CN104465890A - Preparation method for textured AZO thin film used for thin film solar cell front electrode - Google Patents
Preparation method for textured AZO thin film used for thin film solar cell front electrode Download PDFInfo
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- CN104465890A CN104465890A CN201410842463.2A CN201410842463A CN104465890A CN 104465890 A CN104465890 A CN 104465890A CN 201410842463 A CN201410842463 A CN 201410842463A CN 104465890 A CN104465890 A CN 104465890A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000010409 thin film Substances 0.000 title claims abstract description 17
- 239000010408 film Substances 0.000 claims abstract description 39
- 239000011521 glass Substances 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 238000005516 engineering process Methods 0.000 claims abstract description 24
- 238000010884 ion-beam technique Methods 0.000 claims abstract description 20
- 238000005530 etching Methods 0.000 claims abstract description 19
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 12
- 238000004544 sputter deposition Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000003595 mist Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000000151 deposition Methods 0.000 abstract description 5
- 238000001039 wet etching Methods 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical group CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 2
- 239000005368 silicate glass Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
- Drying Of Semiconductors (AREA)
Abstract
Provided is a preparation method for a textured AZO thin film used for a thin film solar cell front electrode. The preparation method includes the following steps that (1), a glass substrate is cleaned and blown to be dry through high-pressure N2; (2), a reaction ion beam technology is adopted for etching the surface of the glass substrate, so that the surface of the glass substrate is of a textured structure; (3) a magnetron sputtering technology is adopted for depositing an AZO thin film of 450 nanometers-750 nanometers on the textured structure of the surface of the glass substrate, so that the AZO thin film of the textured structure is obtained. By the adoption of the ion beam technology, the surface of the glass substrate is etched, so that the glass substrate of the textured structure is obtained, and then the magnetron sputtering technology is used for depositing the AZO thin film of the textured structure on the glass substrate; in this way, it is avoided that the film layer is wasted in thickness by the adoption of an existing etching technology, and by the adoption of a wet etching technology, generated waste acid corrosive liquid pollutes the environment.
Description
Technical field
The present invention relates to the preparation method of the matte AZO film for electrode before thin-film solar cells.
Background technology
The energy that the current mankind use in life and production is mainly from fossil fuels such as coal, oil, natural gases.There is unsustainable and unclean two large problems in fossil fuel, along with the demand of development to the energy of society is increasing, the problem of these two aspects also becomes increasingly conspicuous.And solar energy has widely distributed, inexhaustible, nexhaustible advantage, and can accomplish to environment almost without any pollution, be continuable clean energy resource truly.To the utilization of solar energy, as long as concentrate on solar photovoltaic utilization and solar thermal utilization now, wherein solar photovoltaic utilization mainly relies on solar cell to realize.
In recent years, AZO (Al-Doped ZnO) film, because it is in visible-range, has higher transmissivity; Under the high temperature conditions, not easily with hydrogen generation counterdiffusion, therefore in reactive hydrogen and hydrogen plasma environment, chemical stability is high, not easily makes solar cell material activity reduce; The advantages such as material source is abundant, low price.Thus AZO film is in the fields such as solar cell, liquid crystal display, antistatic, has wide practical use.Before solar film battery requires, electrode has the characteristic such as high transmission, low resistance, prepares various ups and downs suede structure, realize the reflection to sunlight, refraction and diffuse reflection at AZO film surface.Mainly be divided into dry etching and wet etching at present to matte etching, dry etching uses the technology such as ion beam, plasma to etch AZO film surface; Wet etching generally adopt volume fraction be 0.5% watery hydrochloric acid, etch period is generally 10 ~ 30s, the general 20 ~ 150nm of film surface r.m.s. roughness, and mist degree is generally the requirement that 10 ~ 30% performance index can meet electrode before solar film battery.But these two kinds of methods all require higher to AZO film thickness; namely the film with certain suede structure will be formed; the film surface that the AZO film that approximately for no reason will consume more than 1/3rd could realize remaining 2/3rds thickness has the suede structure of expectation; this just causes a large amount of thicknesses of layers losses; add production cost, be unfavorable for long-term large-scale production.
Summary of the invention
The present invention aims to provide a kind of preparation method of the matte AZO film for electrode before thin-film solar cells, and the method does not only have too high requirement to film thickness but also completely avoid because etching is to thicknesses of layers loss, effectively reduces production cost.
In order to reach above-mentioned purpose, provide the preparation method of electrode matte AZO film before a kind of thin-film solar cells, comprise the steps: (1) cleaning glass substrate, rear high pressure N2 dries up; (2) adopt reactive ion beam technology to etch described glass substrate surface, make described glass substrate surface have suede structure; And (3) adopt magnetron sputtering technique on the suede structure of described glass substrate surface, deposit the AZO film of 450 ~ 750 nanometers, thus obtain the AZO film of suede structure.
In some embodiments, in described step (1), the described glass substrate of cleaning, comprises and first uses the ultrasonic 15min of acetone, then use the ultrasonic 15min of alcohol, finally use the ultrasonic 15min of deionized water.
In some embodiments, the etching gas in described step (2) is the mist of Ar2 and CHF3, and its flow-rate ratio is 1:1.5 ~ 2.5;
In some embodiments, the reactive ion beam etching (RIBE) equipment that described step (2) adopts, base vacuum is 8 × 10-4 ~ 6 × 10-3Pa; Operating pressure is 2 ~ 6 × 10-2Pa; Ion beam current energy is 350 ~ 450eV; Line is 60 ~ 90mA; Accelerating voltage 180 ~ 260V; Incidence angle is 25 ~ 45 °; Etch period 3 ~ 5min.
In some embodiments, in described step (3) in magnetron sputtering AZO film, base vacuum≤9 × 10-4Pa; Operating pressure is 5 ~ 7 × 10-1Pa; Sputtering power 150 ~ 250V; Sputtering technology gas Ar2 flow 20 ~ 30sccm; Underlayer temperature 150 ~ 300 DEG C.
This invention exploits a kind of preparation method of the matte AZO film for electrode before thin-film solar cells newly, first adopt ion beam technology, etching processing is carried out to glass substrate surface, obtain the glass substrate of suede structure, then there is with magnetron sputtering technique deposition the AZO film of suede structure on a glass substrate, avoid the waste to thicknesses of layers in existing lithographic technique, it also avoid the spent acid corrosive liquid pollution on the environment produced in wet-etching technology simultaneously.
Below in conjunction with accompanying drawing, the description of purport of the present invention is described by example, to know other aspects of the present invention and advantage.
Accompanying drawing explanation
By reference to the accompanying drawings, by detailed description hereafter, above-mentioned and other feature and advantage of the present invention more clearly can be understood, wherein:
Fig. 1 is the flow chart of the preparation method according to the embodiment of the present invention.
Embodiment
See the accompanying drawing of the specific embodiment of the invention, hereafter in more detail the present invention will be described.But the present invention can realize in many different forms, and should not be construed as by the restriction in the embodiment of this proposition.On the contrary, it is abundant and complete open in order to reach for proposing these embodiments, and makes those skilled in the art understand scope of the present invention completely.
Description describes the preparation method according to the embodiment of the present invention in detail.
As shown in Figure 1, according to the electrode preparation method of matte AZO film before the thin-film solar cells of the embodiment of the present invention, in step S101, cleaning glass substrate, rear high pressure N
2dry up.In step S101, clean described glass substrate, comprise and first use the ultrasonic 15min of acetone, then use the ultrasonic 15min of alcohol, finally use the ultrasonic 15min of deionized water.
In step S102, adopt reactive ion beam technology to etch described glass substrate surface, make described glass substrate surface have suede structure.In step S102, etching gas is Ar
2and CHF
3mist, its flow-rate ratio is 1:1.5 ~ 2.5.
In step S102, reactive ion beam etching (RIBE) equipment, base vacuum is 8 × 10-4 ~ 6 × 10-3Pa; Operating pressure is 2 ~ 6 × 10-2Pa; Ion beam current energy is 350 ~ 450eV; Line is 60 ~ 90mA; Accelerating voltage 180 ~ 260V; Incidence angle is 25 ~ 45 °; Etch period 3 ~ 5min.
In step S103, adopt magnetron sputtering technique on the suede structure of described glass substrate surface, deposit the AZO film of 450 ~ 750 nanometers, thus obtain the AZO film of suede structure.In step S103, in magnetron sputtering AZO film, base vacuum≤9 × 10-4Pa; Operating pressure is 5 ~ 7 × 10-1Pa; Sputtering power 150 ~ 250V; Sputtering technology gas Ar2 flow 20 ~ 30sccm; Underlayer temperature 150 ~ 300 DEG C.
Hereafter will the example implemented according to the preparation method of the embodiment of the present invention be described.
Embodiment one
(1) cleaning of glass substrate surface: select thickness to be that (oxide mass percentage is SiO for the alumina silicate glass of 1.1mm, 20 × 20mm
2: 64%; Al2O3:14%; NaCl:2%; MgO:4%; Na
2o:12%; CaO:2%; K
2o:2%) put into supersonic wave cleaning machine, first use the ultrasonic 15min of acetone, then use the ultrasonic 15min of alcohol, finally use the ultrasonic 15min of deionized water, use high pressure N
2dry up.
(2) be positioned in ion beam apparatus by cleaned glass substrate, etching gas is Ar
2and CHF
3mist, its flow-rate ratio is 1:1.5, and basic parameter is as follows:
Base vacuum :≤6 × 10-3Pa;
Operating pressure: 2 × 10-2Pa;
Ion beam current energy: 400eV;
Line: 60mA;
Accelerating voltage: 220V;
Incidence angle: 25 °;
Etch period: 3min.
(3) take out glass substrate, put into magnetron sputtering apparatus and deposit AZO film, preparation technology parameter is as follows:
Base vacuum :≤9 × 10-4Pa;
Operating pressure: 5 × 10-1Pa;
Sputtering power: 200V;
Sputtering technology gas Ar
2flow: 30sccm;
Sputtering time: 30min;
Underlayer temperature: 300 DEG C.
Embodiment two
(1) cleaning of glass substrate surface: select thickness to be that (oxide mass percentage is SiO for the alumina silicate glass of 1.1mm, 20 × 20mm
2: 64%; Al2O3:14%; NaCl:2%; MgO:4%; Na
2o:12%; CaO:2%; K
2o:2%) put into supersonic wave cleaning machine, first use the ultrasonic 15min of acetone, then use the ultrasonic 15min of alcohol, finally use the ultrasonic 15min of deionized water, use high pressure N
2dry up.
(2) be positioned in ion beam apparatus by cleaned glass substrate, etching gas is Ar
2and CHF
3mist, its flow-rate ratio is 1:2.5, and basic parameter is as follows:
Base vacuum :≤6 × 10-3Pa;
Operating pressure: 2 × 10-2Pa;
Ion beam current energy: 450eV;
Line: 80mA;
Accelerating voltage: 260V;
Incidence angle: 45 °;
Etch period: 3min.
(3) take out glass substrate, put into magnetron sputtering apparatus and deposit AZO film, preparation technology parameter is as follows:
Base vacuum :≤9 × 10-4Pa;
Operating pressure: 5 × 10-1Pa;
Sputtering power: 200V;
Sputtering technology gas Ar
2flow: 30sccm;
Sputtering time: 30min;
Underlayer temperature: 300 DEG C.
With optical profilometer glass substrate to without ion beam etching, the sample directly preparing AZO film thereon characterizes, and r.m.s. roughness Ra is 18.6nm.
At the glass substrate surface deposition AZO film after etching, r.m.s. roughness Ra is that 143.2nm meets the requirement of solar film battery to front electrode light trapping structure completely.
Describe the utilization due to technique scheme according to the embodiment of the present invention in detail hereinafter with reference to accompanying drawing, the present invention compared with prior art has following advantage,
(1) this invention exploits a kind of preparation method of the matte AZO film for electrode before thin-film solar cells newly, first adopt ion beam technology, etching processing is carried out to glass substrate surface, obtain the glass substrate of suede structure, then there is with magnetron sputtering technique deposition the AZO film of suede structure on a glass substrate, avoid the waste to thicknesses of layers in existing lithographic technique, it also avoid the spent acid corrosive liquid pollution on the environment produced in wet-etching technology simultaneously.
(2) the present invention instead of conventional first film forming etching technics again by carrying out etching processing to glass substrate, not only simple possible, and the AZO suede structure prepared, be more suitable for the requirement of electrode pair light trapping structure before thin-film solar cells, effectively can increase sunlight light path of advancing in the film, increase the absorption to sunlight, thus improve the photoelectric conversion efficiency of thin-film solar cells.
(3) present invention employs ion beam etching technology to etch glass substrate, thus have resolution high, controllability is strong, easily is automated, handling safety, easy, the advantages such as processing procedure is pollution-free.。
More than describe preferred embodiment of the present invention in detail.Should be appreciated that those of ordinary skill in the art just design according to the present invention can make many modifications and variations without the need to creative work.All technical staff in the art, all should by the determined protection range of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (5)
1. an electrode preparation method for matte AZO film before thin-film solar cells, is characterized in that, comprise the steps:
(1) glass substrate is cleaned, rear high pressure N
2dry up;
(2) adopt reactive ion beam technology to etch described glass substrate surface, make described glass substrate surface have suede structure; And
(3) adopt magnetron sputtering technique on the suede structure of described glass substrate surface, deposit the AZO film of 450 ~ 750 nanometers, thus obtain the AZO film of suede structure.
2. preparation method according to claim 1, is characterized in that, in described step (1), the described glass substrate of cleaning, comprises and first use the ultrasonic 15min of acetone, then use the ultrasonic 15min of alcohol, finally use the ultrasonic 15min of deionized water.
3. preparation method according to claim 1, is characterized in that, the etching gas in described step (2) is Ar
2and CHF
3mist, its flow-rate ratio is 1:1.5 ~ 2.5.
4. preparation method according to claim 3, is characterized in that, the reactive ion beam etching (RIBE) equipment that described step (2) adopts, and base vacuum is 8 × 10-4 ~ 6 × 10
-3pa; Operating pressure is 2 ~ 6 × 10
-2pa; Ion beam current energy is 350 ~ 450eV; Line is 60 ~ 90mA; Accelerating voltage 180 ~ 260V; Incidence angle is 25 ~ 45 °; Etch period 3 ~ 5min.
5. preparation method according to claim 1, is characterized in that, in described step (3) in magnetron sputtering AZO film, and base vacuum≤9 × 10-4Pa; Operating pressure is 5 ~ 7 × 10
-1pa; Sputtering power 150 ~ 250V; Sputtering technology gas Ar
2flow 20 ~ 30sccm; Underlayer temperature 150 ~ 300 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410842463.2A CN104465890A (en) | 2014-12-25 | 2014-12-25 | Preparation method for textured AZO thin film used for thin film solar cell front electrode |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410842463.2A CN104465890A (en) | 2014-12-25 | 2014-12-25 | Preparation method for textured AZO thin film used for thin film solar cell front electrode |
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| Publication Number | Publication Date |
|---|---|
| CN104465890A true CN104465890A (en) | 2015-03-25 |
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ID=52911622
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108831754A (en) * | 2018-06-22 | 2018-11-16 | 广东工业大学 | A kind of MeN coating of high-specific surface area and preparation method thereof and supercapacitor |
| CN114408852A (en) * | 2020-10-13 | 2022-04-29 | 天津工业大学 | Hydrophobic antireflection novel micro-nano structure CaF2Film and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863156A (en) * | 2012-09-21 | 2013-01-09 | 蚌埠玻璃工业设计研究院 | Preparation method of textured AZO (aluminum-doped zinc oxide) transparent conductive film |
| CN103266302A (en) * | 2013-02-22 | 2013-08-28 | 苏州大学 | Method for preparing AZO film texture structure used for film solar cell |
-
2014
- 2014-12-25 CN CN201410842463.2A patent/CN104465890A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863156A (en) * | 2012-09-21 | 2013-01-09 | 蚌埠玻璃工业设计研究院 | Preparation method of textured AZO (aluminum-doped zinc oxide) transparent conductive film |
| CN103266302A (en) * | 2013-02-22 | 2013-08-28 | 苏州大学 | Method for preparing AZO film texture structure used for film solar cell |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108831754A (en) * | 2018-06-22 | 2018-11-16 | 广东工业大学 | A kind of MeN coating of high-specific surface area and preparation method thereof and supercapacitor |
| CN108831754B (en) * | 2018-06-22 | 2020-08-11 | 广东工业大学 | MeN coating with high specific surface area, preparation method thereof and supercapacitor |
| CN114408852A (en) * | 2020-10-13 | 2022-04-29 | 天津工业大学 | Hydrophobic antireflection novel micro-nano structure CaF2Film and preparation method thereof |
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Application publication date: 20150325 |