CN104868019A - Laser etching grid a-Si/c-Si radial heterojunction battery and preparation method thereof - Google Patents
Laser etching grid a-Si/c-Si radial heterojunction battery and preparation method thereof Download PDFInfo
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- CN104868019A CN104868019A CN201510173010.XA CN201510173010A CN104868019A CN 104868019 A CN104868019 A CN 104868019A CN 201510173010 A CN201510173010 A CN 201510173010A CN 104868019 A CN104868019 A CN 104868019A
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- 229910021417 amorphous silicon Inorganic materials 0.000 title claims abstract description 58
- 229910021419 crystalline silicon Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000010329 laser etching Methods 0.000 title abstract description 4
- 239000000758 substrate Substances 0.000 claims abstract description 61
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 41
- 239000010703 silicon Substances 0.000 claims abstract description 41
- 238000000608 laser ablation Methods 0.000 claims abstract description 24
- 238000000151 deposition Methods 0.000 claims abstract description 20
- 238000005530 etching Methods 0.000 claims abstract description 17
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 15
- 238000004140 cleaning Methods 0.000 claims abstract description 14
- 238000001259 photo etching Methods 0.000 claims abstract description 10
- 238000007639 printing Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 40
- 239000008367 deionised water Substances 0.000 claims description 18
- 230000008021 deposition Effects 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000007650 screen-printing Methods 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002679 ablation Methods 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 5
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 4
- 241000931526 Acer campestre Species 0.000 claims description 3
- 230000003287 optical effect Effects 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
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002061 nanopillar Substances 0.000 claims 3
- 238000005516 engineering process Methods 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 8
- 238000002310 reflectometry Methods 0.000 abstract description 5
- 229910021421 monocrystalline silicon Inorganic materials 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 5
- 239000002800 charge carrier Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000001795 light effect Effects 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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
- H01L31/18—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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
- H01L31/0745—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells
- H01L31/0747—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells comprising a heterojunction of crystalline and amorphous materials, e.g. heterojunction with intrinsic thin layer or HIT® solar cells; solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 relates to a laser etching grid a-Si/c-Si radial heterojunction battery and a preparation method thereof, and belongs to the field of solar batteries. The preparation method comprises the steps of cleaning an N-type double-polished monocrystalline silicon substrate; forming a nanometer column graph by adopting a photoetching technology; forming a silicon nanometer column array by adopting ICP etching and removing a photoresist; forming an electrode trench pattern by adopting laser ablation; cleaning a laser ablation area; depositing intrinsic amorphous silicon at both sides of the N-type substrate; depositing P-type amorphous silicon at the obverse side of the N-type substrate, and depositing N-type amorphous silicon at the reverse side of the N-type substrate; depositing ITO at both sides of a silicon wafer; precisely aligning and printing an Ag electrode in the electrode pattern area formed by laser ablation at the obverse side, baking the Ag electrode, printing a full-Ag electrode at the reverse side and baking the full-Ag electrode. The battery provided by the invention has low reflectivity and good electrode contact, combines an advantage of high open-circuit voltage of a heterojunction battery and an advantage of good photon-generated carrier collecting ability of a radial junction battery, and the battery efficiency is improved obvious compared with a traditional battery.
Description
Technical field
The invention belongs to solar cell field, is a kind ofly relate to the preparation of silicon micron post array and the new and effective a-Si/c-Si solar cell that is combined with laser etching techniques of multiple gas phase deposition technology.
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, has the energy extensive, and region restriction is lacked, safe and reliable many advantages such as grade.
From first piece of silicon solar cell application in 1954 so far, solar cell have passed through first generation single crystal silicon solar cell, the development of second generation hull cell, but current high cost of electricity-generating still seriously limits the further extensive use of solar cell, therefore from the development of current photovoltaic solar battery, its technology trends is that cost reduces, and efficiency improves.
Radial junction battery, relative to planar junction battery, can effectively be separated, reduce the recombination probability of photo-generated carrier to charge carrier, effectively can improve the short circuit current of solar cell.The present invention adopts photoetching to prepare bulk silicon micron post array in conjunction with ICP lithographic technique, and the anti-reflection had to a certain degree falls into light effect, and 300-1200nm average reflectance can be low to moderate 15%, has clear improvement relative to about 36% of planar silicon; Laser ablation forms electrode pattern zygomite reticulated printing and accurately aims at screen printed electrode, significantly can improve silica-based micro-nano structure electrode contact problems; Intrinsic amorphous silicon can realize good passivation effect to crystal silicon surface, and c-Si/a-Si heterojunction has the open circuit voltage higher compared with conventional crystalline silicon battery; The heterojunction formed on this basis, solves the structure problem of original planar junction battery, effectively improves short circuit current.This battery structure has lower reflectivity, strengthens light absorption, electrode contact obviously improves, fill factor, curve factor is improved, radial heterojunction has the compound that high open circuit voltage effectively can also reduce charge carrier simultaneously, is finally converted to photoelectric current, realizes higher battery efficiency.
Summary of the invention
The present invention is intended to solve the aforementioned problems in the prior.The object of the invention is to propose radial hetero-junction solar cell of a kind of laser incising grid c-Si/a-Si and preparation method thereof.
The embodiment of the present invention proposes the preparation method of the radial heterojunction solar cell of a kind of micrometer structure laser incising grid a-Si/c-Si, comprises the following steps:
A) the two monocrystalline substrate (201) of throwing of N-type is cleaned;
B) adopt photoetching process to form a micron post figure on a monocrystaline silicon substrate, this face is called front;
C) adopt in front ICP etching machine to etch, form silicon micron pillar array structure (203);
D) removal step c) N-type substrate residual photoresist (202);
E) laser ablation is adopted to steps d) the N-type silicon substrate tow sides that obtain carry out etching formation electrode trenches pattern (204);
F) to step e) laser ablation electrode trenches pattern (204) district is cleaned, remove laser ablation district damage layer and deposit;
G) in step f) tow sides of N-type substrate deposition intrinsic amorphous silicon (i-a-Si) (205) respectively;
H) in step g) N-type substrate has the front of micron post to be deposited on P-type non-crystalline silicon (p-a-Si) (206), in another side reverse side deposited n-type amorphous silicon (n-a-Si) (207);
I) adopt PVD in step h) N-type substrate tow sides all deposit ITO (208);
J) silk screen printing is adopted in step I) accurately aim in the electrode trenches pattern (204) that formed of laser ablation corresponding to N-type substrate front and print Ag electrode (209), and toast, the full Ag electrode of back face printing, and toast.
Further preferred according to the present invention, described N-type silicon chip carries out the step of cleaning, and be that the RCA cleaning process of use standard cleans silicon chip, washed with de-ionized water afterwards, nitrogen dries up.
Further preferred according to the present invention, the micron post figure that described employing photoetching process is formed is of a size of 2 μm.
Further preferred according to the present invention, the detailed process that described employing photoetching process forms micron post figure comprises:
Gas phase becomes counterdie: adopt HMDS (HMDS) to become counterdie, temperature 200 DEG C, time 20min; , spin coating: adopt sol evenning machine by positive glue (including but not limited to 9912) evenly spin coating in silicon chip one side in N-type substrate; Front baking: the silicon chip after even glue, at 85 DEG C-120 DEG C, vacuum hot plate toasts 30-60s; Aim at exposure; Development; Post bake.
Further preferred according to the present invention, the length of the silicon micron post that described ICP etching is formed is 5 μm.
Further preferred according to the present invention, the detailed process of described removal N-type substrate surface residual photoresist comprises: silicon chip soaks 60min in acetone soln; 10min is soaked in alcohol; Deionized water rinsing 10 times; Nitrogen dries up.
Further preferred according to the present invention, described employing laser ablation carries out N-type silicon substrate two sides etching in the step of formation electrode trenches pattern, and optical maser wavelength used is 1064nm, 532nm or 355nm.
Further preferred according to the present invention, described employing laser ablation carries out N-type silicon substrate two sides etching in the step of formation electrode trenches pattern, and ablation width is determined according to the width of design grid line, and general ablation width is wider than grid line width 15-25 μm.
Further preferred according to the present invention, described cleans laser ablation district, and remove in the step of laser ablation district damage layer and deposit, the corrosive liquid of cleaning is rare NaOH solution, afterwards deionized water rinsing 10 times, and nitrogen dries up.
Further preferred according to the present invention, described includes but not limited to PECVD in the method on N-type substrate two sides difference deposition intrinsic amorphous silicon (i-a-Si).
Further preferred according to the present invention, described is 5-15nm at the thickness on N-type substrate two sides difference deposition intrinsic amorphous silicon (i-a-Si).
Further preferred according to the present invention, described has the one side of micron post to be deposited on P-type non-crystalline silicon (p-a-Si) in N-type substrate, includes but not limited to PECVD in the method for another side deposited n-type amorphous silicon (n-a-Si).
Further preferred according to the present invention, described has the one side of micron post to be deposited on P-type non-crystalline silicon (p-a-Si) in N-type substrate, is 10-20nm at the thickness of another side deposited n-type amorphous silicon (n-a-Si).
Further preferred according to the present invention, described employing PVD includes but not limited to magnetron sputtering in the method for silicon chip two sides deposition ITO.
Further preferred according to the present invention, described employing PVD is respectively front 70-90nm and reverse side 150-250nm at the thickness of silicon chip two sides deposition ITO.
Further preferred according to the present invention, printing Ag electrode is accurately aimed in described employing silk screen printing in the electrode pattern region that face, N-type substrate front laser ablation is formed, and in the step of baking, silk screen printing alignment precision reaches 1 μm.
Further preferred according to the present invention, the temperature of described baking is 150 ~ 200 DEG C, and the time is 200 ~ 600s.
Radial hetero-junction solar cell of laser incising grid a-Si/c-Si of the present invention and preparation method thereof, can preparation size uniform micron post array, combines radial hetero-junction solar cell prepared by laser etching techniques and gas phase deposition technology have plurality of advantages on this basis.This battery structure, because micron post array effectively can increase the propagation path of light, effective reduction reflectivity (reflectivity is about 15%), therefore the light absorpting ability of crystal silicon material can be significantly improved, laser ablation zygomite reticulated printing forms electrode can effectively solve micro-nano structure electrode contact problems, it is parallel with light incident direction that radial junction structure (PN junction is vertical with light incident direction) changes conventional batteries PN junction, carrier transport distance effectively reduces, Carrier recombination probability reduces, improve the transport capability of charge carrier, add photogenerated current, heterostructure also has high open circuit voltage simultaneously, battery conversion efficiency obviously improves.
Radial hetero-junction solar cell of laser incising grid a-Si/c-Si of the present invention and preparation method thereof, under the prerequisite of part with existing solar cell preparation technology compatibility, proposes innovation structure, and provides effective preparation method, to improve the conversion efficiency of solar cell.
The aspect that the present invention adds and advantage will part provide in the following description, and part will become obvious from the following description, or be recognized by practice 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 preparation method's flow chart of the radial hetero-junction solar cell of laser incising grid a-Si/c-Si of the embodiment of the present invention;
Fig. 2-Fig. 9 is the schematic diagram of each production phase of the radial hetero-junction solar cell of laser incising grid a-Si/c-Si of the embodiment of the present invention;
Wherein Fig. 2 is that photoetching forms micron rod structure figure;
Fig. 3 forms silicon micron rod structure (with residual photoresist) figure for adopting ICP etching;
Fig. 4 is the silicon micron rod structure figure after removing photoresist;
Fig. 5 is that employing is laser-ablated in and figure after electrode pattern prepares by silicon micron post substrate face;
Fig. 6 is figure after the deposition intrinsic amorphous silicon of silicon substrate two sides;
Fig. 7 is at silicon substrate front deposition P-type non-crystalline silicon, overleaf figure after deposited n-type amorphous silicon;
Fig. 8 is figure after the deposition ITO of silicon substrate two sides;
Fig. 9 is figure after screen printing electrode.
201 monocrystalline substrate, 202 photoresists, 203 silicon micron pillar array structures, 204 electrode trenches patterns, 205 intrinsic amorphous silicons, 206P type amorphous silicon, 207N type amorphous silicon, 208ITO, 209Ag electrode.
Embodiment
The present invention relates generally to radial hetero-junction solar cell of a kind of laser incising grid a-Si/c-Si and preparation method thereof.Disclosing hereafter provides many different embodiments or example is used for realizing different structure of the present invention.Of the present invention open in order to simplify, hereinafter the parts of specific examples and setting are described.Certainly, they are only example, do not form restriction of the present invention.In addition, the present invention can in different example repeat reference numerals and/or letter.This repetition is to simplify and clearly object, itself does not indicate the relation between discussed various embodiment and/or setting.In addition, the various specific technique that the invention provides and the example of material, but those of ordinary skill in the art can recognize the property of can be applicable to of other techniques and/or the use of other materials.
Embodiment 1
The flow chart of the radial hetero-junction solar cell of laser incising grid c-Si/a-Si according to an embodiment of the invention and preparation method thereof is respectively illustrated with reference to figure 1 and Fig. 2, Fig. 2 and Fig. 1.
(1) in a step 101, first n type single crystal silicon substrate 201 is cleaned.Preferably, concrete technology flow process is: 1, N-shaped monocrystalline substrate is placed in acetone ultrasonic cleaning 15min, deionized water rinsing 10 times; N-shaped monocrystalline substrate is placed in alcohol ultrasonic cleaning 15min by 2, deionized water rinsing 10 times; 3, N-shaped monocrystalline substrate is placed in H
2sO
4: H
2o
210min is cleaned in boiling in mixed solution of=3:1, deionized water rinsing 10 times, removes oxide layer in the HF solution of 5%; 4, N-shaped monocrystalline substrate is placed in NH
3h
2o:H
2o
2: H
270-80 DEG C of cleaning 10min in O=1:1:5 mixed solution, deionized water rinsing 10 times, removes oxide layer in the HF solution of 5%; 5, N-shaped monocrystalline substrate is placed in HCl:H
2o
2: H
270-80 DEG C of cleaning 10min in O=1:1:6 mixed solution, deionized water rinsing 10 times, removes oxide layer in the HF solution of 5%.
(2) then in a step 102, N-shaped monocrystalline substrate 201 adopt the method for photoetching prepare photoresist mask 202, as shown in Figure 2.Preferably, the mask aligner of employing is suss MA6, and model chosen by photoresist is 9912 positive photoresists, and sol evenning machine is even glue 1min under 3000 turns, front baking 60s at 100 DEG C, and the uv-exposure time is 5s, and developing time is 60s, post bake temperature 90s at 120 DEG C.Photoresist mask 202 be cylindrical shape, diameter is 2um, and the cycle is 6um, and thickness is 3um.
(3) in step 103, the N-shaped monocrystalline substrate 201 with photoresist mask 202 is placed in ICP etching machine etches described in Fig. 2, forms silicon micron post 203 array, as shown in Figure 3.Preferably, be ICP etching technics herein.The height of the silicon micron post of etching is 5um.
(4) at step 104, the photoresist 202 that the N-shaped monocrystalline substrate 201 with micron post array participates in is removed, as shown in Figure 4.Preferably, 1, first monocrystalline substrate is placed in acetone soln soaking and washing 30min, washed with de-ionized water; 2, be placed on soaking and washing 20min in alcohol, washed with de-ionized water;
(5) in step 105, use psec or femto-second laser to carry out laser ablation to the N-shaped monocrystalline substrate 201 removing photoresist 202, etch electrode pattern 204 (comprising main grid and thin grid), as shown in Figure 5.Preferably, the optical maser wavelength in step 105 is 355nm, 532nm and 1064nm, and etch period is 0.5-10s, and etching depth is 30um, and ablation width is determined, generally higher than grid line width 15-25 μm according to the width of design grid line.
(6) in step 106, the N-shaped monocrystalline substrate 201 etching electrode pattern 203 is carried out process and remove etch residue and damage layer, then carry out RCA cleaning.Preferably, concrete cleaning process is: the KOH solution 1, N-shaped monocrystalline substrate being placed in 0.1% soaks substrate 10min, deionized water rinsing 10 times; N-shaped monocrystalline substrate is placed in alcohol ultrasonic cleaning 15min by 2, deionized water rinsing 10 times; 3, N-shaped monocrystalline substrate is placed in H
2sO
4: H
2o
210min is cleaned in boiling in mixed solution of=3:1, deionized water rinsing 10 times, removes oxide layer in the HF solution of 5%; 4, N-shaped monocrystalline substrate is placed in NH
3h
2o:H
2o
2: H
270-80 DEG C of cleaning 10min in O=1:1:5 mixed solution, deionized water rinsing 10 times, removes oxide layer in the HF solution of 5%; 5, N-shaped monocrystalline substrate is placed in HCl:H
2o
2: H
270-80 DEG C of cleaning 10min in O=1:1:6 mixed solution, deionized water rinsing 10 times, removes oxide layer in the HF solution of 5%.
(7) in step 107, at N-shaped monocrystalline substrate 201 tow sides deposition intrinsic amorphous silicon 205, as shown in Figure 6.Preferably, PECVD deposition intrinsic amorphous silicon is used, concrete technology condition: back end vacuum is higher than 10
-7torr, underlayer temperature is 150-180 DEG C, and pressure is 0.36-0.5Torr, and radio frequency power density is 30-50mW/cm
2, frequency is 13.56MHz, and gas is SiH
4, gas flow is 4-10sccm, and the thickness of intrinsic amorphous silicon film is 5 ~ 15nm.
(8) in step 108, front intrinsic amorphous silicon 205 deposits P-type non-crystalline silicon 206, deposited n-type amorphous silicon 207 on reverse side intrinsic amorphous silicon 205, as shown in Figure 7.Preferably, PECVD is used to deposit P-type non-crystalline silicon, concrete technology condition: back end vacuum is higher than 10
-7torr, underlayer temperature is 150-180 DEG C, and pressure is 0.36-0.5Torr, and radio frequency power density is 30-80mW/cm
2, frequency is 13.56MHz, and gas is SiH
4, H
2and the BH of hydrogen dilution
3(for 0.5%), gas flow is respectively 4-10sccm, 12-30sccm, 20-60sccm, and the thickness of P-type non-crystalline silicon film is 10 ~ 20nm.Use PECVD deposited n-type amorphous silicon, concrete technology condition: back end vacuum is higher than 10
-7torr, underlayer temperature is 150-180 DEG C, and pressure is 0.36-0.5Torr, and radio frequency power density is 30-80mW/cm
2, frequency is 13.56MHz, and gas is SiH
4, H
2and the PH of hydrogen dilution
3(for 0.5%), gas flow is respectively 4-10sccm, 12-30sccm, 20-60sccm, and the thickness of N-type amorphous silicon membrane is 10 ~ 20nm.
(109) in step 109, P-type non-crystalline silicon 206 and N-type amorphous silicon 207 deposit ITO 208, as shown in Figure 8.Preferably, magnetron sputtering deposition ITO is used, concrete technology condition: back end vacuum is higher than 10
-7torr, underlayer temperature is 150-180 DEG C, and pressure is 10
-4-10
-6torr, radio frequency power density is 50-500mW/cm
2, frequency is 13.56MHz, and gas is Ar, O
2, gas flow is respectively 30-100sccm, 1-2sccm.In P-type non-crystalline silicon 206, the thickness of the ITO 208 of preparation is 70-90nm, and on N-type amorphous silicon 206, the thickness of the ITO 208 of preparation is 150-250nm.
(110) in step 110, silk screen printing, and toasted battery preparation, as shown in Figure 9.The temperature of preferred baking is 150 ~ 200 DEG C, and the time is 200 ~ 600s.
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.
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.
The present invention compared with prior art has following obvious advantage and beneficial effect:
1, micrometer structure is compared with traditional planar structure, can effectively reduce battery surface reflectivity, and has good sunken light effect, improves absorbing of light;
2, micrometer structure has auxiliaring effect to solar cell carrier transport aspect, can reduce carrier transport path, improves carrier collection efficiency, increases photogenerated current density;
In sum, the present invention is the micrometer structure and preparation method thereof for new and effective solar cell, under the prerequisite of part with existing solar cell preparation technology compatibility, proposes innovation structure, to improve the conversion efficiency of crystal silicon solar batteries, reduce the production cost of solar cell.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.
Range of application of the present invention is not limited to the technique of the specific embodiment described in specification, mechanism, manufacture, material composition, means, method and step.From disclosure of the present invention, to easily understand as those of ordinary skill in the art, for the technique existed at present or be about to develop, mechanism, manufacture, material composition, means, method or step later, wherein their perform the identical function of the corresponding embodiment cardinal principle that describes with the present invention or obtain the identical result of cardinal principle, can apply according to the present invention to them.Therefore, claims of the present invention are intended to these technique, mechanism, manufacture, material composition, means, method or step to be included in its protection range.
Claims (10)
1. a preparation method for the radial heterojunction solar cell of micrometer structure laser incising grid a-Si/c-Si, comprises the following steps:
A) the two monocrystalline substrate (201) of throwing of N-type is cleaned;
B) adopt photoetching process to form a micron post figure on a monocrystaline silicon substrate, this face is called front;
C) adopt in front ICP etching machine to etch, form silicon micron pillar array structure (203);
D) removal step c) N-type substrate residual photoresist (202);
E) laser ablation is adopted to steps d) the N-type silicon substrate tow sides that obtain carry out etching formation electrode trenches pattern (204);
F) to step e) laser ablation electrode trenches pattern (204) district is cleaned, remove laser ablation district damage layer and deposit;
G) in step f) tow sides of N-type substrate deposition intrinsic amorphous silicon (i-a-Si) (205) respectively;
H) in step g) N-type substrate has the front of micron post to be deposited on P-type non-crystalline silicon (p-a-Si) (206), in another side reverse side deposited n-type amorphous silicon (n-a-Si) (207);
I) adopt PVD in step h) N-type substrate tow sides all deposit ITO (208);
J) silk screen printing is adopted in step I) accurately aim in the electrode trenches pattern (204) that formed of laser ablation corresponding to N-type substrate front and print Ag electrode (209), and toast, the full Ag electrode of back face printing, and toast.
2. according to the method for claim 1, it is characterized in that described step of cleaning two throwing monocrystalline substrate is that the RCA cleaning process of use standard cleans silicon chip, washed with de-ionized water afterwards, nitrogen dries up;
The detailed process adopting photoetching process to form micron post figure comprises: gas phase becomes counterdie: adopt HMDS (HMDS) to become counterdie, temperature 200 DEG C, time 20min; , spin coating: adopt sol evenning machine by positive glue (including but not limited to 9912) evenly spin coating in silicon chip one side in N-type substrate; Front baking: the silicon chip after even glue, at 85 DEG C-120 DEG C, vacuum hot plate toasts 30-60s; Aim at exposure; Development; Post bake;
The detailed process of described removal N-type substrate surface residual photoresist comprises: silicon chip soaks 60min in acetone soln; 10min is soaked in alcohol; Deionized water rinsing 10 times; Nitrogen dries up;
Described employing laser ablation carries out N-type silicon substrate two sides etching in the step of formation electrode trenches pattern, and optical maser wavelength used is 1064nm, 532nm or 355nm;
To laser ablation, district is cleaned, and remove in the step of laser ablation district damage layer and deposit, the corrosive liquid of cleaning is rare NaOH solution, afterwards deionized water rinsing 10 times, and nitrogen dries up.
3. according to the method for claim 1, it is characterized in that, the nano-pillar figure that described employing photoetching process is formed is of a size of 2 μm.
4. according to the method for claim 1, it is characterized in that, the length of the silicon nano-pillar that described ICP etching is formed is 5 μm.
5. according to the method for claim 1, it is characterized in that, described employing laser ablation carries out N-type silicon substrate two sides etching in the step of formation electrode trenches pattern, and ablation width is determined according to the width of design grid line, and general ablation width is wider than grid line width 15-25 μm.
6. according to the method for claim 1, it is characterized in that, described is 5-15nm at the thickness on N-type substrate two sides difference deposition intrinsic amorphous silicon (i-a-Si).
7. according to the method for claim 1, it is characterized in that, described has the one side of nano-pillar to be deposited on P-type non-crystalline silicon (p-a-Si) in N-type substrate, is 10-20nm at the thickness of another side deposited n-type amorphous silicon (n-a-Si).
8. according to the method for claim 1, it is characterized in that, described is respectively front 70-90nm and reverse side 150-250nm at the thickness of silicon chip two sides deposition ITO.
9. according to the method for claim 1, it is characterized in that, printing Ag electrode is accurately aimed in described employing silk screen printing in the electrode pattern region that N-type substrate front laser ablation is formed, and in the step of baking, silk screen printing alignment precision reaches 1 μm.
10. according to the radial hetero-junction solar cell of laser incising grid a-Si/c-Si that the either method described in claim 1-9 obtains.
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