares nano structure of zinc oxide on ZnO transparent conductive inculating crystal layer 203 surface; Here the preparation of nano structure of zinc oxide can adopt hydro thermal method, sol-gal process, template etc., and preferably, step 105 adopts hydro thermal method to prepare nano structure of zinc oxide, and nano structure of zinc oxide 204 diameter of growth is 1 ~ 10nm, and length is 10 ~ 100nm.
In step 108, form one deck passivation layer, to play the effect of passivation on silicon substrate 201 surface.Here, the passivation layer of growth can be silica, silicon nitride, aluminium oxide etc., and the method for preparation can be dry oxygen autoxidation, wet oxygen autoxidation, and PECVD deposits, ALD growth etc.Thickness is 5 ~ 100nm.Preferably, step 108 adopts dry oxygen autoxidation, forms passivation layer at silicon surface oxidation, reduces surface recombination to the impact of battery performance.The temperature of oxidation is 700 ~ 800 DEG C, 10 ~ 30 minutes time.The thin layer of silicon oxide thickness of growth is 5 ~ 20nm.
Such as in a particular embodiment, adopt tubular type oxidation furnace to be oxidized, temperature is 700 DEG C, and the time is 20 minutes, and the silicon oxide thickness of growth is 10nm.
In step 109, at the back side of silicon substrate 201, namely do not have the one side of extra small suede to make back electrode 205, in the front of silicon substrate 201, namely have extra small suede one side to make positive electrode 206, as shown in Figure 7, to obtain the front and back electrode of solar cell.Make back electrode 205 can adopt screen printing sizing agent and sinter, or the mode that plated metal is also annealed has been come, the metal of slurry or deposition is distinguished to some extent with the difference of substrate: for p-type substrate 201, adopts Al slurry or plated metal Al; For n-type substrate 201, adopt Ag slurry or plated metal Ag, be as the criterion so that good ohmic contact can be formed with substrate 202.Make positive electrode 206 can adopt screen printing sizing agent and sinter, or the mode that plated metal is also annealed has been come, slurry or metal generally select Ag.
Preferably, step 109 adopts silk screen printing Al to starch, and makes back electrode 205 at p-type silicon substrate 201 back side.Adopt silk screen printing Ag slurry, make positive electrode 206 in silicon substrate 201 front.
Step 110, carries out high temperature sintering to the silicon substrate having prepared front and back electrode, to form good ohmic contact, as shown in Figure 7.Sintering can adopt chain-type sintering furnace or pipe type sintering furnace.
Preferably, step 110 adopts chain-type sintering furnace to sinter, and forms ohmic contact.Complete the preparation of the silicon extra small suede solar cell this to nano structure of zinc oxide.
It is pointed out that and be above-mentionedly only the simple clear schematic example describing the principle of the invention about step 101 to the specific embodiment mode of step 110, not any pro forma restriction is done to the present invention, more especially by step that existing technique realizes.
The present invention utilizes wet etching extra small suede as the antireflection layer of solar cell.Extra small suede can obtain extremely low reflectivity, improves light absorption.Add the preparation of nano structure of zinc oxide, by short-wave band photonic absorption can be increased further in conjunction with zinc oxide nano rod simultaneously.The interstitial zinc oxide of silica-based micro-nano structure is filled and is effectively increased electrode contact area on the one hand in addition, forms good electrode contact, can also strengthen extra small suede battery lateral carrier on the other hand and transport and have certain passivation simultaneously.Adopt this method effectively can improve the efficiency of silicon-based nano structure solar cell.
Although the present invention discloses as above with preferred embodiment, but and be not used to limit the present invention.Those of ordinary skill in the art are obviously known, do not departing within the scope of technical solution of the present invention, make a little change when the technology contents of above-mentioned announcement can be utilized or be modified to the Equivalent embodiments of equivalent variations, in every case be the content not departing from technical solution of the present invention, the any simple modification done above embodiment according to technical spirit of the present invention, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (16)
1. in conjunction with a nano structure of zinc oxide extra small suede solar cell, it is characterized in that, this solar cell comprises:
Surface has the silicon chip of extra small suede;
PN junction is formed near nanometer extra small suede structure place at silicon chip;
Grow the nano structure of zinc oxide in extra small suede surface and gap;
There is at silicon chip the passivation layer of extra small suede side;
There is the silver paste of extra small suede side, to form electrode before solar cell at silicon chip; And
The aluminum slurry of extra small suede side is not had, to form the back electrode of solar cell at silicon chip.
2. according to claim 1 in conjunction with nano structure of zinc oxide extra small suede solar cell, it is characterized in that, described extra small suede is silicon chip surface because corroding the suede structure with certain distribution sinking and formed, and its degree of depth is 0.1 ~ 10 μm, and diameter is that tens nanometer arrives hundreds of nanometer.
3. according to claim 1ly it is characterized in that in conjunction with nano structure of zinc oxide extra small suede solar cell, described PN junction depth is tens to hundreds of nanometer.
4. according to claim 1ly it is characterized in that in conjunction with nano structure of zinc oxide extra small suede solar cell, described nano structure of zinc oxide comprises linear and clavate, and diameter is 1 ~ 500nm, and length is 0.01 ~ 10 μm.
5. according to claim 1ly it is characterized in that in conjunction with nano structure of zinc oxide extra small suede solar cell, described passivation layer thickness is 1 ~ 1000nm, and passivation material is individual layer or the lamination of silica, silicon nitride or aluminium oxide.
6. in conjunction with a preparation method for nano structure of zinc oxide extra small suede solar cell, it is characterized in that, comprise the following steps:
A) cleaning silicon chip;
B) wet etching or dry etching formation nanometer extra small suede structure are carried out to silicon chip surface;
C) clean, removal impurity defect and surface metal remain;
D) spread, form PN junction at silicon chip near nanometer extra small suede structure place;
E) carve the diffusion zone that edge is removed on limit, the PSG of silicon chip surface is removed in cleaning;
F) in nanometer extra small suede, ZnO transparent conductive inculating crystal layer is prepared;
G) nano structure of zinc oxide is prepared in ZnO transparent conductive seed crystal surface;
H) at silicon chip, there is extra small suede side and prepare passivation layer;
I) electrode before silicon chip has the making of extra small suede side, does not have extra small suede side to make back electrode at silicon chip, has finally sintered battery preparation.
7. the preparation method in conjunction with nano structure of zinc oxide extra small suede solar cell according to claim 6, is characterized in that,
Step a) described in silicon chip be monocrystalline or polysilicon chip, doping type is P type or N-type;
Step a) described in cleaning, be silicon chip is put into concentrated acid mixed solution to boil, then insert HF solution, finally use washed with de-ionized water, nitrogen dries up.
8. the preparation method in conjunction with nano structure of zinc oxide extra small suede solar cell according to claim 6, is characterized in that,
Step b) described in wet etching be chemical corrosion method;
Step b) described in dry etching be reactive ion etching (RIE);
Step b) described in nanometer extra small suede be size at 1 ~ 500nm, length is at the anti-reflection matte layer of the nanostructure of 0.1 ~ 10 μm.
9. the preparation method in conjunction with nano structure of zinc oxide extra small suede solar cell according to claim 6, it is characterized in that, step c) described in cleaning comprise and silicon chip is placed in nitric acid cleans, the time is 1 ~ 10 hour, put into HF solution again, then use washed with de-ionized water.
10. the preparation method in conjunction with nano structure of zinc oxide extra small suede solar cell according to claim 6, is characterized in that,
Steps d) described in be diffused as N-shaped or p-type diffusion, to P type substrate adopt at least comprise phosphorus source diffusion N-shaped diffusion, to N-type substrate adopt at least comprise boron source diffusion or aluminium advance p-type diffusion;
Steps d) described in PN junction depth be 1 ~ 1000nm.
11. preparation methods in conjunction with nano structure of zinc oxide extra small suede solar cell according to claim 6, is characterized in that, step e) described in the PSG of removal silicon chip surface solution used be acids mixed solution.
12. preparation methods in conjunction with nano structure of zinc oxide extra small suede solar cell according to claim 6, it is characterized in that, step f) described in prepare ZnO transparent conductive inculating crystal layer in silicon nanometer extra small suede and cover one deck zinc oxide coverlay in gap, the method for preparation comprises spin-coating method, ALD method or pulsed laser deposition (PLD) method.
13. preparation methods in conjunction with nano structure of zinc oxide extra small suede solar cell according to claim 6, it is characterized in that, step g) described in prepare nano structure of zinc oxide adopt hydro thermal method, vapor phase method, liquid phase method, template or chemical reaction self-assembly method, wherein, vapor phase method comprises physical vaporous deposition (PVD), chemical vapour deposition technique (CVD), metal organic chemical vapor deposition (MOCVD), plasma reinforced chemical vapour deposition (PECVD) or laser ablation method (LPA), liquid phase method comprises hydro thermal method, electrochemical deposition method or solvent-thermal method.
14. preparation methods in conjunction with nano structure of zinc oxide extra small suede solar cell according to claim 6, is characterized in that,
Step h) described in passivation layer of preparing adopt oxide passivation layer, silicon nitride passivation, aluminium oxide passivation and overlayer passivation, preparation method is dry-oxygen oxidation, wet-oxygen oxidation, PECVD deposition or ALD growth;
Step h) described in passivation layer thickness be 1 ~ 1000nm.
15. preparation methods in conjunction with nano structure of zinc oxide extra small suede solar cell according to claim 6, is characterized in that,
Step I) described in making before electrode adopt screen printing sizing agent sintering, or plated metal the mode of annealing have been come, and slurry or metal select Ag;
Step I) described in making back electrode adopt screen printing sizing agent sintering, or plated metal the mode of annealing have been come, and the metal of slurry or deposition is distinguished to some extent with the difference of substrate: for p-type substrate, adopts Al slurry or plated metal Al; For n-type substrate, adopt Ag slurry or plated metal Ag, so that good ohmic contact can be formed with substrate.
16. preparation methods in conjunction with nano structure of zinc oxide extra small suede solar cell according to claim 6, is characterized in that, step I) described in sintering adopt chain-type sintering furnace or pipe type sintering furnace, to form ohmic contact.
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