CN110098337A - A kind of stannic oxide/zinc oxide compound nano wire material and preparation method thereof - Google Patents
A kind of stannic oxide/zinc oxide compound nano wire material and preparation method thereof Download PDFInfo
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- CN110098337A CN110098337A CN201910405320.8A CN201910405320A CN110098337A CN 110098337 A CN110098337 A CN 110098337A CN 201910405320 A CN201910405320 A CN 201910405320A CN 110098337 A CN110098337 A CN 110098337A
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 167
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000002070 nanowire Substances 0.000 title claims abstract description 66
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 32
- -1 zinc oxide compound Chemical class 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 61
- 239000000758 substrate Substances 0.000 claims abstract description 41
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 30
- 239000004411 aluminium Substances 0.000 claims abstract description 27
- 239000011148 porous material Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- WEUCTTBUEWINIJ-UHFFFAOYSA-N acetic acid;zinc;dihydrate Chemical compound O.O.[Zn].CC(O)=O WEUCTTBUEWINIJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000008021 deposition Effects 0.000 claims abstract description 4
- 230000006698 induction Effects 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 229960001296 zinc oxide Drugs 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000002604 ultrasonography Methods 0.000 claims description 12
- 238000004528 spin coating Methods 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000002207 thermal evaporation Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 238000005137 deposition process Methods 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 abstract description 8
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 8
- 238000005036 potential barrier Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 230000031700 light absorption Effects 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 2
- 238000005215 recombination Methods 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000005755 formation reaction Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000007743 anodising Methods 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000003471 anti-radiation Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
- H10K30/35—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles
- H10K30/352—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles the inorganic nanostructures being nanotubes or nanowires, e.g. CdTe nanotubes in P3HT polymer
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- 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
- H10K30/87—Light-trapping means
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- 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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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to 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
- Y02E10/549—Organic PV cells
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- Engineering & Computer Science (AREA)
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- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electromagnetism (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses a kind of stannic oxide/zinc oxide compound nano wire material and preparation method, which includes the zinc oxide nanowire grown using anodised aluminium nano-pore as tin dioxide nano line array made of template and on it.The first deposition of aluminum in FTO conductive substrates, it is formed in the environment of acidic electrolyte bath using anode oxidation process induction nano-pore again, it is then spin coated onto the stannic oxide colloidal solution diluted and zinc oxide nanowire seed layer solution, finally by treated, FTO conductive substrates are put into the aqueous solution of acetic acid dihydrate zinc and hexa grows zinc oxide nanowire, both.Product of the present invention high perpendicular is orderly, greatly reduces the transmission path of the charge in electron transfer layer, be conducive to the transmission of electron hole pair with separate, increase the scattering of photon and the absorption of light.The adjustment of perovskite and electron transfer layer conduction level reduces electron-transport potential barrier, improves the efficiency of electron extraction, reduces the probability of electronics and hole-recombination.
Description
Technical field
The present invention relates to nanocomposite and preparation method, in particular to a kind of stannic oxide/zinc oxide compound nano
Wire material and preparation method thereof.
Background technique
Stannic oxide nano wire generally uses chemical vapour deposition technique to prepare, and has main steps that glass putty and stannous oxide powder
It uniformly mixes, stannic oxide is generated by chemical reaction under high temperature and is mixed with carrier gas, be uniformly fed into the indoor height of reaction
To which stannic oxide nano wire be made in warm substrate.But the growth of the stannic oxide nano wire prepared by chemical vapor deposition
Crystal face and the direction of growth are different, this randomnesses, increase the path of electron-transport, and then electrons and holes are answered
It closes probability just to greatly increase, the efficiency of entire solar battery can also reduce therewith.Stannic oxide nano wire is perpendicular to FTO conduction
Substrate, electron-transport path greatly reduce, and the recombination probability in electronics and hole also reduces therewith.In addition, stannic oxide is mostly
It is used in the form of nano particle in perovskite solar battery, rarely has the perovskite solar energy with stannic oxide nano wire
Battery.
Summary of the invention
Goal of the invention: it is an object of the present invention to provide conduction band ordered arrangements, stannic oxide/oxidation of reduction electron-transport potential barrier
Zinc composite Nano wire material.
It is a further object of the present invention to provide the stannic oxide/zinc oxide compound nano wire material preparation methods.
Technical solution: the present invention provides a kind of stannic oxide/zinc oxide compound nano wire material, including with anodised aluminium
Nano-pore is tin dioxide nano line array and the zinc oxide nanowire grown on it made of template.
Further, the length of the stannic oxide nano wire is 300~500nm.
Further, the length of the zinc oxide nanowire is 400~500nm.
The stannic oxide/zinc oxide compound nano wire material preparation method, includes the following steps:
(1) it prepares anodised aluminium nano-pore template: using thermal evaporation deposition of aluminum in FTO conductive substrates, taking sun
The formation of pole oxidizing process induction nano-pore；
(2) it prepares tin dioxide nano line array: taking the ultrasound dilution of stannic oxide colloidal solution, the dioxy that will have been diluted
Change tin colloid solution drop in substrate and stop, penetrate into solution in anodised aluminium nano-pore, then spin coating, annealing again, then
It is placed in sodium hydroxide solution and dissolves anodised aluminium, obtain tin dioxide nano line array；
(3) it prepares zinc-oxide nano seed layer: acetic acid dihydrate zinc is dissolved in dehydrated alcohol, ultrasound to clear solution,
Solution is added dropwise in step (2) treated substrate, is soaked completely to substrate, then stand, spin coating, heating, above-mentioned step is repeated
Rapid after annealing obtains zinc oxide nanowire seed layer；
(4) it prepares zinc oxide nano-wire array: weighing acetic acid dihydrate zinc and hexa and be dissolved in respectively in equal volume
Deionized water in, two solution are mixed, are used as zinc oxide nanowire growth solution after heating, will walked to clear solution by ultrasound
Suddenly (3) treated, and substrate is put into above-mentioned growth solution, microwave heating, while keeping the concentration of growth solution constant, is reacted
After the completion, the sundries for removing sample surfaces unreacted and being attached in substrate is rinsed with deionized water, removes sample surfaces later
Moisture, annealing.
The method that technical solution of the present invention first uses anodic oxidation prepares anodised aluminium nano-pore template, recycles rotation
Coating prepares stannic oxide nano wire, then prepares zinc oxide nanowire with microwave heating method.Due to zinc oxide conduction band between
Between stannic oxide and perovskite, the potential barrier of electron-transport can be reduced, electronics is reduced in the accumulation of interface, improves electronics and mention
The efficiency taken, to reach the raising of photoelectric conversion efficiency.
Further, specimen holder is rotated in step (1) deposition process, guarantees that film thickness is uniform, and pass through copper strips
It is contacted with the surface of aluminium and FTO conductive substrates is sealed in electrolytic cell.Step (1) the Anodic Oxidation method is netted with platinum
Electrode and 0.3M oxalic acid aqueous solution simultaneously apply voltage, to induce the formation of nano-pore.The stannic oxide colloid of the step (2)
The stannic oxide colloidal solution and deionized water that solution is 15% by mass concentration are formulated by 1: 6 volume ratio.The step
Suddenly (1) anodized time is 10min.Generally hole can be controlled by changing the anodized time, if
The time is handled less than 10min, then the hole formed is too small, is on the one hand unfavorable for the infiltration of stannic oxide colloidal solution, another party
The stannic oxide nano wire diameter that face is formed is too small to be unfavorable for the growth of zinc oxide nanowire on this basis；And it is big to handle the time
In 10min, then the excessive spacing reduction made between nano wire of the stannic oxide nano wire hole formed is unfavorable for perovskite
It penetrates into.The time that step (2) the Anodic Oxidation aluminium dissolves in sodium hydroxide solution is 2.75min, if dissolution time mistake
Short, anodised aluminium cannot decompose completely, and zinc oxide seed layer cannot be spin-coated on stannic oxide nano wire, so that oxidation
Zinc nano wire good can not be contacted with stannic oxide nano wire, and interface potential barrier increase leads to the decline of entire device performance.If
Dissolution time is too long, and after anodised aluminium is completely broken down, sodium hydroxide solution also can generate decomposition to stannic oxide nano wire
Effect, or even can decompose completely, destroy the structure of entire device.
Stannic oxide band gap is greater than 3.6eV in technical solution of the present invention, and conduction band is deeper compared to titanium dioxide, can be more preferable
Matching MAPbI3Perovskite light-absorption layer.Therefore, more effective electronics transfer can be promoted.In addition, the electron transfer of stannic oxide
Rate is up to 240cm2/ (Vs) is 100 times of titanium dioxide.
Zinc oxide is semiconductor functional material, and zinc oxide not only possesses the energy band band gap of 3.37eV, can be produced in ultraviolet region
The transmitting of raw various excitons and compound.Zinc oxide has higher electron transfer rate (205~300cm2/ (Vs)) compared to two
The 10 of titanium oxide-2cm2/(V·s).Meanwhile some wide bandgap materials are compared, zinc oxide has very high chemical stability, more preferable
Antiradiation injury ability, lower growth temperature and be more suitable for the advantages that doing long lived devices.
Hybrid inorganic-organic perovskite material --- the MAPbI generally used3, the minimum value of conduction band is -3.85eV, two
Tin oxide (SnO2) conduction band minimum be -4.12eV, and the conduction band minimum of zinc oxide (ZnO) be -3.93eV, just between
Between the two, the addition of zinc-oxide nano cable architecture can reduce the potential barrier of electron-transport to a certain extent, reduce electronics and exist
The accumulation of interface improves the efficiency of electron extraction.It is hole transport layer material outside hybrid inorganic-organic perovskite material:
2,2 ', 7,7 '-four [N, N- bis- (4- methoxyphenyl) amino] -9,9 '-spiral shell, two fluorenes (Spiro-OMeTAD).
The orderly nano-wire array optical anode material of high perpendicular advantageously than current mesoporous optical anode material, reason master
Have the following: nano-wire array increases the scattering of photon and the transmission path in electron transfer layer, increases light
It absorbs；Nano-wire array high perpendicular is orderly, this will greatly reduce the transmission path of the charge in electron transfer layer, is conducive to electricity
The transmission and separation in sub- hole pair；Compared with unordered meso-hole structure film, the nano-pore of nanowire array structure film has
Bigger hole, so that perovskite is easier to penetrate into；The nano-wire array diameter that stannic oxide nano wire obtained is formed
Close, length is unified, can promote the uniformity of heterojunction boundary, inhibit electronics and hole caused by the formation of boundary defect
It is compound.
The utility model has the advantages that composite material of the invention has vertical orderly nanowire structure, the structure vertical is in FTO conduction
Substrate greatly reduces the transmission path of the charge in electron transfer layer, is conducive to the transmission and separation of electron hole pair.Titanium dioxide
The nano-wire array of tin and zinc oxide composition increases the scattering of photon and the transmission path in electron transfer layer, increases light
Absorption.Meanwhile the addition of zinc oxide nano-wire array, the energy level difference of perovskite Yu electron-transport interlayer conduction band is had adjusted, is subtracted
The small potential barrier of electron-transport.
Detailed description of the invention
Fig. 1 is the relational graph of stannic oxide nano wire diameter and anodized time prepared by the present invention；
Fig. 2 is stannic oxide of the present invention/zinc oxide compound nano wire material energy diagram；
Fig. 3 is the stannic oxide nano wire system of battle formations prepared by the present invention.
Specific embodiment
Embodiment 1
The stannic oxide of the present embodiment/zinc oxide compound nano wire material, including tin dioxide nano line array matrix and
The zinc oxide nano-wire array being grown on the matrix.Wherein, the length of stannic oxide nano wire be 300nm, diameter 50nm,
The length of zinc oxide nanowire is 500nm.
The preparation method of the composite Nano wire material includes the following steps:
(1) prepare anodised aluminium nano-pore template: respectively with toluene, acetone, ethyl alcohol and deionized water by 1.5 ×
The FTO conductive substrates of 1.5cm are cleaned.Using the method for thermal evaporation, withThermal evaporation rate in FTO conductive substrates sink
Product rotates specimen holder, during the deposition process with a thickness of the aluminium of 300nm to guarantee that film thickness is uniform.Then with copper strips and aluminium
Surface contact, by base plate seals in electrolytic cell, takes the method for anodic oxidation platinum mesh electrode and 0.3M oxalic acid water-soluble
Liquid simultaneously applies 40V voltage, this process continues 10min, to induce the formation of nano-pore；
(2) tin dioxide nano line array is prepared: 15% stannic oxide colloidal solution deionized water by volume 1: 6
Ultrasound dilution 60min, the stannic oxide colloidal solution diluted drop is stopped 10s in substrate penetrates into more solution
In anodised aluminium nano-pore, then then annealed on 150 DEG C of warm table with 4000rpm, the spin coating 30s in substrate again
30min.Sample is placed in 0.25M sodium hydroxide solution and obtains stannic oxide nano wire to dissolve anodised aluminium；
(3) it prepares zinc-oxide nano seed layer: weighing 0.274g acetic acid dihydrate zinc, be dissolved in the dehydrated alcohol of 50ml,
Ultrasound is to clear solution.Solution is added dropwise in clean substrate, in substrate without drying, then 10s is stood, then even
Spin coating 10s under the revolving speed of glue machine 2000r/min.It removes substrate and is placed on 100 DEG C of warm table and heat 1min.Repetition is added dropwise molten
Liquid, spin coating and heating five times, obtain zinc oxide nanowire seed layer with this.Substrate is put into tube furnace, is moved back for 450 DEG C in air
Fiery 30min；
(4) it prepares zinc oxide nano-wire array: weighing the acetic acid dihydrate zinc of 1.374g and the hexa-methylene four of 0.876g
Amine is dissolved in respectively in 1L deionized water, and ultrasound is to clear solution, as growth solution.125mL solution is respectively taken to pour into beaker, and
It is put into micro-wave oven and heats 10min, as zinc oxide nanowire growth solution.Substrate is inserted into bracket, is slowly put into beaker
Mixed growth solution in, then carry out 10min microwave heating.Growth solution is recycled using pump while carrying out microwave heating
The concentration and total amount for extracting to guarantee solution are constant.After the reaction was completed, sample is taken out, is rinsed several times with deionized water, sample is removed
Product surface unreacted and the sundries being attached in substrate, then remove the moisture of sample surfaces.The zinc oxide nanowire that will be prepared
Array is put into 450 DEG C of annealing 30min of annealing in tube furnace, and stannic oxide/zinc oxide compound nano wire material is finally made.
Above-mentioned steps (2), (3), the base material in (4) are previous step treated substrate.
Performance detection:
Stannic oxide/zinc oxide nano-wire array of above-mentioned preparation is subjected to structural analysis using conventional method, is obtained
Tin dioxide nano line array height is consistent, and diameter is unified, and zinc oxide nanowire is uniformly distributed in tin oxide substrate.
Embodiment 2
5 groups of comparative tests are designed, test procedure is substantially the same manner as Example 1, the difference is that the anode in step (1)
Oxidization time, the specific time is shown in Table 1, then the stannic oxide nano wire material diameter of preparation is compared, the result of acquisition
As shown in table 1 below.
The stannic oxide nano wire diameter table of comparisons of the different anodizing time preparation of table 1
As shown in Table 1, with the increase of anodizing time, stannic oxide nano wire diameter is gradually increased.If dioxy
It is too big to change stannum nanowire diameter, is unfavorable for perovskite and penetrates into stannic oxide nano wire, if the diameter of stannic oxide nano wire
Too small, in spin coating zinc oxide nanowire seed layer, seed layer solution can be penetrated into the gap of nano wire, so that zinc oxide
Nano wire cannot be grown on stannic oxide nano wire, so we select anodizing time for 10min, preparing diameter is
The stannic oxide nano wire of 50nm.
Embodiment 3
Stannic oxide of the invention/zinc oxide compound nano wire material, including tin dioxide nano line array matrix and life
The zinc oxide nano-wire array being longer than on the matrix.Wherein, the length of stannic oxide nano wire is 400nm, diameter 60nm, oxygen
The length for changing zinc nano wire is 500nm.
The preparation method of the composite Nano wire material includes the following steps:
(1) prepare anodised aluminium nano-pore template: respectively with toluene, acetone, ethyl alcohol and deionized water by 1.5 ×
The FTO conductive substrates of 1.5cm are cleaned.Using the method for thermal evaporation, withThermal evaporation rate in FTO conductive substrates sink
Product rotates specimen holder, during the deposition process with a thickness of the aluminium of 400nm to guarantee that film thickness is uniform.Then with copper strips and aluminium
Surface contact, by base plate seals in electrolytic cell, takes the method for anodic oxidation platinum mesh electrode and 0.3M oxalic acid water-soluble
Liquid simultaneously applies 40V voltage, this process continues 20min, to induce the formation of nano-pore；
(2) tin dioxide nano line array is prepared: 15% stannic oxide colloidal solution deionized water by volume 1: 6
Ultrasound dilution 60min, the stannic oxide colloidal solution diluted drop is stopped 10s in substrate penetrates into more solution
In anodised aluminium nano-pore, then then annealed on 150 DEG C of warm table with 4000rpm, the spin coating 30s in substrate again
30min.Sample is placed in 0.25M sodium hydroxide solution and obtains stannic oxide nano wire to dissolve anodised aluminium；
(3) it prepares zinc-oxide nano seed layer: weighing 0.274g acetic acid dihydrate zinc, be dissolved in the dehydrated alcohol of 50ml,
Ultrasound is to clear solution.Solution is added dropwise in clean substrate, in substrate without drying, then 10s is stood, then even
Spin coating 10s under the revolving speed of glue machine 2000r/min.It removes substrate and is placed on 100 DEG C of warm table and heat 1min.Repetition is added dropwise molten
Liquid, spin coating and heating five times, obtain zinc oxide nanowire seed layer with this.Substrate is put into tube furnace, is moved back for 450 DEG C in air
Fiery 30min；
(4) it prepares zinc oxide nano-wire array: weighing the acetic acid dihydrate zinc of 1.374g and the hexa-methylene four of 0.876g
Amine is dissolved in respectively in 1L deionized water, and ultrasound is to clear solution, as growth solution.125mL solution is respectively taken to pour into beaker, and
It is put into micro-wave oven and heats 10min, as zinc oxide nanowire growth solution.Substrate is inserted into bracket, is slowly put into beaker
Mixed growth solution in, then carry out 10min microwave heating.Growth solution is recycled using pump while carrying out microwave heating
The concentration and total amount for extracting to guarantee solution are constant.After the reaction was completed, sample is taken out, is rinsed several times with deionized water, sample is removed
Product surface unreacted and the sundries being attached in substrate, then remove the moisture of sample surfaces.The zinc oxide nanowire that will be prepared
Array is put into 450 DEG C of annealing 30min of annealing in tube furnace, and stannic oxide/zinc oxide compound nano wire material is finally made.
Embodiment 4
The present embodiment is substantially the same manner as Example 3, the difference is that:
In step (1), thermal evaporation deposition aluminium with a thickness of 500nm；In step (1), the time of anodic oxidation is 40min.
In stannic oxide/zinc oxide compound nano wire material of embodiment preparation, the length of stannic oxide nano wire is
500nm, diameter 80nm, zinc-oxide nano line length are 400nm.
Claims (9)
1. a kind of stannic oxide/zinc oxide compound nano wire material, it is characterised in that: including using anodised aluminium nano-pore as mould
Tin dioxide nano line array made of plate and the zinc oxide nanowire grown on it.
2. stannic oxide according to claim 1/zinc oxide compound nano wire material, it is characterised in that: the titanium dioxide
The length of stannum nanowire is 300~500nm.
3. stannic oxide according to claim 1/zinc oxide compound nano wire material, it is characterised in that: the zinc oxide
The length of nano wire is 400~500nm.
4. a kind of preparation method of stannic oxide as described in claim 1/zinc oxide compound nano wire material, feature exist
In: include the following steps:
(1) it prepares anodised aluminium nano-pore template: using thermal evaporation deposition of aluminum in FTO conductive substrates, then using anodic oxygen
The formation of change method induction nano-pore；
(2) it prepares tin dioxide nano line array: taking the ultrasound dilution of stannic oxide colloidal solution, the stannic oxide that will have been diluted
Colloidal solution drop in substrate and stop make solution penetrate into anodised aluminium nano-pore in, then again spin coating, annealing, be placed on
Anodised aluminium is dissolved in sodium hydroxide solution, obtains tin dioxide nano line array；
(3) it prepares zinc-oxide nano seed layer: acetic acid dihydrate zinc is dissolved in dehydrated alcohol, ultrasound, will be molten to clear solution
Drop is added in step (2) treated in substrate, soaks completely to substrate, then stand, spin coating, heating, after repeating the above steps
Annealing, obtains zinc oxide nanowire seed layer；
(4) it prepares zinc oxide nano-wire array: weighing acetic acid dihydrate zinc and hexa and be dissolved in isometric go respectively
In ionized water, two solution are mixed, are used as zinc oxide nanowire growth solution after heating, by step (3) by ultrasound to clear solution
Substrate that treated is put into above-mentioned growth solution, microwave heating, while keeping the concentration of growth solution constant, and reaction is completed
Afterwards, the sundries for removing sample surfaces unreacted and being attached in substrate is rinsed with deionized water, removes the water of sample surfaces later
Point, annealing.
5. stannic oxide according to claim 4/zinc oxide compound nano wire material preparation method, it is characterised in that:
Specimen holder is rotated in step (1) deposition process, guarantees that film thickness is uniform, and being contacted by copper strips with the surface of aluminium will
FTO conductive substrates are sealed in electrolytic cell.
6. stannic oxide according to claim 4/zinc oxide compound nano wire material preparation method, it is characterised in that:
Step (1) the Anodic Oxidation method is with platinum mesh electrode and 0.3M oxalic acid aqueous solution and to apply voltage, so that induction is received
The formation of metre hole.
7. stannic oxide according to claim 4/zinc oxide compound nano wire material preparation method, it is characterised in that:
The stannic oxide colloidal solution and deionized water that the stannic oxide colloidal solution of the step (2) is 15% by mass concentration press 1:
6 volume ratio is formulated.
8. stannic oxide according to claim 4/zinc oxide compound nano wire material preparation method, it is characterised in that:
Step (1) the anodized time is 10min.
9. stannic oxide according to claim 4/zinc oxide compound nano wire material preparation method, it is characterised in that:
The time that step (2) the Anodic Oxidation aluminium dissolves in sodium hydroxide solution is 2.75min.
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| CN111739961A (en) * | 2020-06-16 | 2020-10-02 | 湖北文理学院 | Based on ordered SnO2Nanorod array inorganic perovskite solar cell and preparation method thereof |
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| WO2023103650A1 (en) * | 2021-12-08 | 2023-06-15 | 宁德时代新能源科技股份有限公司 | Perovskite solar cell and photovoltaic module |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110629271A (en) * | 2019-09-29 | 2019-12-31 | 深圳大学 | Heterojunction thin film and preparation method thereof |
| CN110629271B (en) * | 2019-09-29 | 2021-02-23 | 深圳大学 | Heterojunction thin film and preparation method thereof |
| CN111739961A (en) * | 2020-06-16 | 2020-10-02 | 湖北文理学院 | Based on ordered SnO2Nanorod array inorganic perovskite solar cell and preparation method thereof |
| CN111739961B (en) * | 2020-06-16 | 2022-03-15 | 湖北文理学院 | Based on ordered SnO2Nanorod array inorganic perovskite solar cell and preparation method thereof |
| CN114284372A (en) * | 2021-11-30 | 2022-04-05 | 湖北文理学院 | Three-layer nanorod array heterojunction structure and preparation method thereof |
| CN114284372B (en) * | 2021-11-30 | 2024-05-24 | 湖北文理学院 | Three-layer nanorod array heterojunction structure and preparation method thereof |
| WO2023103650A1 (en) * | 2021-12-08 | 2023-06-15 | 宁德时代新能源科技股份有限公司 | Perovskite solar cell and photovoltaic module |
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