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 PDFInfo
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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
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%.
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Cited By (5)
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CN111162173A (en) * | 2019-12-30 | 2020-05-15 | 电子科技大学 | Organic photoelectric detector with doped electron transport layer and preparation method thereof |
CN111180587A (en) * | 2019-12-30 | 2020-05-19 | 电子科技大学 | Special doped perovskite solar cell and preparation method thereof |
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CN111384244B (en) * | 2018-12-27 | 2021-05-28 | Tcl科技集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
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CN111180587A (en) * | 2019-12-30 | 2020-05-19 | 电子科技大学 | Special doped perovskite solar cell and preparation method thereof |
CN111180587B (en) * | 2019-12-30 | 2023-04-07 | 电子科技大学 | Special doped perovskite solar cell and preparation method thereof |
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Application publication date: 20180831 |