CN103594555A - Preparation method for black silicon material with self-cleaning function - Google Patents
Preparation method for black silicon material with self-cleaning function Download PDFInfo
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- CN103594555A CN103594555A CN201310553963.XA CN201310553963A CN103594555A CN 103594555 A CN103594555 A CN 103594555A CN 201310553963 A CN201310553963 A CN 201310553963A CN 103594555 A CN103594555 A CN 103594555A
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- 229910021418 black silicon Inorganic materials 0.000 title claims abstract description 36
- 239000002210 silicon-based material Substances 0.000 title claims abstract description 30
- 238000004140 cleaning Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 27
- 239000010703 silicon Substances 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 12
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 12
- 238000005530 etching Methods 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 239000011651 chromium Substances 0.000 claims abstract description 6
- 238000001020 plasma etching Methods 0.000 claims abstract description 6
- 239000002086 nanomaterial Substances 0.000 claims abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000003292 glue Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 4
- 238000005566 electron beam evaporation Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 3
- 238000000992 sputter etching Methods 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 3
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 229920002379 silicone rubber Polymers 0.000 claims description 2
- 239000004945 silicone rubber Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000000737 periodic effect Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 125000003709 fluoroalkyl group Chemical group 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 229910000077 silane Inorganic materials 0.000 abstract 1
- 238000004049 embossing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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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
- H01L31/18—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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/02—Local etching
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/12—Gaseous compositions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
-
- 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
Abstract
The invention provides a preparation method for a black silicon material with a self-cleaning function. The preparation method specifically comprises the following steps: (1) according to a silicon nano array manufacturing process, a silicon substrate is uniformly coated with a polymethyl methacrylate layer and an ultraviolet nano imprinting gel layer sequentially through a spin coater, an ultraviolet nano imprinting composite soft template is used for conducting imprinting so that an imprinted gel nano array structure can be obtained, the silicon substrate is exposed by means of reactive ion etching, the surface of a sample after etching is plated with a chromium layer, a chromium nano array structure is obtained through a lift-off process, and a wedge silicon nano structure, namely the black silicon material, is obtained by means of reactive ion etching with the chromium nano array structure used as a mask; (2) the black silicon material after etching is completed is processed through oxygen and other ions and then subjected to surface chemical treatment through a fluoro-alkyl silane reagent. According to the preparation method, the black silicon material of a periodic nano array structure with the self-cleaning function can be obtained on the silicon substrate, so that the preparation method can be widely applied to preparation of high-performance solar cells and photoelectric effect devices.
Description
Technical field
The invention belongs to area of solar cell, be specifically related to a kind of preparation method with the black silicon material of self-cleaning function.
Background technology
Solar cell, as a kind of renewable and clean energy resource, receives the concern of a lot of countries.Wherein, the market share of silica-based solar cell reaches more than 90%.Black silicon material has the characteristic of wide spectral absorption, therefore on solar cell, has very large application prospect.
Black silicon is the silicon materials that a kind of surface has in order accurate or periodic micro structure.Black silicon has very low reflectivity and very high absorptivity to sunlight, and it is to almost all absorbing near infrared light near ultraviolet.The solar cell that utilizes black silicon to prepare, can improve the absorption rate of sunlight greatly.
Nineteen ninety-five, first professor S.Y.Chou of Princeton University proposed nanometer embossing.Nanometer embossing has high-resolution, high yield, large area, the advantage such as low-cost and be widely used in biomedicine, information storage, subwavelength optical element, the preparation of surface micro-structure in the numerous areas such as nanoelectronics.In numerous nanometer embossings, soft template nanometer embossing can be prepared fast high-resolution nano pattern because of it and more receive publicity in curved surface and Non-planar substrates.
Self-cleaning function refers to that sample surfaces has super-hydrophobicity and very low water droplet adhesiveness, thereby thereby water droplet very easily tumbles on this surface takes away the effect that the pollutant such as dust on surface is realized self-cleaning.The surface with self-cleaning function has very large meaning for the outside work performance of solar cell.
Summary of the invention
The object of this invention is to provide a kind of preparation method with the black silicon material of self-cleaning function, can be applied in area of solar cell.
For achieving the above object, technical scheme of the present invention is:
A preparation method for the black silicon material of self-cleaning function, is characterized in that, the method comprises the following steps:
(1) utilize sol evenning machine on silicon substrate, evenly to apply one deck polymethyl methacrylate;
(2) utilize sol evenning machine in polymethyl methacrylate layers, evenly to apply one deck ultraviolet nanometer impression glue;
(3) utilizing ultraviolet nanometer to impress compound soft template carries out ultraviolet nanometer impression and obtains curing ultraviolet nanometer impression glue nano array structure;
(4) recycling reactive ion etching is worn the remnant layer of ultraviolet nanometer impression glue nano array structure and the polymethyl methacrylate of lower floor exposes silicon substrate;
(5) utilize the sample surfaces plating layer of metal chromium of electron beam evaporation deposition instrument after etching, and obtain crome metal nano array structure with lifting off technique;
(6) take crome metal nano array structure as mask, utilizing the mixed gas reaction ion etching of fluoroform, carbon tetrafluoride and oxygen to obtain wedge silicon nanostructure is black silicon material again;
(7) black silicon material etching being completed carries out the processing of oxygen plasma, and then with silicon fluoride reagent, carries out chemical surface treatment, obtains having the black silicon material of self-cleaning function.
Described silicon substrate is the polished silicon slice that the thickness of (100), (110) or (111) direction is not limit, or is smooth omnidirectional silicon or amorphous silicon surfaces at other Growns.
It is to be that flexible substrate and high durometer polymeric material form as rigid structural layer by flexible silicone rubber material that described ultraviolet nanometer impresses compound soft template.
The invention provides a kind of preparation method with the black silicon material of self-cleaning function, the beneficial effect compared with prior art having is:
(1) on black silicon of the present invention, nano array structure preparation adopts soft template nanometer embossing, do not need complicated Embosser, can also reduce the impact of the pollutants such as dust in traditional nano-imprint process on impression, and can obtain the high-resolution top wedge nanostructure of Large-Area-Uniform, this is very large for high-quality solar cell meaning.
(2) black silicon material with self-cleaning function that prepared by the present invention has very low reflectivity (comparing smooth silicon face) at sunlight wave band, and this can improve the light absorption utilance of black silicon solar cell greatly.
(3) black silicon material with self-cleaning function that prepared by the present invention has excellent ultra-hydrophobicity, can realize self-cleaning function, can improve the outside work performance of black silicon solar cell.
Accompanying drawing explanation
Fig. 1 is the black silicon material preparation flow schematic diagram that the present invention has self-cleaning function; 1-ultraviolet nanometer impression glue-line; 2-polymethyl methacrylate layers; 3-silicon substrate; The compound soft template flexible substrate of 4-; The compound soft template rigid structural layer of 5-; The ultraviolet nanometer impression glue nano array structure that 6-is curing; The crome metal of 7-electron beam evaporation deposition.
Fig. 2 is the electron scanning micrograph of the black silicon material surface nano array structure prepared of embodiment, (a) being the dark silicon trench array of 200 nanometer cycle nanometer and black silicon face water droplet static contact angle digital photograph, is (b) that 158.3 ° of roll angles of water droplet static contact angle are less than 5 °.
Fig. 3 is the reflectance spectrum that the present invention has black silicon material and the smooth silicon face of non-structure of self-cleaning function.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail:
The concrete making step of the black silicon material with self-cleaning function of the present embodiment:
(1) utilize sol evenning machine on silicon substrate 3 with 3000 revs/min, within 60 seconds, evenly apply one deck polymethyl methacrylate 2.
(2) utilize sol evenning machine in polymethyl methacrylate layers with 1600 revs/min, within 40 seconds, evenly apply one deck ultraviolet nanometer impression glue 1.
(3) mode facing to ultraviolet glue is laid on substrate with structural plane ultraviolet nanometer to be impressed to compound soft template, forms impression combination.Ultraviolet stamping glue is known from experience due to capillary force automatic filling template rigid structural layer 5, the flexible substrate 4 of compound soft template can with fit tightly with silicon substrate 3.With ultraviolet mercury lamp 1 minutes that exposes, make ultraviolet stamping glue 1 fully curing again; Separated template obtains curing ultraviolet nanometer impression glue nano array structure 6 again.
(4) that ultraviolet nanometer is impressed to the remnant layer etching of glue nano array structure 6 is complete and expose the polymethyl methacrylate 2 of lower floor for the reactive ion etching of the mist of recycling fluoroform and oxygen.
(5) take ultraviolet nanometer impression glue nano array structure 6 is mask again, the reactive ion etching of utilizing oxygen by polymethyl methacrylate 2 etchings of lower floor wear until expose silicon substrate.
(6) the plated surface a layer thickness 30 nano metal chromium 7 of electron beam evaporation deposition instrument after etching again.
(7) use again supersonic cleaning machine ultrasonic sample in chlorobenzene, remove the crome metal on polymer and polymeric material top, complete and lift off technique and obtain the crome metal nano array structure contrary with ultraviolet nanometer impression glue nano array structure 6 patterns in surface of silicon.
(8) take again crome metal nano array structure as mask, utilize fluoroform, carbon tetrafluoride, the mixed gas reaction ion etching of oxygen is delivered to next silicon substrate by crome metal nano array structure.
(9) on 8 basis, extend etch period, until crome metal mask has been consumed, at the top of silicon nano array structure, etching wedge nanostructure is black silicon material.
(10) black silicon material etching being completed carries out the processing of oxygen plasma, and then with silicon fluoride reagent, carries out chemical surface treatment, has the black silicon material of self-cleaning function described in obtaining.
Claims (3)
1. a preparation method with the black silicon material of self-cleaning function, is characterized in that, the method comprises the following steps:
(1) utilize sol evenning machine on silicon substrate, evenly to apply one deck polymethyl methacrylate;
(2) utilize sol evenning machine in polymethyl methacrylate layers, evenly to apply one deck ultraviolet nanometer impression glue;
(3) utilizing ultraviolet nanometer to impress compound soft template carries out ultraviolet nanometer impression and obtains curing ultraviolet nanometer impression glue nano array structure;
(4) recycling reactive ion etching is worn the remnant layer of ultraviolet nanometer impression glue nano array structure and the polymethyl methacrylate of lower floor exposes silicon substrate;
(5) utilize the sample surfaces plating layer of metal chromium of electron beam evaporation deposition instrument after etching, and obtain crome metal nano array structure with lifting off technique;
(6) take crome metal nano array structure as mask, utilizing the mixed gas reaction ion etching of fluoroform, carbon tetrafluoride and oxygen to obtain wedge silicon nanostructure is black silicon material again;
(7) black silicon material etching being completed carries out the processing of oxygen plasma, and then with silicon fluoride reagent, carries out chemical surface treatment, obtains having the black silicon material of self-cleaning function.
2. a kind of preparation method with the black silicon material of self-cleaning function according to claim 1, it is characterized in that, described silicon substrate is the polished silicon slice that the thickness of (100), (110) or (111) direction is not limit, or is smooth omnidirectional silicon or amorphous silicon surfaces at Grown.
3. a kind of preparation method with the black silicon material of self-cleaning function according to claim 1 and 2, it is characterized in that, it is to be that flexible substrate and high durometer polymeric material form as rigid structural layer by flexible silicone rubber material that described ultraviolet nanometer impresses compound soft template.
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| CN201310553963.XA CN103594555B (en) | 2013-11-08 | 2013-11-08 | A kind of preparation method with the black silicon material of self-cleaning function |
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| CN103594555B CN103594555B (en) | 2016-03-23 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006544A (en) * | 2016-05-24 | 2016-10-12 | 中国人民解放军国防科学技术大学 | Surface hydrophobic anti-icing method |
| CN106653952A (en) * | 2017-01-17 | 2017-05-10 | 南京大学 | Preparation method for silicon intermediate infrared antireflection microstructure |
| CN107403787A (en) * | 2017-08-02 | 2017-11-28 | 武汉新芯集成电路制造有限公司 | The forming method of metal isolated gate |
| CN109609907A (en) * | 2019-01-31 | 2019-04-12 | 中国科学院半导体研究所 | The method that self-priming nano impression prepares metal Nano structure |
| CN109950335A (en) * | 2019-04-08 | 2019-06-28 | 西安工业大学 | A kind of photovoltaic conversion structure and production method of visible light |
| US10808282B2 (en) | 2015-07-07 | 2020-10-20 | Illumina, Inc. | Selective surface patterning via nanoimprinting |
| CN114296168A (en) * | 2021-12-08 | 2022-04-08 | 中国科学技术大学 | Method for manufacturing variable-period narrow grating by using wide-grating nano-imprint template |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10808282B2 (en) | 2015-07-07 | 2020-10-20 | Illumina, Inc. | Selective surface patterning via nanoimprinting |
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| CN109950335A (en) * | 2019-04-08 | 2019-06-28 | 西安工业大学 | A kind of photovoltaic conversion structure and production method of visible light |
| CN114296168A (en) * | 2021-12-08 | 2022-04-08 | 中国科学技术大学 | Method for manufacturing variable-period narrow grating by using wide-grating nano-imprint template |
| CN114296168B (en) * | 2021-12-08 | 2023-03-10 | 中国科学技术大学 | Method for manufacturing variable-period narrow grating by using wide-grating nano-imprinting template |
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