CN106299032B - The method of femtosecond laser etching enhancing amorphous silicon thin-film solar cell performance - Google Patents
The method of femtosecond laser etching enhancing amorphous silicon thin-film solar cell performance Download PDFInfo
- Publication number
- CN106299032B CN106299032B CN201610905685.3A CN201610905685A CN106299032B CN 106299032 B CN106299032 B CN 106299032B CN 201610905685 A CN201610905685 A CN 201610905685A CN 106299032 B CN106299032 B CN 106299032B
- Authority
- CN
- China
- Prior art keywords
- amorphous silicon
- film solar
- solar cell
- silicon thin
- laser pulse
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910021417 amorphous silicon Inorganic materials 0.000 title claims abstract description 160
- 239000010409 thin film Substances 0.000 title claims abstract description 114
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 11
- 238000010329 laser etching Methods 0.000 title claims abstract description 8
- 239000010408 film Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000005516 engineering process Methods 0.000 claims abstract description 27
- 238000012545 processing Methods 0.000 claims abstract description 26
- 230000010287 polarization Effects 0.000 claims abstract description 15
- 239000004065 semiconductor Substances 0.000 claims description 39
- 238000000151 deposition Methods 0.000 claims description 33
- 230000008021 deposition Effects 0.000 claims description 30
- 239000011521 glass Substances 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 28
- 238000004544 sputter deposition Methods 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 9
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- 210000001367 artery Anatomy 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000007738 vacuum evaporation Methods 0.000 claims description 3
- 210000003462 vein Anatomy 0.000 claims description 3
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 239000012495 reaction gas Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 20
- 238000012546 transfer Methods 0.000 abstract description 9
- 230000005693 optoelectronics Effects 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 description 139
- 230000000052 comparative effect Effects 0.000 description 49
- 238000005530 etching Methods 0.000 description 45
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 17
- 229910052710 silicon Inorganic materials 0.000 description 17
- 239000010703 silicon Substances 0.000 description 17
- 230000006698 induction Effects 0.000 description 8
- 239000012528 membrane Substances 0.000 description 6
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910021419 crystalline silicon Inorganic materials 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000000427 thin-film deposition Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002679 ablation Methods 0.000 description 2
- 230000003667 anti-reflective effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000009022 nonlinear effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
A kind of method of femtosecond laser etching enhancing amorphous silicon thin-film solar cell performance, by p i n structure amorphous silicon thin-film solar cells, it is fixed on femtosecond laser micro-nano technology platform, microscopic system vertical incidence of the femto-second laser pulse through 10 times of object lens is focused on thin-film solar cells N-shaped amorphous silicon film surface；Linear polarization femto-second laser pulse will obtain efficient p i n structure amorphous silicon thin-film solar cells to carrying out suede processing on amorphous silicon thin-film solar cell N-shaped amorphous silicon film surface.Advantage is：Simple process and low cost is honest and clean, and opto-electronic conversion performance improves significantly, and obtained solar cell photoelectric transfer efficiency reaches 14.9%, is 2 times of unprocessed amorphous silicon thin-film solar cell transfer efficiency.
Description
Technical field
The present invention relates to technical field of nanometer material preparation more particularly to one kind to pass through femto-second laser pulse lithographic method system
Standby solar cell surface antireflection layer is to enhance the method for amorphous silicon thin-film solar (a-SiTFSCs) battery performance.
Background technology
Environmental pollution at present and traditional energy (including oil, coal and natural gas) shortage, become limitation countries in the world economy
Two hang-ups of development.Solar cell is as a kind of device that solar radiation luminous energy can be converted into electric energy, in light
In electric conversion process, consumption traditional energy is not both needed to, meanwhile, it is also generated completely without environmental contaminants, is that one kind has very much
The optoelectronic semiconductor conversion devices of prospect.The solar cell types that various countries are being studied at present mainly have silica-based solar electricity
Pond, thin-film solar cells, multi-element compounds solar cell (such as CdS/CdTe, Cu (In, Ga) Se2/ CdS etc.), Yi Jiyou
Machine dye-sensitized solar cells etc..Consider the performances such as energy conversion efficiency and service life, non-crystal silicon solar cell
Although transfer efficiency is slightly lower, cost is less expensive, thus as more promising novel silicon base solar cell.Feelings at present
The characteristics of shape, the amorphous silicon thin-film solar cell consumptive material of p-i-n structure is less, and electricity conversion is relatively high determines
It is still the mainstream of thin-film solar cells.Currently, the photoelectricity for how further improving amorphous silicon thin-film solar cell turns
It is still the field urgently one of open question to change efficiency (η).
Up to the present, enhance the method for light absorption by silica-based solar cell film surface " light capture ", it is main to wrap
Include preparation, noble metal nano particles plasmon resonance enhancing light absorption and the metallic slit non-local of antireflective absorbed layer matte
Phasmon enhancing light absorption etc..Antireflection layer matte is prepared relative to phasmon enhanced film battery surface light absorption and
Speech has manufacture craft simply ripe, and performance is stablized relatively, the advantages such as cheap.Python M et al. pass through chemical gaseous phase
The method of deposition (LP-CVD) forms " V-type " and " U-shaped " suede structure on micro crystal silicon solar battery silicon face makes the anti-of battery
It is dramatically increased to saturation current, and Voc(fill factor, are filled out by (open-circuit voltage, open-circuit voltage) and FF
Fill the factor) it is also obviously improved.Sandeep et al. is successfully prepared by way of high annealing on semiconductor silicon material surface
" inverted pyramid type " suede structure so that silicon face absorbing properties are significantly improved.However, above-mentioned antireflection layer matte
Preparation method, and it is not suitable for the amorphous silicon thin-film solar cell that absorber thickness is only 1-2 μm.Maliheh et al. uses
Nanosecond Nd:Under YAG laser pulse radiation parameters, the formation of induction polishing silicon face " dendron shape " light capture micro-nano structure, and then
Achieve the purpose that antireflective.Laser micro/nano processing technology is with its process is simple, to prepare precision high and accurate handling strong
Etc. advantages, be increasingly subject to people concern.
Invention content
It is simple that the technical problems to be solved by the invention are to provide a kind of preparation process, of low cost, opto-electronic conversion performance
It improves significantly, and the method for the femtosecond laser etching enhancing amorphous silicon thin-film solar cell performance without any pollutant.
The present invention technical solution be：
A kind of method of femtosecond laser etching enhancing amorphous silicon thin-film solar cell performance, is as follows：
By p-i-n structure amorphous silicon thin-film solar cell, it is fixed on femtosecond laser micro-nano technology platform, femtosecond laser arteries and veins
The microscopic system vertical incidence through 10 times of object lens (numerical aperture 0.25) is rushed, focuses on thin-film solar cells N-shaped amorphous
On film surface；It is 0.5J/cm to set femto-second laser pulse energy density2~1.25J/cm2With laser pulse etching period interval
It it is 8 μm~30 μm, linear polarization femto-second laser pulse will be to carrying out suede on amorphous silicon thin-film solar cell N-shaped amorphous silicon film surface
Change is handled, and obtains efficient p-i-n structure amorphous silicon thin-film solar cell.
Further, femtosecond laser micro-nano technology platform, rate travel are moved for 1mm/s constant speed, platform motor stepping essence
Spend is 0.1 μm.
Further, femto-second laser pulse energy density (W) is 0.75J/cm2；Laser pulse etching period interval (T) is
15μm。
Further, numerical aperture of the femto-second laser pulse through 10 times of object lens is 0.25.
Further, the preparation process of the p-i-n structure amorphous silicon thin-film solar cell is as follows：
1.1st, tco layer is prepared
First, by radio frequency magnetron sputtering method substrate of glass side sputter thickness for 200nm by SnO2The TCO of composition
Layer；
1.2nd, p-type amorphous silicon semiconductor is prepared
By plasma enhanced chemical vapor deposition method, deposition thickness is the p-type amorphous of 600nm on tco layer
Silicon semiconductor；
1.3rd, i type amorphous silicon semiconductors are prepared
On p-type amorphous silicon semiconductor layer, by plasma enhanced chemical vapor deposition method, deposition thickness is
The i type amorphous silicon semiconductors of 600nm；
1.4, prepare N-shaped amorphous silicon semiconductor
On i type amorphous silicon semiconductor layers or pass through plasma enhanced chemical vapor deposition method, deposition thickness
N-shaped amorphous silicon semiconductor for 600nm；
1.5th, aluminium electrode is made
By way of vacuum evaporation, at the top of the p-i-n structure amorphous silicon thin-film solar cell of preparation, aluminium electricity is made
Pole obtains p-i-n structure amorphous silicon thin-film solar cell.
Further, when preparing tco layer, by In2O3-SnO2Ceramic target is positioned in magnetron sputtering coating system, will be cleaned
Clean substrate of glass is placed horizontally at the center of block substrate, and closed reaction chamber carries out sputter coating；Wherein, sputtering chamber
Vacuum degree be 10-2Pa is passed through argon gas that purity is 99.99% as reaction gas, and argon gas flow velocity is 15.3sccm, substrate temperature
It is 300 DEG C to spend, sputtering power 600W, In2O3-SnO2Ceramic target sputtering voltage is -110V, and sputtering time is 20 minutes, deposition
Rate 10nm/min.
Further, it is when preparing p-type amorphous silicon semiconductor, the substrate of glass of surface deposition TCO conductive layers is horizontal positioned
In the center of magnetron sputtering coating system block substrate, closed reaction chamber carries out enhancing chemical vapor deposition；Wherein, it reacts
Room vacuum degree is 10-5Pa, underlayer temperature are 250 DEG C, and SiH is passed through into reative cell4、B2H6And H2, SiH4、B2H6And H2Flow velocity
Respectively 6sccm, 4sccm and 20sccm, pressure control is in 80Pa during deposition, and radio-frequency power 160W, sputtering time is 15 points
Clock, deposition rate 40nm/min.
Further, when preparing i type amorphous silicon semiconductors, by upper space depositing p-type amorphous silicon semiconductor substrate of glass
It is placed horizontally at the center of magnetron sputtering coating system block substrate, closed reaction chamber；Wherein, reative cell vacuum degree is 10- 5Pa, underlayer temperature are 350 DEG C, and SiH is passed through into reative cell4And H2, SiH4And H2Flow velocity be respectively 6sccm and 24sccm, sink
Pressure control is in 80Pa during product, radio-frequency power 160W, and sputtering time is 15 minutes, deposition rate 40nm/min.
Further, when preparing N-shaped amorphous silicon semiconductor, upper space is deposited into i type amorphous silicon semiconductor substrate of glass
It is placed horizontally at the center of magnetron sputtering coating system block substrate, closed reaction chamber；Wherein, reative cell vacuum degree is 10- 5Pa, underlayer temperature are 300 DEG C；It is passed through SiH4、PH3And H2, SiH4、PH3And H2Flow velocity be respectively 6sccm, 4sccm and
20sccm, pressure control is in 80Pa during deposition, and radio-frequency power 160W, sputtering time is 15 minutes, deposition rate 40nm/min.
Beneficial effects of the present invention：
1st, the extremely short pulse duration (10-15S) so that femto-second laser pulse and amorphous silicon thin-film solar cell phase
During interaction, substantially without the concern for the influence of hydrodynamic processes.Laser energy is deposited directly to silicon fiml solid
Density becomes in skin layers, and the absorption of energy is made more to concentrate, and greatly reduces the ablation threshold of material.Along with light and substance phase
The shortening of interaction time, the fuel factor volume of conduction of heat greatly reduce, when laser energy-flux density be adjusted to be equal to or
Just beyond silicon fiml semi-conducting material ablation threshold when, heat affected area in material actually than focus on can smaller, this is not only
The precision of processing is greatly improved, while also achieves " cold " processing truly；
2nd, based on femtosecond laser micro-nano technology technology high precision machining, fuel factor is small low with damage threshold the characteristics of and
Focusing on femto-second laser pulse nearby has superelevation electric field strength, can induce the nonlinear effects such as Multiphoton Absorbtion, ionization；Fly
During second laser pulse etching amorphous silicon thin-film solar cell, carried out mainly in a manner of carburation by evaporation, semi-conducting material melts
Change, liquid phase flowing and the influences of processes such as condense again and be greatly reduced, it might even be possible to ignore so that surface suede non-crystalline silicon is too
The surface of positive energy battery is more smooth and smooth, improves the controllability and accuracy of micro-nano technology process；
3rd, operating process is simple, whole-course automation, by presetting the etching parameters of laser micro/nano processing system, laser
Pulse energy and etching period interval, in semiconductor material surface, accurate, flexible induced synthesis periodic micro structure；
4th, pass through femtosecond laser micro-nano technology, the amorphous silicon thin-film solar cell surface antireflection layer of preparation, light absorption
Enhancing effect is apparent, and obtained solar cell photoelectric transfer efficiency reaches 14.9%, is the unprocessed amorphous silicon membrane sun
2 times of energy battery conversion efficiency.
Description of the drawings
Fig. 1 (a) is p-i-n amorphous silicon thin-film solar cells structure prepared by the present invention and (b) femtosecond laser etching
Battery surface " groove " structure SEM photograph；
Fig. 2 (a)-(f) is that (embodiment 1- embodiments 3, comparative example 1- comparative examples 3) of the invention is etched without femtosecond laser
(0J/cm2) and different pulsed laser energies etching (0.25J/cm2、0.5J/cm2、0.75J/cm2、1.25J/cm2、2J/cm2)a-
Induction porous microstructure SEM photograph in SiTFSCs surface grooves；
Fig. 3 is that (comparative example 2) femto-second laser pulse energy of the invention is 2J/cm2When, a-SiTFSCs film surface XRD diagram
Spectrum；
Fig. 4 is of the invention (embodiment 1- embodiments 3, comparative example 1- comparative examples 3) identical etching period interval, different femtoseconds
Laser pulse etching energy (0J/cm2、0.25J/cm2、0.5J/cm2、0.75J/cm2、1.25J/cm2、2J/cm2)a-SiTFSCs
I-V characteristic test；
Fig. 5 is the present invention (embodiment 1- embodiments 3, the comparative example 1- comparative examples 3) η of a-SiTFSCs and femtosecond laser arteries and veins
The variation relation of punching etching energy；
Fig. 6 is of the invention (embodiment 1- embodiments 3, comparative example 1- comparative examples 3) identical etching period interval, different femtoseconds
Laser pulse etching energy (0J/cm2、0.25J/cm2、0.5J/cm2、0.75J/cm2、1.25J/cm2) a-SiTFSCs it is ultraviolet-
Visible reflectance absorption spectra；
Fig. 7 is (embodiment 4- embodiments 6, comparative example 4, comparative example 5) of the invention identical femto-second laser pulse W, and difference is carved
Lose the surface suede SEM pictures of cycle T (5 μm, 8 μm, 15 μm, 30 μm, 50 μm) a-SiTFSCs；
Fig. 8 is (embodiment 4- embodiments 6, comparative example 4, comparative example 5) of the invention identical femto-second laser pulse energy W, no
I-V characteristic with laser pulse etching period T (0 μm, 5 μm, 8 μm, 15 μm, 30 μm, 50 μm) a-SiTFSCs is tested；
Fig. 9 is the η of the present invention (embodiment 4- embodiments 6, comparative example 4, comparative example 5) surface suede a-SiTFSCs with flying
The variation relation at second laser pulse etching period interval.
Specific embodiment
The laser that the femtosecond laser micro-nano technology platform of the present invention uses is is commercialized integrated regenerative amplification Ti:
Sapphire fs-laser systems (Coherent Inc.), including microscope focusing system (Nikon, Sony Inc.) and precision
Micro Process platform (Prior Inc.).Femtosecond laser may finally export pulse FWHM after OPA (photoparametric amplifier) system
(half breadth) be 120fs, centre wavelength be 800nm pulse train, tunable repetition rate 1Hz~1kHz, peak energy
30J/cm2, spot diameter is about 6mm；Femto-second laser pulse etching energy can be adjusted by tuning attenuator, so as to fulfill
0~30J/cm2Continuous output, all femtosecond laser micro-nano technology experiments are completed in thousand grades of purification super-clean environments.
Embodiment
As shown in Fig. 2, femto-second laser pulse matte etching period T is certain value, change femto-second laser pulse energy W, system
Standby amorphous silicon thin-film solar cell porous surface micro-structure antireflection layer method is as follows：
1.1st, amorphous silicon thin-film solar cell is attached on glass slide, is then fixed to femtosecond laser micro-nano and adds
Work platform upper mounting plate motor stepping accuracy is 0.1 μm, 1.5 × 1.5cm of solar cell sizes size2；
1.2nd, microscopic system vertical incidence of the femto-second laser pulse through 10 × object lens (numerical aperture 0.25) focuses on
On thin-film solar cells N-shaped amorphous silicon film surface, the hot spot that waist radius is about 0.5 μm is formed；
1.3rd, it is controlled by terminal, the femto-second laser pulse of focusing will be square vertically along platform with the rate of 1mm/s
It is moved to constant speed, setting femto-second laser pulse repetition rate is 1kHz, while sets amorphous silicon thin-film solar cell is identical to fly
Second laser pulse etching period T is 15 μm, different pulsed laser energy W (0.25J/cm2、0.5J/cm2、0.75J/cm2、
1.25J/cm2、2J/cm2) micro Process parameter, linear polarization femto-second laser pulse will be non-to amorphous silicon thin-film solar cell N-shaped
Suede processing is carried out in crystal silicon film surface, obtains efficient p-i-n structure amorphous silicon thin-film solar cell.
Comparative example 1
1.1st, tco layer is prepared
First, by radio frequency magnetron sputtering method, sputtering thickness is 200nm by SnO on the glass substrate2The TCO of composition
Conductive layer, glass substrate area are 1.5 × 1.5cm2；
A. by In2O3-SnO2Ceramic target is positioned in magnetron sputtering coating system, and the substrate of glass level cleaned up is put
It is placed in block substrate center, closed reaction chamber；
B. by vacuum-pumping system, reative cell vacuum degree is evacuated to 10-2Pa, while it is 300 DEG C to set underlayer temperature；
C. argon gas is passed through into reative cell, argon gas flow velocity is 15.3sccm, and radio frequency system is opened after pressure stability, carries out brightness
Light electric discharge sputtering, radio-frequency power 600W, In2O3-SnO2Ceramic target sputtering voltage is -110V, and sputtering time is 20 minutes, is sunk
Product rate 10nm/min；
After d.TCO thin film depositions, argon gas gas circuit, radio-frequency power supply and heating unit are closed, after being cooled to room temperature, is opened
Reative cell takes out；
1.2nd, p-type amorphous silicon semiconductor is prepared
Pass through plasma enhanced chemical vapor deposition method, the p for being about 600nm in TCO conductive layer deposition thickness
Type amorphous silicon semiconductor；
A., the substrate of glass of surface deposition TCO conductive layers is placed horizontally to the center of magnetron sputtering coating system block substrate
Position, closed reaction chamber；
B. by vacuum-pumping system, reative cell vacuum degree is evacuated to 10-5Pa, while it is 250 DEG C to set underlayer temperature；
C. it opens electromagnet cut off valve and SiH is passed through into reative cell4、B2H6And H2, flow velocity be respectively 6sccm, 4sccm and
20sccm, stable gas pressure 80Pa open radio frequency system and carry out glow-discharge sputtering, radio-frequency power 160W, and sputtering time is
15 minutes, deposition rate 40nm/min；
D. after thin film deposition, SiH is closed4And B2H6Gas circuit, radio-frequency power supply and heating unit keep logical H2Until cold
But to after room temperature, it is then shut off H2Gas circuit is opened reative cell and is taken out；
1.3rd, i type amorphous silicon semiconductors are prepared
On p-type amorphous silicon semiconductor layer, by the method for plasma enhanced chemical vapor deposition, thickness is prepared about
I type amorphous silicon semiconductors for 600nm；
A. upper space depositing p-type amorphous silicon semiconductor substrate of glass is placed horizontally at magnetron sputtering coating system substrate
The center of seat, closed reaction chamber；
B. by vacuum-pumping system, reative cell vacuum degree is evacuated to 10-5Pa, while it is 350 DEG C to set underlayer temperature；
C. it opens electromagnet cut off valve and SiH is passed through into reative cell4And H2, flow velocity is respectively 6sccm and 24sccm, air pressure
80Pa is stabilized to, radio frequency system is opened and carries out glow-discharge sputtering, radio-frequency power 160W, sputtering time is 15 minutes, deposition
Rate 40nm/min；
D. after thin film deposition, SiH is closed4Gas circuit, radio-frequency power supply and heating unit keep logical H2Until being cooled to room
Wen Hou is then shut off H2Gas circuit is opened reative cell and is taken out；
1.4th, N-shaped amorphous silicon semiconductor is prepared
Method on i type amorphous silicon semiconductor layers or by plasma enhanced chemical vapor deposition, deposition of thick
Degree is about the N-shaped amorphous silicon semiconductor of 600nm；
A. upper space deposition i type amorphous silicon semiconductor substrate of glass is placed horizontally at magnetron sputtering coating system substrate
The center of seat, closed reaction chamber；
B. by vacuum-pumping system, reative cell vacuum degree is evacuated to 10-5Pa, while it is 300 DEG C to set underlayer temperature；
C. it opens electromagnet cut off valve and SiH is passed through into reative cell4、PH3And H2, flow velocity be respectively 6sccm, 4sccm and
20sccm, stable gas pressure 80Pa open radio frequency system and carry out glow-discharge sputtering, radio-frequency power 160W, and sputtering time is
15 minutes, deposition rate 40nm/min；
D. after thin film deposition, SiH is closed4And PH3Gas circuit, radio-frequency power supply and heating unit keep logical H2Until cooling
To room temperature, it is then shut off H2Gas circuit is opened reative cell and is taken out；
1.5th, aluminium electrode is made
By way of vacuum evaporation, at the top of the p-i-n structure amorphous silicon thin-film solar cell of preparation, aluminium electricity is made
Pole obtains p-i-n structure amorphous silicon thin-film solar cell.Amorphous silicon thin-film solar cell a-SiTFSCs surface SEM scheme
As shown in Fig. 2 (a).
Embodiment 1
1.1st, amorphous silicon thin-film solar cell prepared by comparative example 1 is attached on glass slide, be then fixed to
Femtosecond laser micro-nano technology platform upper mounting plate motor stepping accuracy is 0.1 μm, 1.5 × 1.5cm of solar cell sizes size2；
1.2nd, microscopic system vertical incidence of the femto-second laser pulse through 10 × object lens (numerical aperture 0.25) focuses on
On thin-film solar cells N-shaped amorphous silicon film surface, the hot spot that waist radius is about 0.5 μm is formed；
1.3rd, it is controlled by terminal, the femto-second laser pulse of focusing will be square vertically along platform with the rate of 1mm/s
It is moved to constant speed, setting femto-second laser pulse repetition rate is 1kHz, while amorphous silicon thin-film solar cell femtosecond is set to swash
Light pulse etching period T is 15 μm, pulsed laser energy (W) 0.5J/cm2Micro Process parameter, linear polarization femto-second laser pulse
Efficient p-i-n structure amorphous will be obtained to carrying out suede processing on amorphous silicon thin-film solar cell N-shaped amorphous silicon film surface
Silicon film solar batteries.Induction porous microstructure SEM figures in amorphous silicon thin-film solar cell a-SiTFSCs surface grooves
As shown in Fig. 2 (c).
Embodiment 2
1.1st, amorphous silicon thin-film solar cell prepared by comparative example 1 is attached on glass slide, be then fixed to
Femtosecond laser micro-nano technology platform upper mounting plate motor stepping accuracy is 0.1 μm, 1.5 × 1.5cm of solar cell sizes size2；
1.2nd, microscopic system vertical incidence of the femto-second laser pulse through 10 × object lens (numerical aperture 0.25) focuses on
On thin-film solar cells N-shaped amorphous silicon film surface, the hot spot that waist radius is about 0.5 μm is formed；
1.3rd, it is controlled by terminal, the femto-second laser pulse of focusing will be square vertically along platform with the rate of 1mm/s
It is moved to constant speed, setting femto-second laser pulse repetition rate is 1kHz, while amorphous silicon thin-film solar cell femtosecond is set to swash
Light pulse etching period T is 15 μm, pulsed laser energy (W) 0.75J/cm2Micro Process parameter, linear polarization femto-second laser pulse
Efficient p-i-n structure amorphous will be obtained to carrying out suede processing on amorphous silicon thin-film solar cell N-shaped amorphous silicon film surface
Silicon film solar batteries.Induction porous microstructure SEM figures in amorphous silicon thin-film solar cell a-SiTFSCs surface grooves
As shown in Fig. 2 (d), suede SEM figures in a-SiTFSCs surfaces are as shown in Fig. 7 (c).
Embodiment 3
1.1st, amorphous silicon thin-film solar cell prepared by comparative example 1 is attached on glass slide, be then fixed to
Femtosecond laser micro-nano technology platform upper mounting plate motor stepping accuracy is 0.1 μm, 1.5 × 1.5cm of solar cell sizes size2；
1.2nd, microscopic system vertical incidence of the femto-second laser pulse through 10 × object lens (numerical aperture 0.25) focuses on
On thin-film solar cells N-shaped amorphous silicon film surface, the hot spot that waist radius is about 0.5 μm is formed；
1.3rd, it is controlled by terminal, the femto-second laser pulse of focusing will be square vertically along platform with the rate of 1mm/s
It is moved to constant speed, setting femto-second laser pulse repetition rate is 1kHz, while amorphous silicon thin-film solar cell femtosecond is set to swash
Light pulse etching period T is 15 μm, pulsed laser energy (W) 1.25J/cm2Micro Process parameter, linear polarization femto-second laser pulse
Efficient p-i-n structure amorphous will be obtained to carrying out suede processing on amorphous silicon thin-film solar cell N-shaped amorphous silicon film surface
Silicon film solar batteries.
Induction porous microstructure SEM figure such as Fig. 2 (e) in amorphous silicon thin-film solar cell a-SiTFSCs surface grooves
It is shown.
Comparative example 2
1.1st, amorphous silicon thin-film solar cell prepared by comparative example 1 is attached on glass slide, be then fixed to
Femtosecond laser micro-nano technology platform upper mounting plate motor stepping accuracy is 0.1 μm, 1.5 × 1.5cm of solar cell sizes size2；
1.2nd, microscopic system vertical incidence of the femto-second laser pulse through 10 × object lens (numerical aperture 0.25) focuses on
On thin-film solar cells N-shaped amorphous silicon film surface, the hot spot that waist radius is about 0.5 μm is formed；
1.3rd, it is controlled by terminal, the femto-second laser pulse of focusing will be square vertically along platform with the rate of 1mm/s
It is moved to constant speed, setting femto-second laser pulse repetition rate is 1kHz, while amorphous silicon thin-film solar cell femtosecond is set to swash
Light pulse etching period T is 15 μm, pulsed laser energy (W) 0.25J/cm2Micro Process parameter, linear polarization femto-second laser pulse
Efficient p-i-n structure amorphous will be obtained to carrying out suede processing on amorphous silicon thin-film solar cell N-shaped amorphous silicon film surface
Silicon film solar batteries.Induction porous microstructure SEM figures in amorphous silicon thin-film solar cell a-SiTFSCs surface grooves
As shown in Fig. 2 (b).
Comparative example 3
1.1st, amorphous silicon thin-film solar cell prepared by comparative example 1 is attached on glass slide, be then fixed to
Femtosecond laser micro-nano technology platform upper mounting plate motor stepping accuracy is 0.1 μm, 1.5 × 1.5cm of solar cell sizes size2；
1.2nd, microscopic system vertical incidence of the femto-second laser pulse through 10 × object lens (numerical aperture 0.25) focuses on
On thin-film solar cells N-shaped amorphous silicon film surface, the hot spot that waist radius is about 0.5 μm is formed；
1.3rd, it is controlled by terminal, the femto-second laser pulse of focusing will be square vertically along platform with the rate of 1mm/s
It is moved to constant speed, setting femto-second laser pulse repetition rate is 1kHz, while amorphous silicon thin-film solar cell femtosecond is set to swash
Light pulse etching period T is 15 μm, pulsed laser energy (W) 2J/cm2Micro Process parameter, linear polarization femto-second laser pulse will
To carrying out suede processing on amorphous silicon thin-film solar cell N-shaped amorphous silicon film surface, efficient p-i-n structure non-crystalline silicon is obtained
Thin-film solar cells.Induction porous microstructure SEM schemes such as in amorphous silicon thin-film solar cell a-SiTFSCs surface grooves
Shown in Fig. 2 (f), a-SiTFSCs film surface XRD spectrums are as shown in Figure 3.
Fig. 4 is the surface suede amorphous silicon thin-film solar of 1- of embodiment of the present invention embodiments 3, comparative example 1- comparative examples 3
Cell I-V characteristic test curve, Fig. 5 are that 1- of embodiment of the present invention embodiments 3, comparative example 1- comparative examples 3 are swashed using identical femtosecond
Photoengraving cycle T, different femto-second laser pulse etching energy W (0J/cm2、0.25J/cm2、0.5J/cm2、0.75J/cm2、
1.25J/cm2) a-SiTFSCs η and femto-second laser pulse etching energy variation relation；Fig. 6 is 1- of embodiment of the present invention realities
Apply example 3, comparative example 1- comparative examples 3 use identical femtosecond laser etching period T, different femto-second laser pulse etching energy W (0J/
cm2、0.25J/cm2、0.5J/cm2、0.75J/cm2、1.25J/cm2) the reflection suction of amorphous silicon thin-film solar cell ultraviolet-visible
Receive spectrum.
As seen from Figure 2, with the increase of femto-second laser pulse energy (W), since a-SiTFSCs spatial inductions are formed
The aperture of porous microstructure gradually increases so that the reflectance spectrum intensity on solar cell N-shaped amorphous silicon membrane surface gradually drops
It is low, gradually enhance so as to " photo-induction is caught " ability of amorphous silicon thin-film solar cell.This fully demonstrates micro- by femtosecond laser
It receives processing platform, high performance solar batteries surface antireflection layer can be prepared.
Table 1 is 1- of embodiment of the present invention embodiments 3, the identical femto-second laser pulse etching period T of comparative example 1-3, different
Femto-second laser pulse energy W (0J/cm2、0.25J/cm2、0.5J/cm2、0.75J/cm2、1.25J/cm2、2J/cm2) to non-crystalline silicon
Photoelectric conversion efficiency before and after thin-film solar cells etching processing；
Table 1
| W(J/cm2) | Jsc(mA/cm2) | Voc(V) | FF | η (%) | |
| Comparative example 1 | 0 | 0.51 | 0.87 | 0.18 | 8.0 |
| Embodiment 1 | 0.5 | 0.65 | 0.93 | 0.20 | 12.1 |
| Embodiment 2 | 0.75 | 0.81 | 0.97 | 0.19 | 14.9 |
| Embodiment 3 | 1.25 | 0.71 | 0.95 | 0.19 | 12.8 |
| Comparative example 2 | 0.25 | 0.61 | 0.91 | 0.18 | 10.0 |
| Comparative example 3 | 2 | 0 | 0 | - | - |
It by Fig. 4 and table 1, can clearly observe, amorphous silicon membrane is handled without femto-second laser pulse surface suedeization
The photoelectric conversion efficiency of solar cell is 8.0%；When pulsed laser energy W increases as 0.75J/cm2When, amorphous silicon membrane is too
The photoelectric conversion efficiency of positive energy battery reaches maximum value 14.9%, is almost to handle the sun without femto-second laser pulse surface suedeization
Twice of energy battery conversion efficiency.This is absolutely proved, by femtosecond laser micro-nano technology technology, can make the amorphous silicon membrane sun
The surface suede of energy battery enhances amorphous silicon thin-film solar cell surface " photo-induction is caught " ability, and then improves solar cell
Photoelectric conversion efficiency.
Embodiment
It is as follows to prepare amorphous silicon thin-film solar cell porous surface micro-structure antireflection layer method：
1.1st, amorphous silicon thin-film solar cell is attached on glass slide, is then fixed to femtosecond laser micro-nano and adds
Work platform upper mounting plate motor stepping accuracy is 0.1 μm, 1.5 × 1.5cm of solar cell sizes size2；
1.2nd, microscopic system vertical incidence of the femto-second laser pulse through 10 × object lens (numerical aperture 0.25) focuses on
On thin-film solar cells N-shaped amorphous silicon film surface, the hot spot that waist radius is about 0.5 μm is formed；
1.3rd, it is controlled by terminal, the femto-second laser pulse of focusing will be square vertically along platform with the rate of 1mm/s
It is moved to constant speed, setting femto-second laser pulse repetition rate is 1kHz, while sets amorphous silicon thin-film solar cell is identical to fly
Second pulsed laser energy W is 0.75J/cm2, different femto-second laser pulse etching period T (5 μm, 8 μm, 15 μm, 30 μm, 50 μm)
Micro Process parameter, linear polarization femto-second laser pulse will be to carrying out on amorphous silicon thin-film solar cell N-shaped amorphous silicon film surface
Suedeization processing, obtains efficient p-i-n structure amorphous silicon thin-film solar cell.As shown in fig. 7, femto-second laser pulse energy
(W) it is certain value, changes the surface suede SEM figures of femto-second laser pulse etching period T.
Embodiment 4
1.1st, amorphous silicon thin-film solar cell prepared by comparative example 1 is attached on glass slide, be then fixed to
Femtosecond laser micro-nano technology platform upper mounting plate motor stepping accuracy is 0.1 μm, 1.5 × 1.5cm of solar cell sizes size2；
1.2nd, microscopic system vertical incidence of the femto-second laser pulse through 10 × object lens (numerical aperture 0.25) focuses on
On thin-film solar cells N-shaped amorphous silicon film surface, the hot spot that waist radius is about 0.5 μm is formed；
1.3rd, it is controlled by terminal, the femto-second laser pulse of focusing will be square vertically along platform with the rate of 1mm/s
It is moved to constant speed, setting femto-second laser pulse repetition rate is 1kHz, while amorphous silicon thin-film solar cell femtosecond is set to swash
Optical pulse energy (W) is 0.75J/cm2, femto-second laser pulse etching period (T) is 8 μm of micro Process parameter, linear polarization femtosecond
Laser pulse will obtain efficient p-i-n to carrying out suede processing on amorphous silicon thin-film solar cell N-shaped amorphous silicon film surface
Structure amorphous silicon thin-film solar cell.
Embodiment 5
1.1st, amorphous silicon thin-film solar cell prepared by comparative example 1 is attached on glass slide, be then fixed to
Femtosecond laser micro-nano technology platform upper mounting plate motor stepping accuracy is 0.1 μm, 1.5 × 1.5cm of solar cell sizes size2；
1.2nd, microscopic system vertical incidence of the femto-second laser pulse through 10 × object lens (numerical aperture 0.25) focuses on
On thin-film solar cells N-shaped amorphous silicon film surface, the hot spot that waist radius is about 0.5 μm is formed；
1.3rd, it is controlled by terminal, the femto-second laser pulse of focusing will be square vertically along platform with the rate of 1mm/s
It is moved to constant speed, setting femto-second laser pulse repetition rate is 1kHz, while amorphous silicon thin-film solar cell femtosecond is set to swash
Optical pulse energy (W) is 0.75J/cm2, femto-second laser pulse etching period (T) is 15 μm of micro Process parameter, linear polarization femtosecond
Laser pulse will obtain efficient p-i-n to carrying out suede processing on amorphous silicon thin-film solar cell N-shaped amorphous silicon film surface
Structure amorphous silicon thin-film solar cell.
Embodiment 6
1.1st, amorphous silicon thin-film solar cell prepared by comparative example 1 is attached on glass slide, be then fixed to
Femtosecond laser micro-nano technology platform upper mounting plate motor stepping accuracy is 0.1 μm, 1.5 × 1.5cm of solar cell sizes size2；
1.2nd, microscopic system vertical incidence of the femto-second laser pulse through 10 × object lens (numerical aperture 0.25) focuses on
On thin-film solar cells N-shaped amorphous silicon film surface, the hot spot that waist radius is about 0.5 μm is formed；
1.3rd, it is controlled by terminal, the femto-second laser pulse of focusing will be square vertically along platform with the rate of 1mm/s
It is moved to constant speed, setting femto-second laser pulse repetition rate is 1kHz, while amorphous silicon thin-film solar cell femtosecond is set to swash
Optical pulse energy (W) is 0.75J/cm2, femto-second laser pulse etching period (T) is 30 μm of micro Process parameter, linear polarization femtosecond
Laser pulse will obtain efficient p-i-n to carrying out suede processing on amorphous silicon thin-film solar cell N-shaped amorphous silicon film surface
Structure amorphous silicon thin-film solar cell.
Comparative example 4
1.1st, amorphous silicon thin-film solar cell prepared by comparative example 1 is attached on glass slide, be then fixed to
Femtosecond laser micro-nano technology platform upper mounting plate motor stepping accuracy is 0.1 μm, 1.5 × 1.5cm of solar cell sizes size2；
1.2nd, microscopic system vertical incidence of the femto-second laser pulse through 10 × object lens (numerical aperture 0.25) focuses on
On thin-film solar cells N-shaped amorphous silicon film surface, the hot spot that waist radius is about 0.5 μm is formed；
1.3rd, it is controlled by terminal, the femto-second laser pulse of focusing will be square vertically along platform with the rate of 1mm/s
It is moved to constant speed, setting femto-second laser pulse repetition rate is 1kHz, while amorphous silicon thin-film solar cell femtosecond is set to swash
Optical pulse energy (W) is 0.75J/cm2, femto-second laser pulse etching period (T) is 5 μm of micro Process parameter, linear polarization femtosecond
Laser pulse will obtain efficient p-i-n to carrying out suede processing on amorphous silicon thin-film solar cell N-shaped amorphous silicon film surface
Structure amorphous silicon thin-film solar cell.
Comparative example 5
1.1st, amorphous silicon thin-film solar cell prepared by comparative example 1 is attached on glass slide, be then fixed to
Femtosecond laser micro-nano technology platform upper mounting plate motor stepping accuracy is 0.1 μm, 1.5 × 1.5cm of solar cell sizes size2；
1.2nd, microscopic system vertical incidence of the femto-second laser pulse through 10 × object lens (numerical aperture 0.25) focuses on
On thin-film solar cells N-shaped amorphous silicon film surface, the hot spot that waist radius is about 0.5 μm is formed；
1.3rd, it is controlled by terminal, the femto-second laser pulse of focusing will be square vertically along platform with the rate of 1mm/s
It is moved to constant speed, setting femto-second laser pulse repetition rate is 1kHz, while amorphous silicon thin-film solar cell femtosecond is set to swash
Optical pulse energy (W) is 0.75J/cm2, femto-second laser pulse etching period (T) is 50 μm of micro Process parameter, linear polarization femtosecond
Laser pulse will obtain efficient p-i-n to carrying out suede processing on amorphous silicon thin-film solar cell N-shaped amorphous silicon film surface
Structure amorphous silicon thin-film solar cell.
Fig. 8 is the surface suede amorphous silicon thin-film solar of 4- of embodiment of the present invention embodiments 6, comparative example 4, comparative example 5
Cell I-V characteristic test curve, Fig. 9 are the surface suede a-SiTFSCs of embodiment 4- embodiments 6, comparative example 4, comparative example 5
η and the variation relation at femto-second laser pulse etching period interval.
Table 2 is embodiment 4- embodiments 6, the identical femto-second laser pulse energy W of comparative example 4, comparative example 5, different femtoseconds
Before and after laser pulse etching period T (5 μm, 8 μm, 15 μm, 30 μm, 50 μm) is to amorphous silicon thin-film solar cell etching processing
Photoelectric conversion efficiency；
Table 2
| T(μm) | Jsc(mA/cm2) | Voc(V) | FF | η (%) | |
| Comparative example 1 | 0 | 0.51 | 0.87 | 0.18 | 8.0 |
| Embodiment 1 | 8 | 0.69 | 0.91 | 0.18 | 11.3 |
| Embodiment 2 | 15 | 0.81 | 0.97 | 0.19 | 14.9 |
| Embodiment 3 | 30 | 0.63 | 0.89 | 0.18 | 10.1 |
| Comparative example 4 | 5 | 0.46 | 0.85 | 0.18 | 7.0 |
| Comparative example 5 | 50 | 0.56 | 0.87 | 0.18 | 8.8 |
It can clearly be observed by Fig. 8 and table 2, without femto-second laser pulse surface suedeization processing amorphous silicon membrane too
The photoelectric conversion efficiency of positive energy battery is 8.0%；Amorphous silicon thin-film solar cell through femto-second laser pulse surface suede turns
Efficiency is changed, the variation with femto-second laser pulse etching period T is still in non-linear relation；As femto-second laser pulse etching period T
When being 5 μm, it is 7.0% that solar cell, which has minimum transfer efficiency, even less than without femto-second laser pulse surface suede
Handle the photoelectric conversion efficiency of solar cell.When laser pulse etching period T continues increase, surface suedeization processing non-crystalline silicon
Thin-film solar cells transfer efficiency gradually increases；When laser pulse etching period T increases to 15 μm, suedeization processing in surface is non-
Crystal silicon solar batteries transformation efficiency reaches maximum value 14.9%；Continue to increase with femto-second laser pulse etching period T, too
Positive energy battery conversion efficiency reduces instead, finally, when femto-second laser pulse etching period T increases to 50 μm, at the suede of surface
The photoelectric conversion efficiency of reason amorphous silicon thin-film solar cell is reduced to 8.8%.
The present invention is carried out using femtosecond laser micro-nano technology technology in amorphous silicon thin-film solar cell n-type silicon film surface
" suede " etching processing in " groove " structure of scanning area formation, induces nano level crystalline state porous microstructure to be formed, this
The appearance of sample nanometer aperture can rely on the diffraction effect of incident light, strengthen oscillation of the light quantum in hole, and then increase incident
Light increases the contact probability of light and semiconductor, improves " light capture " energy of non-crystal silicon solar cell in the light path of inside battery
Power, therefore, femto-second laser pulse amorphous silicon thin-film solar cell surface suede, to improving solar cell photoelectric transfer efficiency
It is beneficial.Research shows that the selection of femto-second laser pulse etching period (T) and pulsed laser energy (W), to solar cell
Open-circuit voltage, short-circuit current density and photoelectric conversion efficiency characteristic have a direct impact；When between femto-second laser pulse etching period
Away from being 15 μm, pulse energy 0.75J/cm2When, solar cell photoelectric transfer efficiency reaches 14.9%, is without laser incising
2 times of erosion processing amorphous silicon thin-film solar cell transfer efficiency.
It these are only specific embodiments of the present invention, be not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.Any modification for all within the spirits and principles of the present invention, being made,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (1)
1. a kind of method of femtosecond laser etching enhancing amorphous silicon thin-film solar cell performance, it is characterized in that：
It is as follows：
（1）Prepare p-i-n structure amorphous silicon thin-film solar cell
1.1st, tco layer is prepared
By In2O3-SnO2Ceramic target is positioned in magnetron sputtering coating system, and the substrate of glass cleaned up is placed horizontally at
The center of block substrate, closed reaction chamber carry out sputter coating；Wherein, the vacuum degree of sputtering chamber is 10-2Pa is passed through pure
The argon gas for 99.99 % is spent as reaction gas, and argon gas flow velocity is 15.3 sccm, and underlayer temperature is 300 DEG C, and sputtering power is
600 W, In2O3-SnO2Ceramic target sputtering voltage is -110 V, and sputtering time is 20 minutes, 10 nm/min of deposition rate；In glass
Glass substrate side sputtering thickness is 200 nm by SnO2The tco layer of composition；
1.2nd, p-type amorphous silicon semiconductor is prepared
The substrate of glass of surface deposition TCO conductive layers is placed horizontally to the center of magnetron sputtering coating system block substrate,
Closed reaction chamber carries out enhancing chemical vapor deposition；Wherein, reative cell vacuum degree is 10-5Pa, underlayer temperature are 250 DEG C, to
SiH is passed through in reative cell4、B2H6And H2, SiH4、B2H6And H2Flow velocity be respectively 6 sccm, 4 sccm and 20 sccm, during deposition
For pressure control in 80 Pa, radio-frequency power is 160 W, and sputtering time is 15 minutes, 40 nm/min of deposition rate；On tco layer
Face deposition thickness is the p-type amorphous silicon semiconductor of 600 nm；
1.3rd, i type amorphous silicon semiconductors are prepared
Upper space depositing p-type amorphous silicon semiconductor substrate of glass is placed horizontally in magnetron sputtering coating system block substrate
Heart position, closed reaction chamber；Wherein, reative cell vacuum degree is 10-5Pa, underlayer temperature are 350 DEG C, are passed through into reative cell
SiH4And H2, SiH4And H2Flow velocity be respectively 6 sccm and 24 sccm, pressure control is in 80 Pa, radio-frequency power during deposition
160 W, sputtering time are 15 minutes, 40 nm/min of deposition rate；On p-type amorphous silicon semiconductor layer, deposition thickness is
The i type amorphous silicon semiconductors of 600 nm；
1.4th, N-shaped amorphous silicon semiconductor is prepared
Upper space deposition i type amorphous silicon semiconductor substrate of glass is placed horizontally in magnetron sputtering coating system block substrate
Heart position, closed reaction chamber；Wherein, reative cell vacuum degree is 10-5Pa, underlayer temperature are 300 DEG C；It is passed through SiH4、PH3And H2,
SiH4、PH3And H2Flow velocity be respectively 6 sccm, 4 sccm and 20 sccm, pressure control is in 80 Pa, radio-frequency power during deposition
For 160 W, sputtering time is 15 minutes, 40 nm/min of deposition rate；On i type amorphous silicon semiconductor layers, deposition thickness is
The N-shaped amorphous silicon semiconductor of 600 nm；
1.5th, aluminium electrode is made
By way of vacuum evaporation, at the top of the p-i-n structure amorphous silicon thin-film solar cell of preparation, aluminium electrode is made,
Obtain p-i-n structure amorphous silicon thin-film solar cell；
（2）By p-i-n structure amorphous silicon thin-film solar cell, it is fixed on femtosecond laser micro-nano technology platform, femtosecond laser arteries and veins
The microscopic system vertical incidence through 10 times of object lens is rushed, numerical aperture of the femto-second laser pulse through 10 times of object lens is 0.25, is focused on
On thin-film solar cells N-shaped amorphous silicon film surface, femtosecond laser micro-nano technology platform, rate travel is moved for 1 mm/s constant speed
Dynamic, platform motor stepping accuracy is 0.1 μm；It is 0.75 J/cm to set femto-second laser pulse energy density2It is carved with laser pulse
It is 15 μm to lose period distances, and linear polarization femto-second laser pulse is enterprising to amorphous silicon thin-film solar cell N-shaped amorphous silicon film surface
The processing of row suedeization obtains the efficient p-i-n structure amorphous silicon thin-film solar cell that photoelectric conversion efficiency is 14.9%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610905685.3A CN106299032B (en) | 2016-10-17 | 2016-10-17 | The method of femtosecond laser etching enhancing amorphous silicon thin-film solar cell performance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610905685.3A CN106299032B (en) | 2016-10-17 | 2016-10-17 | The method of femtosecond laser etching enhancing amorphous silicon thin-film solar cell performance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106299032A CN106299032A (en) | 2017-01-04 |
| CN106299032B true CN106299032B (en) | 2018-07-10 |
Family
ID=57719606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610905685.3A Expired - Fee Related CN106299032B (en) | 2016-10-17 | 2016-10-17 | The method of femtosecond laser etching enhancing amorphous silicon thin-film solar cell performance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106299032B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113290320A (en) * | 2021-05-21 | 2021-08-24 | 上海理工大学 | Preparation method of Ag-based film with nonlinear reverse saturable absorption enhancement characteristic |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101290955A (en) * | 2008-06-04 | 2008-10-22 | 胡宏勋 | Manufacturing process of flexible amorphous silicon solar cell |
| CN101431127A (en) * | 2008-12-02 | 2009-05-13 | 华中科技大学 | Production method of flexible amorphous silicon thin-film solar cell |
| CN101866836A (en) * | 2010-05-28 | 2010-10-20 | 常州大学 | Preparation method of nanometer silicon quantum dots and application thereof in film solar batteries |
| CN102626831A (en) * | 2012-04-09 | 2012-08-08 | 镇江大成新能源有限公司 | Femtosecond laser etching equipment of thin-film solar battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI278899B (en) * | 2004-08-23 | 2007-04-11 | Ind Tech Res Inst | Apparatus for manufacturing a quantum-dot element |
-
2016
- 2016-10-17 CN CN201610905685.3A patent/CN106299032B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101290955A (en) * | 2008-06-04 | 2008-10-22 | 胡宏勋 | Manufacturing process of flexible amorphous silicon solar cell |
| CN101431127A (en) * | 2008-12-02 | 2009-05-13 | 华中科技大学 | Production method of flexible amorphous silicon thin-film solar cell |
| CN101866836A (en) * | 2010-05-28 | 2010-10-20 | 常州大学 | Preparation method of nanometer silicon quantum dots and application thereof in film solar batteries |
| CN102626831A (en) * | 2012-04-09 | 2012-08-08 | 镇江大成新能源有限公司 | Femtosecond laser etching equipment of thin-film solar battery |
Non-Patent Citations (1)
| Title |
|---|
| 基于飞秒激光加工的硅太阳能电池;邵珠峰;《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》;20111215;第18-19页、26-35页、图2-5、3-3 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106299032A (en) | 2017-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7058312B2 (en) | Cutting and passivation methods for silicon-based semiconductor devices, and silicon-based semiconductor devices | |
| CN101814553B (en) | Light-assistant method for preparing light absorption layer of copper-indium-gallium-selenium film solar cell | |
| CN104813482B (en) | Molybdenum base material for CIGS photovoltaic devices | |
| CN109768165B (en) | Perovskite solar cell and preparation method thereof | |
| US20240097060A1 (en) | Hybrid passivation back contact cell and fabrication method thereof | |
| CN102254998B (en) | Cadmium-free CuInGaSe thin film solar cell assembly and preparing method of zinc sulfide buffer layer thin film thereof | |
| WO2013185506A1 (en) | Method for preparing copper indium gallium diselenide thin-film solar cell | |
| CN106299032B (en) | The method of femtosecond laser etching enhancing amorphous silicon thin-film solar cell performance | |
| WO2012040917A1 (en) | Shallow junction solar battery and manufacturing method thereof | |
| KR20090004262A (en) | Fabricating method of cigs solar cell | |
| CN100433371C (en) | An a-Si:H solar battery with the boron mixing non-crystal diamond film as the window layer and its making method | |
| CN102569497A (en) | Method for forming anti-reflecting film on base plate as well as solar cell and preparation method thereof | |
| EP4120367A1 (en) | Method to enhance the kesterite solar cell performance | |
| CN106159094A (en) | A kind of perovskite solar cell based on silica-based micro-nano structure and preparation method thereof | |
| CN101237005A (en) | Forming method for micro crystal silicon film | |
| Sobajima et al. | High-rate deposition of microcrystalline silicon photovoltaic active layers by plasma-enhanced chemical vapor deposition at kilo-pascal pressures | |
| CN106229361B (en) | A kind of P I N generating Rotating fields and preparation method thereof and euphotic solar energy battery and preparation method thereof | |
| CN101707218B (en) | Preparation method of common pole-type thin film solar cell | |
| CN102912304B (en) | Preparation method of (211) preferred orientation Mo film | |
| CN102569517A (en) | Nano silicon film solar battery elliptic polarized light real-time monitoring preparation method | |
| Gupta | Laser-induced surface modification for photovoltaic device applications | |
| KR101306459B1 (en) | Solar cell apparatus and method of fabricating the same | |
| Meeth et al. | Pulsed laser deposition of thin film CdTe/CdS solar cells with CdS/ZnS superlattice windows | |
| KR100996162B1 (en) | Thin film solar cell, fabricating method of the same, fabricating method of photoreceptive layer | |
| CN116657107A (en) | Cu (copper) alloy 4 O 3 Film, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180710 Termination date: 20211017 |