CN107262918A - A kind of method that femtosecond laser improves Al-Doped ZnO film photoelectric properties - Google Patents
A kind of method that femtosecond laser improves Al-Doped ZnO film photoelectric properties Download PDFInfo
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- CN107262918A CN107262918A CN201710436553.5A CN201710436553A CN107262918A CN 107262918 A CN107262918 A CN 107262918A CN 201710436553 A CN201710436553 A CN 201710436553A CN 107262918 A CN107262918 A CN 107262918A
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- femtosecond laser
- doped zno
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- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000012545 processing Methods 0.000 claims abstract description 16
- 238000006073 displacement reaction Methods 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 238000003754 machining Methods 0.000 claims description 4
- 230000005622 photoelectricity Effects 0.000 claims 1
- 238000002310 reflectometry Methods 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 230000031700 light absorption Effects 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract 2
- 238000005459 micromachining Methods 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000013519 translation Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 208000000187 Abnormal Reflex Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 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
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000035859 hyperreflexia Effects 0.000 description 1
- 206010020745 hyperreflexia Diseases 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/02—Positioning or observing the workpiece, e.g. with respect to the point of impact; Aligning, aiming or focusing the laser beam
- B23K26/06—Shaping the laser beam, e.g. by masks or multi-focusing
- B23K26/062—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam
- B23K26/0622—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam by shaping pulses
- B23K26/0624—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam by shaping pulses using ultrashort pulses, i.e. pulses of 1ns or less
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/02—Positioning or observing the workpiece, e.g. with respect to the point of impact; Aligning, aiming or focusing the laser beam
- B23K26/04—Automatically aligning, aiming or focusing the laser beam, e.g. using the back-scattered light
- B23K26/042—Automatically aligning the laser beam
-
- 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
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
-
- 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
- H01L31/1876—Particular processes or apparatus for batch treatment of the devices
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention provides a kind of method that femtosecond laser based on dynamic control improves Al-Doped ZnO film photoelectric properties, belongs to technical field of function materials, and this method is based on femtosecond laser micro/nano processing system, comprised the following steps：It is placed on after the substrate sample cleaning treatment that Al-Doped ZnO is deposited in femtosecond laser parallel micromachining light path, the femtosecond laser that femto-second laser is produced is gathered on alumina material by object lens, processing pattern of the state modulator such as energy, repetition rate and substrate sample velocity of displacement by adjusting femtosecond laser in sample surfaces.Prior art is contrasted, the method that the present invention is provided can repair Al-Doped ZnO surface defect, reduce the sheet resistance of material, improve its electric conductivity；The processing pattern produced by sample surfaces can reduce the reflectivity on surface simultaneously, strengthen the absorption of light in solar cell application, improve photoelectric efficiency.
Description
Technical field
The invention belongs to technical field of function materials, dynamic control femtosecond laser is based in particular to one kind
The method for improving Al-Doped ZnO film photoelectric properties.
Background technology
With the development of photoelectric device, transparent conductive oxide film has good electric conductivity because of it, and visible
Light area has the advantages that higher translucency, is widely used in the photoelectric devices such as solar cell, display, LED.At present
Using it is most be tin indium oxide (ITO), but phosphide element is rare element, and amount of storage is relatively low, and involves great expense, and mixes alumina
Zinc (AZO) is because its raw material is readily available, manufacturing cost is cheap and nontoxic, the stability in hydrogen plasma is better than ITO
The advantages of stability in hydrogen plasma, being increasingly becoming ITO substitute turns into new transparent conductive oxide.
But the Al-Doped ZnO film obtained by means such as magnetron sputtering, ald, pulsed depositions is existed
Lattice defect, the excessive shortcoming of its lattice distance significantly impacts the electric conductivity of material.For problem above, general way
It is to increase the thickness of film, but can also increases the square resistance of material while increase film thickness, and as film is thick
The increase of degree, the reflex of film surface can also strengthen.
In solar cells, Al-Doped ZnO surface reflection enhancement can cause excessive light to reflect, so as to reduce light
Photoelectric transformation efficiency；In the led, because the light that light emitting diode is produced can mix alumina first by Al-Doped ZnO film material
Change Zinc material and be much larger than air refraction, for unencapsulated LED bare chips, its internal light produced can be at interface in outgoing
Total reflection phenomenon occurs for place, thus cause substantial amounts of light can not outgoing, strong chip inner total reflection causes the outer quantum of chip
Efficiency is very low.
Therefore, the problem of how solving larger Al-Doped ZnO square resistance, surface hyperreflexia just seriously annoyings work(
Can Material Field technical staff.
The content of the invention
The invention aims to solve the problem of Al-Doped ZnO square resistance is larger, surface is reflected, there is provided one
The method that the femtosecond laser based on dynamic control improves Al-Doped ZnO film photoelectric properties is planted, is obtained by implementing this method
The material character of the Al-Doped ZnO film arrived is stable.
The principle of the present invention is the surface shape for going out pit in Al-Doped ZnO Surface Machining using femtosecond laser system of processing
Looks, the surface topography of pit shape can reduce reflectivity, while increasing the absorption of light.
The purpose of the present invention is achieved through the following technical solutions：
A kind of method that femtosecond laser based on dynamic control improves Al-Doped ZnO film photoelectric properties, based on winged
Second laser micro/nano processing system, comprises the following steps：
Step 1, oneself is prepared or the commercially available material for being coated with Al-Doped ZnO film carries out cleaning pre- place
Reason；
Step 2, the material for being coated with Al-Doped ZnO film is placed in femtosecond laser system of processing, femtosecond laser passes through thing
Mirror focuses on material surface；
Step 3, the regulation energy of femtosecond laser, repetition rate are to control the processing pattern on Al-Doped ZnO surface；
Step 4, regulation is coated with the material displacement speed of Al-Doped ZnO film, between controlling between adjacent machining area
Away from.
Beneficial effect
Prior art is contrasted, the present invention has following features：
1. Al-Doped ZnO surface defect can be repaired, material square resistance is effectively reduced, its electric conductivity is improved；
2. concave shape is presented in the region in the present invention after femtosecond laser processing, the micro-nano structure can increase optical path difference,
Strengthen the absorption of light, the photoelectric transformation efficiency of solar energy can be improved in solar cells；
3. the micro-nano structure of the surface irregularity in the present invention can effectively reduce the reflectivity of film surface.
Brief description of the drawings
The accompanying drawing for constituting the part of the application is used for providing a further understanding of the present invention, schematic reality of the invention
Apply example and its illustrate to be used to explain the present invention, do not constitute inappropriate limitation of the present invention.In the accompanying drawings：
Fig. 1 is the electron microscope picture that femtosecond laser processes micro-nano structure.
Fig. 2 is the atomic force microscope images that femtosecond laser processes micro-nano structure；
Fig. 3 is femtosecond laser system of processing structure composition schematic diagram.
Embodiment
Describe the present invention in detail below with reference to the accompanying drawings and in conjunction with the embodiments.Experiment side used in following embodiments
Method is conventional method unless otherwise specified.
Material used is commercially obtained in following embodiments.
Embodiment：Being coated with the glass of the thick Al-Doped ZnO films of 600nm Al-Doped ZnO is improved using femtosecond laser
The method of film photoelectric performance, based on femtosecond laser system of processing as shown in Figure 3, the system includes femto-second laser, reflection
Mirror, half-wave plate, attenuator, optical shutter, object lens, sextuple mobile platform, beam splitter, imaging device and illuminating lamp, process light path：Fly
The laser that second laser is sent sequentially passes through half-wave plate, attenuator, optical shutter after two speculums reflections, then by beam splitter
Material surface is focused on through object lens after reflection, the illumination light that illuminating lamp is sent is irradiated to material surface by beam splitter and object lens,
Enter imaging CCD by object lens, beam splitter after being reflected by material surface, comprise the following steps：
First, the Al-Doped ZnO material of selection is pre-processed, is cleaned by ultrasonic respectively in absolute ethyl alcohol 5 minutes and causes
Material surface is totally cleaned.
2nd, the Al-Doped ZnO cleaned is centrally disposed wavelength for 800nm, pulsewidth is 50fs, and repetition rate is big
In 100Hz femtosecond laser system of processing, femtosecond laser focuses on material surface by 10 times of object lens.
3rd, the energy for controlling femtosecond laser is 0.2 μ J/ pulses, and repetition rate is 100Hz, and translation stage translational speed is 500
μm/s, process pit array in film surface.
In above-mentioned preparation method, single pulse energy and the processing pulse of femtosecond laser are adjusted in step 3 process
Number, can control to process aperture and the depth of pit, by controlling the speed of translation stage to control array period spacing.Tool
For body, single pulse energy is in 0.2uJ, and the average pore size of micropore can be 5 μm；It is micro- that translational speed is processed when being 500 μm/s
The cycle of micro-nano structure array is 5 μm.
, simultaneously can be with according to the size modification translation stage translational speed in pit aperture in step 3 in above-mentioned preparation method
Prepare the close micro-nano structure array without spacing.
As shown in figure 1, the region after above-mentioned processing can be significantly seen compared to undressed region under an electron microscope
It is smooth that sample surfaces become, and loose grainy surface is vanished from sight；And the undressed region surface in side significantly can see
Loose state is presented in particle.Simultaneously under an atomic force microscope it can be seen that machining area shows pit shape, such as Fig. 2 institutes
Show, the micro-nano structure of processing is tested into its reflectivity with Fourier spectrometer, obtained reflectivity is compared to obtaining before undressed
Obvious reduction；Its square resistance is measured by four probe method, compared to reducing 3 times before undressed.Why resistance reduction is former
Because being that femtosecond laser and Al-Doped ZnO effect make its melting and refreezing knot reparation lattice surface defect, make surface more smooth, drop
Low resistance.It can control to mix the reparation degree of aluminium oxidation surface by changing the parameters such as femtosecond laser energy, umber of pulse, so that
Different degrees of reduction resistance.
In addition, the micro-nano structure processed to prepare easy solar cell, its photoelectric current is obtained by measurement
Density is 10.08mA/cm2, the density of photocurrent 7.03mA/ produced in solar cells compared to unprocessed planar structure
cm2, greatly improve.By controlling the spacing between femtosecond laser and Al-Doped ZnO pit to control resistance and reflectivity.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (2)
1. a kind of method that femtosecond laser based on dynamic control improves Al-Doped ZnO film photoelectric properties, its feature exists
In：Comprise the following steps：
Step 1, the material for being coated with Al-Doped ZnO film is subjected to cleaning pretreatment；
Step 2, the material for being coated with Al-Doped ZnO film is placed in femtosecond laser system of processing, femtosecond laser is poly- by object lens
Jiao arrives material surface；
Step 3, the regulation energy of femtosecond laser, repetition rate are to control the processing pattern on Al-Doped ZnO surface；
Step 4, regulation be coated with Al-Doped ZnO film material displacement speed with control the adjacent machining area of material surface it
Between spacing.
2. a kind of femtosecond laser based on dynamic control according to claim 1 improves Al-Doped ZnO film photoelectricity
The method of performance, it is characterised in that：The object lens are 10 times of object lens, and the femtosecond laser centre wavelength is that 800nm, pulsewidth are
50fs, energy is 0.2 μ J/ pulses, and repetition rate is 100Hz, and the speed for being coated with the material displacement of Al-Doped ZnO film is 500
μm/s。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710436553.5A CN107262918A (en) | 2017-06-12 | 2017-06-12 | A kind of method that femtosecond laser improves Al-Doped ZnO film photoelectric properties |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710436553.5A CN107262918A (en) | 2017-06-12 | 2017-06-12 | A kind of method that femtosecond laser improves Al-Doped ZnO film photoelectric properties |
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| CN107262918A true CN107262918A (en) | 2017-10-20 |
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| CN201710436553.5A Pending CN107262918A (en) | 2017-06-12 | 2017-06-12 | A kind of method that femtosecond laser improves Al-Doped ZnO film photoelectric properties |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109603204A (en) * | 2019-01-10 | 2019-04-12 | 中南大学 | A kind of crude oil separation method and device |
| CN112276386A (en) * | 2020-10-29 | 2021-01-29 | 广东省科学院中乌焊接研究所 | Pre-welding pretreatment method and welding method for high-reflectivity metal material |
| CN113161231A (en) * | 2021-02-22 | 2021-07-23 | 北京理工大学 | Method for enhancing internal quantum efficiency of ultraviolet LED by femtosecond laser |
| CN114769361A (en) * | 2022-04-28 | 2022-07-22 | 同方江新造船有限公司 | Laser heat energy correction method applied to high-strength aluminum alloy material for ship |
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| CN1928687A (en) * | 2006-09-15 | 2007-03-14 | 江苏大学 | Big area laser modeling method and device for bionic periodic micro/nano structure surface |
| CN101219506A (en) * | 2008-01-07 | 2008-07-16 | 江苏大学 | Laser production method for metal base ultra-hydrophobicity micro-structure surface |
| CN102528276A (en) * | 2012-03-02 | 2012-07-04 | 江苏大学 | Laser-assisted surface treatment method for increasing light transmittance of TCO film |
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2017
- 2017-06-12 CN CN201710436553.5A patent/CN107262918A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1928687A (en) * | 2006-09-15 | 2007-03-14 | 江苏大学 | Big area laser modeling method and device for bionic periodic micro/nano structure surface |
| CN101219506A (en) * | 2008-01-07 | 2008-07-16 | 江苏大学 | Laser production method for metal base ultra-hydrophobicity micro-structure surface |
| CN102528276A (en) * | 2012-03-02 | 2012-07-04 | 江苏大学 | Laser-assisted surface treatment method for increasing light transmittance of TCO film |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109603204A (en) * | 2019-01-10 | 2019-04-12 | 中南大学 | A kind of crude oil separation method and device |
| CN109603204B (en) * | 2019-01-10 | 2021-04-06 | 中南大学 | Crude oil separation method and device |
| CN112276386A (en) * | 2020-10-29 | 2021-01-29 | 广东省科学院中乌焊接研究所 | Pre-welding pretreatment method and welding method for high-reflectivity metal material |
| CN113161231A (en) * | 2021-02-22 | 2021-07-23 | 北京理工大学 | Method for enhancing internal quantum efficiency of ultraviolet LED by femtosecond laser |
| CN114769361A (en) * | 2022-04-28 | 2022-07-22 | 同方江新造船有限公司 | Laser heat energy correction method applied to high-strength aluminum alloy material for ship |
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