CN104167460A - Manufacturing method of solar energy cell - Google Patents
Manufacturing method of solar energy cell Download PDFInfo
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- CN104167460A CN104167460A CN201310183407.8A CN201310183407A CN104167460A CN 104167460 A CN104167460 A CN 104167460A CN 201310183407 A CN201310183407 A CN 201310183407A CN 104167460 A CN104167460 A CN 104167460A
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- silicon chip
- solar battery
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- manufacturing solar
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 74
- 239000010703 silicon Substances 0.000 claims abstract description 74
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 63
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 29
- 239000011574 phosphorus Substances 0.000 claims abstract description 29
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000003647 oxidation Effects 0.000 claims abstract description 23
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 238000009792 diffusion process Methods 0.000 claims abstract description 12
- 238000002161 passivation Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000000608 laser ablation Methods 0.000 claims abstract description 4
- 239000003292 glue Substances 0.000 claims abstract description 3
- 238000005530 etching Methods 0.000 claims description 17
- 238000007747 plating Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 15
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 13
- 230000002262 irrigation Effects 0.000 claims description 12
- 238000003973 irrigation Methods 0.000 claims description 12
- 150000003376 silicon Chemical class 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 238000007788 roughening Methods 0.000 claims description 9
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 claims description 7
- 238000000231 atomic layer deposition Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000007496 glass forming Methods 0.000 claims 1
- 150000002926 oxygen Chemical class 0.000 claims 1
- 150000003017 phosphorus Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000003667 anti-reflective effect Effects 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000010329 laser etching Methods 0.000 abstract 1
- 238000007781 pre-processing Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 68
- 210000004027 cell Anatomy 0.000 description 27
- 238000005516 engineering process Methods 0.000 description 20
- 239000010408 film Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000009713 electroplating Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 description 2
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QVMHUALAQYRRBM-UHFFFAOYSA-N [P].[P] Chemical compound [P].[P] QVMHUALAQYRRBM-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000005360 phosphosilicate glass Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000000427 thin-film deposition 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
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—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
-
- 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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
-
- 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 provides a manufacturing method of a solar energy cell. The manufacturing method comprises: providing a silicon chip; performing pre-processing on the silicon chip, and forming a P-N electrode through utilizing diffusion process; then heating the silicon chip in a thermal oxidation method; forming oxide layers on the two opposite surfaces of the silicon chip and forming an anti-reflective layer on the surface of the oxide layer of one side of the silicon chip; forming a trench on the anti-reflective layer through laser ablation or etching glue, and forming a metal electrode layer on the trench through an electrode galvanography. The silicon chip is heated through the thermal oxidation method, so that phosphorus diffusion depth is effectively increased, furthermore depletion region width of a diode is added, and conversion rate of the solar energy cell is more than 19%. In addition, the oxide layer formed on the other side of the silicon chip is favorable of making an emitter and a back passivation cell structure.
Description
Technical field
The invention relates to a kind of manufacture method of solar cell, particularly a kind of phosphorus diffusion depth and can arrange in pairs or groups electroplating technology and emitter-base bandgap grading and passivating back battery (Passivated Emitterand Rear Cell of increasing; PERC) manufacture method of the solar cell of technology.
Background technology
In early days, with the electrode of conventional semiconductors technology manufacturing, need to carry out unavoidably the steps such as gold-tinted, micro-shadow, thin film deposition in its preparation process, but the required floor space of these steps is larger, the required cost of equipment and processing procedure is high, and preparation process is quite complicated.
In the manufacturing process of general solar cell, for stressing under the principle of low manufacturing cost and high generated output, the manufacture of metal electrode also cannot be continued to use expensive semiconductor technology, therefore turns to the screen printing technology of simple and easy high yield again.Fabrography is that metal conductive paste is printed pattern to silicon substrate with direct mode of printing, after going through afterwards baking organic solvent being removed, finally in high temperature sintering mode by metal and silicon substrate formation synthetic to reach ohmic contact.
The pattern of front metal electrode mostly is fence type, can require front electrode to reduce the area coverage to light source shielding, in the hope of reaching the highest photoelectric conversion efficiency at the silicon substrate of fixed-area as far as possible.But for web plate technology, the live width of fence type has a least limit eventually, the fine rule that current best technology can reach 55～50 μ m is wide, estimates that the final limit is 45 μ m.In this, for pursuing advanced solar energy highly effective processing procedure, turn one's attention to electroplating technology, wish to manufacture more careful fence type electrode, also can produce more low-resistance ohmic contact.For solar energy manufacturing process and cost budgeting, the electroplating technology that semiconductor uses is not conform with cost, therefore equipment vendor develops the exclusive photoinduction electroplating technology of solar cell, utilize the characteristic that this element itself can self-generating, make electroplate liquid to form electrode in particular block row redox reaction.
Summary of the invention
In order to address the above problem, the invention provides a kind of manufacture method of solar cell, mainly comprise the following step:
(1) provide a silicon chip, and carry out silicon wafer surface cleaning and roughening processing, make a first surface roughening of silicon chip.
(2) use phosphorus oxychloride (POCl
3) this first surface is carried out to a DIFFUSION TREATMENT, sequentially form a P-N diode on this silicon chip, wherein one of this P-N diode surface and at least one edge form phosphorous phosphorus glass;
(3) remove the phosphorus glass that P-N diode surface and edge form.
(4) utilize thermal oxidation method to heat silicon chip, and form one first oxide layer on the P-N diode surface of removing phosphorus glass (PSG).
(5) form an anti-reflecting layer in the first oxide layer.
(6) remove the anti-reflecting layer of part and form irrigation canals and ditches, and on irrigation canals and ditches, form a metal electrode layer.
In addition, optionally on another surface of silicon chip, form one second oxide layer.
Main purpose of the present invention, is to provide a kind of manufacture method of solar cell, wherein, increases by 0.2 to 0.3 μ m because the lifting of phosphorus concentration can make the thickness of P-N diode, and thus, the conversion ratio of solar cell will maintain more than 1 19.
Another object of the present invention, be to provide a kind of manufacture method of solar cell, wherein, because of used thermal oxidation method be easy to control can operating temperature scope, except can making the defect reduction of silicon chip surface, and there is the effect that absorbs metal impurities at the temperature-fall period of thermal oxidation, and allow solar cell reach better conversion ratio.
Another object of the present invention, is to utilize thermal oxidation method that oxide layer is heated silicon chip, and forms aforesaid the second oxide layer on another surface that is not formed with P-N diode, and this oxide layer will contribute to the cell piece of passivating back technology.Generally speaking, the back side of cell piece can utilize aluminium oxide passivation and reduce surperficial defect, if the layer of oxide layer of growing is in advance carried out alumina deposit again, will contribute to promote the performance of integral surface passivation.The mode of processing at present be before deposition first by silicon chip preheating, but use the mode of the preheating quality of oxide layer of growing to differ, and use thermal oxidation can promote quality.Complete passivating back technology, can promote next battery exploitation from generation to generation, be especially emitter-base bandgap grading and passivating back battery (Passivated Emitter and Rear Cell, PERC).
In solar cell manufacturing technology, nothing more than being that surface etching increases absorptance, next do phosphorus and diffuse to form the exhaustion region in diode, then deposit again anti-reflective film through surface clean, it is achievable that the electrode at the positive back side of relief connects original paper separately.
In the present invention, process POCl on P type silicon
3after phosphorus diffusion, can form thin layer N-type emitter-base bandgap grading, surperficial phosphorus glass can be washed away afterwards, now not have the formation of any electrode.Next can see through high annealing technology proposed by the invention, the degree of depth of emitter-base bandgap grading is done to such an extent that more enter silicon, this object have many and wherein important be can avoid laser ablation surface anti-reflecting layer time, to hurt emitter-base bandgap grading, to facilitate electroplating technology backward, also helpful to the enforcement of emitter-base bandgap grading and passivating back battery manufacturing technology.
Brief description of the drawings
Fig. 1 is method for manufacturing solar battery flow chart of the present invention;
Fig. 2 A-Fig. 2 H is each manufacturing step schematic diagram in method for manufacturing solar battery of the present invention;
Fig. 3 is solar battery structure schematic diagram of the present invention;
Fig. 4 is the curve chart that in method for manufacturing solar battery of the present invention, phosphorus concentration changes.
[main element symbol description]
11 method for manufacturing solar battery
111 provide a silicon chip, and carry out the step of silicon wafer surface cleaning and roughening processing
112 carry out the DIFFUSION TREATMENT of silicon chip surface, form the step of P-N diode
113 remove the phosphorus glass of P-N diode surface formation and the step of marginal layer
114 utilize thermal oxidation method to heat silicon chip, and on the P-N diode surface of removing phosphorus glass, form the step of an oxide layer
115 form the step of an anti-reflecting layer in oxide layer
116 use the laser molten method that disappears to remove part anti-reflecting layer and form the step of irrigation canals and ditches
117 use electrode plating method on irrigation canals and ditches, to form the step of a metal electrode layer
15 solar cells
151 silicon chips
1513 phosphorus glasss
153 P-N diodes
154 oxide layers
155 anti-reflecting layers
1551 irrigation canals and ditches
1553 crystal seed layers
156 metal electrode layers
157 oxide layers
1571 pyramid structures
18 laser beams
Embodiment
The present invention discloses a kind of manufacture method of solar cell, and the silicon chip that wherein used, laser disappear molten method, electrode plating method, be to utilize prior art to reach, therefore in following explanation, do not do complete description.In addition, graphic in following interior literary composition, also not according to the actual complete drafting of relative dimensions, its effect is only being expressed the schematic diagram relevant with feature of the present invention.
First, referring to Fig. 1, is preferred embodiment of the present invention, is a kind of flow chart of method for manufacturing solar battery 11, mainly comprises the following step:
Step 111: provide a silicon chip as substrate, and carry out silicon wafer surface cleaning and roughening processing;
Step 112: carry out the DIFFUSION TREATMENT of silicon chip surface, form P-N diode;
Step 113: remove phosphorus glass (the PhosphorSilicate Glass that P-N diode surface and edge form; PSG);
Step 114: utilize thermal oxidation method to heat silicon chip, and form an oxide layer on the P-N diode surface of removing phosphorus glass (PSG);
Step 115: form an anti-reflecting layer in oxide layer;
Step 116: use disappear molten method or use etching glue to remove part anti-reflecting layer and form irrigation canals and ditches of laser; And
Step 117: use electrode plating method to form a metal electrode layer on irrigation canals and ditches.
Each step 111～117 of above-mentioned method for manufacturing solar battery 11, are described in detail as follows.
First, please refer to Fig. 2 A, in Fig. 2 A, be to provide a silicon chip 151 as substrate, and silicon chip 151 is cleaned, the object of this step is in order to remove cutting damage layer, and makes the surface clean of silicon chip 151, when after the surface clean of silicon chip 151, then carry out the roughening processing of isotropic etching (anisotropic etching) for the surface of silicon chip 151.In the time that silicon chip 151 is monocrystalline silicon, to utilize for example NaOH of alkaline solution (Sodium hydroxide, or potassium hydroxide (Potassium hydroxide NaOH), and isopropyl alcohol (Isopropano KOH), IPA) mix, as etching solution, etching is carried out in silicon chip 151 surfaces, make the surface of silicon chip 151 expose silicon wafer, and make the surface of silicon chip 151 become roughening, make the surface of silicon chip 151 produce several pyramid structures 1571 not of uniform size, and pyramid structure 1571 is the probability of just turning back through first reflection in order to lower incident light.In the time that silicon chip 151 is polysilicon, be to utilize the etching solution that nitric acid and hydrofluoric acid mix to carry out etching to silicon chip 151 surfaces.
Then, refer to Fig. 2 B, Fig. 2 B is the schematic diagram that is illustrated in the structure of the formation P-N diode on silicon chip 151.In Fig. 2 B, utilize phosphorus oxychloride (POCl
3) and carry gas (carrygas), for example nitrogen (N
2) or argon gas (Ar), after both mix mutually, carry out diffusion process in the silicon chip 151 of earlier figures 2A being sent into boiler tube at 850 DEG C of high temperature, use phosphorus oxychloride (POCl
3) make phosphorus (Phosphorus) be doped in silicon chip 151, phosphorus oxychloride (POCl
3) at high temperature with oxygen (O
2) reaction generation phosphorus pentoxide (P
2o
5) be deposited on silicon chip 151 surfaces, phosphorus pentoxide (P
2o
5) reacting the rear phosphorus atoms generating with silicon (Si) can be at the phosphorous silicon dioxide (SiO of silicon chip 151 surface formation
2), then via the mode of diffusion process the doped layer of the formation silicon dioxide on silicon chip 151, formed P-N diode 153.
Refer to Fig. 2 C, in Fig. 2 C, see through the step of diffusion process, the electrode surface of the P-N diode 153 of silicon chip 151 and marginal layer can form phosphorous phosphorus glass (phosphosilicateGlass, PSG), now need carry out via the electric paste etching of dry ecthing (plasmaetching) processing of edge etching (edge etching), the phosphorus glass 1513 at P-N diode 153 surfaces and edge is removed.
Then, refer to Fig. 2 D, in Fig. 2 D, removing after the phosphorus glass (PSG) on silicon chip 151 surfaces, the silicon chip 151 with P-N diode 153 is carried out to thermal oxidation, its operating condition is: initial temperature is 750 ± 10 DEG C, and be heated to 850 ± 10 DEG C with 5 ± 3 DEG C of speed per minute, and maintain ten minutes in 850 ± 10 DEG C, start afterwards to lower the temperature, be cooled to 700 ± 50 DEG C with 5 ± 3 DEG C of speed per minute, and the oxygen flow that control passes into is 5 ± 3L/min.The silicon chip 151 of processing via thermal oxidation method, can have layer of oxide layer 154 on the surface of P-N diode 153, refers to especially for example silicon dioxide (SiO of silicon oxide layer
2), and this oxide layer 154 can be used as protective layer, can anti-scratch, blocks moisture, and its thickness is 0.2 μ m to 0.3 μ m.
Refer to Fig. 2 E, to use plasma enhanced chemical vapor deposition (plasma enhancedchemical vapor deposition, PECVD) method, in oxide layer 154, plating one deck material is silicon nitride (silicon nitride, SiN) antireflection film plating layer 155 (anti-reflection coating, ARC).Because the effect of plasma enhanced chemical vapor deposition has formed antireflection film plating layer 155, its gas source uses silane (silane, SiH
4) and ammonia (ammonia, NH
3), make its antireflection film plating layer 155 can be used to reduce incident reflection of light, and there is the effect of guard electrode.
Referring to Fig. 2 F, after plating antireflection film plating layer 155, is to utilize laser beam 18 to irradiate antireflection film plating layer 155 in oxide layer 154, to remove part antireflection film plating layer 155 at least one irrigation canals and ditches 1551 of the interior formation of antireflection film plating layer 155.In an embodiment of the present invention; it is dark that the laser beam 18 using when utilizing laser to disappear molten method can damage P-N diode 153 surface approximately 0.2 μ m to 0.3 μ m; now; as lack protective layer and protect P-N diode 153; because laser beam 18 easily punctures the structure of P-N diode 153; and cause leakage current significantly to increase, and cause equipment fault.Therefore, previous formed oxide layer 154 can be used to protect the structure of P-N diode 153 in the present invention, and to prevent that laser beam 18 from penetrating the structure of P-N diode 153, in addition, in the present embodiment, the thickness range of oxide layer 154 is about 0.2 μ m to 0.3 μ m.
Refer to Fig. 2 G, can be first at the interior formation crystal seed layers of irrigation canals and ditches 1551 (SeedLayer) 1553 before electroplating, then silicon chip 151 is sent into high temperature furnace and carry out high temperature sintering, for reaching Fast Sintering, high temperature furnace serviceability temperature scope is about 300 DEG C to 600 DEG C.Then, refer to Fig. 2 H, deposit to form metal electrode layer 156 at the enterprising row metal of crystal seed layer 1553, wherein the material of metal deposition can be selected copper or gold, therefore can form copper electrode layer or gold electrode layer.In addition, in another embodiment of the present invention, can utilize electrode plating method to reduce contact resistance, and replace traditional wire mark metal elargol technology by electrode plating method and form metal electrode layer 156, can reduce solar cell surface area coverage, and then reach the object that promotes solar battery efficiency.
Therefore can know according to aforementioned, in solar cell manufacturing technology, nothing more than silicon chip 151 surfaces being etched with to the absorptance that increases whole solar cell.Next utilize phosphorus to be diffused in the interior formation of P-N diode 153 exhaustion region (not representing in the drawings), then deposit antireflection film plating layer 155 through surface clean, it is achievable that the electrode that relief is arranged at the positive back side of solar cell system connects element separately again.
In an embodiment of the present invention, refer to especially on P-type silicon chip 151 through POCl at silicon chip 151
3after phosphorus diffusion, can form thin layer N-type emitter-base bandgap grading (not representing in the drawings), the phosphorus glass 1513 on P-N diode 151 surfaces can be washed away afterwards, now not have the formation of any electrode.Next can see through high annealing technology, the degree of depth of emitter-base bandgap grading is done to such an extent that more enter silicon chip 151, this object is can avoid laser ablation surface antireflection film plating layer 155 time, to hurt emitter-base bandgap grading.
Please then consult Fig. 3, for solar battery structure schematic diagram of the present invention, this solar battery structure is to form via above-mentioned steps 111 to 117 manufacturings, mainly comprises: substrate 151, P-N diode 153, oxide layer 154, anti-reflecting layer 155 and metal electrode layer 156.
Referring again to Fig. 4, be the curve chart that phosphorus concentration in method for manufacturing solar battery of the present invention changes, curve A shown in figure represents the variation of the phosphorus concentration under general method for manufacturing solar battery, there is no via thermal oxidation process; And curve B represents the variation of phosphorus concentration under method for manufacturing solar battery of the present invention, through thermal oxidation step, wherein, reach 50nm when above in the substrate degree of depth, the general performance trend of curve B is all obviously come highly compared with curve A, and meaning i.e. phosphorus concentration after thermal oxidation step is obviously high without thermal oxidation person, in addition, the raising of phosphorus concentration increases by 0.2 to 0.3 μ m by the thickness that makes the second electrode, and the conversion ratio of solar cell maintains more than 19%.Otherwise, do not pass through the solar cell of thermal oxidation step, the conversion efficiency of solar cell can only maintain 18.6%; Contrast again the thermal oxidation process of step 114, its operating temperature not only can reduce silicon slice surface defects, and can absorb metal impurities at the temperature-fall period of thermal oxidation, therefore, see through thermal oxidation of the present invention and can make prepared solar cell reach good conversion efficiency, and be beneficial to the manufacture of solar energy.
In addition, carry out in the step of thermal oxidation at the above-mentioned silicon chip 151 by thering is P-N diode 153 as shown in Figure 2 D, heating operation condition that can also be identical: initial temperature is 750 ± 10 DEG C, and be heated to 850 ± 10 DEG C with 5 ± 3 DEG C of speed per minute, and maintain ten minutes in 850 ± 10 DEG C, start afterwards to lower the temperature, be cooled to 700 ± 50 DEG C with 5 ± 3 DEG C of speed per minute, and the oxygen flow that control passes into is 5 ± 3L/min, form another layer of oxide layer 157 at the back side of silicon chip 151, its thickness is lnm to 5nm, is preferably 1nm to 2nm.In the making of solar cell proposed by the invention, this oxide layer 157 can allow solar cell further have an emitter-base bandgap grading and passivating back battery (Passivated Emitter and Rear Cell; PERC) structure.In other words, can be at the back side of silicon chip 151 with a plasma enhanced chemical vapor deposition method (Plasma-enhanced CVD; PECVD) a, atomic layer deposition method (Atomic LayerDeposition; ALD), an aumospheric pressure cvd method (Atmospheric Pressure CVD; APCVD) or one spraying rubbing method (spray coating) deposition one passivation layer film and as passivating back material, and oxide layer 157 be formed with the chemistry and the physical property that help optimize this passivation layer deposition film, for example help aluminum oxide film maintain itself with electric charge.The material of the passivation layer film here can be aluminium oxide, silicon nitride, titanium dioxide or carborundum.Thus, the passivating back effect that passivation layer film causes can be because of temperature, humidity, also have the environment changes such as acid-base value and decay.
Although the present invention discloses as above with aforesaid preferred embodiment; so it is not in order to limit the present invention; any familiar alike skill person; without departing from the spirit and scope of the present invention; when doing a little change and retouching, therefore scope of patent protection of the present invention must be as the criterion depending on the appended claim person of defining of this specification.
Claims (12)
1. a method for manufacturing solar battery, is characterized in that, comprises the following steps:
(1) provide a silicon chip; A first surface to this silicon chip carries out roughening processing;
(2) use phosphorus oxychloride (POCl
3) this first surface is carried out to a DIFFUSION TREATMENT, sequentially form a P-N diode on this silicon chip, wherein one of this P-N diode surface and at least one edge form phosphorous phosphorus glass;
(3) remove this phosphorus glass forming at this surface and this edge of this P-N diode;
(4) utilize thermal oxidation method to this silicon chip heating, on the P-N diode surface of removing phosphorus glass (PSG), form one first oxide layer; And
(5) form an anti-reflecting layer in the first oxide layer.
2. method for manufacturing solar battery according to claim 1, it is characterized in that, also comprise the following step: remove a part of this anti-reflecting layer, and form irrigation canals and ditches in this part place of being removed of this anti-reflecting layer, and on these irrigation canals and ditches, form a metal electrode layer.
3. method for manufacturing solar battery according to claim 2, is characterized in that, this part that removes this anti-reflecting layer is by disappear molten (Laserablation) method or reach with etching glue of a laser to form the step of these irrigation canals and ditches.
4. method for manufacturing solar battery according to claim 2, is characterized in that, the step that forms this metal electrode layer is to reach by an electrode plating method.
5. method for manufacturing solar battery according to claim 2, is characterized in that, the step that forms this metal electrode layer is to reach by a metaliding.
6. method for manufacturing solar battery according to claim 1, it is characterized in that, also comprise the following step: utilize thermal oxidation method to this silicon chip heating, form one second oxide layer on a second surface of this silicon chip, the thickness of this second oxide layer is 1nm～5nm.
7. method for manufacturing solar battery according to claim 6, it is characterized in that, also comprise the following step: in this second oxide layer, form a passivation layer film, the material of this passivation layer film be aluminium oxide, silicon nitride, titanium dioxide and carborundum one of them.
8. method for manufacturing solar battery according to claim 7, is characterized in that, the step that forms this passivation layer film in this second oxide layer is to be selected from by plasma enhanced chemical vapor deposition method (Plasma-enhanced CVD by one; PECVD), atomic layer deposition method (AtomicLayer Deposition; ALD), aumospheric pressure cvd method (Atmospheric PressureCVD; APCVD) and the mode of the group that forms of spraying rubbing method (spray coating) reach.
9. method for manufacturing solar battery according to claim 1, it is characterized in that, the step that this first surface of this silicon chip is carried out to roughening processing is to use one of them alkaline solution and the etching solution that mixes of isopropyl alcohol (IPA) of NaOH (NaOH) and potassium hydroxide (KOH) to carry out etching to this surface of this silicon chip.
10. method for manufacturing solar battery according to claim 1, is characterized in that, the step of this first surface of this silicon chip being carried out to roughening processing is that the etching etching solution that uses nitric acid and hydrofluoric acid to mix carries out etching to this surface of this silicon chip.
11. method for manufacturing solar battery according to claim 1, is characterized in that, utilize this thermal oxidation method to more comprising the step that passes into an oxygen in the step of this silicon chip heating, and the flow control of this oxygen are at 5 ± 3L/min.
12. method for manufacturing solar battery according to claim 1, is characterized in that, forming the step of this anti-reflecting layer in this oxide layer is by a plasma enhanced chemical vapor deposition (Plasma-enhanced CVD; PECVD) reach.
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| CN105679864A (en) * | 2016-03-21 | 2016-06-15 | 中国科学院半导体研究所 | Solar cell module integrated from silicon cell and chip-type backward diode and production method of solar cell module |
| TWI615992B (en) * | 2015-12-10 | 2018-02-21 | 茂迪股份有限公司 | Method of manufacturing solar cell |
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| CN101499502A (en) * | 2009-03-02 | 2009-08-05 | 苏州阿特斯阳光电力科技有限公司 | Crystalline silicon solar cell and its passivation method |
| KR20090110211A (en) * | 2008-04-17 | 2009-10-21 | 한국세라믹기술원 | The Method for Manufacturing Solar Cell |
| CN102468365A (en) * | 2010-11-18 | 2012-05-23 | 台湾茂矽电子股份有限公司 | Manufacturing method for double-face solar cell |
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| KR20090110211A (en) * | 2008-04-17 | 2009-10-21 | 한국세라믹기술원 | The Method for Manufacturing Solar Cell |
| CN101499502A (en) * | 2009-03-02 | 2009-08-05 | 苏州阿特斯阳光电力科技有限公司 | Crystalline silicon solar cell and its passivation method |
| CN102468365A (en) * | 2010-11-18 | 2012-05-23 | 台湾茂矽电子股份有限公司 | Manufacturing method for double-face solar cell |
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| TWI615992B (en) * | 2015-12-10 | 2018-02-21 | 茂迪股份有限公司 | Method of manufacturing solar cell |
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