CN108305948B - Perovskite material multi-quantum well structure regulation method and application and device thereof - Google Patents
Perovskite material multi-quantum well structure regulation method and application and device thereof Download PDFInfo
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Abstract
The invention discloses a perovskite material multi-quantum well structure regulation method based on film post-treatment, and application and a device thereof, wherein the perovskite material multi-quantum well structure is regulated through a film post-treatment process; the selected material is perovskite material capable of forming multiple quantum well structure by self-assembly, and the material is made of AX1、BX2And MX3 2Prepared according to the molar ratio of a to b to c, wherein A is R1‑Y+，R1‑Is an aliphatic hydrocarbon group having 1 to 50 carbon atoms, an alicyclic hydrocarbon group having 5 to 100 carbon atoms, an optionally substituted aryl group having 6 to 100 carbon atoms or an optionally substituted heterocyclic group having 3 to 100 carbon atoms, Y+Is any one of amine and organic cation containing N heterocycle; b is methylamine, formamidine or metal ions; m is a metal element; x1X2X3Is a halogen element; the film post-treatment conditions were: one or the combination of heating annealing, solvent annealing and vacuum drying; the optimization of the device efficiency can be realized through the regulation and control of the multiple quantum well structure.
Description
Technical Field
An organic-inorganic hybrid perovskite material, in particular to a perovskite material multi-quantum well structure regulation method based on film post-treatment, application and a device thereof.
Background
In recent years, organic-inorganic hybrid perovskite materials have become "stars" in the field of solar cells, the device performance has been rapidly developed, and the energy conversion efficiency of the photovoltaic device has broken through 22% at present. Except in the photovoltaic field, the perovskite material also draws people's extensive attention in the field of luminescence, but at present, the device efficiency and stability are lower, and new materials and new structures are to be adopted to improve the device performance.
Recently, perovskite light emitting devices having a multiple quantum well structure have exhibited advantages of high efficiency and stability (chinese patent application No. 201610051400.4), however, in the current process of manufacturing a perovskite device having a multiple quantum well structure, there is no simple and effective method of adjusting the quantum well structure. Although the method for regulating and controlling the quantum well structure in the traditional inorganic luminescence can be used for reference, the preparation condition of the inorganic quantum well is harsh, the cost is high, and the preparation of devices with low cost and large area is not facilitated. Therefore, it is necessary to further provide a method for optimizing the quantum well structure to improve the performance of the perovskite device.
Disclosure of Invention
The invention aims to solve the technical problem of providing a perovskite material multi-quantum well structure regulation method based on thin film post-treatment, and application and devices thereof.
The technical scheme of the invention is as follows:
a perovskite material multiple quantum well structure regulation and control method based on film post-processing is disclosed, wherein the perovskite material multiple quantum well structure is regulated through a film post-processing process; the selected material is perovskite material capable of forming multiple quantum well structure by self-assembly, and the material is made of AX1、BX2And MX3 2Prepared according to the molar ratio of a to b to c, wherein A is R1-Y+，R1-Is an aliphatic hydrocarbon group having 1 to 50 carbon atoms, an alicyclic hydrocarbon group having 5 to 100 carbon atoms, an optionally substituted aryl group having 6 to 100 carbon atoms or an optionally substituted heterocyclic group having 3 to 100 carbon atoms, Y+Is any one of amine and organic cation containing N heterocycle; b is methylamine, formamidine or metal ions; m is a metal element; x1X2X3Is a halogen element; the film post-treatment conditions were: one or the combination of heating annealing, solvent annealing and vacuum drying; the optimization of the device efficiency can be realized through the regulation and control of the multiple quantum well structure.
The method for regulating and controlling the multi-quantum well structure comprises the following heating and annealing conditions: and (3) placing the substrate coated with the precursor solution on a heating table at a certain temperature for 0-5 h.
The solvent annealing conditions of the multi-quantum well structure regulation and control method are as follows: and placing the substrate coated with the precursor solution in a container keeping a solvent atmosphere for 0-24 h.
The method for regulating and controlling the multi-quantum well structure comprises the following vacuum drying conditions: and placing the substrate coated with the precursor solution in a vacuum chamber for 0-24 h.
The regulation and control method of the multiple quantum well structure and the used representative material AX1Is C10H7CH2NH3I、C10H7CH2NH3Br、C6H5CH2NH3I、C6H5(CH2)2NH3I、C6H5(CH2)4NH3I，BX2Is CH3NH3I、NH2CH＝NH2I、CsI、NH2CH＝NH2Br、NH2CH＝NH2Cl、CH3NH3Br、CH3NH3Cl、CsBr、CsCl，MX3 2Is PbI2、PbBr2、PbCl2Including but not limited to.
The application of any of the regulation and control methods regulates the perovskite material multi-quantum well structure through a film post-treatment process.
A device made according to any of the methods of modulation.
The invention provides a simple film post-processing method aiming at the requirement of adjusting a perovskite film multi-quantum well structure, can realize the regulation and control of the perovskite material multi-quantum well structure, and optimizes the film forming performance and the photoelectric performance of the perovskite film, thereby improving the performance of a perovskite light-emitting device.
Drawings
FIG. 1 is a schematic diagram of the formation of a multiple quantum well structure of a perovskite material provided by the present invention;
FIG. 2 is an absorption spectrum of the perovskite thin film of example 1 provided by the present invention;
FIG. 3 is a photoluminescence spectrum of a perovskite thin film of example 1 provided by the present invention;
FIG. 4 is an absorption spectrum of the perovskite thin film of example 2 provided by the present invention;
FIG. 5 is a photoluminescence spectrum of a perovskite thin film of example 2 provided by the present invention;
FIG. 6 is an absorption spectrum of a perovskite thin film of example 3 provided by the present invention;
FIG. 7 is a photoluminescence spectrum of a perovskite thin film of example 3 provided by the present invention;
FIG. 8 is an absorption spectrum of a perovskite thin film of example 4 provided by the present invention;
FIG. 9 is a photoluminescence spectrum of a perovskite thin film of example 4 provided by the present invention;
FIG. 10 is an X-ray diffraction spectrum of the perovskite thin film of example 4 provided by the present invention;
FIG. 11 is an AFM image of a perovskite thin film of example 4 provided by the present invention;
FIG. 12 is a schematic structural view of a perovskite-type device of example 5 provided by the present invention;
FIG. 13 is the electroluminescence spectrum of the MQW LED device of example 5 provided by the present invention;
FIG. 14 is a voltage-current density-radiation intensity relationship curve for a MQW LED device of example 5 provided by the present invention;
FIG. 15 is a current density-external quantum efficiency relationship curve for the MQW LED device of example 5 provided by the present invention;
Detailed Description
The present invention will be described in detail with reference to specific examples.
The technical scheme of the invention provides a method for adjusting a perovskite material multi-quantum well structure through a film post-treatment process. The selected material is perovskite material capable of forming multiple quantum well structure by self-assembly, and the material is made of AX1、BX2And MX3 2Prepared according to the molar ratio of a to b to c, wherein A is R1-Y+，R1-Is an aliphatic hydrocarbon group having 1 to 50 carbon atoms, an alicyclic hydrocarbon group having 5 to 100 carbon atoms, an optionally substituted aryl group having 6 to 100 carbon atoms or an optionally substituted heterocyclic group having 3 to 100 carbon atoms, Y+Is any one of amine and organic cation containing N heterocycle; b is methylamine, formamidine or metal ions; m is a metal element; x1X2X3Is a halogen element; when X is substituted1、X2、X3When all is represented by X, the structural formula can be represented by A2Bn- 1MnX3n+1And n is the number of layers of the inorganic framework of the perovskite material. Representative Material AX used1Is C10H7CH2NH3I、C10H7CH2NH3Br、C6H5CH2NH3I、C6H5(CH2)2NH3I、C6H5(CH2)4NH3I，BX2Is CH3NH3I、NH2CH＝NH2I、CsI、NH2CH＝NH2Br、NH2CH＝NH2Cl、CH3NH3Br、CH3NH3Cl、CsBr、CsCl，MX3 2Is PbI2、PbBr2、PbCl2Including but not limited to. Film post-treatment conditions: the heating annealing time is 0-5h, the solvent annealing time is 0-24h, and the vacuum drying time is 0-24 h. As shown in fig. 1, the perovskite multiple quantum well structure can be tuned by post-treatment. The optimization of the device efficiency can be realized through the regulation and control of the multiple quantum well structure.
Example 1 a perovskite multiple quantum well structure on a quartz substrate was modulated using a thermal annealing method.
C is to be10H7CH2NH3I、NH2CH＝NH2I (FAI) and PbI2Preparing precursor solution (NFPI) according to the mol ratio of 2:1:27) Spin-coating the precursor solution on a quartz substrate, annealing at 100 ℃ on a heating table for 0min, 5min, 10min, 20min, 30min and 60min respectively, and obtaining the perovskite thin films with different multi-quantum well structures after annealing.
As shown in fig. 2, NFPI after annealing7The film has obvious exciton absorption peak at 567nm, which shows that quantum well structure is formed at the moment, and more n-2 quantum wells exist, the figure also shows that an absorption peak exists at 632nm, which corresponds to the quantum well structure with n-3, and meanwhile, a certain absorption exists near 774nm, which shows that large n quantum well structure (narrow energy gap) also exists in the material, and the large n quantum well structure is close to the junction of the three-dimensional perovskite materialAnd (5) forming. On the unannealed (0 min annealing time) film, no obvious exciton absorption peak was seen, and no absorption of the three-dimensional perovskite material was observed, indicating that no multi-quantum well perovskite structure had been formed inside the unannealed material. FIG. 3 is NFPI7The photoluminescence spectrum of the thin film can be seen that the main peak of the luminescence of the thin film is red-shifted from 743nm to 772nm and is close to three-dimensional FAPBI when the annealing time is increased from 5min to 60min3The luminescence peak of (1) corresponds to the luminescence of a large n quantum well component, which shows that in the layered perovskite material, the amount of a narrow energy gap quantum well component in the thin film is continuously increased in the process of increasing the annealing time from 0min to 60min, namely the width of the narrow energy gap quantum well is widened. In addition to the main emission peak, emission peaks at 516nm, 577nm, 646nm, etc. and a shoulder peak at 688nm were present in the thin film at the same time, and the emission peaks were corresponding to the emission of quantum well structures with n being 1, 2, 3, and 4, respectively. By combining the absorption spectrum, the fact that the multi-quantum well structure in the film can be regulated and controlled by changing the annealing time of the film can be found, and the regulated and controlled multi-quantum well structure can still realize the energy transfer from the quantum well with larger energy to the quantum well with smaller exciton energy.
Example 2 a solvent annealing process was used to manipulate the perovskite multiple quantum well structure on a ZnO/PEIE substrate.
C is to be10H7CH2NH3I、NH2CH＝NH2I (FAI) and PbI2Preparing precursor solution (NFPI) according to the mol ratio of 2:1:27) And spin-coating the precursor solution on a quartz substrate. A closed container having a volume of about 500mL was selected, an open vial containing 100. mu.L of DMF solution was placed in the container, and the container was placed at a constant temperature of 50 ℃ to maintain an atmosphere of DMF in the container. And placing the prepared sample in a closed container, sequentially and respectively placing for 0h, 1h, 2h, 6h, 12h and 24h, and taking out to obtain the perovskite thin film with different multi-quantum well structures.
NFPI after solvent annealing, as shown in FIG. 47The film had a distinct exciton absorption peak at 567nm, corresponding to an n-2 quantum well structure, indicating that a quantum well structure had formed at this time. It can also be seen that there is also an absorption peak at 632nm, corresponding to n ═ n3, and meanwhile, a certain absorption is generated near 805nm, which shows that a large n quantum well structure (narrow energy gap) exists in the material, and the large n quantum well structure is close to the structure of a three-dimensional perovskite material. FIG. 5 shows NFPI7The photoluminescence spectra of the films show that as the annealing time increased from 1h to 24h, the main peak of the film luminescence red-shifted from 786nm to 792nm, corresponding to the luminescence of the large n quantum well component. In the layered perovskite material, in addition to the main emission peak, emission peaks at positions of 518nm, 572nm, 639nm, etc. and shoulder peaks at 684nm are present in the thin film at the same time, and correspond to emission of quantum well structures where n is 1, 2, 3, and 4, respectively. The optical characterization result shows that the perovskite thin film with the quantum well structure can be obtained by the solvent annealing method, and the function of regulating and controlling the multi-quantum well structure in the thin film can be achieved by changing the solvent treatment time of the thin film.
Example 3 a vacuum drying method was used to regulate the perovskite multiple quantum well structure on a quartz substrate.
C is to be10H7CH2NH3I、NH2CH＝NH2I (FAI) and PbI2Preparing precursor solution (NFPI) according to the mol ratio of 2:1:27) And spin-coating the precursor solution on a quartz substrate. And placing the spin-coated sample in a vacuum chamber, vacuumizing the vacuum chamber to enable the vacuum chamber to reach a vacuum atmosphere of less than 10Pa, and taking out the samples placed in the vacuum atmosphere for 0h, 1h, 2h, 5h, 10h and 20h in sequence to obtain the perovskite thin films with different multi-quantum well structures.
As shown in fig. 6, NFPI after annealing7The film has obvious exciton absorption peak at 570nm and more n-2 quantum wells, and the figure also shows that an absorption peak exists at 639nm, which corresponds to a quantum well structure with n-3. FIG. 7 shows NFPI7The photoluminescence spectrogram of the thin film can see that the main peak of the luminescence of the thin film is red-shifted from 752nm to 780nm corresponding to the luminescence of a large n quantum well component as the annealing time is increased from 1h to 20h, which shows that in the layered perovskite material, the amount of the narrow-energy-gap quantum well component in the thin film is continuously increased in the process of increasing the annealing time to 20h, namely the width of the narrow-energy-gap quantum well is widened. Except for the main peak of luminescenceIn addition, the thin film has emission peaks at 516nm, 576nm, 646nm, etc. and a shoulder peak at 688nm, which correspond to emission of quantum well structures with n being 1, 2, 3, and 4, respectively. The optical characterization result shows that the perovskite thin film with the multi-quantum well structure can be obtained by a vacuum drying method, and the function of regulating the multi-quantum well structure in the thin film can be achieved by changing the drying time of the thin film.
Example 4 a heating annealing process was used to manipulate the perovskite multiple quantum well structure on a ZnO/PEIE substrate.
The perovskite thin film is prepared on a ZnO/PEIE substrate, and the morphology and the luminescence property of the perovskite thin film are researched. The preparation method comprises the following steps:
①, ultrasonically cleaning the transparent conductive substrate ITO glass by using an acetone solution, an ethanol solution and deionized water, and drying by using dry nitrogen after cleaning;
② transferring the dried substrate into a vacuum chamber, and performing ultraviolet ozone pretreatment on the ITO glass for 10 minutes under the oxygen pressure environment;
③ respectively spin-coating ZnO and PEIE on the processed substrate, annealing, and transferring to a nitrogen glove box;
④ mixing C with C10H7CH2NH3I、NH2CH＝NH2I (FAI) and PbI2Precursor solution (NFPI) with a molar ratio of 2:1:27) Spin coating on ZnO/PEIE, heating and annealing at 100 deg.C for 0min, 5min, 10min, 20min, 30min and 60min respectively, and annealing to obtain perovskite films with different multiple quantum well structures.
FIG. 8 is NFPI at different annealing times7And (3) a film absorption spectrum prepared from the precursor solution. As shown, NFPI after annealing7The thin film has a distinct exciton absorption peak at 567nm, which indicates that a large number of quantum well structures with n-2 exist in the material. As the annealing time increases, the exciton absorption peak at n-2 gradually decreases, meaning that the composition of the quantum well structure at n-2 decreases. At the same time, obvious absorption near 785nm can be seen, and the absorption is enhanced with the increase of annealing time, which indicates the existence of large n quantum wells in the material, and the larger n component is increased with the increase of annealing timeThe more. FIG. 9 shows that the main photoluminescence peak of the thin film is near 787nm, close to FAPBI in three dimensions3The annealing time is increased, the main peak of the luminescence shows red shift from 778nm to 791nm, and the main peak is closer to FAPBI3The luminescence peak of (1) shows that the amount of the narrow-band-gap quantum well component in the thin film is continuously increased along with the annealing process in the multi-quantum-well perovskite material, and the width of the narrow-band-gap quantum well is widened. In addition, the thin film also has luminescence peaks at 516nm, 574nm and 635nm and a shoulder peak at 681nm, which correspond to perovskite luminescence with n being 1, 2, 3 and 4 quantum well structures respectively. The annealing time increases and the luminescence corresponding to n 2, 3 and 4 is weakened, which shows that the quantum well components of n 2, 3 and 4 in the film are reduced. By combining the absorption spectrum, the fact that the annealing time of the film is changed to play a role in regulating and controlling the multi-quantum well structure in the film can be found, and the regulated and controlled multi-quantum well structure can still achieve the effect that energy is transferred from the quantum well with larger energy to the quantum well with smaller energy.
FIG. 10 corresponds to NFPI at different annealing times7X-ray diffraction spectra (XRD) of the thin film. It was found that the XRD peaks at 13.88 ° and 28.08 ° become stronger with increasing annealing time, and the grains become larger as seen by Scherrer's formula. Contrasting FAPBI3XRD data of (a), peaks at 13.88 ° and 28.08 ° close to the (001) and (002) diffraction peaks of the three-dimensional perovskite, indicating that in NFPI7The large n component in the film is more and more, the crystallinity is better and better, and the film is closer to three-dimensional FAPBI3. In addition, weak diffraction peaks were also observed in the 5min and 10min annealed films near the 11.54 °, 16.20 °, 25.72 ° and 29.29 ° positions, corresponding to layered perovskite crystals of small n quantum well structure. But the four diffraction peaks disappeared gradually at longer annealing times, indicating a decrease in the small n quantum well composition (wide bandgap). FIG. 11 shows NFPI7Atomic Force Microscopy (AFM) images of thin films at different annealing times. It can be seen that the roughness of the film gradually increases as the annealing time increases, but R of all the films increasesrmsThe parameters are all less than 5nm, which indicates NFPI7The material has good film forming property. It is evident from the AFM phase diagram that as the annealing time of the film increases from 0min to 10min, there is crystallizationThe grains gradually increase, and in combination with the XRD pattern, the increased grains correspond to a large n quantum well structure. The annealing treatment is shown to play a role in regulating the quantum well structure.
Example 5 device based on multiple quantum well perovskite material.
The structure of the device is shown in FIG. 12, which comprises a transparent substrate 1-glass, a cathode layer 2-ITO, an electron transport layer 3-ZnO/PEIE and a light emitting layer 4-NFPI from bottom to top in sequence7Hole transport layer 5-TFB and anode layer 6-MoOxand/Au. The preparation method comprises the following steps:
(1) and ultrasonically cleaning the transparent conductive substrate ITO glass by using an acetone solution, an ethanol solution and deionized water, and drying by using dry nitrogen after cleaning. Wherein the sheet resistance of the ITO film of the anode layer is 15 omega/cm2；
(2) Transferring the dried substrate into a vacuum chamber, and carrying out ultraviolet ozone pretreatment on the ITO glass for 10 minutes under the oxygen pressure environment;
(3) and spin-coating a ZnO film on the treated ITO substrate, and then transferring the ITO substrate to a heating table at 150 ℃ for annealing for 30 min. Spin-coating a PEIE film on the ZnO film, annealing for 10min, and then transferring the film into a nitrogen glove box;
(4) c is to be10H7CH2NH3I、NH2CH＝NH2I (FAI) and PbI2Precursor solution (NFPI) with a molar ratio of 2:1:27) Spin coating on ZnO/PEIE, annealing at 100 deg.C for 0min, 5min, 10min, 20min, 30min and 60min respectively, and annealing to obtain perovskite films with different multiple quantum well structures.
(5) TFB solution spin coating on NFPI7And the film is used as a hole transport layer.
(6) MoO is carried out after the preparation of each functional layer is finishedxPreparation of Au composite electrode with air pressure of 6 x 10-7Torr, the deposition rate was 0.1nm/s, and the deposition rate and thickness were monitored by a film thickness meter.
(7) The prepared device was encapsulated in a glove box under 99.9% nitrogen atmosphere.
(8) And testing the current-voltage-radiation intensity characteristic of the device, and simultaneously testing the luminescence spectrum parameters of the device.
FIG. 13 shows the use of NFPI7The Electroluminescence (EL) spectrum of the light emitting device prepared from the precursor has only luminescence of a large n quantum well structure in an EL diagram, but does not have luminescence of a small n quantum well structure in a PL diagram, which shows that when carriers are injected from an electrode, the carriers migrate to the large n quantum well structure as a radiative recombination luminescence center to perform recombination luminescence. The light-emitting position of the device annealed for 5min is near 768nm, the light-emitting position of the device continuously annealed for 10min is red-shifted to be near 785nm, the light-emitting position of the device annealed for 30min is red-shifted to be 787nm, and the light-emitting position is consistent with the PL spectrum of the thin film, so that the content of the narrow-bandgap quantum well in the thin film with long annealing time is increased, and the well width is widened. FIG. 14 shows NFPI7The characteristic curve of voltage-current density-radiation intensity of the multi-quantum well perovskite device is that several devices have very low turn-on voltage (less than 1.5V), and after the device is lightened, the current density and the radiation intensity rise rapidly, which indicates the high-efficiency carrier injection and migration efficiency in the device. FIG. 15 is a characteristic curve diagram of current-external quantum efficiency of the device, and the external quantum efficiency of the device prepared after annealing the thin film for 10min reaches the maximum of 8.6%.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.
Claims (3)
1. A perovskite material multiple quantum well structure regulation and control method based on film post-processing is characterized in that the perovskite material multiple quantum well structure is regulated through a film post-processing process; the selected material is perovskite material capable of forming multiple quantum well structure by self-assembly, and the material is made of AX1、BX2And MX3 2Prepared according to the molar ratio of a to b to c, wherein A is R1-Y+，R1-Is an aliphatic hydrocarbon group having 1 to 50 carbon atoms, an alicyclic hydrocarbon group having 5 to 100 carbon atoms, an optionally substituted aryl group having 6 to 100 carbon atoms or an optionally substituted heterocyclic group having 3 to 100 carbon atoms, Y+Is any one of amine and organic cation containing N heterocycle; b isMethylamine, formamidine or metal ions; m is a metal element; x1X2X3Is a halogen element; the film post-treatment conditions were: one or the combination of heating annealing, solvent annealing and vacuum drying; the optimization of device efficiency can be realized through the regulation and control of a multi-quantum well structure; the heating and annealing conditions are as follows: placing the substrate coated with the precursor solution on a heating table for direct annealing, wherein the annealing temperature is determined by the type of the material and the substrate, and the time is 0-5 h; the solvent annealing conditions were: placing the substrate spin-coated with the precursor solution in a container keeping a solvent atmosphere for 0-24 h; the vacuum drying conditions were: and placing the substrate coated with the precursor solution in a vacuum chamber for 0-24 h.
2. The multiple quantum well structure regulation method of claim 1, wherein AX is1Is C10H7CH2NH3I、C10H7CH2NH3Br、C6H5CH2NH3I、C6H5(CH2)2NH3I、C6H5(CH2)4NH3One of I, BX2Is CH3NH3I、NH2CH＝NH2I、CsI、NH2CH＝NH2Br、NH2CH＝NH2Cl、CH3NH3Br、CH3NH3One of Cl, CsBr and CsCl, MX3 2Is PbI2、PbBr2、PbCl2One of them.
3. Use of a modulation and control method according to claim 1 or 2, characterized in that the perovskite material multiple quantum well structure is modulated by a thin film post-treatment process.
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