CN104157736A - Solar cell manufacturing method and solar cell - Google Patents
Solar cell manufacturing method and solar cell Download PDFInfo
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- CN104157736A CN104157736A CN201410403111.7A CN201410403111A CN104157736A CN 104157736 A CN104157736 A CN 104157736A CN 201410403111 A CN201410403111 A CN 201410403111A CN 104157736 A CN104157736 A CN 104157736A
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- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 238000009792 diffusion process Methods 0.000 claims abstract description 87
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 51
- 239000011574 phosphorus Substances 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 45
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- 238000005516 engineering process Methods 0.000 claims description 38
- 238000002360 preparation method Methods 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 238000012545 processing Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 6
- 230000000630 rising effect Effects 0.000 claims description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 abstract description 33
- 238000005272 metallurgy Methods 0.000 abstract description 22
- 229920005591 polysilicon Polymers 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 238000002203 pretreatment Methods 0.000 abstract 1
- 239000002344 surface layer Substances 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 55
- 230000003287 optical effect Effects 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 210000005056 cell body Anatomy 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005247 gettering Methods 0.000 description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 230000007480 spreading Effects 0.000 description 3
- 239000003708 ampul Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 101150025786 PCLO gene Proteins 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 235000008216 herbs Nutrition 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 210000002268 wool Anatomy 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
- H01L31/1804—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 System
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/2225—Diffusion sources
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/223—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a gaseous phase
-
- 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
- H01L31/1864—Annealing
-
- 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
- Y02E10/547—Monocrystalline silicon PV 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
- 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 solar cell manufacturing method and a solar cell. The method comprises a diffusion process. The process comprises steps: S1, first phosphorus diffusion is carried out on a silicon wafer after pre-treatment, and an N-type region and a PN-junction structure of the solar cell are formed; and S2, second phosphorus diffusion is carried out on the silicon wafer after the first phosphorus diffusion, and phosphorus concentration on the surface layer of the N-type region is increased. The diffusion process also comprises a heat treatment process for 1680 to 1800 seconds at the temperature of 680 to 720 DEG. Thus, the technical problems of open circuit voltage, short circuit current and low conversion efficiency as resistance of a polysilicon original piece obtained through purification in a physical metallurgy method is low and not matched with the PN-junction diffusion condition in the prior art can be solved, the matching problem between the concentration of the surface of the cell and metal-semiconductor contact can be well solved, the entire performance of ohmic contact can be enhanced, and serial resistance of the cell is reduced.
Description
Technical field
The disclosure relates to photovoltaic apparatus technical field, relates in particular to a kind of preparation method of solar battery and solar cell.
Background technology
Solar energy is a kind of clean energy resource, does not produce any environmental pollution.In the middle of effective utilization of solar energy, large sun can photovoltaic utilization be research field with fastest developing speed in the last few years, most active.For this reason, people develop and have developed solar cell.
Polysilicon chip is the main carriers that forms crystal silicon solar energy battery, and polysilicon chip is generally to be formed by raw silicon film-making after multistep is purified.Polysilicon chip is through deoiling technique, and---------------------testing, sorting etc. make solar cell to silicon nitride film processed to periphery etching to diffusion technology for the silk screen printing back of the body, positive electrode---sintering---to remove oxide layer in making herbs into wool to remove damage layer.
In prior art, the technology of purifying polycrystalline silicon mainly contains chemical method and Physical Metallurgy method.Along with the continuous renewal development of photovoltaic technology, reduce costs, raise the efficiency and reduce the demands such as environmental pollution and become increasingly conspicuous, research and development are low-cost, high production capacity and the much higher crystal silicon purification technique of environmental benefit become to attach most importance to.In chemical method purifying polycrystalline silicon technology, need to be polycrystalline silicon purifying to purity more than 8N-10N, then according to using needs, to high purity polycrystalline silicon melting doping high purity boron, this has increased cost undoubtedly.And Physical Metallurgy polycrystalline silicon purifying technology is with the smelting process purifying polycrystalline silicon that is similar to metal, this technology does not need chemical reaction, and feature is that production capacity is large, cost is low.
In recent years, a lot of correlation technique manufacturers and research and development institution were all devoted to research and develop Physical Metallurgy polycrystalline silicon purifying technology, made technique obtain further improvement.For example, the polysilicon that uses at present Physical Metallurgy purification technique to purify, purity has reached 6.0N-6.5N level, and existing enterprise starts small-scale production.And polysilicon solar cell based on Physical Metallurgy method also will improve constantly along with quality of materials, there is wide development potentiality and have the market prospects of competitiveness.Yet, in prior art, in the polysilicon solar cell technique in preparation based on Physical Metallurgy method, still there is the part that much haves much room for improvement.For example:
(1), in Physical Metallurgy method purifying polycrystalline silicon technology, one of main purpose is that the base boron in material is reduced to required purity.But because it is larger to remove the technical difficulty of base boron, thus cause the Physical Metallurgy method boron content of purifying in the polysilicon obtaining slightly high, so the resistivity polysilicon of purifying and obtaining lower than chemical method.For example, general domestic by the purify resistivity of the polycrystalline silicon material that obtains of Physical Metallurgy method, be 0.8-1.5 Ω cm, be starkly lower than the purify resistivity of the polycrystalline silicon material 1.8-2.4 Ω cm that obtains of chemical method.
Like this, if the diffusion technology of the polysilicon solar cell based on chemical method in prior art is applied to make in the technique of the polysilicon solar cell based on Physical Metallurgy method, the obvious unmatched problem of resistivity that there will be doping content and polysilicon original sheet, cause thus PN junction characteristic poor, the open circuit voltage of solar cell and short circuit current are all lower.
(2) battery surface " dead layer " effect causing in order to solve the diffusion of solar cell high concentration, in recent years, in making the diffusion technology of solar cell, constantly reduced the diffusion concentration of skin layer; So cause the sheet resistance (square resistance) of diffusion layer constantly to increase.For example, within 2010, diffusion layer square resistance mostly is 55 Ω/, and diffusion layer square resistance has been increased to 95-100 Ω/ at present.Along with the continuous increase of diffused layer resistance, directly cause the overall performance variation of silicon and silver electrode ohmic contact; And this ohmic contact may have the rectification contact of larger composition, therefore can cause that the conversion efficiency of solar cell declines.
(3), for improving the purify minority carrier life time of the polysilicon original sheet that obtains of Physical Metallurgy method, make before solar cell and can carry out the high temperature phosphorous gettering of approximately 950 ℃ to silicon chip and process, but can in crystalline silicon body, produce a large amount of dislocations like this; Higher temperature diffusion at 830 ℃, also can cause new defect.These all can badly influence the overall performance of the polysilicon solar cell based on Physical Metallurgy method.
Summary of the invention
For some or all of problem of the prior art, the disclosure provides a kind of preparation method of solar battery for promoting the performance of the solar cell of preparation; Further, the disclosure also provides a kind of solar cell of preparing by this preparation method of solar battery.
Other characteristics of the present disclosure and advantage become the detailed description by below obviously, or the partly acquistion by practice of the present disclosure.
According to an aspect of the present disclosure, a kind of preparation method of solar battery, comprises diffusion technology; Described diffusion technology comprises:
S1. pretreated silicon chip is carried out to phosphorus diffusion for the first time, form the PN junction structure of N-type district and solar cell thereon;
S2. the silicon chip after diffusion is for the first time carried out to phosphorus diffusion for the second time, increase the phosphorus concentration on top layer, described N-type district.
In an embodiment of the present disclosure, the described diffusion of phosphorus for the first time comprises:
S11. at 750-850 ℃ of temperature, carry out the 580-620 constant source phosphorus diffusion of second;
S12. by after 20-30 ℃ of temperature rising in described step S11, carry out the 580-620 restriction source phosphorus diffusion of second.
In an embodiment of the present disclosure, in described step S11, constant source phosphorus is diffused in following atmosphere and carries out:
Little nitrogen flow: 1180-1250ml/min;
Large nitrogen flow: 25000-27000ml/min;
Oxygen flow: 950-1050ml/min.
In an embodiment of the present disclosure, in described step S12, limit source phosphorus and be diffused in following atmosphere and carry out:
Large nitrogen flow: 20000-22000ml/min.
In an embodiment of the present disclosure, the described diffusion of phosphorus for the second time comprises:
S21. at 820-830 ℃ of temperature, carry out the 700-760 constant source phosphorus diffusion of second.
In an embodiment of the present disclosure, in described step S21, constant source phosphorus is diffused in following atmosphere and carries out:
Little nitrogen flow: 1220-1250ml/min
Large nitrogen flow: 25000-27000ml/min
Oxygen flow: 1000-1050ml/min.
In an embodiment of the present disclosure, after described step S21, also comprise:
S22: carry out the 280-300 cooling processing of second; Described cooling is processed and is carried out in following atmosphere:
Large nitrogen flow: 20000-22000ml/min.
In an embodiment of the present disclosure, after described diffusion technology, also comprise:
At 680-720 ℃ of temperature, carry out the 1680-1800 Technology for Heating Processing of second.
In an embodiment of the present disclosure, described Technology for Heating Processing is carried out in following atmosphere:
Large nitrogen flow: 20000-22000ml/min.
According to another aspect of the present disclosure, a kind of by the solar cell of preparing according to above-mentioned any one preparation method of solar battery.
The preparation method of solar battery that example embodiment of the present disclosure provides and solar cell, first by diffusion technology simple in the preparation method of the polycrystalline silicon solar cell based on Physical Metallurgy method of the prior art being made into minute diffusion for the first time and spreading for the second time twice diffusion, solved the polysilicon original sheet resistivity obtaining due to the purification of Physical Metallurgy method in prior art lower, and do not mate the technical problem that the open circuit voltage causing, short circuit current and conversion efficiency are low with PN junction diffusion conditions; Also preferably resolve the matching problem that battery surface concentration contacts with metal-semiconductor simultaneously, promoted the overall performance of ohmic contact, reduced battery series resistance, for the popularization of the polycrystalline silicon solar cell based on Physical Metallurgy method provides strong technical support.In addition, by diffusion technology is combined with follow-up Technology for Heating Processing, after diffusion technology finishes, directly cooling is heat-treated battery, solved because of high temperature phosphorous gettering and spread the problem that causes micro-structural variation in solar cell body, eliminate to a certain extent the part defect in solar cell body, improved the crystal structure of solar cell.
Accompanying drawing explanation
By describe its example embodiment in detail with reference to accompanying drawing, above-mentioned and further feature of the present disclosure and advantage will become more obvious.
Fig. 1 is the schematic flow sheet of a kind of preparation method of solar battery in disclosure example embodiment;
Fig. 2 A-2B is the technical process schematic diagram of a kind of preparation method of solar battery in disclosure example embodiment.
Description of reference numerals:
10:P type silicon chip
20:PN junction structure
31:N type district
32:N
+layer
40: silver electrode
S1-S3: step
Embodiment
Referring now to accompanying drawing, example embodiment is more fully described.Yet example embodiment can be implemented in a variety of forms, and should not be understood to be limited to execution mode set forth herein; On the contrary, provide these execution modes to make the disclosure by comprehensive and complete, and the design of example embodiment is conveyed to those skilled in the art all sidedly.Identical in the drawings Reference numeral represents same or similar structure, thereby will omit their detailed description.
In addition, described feature, structure or characteristic can be combined in one or more embodiment in any suitable manner.In the following description, thus provide many details to provide fully understanding embodiment of the present disclosure.Yet, one of skill in the art will appreciate that and can put into practice technical scheme of the present disclosure and there is no one or more in described specific detail, or can adopt other method, material, constituent element etc.In other cases, be not shown specifically or describe known configurations or operation to avoid fuzzy each side of the present disclosure.
First a kind of preparation method of solar battery is provided in this example embodiment.In this preparation method of solar battery, first make One Diffusion Process technique in prior art the combination of twice diffusion technology into, thereby be more applicable for the preparation of the polycrystalline silicon solar cell based on Physical Metallurgy method.Particularly, as shown in fig. 1, in this example embodiment, described diffusion technology comprises:
S1. as shown in Figure 2 A, pretreated silicon chip is carried out to phosphorus diffusion for the first time, form the PN junction structure 20 of N-type district 31 and solar cell thereon; In this example embodiment, described silicon chip is preferably the polysilicon based on Physical Metallurgy method.The main purpose of diffusion technology is the PN junction that forms the polycrystalline silicon solar cell based on Physical Metallurgy method for the first time.For example this step can comprise:
S11. first the P type silicon chip 10 through pretreating process such as process annealing, oxidation processes is carried out to constant source diffusion in diffusion furnace, the diffusion of constant source phosphorus is preferably carried out at 750-850 ℃ of temperature, and the duration is about 580 seconds to 620 seconds.And through inventor's repeatedly practical proof, finding that constant source phosphorus is diffused at 800 ℃ of temperature carries out, and duration while being 600 seconds, whole structure is best.
S12. then at described step S11, stop behind source, rising temperature, carries out the diffusion of restriction source.For example, by after 20-30 ℃ of temperature rising in described step S11, carry out the restriction source phosphorus diffusion of 580 seconds to 620 seconds, form the PN junction structure 20 of N-type district 31 and solar cell.And through inventor's repeatedly practical proof, while finding that the restriction source phosphorus diffusion duration is 600 seconds, whole structure is best.
Battery surface " dead layer " effect causing in order to solve the diffusion of solar cell high concentration, the diffusion concentration in step S1 is conventionally lower; So cause the sheet resistance (square resistance) of diffusion layer constantly to increase; And along with the continuous increase of diffused layer resistance, can cause the overall performance variation of silicon and silver electrode 40 ohmic contact.Therefore in this example embodiment, after described step S1, also comprise:
S2. as shown in Figure 2 B, silicon chip after diffusion is for the first time carried out to phosphorus diffusion for the second time, increase the phosphorus concentration on 31 top layers, described N-type district, thereby can be so that make battery surface and silver electrode 40 form good metal-semiconductor ohmic contact, reduce the series resistance of solar cell, and then promote the conversion efficiency of solar cell.Particularly, the temperature of phosphorus diffusion is for the second time preferably higher than phosphorus diffusion for the first time, and preferably strengthen phosphorus source flux, and so just can improve the phosphorus concentration on top layer, solar cell N-type district 31 (emitter region), ShiNXing district 31 topmost thin layer forms the relatively high heavy doping N of diffusion concentration
+layer 32 and do not affect the phosphorus diffusion concentration of PN junction structure 20 reality, thus part makes up the inferior position that solar cell surface phosphorus concentration is low, at the ohm contact performance that to a certain degree improves solar cell surface.For example this step can comprise:
S21. the silicon chip through obtaining after step S1 is carried out to constant source diffusion.This constant source phosphorus diffusion is preferably carried out at 820-830 ℃ of temperature, and the duration is about 700 seconds to 760 seconds.In step S2, why carry out the restriction source diffusion of short time, to be that the phosphorus in order preventing from spreading in this step too much gos deep into forming under 31 top layers, NXing district in step S1, and significantly to change the concentration of phosphorus diffusion in step S1.
As from the foregoing, in step S1 and step S2, the concentration of phosphorus diffusion, temperature are all different, thereby both can avoid causing solar cell surface " dead layer " effect, meet the requirement of diffusion system knot, can reduce diffusion into the surface resistance again, make solar cell surface and silver electrode 40 form good metal-semiconductor ohmic contact.
For improving high temperature phosphorous gettering, spreading the new defect in the solar cell body bringing, solve the problem of its solar cell micro-structural variation causing, in this example embodiment, also after diffusion technology, increased the Technology for Heating Processing of certain hour, thereby repair to a certain extent the problem that causes solar cell micro-structural variation due to high temperature phosphorous gettering, diffusion, also can reduce Yin Gaowen and cause cell piece warpage and the hidden probability splitting simultaneously.Particularly, the Technology for Heating Processing after diffusion technology can comprise:
S3. at 680-720 ℃ of temperature, carry out the 1680-1800 Technology for Heating Processing of second.And through inventor's repeatedly practical proof, while finding that this Technology for Heating Processing duration is 1800 seconds, whole structure is best.
In addition, oxygen concentration has close relationship in the optical attenuation of solar cell and solar cell body, and oxygen concentration height can cause the optical attenuation of solar cell to increase, so will reduce the oxygen content in the body of solar cell as far as possible; And in whole solar cell manufacturing process, the logical oxygen of diffusion technology is maximum.Therefore, in this example embodiment, in order to reduce the optical attenuation of solar cell, pay particular attention under the prerequisite that guarantees diffusion quality in diffusion technology, reduce oxygen flow; And, at heat treatment process preferred obstructed oxygen, only logical a certain amount of nitrogen.
For example, in this example embodiment, the technological parameter in each step can be as follows:
In described step S11 (diffusion of constant source phosphorus), technological parameter can be:
Phosphorus source: high purity liquid state phosphorus oxychloride (PClO
3);
Time: 600 seconds;
Temperature: 800 ℃;
Little nitrogen (carrying liquid phosphorus source) flow: 1180-1250ml/min (can according to the resistivity adjustment of silicon chip);
Large nitrogen flow: 25000-27000ml/min (can finely tune according to the phosphorus source amount of source bottle);
Oxygen flow: 950-1050ml/min (can finely tune according to logical phosphorus source amount).
In described step S12 (limiting source phosphorus diffusion), technological parameter can be:
Time: 600 seconds;
The temperature of each warm area in quartz ampoule: fire door 842-846 ℃, warm area two 829-832 ℃, warm area three 820-824 ℃, warm area four 820-822 ℃, stove tail 822-830 ℃;
Large nitrogen flow: 20000-22000ml/min.
In described step S21 (diffusion of constant source phosphorus), technological parameter can be:
Time: 700-760 second;
The temperature of each warm area in quartz ampoule: fire door 842-846 ℃, warm area two 829-832 ℃, warm area three 820-824 ℃, warm area four 820-822 ℃, 822-830 ℃, stove tail (different diffusion furnace tubes are fine-tuning);
Little nitrogen (carrying liquid phosphorus source) flow: 1220-1250ml/min;
Large nitrogen flow: 25000-27000ml/min;
Oxygen flow: 1000-1050ml/min.
In an embodiment of the present disclosure, after described step S21, can also comprise:
S22: carry out the 280-300 cooling processing of second; In described step S12, technological parameter can be:
The temperature of each warm area: fire door 832-836 ℃, warm area two 819-822 ℃, warm area three 810-814 ℃, warm area four 810-812 ℃, stove tail 812-820 ℃;
Large nitrogen flow: 20000-22000ml/min.
The technological parameter of the described Technology for Heating Processing after diffusion technology can be:
Temperature: 680-700 ℃;
Large nitrogen flow: 20000-22000ml/min.
Finally, with RTS-4 type four point probe tester and the test of WT-1200 type minority carrier lifetime tester, the solar cell obtaining is tested respectively, the test result obtaining is as follows:
Average sheet resistance after diffusion: 78-85 Ω/;
Average minority carrier lifetime: 4.886-5.310 μ s.
Preparation method of solar battery in this example embodiment is applied in the small-scale production of the polycrystalline silicon solar cell based on Physical Metallurgy method that specification is 156*156mm, the product test result obtaining shows: the open circuit voltage of solar cell (Uoc) on average improves 3-7mV, short circuit current (Isc) on average improves 100-200mA, series resistance (Rs) on average reduces 0.6m Ω, conversion efficiency mean value (η) is increased to more than 17.40% from 17.01%, optical attenuation can be reduced to 0.1% (standard light decay condition, continuous illumination 72 hours).
Can find out, the performance of the solar cell of preparing by the preparation method of solar battery in this example embodiment obviously improves.Therefore, in this example embodiment, also provide a kind of by the solar cell of preparing according to above-mentioned any one preparation method of solar battery.
In sum, in preparation method of solar battery in the present invention and the solar cell of preparing by the method, mainly diffusion technology simple in the preparation method of the polycrystalline silicon solar cell based on Physical Metallurgy method of the prior art made into minute diffusion for the first time and spread twice diffusion for the second time, combining with follow-up Technology for Heating Processing again.Adopt the performance of the polycrystalline silicon solar cell based on Physical Metallurgy method that in the present invention, method is made obviously to improve.For example:
1) open circuit voltage of solar cell (mean value) is brought up to 0.630-0.633V from existing 0.625-0.630V, and short circuit current (mean value) is brought up to 8.35-8.44A from original 8.18-8.30A.
2) there is good ohmic contact diffusion: after sintering, the average series resistance of solar cell is reduced to 2.4-2.7m Ω from original 3.0-3.3m Ω.
3) reduced the optical attenuation of solar cell: the amount of oxygen of whole diffusion process, oxygen-supply quantity is all lower; Therefore the oxygen concentration in solar cell body is lower, so the optical attenuation of cell piece can drop to 0.1%.
4), by last low temperature heat-treatment process, improved the situation of the solar cell crystal structure variation causing due to reasons such as high temperature.
The disclosure is described by above-mentioned related embodiment, yet above-described embodiment is only for implementing example of the present disclosure.Must be pointed out that, the embodiment having disclosed does not limit the scope of the present disclosure.On the contrary, the change of doing within not departing from spirit and scope of the present disclosure and retouching, all belong to scope of patent protection of the present disclosure.
Claims (10)
1. a preparation method of solar battery, comprises diffusion technology; It is characterized in that described diffusion
Technique comprises:
S1. pretreated silicon chip is carried out to phosphorus diffusion for the first time, form the PN junction structure of N-type district and solar cell thereon;
S2. the silicon chip after diffusion is for the first time carried out to phosphorus diffusion for the second time, increase the phosphorus concentration on top layer, described N-type district.
2. preparation method of solar battery according to claim 1, is characterized in that, the described diffusion of phosphorus for the first time comprises:
S11. at 750-850 ℃ of temperature, carry out the 580-620 constant source phosphorus diffusion of second;
S12. by after 20-30 ℃ of temperature rising in described step S11, carry out the 580-620 restriction source phosphorus diffusion of second.
3. preparation method of solar battery according to claim 2, is characterized in that, in described step S11, constant source phosphorus is diffused in following atmosphere and carries out:
Little nitrogen flow: 1180-1250ml/min;
Large nitrogen flow: 25000-27000ml/min;
Oxygen flow: 950-1050ml/min.
4. preparation method of solar battery according to claim 2, is characterized in that, limits source phosphorus and be diffused in following atmosphere and carry out in described step S12:
Large nitrogen flow: 20000-22000ml/min.
5. preparation method of solar battery according to claim 1, is characterized in that, the described diffusion of phosphorus for the second time comprises:
S21. at 820-830 ℃ of temperature, carry out the 700-760 constant source phosphorus diffusion of second.
6. preparation method of solar battery according to claim 5, is characterized in that, in described step S21, constant source phosphorus is diffused in following atmosphere and carries out:
Little nitrogen flow: 1220-1250ml/min
Large nitrogen flow: 25000-27000ml/min
Oxygen flow: 1000-1050ml/min.
7. preparation method of solar battery according to claim 5, is characterized in that, after described step S21, also comprises:
S22: carry out the 280-300 cooling processing of second; Described cooling is processed and is carried out in following atmosphere:
Large nitrogen flow: 20000-22000ml/min.
8. preparation method of solar battery according to claim 1, is characterized in that, after described diffusion technology, also comprises:
At 680-720 ℃ of temperature, carry out the 1680-1800 Technology for Heating Processing of second.
9. preparation method of solar battery according to claim 8, is characterized in that, described Technology for Heating Processing is carried out in following atmosphere:
Large nitrogen flow: 20000-22000ml/min.
10. one kind by the solar cell of preparing according to the preparation method of solar battery described in claim 1-9 any one.
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| CN107093648A (en) * | 2017-03-22 | 2017-08-25 | 横店集团东磁股份有限公司 | A kind of diffusion annealing and dry etching method applied to solar cell |
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Application publication date: 20141119 |