CN103367521B - A kind of method reducing solar cell dead layer - Google Patents
A kind of method reducing solar cell dead layer Download PDFInfo
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- CN103367521B CN103367521B CN201110460084.3A CN201110460084A CN103367521B CN 103367521 B CN103367521 B CN 103367521B CN 201110460084 A CN201110460084 A CN 201110460084A CN 103367521 B CN103367521 B CN 103367521B
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- 238000000034 method Methods 0.000 title claims abstract description 39
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 48
- 239000010703 silicon Substances 0.000 claims abstract description 48
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000001301 oxygen Substances 0.000 claims abstract description 32
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 32
- 238000000746 purification Methods 0.000 claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 238000009792 diffusion process Methods 0.000 claims description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000010453 quartz Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 5
- 125000004437 phosphorous atom Chemical group 0.000 abstract description 9
- 230000003595 spectral effect Effects 0.000 abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 6
- 239000011574 phosphorus Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 description 23
- 238000000151 deposition Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000505 pernicious effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 101100373011 Drosophila melanogaster wapl gene Proteins 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 210000004483 pasc Anatomy 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000008216 herbs Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
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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
- 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
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Abstract
The invention provides a kind of method reducing solar cell dead layer, comprise step: 1) enter boat; 2) heat up; 3) front purification; 4) deposit; 5) after-purification; 6) lower the temperature; 7) boat is gone out; Also be included in step 4) and step 5) between step 41) rear oxidation, with the oxygen of preset flow logical Preset Time under preset temperature or carry out step 5) time carry out rear oxidation.Rear oxidation process is added before the present invention purifies after deposition or in after-purification process, pass into a certain amount of oxygen, another layer oxide film is defined between the oxide-film formed in front purified treatment and PN junction, the thickness of oxide-film is added after the P/N knot formed, when phosphorus atoms spreads to silicon chip through oxide-film and oxygen react, the concentration of PN junction surface phosphorus is reduced further, effectively reduce dead layer, simultaneous oxidation film is got rid of after chemical treatment, make the depth shallower of PN junction, effectively improve the spectral response of battery.
Description
Technical field
The present invention relates to semiconductor processing technology field, more particularly, relate to a kind of production method of polysilicon chip.
Background technology
Crystal silicon solar batteries by large-scale application to every field, its good stability and ripe technological process are the bases of its large-scale application.At present, the manufacturing process fundamental norms of solar cell, please refer to accompanying drawing 1, and its main handling process is: silicon chip is through cleaning and making herbs into wool, and what the silicon chip surface of light was originally become is uneven, increases the absorptivity of silicon chip to light; Through High temperature diffusion, mix N-type impurity by P-type silicon matrix, thus form P/N knot; By plasma etching and dephosphorization silex glass, the oxide layer at the side of silicon chip and the back side is removed again; By the diffusingsurface deposition layer of sin x film of PECVD at silicon chip, reduce silicon chip to the reflection of incident light; Print back electrode, back of the body electric field and front electrode, sintering makes electrode and silicon chip form alloy structure, finally carries out electric performance test and stepping to silicon chip, finally packs warehouse-in.Wherein, second step diffusion technology is most important link in production process, good and the bad performance and the conversion efficiency that directly determine battery of P/N knot, so how being formed good in diffusion process is the emphasis that we study.
The heart of solar cell is a P/N knot, can not just can be formed with together with the semiconductor contact of two pieces dissimilar (p-type and N-shapeds) simply.Manufacture P/N knot, the part that must make one piece of complete semiconductor crystal is territory, p type island region, and another part is N-type region territory.Namely realize contacting of P type and N type semiconductor at crystals.N
+the emitter region N of/P crystal silicon solar batteries
+it is the high concentration shallow junction region diffuseed to form by phosphorus, we know in this diffusion region, phosphorus atoms due to electric torpescence (i.e. electric neutrality) is in interstitial void position can cause lattice defect, simultaneously because the atomic radius of phosphorus, silicon does not mate, the phosphorus of high concentration also can cause lattice mismatch.So in crystal silicon solar batteries top layer the life-span of minority carrier extremely low, the light output contribution of the photo-generated carrier that produces of short-wave photons that top layer absorbs to battery is very micro-, and this top layer is called " dead layer ".In order to reduce the impact of " dead layer ", improve the spectral response of battery, we can reduce diffusion into the surface concentration, junction depth is done shallow, but doing technology difficulty like this can increase and series resistance can increase, and causes conversion efficiency to reduce.
Please refer to Fig. 2, existing solar battery diffusion technology process is: enter boat, and the quartz boat filling silicon chip is put into diffusion furnace assigned address; Heat up, heat in diffusion furnace, make silicon chip reach the temperature of needs; Front purification, in order to ensure the cleannes in boiler tube, needs logical a certain amount of nitrogen and oxygen; Depositing operation, leads to phosphorus trichloride in the diffusion furnace of high temperature and reacts together with oxygen, then its main product five phosphorous oxide and pasc reaction, and what finally generate is elemental phosphorously diffused in crystalline silicon, forms PN junction; After-purification, passes into a large amount of nitrogen and purges boiler tube before oven door opening; Cooling, diffusion terminates rear needs and temperature is dropped to initial temperature; Go out boat, the quartz boat filling silicon chip is taken out.Although logical a certain amount of oxygen, makes P-type silicon substrate Surface Creation one deck thin oxide layer, to reach the effect to shallow junction and minimizing " dead layer " in front purifying step before the deposition.But the bad control of thickness of the oxide-film in presedimentary front purifying step, if the too thick formation that can affect PN junction, and then affects efficiency; Too thin can reduction reduces the effect of dead layer, in order to ensure a good P/N knot general before the thickness of oxide layer of purification all can be very thin, so reduce the effect reducing dead layer.
In sum, reduce solar cell dead layer while the P/N knot how to ensure, to improve the spectral response of battery, become current those skilled in the art's problem demanding prompt solution.
Summary of the invention
In view of this, the invention provides a kind of method reducing solar cell dead layer, to improve the spectral response of battery.
In order to achieve the above object, the invention provides following technical scheme:
Reduce a method for solar cell dead layer, comprise step:
1) enter boat, put the quartz boat filling silicon chip into diffusion furnace assigned address;
2) heat up, make silicon chip from initial heating temperature to diffusion temperature;
3) front purification, passes into nitrogen and oxygen in diffusion furnace;
4) deposit, form PN junction at silicon chip surface;
5) after-purification, passes into nitrogen in diffusion furnace;
6) lower the temperature, after diffusion terminates, the temperature of silicon chip is dropped to initial temperature;
7) go out boat, quartz boat is taken out from diffusion furnace;
Also be included in step 4) and step 5) between or with step 5) step 41 of simultaneously carrying out) rear oxidation, with the oxygen of preset flow logical Preset Time under preset temperature.
Preferably, in the method for above-mentioned minimizing solar cell dead layer, described preset temperature is 810-870 degree.
Preferably, in the method for above-mentioned minimizing solar cell dead layer, described preset flow is 500-1000sccm, and Preset Time is 5-20 minute.
Preferably, in the method for above-mentioned minimizing solar cell dead layer, described oxygen is dry oxygen or wet oxygen.
Preferably, described in the method for above-mentioned minimizing solar cell dead layer, diffusion temperature is 850 degree.
As can be seen from above-mentioned technical scheme, first the method for minimizing solar cell dead layer provided by the invention is that the quartz boat filling silicon chip is put into diffusion furnace; From initial heating temperature to diffusion temperature; Pass into oxygen and nitrogen, keep the cleanliness factor of diffusion furnace to form layer oxide film simultaneously; Deposition, forms PN junction at silicon chip surface; Logical nitrogen makes cleaning in stove; Cooling; Finally take out quartz boat.The present invention is after deposition before after-purification or add rear oxidation process in after-purification process, namely with the oxygen of preset flow logical Preset Time under preset temperature.Another layer oxide film is defined between the oxide-film formed in front purified treatment and PN junction, the thickness of oxide-film is added after the P/N knot formed, when phosphorus atoms spreads to silicon chip through oxide-film and oxygen react, the concentration of PN junction surface phosphorus is reduced further, effectively reduce dead layer, simultaneous oxidation film is got rid of after chemical treatment, makes the depth shallower of PN junction, effectively improves the spectral response of battery.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is battery production technology flow chart in prior art;
The process chart of the method for the minimizing solar cell dead layer that Fig. 2 provides for prior art;
The process chart of the method for the minimizing solar cell dead layer that Fig. 3 provides for an embodiment of the present invention;
The process chart of the method for the minimizing solar cell dead layer that Fig. 4 provides for the another kind of embodiment of the present invention.
Embodiment
The invention provides a kind of method reducing solar cell dead layer, to improve the spectral response of battery.
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Please refer to the process chart of the method for the minimizing solar cell dead layer that accompanying drawing 3, Fig. 3 provides for the embodiment of the present invention; The process chart of the method for the minimizing solar cell dead layer that Fig. 4 provides for the another kind of embodiment of the present invention.
The invention provides a kind of method reducing solar cell dead layer, comprise the following steps:
Step S1: enter boat;
First silicon chip is filled quartz boat, then the quartz boat filling silicon chip put into manipulator the position that diffusion furnace specifies, diffusion furnace is that the diffusion of silicon chip provides environment.
Step S2: heat up;
The initial temperature when quartz boat filling silicon chip puts into diffusion furnace is greatly about about 700 degree, and generally spread the diffusion temperature of needs at about 850 degree, therefore need to heat the silicon chip in diffusion furnace, make the temperature of the silicon chip in diffusion furnace reach temperature required for diffusion.The process of the temperature of silicon chip from initial heating temperature to diffusion temperature is called temperature-rise period, and when the temperature of silicon chip rises to diffusion temperature, heating step terminates.
Step S3: front purification;
Will ensure the cleannes in diffusion furnace before carrying out depositing operation, therefore the front purified treatment of the embodiment of the present invention for pass into nitrogen in diffusion furnace, to discharge the foreign gas in diffusion furnace, ensures the cleannes in diffusion furnace.Simultaneously in order to reduce the dead layer of solar cell, a certain amount of oxygen is passed into when logical nitrogen, make P-type silicon substrate Surface Creation one deck thin oxide layer, phosphorus atoms diffuses in silicon body through oxide layer again, because phosphorus atoms and oxygen react, reduce the concentration of diffusion into the surface, decrease the dead layer of solar cell.
Step S4: deposition;
Depositing operation is the most important step process of diffusing procedure in crystal silicon battery manufacture process, main process is that phosphorus oxychloride to be led in the diffusion furnace of high temperature and to participate in reaction together with oxygen, reacted primary product phosphorus pentoxide and pasc reaction, finally generate elemental phosphorous, elemental phosphorously be diffused in crystalline silicon through oxide layer, form N-type on the surface of P-type silicon sheet, form P/N knot.Good and the bad performance and the conversion efficiency that directly determine battery of P/N knot.
Because while nitrogen logical in front purification process, mixture of oxygen passes into together, at P-type silicon substrate Surface Creation one deck thin oxide layer, phosphorus atoms diffuses in silicon body through oxide layer again, because phosphorus atoms and oxygen react, although the dead layer of solar cell can be reduced, but the bad control of the thickness of the oxide-film in front purification process, can affect the formation of P/N knot, and then affect efficiency if too thick; Just will reduce the effect of effect reducing dead layer if too thin, general all thinner at the thickness of the oxide layer of front purification in order to ensure a good P/N knot, the effect reducing dead layer will be reduced like this.
Object of the present invention is exactly can reduce dead layer again while the P/N knot that formation one is good, adds a step S41 after step s4: rear oxidation in order to reach the present invention of this object;
Rear oxidation technique is with the oxygen of the flow preset logical Preset Time at the temperature preset after depositing operation terminates, continue to produce oxide-film on the surface of P/N knot like this, phosphorus atoms when spreading to silicon chip through oxide-film and oxygen react, the concentration making P/N tie the phosphorus on surface reduces, and effectively reduces the dead layer of solar cell.After machining, oxide layer all can be removed after chemical treatment simultaneously, makes the depth shallower that P/N ties, thus improves the spectral response of battery.
Step S5: after-purification;
When oven door opening, non-volatile in operating personnel's operational environment in order to ensure the pernicious gas in diffusion furnace, need the pernicious gas in diffusion furnace to drain in advance, in diffusion furnace, therefore pass into a large amount of nitrogen when after-purification process the pernicious gas in diffusion furnace is purged.
Pass into after this step that oxygen forms oxide layer further only needs namely to form P/N knot after step s4 and increase, and step S5 after-purification passes into a large amount of nitrogen in diffusion furnace, what it will be appreciated by those skilled in the art that is that rear oxidation can carry out in the process of after-purification simultaneously, namely the flow preset to diffusion furnace while logical nitrogen leads to the oxygen of Preset Time at the temperature preset, the effect reducing solar cell dead layer can be reached equally, improve the object of the spectral response of battery.
Step S6: cooling;
Diffusion terminate after, we need temperature is dropped to initial temperature about 700 degree, cooling process process generally from depositing operation terminate rear, silicon chip is dropped to initial temperature about 700 degree end from diffusion temperature.
Step S7: go out boat;
Manipulator takes out the quartz boat filling silicon chip processed in diffusion furnace, and the silicon chip processed is used for follow-up application.
The preset temperature provided in specific embodiments of the invention is 810-870 degree, namely after diffusion technology completes, directly can pass into oxygen in diffusion furnace.
In order to make the thickness of oxide layer even, with the preset flow of 500-1000sccm logical oxygen in diffusion furnace in the embodiment of the present invention.In order to avoid waste can not make again the thickness of oxide-film too thin simultaneously, Preset Time is set to 5-20 minute.
The oxygen provided in the embodiment of the present invention can be dry oxygen also can be the wet oxygen being mixed with water vapour, and operating personnel can select as required.
The temperature that phosphorus atoms spreads in silicon chip is about 850 degree, and the diffusion temperature therefore in the present invention is 850 degree, needs first the temperature in diffusion furnace to be risen to diffusion temperature before depositing operation, namely about 850 degree.
In this specification, each embodiment adopts the mode of going forward one by one to describe, and what each embodiment stressed is the difference with other embodiments, between each embodiment identical similar portion mutually see.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (3)
1. reduce a method for solar cell dead layer, comprise step:
1) enter boat, put the quartz boat filling silicon chip into diffusion furnace assigned address;
2) heat up, make silicon chip from initial heating temperature to diffusion temperature;
3) front purification, passes into nitrogen and oxygen in diffusion furnace;
4) deposit, form PN junction at silicon chip surface;
5) after-purification, passes into nitrogen in diffusion furnace;
6) lower the temperature, after diffusion terminates, the temperature of silicon chip is dropped to initial temperature;
7) go out boat, quartz boat is taken out from diffusion furnace;
It is characterized in that, be also included in step 4) and step 5) between or step 5) step 41 of simultaneously carrying out) rear oxidation, with the oxygen of preset flow logical Preset Time under preset temperature;
Described preset temperature is 810-870 degree, and described preset flow is 500-1000sccm, and Preset Time is 5-20 minute.
2. the method for minimizing solar cell dead layer according to claim 1, is characterized in that, described oxygen is dry oxygen or wet oxygen.
3. the method for minimizing solar cell dead layer according to claim 1, is characterized in that, described diffusion temperature is 850 degree.
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| CN103367521B true CN103367521B (en) | 2016-04-06 |
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| CN103632933B (en) * | 2013-11-29 | 2016-08-17 | 英利集团有限公司 | The Boron diffusion method of N-type silicon chip, crystal silicon solar energy battery and preparation method thereof |
| CN103632934B (en) * | 2013-11-29 | 2017-09-19 | 英利集团有限公司 | The Boron diffusion methods of N type silicon chips, crystal silicon solar energy battery and preparation method thereof |
| CN103632935B (en) * | 2013-11-29 | 2016-08-24 | 英利集团有限公司 | The Boron diffusion method of N type silicon chip, crystal silicon solar energy battery and preparation method thereof |
| CN104701425A (en) * | 2015-04-08 | 2015-06-10 | 常州时创能源科技有限公司 | Diffusion post treatment technique of crystalline silicon solar cell |
| CN105200525A (en) * | 2015-08-20 | 2015-12-30 | 黄冬焱 | Battery diffusion aftertreatment process |
| CN105489711B (en) * | 2016-01-26 | 2017-11-07 | 常州天合光能有限公司 | A kind of preparation method of all back-contact electrodes solar cell ultra low surface concentration front-surface field |
| CN109888062B (en) * | 2019-03-29 | 2021-03-30 | 江苏日托光伏科技股份有限公司 | MWT solar cell laser SE + alkali polishing diffusion process |
| CN114744072A (en) * | 2021-01-07 | 2022-07-12 | 徐州中辉光伏科技有限公司 | A kind of monocrystalline silicon cell sheet diffusion efficiency improvement and post-diffusion treatment oxidation process |
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