CN106356425B - A kind of preparation method of the open-type silicon thin film spherical shell array structure of light absorbs enhancing - Google Patents

A kind of preparation method of the open-type silicon thin film spherical shell array structure of light absorbs enhancing Download PDF

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CN106356425B
CN106356425B CN201610954124.2A CN201610954124A CN106356425B CN 106356425 B CN106356425 B CN 106356425B CN 201610954124 A CN201610954124 A CN 201610954124A CN 106356425 B CN106356425 B CN 106356425B
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thin film
spherical shell
open
silicon thin
silicon
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CN106356425A (en
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李本强
杨欢
丁秋玉
江新兵
于伟
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Xian Jiaotong University
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Xian Jiaotong University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/02Details
    • H01L31/0236Special surface textures
    • H01L31/02363Special surface textures of the semiconductor body itself, e.g. textured active layers
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

A kind of preparation method of the open-type silicon thin film spherical shell array structure of light absorbs enhancing, layer of metal material is prepared in substrate surface, the array of particles of compact arranged individual layer silica nanometer is prepared in layer on surface of metal, then the deposit thin films of silicon in array of particles, polymeric layer is prepared in silicon film surface, metal level is dissolved using acid solution again causes silicon fiml structure to depart from base material, then using polymeric layer as substrate, the silicon thin film on selective etch Nano particles of silicon dioxide surface simultaneously partly exposes silicon dioxide granule array, finally silicon dioxide granule is removed with hydrofluoric acid, form the open-type silicon thin film spherical shell array structure using polymeric layer as substrate, open-type silicon thin film spherical shell array structure can realize that silicon fiml absorption efficiency greatly improves.

Description

A kind of preparation method of the open-type silicon thin film spherical shell array structure of light absorbs enhancing
Technical field
The present invention relates to silicon thin film technical field of structures, and in particular to a kind of open-type silicon thin film spherical shell of light absorbs enhancing The preparation method of array structure.
Background technology
In order at utmost absorb the energy of visible light wave range, current most solar cell be still with 180um-300um silicon substrate as carrier, so the consumption of a large amount of silicon materials and its energy absorption efficiency it is not high be still silicon too The deficiency of positive energy industry.It is a kind of that can to reduce material consumption and the possible manufacture method of manufacturing cost be to utilize nano thin-film silicon As absorbed layer.But the factor such as dielectric constant and band gap width due to silicon, simple Nano thin film is to close to band gap ripple The energy absorption efficiency of section is very low.So if the absorption efficiency in the solar energy of long-wave band can be improved, it is possible to obtain efficiently, Economic solar absorbing layer.
The content of the invention
The shortcomings that in order to overcome above-mentioned prior art, it is an object of the invention to provide a kind of open-type of light absorbs enhancing The preparation method of silicon thin film spherical shell array structure, open-type silicon thin film spherical shell array structure realize that silicon fiml absorption efficiency significantly carries It is high.
In order to achieve the above object, the technical scheme taken of the present invention is:
A kind of preparation method of the open-type silicon thin film spherical shell array structure of light absorbs enhancing, comprises the following steps:
1) layer of metal material is prepared in substrate surface, prepares compact arranged individual layer silica in layer on surface of metal and receive The array of particles of rice;
2) deposit thin films of silicon in array of particles;
3) polymeric layer is prepared in silicon film surface;
4) dissolving metal level using acid solution causes silicon fiml structure to depart from base material;
5) using polymeric layer as substrate, the silicon thin film on selective etch Nano particles of silicon dioxide surface simultaneously partly exposes Silicon dioxide granule array;
6) silicon dioxide granule is removed with hydrofluoric acid, forms the open-type silicon thin film spherical shell array using polymeric layer as substrate Structure.
Base material is nonmetallic materials in described step 1), including glass, plastics or silicon chip.
Metal material is aluminium or chromium in described step 1), and thickness is 200~500nm.
Compact arranged individual layer Nano particles of silicon dioxide array utilizes monofilm transfer method or rotation in described step 1) It is prepared by coating.
Silicon thin film utilizes low-pressure chemical vapor deposition (LPCVD), PECVD in described step 2) Deposit (PECVD) or be prepared by magnetically controlled sputter method.
Described step 3) middle polymeric layer material is dimethyl silicone polymer (PDMS) or epoxide resin polymer.
Acid solution is dilute sulfuric acid or watery hydrochloric acid in described step 4), and metal level is dissolved.
Hydrofluoric acid is the dilute solution of volume fraction 3~7% in described step 6).
Beneficial effects of the present invention are:
(1) open-type silicon thin film spherical shell array structure can improve silicon thin film absorption efficiency:When sunshine is incident to opening During type silicon thin film spherical shell array structure surface, due to its upper surface open structure, it is possible to enter more projectile energies In silicon thin film spherical shell, the silicon ghost membrane structure of this opening is considered as an approximate optical resonator again, into spherical shell The incident light of interior specific wavelength can form stable mode of resonance in spherical shell, and this mode of resonance can be understood as Whispering-gallery-mode (Whispering gallerymode), because the diameter of spherical shell is submicron order, so mode of resonance is returning for low-quality factor Sound wall pattern, the top end opening of spherical shell structure are influenceed less, so the incident energy of the Whispering-gallery-mode resonant wavelength on mode of resonance Measuring effective light propagation length in spherical shell can be significantly increased, and due to the close-packed array structure of spherical shell, adjacent spherical shell it Between resonance coupling can also occur so that silicon ball shell is also greatly enhanced to the energy absorption of the resonant wavelength, and With reference to the dielectric constant and band gap width of silicon materials, resonant check is more obvious in long-wave band, and this also just solves most of Light absorbing material is long-wave band absorption efficiency is low the problem of.
(2) silicon dioxide granule and nisi single diameter that prepared by the present invention, so the internal diameter of obtained silicon ball shell Nor uniformly unified, this make it that Echo Wall resonant wavelength of the incident light in silicon ball shell is a wider frequency band, without It is the resonant check of specific single wavelength, so can more improve energy absorption of the silicon ball shell to long-wave band.
Brief description of the drawings
Fig. 1 is transferred into the schematic cross-section of the silicon dioxide granule solid matter monolayer array on base material.
Fig. 2 is the schematic cross-section after the spherical particle solid matter monolayer array deposited silicon film of silica.
Fig. 3 is to make the schematic diagram of PDMS layer on the print surface of deposited silicon film.
Fig. 4 is that silicon dioxide granule and silicon layer are transferred to schematic diagram behind PDMS surfaces.
Fig. 5 is that the upper surface silicon layer of silicon dioxide granule is removed to the cross-sectional view behind part.
Fig. 6 is to remove the open-type silicon thin film spherical shell array structure schematic diagram after silicon dioxide granule.
Fig. 7 is that print after plasma reinforced chemical vapour deposition silicon fiml is carried out on silicon dioxide granule close-packed array surface Pictorial diagram, wherein figure (a) is schemed before being deposited silicon film;Figure (b) is schemed after etching.
Fig. 8 is diameter D=400nm silicon dioxide granule close-packed arrays surface deposition 50nm silicon fimls and is transferred to PDMS surfaces The structure that is obtained after performing etching afterwards and emulate the Structure Calculation in finite time-domain difference software FDTD solution and obtain Absorption efficiency curve and the simple silicon fimls of 50nm experiment absorption efficiency curve.
Fig. 9 is marked in the absorption curve of the FDTD simulation calculations of the structure in fig. 8 as at 1 position crest Be open electric-field intensity distribution figure of the spherical shell structure of silicon thin film along the cross section of symmetry axis during wavelength X=775nm.
Figure 10 be the FDTD simulation calculations of the structure in fig. 8 absorption curve in mark be 2 position ripples Be open electric-field intensity distribution figure of the spherical shell structure of silicon thin film along the cross section of symmetry axis at peak during wavelength X=665nm.
Embodiment
The present invention is described in detail with reference to the accompanying drawings and examples.
Embodiment, a kind of preparation method of the open-type silicon thin film spherical shell array structure of light absorbs enhancing, including following step Suddenly:
1) reference picture 1, it is 1mm ITO slides as base material 1 first using thickness, and using acetone, ethanol and goes successively Ionized water is cleaned by ultrasonic, and after baking 1h, thickness 250nm simultaneously is sputtered on the surface of slide 1 in 150 DEG C of baking ovens for nitrogen drying ~300nm aluminium lamination 2;Be ready for diameter D=400 ± 10nm SiO2 nanometer spherical particles, after ultrasonic cleaning by SiO2 with The ratio of mass fraction 15% is dispersed in n-butanol, then ultrasound is allowed to dispersed, takes micro dropwise addition water-soluble in culture dish Continuous SiO2 single thin films are formed on liquid surface;The particle film of the water surface is finally transferred to the surface of aluminium lamination 2 and 50 DEG C of dryings, obtained To the array of particles 3 of the compact arranged individual layer silica nanometer on base material;
2) reference picture 2,50~60nm of plasma enhanced chemical vapor deposition PECVD thickness is utilized in array of particles 3 Indefinite form silicon thin film 4;
3) reference picture 3, dimethyl silicone polymer (PDMS) and curing agent are pressed into mass fraction 10:1 colloid substance prepared The surface of silicon thin film 4 is applied to, vacuum pumps bubble solidify afterwards and forms the PDMS film 5 for being covered in the surface of silicon thin film 4;
4) reference picture 4, aluminium lamination 2 is dissolved using acid solution silicon fiml structure is departed from base material:Print is placed in volume Aluminium lamination 2 is corroded after 16~24 hours in the hydrochloric acid of fraction 8~10% (HCl) solution and in 50 DEG C of oven environments so that silicon fiml Structure departs from base material, i.e., the silicon fiml of silicon dioxide structure is transferred into PDMS surfaces;
5) reference picture 5, using polymeric layer as substrate, transferred silicon fiml is carried out to the silicon dry etching of selectivity, made The part indefinite form silicon thin film 4 for obtaining silicon dioxide granule array upper surface is etched, and exposes silicon dioxide granule array;
6) reference picture 6, the film of the structuring is placed in volume fraction 3~7%HF solution, silicon dioxide granule is gone Remove, form the open-type silicon thin film spherical shell array structure using polymeric layer as substrate.
For single particle diameter D=~400nm in silicon dioxide granule array in the present embodiment, as shown in Fig. 7 (a); It is 60nm silicon deposited films through thickness, section radius d=~200nm of silicon shell after etching, such as Fig. 7 (b).Work as silicon dioxide granule After being removed, the open-type silicon thin film spherical shell array structure on PDMS surfaces of formation.Comparative example is that the simple silicon thin films of 50nm sink Product is on slide.Its reflectivity and transmissivity is tested using ultraviolet-uisible spectrophotometer, and its absorption efficiency is calculated as schemed Shown in 8, the absorption efficiency of comparative example experiment test absorption curve and FDTD simulation calculations, it can be seen that experiment is bent with emulation Line variation tendency is coincide substantially, and obtains very big enhancing compared to the simple silicon thin film absorption efficiencies of 50nm in comparative example.Implement All there is an apparent absworption peak near wavelength X=775nm in the emulation and empirical curve of example, and this is due in wavelength During λ=775nm, incident light forms the Echo Wall resonance mode of sextupole in spherical shell, as shown in Figure 9.And due in experiment Spherical shell internal diameter has the change of small range near 400nm, so the formant half-peak breadth of the absorption curve of experiment test is than emulation The half-peak for the curve being calculated is roomy.There is an obvious ends of the earth to return at λ=665nm in the absorption curve being calculated Sound wall mode resonance peak, as shown in Figure 10.This resonance peak but unobvious in experiment test curve, this is due in the wavelength Locating the dielectric constant of silicon fiml, imaginary part is larger, and due to the change of spherical shell internal diameter, formant surface at the wavelength be compared with The gentle resonant check of wide wavelength.

Claims (8)

1. a kind of preparation method of the open-type silicon thin film spherical shell array structure of light absorbs enhancing, it is characterised in that including following Step:
1) layer of metal material is prepared in substrate surface, compact arranged individual layer silica nanometer is prepared in layer on surface of metal Array of particles;
2) deposit thin films of silicon in array of particles;
3) polymeric layer is prepared in silicon film surface;
4) dissolving metal level using acid solution causes silicon fiml structure to depart from base material;
5) using polymeric layer as substrate, the silicon thin film on selective etch Nano particles of silicon dioxide surface simultaneously partly exposes dioxy SiClx array of particles;
6) silicon dioxide granule is removed with hydrofluoric acid, forms the open-type silicon thin film spherical shell array junctions using polymeric layer as substrate Structure.
2. a kind of preparation method of the open-type silicon thin film spherical shell array structure of light absorbs enhancing according to claim 1, It is characterized in that:Base material is nonmetallic materials in described step 1), including glass, plastics or silicon chip.
3. a kind of preparation method of the open-type silicon thin film spherical shell array structure of light absorbs enhancing according to claim 1, It is characterized in that:Metal material is aluminium or chromium in described step 1), and thickness is 200~500nm.
4. a kind of preparation method of the open-type silicon thin film spherical shell array structure of light absorbs enhancing according to claim 1, It is characterized in that:In described step 1) compact arranged individual layer Nano particles of silicon dioxide array using monofilm transfer method or It is prepared by spin-coating method.
5. a kind of preparation method of the open-type silicon thin film spherical shell array structure of light absorbs enhancing according to claim 1, It is characterized in that:Silicon thin film utilizes low-pressure chemical vapor deposition (LPCVD), plasma enhanced chemical gas in described step 2) Mutually prepared by deposition (PECVD) or magnetically controlled sputter method.
6. a kind of preparation method of the open-type silicon thin film spherical shell array structure of light absorbs enhancing according to claim 1, It is characterized in that:Described step 3) middle polymeric layer material is dimethyl silicone polymer (PDMS) or polymerization of epoxy resins Thing.
7. a kind of preparation method of the open-type silicon thin film spherical shell array structure of light absorbs enhancing according to claim 1, It is characterized in that:Acid solution is dilute sulfuric acid or watery hydrochloric acid in described step 4), and metal level is dissolved.
8. a kind of preparation method of the open-type silicon thin film spherical shell array structure of light absorbs enhancing according to claim 1, It is characterized in that:Hydrofluoric acid is the dilute solution of volume fraction 3~7% in described step 6).
CN201610954124.2A 2016-11-03 2016-11-03 A kind of preparation method of the open-type silicon thin film spherical shell array structure of light absorbs enhancing Expired - Fee Related CN106356425B (en)

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CN101698961A (en) * 2009-11-19 2010-04-28 南京大学 Preparation method of surface plasmonic crystal
CN102691102A (en) * 2012-06-04 2012-09-26 中国科学院半导体研究所 Method for manufacturing substrate of sapphire nanometer bowl array pattern
CN103022267A (en) * 2013-01-14 2013-04-03 厦门大学 Production method of ZnO spherical-empty-shell nanoparticle array
CN105529404A (en) * 2015-12-21 2016-04-27 吉林大学 Organic solar cell with two-dimensional nano-bowl array light trapping structure and preparation method of organic solar cell

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US20090316417A1 (en) * 2008-06-20 2009-12-24 Rohm And Haas Denmark Finance A/S Light-redirecting article

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Publication number Priority date Publication date Assignee Title
CN101698961A (en) * 2009-11-19 2010-04-28 南京大学 Preparation method of surface plasmonic crystal
CN102691102A (en) * 2012-06-04 2012-09-26 中国科学院半导体研究所 Method for manufacturing substrate of sapphire nanometer bowl array pattern
CN103022267A (en) * 2013-01-14 2013-04-03 厦门大学 Production method of ZnO spherical-empty-shell nanoparticle array
CN105529404A (en) * 2015-12-21 2016-04-27 吉林大学 Organic solar cell with two-dimensional nano-bowl array light trapping structure and preparation method of organic solar cell

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