CN105469996A - Perovskite solar cell based on metal nanoparticle interface modification and preparation method of perovskite solar cell - Google Patents
Perovskite solar cell based on metal nanoparticle interface modification and preparation method of perovskite solar cell Download PDFInfo
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- CN105469996A CN105469996A CN201610005162.3A CN201610005162A CN105469996A CN 105469996 A CN105469996 A CN 105469996A CN 201610005162 A CN201610005162 A CN 201610005162A CN 105469996 A CN105469996 A CN 105469996A
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- perovskite
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- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 230000004048 modification Effects 0.000 title abstract 3
- 238000002715 modification method Methods 0.000 title 1
- 239000002105 nanoparticle Substances 0.000 claims abstract description 58
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000005540 biological transmission Effects 0.000 claims abstract description 14
- 239000010931 gold Substances 0.000 claims abstract description 14
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052737 gold Inorganic materials 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 70
- 238000004528 spin coating Methods 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 10
- 239000010409 thin film Substances 0.000 claims description 9
- 239000010408 film Substances 0.000 claims description 7
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 239000002346 layers by function Substances 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 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
- 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
- 229910003472 fullerene Inorganic materials 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
- 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
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 6
- 229910052906 cristobalite Inorganic materials 0.000 abstract 6
- 229910052682 stishovite Inorganic materials 0.000 abstract 6
- 229910052905 tridymite Inorganic materials 0.000 abstract 6
- 238000012986 modification Methods 0.000 abstract 2
- 230000003287 optical effect Effects 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- 238000000151 deposition Methods 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 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
- 238000000137 annealing Methods 0.000 description 3
- 239000007864 aqueous solution Substances 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
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation 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
- 238000012546 transfer 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GBMPPHPJKKUMPS-UHFFFAOYSA-N [Br].CN Chemical compound [Br].CN GBMPPHPJKKUMPS-UHFFFAOYSA-N 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- QEZYDNSACGFLIC-UHFFFAOYSA-N CN.[I] Chemical compound CN.[I] QEZYDNSACGFLIC-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 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
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- 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
-
- 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
Abstract
The invention discloses a perovskite solar cell based on metal nanoparticle interface modification and a preparation method of the perovskite solar cell. In the perovskite solar cell, a thin layer of silicon dioxide coated gold (Au@SiO2) nanoparticles is additionally arranged between a hole transmission layer and a perovskite active layer of a planar heterojunction perovskite solar cell, the length of the Au@SiO2 nanoparticles is ranging from 20 nanometers to 60 nanometers, and the width of the Au@SiO2 nanoparticles is ranging from 5 nanometers to 25 nanometers; surface plasma resonance can be generated by the Au@SiO2 nanoparticles, so that the optical path of light in the perovskite active layer is increased, the absorption of the perovskite active layer to the light is improved, and the photoelectric conversion efficiency of the perovskite solar cell can be obviously improved; and compared with the perovskite solar cell without the Au@SiO2 nanoparticles, the photoelectric conversion efficiency of the perovskite soalr cell with the Au@SiO2 nanoparticles can be improved by over 35%. The preparation method of the perovskite solar cell based on metal nanoparticle interface modification, disclosed by the invention, is implemented by a solution technique at a low temperature, is high in repeatability and low in cost, and has a wide application prospect.
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 is owing to having high efficiency, low cost and can the advantage such as volume to volume printing preparation, receive much concern at photovoltaic art, photoelectric conversion efficiency is by 3.8% soaring more than the 20% (J.Am.Chem.Soc. that can compare with silica-based solar cell till now, 2009,131,6050; Nature, 2013,499,316; Nature, 2013,501,395; 2014,345,542; Science, 2014,344,458), in application such as photovoltaic roof integration, mobile electronic device power supply and space flight, there are very large potentiality.Although multi-disciplinary effort has made the efficiency of perovskite solar cell to have risen the level can be able to compared with silica-based solar cell; but in order to advance commercialization and the large-scale production of perovskite solar cell, also have a lot of problem in science and technical problem to need to solve.In order to improve photoelectric conversion efficiency, one the most simply and easily means be exactly the thickness increasing active layer, to increase the absorption of light.But due to reasons such as charge carrier mobility in vivo or diffusion lengths, increase active layer thickness and photo-generated carrier usually can be caused in the compound of active layer inside, because which limit to increase active layer thickness to improve the efficiency of solar cell.The optimum thickness of usual perovskite solar cell is in about 350nm (EnergyEnvironSci., 2014,7,2619; Org.Electron., 2015,26,265), but this thickness can not absorb sunlight fully.
Metal nanoparticle, owing to having surface plasma effect, has had preliminary application at organic solar batteries and DSSC, and can improve battery performance (NanoLett., 2013,13,2204 to a certain extent; NanoLett., 2013,13,4505).The shape of metal nanoparticle, size, kind and dielectric mechanism constant play very important effect to the optics of solar cell, electricity and efficiency.Surfaces of metal nanoparticles can excite plasma resonance, thus increases the absorption of light and cause the generation rate of exciton to increase, and the metal nanoparticle of different size has different surface plasma resonance peaks.The metal nano that usual dielectric is coated, in the raising of solar cell properties, better performance is embodied than exposed metal nanoparticle, its reason is because insulating barrier increase avoids the contact of metal nanoparticle and active layer, decreases harmful Carrier recombination.Bar-shaped metal nanoparticle has more superior optics and electric property than the nano particle of ball-type, because bar-shaped nano particle has two plasma resonance peaks, and the nano particle of ball-type only has a formant.Based on this, the present invention is first by the gold (AuSiO of coated with silica
2) nanometer rods is applied to planar heterojunction perovskite solar cell prepared by low temperature solution polycondensation, greatly can improve the photoelectric conversion efficiency of perovskite solar cell, there is important application prospect.
Summary of the invention
Technical problem to be solved by this invention overcomes the insufficient shortcoming of the absorption of traditional perovskite solar cell active layer to light, a kind of novel metal nano material with surface plasma resonance is introduced as decorative layer between the hole transmission layer and perovskite active layer of traditional perovskite solar cell, object improves the absorbing ability of perovskite active layer, improves the photoelectric conversion efficiency of perovskite solar cell.
The invention provides a kind of perovskite solar cell based on metal nanoparticle modifying interface, this solar cell accompanies four one functional layer between lower floor's transparent electrode layer and upper electrode layer; Four described one functional layer, are followed successively by hole transmission layer, metal nanoparticle layer from top to bottom, perovskite active layer and electron transfer layer; Four described one functional layer all prepare film forming by low temperature solution polycondensation.
Lower floor of the present invention transparent electrode layer draws together the tin oxide (FTO) of Fluorin doped, the tin oxide (ITO) of indium doping, Graphene, carbon nanotube layer or nano silver wire.
Hole transmission layer of the present invention comprises PEDOT:PSS, P3HT, PCDTBT, PTB7, MoO
x, graphene oxide, hole transmission layer film thickness is between 30 nanometers to 100 nanometers.
Metallic nanoparticle of the present invention is the gold (AuSiO of coated with silica
2) nanometer rods; AuSiO
2nanorod length is between 20 nanometers to 60 nanometers, and width is between 5 nanometers to 25 nanometers; AuSiO
2nanometer rods shows two formants, wavelength respectively in 510 nanometers to 530 nanometers and 690 nanometers to 710 nanometers; AuSiO
2nanometer rods layer thickness controls between 5 nanometers to 50 nanometers.
Perovskite active layer of the present invention is CH
3nH
3pbI
3, CH
3nH
3pbBr
3, CH
3nH
3pbCl
3, CH
3nH
3pbI
xbr
3-x, CH
3nH
3pbI
xcl
3-x, different according to solution preparation mode, the value of x is between 1 to 3, and perovskite active layer thin film layer thickness is between 300 nanometers to 600 nanometers.
Electron transfer layer of the present invention comprises PC
60bM, PC
70bM, ICBA, and fullerene derivate, thin film layer thickness is between 30 nanometers to 120 nanometers.
Low temperature of the present invention refers to that temperature is between room temperature is to 150 degree.
Solwution method of the present invention comprises spin coating, blade coating, inkjet printing, volume to volume printing technology.
Upper electrode of the present invention comprises aluminium, silver, gold, ITO, Graphene, carbon nano-tube.
Principle and advantage
Principle of the present invention: the present invention is through repeatedly testing, and research finds the frequency and the AuSiO that work as incident light
2when the natural frequency of nano particle is identical, will at AuSiO
2the surface of nano particle produces surface plasma body resonant vibration, during surface plasma resonance, due to AuSiO
2nanoparticle surface scattering increases incident light at the light path of active layer, thus increases the absorption of light in active layer, increases the generation rate of charge carrier, and experiment repeatedly also shows AuSiO in a large number
2the surface plasma body resonant vibration of nano particle can improve AuSiO
2local electromagnetic field around nano particle, this local electromagnetic field can improve and improve solar cell electrical properties, thus improves the fill factor, curve factor of solar cell, due to the increase of light absorption, improves the short circuit current of solar cell.Simultaneously due to AuSiO
2the increase of nano particle peripheral electromagnetic field, improves the carrier separation ability in perovskite active layer, thus improves the electricity conversion of solar cell.
Beneficial effect of the present invention: compared with the perovskite solar cell prepared with traditional preparation methods, perovskite solar cell prepared by the inventive method has high smooth perovskite thin film, there is higher short circuit current, higher fill factor, curve factor, thus there is higher electricity conversion, photoelectric conversion efficiency improves more than 35%.
Accompanying drawing explanation
[Fig. 1] is solar cell device structural representation of the present invention, AuSiO
2nano particle stratum boundary is in hole transmission layer PEDOT:PSS and perovskite CH
3nH
3pbI
3between layer.
[Fig. 2] is the AuSiO in the present invention
2nano particle transmission electron microscope shape appearance figure.
[Fig. 3] is the selected AuSiO in the present invention
2nano particle transmission electron microscope shape appearance figure, clearly can find out that Au nano particle is by SiO
2coated.
[Fig. 4] is the AuSiO in the present invention
2the size distribution plot of nano particle.
[Fig. 5] is the AuSiO in the present invention
2nano particle abosrption spectrogram in ethanol, can find out AuSiO
2nano particle has two formants, and one is 522 nanometers in shortwave direction and 700 nanometers in a long wave direction.
[Fig. 6] introduces the AuSiO that concentration is 0.032pM, 0.047pM and 0.095pM respectively between PEDOT:PSS and active layer interface
2the current-voltage curve figure of perovskite solar cell during nano particle, and with there is no AuSiO
2the perovskite solar energy of nano particle contrasts, and finds to have AuSiO
2the short circuit current of the perovskite solar cell of nano particle, fill factor, curve factor and electricity conversion are improved significantly, and the AuSiO of 0.047pM concentration
2the performance of the perovskite solar cell of nano particle is best.
Embodiment and embodiment
Following execution mode and embodiment are further illustrating content of the present invention, instead of limit the scope of the invention.
Embodiment 1
Device preparation is carried out according to Fig. 1 perovskite solar cell device structural representation.
By business ITO through acetone, liquid detergent, deionized water and isopropyl alcohol in supersonic cleaning machine ultrasonic each ultrasonic 15 minutes, then dry up with nitrogen stream, then ozone treatment 20 minutes.
The ito glass with ozone treatment will be cleaned, be placed on spin coating instrument, prepare hole transmission layer PEDOT:PSS with the speed spin coating of 3000 revs/min, then anneal 15 minutes on 150 degree of heating stations.
AuSiO
2nano particle is made into concentration and is respectively 0.032pM, the ethanolic solution of 0.047pM and 0.095pM, then ultrasonic 5 minutes, fully disperses, is spin-coated on PEDOT:PSS layer with the speed of 3000 revs/min, then 120 degree of annealing 5 minutes, the AuSiO of preparation
2the pattern of nanoparticle layers and distribution of sizes are as Fig. 2, Fig. 3 and Fig. 4; Fig. 3 can know and sees that Au nano particle is by SiO
2coated; Fig. 4 clearly illustrates that AuSiO
2nano particle length between 20 nanometers to 60 nanometers, width between 5 nanometers to 25 nanometers, SiO
2thickness is between 8 nanometers to 12 nanometers; Fig. 5 shows AuSiO
2nano particle has two formants, and one is 522 nanometers in shortwave direction, 700 nanometers in a long wave direction.
By lead iodide and iodine methylamine, 1:1 is made into concentration is in molar ratio 550mg/mlDMF solution, 60 degree of heating one hour, then by perovskite CH
3nH
3pbI
3precursor aqueous solution with the speed rotating and depositing of 4000 revs/min to AuSiO
2on nano particle thin layer, then anneal 10 minutes in the thermal station of 100 degree; A small amount of chlorobenzene solvent induction perovskite thin film coring and increment is introduced fast in spin coating process.
By the PCBM chlorobenzene solution of 15mg/ml so that the speed spin-on deposition of 3000 revs/min to perovskite thin film layer to be used as electron transfer layer.
Four layer function film samples spin coating prepared transfer in vacuum evaporation instrument that (vacuum degree is ~ 4 × 10
-4pa), evaporation 100 nanometer Al is as upper electrode.
Fig. 6 is the representational current-voltage curve figure of perovskite solar cell, comprises and does not have AuSiO
2the AuSiO of nano particle, spin-on deposition 0.032pM, 0.047pM and 0.095pM concentration
2the perovskite solar cell of nano particle.Result shows there is AuSiO
2perovskite solar cell properties obtain very large raising.There is no AuSiO
2during nano particle, the open circuit voltage of perovskite solar cell, short circuit current, fill factor, curve factor and photoelectric conversion efficiency are respectively 1.01V, 18.0mA/cm
2, 65.9% and 12.1%; When spin-on deposition concentration is the AuSiO of 0.032pM
2during nano particle, fill factor, curve factor and open circuit voltage are substantially constant, and short circuit current and photoelectric conversion efficiency bring up to 19.7mA/cm respectively
2with 12.5%; When spin-on deposition concentration is the AuSiO of 0.047pM
2during nano particle, open circuit voltage is substantially constant, and short circuit current, fill factor, curve factor and photoelectric conversion efficiency significantly rise to 22.0mA/cm respectively
2, 70.6% and 16.1%; But when the concentration increasing golden nanometer particle is further 0.095pM, photoelectric conversion efficiency is slightly reduced to 14.3%, and short circuit current and fill factor, curve factor are also reduced to 20.6mA/cm respectively
2with 67.9%, open circuit voltage is almost constant.The above results shows, adds AuSiO
2nanoparticle layers, perovskite solar cell properties significantly improves, and particularly working concentration is 0.047pMAuSiO
2nano particle, and does not have AuSiO
2nano particle is compared, and the photoelectric conversion efficiency of perovskite solar cell improves more than 40%.
Perovskite solar cell is at 0.032pM, 0.047pM and 0.095pM tri-AuSiO
2short circuit current under nanoparticle concentration, open circuit voltage, fill factor, curve factor and electricity conversion distribution results show that this perovskite solar cell is adding AuSiO
2have good repeatability after nano particle, and have smaller standard deviation, detailed results and deviation are as table 1.
Table 1 perovskite solar cell is at different AuSiO
2performance parameter statistics under nanoparticle concentration.It is the peak of device parameter performance in bracket.
Embodiment 2
By business ITO through acetone, liquid detergent, deionized water and isopropyl alcohol in supersonic cleaning machine ultrasonic each ultrasonic 15 minutes, then dry up with nitrogen stream, then ozone treatment 20 minutes.
The ito glass with ozone treatment will be cleaned, be placed on spin coating instrument, prepare hole transmission layer PEDOT:PSS with the speed spin coating of 3000 revs/min, then anneal 15 minutes on 150 degree of heating stations.
AuSiO
2nano particle is made into the ethanolic solution that concentration is 0.047pM, then ultrasonic 5 minutes, fully disperses, then is spin-coated on PEDOT:PSS layer with the speed of 3000 revs/min, 120 degree of annealing 5 minutes.
By lead bromide and bromine methylamine, 1:1 is made into concentration is in molar ratio 500mg/mlDMF solution, 60 degree of heating one hour, then by perovskite CH
3nH
3pbBr
3precursor aqueous solution with the speed rotating and depositing of 4000 revs/min to AuSiO
2on nano particle thin layer, rotational time is 30 seconds, then anneals 10 minutes in the thermal station of 80 degree.
By the PCBM chlorobenzene solution of 15mg/ml so that the speed spin-on deposition of 3000 revs/min to perovskite thin film layer to be used as electron transfer layer.
Four layer function film samples spin coating prepared transfer in vacuum evaporation instrument that (vacuum degree is ~ 4 × 10
-4pa), evaporation 100 nanometer Al is as upper electrode.
There is no AuSiO
2nano particle perovskite CH
3nH
3pbBr
3the open circuit voltage of solar cell, short circuit current, fill factor, curve factor and photoelectric conversion efficiency are respectively 0.96V, 16.5mA/cm
2, 62.5% and 9.9%; When spin-on deposition concentration is the AuSiO of 0.047pM
2during nano particle, open circuit voltage, short circuit current, fill factor, curve factor all bring up to 1.12V, 18.2mA/cm
2, 68.2%, thus photoelectric conversion efficiency improves 40.4%, reaches 13.9%.Explanation adds AuSiO
2nanoparticle layers significantly improves perovskite CH
3nH
3pbBr
3the photoelectric conversion efficiency of solar cell.
Embodiment 3
By business ITO through acetone, liquid detergent, deionized water and isopropyl alcohol in supersonic cleaning machine ultrasonic each ultrasonic 15 minutes, then dry up with nitrogen stream, then ozone treatment 20 minutes.
The ito glass with ozone treatment will be cleaned, be placed on spin coating instrument, prepare hole transmission layer PEDOT:PSS with the speed spin coating of 3000 revs/min, then anneal 15 minutes on 150 degree of heating stations.
AuSiO
2nano particle is made into the ethanolic solution that concentration is 0.047pM, then ultrasonic 5 minutes, fully disperses, then is spin-coated on PEDOT:PSS layer with the speed of 3000 revs/min, 120 degree of annealing 5 minutes.
By lead chloride, lead iodide and bromine methylamine, 1:1:1 is made into concentration is in molar ratio 580mg/mlDMF solution, 60 degree of heating one hour, then by perovskite CH
3nH
3pbI
xcl
3-xprecursor aqueous solution with the speed rotating and depositing of 4000 revs/min to AuSiO
2on nano particle thin layer, rotational time is 30 seconds, then anneals 10 minutes in the thermal station of 80 degree.
By the PCBM chlorobenzene solution of 15mg/ml so that the speed spin-on deposition of 3000 revs/min to perovskite thin film layer to be used as electron transfer layer.
Four layer function film samples spin coating prepared transfer in vacuum evaporation instrument that (vacuum degree is ~ 4 × 10
-4pa), evaporation 100 nanometer Al is as upper electrode.
There is no AuSiO
2nano particle perovskite CH
3nH
3pbI
xcl
3-xthe open circuit voltage of solar cell, short circuit current, fill factor, curve factor and photoelectric conversion efficiency are respectively 1.02V, 18.8mA/cm
2, 64.5% and 12.4%; When spin-on deposition concentration is the AuSiO of 0.047pM
2during nano particle, open circuit voltage, short circuit current, fill factor, curve factor all bring up to 1.05V, 22.6mA/cm
2, 71.2%, thus photoelectric conversion efficiency improves 36.3%, reaches 16.9%.Explanation adds AuSiO
2nanoparticle layers significantly improves perovskite CH
3nH
3pbI
xcl
3-xthe photoelectric conversion efficiency of solar cell.
Claims (9)
1. perovskite solar cell based on metal nanoparticle modifying interface and preparation method thereof, is characterized in that, accompany four one functional layer between lower floor's transparent electrode layer and upper electrode layer; Four described one functional layer, are followed successively by hole transmission layer, metal nanoparticle layer from top to bottom, perovskite active layer and electron transfer layer; Four described one functional layer all prepare film forming by low temperature solution polycondensation.
2. a kind of perovskite solar cell based on metal nanoparticle modifying interface and preparation method thereof as claimed in claim 1, it is characterized in that, described lower floor transparent electrode layer comprises the tin oxide (FTO) of Fluorin doped, the tin oxide (ITO) of indium doping, Graphene, carbon nanotube layer or nano silver wire.
3. a kind of perovskite solar cell based on metal nanoparticle modifying interface and preparation method thereof as claimed in claim 1, it is characterized in that, described hole transmission layer comprises PEDOT:PSS, P3HT, PCDTBT, PTB7, MoO
x, graphene oxide, hole transmission layer film thickness is between 30 nanometers to 100 nanometers.
4. a kind of perovskite solar cell based on metal nanoparticle modifying interface and preparation method thereof as claimed in claim 1, it is characterized in that, described metallic nanoparticle is the gold (AuSiO of coated with silica
2) nanometer rods; AuSiO
2nano particle length is between 20 nanometers to 60 nanometers, and width is between 5 nanometers to 25 nanometers; AuSiO
2nano particle shows two formants, and wavelength is respectively between 510 nanometers to 530 nanometers and between 690 nanometers to 710 nanometers; AuSiO
2nanoparticle layers THICKNESS CONTROL is between 5 nanometers to 50 nanometers.
5. a kind of perovskite solar cell based on metal nanoparticle modifying interface and preparation method thereof as claimed in claim 1, it is characterized in that, described perovskite active layer is CH
3nH
3pbI
3, CH
3nH
3pbBr
3, CH
3nH
3pbCl
3, CH
3nH
3pbI
xbr
3-x, CH
3nH
3pbI
xcl
3-x, different according to solution preparation mode, the value of x is between 1 to 3, and perovskite active layer thin film layer thickness is between 300 nanometers to 600 nanometers.
6. a kind of perovskite solar cell based on metal nanoparticle modifying interface and preparation method thereof as claimed in claim 1, it is characterized in that, described electron transfer layer comprises PC
60bM, PC
70bM, ICBA, and fullerene derivate, thin film layer thickness is between 30 nanometers to 120 nanometers.
7. a kind of perovskite solar cell based on metal nanoparticle modifying interface and preparation method thereof as claimed in claim 1, it is characterized in that, described low temperature refers to that temperature is between room temperature is to 150 degree.
8. a kind of perovskite solar cell based on metal nanoparticle modifying interface and preparation method thereof as claimed in claim 1, it is characterized in that, described solwution method comprises spin coating, blade coating, inkjet printing, volume to volume printing technology.
9. a kind of perovskite solar cell based on metal nanoparticle modifying interface and preparation method thereof as claimed in claim 1, it is characterized in that, described upper electrode comprises aluminium, silver, gold, ITO, Graphene, carbon nano-tube.
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