CN103972324B - Silicon-film solar-cell surface based on nano impression light trapping structure preparation method - Google Patents
Silicon-film solar-cell surface based on nano impression light trapping structure preparation method Download PDFInfo
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- CN103972324B CN103972324B CN201310039892.1A CN201310039892A CN103972324B CN 103972324 B CN103972324 B CN 103972324B CN 201310039892 A CN201310039892 A CN 201310039892A CN 103972324 B CN103972324 B CN 103972324B
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- 239000010408 film Substances 0.000 claims abstract description 55
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 44
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- 239000000243 solution Substances 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
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- 239000011651 chromium Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 229920002120 photoresistant polymer Polymers 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000001259 photo etching Methods 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- QLNOVKKVHFRGMA-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical group [CH2]CC[Si](OC)(OC)OC QLNOVKKVHFRGMA-UHFFFAOYSA-N 0.000 claims description 3
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
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- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 3
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- 229910021419 crystalline silicon Inorganic materials 0.000 description 3
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
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- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 235000008216 herbs Nutrition 0.000 description 1
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- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
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Classifications
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
-
- 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)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a kind of silicon-film solar-cell surface based on nano impression light trapping structure preparation method.First preparing impressing glass template, impressing glass template is immersed in the toluene solution of flucride siloxane base modification, nitrogen purge dries up standby.The Watch glass of silicon-based film solar cells is carried out simultaneously, and dry up with nitrogen and to hang and only to make the surface portion of Watch glass of silicon-base thin-film battery to be immersed in modify containing in olefin(e) acid ester siloxy group decorating liquid, nitrogen purge dries up afterwards, Watch glass spin coating layer of transparent at silicon-based film solar cells imprints glue again, and figure is transferred on the impressing colloid on the Watch glass of silicon-based film solar cells by the technology that is imprinted with.The present invention not only reduces reflection but also can fall into light and not change silicon-based film solar cells preparation technology, can be prevented effectively from the generation of hull cell defect, and need not the conditions such as complex device, High Temperature High Pressure, is conducive to improving solar cell photoelectric conversion efficiency.
Description
Technical field
The present invention relates to a kind of silicon-film solar-cell surface based on nano impression light trapping structure preparation method,
Especially large area is prepared not only antireflection but also is fallen into the method for surface texture of light, belongs to nanometer manufacture, energy technology
With micro-nano field of electronic devices.
Background technology
Along with the day of world energy sources is becoming tight, people refer to unprecedented height to the attention of regenerative resource
Degree.Solar energy enriches due to it, stable and environmental friendliness and become the focus of research.
Commercialization solaode is based on monocrystal silicon and non-crystalline silicon at present.But monocrystalline silicon battery and non-crystalline silicon electricity
It is many that material is expended in pond, and manufacturing cost is expensive.Thin-film solar cells receives much concern due to its low-material-consumption, but
Hull cell absorbed layer is the thinnest and is difficult to effective absorbing light.Had with thin-film solar cells by nanometer light trapping structure
Hope the solaode of overcast of high efficiency of preparation.Various light trapping structure solaodes are devised in succession,
Mainly there is conductive layer making herbs into wool [Muller J, Rech B, Springer J, Vanecek M.TCO and light trapping
in silicon thin film solar cells.Solar Energy.2004;77:917-30], diffraction grating [Zeng L, YiY,
Hong C,Liu J,Feng N,Duan X,et al.Efficiency enhancement in Si solar cells by
textured photonic crystal back reflector.Applied Physics Letters.2006;89:111111-3],
Photon crystal structure [Biswas R, Bhattacharya J, Lewis B, Chakravarty N, Dalal V.
Enhanced nanocrystalline silicon solar cell with a photonic crystal back-reflector.
Solar Energy Materials and Solar Cells.2010;94:2337-42] and surface plasma structure
[Atwater HA,Polman A.Plasmonics for improved photovoltaic devices.Nature
Materials.2010;9:865-]。
Currently available technology mainly first prepares light trapping structure, the most structurally face depositing solar battery,
And this will affect battery preparation technique [Hsu CM, Battaglia C, Pahud C, Ruan ZC, Haug FJ, Fan
SH,et al.High-Efficiency Amorphous Silicon Solar Cell on a Periodic Nanocone
Back Reflector.Advanced Energy Materials.2012;2:628-33], even produce too much defect,
Reduce open-circuit voltage and fill factor, curve factor, and then reduce the efficiency of battery.
Summary of the invention
For defect of the prior art, it is an object of the invention to provide a kind of silicon based on nano impression thin
Film solar cell surface light trapping structure preparation method, by nanometer embossing system on existing silicon-base thin-film battery
Standby one layer of reduction catoptric arrangement falls into light to extend battery light path simultaneously, prepares with tradition and has the silica-based of light trapping structure
Thin-film solar cells is compared, it is not necessary to the complex device such as reactive ion etching, can be prevented effectively from defect simultaneously
Formation, be conveniently used on solaode and improve solar battery efficiency.
For achieving the above object, the present invention is by the following technical solutions:
A kind of silicon-film solar-cell surface based on nano impression light trapping structure preparation method, described method includes
Following steps:
The first step, prepares the impression block modified.
(1) select Lithographic template, use business photoresist according to minimum feature, by traditional photoetching technique
The structure of periodically or non-periodically Lithographic template is transferred in the layers of chrome in glass substrate；
Preferably, described selection Lithographic template, refer to the selection cycle two Dimensional Periodic battle array in 500nm-20 μm
Row (square, hexagonal etc.) or aperiodicity Lithographic template.
Preferably, described layers of chrome thickness is 50nm 1 μm.
(2) use exposed glass below Fluohydric acid. buffer solution etching layers of chrome, formed periodically hemispherical array or
Aperiodicity semiglobe；
Preferably, described Fluohydric acid. buffer solution is (10wt%-40wt%) NH4F's and (5wt%-49wt%) HF
Mixed solution, both mixed volumes are than for 5:1, and etch period is 10s-10min, and etching temperature is
15℃-35℃.Under different hydro fluoric acid buffer concentration, different etching time and different etching temperature conditions,
Form different cycles hemispherical array structure.
(3) use the layers of chrome going chromium solution to remove residual, then cleaned by deionized water, and then form nanometer
Impressing glass template.
(4) according to standard semiconductor cleaning standard step to cleaning as nano impression glass template, and
Dry up with nitrogen, afterwards nano impression glass template be immersed in the toluene solution of flucride siloxane base modification,
Alcohol washes nitrogen dries up standby afterwards.
Preferably, the toluene solution of described flucride siloxane base refers to 3-(the trimethoxy first of (0.2wt%-3wt%)
Silylation) toluene solution of propyl group-2-methyl-2-acrylate, temperature is 15 DEG C-35 DEG C, and different modifying liquid is dense
Degree and at a temperature of the modification time be 1h-12h.
Preferably, solution composition of dechromising described in is: ammonium ceric nitrate Ce (NH4)2(NO3)6, perchloric acid HClO4With
Deionized water, mass ratio is 9:6:85.
Second step, is carried out the Watch glass of silicon-based film solar cells, and with nitrogen dry up suspension and
The surface portion only making the Watch glass of silicon-base thin-film battery is immersed in the toluene solution containing olefin(e) acid ester siloxy group
Middle modification, is dried up by alcohol washes nitrogen afterwards.
Preferably, the described toluene solution containing olefin(e) acid ester siloxy group is the 4-methyl-(complete of (0.2wt%-3wt%)
Fluorine base ethyl) toluene solution of propyl trimethoxy silicane, temperature is 15 DEG C-35 DEG C, different modifying liquid concentration
The modification time at a temperature of with is 1h-12h.
3rd step, then the Watch glass spin coating layer of transparent impressing glue at silicon-based film solar cells, by pressure
Nano-imprint stamp figure is transferred to the impressing glue on the Watch glass of silicon-based film solar cells by print technology
On body.
In the present invention, described silicon-film solar-cell surface light trapping structure is to use nanometer embossing to be prepared from
, its cycle is 500nm-20 μm, and the degree of depth is 200nm-5 μm.
In the present invention, described nanometer embossing, comprise hot padding solidification and ultraviolet stamping curing technology.
In the present invention, the material that described nanometer embossing relates to is transparent material, can be that business imprints glue,
Commercial polydimethyl siloxanes (PDMS), business polymethyl methacrylate (PMMA), methyl methacrylate
The transparent impressing colloids such as ester (MMA) and firming agent mixing liquid thereof.
In the present invention, described solar cell layer and front and back electrode can be the unijunction of various commercialization, binode
And multijunction cell.
Compared with prior art, the present invention has a following beneficial effect:
The surface texture based on nanometer embossing prepared by a kind of relatively easy scheme not only reduced reflection but also
Light and do not change silicon-based film solar cells preparation technology can be fallen into, and on substrate, first prepare light trapping structure,
The most structurally face carries out the technology of silicon-base thin-film battery deposition and compares, and can be prevented effectively from hull cell defect
Produce, and need not the conditions such as complex device, High Temperature High Pressure.Additionally, surface texture is not only at vertical incidence bar
The reflectance of silicon-based film solar cells can also be effectively reduced under the conditions of high tilt angle incidence simultaneously under part
There is diffraction fall into light and extend the light distance at battery obsorbing layer, be conducive to improving solar cell photoelectric conversion effect
Rate.The present invention is conducive to improving further silicon-base thin-film battery photoelectric transformation efficiency, reduces battery cost, is expected to
Realize batch production.
Accompanying drawing explanation
By the detailed description non-limiting example made with reference to the following drawings of reading, its of the present invention
Its feature, purpose and advantage will become more apparent upon:
Fig. 1 is silicon-based film solar cells schematic diagram based on nanometer embossing；
Fig. 2 is the process chart of the inventive method, and wherein (a)-(e) is the preparation of nanometer embossing template,
F ()-(h) is for prepare surface antireflection and the preparation of diffraction light trapping structure at silicon-based film solar cells；
Fig. 3 is unijunction silicon-based film solar cells schematic diagram based on nanometer embossing；
Fig. 4 binode based on nanometer embossing silicon-based film solar cells schematic diagram；
Fig. 5 is the nano-imprint stamp SEM figure with periodically hemispherical array that embodiment 1 step 2 obtains；
Fig. 6 is the nano impression soft template SEM figure that embodiment 2 step 6 obtains；
Fig. 7 is the SEM figure of the binode silicon-based film solar cells that embodiment 2 step 7 obtains；
Fig. 8 be the binode silicon-base thin-film battery with surface anti-reflection structure that obtains of embodiment 2 step 7 with
And there is no the reflectivity curve comparison diagram of the identical binode silicon-base thin-film battery of surface anti-reflection structure；
Fig. 9 be the binode silicon-base thin-film battery with surface anti-reflection structure that obtains of embodiment 2 step 7 with
And there is no the I-V curve comparison diagram of the identical binode silicon-base thin-film battery of surface anti-reflection structure.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.Following example will assist in this area
Technical staff is further appreciated by the present invention, but limits the present invention the most in any form.It should be pointed out that, to this
For the those of ordinary skill in field, without departing from the inventive concept of the premise, it is also possible to make some deformation
And improvement.These broadly fall into protection scope of the present invention.
As it is shown in figure 1, be silicon-based film solar cells based on nanometer embossing, wherein 1 nanometer pressure
Print structure, 2 silicon-based film solar cells front surface protective glass layers, 3 solar cell layers and front and back electricity
Pole.
As in figure 2 it is shown, nanometer embossing comprises hot padding solidification and ultraviolet stamping curing technology.Nanometer pressure
The some processes step of print technology is as shown in Figure 2.
See (a)-(e) in Fig. 2, for the preparation of nanometer embossing template: first passing through traditional photoetching technique will
The structure of template is transferred to, in the layers of chrome in glass substrate, then be etched by buffered hydrofluoric acid solution, pass through afterwards
Go chromium solution to remove the layers of chrome of residual, clean finally by deionized water, and then form nano impression glass template.
After cleaning, drying, nano impression glass template is immersed in the toluene solution of flucride siloxane base modification, afterwards
Alcohol washes nitrogen dries up standby.
See (f)-(h) in Fig. 2, for preparing surface antireflection and diffraction light trapping structure at silicon-based film solar cells
Preparation: first prepare the impressing glass template that flucride siloxane base is modified, then to silicon-based film solar cells
Watch glass be carried out, and dry up the surface of Watch glass hanging and only making silicon-base thin-film battery with nitrogen
It is partially soaked in the decorating liquid containing olefin(e) acid ester siloxy group modification, is dried up by alcohol washes nitrogen afterwards, then
Watch glass spin coating layer of transparent at silicon-based film solar cells imprints glue, and the technology that is imprinted with is by fluorine silicon
The figure of the impressing glass template that oxyalkyl is modified is transferred on the Watch glass of silicon-based film solar cells
On impressing colloid.
Fig. 3 is unijunction silicon-based film solar cells schematic diagram based on nanometer embossing；In figure: 1 nanometer
Stamping structure, 2 silicon-based film solar cells front surface protective glass layers, 3 solar cell layers and front and back
Electrode, transparent conductive electrode before 4 unijunction silicon-based film solar cells, 5a-Si (p i-n) battery layers, 6 is single
Knot silicon-based film solar cells back metal electrode.
Fig. 4 binode based on nanometer embossing silicon-based film solar cells schematic diagram；In figure: 1 nanometer pressure
Print structure, 2 silicon-based film solar cells front surface protective glass layers, 3 double-junction solar battery layers and front
Rear electrode, transparent conductive electrode before 4 binode silicon-based film solar top batteries, 5 binode silicon-based film solars
Top battery a-Si (p-i-n) layer, 6 binode silicon-based film solar back of the body cell backside metal electrodes, reflection in the middle of 7
Layer, 8 binode silicon-based film solar back of the body battery μ c-Si (pi-n) layers.
Embodiment 1
1, Lithographic template is prepared.The template of this embodiment is to be 10 μm in the cycle, and Circularhole diameter is the chromium of 5 μm
Template.
2, standard (RCA) step is cleaned to using the glass template as nano impression according to standard semiconductor,
Soft template glass cleaning, and drying up at high temperature of 120 DEG C baking 3h standby with nitrogen.First at nano impression
100nm layers of chrome, afterwards spin coating AZ4620 light in nano-imprint stamp glass layers of chrome is sputtered on template glass
Photoresist 5 μm, then at litho machine (Karl Suss MA6, Germany) exposure 30s, afterwards through AZ400MIF
Development 60s, cleans remaining developer solution by deionized water, and then the structure on Lithographic template is transferred to nanometer
On AZ4620 photoresist in impression block glass layers of chrome, by removing chromium solution (ammonium ceric nitrate
Ce(NH4)2(NO3)6, perchloric acid HClO4And deionized water, mass ratio is 9:6:85), by nano impression mould
On AZ4620 photoresist in glass sheet layers of chrome, exposed layers of chrome is removed, then is washed with deionized water clean residual and dechromises
Solution.The AZ4620 photoresist in nano-imprint stamp glass layers of chrome, now Lithographic template is removed again with acetone
Structure transfers in nano-imprint stamp glass layers of chrome.Again by Fluohydric acid. buffer solution 40wt%NH4F and
49%wt%HF (5:1, volume ratio) mixed solution at room temperature 20 DEG C of etching 3-5min, then go with deionized water
Fall remaining hydrogen fluoric acid buffer solution, then spend chromium solution (ammonium ceric nitrate Ce (NH4)2(NO3)6, perchloric acid HClO4
And deionized water, mass ratio is 9:6:85) residual chromium is removed, finally it is washed with deionized water clean nitrogen and dries up standby
With.The different etching time, form different hemispherical array structures, the degree of depth is about 5 μm.See SEM
Fig. 5, it can be seen that this square array is highly uniform.
3, standard (RCA) step is cleaned to using the template clearing glass as nano impression according to standard semiconductor
Wash, and toast 3h drying up with nitrogen at high temperature of 120 DEG C.Put into after cooling (2wt%) 4-methyl-(perfluor is
Base ethyl) propyl trimethoxy silicane toluene solution in modify 4h, alcohol washes nitrogen dries up standby afterwards.
4, use acetone, ethanol and deionized water that the Watch glass of silicon-based film solar cells is carried out successively
Clean, and dry up with nitrogen and hang and only make the surface portion of Watch glass of unijunction silicon-base thin-film battery to be immersed in
(2wt%) the toluene solution 4h of 3-(trimethoxysilyl) propyl group-2-methyl-2-acrylate, it
Rear alcohol washes nitrogen dries up standby.
5, the existing metering system of Watch glass spin coating 5 μ m-thick of unijunction silicon-base thin-film battery in step 4
Acid methyl ester (MMA) and firming agent mixing liquid thereof, by the nano-imprint stamp concora crush modified in step 2
On base acrylic acid methyl ester. (MMA) and firming agent mixing liquid thereof, 70 DEG C of guarantors on heat cure nano marking press
Temperature 1h.The demoulding, transfers to the Watch glass of unijunction silicon-base thin-film battery by the antistructure of nano-imprint stamp
On polymethyl methacrylate (PMMA).
Embodiment 2
The present embodiment makes the appropriate adjustments on the basis of embodiment 1, wherein: layers of chrome thickness is 1 μm；Fluohydric acid.
Buffer solution is 10wt%NH4The mixed solution of F and 5wt%HF；Etch period is 10min, etching temperature
It it is 15 DEG C；The modification time is 1h.Other operations are same as in Example 1.
It is 500nm-20 μm that the present embodiment can obtain the cycle, and the degree of depth is that the unijunction silicon of 200nm-10 μm is thin
Film solar cell surface light trapping structure.
Embodiment 3
The present embodiment makes the appropriate adjustments on the basis of embodiment 1, wherein: layers of chrome thickness is 50nm；Fluohydric acid.
Buffer solution is 40wt%NH4The mixed solution of F and 49wt%HF；Etch period is 10s, etching temperature
It it is 35 DEG C；The modification time is 12h；Other operations are same as in Example 1.
It is 500nm-20 μm that the present embodiment can obtain the cycle, and the degree of depth is the unijunction silicon thin film of 200nm-5 μm
Solar battery surface light trapping structure.
Embodiment 4
1, Lithographic template is prepared.The template of this embodiment is to be 10 μm in the cycle, and Circularhole diameter is the chromium of 5 μm
Template.
2, standard (RCA) step is cleaned to using the template glass as nano impression according to standard semiconductor,
Soft template glass cleaning, and drying up at high temperature of 120 DEG C baking 3h standby with nitrogen.First at nano impression
100nm layers of chrome, afterwards spin coating AZ4620 light in nano-imprint stamp glass layers of chrome is sputtered on template glass
Photoresist 5 μm, then at litho machine (Karl Suss MA6, Germany) exposure 30s, afterwards through AZ400MIF
Development 60s, cleans remaining developer solution by deionized water, and then the structure on Lithographic template is transferred to nanometer
On AZ4620 photoresist in impression block glass layers of chrome, by removing chromium solution (ammonium ceric nitrate
Ce(NH4)2(NO3)6, perchloric acid HClO4And deionized water, mass ratio is 9:6:85) by nano-imprint stamp
On AZ4620 photoresist in glass layers of chrome, exposed layers of chrome is removed, then is washed with deionized water clean residual and dechromises molten
Liquid.The AZ4620 photoresist in nano-imprint stamp glass layers of chrome, now Lithographic template knot is removed again with acetone
Structure transfers in nano-imprint stamp glass layers of chrome.Again by Fluohydric acid. buffer solution 40wt%NH4F and
49wt%HF (5:1, volume ratio) mixing liquid at room temperature 20 DEG C of etching 3-5min, then remove with deionized water
Remaining hydrogen fluoric acid buffer solution, then spend chromium solution (ammonium ceric nitrate Ce (NH4)2(NO3)6, perchloric acid HClO4
And deionized water, mass ratio is 9:6:85) residual chromium is removed, finally it is washed with deionized water clean nitrogen and dries up standby
With.The different etching time, form different hemispherical array structures, the degree of depth is about 5 μm.See SEM
Fig. 5, it can be seen that this square array is highly uniform.
3, standard (RCA) step is cleaned to using the template clearing glass as nano impression according to standard semiconductor
Wash, and toast 3h drying up with nitrogen at high temperature of 120 DEG C.The 4-methyl-(perfluor of (2wt%) is put into after cooling
Base ethyl) propyl trimethoxy silicane toluene solution modify in 4h, alcohol washes nitrogen dries up standby afterwards.
4, use acetone, ethanol and deionized water that the Watch glass of silicon-based film solar cells is carried out successively
Clean, and dry up with nitrogen and hang and only make the surface portion of Watch glass of binode silicon-base thin-film battery to be immersed in
(2wt%) the toluene solution 4h of 3-(trimethoxysilyl) propyl group-2-methyl-2-acrylate, it
Rear alcohol washes nitrogen dries up standby.
5, standard (RCA) step is cleaned to using as nano impression soft template substrate according to standard semiconductor
Glass cleaning, and dry up at high temperature of 120 DEG C baking 3h with nitrogen again.It is immersed in 3-(the front three of (2wt%) again
Epoxide silicyl) propyl group-2-methyl-2-acrylate toluene solution in modify 4h, afterwards alcohol washes nitrogen
Air-blowing is done standby.
6, the laboratory of spin-on-glass 5 μ m-thick of nano impression soft template substrate in steps of 5 synthesizes
(concrete material and proportioning thereof are referred to Lin Hong, Jiang Xuesong, Yin Jie, Makoto to fluorine-containing ultraviolet stamping glue composition
Kaji contains sulfydryl multi-functional low power multi-polysiloxane compound and combinations thereof thing and the soft template of impressing, in
State's invention number of patent application: 201110332455.X), template prepared by step 2 after step 3 is modified,
Concora crush on binode silicon-based film solar cells, uv-exposure on the sample stage inserting ultraviolet nanometer marking press
10min, keeps 0.2 bar pressure simultaneously.The demoulding, transfers to nano impression by the structure of nano-imprint stamp soft
On fluorine-containing ultraviolet stamping glue composition on template glass.See SEM Fig. 6, it can be seen that nanometer pressure
The structure of nano-imprint stamp is well transferred on fluorine-containing ultraviolet stamping glue by print technology, and then protects forming height
Genuine square hemispherical array soft template.
7, the laboratory of Watch glass spin coating 5 μ m-thick of binode silicon-base thin-film battery in step 4 synthesizes
Fluorine-containing ultraviolet stamping glue composition liquid (concrete material and proportioning thereof are referred to Lin Hong, Jiang Xuesong, Yin Jie,
Makoto Kaji is soft containing sulfydryl multi-functional low power multi-polysiloxane compound and combinations thereof thing and impressing
Template, Chinese invention patent application number: 201110332455.X), by the nano impression soft template in step 6
Concora crush, on the ultraviolet stamping glue body on binode silicon-base thin-film battery front glass surface, is inserting ultraviolet nanometer impressing
Uv-exposure 6min on the sample stage of machine, keeps 0.2 bar pressure simultaneously.The demoulding, the most at last nano impression soft mode
The structure of plate is transferred on the fluorine-containing ultraviolet stamping glue composition of the Watch glass of binode silicon-base thin-film battery.
See SEM Fig. 7, it can be seen that nanometer embossing well will have square hemispherical array
The structure of soft template is transferred on fluorine-containing ultraviolet stamping glue-line, forms the square hemispherical array of high-fidelity, its structure
Meet very much with original nano-glass impression block, illustrate that this fluorine-containing ultraviolet stamping glue both can be as silica-base film
The surface light trapping structure of battery can shift soft template as the figure of nano impression again.There is surface anti-reflection structure
Binode silicon-base thin-film battery and the identical binode silicon-base thin-film battery that do not has surface anti-reflection structure anti-
Penetrate curve (UV, visible light near infrared spectrometer, Lambda-1050, Perkin Elmer, 8 ° be equipment
Low angle of incidence) contrast (Fig. 8) and I-V curve ((AM1.5G, 100mW/cm2, 25 ° of C)) contrast (figure
9), as can be seen from Fig. 8, under the conditions of identical incidence, compare silicon-base thin-film battery surface do not have structured instead
Penetrating curve, silicon-base thin-film battery surface has cycle hemispherical array structure can well reduce reflection.Along with entering
Firing angle degree increases to 45 °, compares silicon-base thin-film battery surface and has the reflection song that cycle hemispherical array structure is at 8 °
Line, silicon-base thin-film battery surface has cycle hemispherical array structure in the range of 300-800nm, and reflection has increasing
Adding, and in the range of 800-1200nm, reflection reduces, its reason is to use this 10 μm pros hemispherical array
Caused.As can be seen from Fig. 9, echoing with Fig. 8 phase, surface has the silica-base film of cycle hemispherical array structure
The photoelectric transformation efficiency of battery, the opto-electronic conversion comparing the flat board silicon-base thin-film battery under same test condition is imitated
Rate, its efficiency significantly improves.
Embodiment 5
The present embodiment makes the appropriate adjustments on the basis of embodiment 4, wherein: layers of chrome thickness is 1 μm；Fluohydric acid.
Buffer solution is (10wt%) NH4The mixed solution of F and (5wt%) HF；Etch period is 10min, etching temperature
Degree is 15 DEG C；The modification time is 12h；Other operations are the same as in Example 4.
It is 500nm-20 μm that the present embodiment can obtain the cycle, and the degree of depth is that the binode silicon of 200nm-10 μm is thin
Film solar cell surface light trapping structure.
Above the specific embodiment of the present invention is described.It is to be appreciated that the present invention not office
Being limited to above-mentioned particular implementation, those skilled in the art can make various within the scope of the claims
Deformation or amendment, this has no effect on the flesh and blood of the present invention.
Claims (9)
1. silicon-film solar-cell surface based on a nano impression light trapping structure preparation method, its feature exists
In, described method comprises the steps:
The first step, prepares the impression block modified
(1) select Lithographic template, use different business photoresist according to minimum feature, by traditional photoetching
The structure of periodically or non-periodically Lithographic template is transferred in the layers of chrome in glass substrate by technology；
(2) use exposed glass below Fluohydric acid. buffer solution etching layers of chrome, formed periodically hemispherical array or
Aperiodicity semiglobe；
(3) use the layers of chrome going chromium solution to remove residual, then cleaned by deionized water, and then form nanometer
Impressing glass template；
(4) clean standard step according to quasiconductor nano impression glass template is cleaned, then dry up with nitrogen,
Afterwards nano impression glass template is immersed in the toluene solution of flucride siloxane base modification, alcohol washes afterwards
Nitrogen dries up standby；The toluene solution of described flucride siloxane base be 0.2wt%-3wt% 4-methyl-(perfluor is
Base ethyl) toluene solution of propyl trimethoxy silicane, modifying temperature in this solution is 15 DEG C-35 DEG C, repaiies
The decorations time is 1h-12h；
Second step, is carried out the Watch glass of silicon-based film solar cells, and with nitrogen dry up suspension and
The surface portion only making the Watch glass of silicon-base thin-film battery is immersed in the toluene solution containing olefin(e) acid ester siloxy group
Middle modification, is dried up by alcohol washes nitrogen afterwards；
3rd step, the Watch glass spin coating layer of transparent at silicon-based film solar cells imprints glue, is imprinted with
Nano impression glass template graphics is transferred to the impressing on the Watch glass of silicon-based film solar cells by technology
On colloid.
Silicon-film solar-cell surface based on nano impression the most according to claim 1 light trapping structure system
Preparation Method, it is characterised in that in described (1), layers of chrome thickness is 50nm 1 μm.
Silicon-film solar-cell surface based on nano impression the most according to claim 1 light trapping structure system
Preparation Method, it is characterised in that exposed glass below described use Fluohydric acid. buffer solution etching layers of chrome, Qi Zhongsuo
Stating Fluohydric acid. buffer solution is 10wt%-40wt%NH4The mixed solution of F and 5wt%-49wt%HF, both
Mixed volume than for 5:1.
Silicon-film solar-cell surface based on nano impression the most according to claim 3 light trapping structure system
Preparation Method, it is characterised in that described etch period is 10s-10min, etching temperature is 15 DEG C-35 DEG C.
Silicon-film solar-cell surface based on nano impression the most according to claim 1 light trapping structure system
Preparation Method, it is characterised in that described in solution composition of dechromising be: ammonium ceric nitrate Ce (NH4)2(NO3)6, perchloric acid
HClO4And deionized water, mass ratio is 9:6:85.
Silicon-film solar-cell surface based on nano impression the most according to claim 1 light trapping structure system
Preparation Method, it is characterised in that the described toluene solution containing olefin(e) acid ester siloxy group refers to 0.2wt%-3wt%'s
The toluene solution of 3-(trimethoxysilyl) propyl group-2-methyl-2-acrylate, modifies temperature in this solution
Degree is 15 DEG C-35 DEG C, and the modification time is 1h-12h.
7. fall into according to the silicon-film solar-cell surface based on nano impression described in any one of claim 1-6
Photo structure preparation method, it is characterised in that the described Watch glass to silicon-based film solar cells is carried out,
Refer to use acetone, ethanol and deionized water that the Watch glass of silicon-based film solar cells is carried out clearly successively
Wash.
8. fall into according to the silicon-film solar-cell surface based on nano impression described in any one of claim 1-6
Photo structure preparation method, it is characterised in that described silicon-film solar-cell surface light trapping structure is to use nanometer pressure
Print technology is prepared from, and its cycle is 500nm-20 μm, and the degree of depth is 200nm-5 μm.
Prepared by silicon-film solar-cell surface based on nano impression the most according to claim 8 light trapping structure
Method, it is characterised in that described nanometer embossing comprises hot padding solidification and ultraviolet stamping curing technology.
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| CN108428746A (en) * | 2017-02-12 | 2018-08-21 | 无锡马丁格林光伏科技有限公司 | A kind of absorbing film for thermophotovoltaic |
| CN107633896A (en) * | 2017-08-30 | 2018-01-26 | 中国科学院宁波材料技术与工程研究所 | A kind of transparent conductive film of haze and preparation method thereof |
| CN109065732A (en) * | 2018-07-05 | 2018-12-21 | 南京航空航天大学 | A kind of perovskite battery and its glass cover-plate having both wide spectrum dimmer reflecting and ultraviolet filtering function |
| CN111892303A (en) * | 2019-05-06 | 2020-11-06 | 苏州苏大维格科技集团股份有限公司 | Preparation method of micro-nano structure for glass anti-counterfeiting |
| CN112952006B (en) * | 2019-12-11 | 2024-03-12 | 中国科学院大连化学物理研究所 | Perovskite solar cell perovskite light absorption layer surface texturing method |
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