CN108470833A - Application of the nanometic zinc oxide rod array of modifying interface as electron transfer layer in preparing perovskite solar cell - Google Patents

Application of the nanometic zinc oxide rod array of modifying interface as electron transfer layer in preparing perovskite solar cell Download PDF

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CN108470833A
CN108470833A CN201810165850.5A CN201810165850A CN108470833A CN 108470833 A CN108470833 A CN 108470833A CN 201810165850 A CN201810165850 A CN 201810165850A CN 108470833 A CN108470833 A CN 108470833A
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zinc oxide
rod array
spin coating
layer
oxide rod
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杨纪恩
张琼
张彬
刘志勇
刘海瑞
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Henan Normal University
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30Organic 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
    • H10K30/35Organic 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10Deposition of organic active material
    • H10K71/12Deposition of organic active material using liquid deposition, e.g. spin coating
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00Constructional details relating to the organic devices covered by this subclass
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/549Organic PV cells

Abstract

A kind of application the invention discloses nanometic zinc oxide rod array of modifying interface as electron transfer layer in preparing perovskite solar cell, belongs to perovskite technical field of solar batteries.Technical scheme of the present invention main points are:Grow evenly distributed nanometic zinc oxide rod array on a transparent substrate by immersion method, spin coating PCBA solution modifies interface on nanometic zinc oxide rod array again, then spin coating perovskite light-absorption layer and hole transmission layer successively on the nanometic zinc oxide rod array after modifying interface, perovskite solar cell of the nanometic zinc oxide rod array of modifying interface as electron transfer layer is made in last electrode evaporation, and the wherein structural formula of PCBA is:.Nanometic zinc oxide rod array after PCBA carries out modifying interface can effectively improve the absorption of sunlight, increase the transmission of carrier and reduce the compound of electron hole as perovskite solar cell made from electron transfer layer, and then promote the photoelectric conversion efficiency of perovskite solar cell.

Description

The nanometic zinc oxide rod array of modifying interface is preparing perovskite as electron transfer layer Application in solar cell
Technical field
The invention belongs to perovskite technical field of solar batteries, and in particular to a kind of zinc oxide nano rod of modifying interface Application of the array as electron transfer layer in preparing perovskite solar cell.
Background technology
With the development of human society, energy shortage has become the significant problem that the mankind are faced with environmental degradation.Too Sun more and more can be paid close attention to and study by people as a kind of inexhaustible, nexhaustible environmentally protective energy.
Perovskite solar cell is a kind of novel solar battery developed in recent years, mainly with organic/nothing The ABX with perovskite crystal form of machine hydridization3As active layer, have preparation process is simple, of low cost, carrier diffusion away from The advantages that wide from long and light abstraction width, photoelectric conversion efficiency is constantly soaring, and the efficiency for obtaining certification at present is 22.7%.Cause This, perovskite solar cell has good commercial application prospect, and then causes the extensive concern of researcher.
The structure of perovskite solar cell is generally p-i-n types or n-i-p types, and core composition is active layer(I layers), Simultaneously n-layer and p layers it is also extremely important.N layers are electron transfer layer, its basic role is to form electronics with perovskite absorbed layer Selective exposure improves light induced electron extraction efficiency, and effectively blocking hole is migrated to cathode direction;P layers are that hole passes Defeated layer, main function are transporting holes blocking electronics.Up to the present, as the electron-transport material of perovskite solar cell Material mainly has metal oxide-type and an Organic Electron Transport Material two major classes of fullerene, wherein titanium oxide be perovskite too Most widely used electron transport material in positive energy battery, CBM are less than the LUMO [1] of perovskite, are conducive to electronics in this way Injection, while broad-band gap makes its VBM be in a deeper position, can effectively stop the injection in hole.However high quality Titanium oxide layer usually requires to prepare at high temperature, because the titanium oxide prepared at low temperature obtains the boundary of perovskite solar cell Face is poor, and defect is more, causes combined resistance serious, to reduce the efficiency of solar cell device.But zinc oxide and calcium The lumo energy and HOMO energy levels of titanium ore quite match [2], ensure that the extraction efficiency of electronics, simultaneous oxidation zinc are burnt without high temperature Knot, it is easily prepared, there is higher electron mobility [3] compared to titanium oxide.And nanometer rods can utilize C compared to nano particle The built in field of axis direction enhances electron-transport, makes electronics can be to avoid compound caused by interface resistance when being transmitted in nanometer rods Loss.However, the perovskite solar cell of nanometic zinc oxide rod array can have that spreadability is poor, to overcome this Doped electrode or modification array surface is usually taken to improve its stability [4] in problem.
[1]Jung, H.S. and N.G.Park, Perovskite Solar Cells: From Materials to Devices. 2014. 10–25。
[2] Kim, J., et al., Efficient planar-heterojunctionperovskite solar cells achieved via interfacial modification of a sol-gel ZnO electron collection layer. Journal of Materials Chemistry A, 2014. 2(41): p. 17291- 17296。
[3] Zhang, Q., et al., ZnO Nanostructures for Dye‐Sensitized Solar Cells. Advanced Materials, 2010. 21(41): p. 4087-4108。
[4]Xu, Y., et al., Performance Improvement of Perovskite Solar Cells Based on PCBM-Modified ZnO-Nanorod Arrays. IEEE Journal of Photovoltaics, 2016. 6(6): p. 1530-1536。
Invention content
The technical problem to be solved by the present invention is to provide a kind of nanometic zinc oxide rod arrays of modifying interface to pass as electronics Application of the defeated layer in preparing perovskite solar cell, the process is simple and of low cost, and interface is carried out by PCBA Modification makes the parameters such as the photoelectric conversion efficiency of perovskite solar cell after modification be obviously improved.
The present invention adopts the following technical scheme that the nanometic zinc oxide rod array of modifying interface is made to solve above-mentioned technical problem For application of the electron transfer layer in preparing perovskite solar cell, it is characterised in that:On a transparent substrate by immersion method Evenly distributed nanometic zinc oxide rod array is grown, then spin coating PCBA solution modifies interface on nanometic zinc oxide rod array, Then spin coating perovskite light-absorption layer and hole transmission layer successively on the nanometic zinc oxide rod array after modifying interface, are finally deposited Perovskite solar cell of the nanometic zinc oxide rod array of modifying interface as electron transfer layer is made in electrode, wherein PCBA's Structural formula is:
Nanometic zinc oxide rod array after PCBA carries out modifying interface is as perovskite solar-electricity made from electron transfer layer Pond can effectively improve the absorption of sunlight, increases the transmission of carrier and reduce the compound of electron hole, and then promote calcium titanium The photoelectric conversion efficiency of mine solar cell.
The nanometic zinc oxide rod array of modifying interface of the present invention is preparing the perovskite sun as electron transfer layer Application that can be in battery, it is characterised in that detailed process is:
Step(1), prepare electron transfer layer
Acetic acid dihydrate zinc is dissolved in ethylene glycol monomethyl ether and is stirred evenly under room temperature, then is added dropwise and two into above-mentioned solution The ethanol amine of acetate hydrate zinc equimolar amounts, and be uniformly mixed in 60 DEG C to obtain seed layer solution, seed layer solution is revolved Be applied to the conductive glass surface cleaned up, rotating speed be 4000rpm under conditions of rejection film 30s, be subsequently placed in Muffle furnace in The electro-conductive glass of zinc oxide seed layer is coated after 300 DEG C of heating 10min then at 500 DEG C of heating 1h;
The aqueous solution of zinc nitrate hexahydrate and sodium hydroxide is put into coating zinc oxide seed layer obtained above after mixing Electro-conductive glass rinse film surface with deionized water and absolute ethyl alcohol, be subsequently placed in Muffle in 83 DEG C of heating water bath 10min Evenly distributed nanometic zinc oxide rod array is grown on electro-conductive glass in 450 DEG C of annealing 30min in stove, then in zinc oxide nano Rice stick array surface spin coating PCBA solution, rotating speed is 3000rpm, spin-coating time 30s when spin coating, after spin coating in 80 DEG C plus Nanometic zinc oxide rod array film, that is, electron transfer layer of modifying interface is made in hot 10min;
Step(2), prepare light-absorption layer
By the precursor solution PbI of perovskite2With CH3NH3It is 4 that I, which is dissolved in volume ratio,:In the mixed solution of 1 DMF and DMSO Obtain spin coating liquid, wherein PbI2A concentration of 645mg/mL, CH3NH325 μ L spin coating liquid are spun on by a concentration of 223mg/mL of I Electron-transport layer surface, rotating speed is 6000rpm when spin coating, and chlorobenzene solution, spin coating is added dropwise in spin-coating time 20s after spin coating 7s After heat 10min in 80 DEG C brownish black film, that is, light-absorption layers be made;
Step(3), prepare hole transmission layer
In one layer of hole transport layer material of surface spin coating of brownish black film, spin coating, rotating speed is 4000rpm, and spin-coating time is 30s, being stood after spin coating makes hole transport layer material fully penetrated be made hole transmission layer, wherein hole transport layer material Group becomes Spiro-OMeTAD, and solvent is chlorobenzene;
Step(4), prepare to electrode
Vacuum plating silver is carried out in hole transport layer surface, the electric current for steaming silver is 400A, and vacuum degree is 5.0 × 10-4Pa is hereinafter, most Perovskite solar cell of the nanometic zinc oxide rod array of obtained modifying interface as electron transfer layer eventually, the perovskite sun The photoelectric conversion efficiency of energy battery is 5.06%.
The present invention is directed to nanometic zinc oxide rod array, and carrying out modifying interface to nanometic zinc oxide rod array by PCBA makes The parameters such as the photoelectric conversion efficiency of perovskite solar cell after modification are obviously improved, while after modifying interface Nanometic zinc oxide rod array can also improve the absorption of light, increases the transmission of carrier and reduce the compound of electron hole.
Description of the drawings
Fig. 1 is the structural schematic diagram that perovskite solar cell is made in embodiment;
Fig. 2 is the photoelectric conversion efficiency figure of embodiment and perovskite solar cell obtained by comparative example.
Specific implementation mode
The above of the present invention is described in further details by the following examples, but this should not be interpreted as to this The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on the above of the present invention belong to this hair Bright range.
Comparative example
Step(1), prepare electron transfer layer
Acetic acid dihydrate zinc is dissolved in ethylene glycol monomethyl ether and is stirred evenly under room temperature, then is added dropwise and two into above-mentioned solution The ethanol amine of acetate hydrate zinc equimolar amounts, and be uniformly mixed in 60 DEG C to obtain seed layer solution, seed layer solution is revolved Be applied to the conductive glass surface cleaned up, rotating speed be 4000rpm under conditions of rejection film 30s, be subsequently placed in Muffle furnace in After 300 DEG C of heating 10min the electro-conductive glass of coating zinc oxide seed layer is obtained then at 500 DEG C of heating 1h;
The aqueous solution of zinc nitrate hexahydrate and sodium hydroxide is put into coating zinc oxide seed layer obtained above after mixing Electro-conductive glass rinse film surface with deionized water and absolute ethyl alcohol, be subsequently placed in Muffle in 83 DEG C of heating water bath 10min Nanometic zinc oxide rod array film, that is, electron transfer layer is made in 450 DEG C of annealing 30min in stove;
Step(2), prepare light-absorption layer
By the precursor solution PbI of perovskite2With CH3NH3It is 4 that I, which is dissolved in volume ratio,:In the mixed solution of 1 DMF and DMSO Obtain spin coating liquid, wherein PbI2A concentration of 645mg/mL, CH3NH325 μ L spin coating liquid are spun on by a concentration of 223mg/mL of I Electron-transport layer surface, rotating speed is 6000rpm when spin coating, and chlorobenzene solution, spin coating is added dropwise in spin-coating time 20s after spin coating 7s After heat 10min in 80 DEG C brownish black film, that is, light-absorption layers be made;
Step(3), prepare hole transmission layer
In one layer of hole transport layer material of surface spin coating of brownish black film, spin coating, rotating speed is 4000rpm, and spin-coating time is 30s, being stood after spin coating makes hole transport layer material fully penetrated be made hole transmission layer, wherein hole transport layer material Group becomes Spiro-OMeTAD, and solvent is chlorobenzene;
Step(4), prepare to electrode
Vacuum plating silver is carried out in hole transport layer surface, the electric current for steaming silver is 400A, and vacuum degree is 5.0 × 10-4Pa is hereinafter, most Obtained perovskite solar cell eventually.
Perovskite solar cell is it is possible that short circuit current is close made from unmodified nanometic zinc oxide rod array Small problem is spent, mainly the possible reason is perovskite covers on the nanometic zinc oxide rod array as electron transfer layer The poor phenomenon of lid, therefore the photoelectric conversion efficiency of final perovskite solar cell obtained is 3.14%.
Embodiment
Step(1), prepare electron transfer layer
Acetic acid dihydrate zinc is dissolved in ethylene glycol monomethyl ether and is stirred evenly under room temperature, then is added dropwise and two into above-mentioned solution The ethanol amine of acetate hydrate zinc equimolar amounts, and be uniformly mixed in 60 DEG C to obtain seed layer solution, seed layer solution is revolved Be applied to the conductive glass surface cleaned up, rotating speed be 4000rpm under conditions of rejection film 30s, be subsequently placed in Muffle furnace in After 300 DEG C of heating 10min the electro-conductive glass of coating zinc oxide seed layer is obtained then at 500 DEG C of heating 1h;
The aqueous solution of zinc nitrate hexahydrate and sodium hydroxide is put into coating zinc oxide seed layer obtained above after mixing Electro-conductive glass rinse film surface with deionized water and absolute ethyl alcohol, be subsequently placed in Muffle in 83 DEG C of heating water bath 10min Evenly distributed nanometic zinc oxide rod array is grown on electro-conductive glass in 450 DEG C of annealing 30min in stove, then in zinc oxide nano Rice stick array surface spin coating PCBA solution, rotating speed is 3000rpm, spin-coating time 30s when spin coating, after spin coating in 80 DEG C plus Nanometic zinc oxide rod array film, that is, electron transfer layer of modifying interface is made in hot 10min;
Step(2), prepare light-absorption layer
By the precursor solution PbI of perovskite2With CH3NH3It is 4 that I, which is dissolved in volume ratio,:In the mixed solution of 1 DMF and DMSO Obtain spin coating liquid, wherein PbI2A concentration of 645mg/mL, CH3NH325 μ L spin coating liquid are spun on by a concentration of 223mg/mL of I Electron-transport layer surface, rotating speed is 6000rpm when spin coating, and chlorobenzene solution, spin coating is added dropwise in spin-coating time 20s after spin coating 7s After heat 10min in 80 DEG C brownish black film, that is, light-absorption layers be made;
Step(3), prepare hole transmission layer
In one layer of hole transport layer material of surface spin coating of brownish black film, spin coating, rotating speed is 4000rpm, and spin-coating time is 30s, being stood after spin coating makes hole transport layer material fully penetrated be made hole transmission layer, wherein hole transport layer material Group becomes Spiro-OMeTAD, and solvent is chlorobenzene;
Step(4), prepare to electrode
Vacuum plating silver is carried out in hole transport layer surface, the electric current for steaming silver is 400A, and vacuum degree is 5.0 × 10-4Pa is hereinafter, most Perovskite solar cell of the nanometic zinc oxide rod array of obtained modifying interface as electron transfer layer eventually.
Modifying interface is carried out to nanometic zinc oxide rod array by PCBA and makes the perovskite solar cell after modification The parameters such as photoelectric conversion efficiency are obviously improved, and the photoelectric conversion efficiency of wherein perovskite solar cell is promoted to 5.06%, at the same the nanometic zinc oxide rod array after modifying interface can also improve light absorption, increase carrier transmission and Reduce the compound of electron hole.
Embodiment above describes the basic principles and main features and advantage of the present invention, and the technical staff of the industry should Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe the originals of the present invention Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within In the scope of protection of the invention.

Claims (2)

1. application of the nanometic zinc oxide rod array of modifying interface as electron transfer layer in preparing perovskite solar cell, It is characterized in that:Grow evenly distributed nanometic zinc oxide rod array on a transparent substrate by immersion method, then in zinc oxide Spin coating PCBA solution modifies interface, then spin coating successively on the nanometic zinc oxide rod array after modifying interface on nanometer stick array Perovskite light-absorption layer and hole transmission layer, the nanometic zinc oxide rod array that modifying interface is made in last electrode evaporation are passed as electronics The perovskite solar cell of defeated layer, the wherein structural formula of PCBA are:
Nanometic zinc oxide rod array after PCBA carries out modifying interface is as perovskite solar-electricity made from electron transfer layer Pond can effectively improve the absorption of sunlight, increases the transmission of carrier and reduce the compound of electron hole, and then promote calcium titanium The photoelectric conversion efficiency of mine solar cell.
2. the nanometic zinc oxide rod array of modifying interface according to claim 1 is preparing perovskite as electron transfer layer Application in solar cell, it is characterised in that detailed process is:
Step(1), prepare electron transfer layer
Acetic acid dihydrate zinc is dissolved in ethylene glycol monomethyl ether and is stirred evenly under room temperature, then is added dropwise and two into above-mentioned solution The ethanol amine of acetate hydrate zinc equimolar amounts, and be uniformly mixed in 60 DEG C to obtain seed layer solution, seed layer solution is revolved Be applied to the conductive glass surface cleaned up, rotating speed be 4000rpm under conditions of rejection film 30s, be subsequently placed in Muffle furnace in The electro-conductive glass of zinc oxide seed layer is coated after 300 DEG C of heating 10min then at 500 DEG C of heating 1h;
The aqueous solution of zinc nitrate hexahydrate and sodium hydroxide is put into coating zinc oxide seed layer obtained above after mixing Electro-conductive glass rinse film surface with deionized water and absolute ethyl alcohol, be subsequently placed in Muffle in 83 DEG C of heating water bath 10min Evenly distributed nanometic zinc oxide rod array is grown on electro-conductive glass in 450 DEG C of annealing 30min in stove, then in zinc oxide nano Rice stick array surface spin coating PCBA solution, rotating speed is 3000rpm, spin-coating time 30s when spin coating, after spin coating in 80 DEG C plus Nanometic zinc oxide rod array film, that is, electron transfer layer of modifying interface is made in hot 10min;
Step(2), prepare light-absorption layer
By the precursor solution PbI of perovskite2With CH3NH3It is 4 that I, which is dissolved in volume ratio,:In the mixed solution of 1 DMF and DMSO Obtain spin coating liquid, wherein PbI2A concentration of 645mg/mL, CH3NH325 μ L spin coating liquid are spun on by a concentration of 223mg/mL of I Electron-transport layer surface, rotating speed is 6000rpm when spin coating, and chlorobenzene solution, spin coating is added dropwise in spin-coating time 20s after spin coating 7s After heat 10min in 80 DEG C brownish black film, that is, light-absorption layers be made;
Step(3), prepare hole transmission layer
In one layer of hole transport layer material of surface spin coating of brownish black film, spin coating, rotating speed is 4000rpm, and spin-coating time is 30s, being stood after spin coating makes hole transport layer material fully penetrated be made hole transmission layer, wherein hole transport layer material Group becomes Spiro-OMeTAD, and solvent is chlorobenzene;
Step(4), prepare to electrode
Vacuum plating silver is carried out in hole transport layer surface, the electric current for steaming silver is 400A, and vacuum degree is 5.0 × 10-4Pa is hereinafter, final Perovskite solar cell of the nanometic zinc oxide rod array of modifying interface as electron transfer layer, the perovskite solar energy is made The photoelectric conversion efficiency of battery is 5.06%.
CN201810165850.5A 2018-02-28 2018-02-28 Application of the nanometic zinc oxide rod array of modifying interface as electron transfer layer in preparing perovskite solar cell Pending CN108470833A (en)

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CN112117383A (en) * 2020-09-11 2020-12-22 东北师范大学 Structure-adjustable electron transport layer and preparation method thereof, and solar cell and preparation method thereof

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Application publication date: 20180831