CN109671802A - A kind of back passivation efficient polycrystalline silicon PERC double-side cell technique - Google Patents
A kind of back passivation efficient polycrystalline silicon PERC double-side cell technique Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 70
- 238000002161 passivation Methods 0.000 title claims abstract description 33
- 229910021420 polycrystalline silicon Inorganic materials 0.000 title claims abstract description 27
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 title claims abstract description 24
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 title claims abstract description 24
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 title claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 82
- 239000010703 silicon Substances 0.000 claims abstract description 82
- 238000000151 deposition Methods 0.000 claims abstract description 26
- 230000008021 deposition Effects 0.000 claims abstract description 22
- 238000005498 polishing Methods 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 238000009792 diffusion process Methods 0.000 claims abstract description 10
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims abstract description 10
- 238000007650 screen-printing Methods 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 9
- 239000011521 glass Substances 0.000 claims abstract description 7
- 238000001039 wet etching Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 36
- 230000008569 process Effects 0.000 claims description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 14
- 238000012545 processing Methods 0.000 claims description 14
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 13
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- 239000013528 metallic particle Substances 0.000 claims description 10
- 230000006378 damage Effects 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 238000005034 decoration Methods 0.000 claims description 8
- -1 hydrogen potassium oxide Chemical class 0.000 claims description 8
- 239000002086 nanomaterial Substances 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 238000001259 photo etching Methods 0.000 claims description 7
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 229940037003 alum Drugs 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 229910000562 Gilding metal Inorganic materials 0.000 claims description 5
- 229910019213 POCl3 Inorganic materials 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 230000006872 improvement Effects 0.000 claims description 5
- 239000002923 metal particle Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl chloride Substances ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 238000002525 ultrasonication Methods 0.000 claims description 5
- 206010057071 Rectal tenesmus Diseases 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- 208000012271 tenesmus Diseases 0.000 claims description 4
- 238000003631 wet chemical etching Methods 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 238000012937 correction Methods 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 229910021418 black silicon Inorganic materials 0.000 abstract description 14
- 238000005516 engineering process Methods 0.000 abstract description 12
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 238000005215 recombination Methods 0.000 abstract description 5
- 230000006798 recombination Effects 0.000 abstract description 5
- 229910017107 AlOx Inorganic materials 0.000 abstract description 4
- 230000005611 electricity Effects 0.000 abstract description 3
- 235000008216 herbs Nutrition 0.000 abstract description 3
- 210000002268 wool Anatomy 0.000 abstract description 3
- 239000004411 aluminium Substances 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 230000004298 light response Effects 0.000 abstract 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 8
- 229910004205 SiNX Inorganic materials 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 229920005591 polysilicon Polymers 0.000 description 7
- 238000005530 etching Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 229910021426 porous silicon Inorganic materials 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002061 nanopillar Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000006388 chemical passivation reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 238000010329 laser etching Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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Classifications
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- 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
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- 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
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- H01L31/0236—Special surface textures
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- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
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- H01L31/0684—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells double emitter cells, e.g. bifacial solar cells
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- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
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Abstract
The present invention relates to a kind of back to be passivated efficient polycrystalline silicon PERC double-side cell technique, removes damaged layer on surface of silicon slice and carries out twin polishing, carries out two-sided black silicon making herbs into wool with metal Aided Wet etching method, then carry out metal salt and clean.Then, reaming modification is carried out to flannelette using the two step aqueous slkalis for having concentration gradient；POCl in high temperature furnace3Double-sided deposition diffusion, polished backside remove phosphorosilicate glass and diffusion layer simultaneously；Then silicon chip back side ALD deposition AlOxAnd with PECVD device in AlOxThe SiN that film and front surface diffusion layer deposit respectivelyxFilm；With laser technology the step of carrying on the back the aperture of passivation layer fluting, silk-screen printing sintering back aluminium paste, back electrode and positive electrode.Battery of the invention can effectively improve single polycrystalline light trapping structure by special making herbs into wool technology, while guarantee that cell photoelectric transfer efficiency can be substantially improved in conjunction with the generating electricity on two sides advantage and dim light response characteristic of double-side cell in relatively low surface recombination velocity (S.R.V.).
Description
Technical field
The present invention relates to crystal silicon solar batteries fields, are passivated the two-sided electricity of efficient polycrystalline silicon PERC more particularly, to a kind of back
Pool process.
Background technique
P-type polysilicon battery is since mature production technology, manufacturing cost are low, at present and from now on for quite a long time
Inside still occupy most market shares.As what State Council issued creates production capacity single crystal battery efficiency about photovoltaic industry and is greater than
20%, polycrystalline battery efficiency is greater than 18% several instructions, and selection is easy to be compatible with existing large-scale production line, and easily controllable
The scheme of production cost, quickly updating core technology is trend of the times.P-type crystal silicon solar battery competes to continue holding
Power obtains bigger development and application, it is necessary to further increase transfer efficiency, while reduce production cost.
Currently, in the production technology of p-type polysilicon solar cell, the suede structure how to have been obtained in front surface, with
Promoting anti-reflective effect is to prepare high-efficiency polycrystalline silion cell top priority, and common process includes mechanical carving groove method, laser
Etching method, reactive ion etching method (RIE), chemical corrosion method (i.e. metal Aided Wet corrodes) etc..Wherein, mechanical carving groove method
Available lower surface reflectivity, but this method causes the mechanical damage of silicon chip surface than more serious, and its finished product
Rate is relatively low, so in the industrial production using less.It is that different cutting flowers is made of laser for laser ablation method
The surface of sample, striated and inverted pyramid shape all is produced out, and reflectivity can be down to 8.3%, but by it
The efficiency of battery obtained is all relatively low, not can be effectively used to production.RIE method can use different templates to be carved
Erosion, etching are usually dry etching, can form so-called black silicon structure in silicon chip surface, reflectivity can down to 4%,
But due to equipment valuableness, production cost is higher, therefore less at using in production in industry.And chemical corrosion method has technique letter
The features such as single, cheap price and excellent quality and prior art are compatible with well becomes most commonly used method in existing industry.
Almost at the same time, PERC structure and PERC two-sided structure technology are conceived to the back side of battery, significantly using passivation
It reduces the recombination velocity at the back side while increasing the back side and enter light, which gradually obtains in P-type crystal silicon battery greatly in recent years
Sizable application makes the efficiency of polycrystalline and single crystal battery promote~0.5% and~1% or more respectively.But PERC technology is to battery
Front without significantly improving, meet that serious and light loss is serious, and p-type polysilicon is using PERC and its two-sided structure better than front surface
The advantage of battery is difficult to give full play to.
Therefore, it is that current polysilicon realizes the effective of 20% battery efficiency that black silicon technology, which combines back passivation two-sided structure battery,
Approach, technology path are based on passivation cell emitter junction and rear side local contact (PERC) battery structure, pass through the corrosion of optimization
Solution realizes the micro-nano surface state for being easy to be passivated in the black silicon wool-weaving machine of industrialization, and silk-screen printing aluminium paste electrode is realized two-sided
Light-entry structure, the high-efficiency crystal silicon cell technology path that processing compatibility is strong and battery cost is controllable.But efficiently back passivation is double
Battery process route needs in face solve the problems, such as several aspects:
1) how while polysilicon surface promotes light trapping effect to guarantee excellent surface state, and then set in PECVD
The standby middle effective passivation for realizing silicon front surface；
2) excellent surface passivation effect is formed in cell backside；
3) cell backside forms effective electrode ohmic contact, reduces the contact resistance of battery.
Currently, being prepared using wet process metal catalytic chemical etching method black in the black silicon material manufacturing technology having disclosed
The patent of silicon, such as CN 102051618 A, CN 102768951 A be all that a nanometer suede is realized by one-step method (acid or alkali)
Face reaming controls surface state, and reaction speed is fast, and reaction process is not easy to control.It and be 104393114 A of CN is then in micron
Nanometer suede is prepared on the basis of flannelette, then carries out surface modification etching.It is uneven to there may be micro nano structure, after reduction
The passivation effect of continuous technique.Recombination velocity requirement for efficient crystal silicon battery, with the continuous promotion of body performance, to front surface
It is higher.
Aluminium oxide silicon nitride multilayer passivation film structure has both chemical passivation and field passivation in p-type crystalline silicon application aspect
Effect effectively reduces the recombination velocity of p-type silicon chip back surface, improves stability of the aluminum oxide film in prior art.
However, backside laser is slotted, the localized contact to be formed introduces considerable contact loss.Therefore, the compound speed of back surface how is reduced
Degree, so that subsequent silk-screen printing and high-sintering process be avoided to have become skill urgently to be resolved to the destruction of passivation layer
Art problem.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind will be provided with black silicon suede
The polysilicon in face is applied to a kind of simplification of efficient PERC two-sided structure solar cell, and is easy to the back passivation of scale of mass production
High-efficiency battery technique.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of back passivation efficient polycrystalline silicon PERC double-side cell technique, using following steps:
(1) silicon wafer is cleaned in NaOH/NaClO mixed ammonium/alkali solutions, removal surface damage layer, cutting stria, while complete
At twin polishing；
(2) silicon wafer after polishing is put into falling decoration metallic particles in metal salt solution,
(3) by above-mentioned silicon wafer in HF/H2O2The preparation of nanostructure flannelette is carried out in oxidizing solution；
(4) metallic particles removal processing is carried out to silicon wafer；
(5) silicon wafer with nanometer suede is put into potassium hydroxide solution improves nanometer suede structure；
(6) silicon wafer is put into progress flannelette amendment in low-concentration hydrogen potassium oxide solution；
(7) by above-mentioned silicon wafer in high temperature furnace POCl3Single sided deposition diffusion；
(8) using one-step method wet etching removal phosphorosilicate glass and the polished silicon slice back side；
(9) in board-like ALD equipment by front side of silicon wafer depositing Al2O3Layer；
(10) using PECVD device in above-mentioned silicon wafer polishing face and front deposition SiNxFilm；
(11) it slots aperture on the back passivation layer that silicon chip back side is formed；
(12) silk-screen printing sintering back alum gate line electrode, back silver electrode and positive silver electrode.
It is the potassium hydroxide solution of 0.5-2wt% in 20-50 DEG C of improvement nanometer suede structure that step (5), which uses concentration, is adopted
First time peak clipping and reaming are carried out with the potassium hydroxide solution of above-mentioned concentration, modifies black silicon flannelette, the modification time is 60-240s.
Under room temperature, appropriate reaction speed improves the amendment process window time, and higher alkaline concentration has preferably
Isotropic etch characteristic can effectively correct the depth (or height of nano-pillar) of nano aperture first.Based on (5) high concentration
Peak clipping characteristic can also promote the process time of above-mentioned processing step (3), so as to improve the depth and uniformity of nano-pore, be
The micro-nano flannelette of final uniformly appropriateness provides basis.
Step (6) uses concentration to repair for the low-concentration hydrogen potassium oxide solution of 0.05-0.1wt% in 20-50 DEG C of progress flannelette
Just, the processing time is 60-240s, to be finely adjusted to black silicon suede structure, the potassium hydroxide solution of low concentration embodies excellent
Anisotropic etch characteristic, can preferentially remove removal porous silicon residual, reduce interfacial state it is compound to subsequent photogenerated current
It influences.
Micro-nano sunken light flannelette is prepared using two step alkaline process alkali reamings using step (5), (6), responding speed is controllable, application
The anisotropic etching difference that various concentration aqueous slkali has, can be effectively improved the depth of black silicon nanostructure, and avoid
Black hole residual, guarantees excellent sunken light characteristic while silicon face state is effectively reduced.
It should also be noted that, step (6) give full play to aqueous slkali anisotropy preferential etch using low concentration alkali solution
Characteristic, achieve the purpose that correct micro-nano flannelette inclination angle and interfacial state, in favor of front surface diffusion and surface passivation.Such as
Fruit persistently uses high concentration alkali solution (such as concentration range in step (5)) to be modified, it is easy to cause to fall into light substantially
Lose and cause the optical loss of solar cell.And alkaline concentration is too low, it is possible to cause to remain effectively removing for porous silicon,
And then influence the photoelectric yield characteristic and its stability of solar cell.
In addition, step (5), (6) aqueous slkali chambering process at room temperature exploitation, also effectively reduce disappearing for acid solution
Consumption.
NaOH/NaClO mixed ammonium/alkali solutions described in step (1) (volume ratio 3:1~1:1), the step have both cleaning and
Polishing process, clear process procedure before saving promote production capacity.
Concentration is used to drop for the silver nitrate of 0.003-0.05mol/L or copper nitrate solution in ultrasonication in step (2)
Gilding metal particles, supersonic frequency 20-40kHz, ultrasonic power 0.2-0.5W/cm2.In the water environment of ultrasonic wave into
Row, can effectively control the size of Argent grain after falling decoration, to control the size and density of nano-porous structure.
Al described in step (9)2O3Layer with a thickness of 10-20nm.
In the SiN of silicon wafer polishing face deposition in step (10)xFilm with a thickness of 50-100nm, deposited in silicon wafer front surface
SiNxFilm with a thickness of 75-85nm.
Step (11) is carrying on the back passivation layer fluting aperture using laser slotting, selective wet chemical etching, photoetching or class photoetching process,
It is preferred that realizing back-contact electrode structure using laser slotting, it is capable of forming enhancing Al-BSF in this way.
The back side that step (12) can increase efficient polycrystalline silicon enters light, increases the output power of solar cell.
Compared with prior art, the present invention is directed to by merging black silicon flannelette and the preparation of efficient back passivated battery structure process
Polycrystalline silicon solar cell is produced low-cost high-efficiency structure solar cell, is finally realized scale based on existing extensive producing line
Volume production effect.According to above-mentioned high-efficiency polycrystalline PERC double-side cell process route, in terms of the black silicon making herbs into wool of battery simple process effectively,
Cost is controllable.The overlayer passivation of aluminium oxide and silicon nitride film reduces back surface recombination velocity, avoids subsequent silk-screen printing
Destruction with high-sintering process to passivation layer.Double-side cell structure increases incidence surface, effectively promotion output power.
The present invention has obtained having industrial application prospect by novel alkali chambering process, using metal auxiliary caustic solution
Novel micro nanometer rice flannelette, can not only realize good light trapping structure in polysilicon chip front surface, meanwhile, in conjunction with the two-sided electricity of PERC
Pool structure also achieves the excellent passivation effect of front surface and the back side, according to preliminary test, realizes the prominent of efficiency 20.6%
It is broken.
Detailed description of the invention
Fig. 1 is the stereoscan photograph of silicon wafer after flannelette amendment.
Specific embodiment
A kind of back passivation efficient polycrystalline silicon PERC double-side cell technique, using following steps:
(1) silicon wafer is cleaned in NaOH/NaClO mixed ammonium/alkali solutions, the volume ratio of NaOH and NaClO can control 3:
1~1:1, the step have both cleaning and polishing process, clear process procedure before saving, and promote production capacity removal surface damage layer, cut
Secant trace, is completed at the same time twin polishing；
(2) silicon wafer after polishing is put into falling decoration metallic particles in metal salt solution, for example, can use concentration for
The silver nitrate or copper nitrate solution of 0.003-0.05mol/L is in ultrasonication tenesmus gilding metal particles, supersonic frequency 20-
40kHz, ultrasonic power 0.2-0.5W/cm2.It is carried out in the water environment of ultrasonic wave, can effectively control silver after falling decoration
The size of grain, to control the size and density of nano-porous structure；
(3) by above-mentioned silicon wafer in HF/H2O2The preparation of nanostructure flannelette is carried out in oxidizing solution；
(4) metallic particles removal processing is carried out to silicon wafer；
(5) using concentration is the potassium hydroxide solution of 0.5-2wt% in 20-50 DEG C of improvement nanometer suede structure, use
The potassium hydroxide solution for stating concentration carries out first time peak clipping and reaming, modifies black silicon flannelette, and the modification time is 60-240s.Room temperature
Under the conditions of, appropriate reaction speed improve amendment the process window time, and higher alkaline concentration have preferably respectively to
Same sex etching characteristic can effectively correct the depth (or height of nano-pillar) of nano aperture first.Based on (5) high concentration peak clipping
Characteristic can also promote the process time of above-mentioned processing step (3), be final so as to improve the depth and uniformity of nano-pore
Uniformly the micro-nano flannelette of appropriateness provides basis；
(6) using concentration is the low-concentration hydrogen potassium oxide solution of 0.05-0.1wt% at 20-50 DEG C of progress flannelette amendment, place
The reason time is 60-240s, to be finely adjusted to black silicon suede structure, the potassium hydroxide solution of low concentration embody it is excellent it is each to
Anisotropic etch characteristic can preferentially remove removal porous silicon residual, reduce the interfacial state influence compound to subsequent photogenerated current；
(7) by above-mentioned silicon wafer in high temperature furnace POCl3Single sided deposition diffusion；
(8) using one-step method wet etching removal phosphorosilicate glass and the polished silicon slice back side；
(9) Al for being 10-20nm by front side of silicon wafer deposition thickness in board-like ALD equipment2O3Layer；
(10) using PECVD device in above-mentioned silicon wafer polishing face and front deposition SiNxFilm, wherein silicon wafer polishing face is heavy
Long-pending SiNxFilm with a thickness of 50-100nm, in the SiN of silicon wafer front surface depositionxFilm with a thickness of 75-85nm；
(11) using laser slotting, selective wet chemical etching, photoetching or class photoetching process in back passivation layer fluting aperture, preferably
Back-contact electrode structure is realized using laser slotting, is capable of forming enhancing Al-BSF in this way；
(12) silk-screen printing sintering back alum gate line electrode, back silver electrode and positive silver electrode, increase the back side of efficient polycrystalline silicon
Enter light, increases the output power of solar cell.
In the above method most critical be technically characterized in that using step (5), (6) using two step alkaline process alkali reamings prepare it is micro-
The sunken light flannelette of nanometer, responding speed is controllable, and the anisotropic etching difference having using various concentration aqueous slkali can effectively change
It is apt to the depth of black silicon nanostructure, and black hole is avoided to remain, guarantees excellent sunken light while silicon face state is effectively reduced
Characteristic.It should also be noted that, step (6) give full play to the spy of aqueous slkali anisotropy preferential etch using low concentration alkali solution
Property, achieve the purpose that inclination angle and the interfacial state of correcting micro-nano flannelette, in favor of front surface diffusion and surface passivation.If held
It is continuous to be modified using high concentration alkali solution (such as concentration range in step (5)), it is easy to cause to fall into the substantially loss of light
And lead to the optical loss of solar cell.And alkaline concentration is too low, it is possible to cause to remain effectively removing for porous silicon, in turn
Influence the photoelectric yield characteristic and its stability of solar cell.In addition, step (5), (6) aqueous slkali chambering process at room temperature
Exploitation, also effectively reduce the consumption of acid solution.
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
A kind of back passivation efficient polycrystalline silicon PERC two-sided structure battery process, using following steps:
(1) volume ratio of former silicon wafer cleaning polishing in NaOH/NaClO mixed ammonium/alkali solutions, NaOH and NaClO are 2:1, are gone
Except surface damage layer, cutting stria etc.；
(2) silicon wafer after polishing is carried out to silver-colored falling decoration in a solution of hydrofluoric acid, uses concentration for the silver nitrate of 0.02mol/L
What solution carried out in the water-bath of additional ultrasonic.Wherein, supersonic frequency 30kHz, ultrasonic power 0.4W/cm2.By drawing
Excess of imports acoustic control, can effectively control the size and density of Argent grain, to reach the optimization (nano-pore to nanometer suede structure
The aperture size and density in hole)；
(3) above-mentioned silicon wafer is put into HF/H2O2Nanometer suede preparation is carried out in mixed solution；
(4) above-mentioned silicon wafer is put into hydrogen peroxide and ammonium hydroxide mixed solution and removes anionic metal；
(5) by above-mentioned silicon wafer in 1wt%KOH aqueous slkali, controlled at 30 DEG C of processing 120s, reaming and reduction are carried out
Nano-void height；
(6) above-mentioned silicon wafer is carried out to flannelette modification in the KOH aqueous slkali of 0.1wt%, is handled controlled at 30 DEG C
120s, the Porous Silicon structures that removal metal auxiliary corrosion step (4) leaves, as shown in Fig. 1 scanning electron microscope microscope.
(7) surface phosphorosilicate glass (PSG) is removed using wet-method etching equipment and realizes polished backside；
(8) in tubular type or board-like PECVD device front deposition thickness about 80nm SiNx,
(9) using ALD equipment in silicon wafer polishing face backside deposition 10-20nm or so AlOx, then set using tubular type PECVD
The SiN of standby deposition 50-100nm or soxLayer is in AlOxPassivation layer；
(10) 85nm silicon nitride layer is deposited in Tubular PECVD device；
(11) using laser or wet process back passivation layer fluting aperture；
(12) silk-screen printing sintering back alum gate line, back electrode and positive electrode, test battery efficiency, the data tested are such as
Shown in table 1.
1 battery testing data list of table
The data of table 1 further illustrate which kind of technical effect the prepared battery of the above method can obtain.It is double
Face PERC structure solar cell significantly reduces the compound action of traditional Al-BSF, hence it is evident that improves open-circuit voltage.But it is same to close
Key is that factor is, using the aqueous slkali amendment technique for having concentration gradient, while keeping high light trapping effect (Jsc >
39.7mA), it is compound to effectively reduce solar cell front surface.For example, claiming to realize efficiency in beneficial effects of the present invention
20.6% breakthrough.
Embodiment 2
A kind of back passivation efficient polycrystalline silicon PERC double-side cell technique, using following steps:
(1) silicon wafer is cleaned in NaOH/NaClO mixed ammonium/alkali solutions, removal surface damage layer, cutting stria, while complete
At twin polishing, the volume ratio of NaOH and NaClO are 3:1；
(2) silicon wafer after polishing is put into falling decoration metallic particles in metal salt solution, uses concentration for 0.003mol/L's
Copper nitrate solution is in ultrasonication tenesmus gilding metal particles, supersonic frequency 20kHz, ultrasonic power 0.5W/cm2；
(3) by above-mentioned silicon wafer in HF/H2O2The preparation of nanostructure flannelette is carried out in oxidizing solution；
(4) metallic particles removal processing is carried out to silicon wafer；
(5) use concentration for the potassium hydroxide solution of 0.5wt%, in 20 DEG C of at a temperature of processing silicon wafer 240s, improvement is received
Rice porous structure；
(6) at a temperature of processing silicon wafer 240s of the concentration for the low-concentration hydrogen potassium oxide solution of 0.05wt% at 20 DEG C is used,
Second-order correction is carried out to flannelette；
(7) by above-mentioned silicon wafer in high temperature furnace POCl3Single sided deposition diffusion；
(8) using one-step method wet etching removal phosphorosilicate glass and the polished silicon slice back side；
(9) Al for being 10nm by front side of silicon wafer deposition thickness in board-like ALD equipment2O3Layer；
(10) use PECVD device in above-mentioned silicon wafer polishing face deposition thickness for the SiN of 50nmxFilm, in step (9)
Front deposition thickness be 75nm SiNxFilm；
(11) it is slotted on the back passivation layer that silicon chip back side is formed aperture using the method for selective wet chemical etching；
(12) silk-screen printing sintering back alum gate line electrode, back silver electrode and positive silver electrode.
Embodiment 3
A kind of back passivation efficient polycrystalline silicon PERC double-side cell technique, using following steps:
(1) silicon wafer is cleaned in NaOH/NaClO mixed ammonium/alkali solutions, removal surface damage layer, cutting stria, while complete
At twin polishing, the volume ratio of NaOH and NaClO are 1:1；
(2) silicon wafer after polishing is put into falling decoration metallic particles in metal salt solution, uses concentration for the nitre of 0.05mol/L
Sour silver solution is in ultrasonication tenesmus gilding metal particles, supersonic frequency 40kHz, ultrasonic power 0.2W/cm2；
(3) by above-mentioned silicon wafer in HF/H2O2The preparation of nanostructure flannelette is carried out in oxidizing solution；
(4) metallic particles removal processing is carried out to silicon wafer；
(5) it uses concentration for the potassium hydroxide solution of 2wt%, in 50 DEG C of at a temperature of processing silicon wafer 60s, it is more to improve nanometer
Pore structure；
(6) use concentration for the low-concentration hydrogen potassium oxide solution of 0.1wt% 50 DEG C at a temperature of handle silicon wafer 60s, it is right
Flannelette carries out second-order correction；
(7) by above-mentioned silicon wafer in high temperature furnace POCl3Single sided deposition diffusion；
(8) using one-step method wet etching removal phosphorosilicate glass and the polished silicon slice back side；
(9) Al for being 20nm by front side of silicon wafer deposition thickness in board-like ALD equipment2O3Layer；
(10) use PECVD device in above-mentioned silicon wafer polishing face deposition thickness for the SiN of 100nmxFilm, in step (9)
In front deposition thickness be 85nm SiNxFilm；
(11) it is slotted on the back passivation layer that silicon chip back side is formed aperture using photo-etching processes；
(12) silk-screen printing sintering back alum gate line electrode, back silver electrode and positive silver electrode.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (8)
1. a kind of back is passivated efficient polycrystalline silicon PERC double-side cell technique, which is characterized in that the technique uses following steps:
(1) silicon wafer is cleaned in NaOH/NaClO mixed ammonium/alkali solutions, removal surface damage layer, cutting stria are completed at the same time double
Face polishing；
(2) silicon wafer after polishing is put into falling decoration metallic particles in metal salt solution,
(3) by above-mentioned silicon wafer in HF/H2O2The preparation of nanostructure flannelette is carried out in oxidizing solution；
(4) metallic particles removal processing is carried out to silicon wafer；
(5) silicon wafer with nanometer suede is put into potassium hydroxide solution improves nanometer suede structure；
(6) silicon wafer is put into progress flannelette amendment in low-concentration hydrogen potassium oxide solution；
(7) by above-mentioned silicon wafer in high temperature furnace POCl3Single sided deposition diffusion；
(8) using one-step method wet etching removal phosphorosilicate glass and the polished silicon slice back side；
(9) in board-like ALD equipment by front side of silicon wafer depositing Al2O3Layer；
(10) the front deposition SiN using PECVD device in above-mentioned silicon wafer polishing face and step (9)xFilm；
(11) it slots aperture on the back passivation layer that silicon chip back side is formed；
(12) silk-screen printing sintering back alum gate line electrode, back silver electrode and positive silver electrode.
2. a kind of back according to claim 1 is passivated efficient polycrystalline silicon PERC double-side cell technique, which is characterized in that step
(5) use concentration for the potassium hydroxide solution of 0.5-2wt%, in 20-50 DEG C of at a temperature of processing silicon wafer 60-240s, improvement is received
Rice porous structure.
3. a kind of back according to claim 1 is passivated efficient polycrystalline silicon PERC double-side cell technique, which is characterized in that step
(6) use concentration for the low-concentration hydrogen potassium oxide solution of 0.05-0.1wt% 20-50 DEG C at a temperature of handle silicon wafer 60-
240s carries out second-order correction to flannelette.
4. a kind of back according to claim 1 is passivated efficient polycrystalline silicon PERC double-side cell technique, which is characterized in that step
(1) volume ratio of NaOH and NaClO is 3:1~1:1 in the NaOH/NaClO mixed ammonium/alkali solutions described in.
5. a kind of back according to claim 1 is passivated efficient polycrystalline silicon PERC double-side cell technique, which is characterized in that step
(2) it is the silver nitrate of 0.003-0.05mol/L or copper nitrate solution in ultrasonication tenesmus gilding metal particles that concentration is used in, is surpassed
Acoustic frequency is 20-40kHz, ultrasonic power 0.2-0.5W/cm2。
6. a kind of back according to claim 1 is passivated efficient polycrystalline silicon PERC double-side cell technique, which is characterized in that step
(9) Al described in2O3Layer with a thickness of 10-20nm.
7. a kind of back according to claim 1 is passivated efficient polycrystalline silicon PERC double-side cell technique, which is characterized in that step
(10) in the SiN of silicon wafer polishing face deposition inxFilm with a thickness of 50-100nm, in the SiN of front side of silicon wafer depositionxThe thickness of film
Degree is 75-85nm.
8. a kind of back according to claim 1 is passivated efficient polycrystalline silicon PERC double-side cell technique, which is characterized in that step
(11) using laser slotting, selective wet chemical etching, photoetching or class photoetching process in back passivation layer fluting aperture.
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| CN111029441A (en) * | 2019-12-24 | 2020-04-17 | 遵义师范学院 | Grid line passivation contact PERC solar cell and preparation method thereof |
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