CN107706269B - A kind of diffusion technique and front surface processing method of solar energy polycrystal battery P-N junction - Google Patents
A kind of diffusion technique and front surface processing method of solar energy polycrystal battery P-N junction Download PDFInfo
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- 238000009792 diffusion process Methods 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000003672 processing method Methods 0.000 title claims description 9
- 238000000151 deposition Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 176
- 229910052757 nitrogen Inorganic materials 0.000 claims description 89
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 55
- 239000001301 oxygen Substances 0.000 claims description 55
- 229910052760 oxygen Inorganic materials 0.000 claims description 55
- 239000007789 gas Substances 0.000 claims description 46
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 36
- 229920005591 polysilicon Polymers 0.000 claims description 33
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 22
- 238000005520 cutting process Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 238000004381 surface treatment Methods 0.000 claims description 10
- 238000010926 purge Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 230000003667 anti-reflective effect Effects 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000001039 wet etching Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
- 230000004907 flux Effects 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 230000001458 anti-acid effect Effects 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003518 caustics Substances 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000010129 solution processing Methods 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 abstract description 8
- 239000010703 silicon Substances 0.000 abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 7
- 125000004437 phosphorous atom Chemical group 0.000 abstract description 7
- 230000006798 recombination Effects 0.000 abstract description 7
- 238000005215 recombination Methods 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 5
- 238000013459 approach Methods 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XFDJMIHUAHSGKG-UHFFFAOYSA-N chlorethoxyfos Chemical compound CCOP(=S)(OCC)OC(Cl)C(Cl)(Cl)Cl XFDJMIHUAHSGKG-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
- H01L31/1812—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table including only AIVBIV alloys, e.g. SiGe
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention relates to new approaches to form N-type P-N junction in crystal silicon solar batteries front surface doping phosphorus atoms.Pass through four kinds of different modes (low surface source low temperature deposition methods, high-temperature mixed gas propelling method, chemical conversion facture, Surface heat-treatent method) successively pusher combination, reduce crystal silicon solar batteries diffusion layer-phosphorus atoms surface concentration, realization completely eliminates diffusing surface " dead layer ", so that crystal silicon solar batteries surface recombination be greatly lowered, promotes open-circuit voltage and short circuit current.Meanwhile relatively conventional diffusion technique, and doping concentration is improved, relatively conventional high square resistance diffusion technique shows as fill factor height, final to realize that crystal silicon solar batteries transfer efficiency promotes 0.1-0.2%.
Description
Technical field
The invention belongs to area of solar cell, and in particular to a kind of polycrystalline silicon solar cell front diffusion technique and preceding table
Surface treatment method.
Background technique
Industrialized production crystal-silicon solar cell technology continues to develop, and the polycrystalline silicon solar cell transfer efficiency that is averaged has been more than
18.6%.To further reduce the cost, transfer efficiency is improved, polysilicon chip uses Buddha's warrior attendant wire cutting, just gradually replacing mortar and cutting
It cuts.And the polysilicon chip of Buddha's warrior attendant wire cutting is used, by wet process/dry method modification of surfaces, reflectivity compares conventional polycrystalline silicon wafer,
It can be greatly lowered, to reduce the optical loss of crystal silicon solar batteries.
But due to the special microstructure in polysilicon chip surface after etching, cause silicon wafer after DIFFUSION TREATMENT, surface
Auger recombination and surface recombination it is serious.
It is reduction using the recombination rate after the polysilicon chip diffusion of Buddha's warrior attendant wire cutting, can uses:
(1) process for etching is adjusted, adjusts surface microstructure to reduce the recombination losses after diffusion；
(2) diffusion technique is adjusted, the recombination losses after reducing diffusion；
The present invention solves the high recombination rate of the polysilicon chip of Buddha's warrior attendant wire cutting after the diffusion using second scheme.
Summary of the invention
The purpose of the present invention is to provide a kind of diffusion technique of solar energy polycrystal battery P-N junction and front surface processing sides
Method, this method by four kinds it is different reduce diffusion phosphorus atoms surface concentrations, change the mode of the doping curve of P-N junction, progressive group
It closes, finally realizes and thoroughly eliminate diffusion " dead layer ", promote polysilicon solar cell transfer efficiency 0.1-0.2%.
Above-mentioned purpose of the invention is achieved by the following technical solution:
1. the diffusion technique and front surface processing method of a kind of solar energy polycrystal battery P-N junction, the specific steps are as follows:
(1) it prepares antireflective flannelette: passing through the Buddha's warrior attendant wire cutting polysilicon chip of 156.75*156.75 first, then with gold
Belong to ion Aided Wet etching；
(2) it spreads: the polysilicon chip for preparing flannelette being loaded into normal pressure diffusion furnace and is diffused, diffusion includes following
Step: low surface source low temperature depositing, high-temperature mixed gas promote；
(3) front surface is handled: its sequence is followed successively by conventional wet lay etching, chemical surface treatment, Surface heat-treatent；
2. step (2) the low surface source low temperature depositing, what high-temperature mixed gas promoted specifically comprises the processes of:
Into boat: the control of boat speed is 500-800mm/min, and 4-8min is completed into boat;Into keeping during boat holding in boiler tube
Continuous logical nitrogen, nitrogen flow are 1-4 L/min;Heating: temperature is set in 770-790 DEG C, and 3-8min reaches set temperature;Heating
In the process, nitrogen is led into boiler tube, nitrogen flow is 4-12 L/min;Oxidation: under the conditions of 770-790 DEG C of temperature, to boiler tube
Inside persistently lead to the nitrogen of 1-6min, oxygen mixed gas;Wherein nitrogen flow is 4-12 L/min, oxygen flow 0.5-1.8
L/min;
Low surface source low temperature deposition methods: 770-790 DEG C in diffusion furnace, constant temperature 5-13min, within this time range to expansion
Dissipate furnace in be passed through nitrogen, oxygen, phosphorus oxychloride mixed gas, the phosphorus oxychloride flow be 1-2L/min, the flow of oxygen
For 0.2-0.8L/min, the flow of nitrogen is 6-12L/min；
High-temperature mixed gas propelling method: being warming up to 840-860 DEG C for temperature in diffusion furnace tube, persistently leads to the nitrogen of 8-15min
Gas, oxygen, the flow of the oxygen are 0.5L-5L/min, and the flow of nitrogen is 8-15L/min；
Cooling: temperature is set in 700-780 DEG C, and 0.5-10min completion reaches set temperature;Continue in temperature-fall period to furnace
Logical nitrogen, oxygen mixed gas in pipe;Wherein nitrogen flow is 4-12 L/min, and oxygen flow is 0.5-1.2 L/min, out
Boat: the control of boat speed is 600-1200mm/min, and 4-8min completes out boat;Maintaining nitrogen purge in boiler tube, nitrogen are kept during this
Throughput is 1-4 L/min.
4. front surface described in step (3) is handled specifically comprises the processes of:
Chemical conversion processing: it after the polysilicon chip spread goes out diffusion furnace, etches by conventional wet lay in HF and HNO3
Mixed solution processing after, be fitted into the gaily decorated basket of antiacid caustic corrosion, be surface-treated using groove-type cleaning machine, the slot
Formula cleaning machine is made of four groove bodies, and 1# groove body is alkaline solution, and the alkaline solution is KOH, NH4In OH, TMAOH, NaOH
One or several kinds of solvents, the concentration control of every kind of solvent is in 0.1%-3%, and reaction temperature control is at 25-80 DEG C, the reaction time
Control is in 20-180s, and 2# groove body is in acid solution, and the acid solution is HF, and HNO3, one or more of HCl are molten
Agent, every kind of solvent strength control is within 3%-15%, and in 30-200s, reaction temperature is controlled at 18-25 DEG C for reaction time control,
3# groove body is DI, and wherein temperature control is at 25 DEG C, and in 60-120s, 4# groove body is nitrogen drying tank, medium temperature for reaction time control
At 75-95 DEG C, the reaction time is controlled in 500-800s for degree control.
Surface heat-treatent: it by chemical conversion treated polysilicon chip, inserts on quartz boat device, is put into high temperature
In furnace, Surface heat-treatent is carried out, at 550-850 DEG C, the time is controlled in 10-25min, pressure for temperature control in high temperature furnace
0.1MPa, in heat treatment process, the mixed gas of maintaining nitrogen purge and oxygen, nitrogen flow is controlled in 8-15L/min, oxygen stream
Amount control is in 0.8-5L/min.
Compared with existing diffusion technique, the present invention has the advantage that
(1) diffusion technique and front surface processing method of a kind of solar energy polycrystal battery P-N junction provided by the invention, diffusion
Polysilicon chip afterwards has ultralow phosphorus atoms surface concentration, thoroughly eliminates due to the nonactive phosphorus in surface caused by excessive adulterate
Atomic layer, that is, so-called " diffusion death layer ".
(2) present invention is lifted at 0.1%-0.2% to using the transfer efficiency of Buddha's warrior attendant wire cutting polycrystalline battery, high compared to conventional
Sheet resistance diffusion technique efficiency exceeds 0.15% or more.
(3) the relatively conventional high square resistance diffusion technique of the present invention, increases twice polycrystal silicon cell front surface processing technology.This
Equipment used by twice technique and simple process are stablized, and easily controllable, advantage of lower cost is, it can be achieved that productionization volume production.
Specific embodiment
The present invention is described further combined with specific embodiments below, to help the contents of the present invention are understood.
Embodiment 1:
A kind of diffusion technique and front surface processing method of solar energy polycrystal battery P-N junction, the specific steps are as follows:
(1) polysilicon chip using metal ion Aided Wet etching method in 156.75*156.75 Buddha's warrior attendant wire cutting, preparation
Antireflective flannelette；
(2) normal pressure diffusion furnace is used, the polysilicon chip for preparing flannelette is loaded into diffusion furnace and is diffused, diffusion step
Rapid low surface source low temperature deposition methods, specific step is as follows for high-temperature mixed gas propelling method:
Into boat: the control of boat speed is 650mm/min, and 6min is completed into boat.Into keeping during boat persistently leading to nitrogen in boiler tube
Gas, nitrogen flow 2.5L/min.Heating: temperature is set in 780 DEG C, and 5min reaches set temperature.In temperature-rise period, to boiler tube
Interior logical nitrogen, nitrogen flow 8L/min.Oxidation: under the conditions of 780 DEG C of temperature, the nitrogen of 4min, oxygen are persistently led into boiler tube
Oxygen mixture.Wherein nitrogen flow is 8 L/min, and oxygen flow is 1.1 L/min.
Low surface source low temperature deposition methods: 785 DEG C in diffusion furnace, 5min is heated, to the constant 785 DEG C of backward diffusion furnaces of temperature
Inside be passed through nitrogen, oxygen, phosphorus oxychloride mixed gas 8min, control phosphorus oxychloride flow be 1.25L/min, the flow of oxygen
For 0.45L/min, the flow of nitrogen is 10L/min.
High-temperature mixed gas propelling method: after temperature in diffusion furnace tube is warming up to 850 DEG C of stabilizations, persistently lead to the nitrogen of 12min
Gas, oxygen, the flow for controlling oxygen is 2L/min, and the flow of nitrogen is 12L/min.
Cooling: temperature is set in 740 DEG C, and 5min completion reaches set temperature.Continue to lead to nitrogen into boiler tube in temperature-fall period
Gas, oxygen mixed gas.Wherein nitrogen flow is 8 L/min, and oxygen flow is 0.8 L/min.
Boat out: the control of boat speed is 900mm/min, and 6min completes out boat.Maintaining nitrogen purge in boiler tube is kept during this,
Nitrogen flow is 2.5 L/min, and the phosphorus atoms surface concentration after diffusion is in 1.0-1.5*e20, wherein the square resistance after diffusion exists
95-100□Ω。
(3) polysilicon chip spread is etched by conventional wet lay, removes polysilicon front phosphorosilicate glass and edge
Then P-N junction carries out chemical surface treatment by groove-type cleaning machine, 1# groove body: 0.1%KOH alkaline solution is in 25 DEG C of processing 60s；
2# groove body: HF5%, 5%HCl acid solution are in 25 DEG C of processing 60s；3# groove body;DI is in 25 DEG C of processing 80s；4# groove body: logical nitrogen
80 DEG C of processing 650s.
(4) it by (3) treated polysilicon chip, inserts on quartz boat device, puts into high temperature furnace, carry out surface heat
Processing.Wherein at 650 DEG C, the time is controlled in 15min, pressure 0.1MPa for temperature control.During heat treatment, maintaining nitrogen purge
With the mixed gas of oxygen, wherein nitrogen flow controls 10L/min, oxygen flux control 2.5L/min.
Embodiment 2:
A kind of diffusion technique and front surface processing method of solar energy polycrystal battery P-N junction, the specific steps are as follows:
(1) polysilicon chip using metal ion Aided Wet etching method in 156.75*156.75 Buddha's warrior attendant wire cutting, preparation
Antireflective flannelette.
(2) normal pressure diffusion furnace is used, the polysilicon chip for preparing flannelette is loaded into diffusion furnace and is diffused, diffusion step
Rapid low surface source low temperature deposition methods, specific step is as follows for high-temperature mixed gas propelling method:
Into boat: the control of boat speed is 400mm/min, and 4min is completed into boat.Into keeping during boat persistently leading to nitrogen in boiler tube
Gas, nitrogen flow 1L/min.Heating: temperature is set in 770 DEG C, and 3min reaches set temperature.In temperature-rise period, into boiler tube
Logical nitrogen, nitrogen flow 4L/min.Oxidation: under the conditions of 770 DEG C of temperature, the nitrogen of 1min, oxygen are persistently led into boiler tube
Mixed gas.Wherein nitrogen flow is 4 L/min, and oxygen flow is 0.5 L/min.
Low surface source low temperature deposition methods: 785 DEG C in diffusion furnace, 5min is heated, to the constant 785 DEG C of backward diffusion furnaces of temperature
Inside be passed through nitrogen, oxygen, phosphorus oxychloride mixed gas 8min, control phosphorus oxychloride flow be 1.15L/min, the flow of oxygen
For 0.45L/min, the flow of nitrogen is 10L/min.
High-temperature mixed gas propelling method: after temperature in diffusion furnace tube is warming up to 850 DEG C of stabilizations, persistently lead to the nitrogen of 15min
Gas, oxygen, the flow for controlling oxygen is 2L/min, and the flow of nitrogen is 12L/min.
Cooling: temperature is set in 700 DEG C, and 0.5min completion reaches set temperature.Continue to lead into boiler tube in temperature-fall period
Nitrogen, oxygen mixed gas.Wherein nitrogen flow is 4 L/min, and oxygen flow is 0.5 L/min.
Boat out: the control of boat speed is 600mm/min, and 4min completes out boat.Maintaining nitrogen purge in boiler tube is kept during this,
Nitrogen flow is 1 L/min, and the phosphorus atoms surface concentration after diffusion is in 8.0*e19-1.0*e20, wherein the square electricity after diffusion
Resistance is in 100-110 Ω.
(3) polysilicon chip spread is etched by conventional wet lay, removes polysilicon front phosphorosilicate glass and edge
P-N junction.Then chemical surface treatment is carried out by groove-type cleaning machine, 1# groove body: 0.1%KOH alkaline solution is in 25 DEG C of processing 80s；
2# groove body: HF5%, 5%HCl acid solution are in 25 DEG C of processing 60s；3# groove body;DI is in 25 DEG C of processing 80s；4# groove body: logical nitrogen
80 DEG C of processing 650s.
(4) it by (3) treated polysilicon chip, inserts on quartz boat device, puts into high temperature furnace, carry out surface heat
Processing.Wherein at 750 DEG C, the time is controlled in 10min, pressure 0.1MPa for temperature control.During heat treatment, maintaining nitrogen purge
With the mixed gas of oxygen, wherein nitrogen flow controls 10L/min, oxygen flux control 4L/min.
Embodiment 3:
A kind of diffusion technique and front surface processing method of solar energy polycrystal battery P-N junction, the specific steps are as follows:
(1) polysilicon chip using metal ion Aided Wet etching method in 156.75*156.75 Buddha's warrior attendant wire cutting, preparation
Antireflective flannelette.
(2) normal pressure diffusion furnace is used, the polysilicon chip for preparing flannelette is loaded into diffusion furnace and is diffused, diffusion step
Rapid low surface source low temperature deposition methods, high-temperature mixed gas propelling method specific step is as follows I, low surface source low temperature deposition methods:
Into boat: the control of boat speed is 800mm/min, and 8min is completed into boat.Into keeping during boat persistently leading to nitrogen in boiler tube
Gas, nitrogen flow are 4 L/min.Heating: temperature is set in 790 DEG C, and 8min reaches set temperature.In temperature-rise period, to boiler tube
Interior logical nitrogen, nitrogen flow are 12 L/min.Oxidation: under the conditions of 790 DEG C of temperature, the nitrogen of 6min is persistently led into boiler tube,
Oxygen mixed gas.Wherein nitrogen flow is 12 L/min, and oxygen flow is 1.8 L/min.
785 DEG C in diffusion furnace, 5min is heated, to be passed through nitrogen, oxygen, three in constant 785 DEG C of temperature backward diffusion furnaces
The mixed gas 8min of chlorethoxyfos, control phosphorus oxychloride flow are 1.1L/min, and the flow of oxygen is 0.45L/min, nitrogen
Flow is 10L/min.
High-temperature mixed gas propelling method: after temperature in diffusion furnace tube is warming up to 850 DEG C of stabilizations, persistently lead to the nitrogen of 18min
Gas, oxygen, the flow for controlling oxygen is 1.5L/min, and the flow of nitrogen is 12L/min.
Cooling: temperature is set in 780 DEG C, and 10min completion reaches set temperature.Continue to lead to nitrogen into boiler tube in temperature-fall period
Gas, oxygen mixed gas.Wherein nitrogen flow is 12 L/min, and oxygen flow is 1.2 L/min.
Boat out: the control of boat speed is 1200mm/min, and 8min completes out boat.It keeps persistently leading to nitrogen in boiler tube during this
Gas, nitrogen flow are 4 L/min.
Phosphorus atoms surface concentration after diffusion is in 7.5*e19-9.0*e19, wherein the square resistance after diffusion is in 115-125
□Ω。
(3) polysilicon chip spread is etched by conventional wet lay, removes polysilicon front phosphorosilicate glass and edge
P-N junction.Then chemical surface treatment is carried out by groove-type cleaning machine.1# groove body: 0.1%KOH alkaline solution is handled at 25 DEG C
120s；2# groove body: HF5%, 5%HCl acid solution are in 25 DEG C of processing 60s；3# groove body;DI is in 25 DEG C of processing 80s；4# groove body:
Logical 80 DEG C of processing 650s of nitrogen.
(4) it by (3) treated polysilicon chip, inserts on quartz boat device, puts into high temperature furnace, carry out surface heat
Processing.Wherein at 800 DEG C, the time is controlled in 10min, pressure 0.1MPa for temperature control.During heat treatment, maintaining nitrogen purge
With the mixed gas of oxygen, wherein nitrogen flow controls 10L/min, oxygen flux control 4L/min.
Comparative example 1:
A kind of routine prepares the diffusion technique of solar energy polycrystal battery P-N junction, the specific steps are as follows:
(1) polysilicon chip using metal ion Aided Wet etching method in 156.75*156.75 Buddha's warrior attendant wire cutting, preparation
Antireflective flannelette.
(2) normal pressure diffusion furnace is used, the polysilicon chip for preparing flannelette is loaded into diffusion furnace and is diffused, diffusion step
Rapid low surface source low temperature deposition methods, high-temperature mixed gas propelling method specific step is as follows I, low surface source low temperature deposition methods.
Low surface source low temperature deposition methods: 785 DEG C in diffusion furnace, 5min is heated, to the constant 785 DEG C of backward diffusion furnaces of temperature
Inside be passed through nitrogen, oxygen, phosphorus oxychloride mixed gas 8min, control phosphorus oxychloride flow be 1.3L/min, the flow of oxygen
For 0.45L/min, the flow of nitrogen is 10L/min.
High-temperature mixed gas propelling method: after temperature in diffusion furnace tube is warming up to 850 DEG C of stabilizations, persistently lead to the nitrogen of 12min
Gas, oxygen.The flow of oxygen is 1L/min, and the flow of nitrogen is 12L/min.
Phosphorus atoms surface concentration after diffusion is in 2.4-3.0*e20, wherein the square resistance after diffusion is in 88-98 Ω.
Using the polysilicon solar cell performance parameter for the Buddha's warrior attendant wire cutting that diffusion technique and surface treatment method obtain
It is as shown in the table:
A kind of diffusion technique of solar energy polycrystal battery P-N junction of the invention and front surface processing side as can be seen from the above table
Method compares conventional diffusion processes method, and battery conversion efficiency has 0.1-0.2% promotion.
The present invention will be described for specific embodiment listed above.It should be pointed out that above embodiments are served only for this
Invention is described further, and does not represent protection scope of the present invention, other people prompts according to the present invention are made nonessential
Modification and adjustment, still fall within protection scope of the present invention.
Claims (2)
1. the diffusion technique and front surface processing method of a kind of solar energy polycrystal battery P-N junction, it is characterised in that:
The following steps are included:
(1) prepare antireflective flannelette: first by the Buddha's warrior attendant wire cutting polysilicon chip of 156.75*156.75, then with metal from
Sub- Aided Wet etching；
(2) it spreads: the polysilicon chip for preparing flannelette being loaded into normal pressure diffusion furnace and is diffused, diffusion includes low surface source
Low temperature depositing, high-temperature mixed gas promote；
Specifically comprises the processes of:
Into boat: the control of boat speed is 500-800mm/min, and 4-8min is completed into boat, into keeping persistently leading in boiler tube during boat
Nitrogen, nitrogen flow are 1-4 L/min, and heating: temperature is set in 770-790 DEG C, and 3-8min reaches set temperature, temperature-rise period
In, nitrogen is led into boiler tube, nitrogen flow is 4-12 L/min, oxidation: under the conditions of 770-790 DEG C of temperature, is held into boiler tube
The nitrogen of continuous logical 1-6min, oxygen mixed gas, wherein nitrogen flow is 4-12 L/min, and oxygen flow is 0.5-1.8 L/
min；
Low surface source low temperature depositing: 770-790 DEG C in diffusion furnace, constant temperature 5-13min, within this time range into diffusion furnace
Be passed through nitrogen, oxygen, phosphorus oxychloride mixed gas, the phosphorus oxychloride flow is 1-2L/min, and the flow of oxygen is 0.2-
0.8L/min, the flow of nitrogen are 6-12L/min；
High-temperature mixed gas promotes: temperature in diffusion furnace tube being warming up to 840-860 DEG C, persistently leads to nitrogen, the oxygen of 8-15min
Gas, the flow of the oxygen are 0.5L-5L/min, and the flow of nitrogen is 8-15L/min；
Cooling: temperature is set in 700-780 DEG C, and 0.5-10min completion reaches set temperature, continues in temperature-fall period into boiler tube
Logical nitrogen, oxygen mixed gas, wherein nitrogen flow is 4-12 L/min, and oxygen flow is 0.5-1.2 L/min；
Boat out: the control of boat speed is 600-1200mm/min, and 4-8min completes out boat, keeps persistently leading to nitrogen in boiler tube during this
Gas, nitrogen flow are 1-4 L/min;
(3) front surface is handled: its sequence is followed successively by conventional wet lay etching, chemical surface treatment, Surface heat-treatent.
2. the diffusion technique and front surface processing method of a kind of solar energy polycrystal battery P-N junction according to claim 1,
It is characterized in that: the chemical surface treatment in the step (3), Surface heat-treatent specifically comprises the processes of:
Chemical surface treatment: after the polysilicon chip spread goes out diffusion furnace, the mixing in HF and HNO3 is etched by conventional wet lay
After solution processing, it is fitted into the gaily decorated basket of antiacid caustic corrosion, is surface-treated using groove-type cleaning machine, the slot type cleaning
Machine is made of four groove bodies, and 1# groove body is alkaline solution, and the alkaline solution is KOH, NH4 One of OH, TMAOH, NaOH
Or several solvents, the concentration control of every kind of solvent is in 0.1%-3%, and at 25-80 DEG C, reaction time control exists for reaction temperature control
20-180s, 2# groove body are in acid solution, and the acid solution is HF, HNO3 , one or more of HCl solvent, every kind
Solvent strength controls within 3%-15%, and reaction time control is in 18-25 DEG C, 3# groove body in 30-200s, reaction temperature control
DI, wherein temperature control is at 25 DEG C, and in 60-120s, 4# groove body is nitrogen drying tank for reaction time control, and wherein temperature control exists
75-95 DEG C, the reaction time controls in 500-800s；
Surface heat-treatent: it by the polysilicon chip after chemical surface treatment, inserts on quartz boat device, is put into high temperature furnace
In, Surface heat-treatent is carried out, at 550-850 DEG C, the time is controlled in 10-25min, pressure 0.1MPa for temperature control in high temperature furnace,
In heat treatment process, the mixed gas of maintaining nitrogen purge and oxygen, nitrogen flow is controlled in 8-15L/min, oxygen flux control
In 0.8-5L/min.
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