CN109065733A - A kind of full-inorganic perovskite solar battery and preparation method thereof - Google Patents

A kind of full-inorganic perovskite solar battery and preparation method thereof Download PDF

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CN109065733A
CN109065733A CN201810897148.8A CN201810897148A CN109065733A CN 109065733 A CN109065733 A CN 109065733A CN 201810897148 A CN201810897148 A CN 201810897148A CN 109065733 A CN109065733 A CN 109065733A
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solar battery
inorganic perovskite
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叶轩立
田晶晶
薛启帆
鄢磊
刘梅月
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South China Institute of Collaborative Innovation
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    • H—ELECTRICITY
    • H01—BASIC ELECTRIC ELEMENTS
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Abstract

The invention belongs to solar cell device technical field, a kind of full-inorganic perovskite solar battery and preparation method thereof is disclosed.The solar battery is bielectron transport layer, structure SnO2@ZnO.The bielectron transport layer is by successive spin coating SnO2Solution and the butanol solution of ZnO nanoparticle, then thermal anneal process is made.Most common inorganic electronic transmission material ZnO nanoparticle is produced on to the light absorbing layer and SnO of photovoltaic device by the method that solution is processed2Between electron transfer layer, superior staged energy level is formd, realizes better level-density parameter, while electronics Extracting Ability enhances, it is compound to greatly reduce electron-hole in light absorbing layer, to achieve the purpose that improve full-inorganic perovskite solar battery open-circuit voltage and photoelectric conversion efficiency.Based on this bielectron transport layer structure, the full-inorganic perovskite solar cell device of high photovoltaic performance can be obtained.

Description

A kind of full-inorganic perovskite solar battery and preparation method thereof
Technical field
The invention belongs to solar cell device technical field, in particular to a kind of full-inorganic perovskite solar battery and Preparation method.
Background technique
In recent years, energy scarcity problem and problem of environmental pollution are more prominent, become the mankind and realize Sustainable Development in Future Significant obstacle, and greatly develop and promote cleaning, renewable energy technologies are the most effective hands for solving this two hang-up simultaneously Section.How more sufficiently on earth in numerous available clean energy resourcies, solar energy is most abundant, the most fundamental energy form, Effectively, solar energy is utilized at low cost, is scientists from all over the world's focus of attention.Solar battery can directly turn solar energy Electric energy is turned to, is utilized for human society, is one of the optimal path for efficiently using solar energy.
Solar battery obtains significant progress in the past years, has studied because of its safe and stable feature With develop a variety of different types.Emerging perovskite solar battery (PSCs) in recent years uses perovskite material and makees For light absorbent.Perovskite can be prepared using easy solwution method as a kind of direct band gap material, have absorption coefficient Numerous features such as bipolarity charge transmission high, carrier lifetime is long, band gap is easily adjusted and balanced；Its raw material reserves is rich simultaneously It is rich, at low cost, be easy to be mass produced, there is good economy, these advantages make PSCs rapidly become grinding for photovoltaic art Study carefully hot spot.
Hybrid perovskite APbX3(A=MA+、FA+,…；X=Cl, Br, I) solar battery and full-inorganic CsPbX3(X=Cl, Br, I) perovskite solar battery is the two major classes of current primary study.Hybrid perovskite Solar battery was applied to photovoltaic art in 2009 for the first time, and photoelectric conversion efficiency is rapid from 3.8% in a few years It is promoted to 23.3%.However, problem is that hygroscopicity and volatility organic cation component " A " in perovskite frequently result in it Be exposed to heat and wet environment in when, the stability of film is poor, this be to the long-time stability of solar battery it is very unfavorable, Device is easily decayed.
Full-inorganic CsPbX for comparing, equally as light absorbing material3Perovskite, due to contained all nothings Machine component has better thermal stability.But its photoelectric conversion efficiency is but far below hybrid perovskite solar energy Battery efficiency.CsPbX based on the preparation of solution processing method3Perovskite solar cell device structure is ITO/ tin oxide (SnO2)/ Perovskite/2,2', two fluorenes (Spiro-OMeTAD) of 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell/oxidation Molybdenum (MoO3)/silver-colored (Ag), wherein SnO2Between perovskite and non-optimized interfacial contact, SnO2Conduction level (- 4.43eV) with Perovskite conduction level (- 4.16eV) mismatches, and has larger energy level drop, this results in full-inorganic calcium titanium to a certain extent The open-circuit voltage of mine solar battery is lower, so that device photoelectric transfer efficiency reduces.
Summary of the invention
In order to solve the disadvantage that the prior art and shortcoming, primary and foremost purpose of the invention are to provide a kind of full-inorganic calcium titanium Mine solar battery, the solar battery include SnO2Electron transfer layer and ZnO electron transfer layer.
Another object of the present invention is to provide the preparation method of above-mentioned full-inorganic perovskite solar battery.
The purpose of the present invention is achieved through the following technical solutions:
A kind of full-inorganic perovskite solar battery, full-inorganic perovskite solar cell device structure is from bottom to top successively Including substrate, cathode layer, with a thickness of the SnO of 10~30nm2Electron transfer layer, with a thickness of 10~30nm ZnO electron transfer layer, Perovskite light absorbing layer, hole transmission layer, anode modification layer and anode layer.
Preferably, the SnO2Electron transfer layer with a thickness of 30nm, the ZnO electron transfer layer with a thickness of 10nm.
Preferably, the perovskite light absorbing layer is CsPbI3-xBrx, 0≤x≤3；The thickness of the perovskite light absorbing layer Degree is 300~400nm, it is furthermore preferred that the perovskite light absorbing layer is CsPbI2Br, with a thickness of 350nm.
Preferably, the substrate is glass or transparent plastic film.
Preferably, the oxidation that the cathode layer is the SnO 2 thin film of indium doping, the SnO 2 thin film of Fluorin doped, aluminium adulterate One of zinc film, metallic silver or gold thin film.
Preferably, the hole transmission layer is 2 doped with 4- tert .-butylpyridine and double trifluoromethanesulfonimide lithium salts, Two fluorenes film of 2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell.
Preferably, the anode modification layer is Electrochromic Molybdenum Oxide Coatings.
Preferably, the anode layer is metallic silver.
The preparation method of above-mentioned full-inorganic perovskite solar battery, comprising the following steps:
(1) cathode layer is prepared by solution processing method or vacuum vapour deposition on substrate；
(2) by SnO2Solution forms SnO by solution processing method on cathode layer2Electron transfer layer；
(3) butanol solution of ZnO nanoparticle is taken, solution processing method SnO made from step (2) is then passed through2Electricity ZnO electron transfer layer is formed in sub- transport layer, in 145~155 DEG C of 25~30min of thermal anneal process；
(4) it is steamed on step (3) the ZnO electron transfer layer obtained by annealing by solution processing method or vacuum Plating method sequentially forms perovskite light absorbing layer, hole transmission layer, anode modification layer and anode layer, obtains the full-inorganic perovskite Solar battery.
Preferably, the temperature of annealing described in step (3) is 150 DEG C, annealing time 30min.
Preferably, the preparation step of step (4) the perovskite light absorbing layer are as follows: press CsPbI first3-xBrx(0≤x≤ 3) molecular formula, in CsBr, PbI2, CsI and PbBr2It is middle to select corresponding raw material mixing, it is re-dissolved in organic solvent and forms perovskite Perovskite precursor solution is coated on ZnO electron transfer layer by precursor solution, and the first heating 40s at 50~55 DEG C~ It heats 10s~1min after 1min at 240~260 DEG C again, forms perovskite light absorbing layer.
It is furthermore preferred that the preparation step of step (4) the perovskite light absorbing layer are as follows: press CsPbI first3-xBrx(0≤x ≤ 3) molecular formula, in CsBr, PbI2, CsI and PbBr2It is middle to select corresponding raw material mixing, it is re-dissolved in organic solvent and forms calcium titanium Perovskite precursor solution is coated on ZnO electron transfer layer by mine precursor solution, is existed again after first heating 1min at 55 DEG C 1min is heated at 260 DEG C, forms perovskite light absorbing layer.
Preferably, the organic solvent is one or more of dimethyl sulfoxide, n,N-Dimethylformamide, institute The concentration for stating perovskite precursor solution is 1.0~1.5mol L-1, it is furthermore preferred that the concentration of the perovskite precursor solution For 1.0mol L-1。
Preferably, SnO described in step (2)2Solution is the SnO of 15wt%2Aqueous colloidal dispersion, step (3) described ZnO receive The concentration of the butanol solution of rice corpuscles is 5mg mL-1。
Preferably, solution processing method described in step (1), (2), (3) and (4) is spin coating, brushing, spraying, dip-coating, roller One of painting, silk-screen printing, printing and inkjet printing.
Preferably, the vacuum degree of step (1) and (4) described vacuum vapour deposition is 10-6~10-7Pa。
Compared with prior art, the present invention has the following advantages and beneficial effects:
SnO of the present invention in full-inorganic perovskite solar battery2Draw between electron transfer layer and perovskite light absorbing layer Enter ZnO electron transfer layer, perovskite film forming, and the conduction level of ZnO and full-inorganic perovskite material can be advantageously promoted Conduction level more match, SnO2, ZnO, superior staged energy level is formd between perovskite, while electronics Extracting Ability increases By force, reduce that electron-hole in perovskite light absorbing layer is compound, generally greatly improve solar battery open-circuit voltage and Device performance.
Detailed description of the invention
Fig. 1 is the device junction composition and energy level of full-inorganic perovskite solar cell prepared by the embodiment of the present invention 1~3 Figure, wherein the left side is structure chart, and the right is energy diagram.
The photic hair of the light absorbing layer of full-inorganic perovskite solar cell device prepared by Fig. 2 embodiment 1 and comparative example 1 The photoluminescence spectra figure of light spectrum and perovskite.
Fig. 3 is the transient state photocurrent experiment curv of full-inorganic perovskite solar cell made from embodiment 1 and comparative example 1.
Fig. 4 is the transient photocurrents experiment curv of full-inorganic perovskite solar cell made from embodiment 1 and comparative example 1.
Fig. 5 is that the Current density-voltage (I-V) of full-inorganic perovskite solar cell made from embodiment 1 and comparative example 1 is special Curve graph and external quantum efficiency (EQE) spectrogram are levied, wherein (a) is Current density-voltage (I-V) characteristic curve diagram, it is (b) outer Portion's quantum efficiency (EQE) spectrogram.
Fig. 6 is that the embodiment of the present invention 1~3 and the electric current of full-inorganic perovskite solar cell made from comparative example 1~2 are close Degree-voltage (I-V) characteristic curve diagram.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, embodiments of the present invention are not limited thereto.
ZnO nanoparticle butanol solution involved in following embodiment be according to document (J.Phys.Chem.B 2005, 109,9505) prepared by published method, and concentration is 5mg mL-1。
Embodiment 1
A kind of preparation method of full-inorganic perovskite solar cell device, includes the following steps:
(1) glass substrate coated with ITO layer successively uses acetone, micron level semiconductor detergent, deionized water, isopropanol Ultrasonic cleaning, is put in constant temperature oven drying for standby.
(2) it before use, the substrate after will be dry in step (1) is placed in culture dish, is put into vacuum plasma cleaning machine Processing 4 minutes.Then by SnO2Solution (15wt%in H2O colloidal dispersion is purchased from Alfa Aesar) spin coating In in ITO layer, spincoating conditions are that 4000r/min turns 30s, film thickness 30nm, and SnO is made2Electron transfer layer.
(3) by the butanol solution of ZnO nanoparticle (5mg mL-1) it is spun on SnO made from step (2)2Electron-transport On layer, ZnO electron transfer layer is made, as second layer electron transfer layer, spin coating rate is 5500r/min, and spin-coating time is 30s, with a thickness of 10nm；Then in 150 DEG C of thermal anneal process 30min, substrate is passed to glove box later.
(4) by 212.8mg CsBr, 461.0mg PbI2Mixing, is dissolved in 900 μ l dimethyl sulfoxides and 100 μ l N, N- bis- The in the mixed solvent of methylformamide, the atomic molar concentration that Pb is made is 1.0mol L-1CsPbI2Br perovskite presoma Solution；In glove box, by CsPbI2Br perovskite precursor solution is spun on ZnO electron transfer layer made from step (3), Spincoating conditions are that elder generation 1500r/min turns 15s 5000r/min turns 30s again, obtain the calcium titanium ore bed with a thickness of 350nm；Then first exist 1min is heated at 260 DEG C again after heating 1min at 55 DEG C, so that perovskite crystalline, forms perovskite light absorbing layer.
(5) by perovskite light absorbing layer room temperature cooling made from step (4) to room temperature, 72.3mg 2,2', 7,7'- tetra- is taken [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell, two fluorenes (Spiro-OMeTAD) solid is dissolved in 1mL chlorobenzene solvent, then 28.8 μ l 4- tert .-butylpyridines (tBP) are added and 17.5 μ l concentration are 520mg mL-1Double trifluoromethanesulfonimide lithium salts (Li- TFSI)/acetonitrile solution is configured to mixed solution, and then mixed solution is spun on perovskite light absorbing layer after cooling, makees For hole transmission layer, spin coating rate is 4000r/min, spin-coating time 30s, with a thickness of 150nm.
(6) it is the molybdenum oxide of 12nm as anode modification that a layer thickness is deposited on the hole transmission layer made from step (5) Layer.
(7) the metal silver electrode that a layer thickness is 100nm is deposited in the anode modification layer made from step (6), as sun Pole layer.
Embodiment 1 finally obtains structure are as follows: glass/ITO/SnO2@ZnO(30nm@10nm)/CsPbI2Br(350nm)/ Spiro-OMeTAD(150nm)/MoO3The device of (12nm)/Ag (100nm).
Embodiment 2
A kind of preparation method of full-inorganic perovskite solar cell device, includes the following steps:
(1) glass substrate coated with ITO layer successively uses acetone, micron level semiconductor detergent, deionized water, isopropanol Ultrasonic cleaning, is put in constant temperature oven drying for standby.
(2) it before use, the substrate after will be dry in step (1) is placed in culture dish, is put into vacuum plasma cleaning machine Processing 4 minutes.Then by SnO2Solution (15wt%in H2O colloidal dispersion is purchased from Alfa Aesar) spin coating In in ITO layer, spin coating rate is 5000r/min, spin-coating time 30s, film thickness 20nm, and SnO is made2Electron transfer layer.
(3) by the butanol solution of ZnO nanoparticle (5mg mL-1) it is spun on SnO made from step (2)2Electron-transport On layer, ZnO electron transfer layer is made, as second layer electron transfer layer, spin coating rate is 4000r/min, and spin-coating time is 30s, with a thickness of 20nm；Then in 150 DEG C of thermal anneal process 30min, substrate is passed to glove box later.
(4) by 212.8mg CsBr, 461.0mg PbI2Mixing, is dissolved in 900 μ l dimethyl sulfoxides and 100 μ l N, N- bis- The in the mixed solvent of methylformamide, the atomic molar concentration that Pb is made is 1.0mol L-1CsPbI2Br perovskite presoma Solution；In glove box, by CsPbI2Br perovskite precursor solution is spun on ZnO electron transfer layer made from step (3), Spincoating conditions are that elder generation 1500r/min turns 15s 5000r/min turns 30s again, obtain the calcium titanium ore bed with a thickness of 350nm；Then first exist 1min is heated at 55 DEG C and heats 1min at 260 DEG C again, so that perovskite crystalline, is made perovskite light absorbing layer.
(5) by perovskite light absorbing layer room temperature cooling made from step (4) to room temperature, 72.3mg 2,2', 7,7'- tetra- is taken [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell, two fluorenes (Spiro-OMeTAD) solid is dissolved in 1mL chlorobenzene solvent, then 28.8 μ l 4- tert .-butylpyridines (tBP) and bis- trifluoromethanesulfonimide lithium salts (the Li-TFSI)/acetonitrile solutions of 17.5 μ l are added (520mg mL-1), it is configured to mixed solution, then mixed solution is spun on perovskite light absorbing layer after cooling, as Hole transmission layer, spin coating rate switch to 4000r/min, spin-coating time 30s, with a thickness of 150nm.
(6) it is the molybdenum oxide of 12nm as anode modification that a layer thickness is deposited on the hole transmission layer made from step (5) Layer.
(7) the metal silver electrode that a layer thickness is 100nm is deposited in the anode modification layer made from step (6), as sun Pole layer.
Embodiment 2 finally obtains structure are as follows: glass/ITO/SnO2@ZnO(20nm@20nm)/CsPbI2Br(350nm)/ Spiro-OMeTAD(150nm)/MoO3The device of (12nm)/Ag (100nm).
Embodiment 3
A kind of preparation method of full-inorganic perovskite solar cell device, includes the following steps:
(1) glass substrate coated with ITO layer successively uses acetone, micron level semiconductor detergent, deionized water, isopropanol Ultrasonic cleaning, is put in constant temperature oven drying for standby.
(2) it before use, the substrate after will be dry in step (1) is placed in culture dish, is put into vacuum plasma cleaning machine Processing 4 minutes.Then by SnO2Solution (15wt%in H2O colloidal dispersion is purchased from Alfa Aesar) spin coating In in ITO layer, spin coating rate is 6500r/min, spin-coating time 30s, film thickness 10nm, and SnO is made2Electron transfer layer.
(3) by the butanol solution of ZnO nanoparticle (5mg mL-1) it is spun on SnO made from step (2)2Electron-transport On layer, ZnO electron transfer layer is made, as second layer electron transfer layer, spin coating rate is 3000r/min, and spin-coating time is 30s, with a thickness of 30nm；Then in 150 DEG C of thermal anneal process 30min, substrate is passed to glove box later.
(4) by 212.8mg CsBr, 461.0mg PbI2Mixing, is dissolved in 900 μ l dimethyl sulfoxides and 100 μ l N, N- bis- The in the mixed solvent of methylformamide, the atomic molar concentration that Pb is made is 1.0mol L-1CsPbI2Br perovskite presoma Solution；In glove box, by CsPbI2Br perovskite precursor solution is spun on ZnO electron transfer layer made from step (3), First to turn 15s in 1500r/min, 5000r/min turns 30s to spincoating conditions again, obtains the calcium titanium ore bed with a thickness of 350nm；Then first 1min is heated at 260 DEG C again after heating 1min at 55 DEG C, so that perovskite crystalline, is made perovskite light absorbing layer.
(5) by perovskite light absorbing layer room temperature cooling made from step (4) to room temperature, 72.3mg 2,2', 7,7'- tetra- is taken [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell, two fluorenes (Spiro-OMeTAD) solid is dissolved in 1mL chlorobenzene solvent, then 28.8 μ l 4- tert .-butylpyridines (tBP) and bis- trifluoromethanesulfonimide lithium salts (the Li-TFSI)/acetonitrile solutions of 17.5 μ l are added (520mg mL-1), it is configured to mixed solution, then mixed solution is spun on perovskite light absorbing layer after cooling, as Hole transmission layer, spin coating rate are 4000r/min, spin-coating time 30s, with a thickness of 150nm.
(6) it is the molybdenum oxide of 12nm as anode modification that a layer thickness is deposited on the hole transmission layer made from step (5) Layer.
(7) the metal silver electrode that a layer thickness is 100nm is deposited in the anode modification layer made from step (6), as sun Pole layer.
Embodiment 3 finally obtains structure are as follows: glass/ITO/SnO2@ZnO(10nm@30nm)/CsPbI2Br(350nm)/ Spiro-OMeTAD(150nm)/MoO3The device of (12nm)/Ag (100nm).
Comparative example 1
A kind of preparation method of full-inorganic perovskite solar cell device, includes the following steps:
(1) glass substrate coated with ITO layer successively uses acetone, micron level semiconductor detergent, deionized water, isopropanol Ultrasonic cleaning, is put in constant temperature oven drying for standby.
(2) it before use, the substrate after will be dry in step (1) is placed in culture dish, is put into vacuum plasma cleaning machine Processing 4 minutes.Then by SnO2Solution (15wt%in H2O colloidal dispersion is purchased from Alfa Aesar) spin coating In in ITO layer, spincoating conditions are that 3000r/min turns 30s, film thickness 40nm, as electron transfer layer；In 150 DEG C of thermal anneal process 30 minutes, substrate is passed to glove box later, SnO is made2Electron transfer layer.
(3) by 212.8mg CsBr, 461.0mg PbI2Mixing, is dissolved in 900 μ l dimethyl sulfoxides and 100 μ l N, N- bis- The in the mixed solvent of methylformamide, the atomic molar concentration that Pb is made is 1.0mol L-1CsPbI2Br perovskite presoma Solution；In glove box, by CsPbI2Br perovskite precursor solution is spun on SnO made from step (1)2On electron transfer layer, Spincoating conditions are that elder generation 1500r/min turns 15s 5000r/min turns 30s again, obtain the calcium titanium ore bed with a thickness of 350nm；Then 55 1min is heated at 260 DEG C again after DEG C heating 1min, so that perovskite crystalline, forms perovskite light absorbing layer.
(4) by perovskite light absorbing layer room temperature cooling made from step (3) to room temperature, 72.3mg 2,2', 7,7'- tetra- is taken [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell, two fluorenes (Spiro-OMeTAD) solid is dissolved in 1mL chlorobenzene solvent, then 28.8 μ l 4- tert .-butylpyridines (tBP) are added and 17.5 μ l concentration are 520mg mL-1Double trifluoromethanesulfonimide lithium salts (Li-TFSI)/acetonitrile solution is configured to mixed solution, and mixed solution is then spun on perovskite light absorbing layer after cooling On, as hole transmission layer, spincoating conditions 4000r/min, time 30s, with a thickness of 150nm.
(5) it is the molybdenum oxide of 12nm as anode modification that a layer thickness is deposited on the hole transmission layer made from step (4) Layer.
(6) the metal silver electrode that vapor deposition a layer thickness is 100nm in anode modification layer is made to obtain in step (5), as sun Pole layer.
This comparative example 1 finally obtains structure are as follows: glass/ITO/SnO2(40nm)/CsPbI2Br(350nm)/Spiro- OMeTAD(150nm)/MoO3The device of (12nm)/Ag (100nm).
Comparative example 2
A kind of preparation method of full-inorganic perovskite solar cell device, includes the following steps:
(1) glass substrate coated with ITO layer successively uses acetone, micron level semiconductor detergent, deionized water, isopropanol Ultrasonic cleaning, is put in constant temperature oven drying for standby.
(2) it before use, the substrate after will be dry in step (1) is placed in culture dish, is put into vacuum plasma cleaning machine Processing 4 minutes.Then by the butanol solution of ZnO nanoparticle (5mg mL-1) be spun in ITO layer, spin coating rate is ZnO electron transfer layer is made in 2500r/min, spin-coating time 30s, film thickness 40nm；In 150 DEG C of thermal anneal process 30min, it Substrate is passed to glove box afterwards.
(3) by 212.8mg CsBr, 461.0mg PbI2Mixing, is dissolved in 900 μ l dimethyl sulfoxides and 100 μ l N, N- bis- The in the mixed solvent of methylformamide, the atomic molar concentration that Pb is made is 1.0mol L-1CsPbI2Br perovskite presoma Solution；In glove box, by CsPbI2Br perovskite precursor solution is spun on ZnO electron transfer layer made from step (2), Spincoating conditions are that elder generation 1500r/min turns 15s 5000r/min turns 30s again, obtain the calcium titanium ore bed with a thickness of 350nm；Then first exist 1min is heated at 55 DEG C and heats 1min at 260 DEG C again, so that perovskite crystalline, is made perovskite light absorbing layer.
(4) by perovskite light absorbing layer room temperature cooling made from step (3) to room temperature, 72.3mg 2,2', 7,7'- tetra- is taken [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell, two fluorenes (Spiro-OMeTAD) solid is dissolved in 1mL chlorobenzene solvent, then 28.8 μ l 4- tert .-butylpyridines (tBP) and bis- trifluoromethanesulfonimide lithium salts (the Li-TFSI)/acetonitrile solutions of 17.5 μ l are added (520mg mL-1), it is configured to mixed solution, then mixed solution is spun on perovskite light absorbing layer after cooling, is made Hole transmission layer, spin coating rate are 4000r/min, spin-coating time 30s, with a thickness of 150nm.
(5) it is the molybdenum oxide of 12nm as anode modification that a layer thickness is deposited on the hole transmission layer made from step (4) Layer.
(6) the metal silver electrode that a layer thickness is 100nm is deposited in the anode modification layer made from step (5), as sun Pole layer.
Comparative example 2 finally obtains structure are as follows: glass/ITO/ZnO (40nm)/CsPbI2Br(350nm)/Spiro-OMeTAD (150nm)/MoO3The device of (12nm)/Ag (100nm).
Examples 1 to 3 preparation two-layer electronic transport layer full-inorganic perovskite solar battery device junction composition and Energy diagram is as shown in fig. 1.Wherein, the left side is device junction composition in Fig. 1, and the right is energy diagram.Energy level map analysis from the right Find out, SnO2Between full-inorganic perovskite and non-optimized interfacial contact, SnO2Conduction level (- 4.43eV) is led with perovskite Band energy level (- 4.16eV) mismatches, and has larger energy level drop, so energy loss is larger, photovoltaic device open-circuit voltage is smaller. And in SnO2The conduction level (- 4.21eV) of the ZnO layer introduced between perovskite and perovskite material conduction level (- It 4.43eV) more matches, SnO2, ZnO, superior staged energy level is formd between perovskite, energy loss reduces.
The luminescence generated by light of the light absorbing layer of full-inorganic perovskite solar cell device prepared by embodiment 1 and comparative example 1 The photoluminescence spectra figure of spectrum and perovskite is shown in Fig. 2.It can find out from spectrum: CsPbI2Br perovskite has one to be located at The strong peak of 640nm or so, and for the SnO in comparative example 12/CsPbI2For Br structure, peak intensity is substantially reduced, and main cause is SnO2As electron transfer layer, can rapidly the electronics in perovskite light absorbing layer be extracted and be transferred out, greatly reduced Wherein hole-electron is compound, this is advantageous preparation high-performance solar cell；SnO in embodiment 12@ZnO/CsPbI2Br The peak intensity of structure further decreases, and quickening is quenched in luminescence generated by light, illustrate this kind of structure improve extraction to electronics with Transmittability, hole-electron is compound in calcium titanium ore bed is further reduced.
The transient state photocurrent experiment curv of full-inorganic perovskite solar cell device prepared by embodiment 1 and comparative example 1 As shown in figure 3, its transient photocurrents experiment curv is as shown in Figure 4.In conjunction with Fig. 3 and Fig. 4 it follows that SnO in comparative example 12/ CsPbI2The charge recombination service life is 2.4 μ s in perovskite light absorbing layer in Br structure, and the charge extraction time is 0.45 μ s；Embodiment SnO in 12@ZnO/CsPbI2The charge recombination service life is 4.3 μ s in perovskite light absorbing layer in Br structure, and the charge extraction time is 0.36μs.The two is compared, and illustrates SnO2@ZnO/CsPbI2More accurate level-density parameter can effectively inhibit charge multiple in Br structure Conjunction process obtains lower charge trap and higher charge extraction efficiency.The embodiment 1 shown in this result and Fig. 2 is made Peak intensity reduction of the light absorbing layer of the solar cell device obtained at the place 640nm or so is consistent, and charge recombination is reduced.
The Current density-voltage (I-V) of full-inorganic perovskite solar cell device prepared by embodiment 1 and comparative example 1 (b) shown in (a) in indicatrix such as Fig. 5, in external quantum efficiency (EQE) spectrogram such as Fig. 5.Made from comparative example 1 SnO2/CsPbI2Br structure devices, in AM 1.5,100mW/cm2Standard test condition under, open-circuit voltage 1.06V, short circuit Electric current is 14.7mA/cm2, fill factor 75.7%, photoelectric conversion efficiency 11.9%, maximum external quantum efficiency (EQE) Close to 90%, but for band gap 1.92eV (band gap=(- 4.16eV)-(- 6.08eV)=1.92eV) CsPbI2Br calcium For titanium ore battery, open-circuit voltage only has 1.06V, energy loss greatly (energy loss=1.92eV-e1.06V= 0.86eV)；SnO made from embodiment 12@ZnO/CsPbI2Br structure devices, in AM 1.5,100mW/cm2Standard testing item Under part, open-circuit voltage 1.23V, short circuit current 15.0mA/cm2, fill factor 78.8%, photoelectric conversion efficiency is 14.6%, maximum external quantum efficiency (EQE) is more than 90%.
The performance parameter of device prepared by comparative example 1~2, Examples 1 to 3 is as shown in table 1.It can be obtained by Fig. 5 and table 1 Out, by the addition of ZnO layer, the open-circuit voltage of photovoltaic device can be made to be considerably improved, is eventually exhibited as being added The photovoltaic device of ZnO electron transfer layer has higher photoelectric conversion efficiency, and the open-circuit voltage of photovoltaic device is substantially mentioned by 1.06V Height arrives 1.23V, and short circuit current and fill factor also have small increase, and device photoelectric transfer efficiency is increased to from 11.9% 14.6%.
The Current density-voltage of full-inorganic perovskite solar cell device prepared by Examples 1 to 3 and comparative example 1~2 (I-V) indicatrix is as shown in Figure 6.By Fig. 6 and table 1 it follows that bielectron transport layer SnO2The full-inorganic perovskite of@ZnO The photoelectric conversion efficiency of solar battery is better than single layer SnO2The device of electron transfer layer and single layer ZnO electron transfer layer, and Bielectron transport layer SnO2There are an optimum thickness to arrange in pairs or groups for the thickness of@ZnO, 30nm SnO in embodiment 12With 10nm ZnO's Effect is best, device photoelectric transfer efficiency highest.
1 device parameter performance list of table
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (10)

1. a kind of full-inorganic perovskite solar battery, which is characterized in that full-inorganic perovskite solar cell device structure by Under to it is upper successively include substrate, cathode layer, with a thickness of the SnO of 10~30nm2Electron transfer layer, the ZnO with a thickness of 10~30nm Electron transfer layer, perovskite light absorbing layer, hole transmission layer, anode modification layer and anode layer.
2. full-inorganic perovskite solar battery according to claim 1, which is characterized in that the perovskite light absorbing layer For CsPbI3-xBrx, 0≤x≤3；The perovskite light absorbing layer with a thickness of 300~400nm.
3. full-inorganic perovskite solar battery according to claim 1 or 2, which is characterized in that the substrate is glass Or transparent plastic film；The oxidation that the cathode layer is the SnO 2 thin film of indium doping, the SnO 2 thin film of Fluorin doped, aluminium adulterate One of zinc film, metallic silver or gold thin film.
4. full-inorganic perovskite solar battery according to claim 3, which is characterized in that the hole transmission layer is to mix The miscellaneous 2,2' for having 4- tert .-butylpyridine and double trifluoromethanesulfonimide lithium salts, [N, N- bis- (4- methoxyphenyl) ammonia of 7,7'- tetra- Base] two fluorenes film of -9,9'- spiral shell；The anode modification layer is Electrochromic Molybdenum Oxide Coatings；The anode layer is metallic silver.
5. the preparation method of the described in any item full-inorganic perovskite solar batteries of Claims 1 to 4, which is characterized in that packet Include following steps:
(1) cathode layer is prepared by solution processing method or vacuum vapour deposition on substrate；
(2) by SnO2Solution forms SnO by solution processing method on cathode layer2Electron transfer layer；
(3) butanol solution of ZnO nanoparticle is taken, solution processing method SnO made from step (2) is then passed through2Electron-transport ZnO electron transfer layer is formed on layer, then in 145~155 DEG C of 25~30min of thermal anneal process；
(4) pass through solution processing method or vacuum evaporation on step (3) the ZnO electron transfer layer obtained Jing Guo thermal anneal process Method sequentially forms perovskite light absorbing layer, hole transmission layer, anode modification layer and anode layer, obtains the full-inorganic perovskite too Positive energy battery.
6. the preparation method of full-inorganic perovskite solar battery according to claim 5, which is characterized in that step (4) The preparation step of the perovskite light absorbing layer are as follows: press CsPbI first3-xBrx, the molecular formula of 0≤x≤3, in CsBr, PbI2、 CsI and PbBr2It is middle to select corresponding raw material mixing, it is re-dissolved in organic solvent and forms perovskite precursor solution, before perovskite It drives liquid solution to be coated on ZnO electron transfer layer, add at 240~260 DEG C again after 40s~1min is first heated at 50~55 DEG C Hot 10s~1min forms perovskite light absorbing layer.
7. the preparation method of full-inorganic perovskite solar battery according to claim 6, which is characterized in that described organic Solvent be one or more of dimethyl sulfoxide, n,N-Dimethylformamide, the perovskite precursor solution it is dense Degree is 1.0~1.5mol L-1。
8. the preparation method of full-inorganic perovskite solar battery according to claim 5, which is characterized in that step (2) The SnO2Solution is the SnO of 15wt%2Aqueous colloidal dispersion, the butanol solution of step (3) described ZnO nanoparticle it is dense Degree is 5mg mL-1。
9. the preparation method of full-inorganic perovskite solar battery according to claim 5, which is characterized in that step (1), (2), solution processing method described in (3) and (4) is that spin coating, brushing, spraying, dip-coating, roller coating, silk-screen printing, printing and ink-jet are beaten One of print.
10. the preparation method of full-inorganic perovskite solar battery according to claim 5, which is characterized in that step (1) (4) vacuum degree of the vacuum vapour deposition is 10-6~10-7Pa。
CN201810897148.8A 2018-08-08 2018-08-08 A kind of full-inorganic perovskite solar battery and preparation method thereof Pending CN109065733A (en)

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CN113035991A (en) * 2021-03-01 2021-06-25 长沙理工大学 Low-temperature preparation CsPbI3Method for flexible perovskite solar cell
CN113889574A (en) * 2021-12-03 2022-01-04 中国华能集团清洁能源技术研究院有限公司 Preparation method and application of perovskite material layer in concentrating perovskite solar cell

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