CN104538470A - Silicon nanowire array based solar battery and preparation method thereof - Google Patents
Silicon nanowire array based solar battery and preparation method thereof Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 109
- 239000010703 silicon Substances 0.000 title claims abstract description 109
- 239000002070 nanowire Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 75
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 24
- 238000005566 electron beam evaporation Methods 0.000 claims abstract description 20
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 13
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 4
- 238000001312 dry etching Methods 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 27
- 229910052782 aluminium Inorganic materials 0.000 claims description 26
- 239000004411 aluminium Substances 0.000 claims description 26
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- 238000000151 deposition Methods 0.000 claims description 18
- 230000008021 deposition Effects 0.000 claims description 18
- 239000008187 granular material Substances 0.000 claims description 15
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- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000006056 electrooxidation reaction Methods 0.000 claims description 10
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 5
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- -1 titanium-nickel-aluminium Chemical compound 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000007853 buffer solution Substances 0.000 claims description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 2
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- 238000010248 power generation Methods 0.000 abstract 1
- 238000002310 reflectometry Methods 0.000 abstract 1
- 230000002463 transducing effect Effects 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000010408 film Substances 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
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- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 238000000137 annealing Methods 0.000 description 1
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- 230000031700 light absorption Effects 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
- H01L31/202—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials including only elements of Group IV of the Periodic System
-
- 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
Abstract
The invention discloses a silicon nanowire array based solar battery and a preparation method of the silicon nanowire array based solar battery, aiming at solving the problems that the textured structure of the existing solar battery has high reflectivity and the carrier collection efficiency is low. The silicon nanowire array based solar battery comprises an N back electrode (6) and an N type silicon substrate (5), wherein a nanowire array structure is formed on the upper surface of the N type silicon substrate (5) through dry etching, an intrinsic amorphous silicon layer (4) and a P-type amorphous silicon layer (3) are sequentially formed on the upper surface of the nanowire array structure through plasma chemical vapor deposition, the magnetron sputtering process is adopted to form an ITO (indium tin oxide) transparent conductive membrane (2), and a positive electrode (1) is formed at the top end of the a nanowire array structure through electron beam evaporation. As the silicon nanowire array structure is adopted, the solar battery has a good light trapping effect, the carrier collection efficiency is improved, a transducing mechanism is facilitated to absorb and utilize photons, the conversion efficiency of the solar battery is improved and the solar battery can be applied to the photovoltaic power generation.
Description
Technical field
The present invention relates to the technical field of solar cell, particularly relate to a kind of solar cell based on silicon nanowire array, can be used for photovoltaic generation.
Background technology
Because solar energy is abundant and clean, for energy related application widely, photovoltaic device very attractive.But, silica-based low with electricity conversion that is other solar cells at present, make the cost of solar cell higher, hinder its development and application.The optoelectronic transformation efficiency of solar cell is defined as the electricity output of solar cell and the ratio of the solar energy of solar cell surface region incidence.In the making of actual solar cell, there is several factors to limit the performance of device, thus must consider the impact of these factors in the design of solar cell and the selection of material etc.
In order to improve the optoelectronic transformation efficiency of solar cell, needing to adopt and falling into light technology.When light is through these structures, can scattering be there is in light beam, scattered light enters the absorbed layer of hull cell with larger incidence angle, and because the refraction coefficient of absorbed layer material is usually high than the refractive index of surrounding material, the light beam of large-angle scatter is easy to total reflection occurs in absorbed layer.Total reflection light beam oscillate in absorbed layer, until the generation photo-generated carrier that is absorbed by the absorption layer.Like this by falling into light technology, effectively can improve the light absorption of thin-film solar cells, thus improve cell conversion efficiency.
The light trapping structure of existing solar cell surface adopts three-dimensional inverted trapezoidal structure usually, and section as shown in Figure 2.Its structure is respectively from top to bottom: metal electrode 1, ITO indium tin oxide transparent conducting film 2, P-type non-crystalline silicon layer 3, intrinsic amorphous silicon layer 4, N-type silicon substrate 5, back electrode 6.Substrate surface by wet etching, forms the surface having three-dimensional inverted trapezoidal repetitive, then plasma chemical vapor deposition PECVD intrinsic amorphous silicon layer and P-type non-crystalline silicon layer thereon, forms the energy transfer mechanism with three-dimensional inverted trapezoidal light trapping structure.When the incident battery surface light of light can in its surperficial continuous reflection, increase the effective exercise length of light in battery surface light trapping structure and order of reflection, thus energization switching mechanism is to the absorption efficiency of light.But this structure due to matte size uneven and distributed more widely, substrate surface defect concentration is increased greatly, is difficult to obtain high-quality matte at front surface and falls into light, not easily reduce substrate to the reflection coefficient of light.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, proposes a kind of solar cell based on silicon nanowire array, to reduce the reflection of light, improves the absorption to photon and utilization, improves the transformation efficiency of solar cell.
For achieving the above object, the solar cell based on silicon nanowire array that the present invention proposes, comprise back electrode 6 and N-type silicon substrate 5, it is characterized in that: the upper surface of N-type silicon substrate 5 adopts nanowire array structure, this nanowire array structure upper surface is sequentially laminated with intrinsic amorphous silicon layer 4, P-type non-crystalline silicon layer 3 and ITO Indium-tin Oxide Transparent Conductive Film 2, and the top of nanowire array structure is provided with positive electrode 1.
As preferably, described P-type non-crystalline silicon layer 3 thickness is 10-15nm.
As preferably, described intrinsic amorphous silicon layer 4 thickness is 10-15nm
As preferably, described N-type silicon substrate 5 thickness is 200-400 μm.
As preferably, in described nano-wire array, the diameter of every root silicon nanowires is 40-80nm, and length is 5-10 μm.
As preferably, described positive electrode 1 adopts thickness to be the titanium-nickel-aluminium multiple layer metal material of 20nm/20nm/40nm.
For achieving the above object, preparation method of the present invention comprises the steps:
1) N-type silicon substrate is cleaned;
2) N-type silicon substrate after cleaning is placed in the KOH solution that concentration is 15%-30%, is heated to 65-70 DEG C, soaks 10 minutes, polishing is carried out to it, remove the surperficial mechanical damage of N-type silicon substrate;
3) in N-type silicon substrate, etching forms silicon nanowire array;
3a) in N-type silicon substrate, electron beam evaporation thickness is the metallic aluminium of 50nm-10 μm;
3b) evaporation is had the print of metallic aluminium be placed in 0.3mol/L oxalic acid or mass fraction be 15% sulfuric acid solution carry out electrochemical corrosion, form aperture;
3c) print after electrochemical corrosion is put into mass fraction be 5% phosphoric acid or mass fraction be 6% phosphoric acid and mass fraction be 1.8% chromic acid mixture soak, remove the aluminium oxide that contacts with lower floor silicon bottom aperture and change the size of aperture, the mesh structural porous anodised aluminium thin layer of formation rule;
3d) in step 3c) the porous anodic aluminium oxide thin layer surface that formed is the metal nickel dam of 5-10nm in electron beam evaporation a layer thickness, and removes anodised aluminium thin layer with aqueous slkali, and N-type silicon substrate obtains metallic nickel nano granule dot matrix;
3e) utilizing step 3d) the metallic nickel nano granule dot matrix that obtains is as template, and dry etching silicon substrate, obtains silicon nanowire array, then removes metallic nickel nano granule with acid solution;
4) having using plasma in the N-type substrate of silicon nanowire array structure to strengthen chemical vapour deposition (CVD) PECVD deposition thickness on surface is the intrinsic amorphous silicon layer of 10-15nm;
5) in intrinsic amorphous silicon layer, using plasma strengthens the P-type non-crystalline silicon layer that chemical vapour deposition (CVD) PECVD deposition thickness is 15-20nm;
6) on P-type non-crystalline silicon layer, magnetron sputtering deposition ITO indium tin oxide transparent conducting film is adopted, as transparent conductive electrode;
7) adopt on ITO indium tin oxide transparent conducting film electron beam evaporation process successively deposit thickness be Titanium, nickel, the aluminium of 20nm/20nm/40nm, and etching formed positive electrode;
8) electron beam evaporation process deposit thickness is adopted to be that 60nm aluminium is as back electrode at the N-type silicon substrate back side;
9) there is the print of metal electrode to carry out thermal anneal process front and back evaporation, make the material alloys that the metal of electron beam evaporation contacts with them, form electrode.Complete the preparation based on silicon nanowire array solar cell.
The invention has the advantages that:
1. preparing what use in the whole process of this solar cell is all conventional semiconductor equipment, and technique is simple;
2. adopt nanowire array structure, there is good sunken light effect, and improve the collection efficiency of charge carrier, improve the energy conversion efficiency of solar cell.
Accompanying drawing explanation
Fig. 1 is cross-sectional view of the present invention.
Fig. 2 is existing non-crystal silicon solar cell structural representation.
Fig. 3 is fabrication processing figure of the present invention.
Embodiment
With reference to Fig. 1, the present invention sends out and draws together positive electrode 1, ITO Indium-tin Oxide Transparent Conductive Film 2, P-type non-crystalline silicon layer 3, intrinsic amorphous silicon layer 4, N-type silicon substrate 5 and back electrode 6, wherein back electrode 6 is positioned at N-type silicon substrate 5 back side, the upper surface of N-type silicon substrate 5 adopts nanowire array structure, intrinsic amorphous silicon layer 4, P-type non-crystalline silicon layer 3 and ITO Indium-tin Oxide Transparent Conductive Film 2 are sequentially laminated on this nanowire array structure surface, and positive electrode 1 is arranged on the top of nanowire array structure.Described front electrode 1 adopts thickness to be the titanium-nickel-aluminium multilayer metallic electrode of 20nm/20nm/40nm; Described P-type non-crystalline silicon layer 3 is 10-15nm with intrinsic amorphous silicon layer 4 thickness; In described silicon nanowire array, the diameter of every root silicon nanowires is 40-80nm, and length is 5-10 μm; The thickness of described N-type silicon substrate 5 is 200-400 μm.
Below provide three embodiments made based on the solar cell of silicon nanowire array:
Embodiment 1, the diameter making every root silicon nanowires is 40nm, and length is the solar cell of the silicon nanowire array of 5 μm.
With reference to Fig. 3, the making step of this example is as follows:
Step 1: cleaning, polishing N-type silicon substrate, to remove surface contaminant and surperficial mechanical damage.
(1.1) acetone and isopropyl alcohol is used to hocket Ultrasonic Cleaning to N-type silicon substrate 5, to remove substrate surface Organic Pollution;
(1.2) mixed solution of the ammoniacal liquor of 1:1:3, hydrogen peroxide, deionized water is configured, and be heated to 120 DEG C, N-type silicon substrate 5 is placed in this mixed solution to soak 12 minutes, uses a large amount of deionized water rinsing after taking-up, to remove N-type silicon substrate 5 surface inorganic pollutant;
(1.3) N-type silicon substrate 5 HF acid buffer is soaked 2 minutes, remove the oxide layer on surface.
(1.4) N-type silicon substrate 5 after cleaning is placed in the KOH solution that concentration is 15%, is heated to 65 DEG C, soaks 10 minutes, polishing is carried out to it, go the surperficial mechanical damage of N-type silicon substrate 5.
Step 2: adopt dry etch process to make silicon nanowire array in N-type silicon substrate.
2.1) in N-type silicon substrate, electron beam evaporation thickness is the metallic aluminium of 50nm;
2.2) there is the print of metallic aluminium to be placed in 0.3mol/L oxalic acid solution evaporation and carry out electrochemical corrosion, form aperture;
2.3) print after electrochemical corrosion is put into mass fraction be 5% phosphoric acid and mass fraction be 1.8% chromic acid mixture soak, remove the aluminium oxide that contacts with lower floor silicon bottom aperture and change the size of aperture, the mesh structural porous anodised aluminium thin layer of formation rule;
2.4) in step 2.3) the porous anodic aluminium oxide thin layer surface that formed is the metal nickel dam of 5nm in electron beam evaporation a layer thickness, remove anodised aluminium thin layer by the NaOH solution that concentration is 0.4mol/L, N-type silicon substrate obtains metallic nickel nano granule dot matrix;
2.5) step 2.4 is utilized) the metallic nickel nano granule dot matrix that obtains is as template, adopt sense coupling N-type silicon substrate, obtain silicon nanowire array, every root silicon nanowires diameter is 40nm, length is 5 μm, then removes metallic nickel nano granule with the nitre acid that concentration ratio is 1:1 with the mixed solution of hydrofluoric acid.
Step 3: carry out twice deposit in the N-type silicon substrate forming nano-wire array, forms intrinsic amorphous silicon layer and P-type non-crystalline silicon layer respectively.
3.1) using plasma strengthens chemical vapour deposition (CVD) PECVD deposition thickness in the N-type silicon substrate forming nanowire array structure is the intrinsic amorphous silicon layer of 10nm, and its deposition power is 100W, SiH
4with H
2concentration ratio is 1:200, reative cell pressure 100Pa, and substrate temperature 300 DEG C, as Fig. 3-c;
3.2) in intrinsic amorphous silicon layer, using plasma strengthens the P-type non-crystalline silicon layer that chemical vapor deposition PECVD deposition thickness is 10nm, its deposition power 100W, SiH
4with B
2h
6concentration ratio is 100:1, SiH
4with CH
4concentration ratio is 5:1, reative cell pressure 100Pa, and substrate temperature 250 DEG C, as Fig. 3-d.
Step 4: adopt magnetron sputtering deposition ITO indium tin oxide transparent conducting film on P-type non-crystalline silicon layer, as transparency electrode, as Fig. 3-e.
Step 5: adopt on ITO indium tin oxide transparent conducting film electron beam evaporation process successively deposit thickness be Titanium, nickel, the aluminium of 20nm/20nm/40nm, and etching formed front electrode, as Fig. 3-f.
Step 6: adopt at the N-type silicon substrate back side electron beam evaporation process deposit thickness be 60nm aluminium as back electrode, as Fig. 3-g.
Step 7: have the print of metal electrode to carry out annealing in process front and back evaporation, make the material alloys that the metal of electron beam evaporation contacts with them, form the electrode of battery, as Fig. 3-h, complete the preparation of whole solar cell.
Embodiment 2, the diameter making every root silicon nanowires is 60nm, and length is the solar cell of the silicon nanowire array of 8 μm.
With reference to Fig. 3, the making step of this example is as follows:
Step one: cleaning, polishing N-type silicon substrate, to remove surface contaminant and surperficial mechanical damage.
This step is identical with the step 1 of embodiment 1.
Step 2: adopt dry etch process to make silicon nanowire array in N-type silicon substrate.
2a) in N-type silicon substrate, electron beam evaporation thickness is the metallic aluminium of 1 μm;
2b) there is the print of metallic aluminium to be placed in 0.3mol/L oxalic acid solution evaporation and carry out electrochemical corrosion, form aperture;
2c) print after electrochemical corrosion is put into mass fraction be 5% phosphoric acid and mass fraction be 1.8% chromic acid mixture soak, remove the aluminium oxide that contacts with lower floor silicon bottom aperture and change the size of aperture, the mesh structural porous anodised aluminium thin layer of formation rule;
2d) in step 2c) the porous anodic aluminium oxide thin layer surface that formed is the metal nickel dam of 8nm in electron beam evaporation a layer thickness, remove anodised aluminium thin layer by the NaOH solution that concentration is 0.4mol/L again, N-type silicon substrate obtains metallic nickel nano granule dot matrix;
2e) utilizing step 2d) the metallic nickel nano granule dot matrix that obtains is as template, adopt sense coupling N-type silicon substrate, obtain silicon nanowire array, every root silicon nanowires diameter is 60nm, length is 8 μm, then removes metallic nickel nano granule with the nitre acid that concentration ratio is 1:1 with the mixed solution of hydrofluoric acid.
Step 3: carry out twice deposit in the N-type silicon substrate forming nano-wire array, forms intrinsic amorphous silicon layer and P-type non-crystalline silicon layer respectively.
3a) using plasma strengthens chemical vapour deposition (CVD) PECVD deposition thickness in the N-type silicon substrate forming nanowire array structure is the intrinsic amorphous silicon layer of 13nm, and its deposition power is 100W, SiH
4with H
2concentration ratio is 1:200, reative cell pressure 100Pa, and substrate temperature 300 DEG C, as Fig. 3-c.
3b) in intrinsic amorphous silicon layer, using plasma strengthens the P-type non-crystalline silicon layer that chemical vapor deposition PECVD deposition thickness is 13nm, SiH
4with B
2h
6concentration ratio is 100:1, SiH
4with CH
4concentration ratio is 5:1, reative cell pressure 100Pa, and substrate temperature 250 DEG C, as Fig. 3-d.
Step 4: identical with the step 4 of embodiment 1.
Step 5: identical with the step 5 of embodiment 1.
Step 6: identical with the step 6 of embodiment 1.
Step 7: identical with the step 7 of embodiment 1, completes the preparation of whole solar cell.
Embodiment 3, the diameter making every root silicon nanowires is 80nm, and length is the solar cell of the silicon nanowire array of 10 μm.
With reference to Fig. 3, the making step of this example is as follows:
Steps A: cleaning, polishing N-type silicon substrate, to remove surface contaminant and surperficial mechanical damage.
This step is identical with the step 1 of embodiment 1.
Step B: adopt dry etch process to make silicon nanowire array in N-type silicon substrate.
B.1) in N-type silicon substrate, electron beam evaporation thickness is the metallic aluminium of 10 μm;
B.2) by evaporation have the print of metallic aluminium be placed in mass fraction be 15% sulfuric acid solution carry out electrochemical corrosion, formed aperture;
B.3) print after electrochemical corrosion is put into mass fraction be 6% phosphoric acid and mass fraction be 1.8% chromic acid mixture soak, remove the aluminium oxide that contacts with lower floor silicon bottom aperture and change the size of aperture, the mesh structural porous anodised aluminium thin layer of formation rule;
B.4) the porous anodic aluminium oxide thin layer surface in step B.3) formed is the metal nickel dam of 10nm in electron beam evaporation a layer thickness, and remove anodised aluminium thin layer by the NaOH solution that concentration is 0.4mol/L, N-type silicon substrate obtains metallic nickel nano granule dot matrix;
B.5) step is utilized B.4) the metallic nickel nano granule dot matrix that obtains is as template, adopt sense coupling N-type silicon substrate, obtain silicon nanowire array, every root silicon nanowires diameter is 80nm, length is 10 μm, then removes metallic nickel nano granule with the nitre acid that concentration ratio is 1:1 with the mixed solution of hydrofluoric acid.
Step C: carry out twice deposit in the N-type silicon substrate forming nano-wire array, forms intrinsic amorphous silicon layer and P-type non-crystalline silicon layer respectively.
C.1) using plasma strengthens chemical vapour deposition (CVD) PECVD deposit in the N-type silicon substrate forming nanowire array structure is the intrinsic amorphous silicon layer of thickness 15nm, and its deposition power is 100W, SiH
4with H
2concentration ratio is 1:200, reative cell pressure 100Pa, and substrate temperature 300 DEG C, as Fig. 3-c.
C.2) in intrinsic amorphous silicon layer, using plasma strengthens the P-type non-crystalline silicon layer of chemical vapor deposition PECVD deposition thickness 15nm, SiH
4with B
2h
6concentration ratio is 100:1, SiH
4with CH
4concentration ratio is 5:1, reative cell pressure 100Pa, and substrate temperature 250 DEG C, as Fig. 3-d.
Step D: identical with the step 4 of embodiment 1.
Step e: identical with the step 5 of embodiment 1.
Step F: identical with the step 6 of embodiment 1.
Step G: identical with the step 7 of embodiment 1, completes the preparation of whole solar cell.
Claims (10)
1. the solar cell based on silicon nanowire array, comprise back electrode (6) and N-type silicon substrate (5), it is characterized in that: the upper surface of N-type silicon substrate (5) adopts nanowire array structure, this nanowire array structure upper surface is sequentially laminated with intrinsic amorphous silicon layer (4), P-type non-crystalline silicon layer (3) and ITO Indium-tin Oxide Transparent Conductive Film (2), and the top of nanowire array structure is provided with positive electrode (1).
2. the solar cell based on silicon nanowire array according to claim 1, is characterized in that: the thickness of P-type non-crystalline silicon layer (3) and intrinsic amorphous silicon layer (4) is 10-15nm.
3. the solar cell based on silicon nanowire array according to claim 1, is characterized in that: in silicon nanowire array structure, the diameter of every root silicon nanowires is 40-80nm, and length is 5-10 μm.
4. the solar cell based on silicon nanowire array according to claim 1, is characterized in that: N-type silicon substrate (5) thickness is 200-400 μm.
5. the solar cell based on silicon nanowire array according to claim 1, is characterized in that: front electrode (1) employing thickness is the titanium-nickel-aluminium multiple layer metal material of 20nm/20nm/40nm.
6. the solar cell based on silicon nanowire array according to claim 1, is characterized in that: back electrode (6) adopts thickness to be the metallic aluminum material of 60nm.
7., based on a preparation method for the solar cell of silicon nanowire array, comprise the steps:
1) N-type silicon substrate is cleaned;
2) N-type silicon substrate after cleaning is placed in the KOH solution that concentration is 15%-30%, is heated to 65-70 DEG C, soaks 10 minutes, polishing is carried out to it, remove the surperficial mechanical damage of N-type silicon substrate;
3) in N-type silicon substrate, etching forms silicon nanowire array;
3a) in N-type silicon substrate, electron beam evaporation thickness is the metallic aluminium of 50nm-10 μm;
3b) evaporation is had the print of metallic aluminium be placed in 0.3mol/L oxalic acid or mass fraction be 15% sulfuric acid solution carry out electrochemical corrosion, form aperture;
3c) print after electrochemical corrosion is put into mass fraction be 5% phosphoric acid or mass fraction be 6% phosphoric acid and mass fraction be 1.8% chromic acid mixture soak, remove the aluminium oxide that contacts with lower floor silicon bottom aperture and change the size of aperture, the mesh structural porous anodised aluminium thin layer of formation rule;
3d) in step 3c) the porous anodic aluminium oxide thin layer surface that formed again electron beam evaporation a layer thickness be the metal nickel dam of 5-10nm, and remove electric anodised aluminium thin layer with aqueous slkali, N-type substrate obtain metallic nickel nano granule dot matrix;
3e) utilizing step 3d) the metallic nickel nano granule dot matrix that obtains is as template, and dry etching N-type silicon substrate, obtains silicon nanowire array, then removes metallic nickel nano granule with acid solution;
4) there is using plasma in the N-type substrate of silicon nanowire array structure to strengthen the intrinsic amorphous silicon layer of chemical vapour deposition (CVD) PECVD deposition thickness 10-15nm on surface;
5) in intrinsic amorphous silicon layer, using plasma strengthens the P-type non-crystalline silicon layer that chemical vapour deposition (CVD) PECVD deposition thickness is 15-20nm;
6) on P-type non-crystalline silicon layer, magnetron sputtering deposition ITO indium tin oxide transparent conducting film is adopted, as transparent conductive electrode;
7) adopt on ITO indium tin oxide transparent conducting film electron beam evaporation process successively deposit thickness be Titanium, nickel, the aluminium of 20nm/20nm/40nm, and etching formed positive electrode;
8) electron beam evaporation process deposit thickness is adopted to be that 60nm aluminium is as back electrode at the N-type silicon substrate back side;
9) there is the print of metal electrode to carry out thermal anneal process front and back evaporation, make the material alloys that the metal of electron beam evaporation contacts with them, form electrode, complete the preparation based on silicon nanowire array solar cell.
8. method according to claim 7, is characterized in that step 1) described in clean its step to N-type silicon substrate as follows:
Acetone and isopropyl alcohol 1a) is used to hocket Ultrasonic Cleaning to N-type silicon substrate, to remove substrate surface Organic Pollution;
1b) configure the mixed solution of the ammoniacal liquor of 1:1:3, hydrogen peroxide, deionized water, and be heated to 120 DEG C, N-type silicon substrate is placed in this mixed solution and soaks 12 minutes, take out rear deionized water rinsing, to remove N-type silicon substrate surface inorganic pollutant;
1c) N-type silicon substrate HF acid buffer is soaked 2 minutes, remove the oxide layer on surface.
9. method according to claim 7, is characterized in that step 4) described in plasma enhanced CVD, its deposition power is 100W, SiH
4with H
2concentration ratio is 1:200, reative cell pressure 100Pa, substrate temperature 300 DEG C.
10. method according to claim 7, is characterized in that step 5) described in plasma enhanced chemical vapor deposition, its deposition power is 100W, SiH
4with B
2h
6concentration ratio is 100:1, SiH
4with CH
4concentration ratio is 5:1, reative cell pressure 100Pa, substrate temperature 250 DEG C.
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