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 PDFInfo
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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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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000010703 silicon Substances 0.000 title claims abstract description 79
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 79
- 239000010409 thin film Substances 0.000 title claims abstract description 47
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 30
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 25
- 239000008187 granular material Substances 0.000 claims abstract description 17
- 239000010410 layer Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000013047 polymeric layer Substances 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010408 film Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000007769 metal material Substances 0.000 claims abstract description 5
- 239000002105 nanoparticle Substances 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004518 low pressure chemical vapour deposition Methods 0.000 claims description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 229910003978 SiClx Inorganic materials 0.000 claims 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 238000004528 spin coating Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 19
- 238000002474 experimental method Methods 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- H01L31/02363—
-
- 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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- Laminated Bodies (AREA)
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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
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).
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| CN114289881A (en) * | 2021-12-31 | 2022-04-08 | 杭州电子科技大学 | Method and equipment for forming spherical cavity in silicon-based material |
| CN115219477A (en) * | 2022-07-21 | 2022-10-21 | 西安电子科技大学 | Manufacturing method of surface-enhanced Raman scattering substrate for virus macromolecule detection |
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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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| 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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