CN108365023A - Coating process for the black silicon face passivation of polycrystalline - Google Patents
Coating process for the black silicon face passivation of polycrystalline Download PDFInfo
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- CN108365023A CN108365023A CN201810091392.5A CN201810091392A CN108365023A CN 108365023 A CN108365023 A CN 108365023A CN 201810091392 A CN201810091392 A CN 201810091392A CN 108365023 A CN108365023 A CN 108365023A
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- 229910021418 black silicon Inorganic materials 0.000 title claims abstract description 55
- 238000002161 passivation Methods 0.000 title claims abstract description 26
- 238000000576 coating method Methods 0.000 title claims abstract description 16
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 59
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 59
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 34
- 239000010703 silicon Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 25
- 230000007797 corrosion Effects 0.000 claims abstract description 10
- 238000005260 corrosion Methods 0.000 claims abstract description 10
- 238000005520 cutting process Methods 0.000 claims abstract description 8
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims abstract description 8
- 229920005591 polysilicon Polymers 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims abstract description 7
- 238000005530 etching Methods 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 52
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 33
- 229910000077 silane Inorganic materials 0.000 claims description 33
- 238000000151 deposition Methods 0.000 claims description 31
- 229910021529 ammonia Inorganic materials 0.000 claims description 26
- 230000035484 reaction time Effects 0.000 claims description 16
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 235000013842 nitrous oxide Nutrition 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910003978 SiClx Inorganic materials 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 65
- 230000000694 effects Effects 0.000 abstract description 9
- 229920001296 polysiloxane Polymers 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000010409 thin film Substances 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 description 17
- 238000002310 reflectometry Methods 0.000 description 13
- 229910003460 diamond Inorganic materials 0.000 description 10
- 239000010432 diamond Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 230000003321 amplification Effects 0.000 description 4
- 230000003667 anti-reflective effect Effects 0.000 description 4
- 238000003199 nucleic acid amplification method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 2
- 235000008216 herbs Nutrition 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- SBEQWOXEGHQIMW-UHFFFAOYSA-N silicon Chemical compound [Si].[Si] SBEQWOXEGHQIMW-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/308—Oxynitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/345—Silicon nitride
-
- 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
- H01L31/1868—Passivation
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
- Formation Of Insulating Films (AREA)
Abstract
The present invention relates to a kind of coating process for the black silicon face passivation of polycrystalline, characterized in that includes the following steps：（1）The matte that the polysilicon chip of Buddha's warrior attendant wire cutting is prepared to nano aperture by metal catalytic chemical corrosion method, by diffuseing to form PN junction, etching removal edge and back side PN junction；（2）Using PECVD filming equipments first layer silicon nitride film is deposited in front side of silicon wafer；（3）Second layer silicon nitride film is deposited on first layer silicon nitride film；（4）Third layer silicon nitride film or silicon oxynitride film are deposited on second layer silicon nitride film.Coating process of the present invention for the black silicon face passivation of polycrystalline, compared with duplicature, continue growing the refractive index of innermost layer antireflection film layer, the silicone content in film is set to increase, film is in Silicon-rich state, increase passivation effect of the thin film dielectric layer to black silicon face, reduces the compound increase of photo-generated carrier brought due to specific surface area increase, improve black silion cell transfer efficiency.
Description
Technical field
The present invention relates to a kind of coating process for the black silicon face passivation of polycrystalline, belong to optoelectronic device manufacturing technology neck
Domain.
Background technology
Photovoltaic generation still can not replace traditional energy since its cost is too high, reduce cost, improve solar cell conversion
Efficiency, which is the key that photovoltaic industry, can gradually replace traditional energy.Photovoltaic generation product is still with polycrystalline sun electricity currently on the market
It is to drop this key based on the component of pond, to reduce polycrystalline solar cell cost, improve polycrystalline battery conversion efficiency.
It is the tireless pursuit of photovoltaic practitioner that drop, which originally puies forward effect,.At silicon chip end, diamond wire microtomy has been shown very
Big advantage.Buddha's warrior attendant wire cutting has many advantages, such as that cutting speed is fast, loss is low, environmentally friendly relative to abrasive wire sawing.Single crystal diamond line
It is sliced extensive use, manufacturing cost is greatly reduced, and the far super expection of the polycrystalline diamond line of scale of construction bigger slice promotion rate,
It is expected that whole industry polycrystalline in 2018 accounts for 90% or more with Buddha's warrior attendant wire cutting.However, the polysilicon chip that diamond wire is cut is made using conventional
After suede technique, surface reflectivity is high and has the open defects such as apparent stria, seriously affects battery efficiency.In this context, silicon
Piece and cell piece enterprise, which are actively laid out and research and develop, imports black silicon technology, accelerates that diamond wire is promoted to cut polycrystalline popularization and application, slice
What link mainly solved be this problem drops, and mating black silicon technology then drop this, carry efficacious prescriptions face and have room for promotion.It prepares black
The method of silicon has the black silicon of dry method and the black silicon two major classes of wet method.The black silicon technology of dry method include reactive ion etching method, laser ablation method,
Gaseous corrosion method, the black silicon technology of wet method include electrochemical erosion method, metal catalytic chemical corrosion method.The black silicon technology equipment of dry method is high
Expensive, complex process affects the significantly popularization in the black silicon market of dry method.Metal catalytic chemical corrosion method in the black silicon of wet method uses
The electronegativity such as silver, copper form porous structure under the action of chemical corrosion liquid higher than the metallic particles of silicon in silicon chip surface, to
Silicon chip surface reflectivity is reduced, simple process and low cost is more suitable for industrial production.The black silicon technology of wet method is ground by lower
Hair input cuts for diamond wire line and has paved road in polycrystalline being widely applied for field of slice.
It is one of the effective ways for improving solar cell transfer efficiency to reduce silicon chip surface reflectivity.Polysilicon uses hydrogen fluorine
Sour and nitric acid system making herbs into wool prepares micron order vermicular texture, and the control of polysilicon chip surface reflectivity is in 22-24% after making herbs into wool
Left and right.As shown in Figure 1, for the comparison diagram of diamond wire black silion cell and conventional batteries reflectivity.Although black silicon face reflectivity is low,
With excellent anti-reflective effect, but black silicon face out-of-flatness, the nano grade pore hole dia about 300-700nm of formation, depth
According to corrosion temperature and time control.There is black silicon larger aspect ratio to increase specific surface area compared with conventional batteries.It is black
Silicon is while reducing surface reflectivity, because being provided with the specific surface area of bigger and introducing more defects so that light
Raw carrier increases in surface recombination, reduces minority carrier life time, restricts the promotion of black silicon efficiency.It is illustrated in figure 2 conventional slurry
The SEM figures (5000 times of amplification) of silicon wafer suede structure are illustrated in figure 3 the SEM figure (amplifications of the black silicon suede structure of diamond wire polycrystalline
5000 times).
Invention content
The purpose of the present invention is overcoming the deficiencies in the prior art, provide a kind of for the black silicon face passivation of polycrystalline
Coating process can improve black silicon face passivation effect, reduce the compound increasing of photo-generated carrier brought due to specific surface area increase
Add, improves black silion cell transfer efficiency.
According to technical solution provided by the invention, the coating process for the black silicon face passivation of polycrystalline, characterized in that
Include the following steps：
(1) polysilicon chip of Buddha's warrior attendant wire cutting is prepared to the matte of nano aperture by metal catalytic chemical corrosion method,
By diffuseing to form PN junction, etching removal edge and back side PN junction；
(2) PECVD filming equipments are used to deposit first layer silicon nitride film in front side of silicon wafer；
(3) second layer silicon nitride film is deposited on first layer silicon nitride film；
(4) third layer silicon nitride film or silicon oxynitride film are deposited on second layer silicon nitride film.
Further, the first layer silicon nitride film deposition technique is：Silane flow rate 100-1000sccm, ammonia flow
3000-5000sccm, silane is with ammonia flow than 1:4-1:6,300-500 DEG C of depositing temperature, power 3000-5000W, pressure
1500-2000mTorr, reaction time 80-220s, silicon nitride film thickness 10-20nm, refractive index 2.3-2.4.
Further, the second layer silicon nitride film deposition technique is：Silane flow rate 100-1000sccm, ammonia flow
3000-6000sccm, silane is with ammonia flow than 1:7-1:10,300-500 DEG C of depositing temperature, power 3000-5000W, pressure
1500-2000mTorr, reaction time 80-150s, silicon nitride film thickness 15-25nm, refractive index 2.04-2.08.
Further, the second layer silicon nitride film deposition technique is：Silane flow rate 100-1000sccm, ammonia flow
3000-6000sccm, silane is with ammonia flow than 1:7-1:10,300-500 DEG C of depositing temperature, power 3000-5000W, pressure
1500-2000mTorr, reaction time 200-350s, silicon nitride film thickness 30-45nm, refractive index 2.04-2.08.
Further, the third layer silicon nitride film deposition technique is：Silane flow rate 100-1000sccm, ammonia flow
3000-6000sccm, silane is with ammonia flow than 1:8-1:14,300-500 DEG C of depositing temperature, power 3000-5000W, pressure
1500-2000mTorr, reaction time 200-350s, silicon nitride film thickness 30-55nm, refractive index 1.98-2.04.
Further, the silicon oxynitride film depositing operation of the third layer is：Silane flow rate 100-1000sccm, laughing gas stream
Measure 2000-5000sccm, silane and laughing gas flow-rate ratio 1:8-1:14,300-500 DEG C of depositing temperature, power 3000-5000W, pressure
Strong 1500-2000mTorr, reaction time 50-150s, silicon oxynitride film thickness 20-30nm, refractive index 1.50-1.90.
Further, the first layer silicon nitride film, second layer silicon nitride film and third layer silicon nitride film or silicon oxynitride
The overall thickness of film is 75-85nm, mean refractive index 2.04-2.14.
Coating process of the present invention for the black silicon face passivation of polycrystalline continues growing innermost layer compared with duplicature
The refractive index of antireflection film layer makes the silicone content in film increase, and film is in Silicon-rich state, increases thin film dielectric layer to black silicon table
The passivation effect in face reduces the compound increase of photo-generated carrier brought due to specific surface area increase, improves black silion cell conversion
Efficiency.
Description of the drawings
Fig. 1 is the comparison diagram of diamond wire black silion cell and conventional batteries reflectivity.
Fig. 2 is the SEM figures (5000 times of amplification) of conventional slurry silicon wafer suede structure.
Fig. 3 is the SEM figures (5000 times of amplification) of the black silicon suede structure of diamond wire polycrystalline.
Fig. 4 is black silicon face reflectivity comparison diagram after two membranes and trilamellar membrane plated film.
Fig. 5 is that black silicon duplicature and trilamellar membrane battery conversion efficiency profiles versus scheme.
Specific implementation mode
With reference to specific attached drawing, the invention will be further described.
The present invention is developed through plasma enhanced chemical vapor deposition (PECVD) in black silicon silicon chip surface cvd nitride
Silicon antireflection film layer not only reduces surface reflectivity, while can preferably be passivated the surface defect of black silicon solar cell, improves
The transfer efficiency of black silicon solar cell.
Silicon nitride film is widely used as surface media in the manufacture of conventional crystalline silicon solar cell, but different nitrogen
SiClx depositing technics scheme is larger to solar battery surface passivation effect difference.Black silicon specific surface area is much larger than conventional polycrystalline, often
The silicon nitride deposition technique of rule cannot be passivated black defects on silicon surfaces well, and therefore, exploitation is a kind of to be suitable for the passivation of black silicon face
Silicon nitride deposition technique be to promote the most important condition of black silion cell transfer efficiency.
Usually during deposit silicon nitride, increasing silane flow rate makes silicone content in silicon nitride film layer increase to enhance passivation
Effect.After silicone content increases in silicon nitride film layer, refractive index and extinction coefficient accordingly increase, and silicon nitride increases the absorption of light therewith
By force, high refractive index, high extinction coefficient film be not suitable as antireflective film, but the content of silicon increases in film, surface passivation
Enhancing trend is presented in effect.The antireflective of silicon nitride film layer and passivation effect in order to balance, conventional polycrystalline battery generally use double
The antireflection film layer of layer silicon nitride, i.e., first deposit the surface of the silicon nitride passivation solar cell of a floor height refractive index, then deposit
The silicon nitride of low-refraction is for reducing surface refractive index, to effectively improve the transfer efficiency of solar cell.
It is characteristic of the invention that three layers of antireflection film layer are deposited in black silicon face, compared with duplicature, in continuing growing most
The refractive index of layer antireflection film layer, makes the silicone content in film increase, and film is in Silicon-rich state, increases thin film dielectric layer to black silicon
The passivation effect on surface.It is continuously decreased from first layer (film layer contacted with silicon face) to outermost layer refractive index, each tunic is thick
It is adjusted according to refractive index and total film thickness, total film thickness 75-85nm, mean refractive index 2.04-2.14, can preferably be passivated black silicon table
Including the dangling bonds or defect in face, improve the open-circuit voltage of black silion cell, while black silicon trilamellar membrane can make incident sunlight
Portion's multiple reflections and interference increase the absorption of incident light, therefore trilamellar membrane has lower reflectivity than duplicature, can obtain
Excellent anti-reflective effect improves the short circuit current of black silion cell.Compared with duplicature, trilamellar membrane can promote black silicon by a larger margin
The transfer efficiency of battery.
Embodiment one：
(1) polysilicon chip of Buddha's warrior attendant wire cutting, P type substrate, resistivity 1-3 Ω cm, 200 ± 20 μm of thickness, silicon are used
Piece prepares the matte of nano aperture by metal catalytic chemical corrosion method, by diffuseing to form pn-junction, etching removal edge and
Back side pn-junction；
(2) PECVD filming equipments are used to deposit three layers of silicon nitride anti-reflecting film layer in front：
Silane flow rate 850sccm when depositing first layer silicon nitride, ammonia flow 4200sccm, silane is with ammonia flow than 1:
5,430 DEG C, power 4400W, pressure 1700mTorr, reaction time 180s, silicon nitride film thickness 20nm of depositing temperature, refractive index
2.35；
And then second layer silicon nitride film, silane flow rate 420sccm, ammonia flow are deposited on first layer silicon nitride
4000sccm, silane is with ammonia flow than 1:9,430 DEG C, power 4400W, pressure 1700mTorr of depositing temperature, the reaction time
100s, silicon nitride film thickness 20nm, refractive index 2.05；
Third layer silicon nitride film, silane flow rate 400sccm, ammonia flow are deposited on second layer silicon nitride film
5000sccm, silane is with ammonia flow than 1:12,430 DEG C, power 4400W, pressure 1700mTorr of depositing temperature, the reaction time
270s, silicon nitride film thickness 30-55nm, refractive index 2.02；
(3) pass through silk-screen printing backplate, Al-BSF, front electrode and high temperature sintering and battery is made, test electrical property.
Since the silicon nitride film layer of bottom in trilamellar membrane technique in wafer bulk with surface passivation to obtaining more preferably, with black silicon duplicature work
The battery of skill is compared, the black silion cell open-circuit voltage higher of trilamellar membrane, since trilamellar membrane has lower reflectivity than duplicature,
The black silion cell short circuit current of trilamellar membrane also higher.Black silicon trilamellar membrane coating process scheme of the present invention effectively increases black
The transfer efficiency of silicon solar cell.
As shown in figure 4, for black silicon face reflectivity comparison after two membranes and trilamellar membrane plated film.It is double to be illustrated in figure 5 black silicon
Tunic and trilamellar membrane battery conversion efficiency profiles versus figure.As shown in table 1, it is that black silicon duplicature and trilamellar membrane battery electrical property are joined
Number comparison.
1 black silicon duplicature of table and trilamellar membrane battery electrical property parameter comparison
| Classification | Voc/V | Isc/A | Rs/mΩ | Rsh/Ω | FF/% | Eff. | Irev2/A | The piece number |
| Duplicature | 0.6408 | 9.0741 | 1.2 | 87.65 | 80.34 | 19.01% | 0.2461 | 507 |
| Trilamellar membrane | 0.6430 | 9.1089 | 1.2 | 106.56 | 80.32 | 19.15% | 0.1726 | 507 |
Embodiment two：
(1) polysilicon chip of Buddha's warrior attendant wire cutting, P type substrate, resistivity 1-3 Ω cm, 200 ± 20 μm of thickness, silicon are used
Piece prepares the matte of nano aperture by metal catalytic chemical corrosion method, by diffuseing to form pn-junction, etching removal edge and
Back side pn-junction；
(2) use PECVD filming equipments in front deposited silicon nitride/three layers of silicon nitride/silicon oxynitride antireflection film layer：
Silane flow rate 850sccm when depositing first layer silicon nitride, ammonia flow 4200sccm, silane is with ammonia flow than 1:
5,430 DEG C, power 4400W, pressure 1700mTorr, reaction time 180s, silicon nitride film thickness 20nm of depositing temperature, refractive index
2.35；
And then second layer silicon nitride film, silane flow rate 420sccm, ammonia flow are deposited on first layer silicon nitride
4000sccm, silane is with ammonia flow than 1:9,430 DEG C, power 4400W, pressure 1700mTorr of depositing temperature, the reaction time
280s, silicon nitride film thickness 40nm, refractive index 2.05；
Third layer silicon oxynitride film, silane flow rate 400sccm, laughing gas flow are deposited on second layer silicon nitride film
3500sccm, silane and laughing gas flow-rate ratio 1:9,430 DEG C, power 4400W, pressure 1700mTorr of depositing temperature, the reaction time
80s, silicon oxynitride film thickness 20nm, refractive index 1.85.
As shown in table 2, it is the black silicon solar cell unit for electrical property parameters of two technique of embodiment preparation.
The black silicon solar cell unit for electrical property parameters that table 2 is prepared using two technique of embodiment
Claims (7)
1. a kind of coating process for the black silicon face passivation of polycrystalline, characterized in that include the following steps：
（1）The matte that the polysilicon chip of Buddha's warrior attendant wire cutting is prepared to nano aperture by metal catalytic chemical corrosion method, passes through
Diffuse to form PN junction, etching removal edge and back side PN junction；
（2）Using PECVD filming equipments first layer silicon nitride film is deposited in front side of silicon wafer；
（3）Second layer silicon nitride film is deposited on first layer silicon nitride film；
（4）Third layer silicon nitride film or silicon oxynitride film are deposited on second layer silicon nitride film.
2. the coating process for the black silicon face passivation of polycrystalline as described in claim 1, it is characterized in that：The first layer nitridation
Film deposition technique is：Silane flow rate 100-1000sccm, ammonia flow 3000-5000sccm, silane is with ammonia flow than 1:
4-1:6,300-500 DEG C of depositing temperature, power 3000-5000W, pressure 1500-2000mTorr, reaction time 80-220s, nitrogen
SiClx film thickness 10-20nm, refractive index 2.3-2.4.
3. the coating process for the black silicon face passivation of polycrystalline as described in claim 1, it is characterized in that：The second layer nitridation
Film deposition technique is：Silane flow rate 100-1000sccm, ammonia flow 3000-6000sccm, silane is with ammonia flow than 1:
7-1:10,300-500 DEG C of depositing temperature, power 3000-5000W, pressure 1500-2000mTorr, reaction time 80-150s, nitrogen
SiClx film thickness 15-25nm, refractive index 2.04-2.08.
4. the coating process for the black silicon face passivation of polycrystalline as described in claim 1, it is characterized in that：The second layer nitridation
Film deposition technique is：Silane flow rate 100-1000sccm, ammonia flow 3000-6000sccm, silane is with ammonia flow than 1:
7-1:10,300-500 DEG C of depositing temperature, power 3000-5000W, pressure 1500-2000mTorr, reaction time 200-350s,
Silicon nitride film thickness 30-45nm, refractive index 2.04-2.08.
5. the coating process for the black silicon face passivation of polycrystalline as described in claim 1, it is characterized in that：The third layer nitridation
Film deposition technique is：Silane flow rate 100-1000sccm, ammonia flow 3000-6000sccm, silane is with ammonia flow than 1:
8-1:14,300-500 DEG C of depositing temperature, power 3000-5000W, pressure 1500-2000mTorr, reaction time 200-350s,
Silicon nitride film thickness 30-55nm, refractive index 1.98-2.04.
6. the coating process for the black silicon face passivation of polycrystalline as described in claim 1, it is characterized in that：The nitrogen of the third layer
Silicon oxide film depositing operation is：Silane flow rate 100-1000sccm, laughing gas flow 2000-5000sccm, silane and laughing gas flow
Than 1:8-1:14,300-500 DEG C of depositing temperature, power 3000-5000W, pressure 1500-2000mTorr, reaction time 50-
150s, silicon oxynitride film thickness 20-30nm, refractive index 1.50-1.90.
7. the coating process for the black silicon face passivation of polycrystalline as described in claim 1, it is characterized in that：The first layer nitridation
Silicon fiml, second layer silicon nitride film and the overall thickness of third layer silicon nitride film or silicon oxynitride film are 75-85nm, and mean refractive index is
2.04-2.14。
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