CN105469996B - A kind of perovskite solar cell based on metal nanoparticle modifying interface and preparation method thereof - Google Patents
A kind of perovskite solar cell based on metal nanoparticle modifying interface and preparation method thereof Download PDFInfo
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- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000010931 gold Substances 0.000 claims abstract description 64
- 239000002105 nanoparticle Substances 0.000 claims abstract description 55
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 45
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 45
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 45
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 45
- 230000005540 biological transmission Effects 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 229910052737 gold Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 68
- 238000004528 spin coating Methods 0.000 claims description 12
- 239000010408 film Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 230000005611 electricity Effects 0.000 claims description 7
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 7
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 239000002346 layers by function Substances 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 3
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 2
- -1 ITO Chemical compound 0.000 claims description 2
- 229910015711 MoOx Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims description 2
- 229910003472 fullerene Inorganic materials 0.000 claims description 2
- 230000005525 hole transport Effects 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 238000007641 inkjet printing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000002071 nanotube Substances 0.000 claims 1
- 230000009466 transformation Effects 0.000 abstract description 18
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 12
- 238000000151 deposition Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 6
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000005672 electromagnetic field Effects 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- GBMPPHPJKKUMPS-UHFFFAOYSA-N [Br].CN Chemical compound [Br].CN GBMPPHPJKKUMPS-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- QEZYDNSACGFLIC-UHFFFAOYSA-N CN.[I] Chemical compound CN.[I] QEZYDNSACGFLIC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
-
- 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
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
- H10K30/821—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes comprising carbon nanotubes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic 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
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- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a kind of perovskite solar cell based on metal nanoparticle modifying interface and preparation method thereof；Gold (the Au@SiO of a thin layer coated with silica are added between the hole transmission layer and perovskite active layer of planar heterojunction perovskite solar cell2) nano-particle, Au@SiO2Nano-particle length is between 20 nanometers to 60 nanometers, and width is between 5 nanometers to 25 nanometers；Au@SiO2Nano-particle can produce surface plasma body resonant vibration, light path of the increase light in perovskite active layer, absorption of the perovskite active layer to light be improved, so as to significantly improve the photoelectric transformation efficiency of perovskite solar cell；With no Au@SiO2The perovskite solar cell of nano-particle is compared, and has Au@SiO2The photoelectric transformation efficiency of the perovskite solar cell of nano-particle can improve more than 35%；The present invention based on the perovskite solar cell preparation method of metal nanoparticle modifying interface by solution technique low temperature preparation, reproducible, cost is low, is with a wide range of applications.
Description
Technical field
The present invention relates to a kind of perovskite solar cell based on metal nanoparticle modifying interface and preparation method thereof,
Belong to solar cell field.
Background technology
Perovskite solar cell due to high efficiency, low cost and can volume to volume printing prepare etc. advantage, in photovoltaic
Field receives much concern, and photoelectric transformation efficiency is risen by 3.8% till now can be with more than the 20% of silica-based solar cell analogy
(J.Am.Chem.Soc.,2009,131,6050；Nature,2013,499,316；Nature,2013,501,395；2014,
345,542；Science, 2014,344,458), in applications such as photovoltaic roof integration, mobile electronic device power supply and space flight
With very big potentiality.Although multi-disciplinary effort has caused the efficiency of perovskite solar cell has risen can be with silicon substrate
The level that solar cell can compare, but in order to promote the commercialization of perovskite solar cell and large-scale production, also
There are many problem in science and technical problem to need to solve.In order to improve photoelectric transformation efficiency, a most simple and convenient means
Exactly increase the thickness of active layer, to increase the absorption of light.But mobility or diffusion length due to carrier in vivo
Etc. reason, it is compound inside active layer that increase active layer thickness normally results in photo-generated carrier, therefore limits to increase
Active layer thickness improves the efficiency of solar cell.The optimum thickness of usual perovskite solar cell is in 350nm or so
(Energy Environ Sci.,2014,7,2619；Org.Electron., 2015,26,265), but this thickness can not
Fully absorb sunshine.
Metal nanoparticle is due to surface plasma effect, in organic solar batteries and dye sensitization of solar electricity
Pond has preliminary application, and can improve to a certain extent battery performance (Nano Lett., 2013,13,
2204；Nano Lett.,2013,13,4505).Shape, size, species and the dielectric mechanism constant of metal nanoparticle are to too
Optics, electricity and the efficiency of positive energy battery play very important effect.Surfaces of metal nanoparticles can excite plasma to be total to
Shake, so as to increase the absorption of light and cause the generation rate of exciton to increase, and various sizes of metal nanoparticle have it is different
Surface plasma resonance peak.The metal nano of usual dielectric cladding, than exposed metal nanoparticle in solar cell
Better performance is embodied in terms of the raising of performance, its reason is due to that insulating barrier increase avoids metal nanoparticle and activity
The contact of layer, reduces harmful Carrier recombination.Bar-shaped metal nanoparticle has more superior than the nano-particle of ball-type
Optics and electric property because bar-shaped nano-particle has two plasma resonance peaks, and the nano-particle of ball-type only has
One formant.Based on this, the present invention is first by gold (the Au@SiO of coated with silica2) nanometer rods are applied to low temperature solution polycondensation
The planar heterojunction perovskite solar cell of preparation, the photoelectric transformation efficiency of perovskite solar cell can be greatly improved,
With important application prospect.
The content of the invention
The technical problems to be solved by the invention are to overcome absorption of traditional perovskite solar cell active layer to light not
The shortcomings that abundant, introducing one kind has between the hole transmission layer and perovskite active layer of traditional perovskite solar cell
The novel metal nano material of surface plasma resonance is as decorative layer, it is therefore an objective to the absorbing ability of perovskite active layer is improved,
Improve the photoelectric transformation efficiency of perovskite solar cell.
The invention provides a kind of perovskite solar cell based on metal nanoparticle modifying interface, the solar-electricity
Pond accompanies four one functional layers between lower floor's transparent electrode layer and upper electrode layer；Four described one functional layers, from top to bottom according to
Secondary is hole transmission layer, metal nanoparticle layer, perovskite active layer and electron transfer layer；Four described one functional layers are all logical
Cross low temperature solution polycondensation and prepare film forming.
Lower floor's transparent electrode layer of the present invention include the tin oxide (FTO) of Fluorin doped, indium doping tin oxide (ITO),
Graphene, carbon nanotube layer or nano silver wire.
Hole transmission layer of the present invention includes PEDOT:PSS, P3HT, PCDTBT, PTB7, MoOx, graphene oxide,
Hole transmission layer film thickness is between 30 nanometers to 100 nanometers.
Metallic nanoparticle of the present invention is gold (the Au@SiO of coated with silica2) nanometer rods；Au@SiO2Nanometer rods
Length is between 20 nanometers to 60 nanometers, and width is between 5 nanometers to 25 nanometers；Au@SiO2Nanometer rods show two resonance
Peak, wavelength is respectively at 510 nanometers to 530 nanometers and 690 nanometers to 710 nanometers；Au@SiO2Nanometer rods layer thickness control is received 5
Rice is between 50 nanometers.
Perovskite active layer of the present invention is CH3NH3PbI3, CH3NH3PbBr3, CH3NH3PbCl3,
CH3NH3PbIxBr3-x, CH3NH3PbIxCl3-x, different according to solution manner of formulation, x value is between 1 to 3, perovskite activity
Layer film thickness degree is between 300 nanometers to 600 nanometers.
Electron transfer layer of the present invention includes PC60BM, PC70BM, ICBA, and fullerene derivate, film thickness
Degree is between 30 nanometers to 120 nanometers.
Low temperature of the present invention refers to temperature in room temperature between 150 degree.
Solwution method of the present invention includes spin coating, blade coating, inkjet printing, volume to volume printing technology.
Upper electrode of the present invention includes aluminium, silver, gold, ITO, graphene, CNT.
Principle and advantage
The principle of the present invention：For the present invention by testing repeatedly, research finds the frequency and Au@SiO when incident light2Nanoparticle
When the intrinsic frequency of son is identical, it will in Au@SiO2The surface of nano-particle produces surface plasma body resonant vibration, surface plasma
During resonance, due to Au@SiO2Nanoparticle surface scattering increases light path of the incident light in active layer, so as to increase light in active layer
In absorption, increase the generation rate of carrier, largely experiment repeatedly also shows Au@SiO2The surface plasma of nano-particle
Resonance can improve Au@SiO2Local electromagnetic field around nano-particle, this local electromagnetic field can improve and improve the sun
Energy battery electrical properties, so as to improve the fill factor, curve factor of solar cell, due to the increase of light absorbs, improve solar cell
Short circuit current.Simultaneously because Au@SiO2The increase of nano-particle peripheral electromagnetic field, improve the current-carrying in perovskite active layer
Sub- separating capacity, so as to improve the electricity conversion of solar cell.
Beneficial effects of the present invention：Compared with perovskite solar cell prepared by traditional preparation methods, the inventive method system
Standby perovskite solar cell has high smooth perovskite thin film, has a higher short circuit current, higher fill factor, curve factor, so that
With higher electricity conversion, photoelectric transformation efficiency improves more than 35%.
Brief description of the drawings
【Fig. 1】Be the present invention solar cell device structural representation, Au@SiO2Nano-particle stratum boundary is in hole transport
Layer PEDOT:PSS and perovskite CH3NH3PbI3Between layer.
【Fig. 2】It is the Au@SiO in the present invention2Nano-particle transmission electron microscope shape appearance figure.
【Fig. 3】It is the selected Au@SiO in the present invention2Nano-particle transmission electron microscope shape appearance figure, Ke Yiqing
Chu finds out Au nano-particles by SiO2Cladding.
【Fig. 4】It is the Au@SiO in the present invention2The size distribution plot of nano-particle.
【Fig. 5】It is the Au@SiO in the present invention2The abosrption spectrogram of nano-particle in ethanol, it can be seen that Au@SiO2Receive
Rice corpuscles has two formants, and one is 700 nanometers of 522 nanometers and one long wave directions of shortwave direction.
【Fig. 6】It is in PEDOT:It is 0.032pM to introduce concentration between PSS and active bed boundary respectively, 0.047pM and
0.095pM Au@SiO2The current -voltage curve figure of perovskite solar cell during nano-particle, and with no Au@SiO2
The perovskite solar energy of nano-particle is contrasted, and discovery has Au@SiO2The perovskite solar cell of nano-particle it is short
Road electric current, fill factor, curve factor and electricity conversion are improved significantly, and the Au@SiO of 0.047pM concentration2Nano-particle
The performance of perovskite solar cell is best.
Embodiment and embodiment
Implementation below and embodiment are the further explanations to present invention, rather than the protection of the limitation present invention
Scope.
Embodiment 1
Device preparation is carried out according to Fig. 1 perovskite solar cell devices structural representation.
Business ITO is passed through into acetone, liquid detergent, deionized water and isopropanol each ultrasonic 15 points of ultrasound in supersonic cleaning machine
Clock, then dried up with nitrogen stream, then ozone is handled 20 minutes.
The ito glass with ozone processing will be cleaned, will be placed on spin coating instrument, will be prepared with 3000 revs/min of speed spin coating empty
Cave transport layer PEDOT:PSS, then annealed 15 minutes on 150 degree of warm tables.
Au@SiO2Nano-particle is made into the ethanol solution that concentration is respectively 0.032pM, 0.047pM and 0.095pM, then
Ultrasound 5 minutes, it is fully dispersed, PEDOT is spin-coated on 3000 revs/min of speed:In PSS layer, then 120 degree anneal 5 minutes,
The Au@SiO of preparation2Pattern and Size Distribution such as Fig. 2, Fig. 3 and Fig. 4 of nanoparticle layers；Fig. 3 is apparent that Au nanoparticles
Son is by SiO2Cladding；Fig. 4 clearly illustrates Au@SiO2Nano-particle length is between 20 nanometers to 60 nanometers, and width is at 5 nanometers
To between 25 nanometers, SiO2Thickness is between 8 nanometers to 12 nanometers；Fig. 5 shows Au@SiO2Nano-particle has two formants,
One is 522 nanometers, 700 nanometers of a long wave direction of shortwave direction.
By lead iodide and iodine methylamine in molar ratio 1:1 to be made into concentration be 550mg/ml DMF solutions, and one is heated at 60 degree
Hour, then by perovskite CH3NH3PbI3Precursor aqueous solution is with 4000 revs/min of speed rotating and depositing to Au@SiO2Nanoparticle
On sub- thin layer, then annealed 10 minutes in 100 degree of thermal station；A small amount of chlorobenzene solvent induction calcium is rapidly introduced into spin coating process
Titanium ore film is nucleated and growth.
By 15mg/ml PCBM chlorobenzene solutions to be used in 3000 revs/min of speed spin-on deposition to perovskite thin film layer
Make electron transfer layer.
The four layer function film samples that spin coating is prepared be transferred in vacuum evaporation instrument (vacuum be~4 × 10-4Pa),
100 nanometers of Al are deposited as upper electrode.
Fig. 6 is the representational current -voltage curve figure of perovskite solar cell, including no Au@SiO2Nano-particle,
The Au@SiO of spin-on deposition 0.032pM, 0.047pM and 0.095pM concentration2The perovskite solar cell of nano-particle.As a result
Show there are Au@SiO2Perovskite solar cell properties obtain very big raising.There is no Au@SiO2During nano-particle, calcium titanium
Open-circuit voltage, short circuit current, fill factor, curve factor and the photoelectric transformation efficiency of ore deposit solar cell are respectively 1.01V, 18.0mA/cm2,
65.9% and 12.1%；As the Au@SiO that spin-on deposition concentration is 0.032pM2During nano-particle, fill factor, curve factor and open-circuit voltage
It is basically unchanged, and 19.7mA/cm is respectively increased in short circuit current and photoelectric transformation efficiency2With 12.5%；When spin-on deposition concentration
For 0.047pM Au@SiO2During nano-particle, open-circuit voltage is basically unchanged, short circuit current, fill factor, curve factor and photoelectric transformation efficiency
22.0mA/cm is significantly risen to respectively2, 70.6% and 16.1%；But the concentration that ought further increase golden nanometer particle is
During 0.095pM, photoelectric transformation efficiency is slightly reduced to 14.3%, and short circuit current and fill factor, curve factor are also reduced to 20.6mA/cm2
With 67.9%, open-circuit voltage is almost unchanged.The above results show, add Au@SiO2Nanoparticle layers, perovskite solar cell
Performance significantly improves, and is 0.047pMAu@SiO especially with concentration2Nano-particle, with no Au@SiO2Nano-particle
Compare, the photoelectric transformation efficiency of perovskite solar cell improves more than 40%.
Perovskite solar cell is in tri- Au@SiO of 0.032pM, 0.047pM and 0.095pM2Under nanoparticle concentration
Short circuit current, open-circuit voltage, fill factor, curve factor and electricity conversion distribution results show that the perovskite solar cell is adding
Au@SiO2There is good repeatability after nano-particle, and there is smaller standard deviation, detailed results and deviation such as table 1.
The perovskite solar cell of table 1 is in different Au@SiO2Performance parameter statistical result under nanoparticle concentration.Include
It is the peak of device parameter performance in number.
Embodiment 2
Business ITO is passed through into acetone, liquid detergent, deionized water and isopropanol each ultrasonic 15 points of ultrasound in supersonic cleaning machine
Clock, then dried up with nitrogen stream, then ozone is handled 20 minutes.
The ito glass with ozone processing will be cleaned, will be placed on spin coating instrument, will be prepared with 3000 revs/min of speed spin coating empty
Cave transport layer PEDOT:PSS, then annealed 15 minutes on 150 degree of warm tables.
Au@SiO2Nano-particle is made into the ethanol solution that concentration is 0.047pM, and then ultrasound 5 minutes, fully dispersed, then
PEDOT is spin-coated on 3000 revs/min of speed:In PSS layer, 120 degree are annealed 5 minutes.
By lead bromide and bromine methylamine in molar ratio 1:1 to be made into concentration be 500mg/ml DMF solutions, and one is heated at 60 degree
Hour, then by perovskite CH3NH3PbBr3Precursor aqueous solution is with 4000 revs/min of speed rotating and depositing to Au@SiO2Nanoparticle
On sub- thin layer, rotational time is 30 seconds, is then annealed 10 minutes in 80 degree of thermal station.
By 15mg/ml PCBM chlorobenzene solutions to be used in 3000 revs/min of speed spin-on deposition to perovskite thin film layer
Make electron transfer layer.
The four layer function film samples that spin coating is prepared be transferred in vacuum evaporation instrument (vacuum be~4 × 10-4Pa),
100 nanometers of Al are deposited as upper electrode.
There is no Au@SiO2Nano-particle perovskite CH3NH3PbBr3The open-circuit voltage of solar cell, short circuit current, filling
The factor and photoelectric transformation efficiency are respectively 0.96V, 16.5mA/cm2, 62.5% and 9.9%；When spin-on deposition concentration is
0.047pM Au@SiO2During nano-particle, open-circuit voltage, short circuit current, fill factor, curve factor all bring up to 1.12V, 18.2mA/cm2,
68.2%, so as to which photoelectric transformation efficiency improves 40.4%, reach 13.9%.Illustrate to add Au@SiO2Nanoparticle layers show
Work improves perovskite CH3NH3PbBr3The photoelectric transformation efficiency of solar cell.
Embodiment 3
Business ITO is passed through into acetone, liquid detergent, deionized water and isopropanol each ultrasonic 15 points of ultrasound in supersonic cleaning machine
Clock, then dried up with nitrogen stream, then ozone is handled 20 minutes.
The ito glass with ozone processing will be cleaned, will be placed on spin coating instrument, will be prepared with 3000 revs/min of speed spin coating empty
Cave transport layer PEDOT:PSS, then annealed 15 minutes on 150 degree of warm tables.
Au@SiO2Nano-particle is made into the ethanol solution that concentration is 0.047pM, and then ultrasound 5 minutes, fully dispersed, then
PEDOT is spin-coated on 3000 revs/min of speed:In PSS layer, 120 degree are annealed 5 minutes.
By lead chloride, lead iodide and bromine methylamine in molar ratio 1:1:1 to be made into concentration be 580mg/ml DMF solutions, at 60 degree
A hour is heated, then by perovskite CH3NH3PbIxCl3-xPrecursor aqueous solution is arrived with 4000 revs/min of speed rotating and depositing
Au@SiO2On nano-particle thin layer, rotational time is 30 seconds, is then annealed 10 minutes in 80 degree of thermal station.
By 15mg/ml PCBM chlorobenzene solutions to be used in 3000 revs/min of speed spin-on deposition to perovskite thin film layer
Make electron transfer layer.
The four layer function film samples that spin coating is prepared be transferred in vacuum evaporation instrument (vacuum be~4 × 10-4Pa),
100 nanometers of Al are deposited as upper electrode.
There is no Au@SiO2Nano-particle perovskite CH3NH3PbIxCl3-xThe open-circuit voltage of solar cell, short circuit current,
Fill factor, curve factor and photoelectric transformation efficiency are respectively 1.02V, 18.8mA/cm2, 64.5% and 12.4%；When spin-on deposition concentration is
0.047pM Au@SiO2During nano-particle, open-circuit voltage, short circuit current, fill factor, curve factor all bring up to 1.05V, 22.6mA/cm2,
71.2%, so as to which photoelectric transformation efficiency improves 36.3%, reach 16.9%.Illustrate to add Au@SiO2Nanoparticle layers show
Work improves perovskite CH3NH3PbIxCl3-xThe photoelectric transformation efficiency of solar cell.
Claims (7)
1. a kind of perovskite solar cell based on metal nanoparticle modifying interface, it is characterised in that in the transparent electricity of lower floor
Four one functional layers are accompanied between pole layer and upper electrode layer；Four described one functional layers, are followed successively by hole transmission layer from top to bottom,
Metal nanoparticle layer, perovskite active layer and electron transfer layer；Four described one functional layers are all arrived by temperature in room temperature
Low temperature solution polycondensation between 150 degrees Celsius prepares film forming；
Described metal nanoparticle is gold (the Au@SiO of coated with silica2) nanometer rods；Au@SiO2Nano-particle length exists
Between 20 nanometers to 60 nanometers, width is between 5 nanometers to 25 nanometers；Au@SiO2Nano-particle shows two formants, ripple
Length is respectively between 510 nanometers to 530 nanometers between 690 nanometers to 710 nanometers；
Described metal nanoparticle layer is Au@SiO2Nanoparticle layers, thickness control is between 5 nanometers to 50 nanometers.
2. a kind of perovskite solar cell based on metal nanoparticle modifying interface as claimed in claim 1, its feature
It is, lower floor's transparent electrode layer includes tin oxide (FTO), tin oxide (ITO), graphene, the carbon of indium doping of Fluorin doped
Nanotube layer or nano silver wire.
3. a kind of perovskite solar cell based on metal nanoparticle modifying interface as claimed in claim 1, its feature
It is, described hole transmission layer includes PEDOT:PSS、P3HT、PCDTBT、PTB7、MoOxOr graphene oxide, hole transport
Layer film thickness is between 30 nanometers to 100 nanometers.
4. a kind of perovskite solar cell based on metal nanoparticle modifying interface as claimed in claim 1, its feature
It is, described perovskite active layer includes CH3NH3PbI3、CH3NH3PbBr3、CH3NH3PbCl3、CH3NH3PbIxBr3-xOr
CH3NH3PbIxCl3-x, different according to solution manner of formulation, between 1 to 3, perovskite active layer thin film layer thickness exists x value
Between 300 nanometers to 600 nanometers.
5. a kind of perovskite solar cell based on metal nanoparticle modifying interface as claimed in claim 1, its feature
It is, described electron transfer layer includes PC60BM、PC70BM, ICBA or fullerene derivate, thin film layer thickness arrive at 30 nanometers
Between 120 nanometers.
6. a kind of perovskite solar cell based on metal nanoparticle modifying interface as claimed in claim 1, its feature
It is, described solwution method includes spin coating, blade coating, inkjet printing or volume to volume printing technology.
7. a kind of perovskite solar cell based on metal nanoparticle modifying interface as claimed in claim 1, its feature
It is, described upper electrode includes aluminium, silver, gold, ITO, graphene or CNT.
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