CN113972329B - Surface plasmon polariton synergistically enhanced quasi-two-dimensional perovskite light-emitting diode and preparation method thereof - Google Patents

Surface plasmon polariton synergistically enhanced quasi-two-dimensional perovskite light-emitting diode and preparation method thereof Download PDF

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CN113972329B
CN113972329B CN202111094210.8A CN202111094210A CN113972329B CN 113972329 B CN113972329 B CN 113972329B CN 202111094210 A CN202111094210 A CN 202111094210A CN 113972329 B CN113972329 B CN 113972329B
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CN113972329A (en
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张曙光
诸葛有强
谭毅瑛
彭俊彪
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South China University of Technology SCUT
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Abstract

The invention discloses a quasi-two-dimensional perovskite light-emitting diode with synergistically enhanced surface plasmons and a preparation method thereof, wherein the perovskite light-emitting device sequentially comprises an anode, a hole injection layer, a two-dimensional atomic crystal material layer, a perovskite light-emitting layer, a metal nanoparticle core-shell structure layer, an electron transmission layer, an electron injection layer and a cathode from bottom to top; the two-dimensional atomic crystal material comprises a transition metal sulfide two-dimensional crystal, the perovskite luminescent layer is a quasi two-dimensional perovskite, and the quasi two-dimensional perovskite is realized by adding organic halide ammonium salt into a precursor; the metal nano particle core-shell structure layer comprises a metal nano particle core layer and a shell layer; the metal nano-particle core layer is one of Au and Ag or AlAg alloy, and the shell layer is SiO 2 (ii) a The surface ligand of the metal nano-particle core-shell structure layer is polystyrene. The preparation method has simple process and lower cost, and the luminous performance of the obtained light-emitting diode is obviously improved.

Description

Surface plasmon polariton synergistically enhanced quasi-two-dimensional perovskite light-emitting diode and preparation method thereof
Technical Field
The invention relates to the field of light emitting diodes, in particular to a surface plasmon polariton synergistically enhanced quasi-two-dimensional perovskite light emitting diode and a preparation method thereof.
Background
In recent years, metal halide perovskite materials have attracted attention for application to photoelectric devices such as photodetectors, light emitting diodes, and X-ray detectors due to their excellent properties such as adjustable spectral absorption range, long diffusion length, and high fluorescence quantum yield, and have become one of the research hotspots in academia. However, the LED device prepared based on the three-dimensional perovskite material has a perovskite light emitting layer with smaller exciton confinement energy and more surface defects, resulting in generally lower quantum yield. Researches show that perovskite with a quasi-two-dimensional structure can be prepared by introducing long-chain organic cations, and a structure similar to a multi-quantum well is formed between the perovskite and a ligand, so that the photoelectric property of a device can be effectively improved; on the other hand, a high performance device must satisfy the charge injection balance of electrons and holes as much as possible, and satisfy that the device has better stability under the condition of stable current injection. Therefore, the research on how to improve the stability of the device while keeping the high external quantum efficiency of the device and effectively simplify the preparation process cost of the device has very important significance.
At present, the metal halide perovskite light emitting diode still faces the bottlenecks of low luminous efficiency and stability. In order to further improve the performance of the device, people usually take measures such as preparing a quasi-two-dimensional light-emitting layer by A-site cation engineering, mixing ligand engineering and the like and improve the light-emitting efficiency of the device to a certain extent. Meanwhile, the Fuzhou university in 2020 discloses a preparation method of a perovskite light-emitting diode device containing silver nanoparticles. Specifically, ag nano-particles are synchronously synthesized in the process of preparing a perovskite precursor, and the Ag nano-particles are doped in a perovskite layer to hopefully prepare the high-performance perovskite light-emitting diode. However, the doping of Ag nano-particles can cause the defect density of the light-emitting layer to be increased, which is not favorable for the performance of the device. Therefore, how to prepare the high-efficiency metal halide perovskite light-emitting diode on the basis of maintaining a high-quality light-emitting layer becomes a key problem to be solved urgently.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a quasi-two-dimensional perovskite light-emitting diode with synergistically enhanced surface plasmons, and the performance and stability of the device are obviously improved.
The invention also aims to provide a preparation method of the quasi-two-dimensional perovskite light-emitting diode with the synergistically enhanced surface plasmons.
The purpose of the invention is realized by the following technical scheme:
a surface plasmon polariton synergistically enhanced quasi-two-dimensional perovskite light-emitting diode comprises an anode, a hole injection layer, a two-dimensional atomic crystal material layer, a perovskite light-emitting layer, a metal nanoparticle core-shell structure layer, an electron transmission layer, an electron injection layer and a cathode from bottom to top in sequence; the two-dimensional atomic crystal material comprises a transition metal sulfide two-dimensional crystal, the perovskite luminescent layer is a quasi two-dimensional perovskite, and the quasi two-dimensional perovskite is realized by adding organic halide ammonium salt into a precursor.
Preferably, the metal nanoparticle core-shell structure layer comprises a metal nanoparticle core layer and a shell layer; the metal nano-particle core layer is one of Au and Ag or AlAg alloy, and the shell layer is SiO 2 (ii) a The surface of the metal nano-particle core-shell structure layer is provided with a surface ligand, and the surface ligand is polystyrene.
Further preferably, the metal nanoparticles have a size of 5 to 30 nm;
further preferably, the size of the surface ligand of the metal nanoparticle core-shell structure layer is 10-100 nm.
Preferably, the quasi-two-dimensional perovskite material has a molecular formula of L 2 M x Pb 3 Br 10 L is monovalent organic ammonium ion, including PPA + 、PEA + 、PBA + 、i-BA + One or more of (A), M is MA + ,FA + , Cs + Wherein x =2 to 3.
Preferably, the two-dimensional crystal of transition metal sulfide comprises MoS 2 、WS 2 The thickness of the two-dimensional crystal is 0.5-10 nanometers;
preferably, the hole injection layer comprises PEDOT PSS, PVK, TPD or TFB.
Preferably, the electron injection layer is made of LiF material, and the thickness of the electron injection layer is 2-10 nanometers; the material of the electron transport layer comprises TPBi, BCP and PCBM, and the thickness of the electron transport layer is 50-200 nanometers.
Preferably, the anode substrate is an ITO substrate, an IZO substrate or an FTO substrate; the cathode is metal or metal oxide, and the thickness of the cathode is 80-200nm.
More preferably, the cathode is Al.
The preparation method of the quasi-two-dimensional perovskite light-emitting diode with the synergistically enhanced surface plasmons comprises the following steps:
(1) Cleaning an anode substrate;
(2) Preparation of hole injection layer:
forming a hole injection layer film on the anode substrate by a spin coating process, and annealing to obtain a hole injection layer;
(3) Deposition of a two-dimensional atomic crystal material layer:
spin-coating two-dimensional atomic crystal dispersion liquid on the hole injection layer, and annealing to obtain a two-dimensional atomic crystal material layer;
(4) Preparation of perovskite luminescent layer:
dripping a quasi-two-dimensional perovskite precursor mixed solution on the two-dimensional atomic crystal material layer, spin-coating to form a film, and annealing to obtain a perovskite light-emitting layer;
(5) Preparing a metal nano particle core-shell structure layer:
preparing a metal nanoparticle core-shell structure by adopting a template method, wherein the metal nanoparticle core-shell structure layer is prepared by adopting a spin-coating method;
(6) Preparation of an electron transport layer:
evaporating an electronic transmission layer on the surface of the metal nanoparticle core-shell structure layer by adopting a vacuum evaporation method;
(7) Preparation of an electron injection layer:
vacuum thermal evaporation of an electron injection layer on the electron transport layer;
(8) Preparing a cathode:
the cathode is prepared by adopting a vacuum evaporation method, a sputtering method or ink-jet printing.
Preferably, the anode substrate in step (1) is one of an ITO substrate, an IZO substrate or an FTO substrate; the anode substrate cleaning method comprises the following specific steps: placing the anode substrate in the tetrahydroUltrasonically cleaning furan, isopropanol, washing liquid and deionized water, and then ultrasonically cleaning in isopropanol, wherein the ultrasonic time is 15-30 min each time; after the ultrasonic treatment is finished, the substrate is placed in an oven to be dried for more than 4 hours, and then the substrate is subjected to UV or O treatment for 15-20 min 2 -Plasma surface treatment;
preferably, the spin coating speed in the step (2) is 3000-4000 rpm, and the spin coating time is 30-40 s; the annealing temperature is 130-170 ℃, and the annealing time is 10-20min.
Further preferably, the spin-coating speed is 3000 rpm, the spin-coating dosage is 45 μ l, the spin-coating time is 30s, the annealing temperature is 150 ℃, and the annealing time is 15min.
Preferably, the two-dimensional atomic crystal dispersion liquid in step (3) is MoS 2 Dispersion liquid and MoS 2 Quantum dot solution, WS 2 Dispersion liquid, WS 2 A quantum dot solution; the solvent of the two-dimensional atomic crystal dispersion liquid is water, ethanol, DMF, IPA and NMP; the concentration of the two-dimensional atomic crystal dispersion liquid is 1-10mg/ml; the preparation process needs spin coating in a glove box, wherein the spin coating speed is 2000-5000 r/min, and the spin coating time is 30-100 seconds; the temperature of the annealing treatment is 50-150 ℃, and the time of the annealing treatment is 10-30 minutes;
further preferably, the spin-coating speed is 3000 rpm, the solution dosage is 50 μ l, the spin-coating time is 60 seconds, and annealing is carried out for 15 minutes at 80 ℃ after the spin-coating is finished.
Preferably, the quasi-two-dimensional perovskite precursor mixed solution in the step (4) comprises pbambr, MABr and PbBr 2 Wherein PBABR, MABr, pbBr 2 The molar ratio of (1-2) to (2-3) to (3) PBABR, MABr and PbBr 2 The total mass fraction of (1) is 3-10wt.%, and the solvent is anhydrous N, N-dimethylformamide or dimethyl sulfoxide; the spin coating speed is 2000-8000 rpm; the spin coating time is 30-100s; the annealing temperature is 30-80 ℃, and the annealing time is 10-40min.
The size of the metal nano particles with the metal nano particle core-shell structure in the step (5) is 5-30 nanometers, and the size of the surface polystyrene ligand is 10-100nm; the spin coating is carried out in a glove box; the concentration of the spin-coating solution is 5-20mg/ml, the rotating speed is 1000-3000 r/min, and the time is 30-200s.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) According to the quasi-two-dimensional perovskite light-emitting diode, the Au nuclear shell structure metal nanoparticles are introduced into the quasi-two-dimensional perovskite light-emitting diode, the injection efficiency of carriers is improved by utilizing the hot electron injection of the Au nanoparticles, the radiation recombination efficiency of excitons is improved by utilizing a strong local field around the nanoparticles, and finally the higher brightness and current efficiency of the quasi-two-dimensional perovskite light-emitting diode are realized.
(2) The invention obviously reduces the injection potential barrier of the current carrier by introducing the two-dimensional atomic crystal material, improves the injection balance of the charge and finally effectively improves the performance of the device.
(3) The preparation method is simple and effective, the cost of the device preparation process is obviously reduced, and the performance enhancement effect of the prepared quasi-two-dimensional perovskite light-emitting diode is obvious.
Drawings
Fig. 1 is a schematic structural diagram of a quasi-two-dimensional perovskite light emitting diode with synergistically enhanced surface plasmons according to an embodiment of the present invention.
Fig. 2 is a transmission electron microscope photograph of Au nanoparticles of example 1 of the present invention.
Fig. 3 is a current efficiency-current density relationship curve of the quasi-two-dimensional perovskite light emitting diode of example 1 of the present invention.
Fig. 4 is a current density-voltage relationship graph of a quasi-two-dimensional perovskite light emitting diode according to example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
As shown in fig. 1, the quasi-two-dimensional perovskite light emitting diode with synergistically enhanced surface plasmons of this embodiment has a structure that includes, from bottom to top, an anode 1, a hole injection layer 2, a two-dimensional atomic crystal material 3, a perovskite light emitting layer 4, a metal (alloy) nanoparticle core-shell structure layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode 8.
Surface plasmon polariton synergistically enhanced quasi-two-dimensional perovskite light emitting diode (MoS) of the present embodiment 2 @ Au), comprising the following steps:
(1) Cleaning an anode substrate:
the anode substrate in the step (1) is an ITO substrate. The method comprises the following specific steps of sequentially placing an anode substrate into tetrahydrofuran, isopropanol, washing liquor and deionized water for ultrasonic cleaning, and then placing the anode substrate into the isopropanol for ultrasonic cleaning, wherein the ultrasonic time is 15min each time; after the ultrasonic treatment is finished, the substrate is placed in an oven to be dried for more than 4 hours, and then O is carried out on the substrate for 15min 2 -Plasma surface treatment.
(2) Preparation of hole injection layer:
the preparation method of the hole injection layer in the step (2) comprises the following steps: and the hole injection layer polymer solution is PEDOT, namely PSS aqueous solution, is filtered by a 0.22 mu m aqueous filter head and then is dripped on the anode substrate to form a hole injection layer film by a spin coating process, the spin coating speed is 3000 r/min, the spin coating time is 30s, and the hole injection layer film is annealed for 15min at 130 ℃ in an atmospheric environment.
(3) Deposition of a two-dimensional atomic crystal matching layer:
the two-dimensional atomic crystal dispersion liquid in the step (3) is MoS 2 The solvent of the quantum dot solution is ethanol, the concentration of the solution is 5mg/ml, the solution needs to be spin-coated in a glove box in the preparation process, the preferred rotation speed of the spin-coating is 3000 r/min, the dosage of the solution is 50 mu l, the spin-coating time is 60 seconds, and annealing is carried out for 15 minutes at 80 ℃ after the spin-coating is finished.
(4) Preparation of perovskite luminescent layer:
in the preparation process, a certain amount of perovskite solution is dripped on the two-dimensional atomic crystal film by a liquid-transferring gun in a glove box, and annealing treatment is carried out after the preparation is finished so as to improve the film-forming quality of the perovskite film; the method comprises the following specific steps:
the novel quasi-two-dimensional perovskite precursor mixed solution in the step (4) is prepared from PBABR, MABr and PbBr 2 Preparation, wherein PBABR, MABr, pbBr 2 1.5, solutes PbBr, MABr and PbBr 2 Total mass fraction ofThe number was 5wt.%, and the solvent was anhydrous N, N-Dimethylformamide (DMF).
When the perovskite precursor mixed solution is spin-coated in a glove box, the content of water and oxygen in the glove box is not more than 0.1ppm, the spin-coating speed of the perovskite precursor mixed solution in the preparation process is 5000 revolutions per minute, and the spin-coating time is 60 seconds. And after the spin coating preparation is finished, annealing the substrate on a hot table in a glove box nitrogen environment at the annealing temperature of 60 ℃ for 10min.
(5) Preparation of metal nano-particle core-shell structure layer
The gold @ silicon dioxide nanoparticle core-shell structure is prepared by a template method, specifically referring to Nature Nanotech.8, 426-431 (2013), and the preparation method is as follows: firstly, beta-cyclodextrin (beta-cyclodextrin, beta-CD) and 2-bromo-2-methylpropiononate react to generate 21 Br-beta-CD, the 21 Br-beta-CD is used as an initiator, the Atom Transfer Radical Polymerization (ATRP) is firstly carried out with 4-vinylpyridine (4-VP) to generate P4VP star polymer molecules taking beta-CD as a core, then the Atom Transfer Radical Polymerization (ATRP) is carried out with tert-butyl acrylate (t-butyl acrylate, tBA) to generate star-shaped P4VP-b-PtBA high polymer molecules, the star-shaped P4VP-b-PtBA molecules can carry out atom transfer radical polymerization with Styrene molecules (Styrene) to generate star-shaped P4VP-b-PtBA-b-PS polymer molecules, and Au precursor HACl of tetrachloroaurate is added into the solution 4 Gold nanoparticles can be generated with PtBA-b-PS as ligand, ptBA in the ligand is hydrolyzed to form PAA, tetraethoxysilane (TEOS) is added as SiO 2 Finally generating a gold @ silicon dioxide nano particle core-shell structure taking Polystyrene (PS) as a ligand. The average size of the gold @ silicon dioxide nanoparticle core-shell structure in the preparation process is 10 nanometers, and the size of the surface polystyrene ligand is 15nm;
the nano-particle core-shell structure layer is prepared in a glove box by adopting a spin-coating method, the concentration of a solution in the spin-coating process is 10mg/ml, the rotating speed is 3000 revolutions per minute, and the time is 60s.
(6) Preparation of an electron transport layer:
evaporating a TPBi layer on the surface of the perovskite luminescent layer in the step (5) by adopting a vacuum evaporation method under high vacuum to obtain an electron transport layer, wherein the thickness of the electron transport layer is 60 nanometers;
(7) Preparation of an electron injection layer:
under high vacuum, an electron injection layer LiF is thermally evaporated on the electron transport layer in vacuum, and the thickness is 2 nanometers;
(8) Preparation of the cathode
A layer of Al cathode is prepared by a vacuum evaporation method, and the thickness is 100nm.
The contrast device comprises an anode, a hole injection layer, a perovskite luminescent layer, an electron transport layer, an electron injection layer and a cathode from bottom to top in sequence, and the preparation method refers to the MoS 2 @ Au devices;
the gold nanoparticle device comprises an anode, a hole injection layer, a perovskite luminescent layer, a metal (alloy) nanoparticle core-shell structure layer, an electron transport layer, an electron injection layer and a cathode from bottom to top in sequence. Preparation method refer to MoS 2 @ Au devices;
fig. 2 is a transmission electron micrograph of the Au nanoparticles of this example, from which it can be seen that the distribution of the Au nanoparticles is very uniform, and the average diameter of the particles is about 10 nm. FIG. 3 is a current efficiency-current density relationship curve for a quasi-two-dimensional perovskite light emitting diode. The introduction of Au nanoparticles can obviously improve the current efficiency of the device, and the introduction of the two-dimensional material layer enables the electron-hole injection to be more balanced, so that the current efficiency of the perovskite light-emitting diode is further improved. It can be seen from the current density-voltage relationship curve of fig. 4 that the turn-on voltage of the device is higher and the leakage current is larger, and the leakage current of the device is obviously reduced by introducing Au nanoparticles, thereby effectively improving the current-voltage relationship.
According to the quasi-two-dimensional perovskite light-emitting diode, the Au core-shell structure metal nanoparticles are introduced into the quasi-two-dimensional perovskite light-emitting diode, the injection efficiency of carriers is improved by utilizing the hot electron injection of the Au nanoparticles, the radiation recombination efficiency of excitons is improved by utilizing a strong local field around the nanoparticles, and finally the higher brightness and current efficiency of the quasi-two-dimensional perovskite light-emitting diode are realized. Meanwhile, the injection potential barrier of a current carrier is obviously reduced by introducing a two-dimensional atomic crystal material, the injection balance of charges is improved, and finally the performance of the device is effectively improved. The preparation method is simple and effective, the cost of the device preparation process is obviously reduced, and the performance enhancement effect of the prepared quasi-two-dimensional perovskite light-emitting diode is obvious.
Example 2
The preparation method of the surface plasmon polariton synergistically enhanced quasi-two-dimensional perovskite light-emitting diode comprises the following steps:
(1) Cleaning an anode substrate:
further, the anode substrate in the step (1) is an ITO substrate. The method comprises the following specific steps of sequentially placing an anode substrate into tetrahydrofuran, isopropanol, washing liquor and deionized water for ultrasonic cleaning, and then placing the anode substrate into the isopropanol for ultrasonic cleaning, wherein the ultrasonic time is 10min each time; after the ultrasonic treatment is finished, the substrate is placed in an oven to be dried for more than 4 hours, and then O is carried out on the substrate for 10min 2 -Plasma surface treatment.
(2) Preparation of hole injection layer:
further, the method for preparing the hole injection layer in the step (2) comprises the following steps: and the hole injection layer polymer solution is PEDOT, namely PSS aqueous solution, is filtered by a 0.22 mu m aqueous filter head and then is dripped on the anode substrate to form a hole injection layer film by a spin coating process, the spin coating speed is 3000 r/min, the spin coating time is 30s, and the hole injection layer film is annealed for 10min at 130 ℃ in the atmospheric environment.
(3) Deposition of a two-dimensional atomic crystal matching layer:
the two-dimensional atomic crystal dispersion liquid in the step (3) adopts WS 2 The quantum dot solution is prepared by spin-coating in a glove box at a rotation speed of 3000 rpm in the preparation process, wherein the solvent of the solution is water, the concentration of the solution is 1mg/ml, the rotation speed is preferably 3000 rpm, the solution dosage is 45 mu l, the spin-coating time is 60 seconds, and annealing is carried out for 15 minutes at 80 ℃ after the spin-coating is finished.
(4) Preparation of perovskite luminescent layer:
in the preparation process, a certain amount of perovskite solution is dripped on the two-dimensional atomic crystal film by adopting a liquid-transferring gun in a glove box, and annealing treatment is carried out after the preparation is finished so as to improve the film-forming quality of the perovskite film;
further, the novel quasi-two-dimensional calcium in the step (4)The titanium ore precursor mixed solution is prepared from PBABr, FABr and PbBr 2 Preparation, wherein PBABR, FABr and PbBr 2 2, solutes PbBr, FABr and PbBr 2 The total mass fraction of (b) is 8wt.%, and the solvents are all anhydrous N, N-Dimethylformamide (DMF).
When the perovskite precursor mixed solution is spin-coated in a glove box, the content of water and oxygen in the glove box is not more than 0.1ppm, and the spin-coating speed of the perovskite precursor mixed solution in the preparation process is 5000 revolutions per minute. The spin coating time was 60s. And after the spin coating preparation is finished, annealing the substrate on a hot table in a glove box under a nitrogen environment at the annealing temperature of 60 ℃ for 15min.
(5) Preparation of metal nano-particle core-shell structure layer
The silver @ silicon dioxide nanoparticle core-shell structure was prepared by a template method (reference example 1), the average size of the nanoparticle core-shell structure was 8nm, the average size of the surface polystyrene ligand was 15nm, the nanoparticle core-shell structure layer was prepared in a glove box by a spin-coating method, the solution concentration was 10mg/ml during the spin-coating process, the rotation speed was 4000 revolutions per minute, and the time was 80s.
(6) Preparation of an electron transport layer:
under high vacuum, evaporating a TPBi layer on the surface of the perovskite luminescent layer by adopting a vacuum evaporation method to obtain an electron transport layer, wherein the thickness of the electron transport layer is 60 nanometers;
(7) Preparation of an electron injection layer:
under high vacuum, an electron injection layer LiF is thermally evaporated on the electron transport layer in vacuum, and the thickness is 1 nanometer;
(8) Preparation of the cathode
And preparing a layer of Al cathode with the thickness of 100nm by adopting a vacuum evaporation method, a sputtering method or ink-jet printing method.
The test results of the quasi-two-dimensional perovskite light emitting diode with the synergistic enhancement of plasmon polaritons in the embodiment are similar to those of embodiment 1, and are not repeated herein.
Example 3
The preparation method of the surface plasmon polariton synergistically enhanced quasi-two-dimensional perovskite light-emitting diode comprises the following steps:
(1) Cleaning an anode substrate:
further, the anode substrate in the step (1) is an ITO substrate. The method comprises the following specific steps of sequentially placing an anode substrate into tetrahydrofuran, isopropanol, washing liquor and deionized water for ultrasonic cleaning, and then placing the anode substrate into the isopropanol for ultrasonic cleaning, wherein the ultrasonic time is 10min each time; after the ultrasonic treatment is finished, the substrate is placed in an oven to be dried for more than 4 hours, and then O is carried out on the substrate for 10min 2 -Plasma surface treatment.
(2) Preparation of hole injection layer:
further, the method for preparing the hole injection layer in the step (2) comprises the following steps: PSS water solution is filtered by a 0.22-micron water-based filter head, and then is dripped on an anode substrate to form a hole injection layer film by a spin coating process, wherein the spin coating speed is 3000 r/min, the spin coating time is 30s, and annealing is carried out at 130 ℃ for 10min at room temperature.
(3) Deposition of a two-dimensional atomic crystal matching layer:
the two-dimensional atomic crystal dispersion liquid in the step (3) adopts MoS 2 The method comprises the steps of preparing a quantum dot solution, wherein a solvent of the solution is water, the concentration of the solution is 2mg/ml, spin coating is needed in a glove box in the preparation process, the spin coating rotating speed is 4000 revolutions per minute, the using amount of the solution is 50 mu l, the spin coating time is 80 seconds, and annealing is carried out for 10 minutes at 80 ℃ after the spin coating is completed.
(4) Preparing a perovskite luminescent layer:
in the preparation process, a certain amount of perovskite solution is dripped on the two-dimensional atomic crystal film by adopting a liquid-transferring gun in a glove box, and annealing treatment is carried out after the preparation is finished so as to improve the film-forming quality of the perovskite film;
further, the novel quasi-two-dimensional perovskite precursor mixed solution in the step (4) is prepared from PEABr, FABr and PbBr 2 Preparation, wherein PEABr is FABr and PbBr 2 The molar ratio between 2 2 The total mass fraction of (b) is 8wt.%, and the solvents are all anhydrous N, N-Dimethylformamide (DMF).
The content of water and oxygen in the glove box is not more than 0.1ppm when the glove box is subjected to spin coating, and the spin coating speed of the perovskite precursor mixed solution in the preparation process is 4000 revolutions per minute. The spin coating time was 80s. And after the spin coating preparation is finished, annealing the substrate on a hot table in a glove box nitrogen environment at the annealing temperature of 60 ℃ for 10min.
(5) Preparation of metal nano-particle core-shell structure layer
The gold @ silicon dioxide nanoparticle core-shell structure was prepared by a template method (reference example 1), the average size of the nanoparticle core-shell structure was 15nm, the average size of the surface polystyrene ligand was 10nm, the nanoparticle core-shell structure layer was prepared in a glove box by a spin-coating method, the solution concentration was 5mg/ml, the rotation speed was 5000 rpm, and the time was 60s during the spin-coating process.
(6) Preparation of an electron transport layer:
evaporating a TPBi layer on the surface of the perovskite luminescent layer by adopting a vacuum evaporation method under high vacuum to obtain an electron transmission layer, wherein the thickness of the electron transmission layer is 50 nanometers;
(7) Preparation of an electron injection layer:
under high vacuum, an electron injection layer LiF is thermally evaporated on the electron transport layer in vacuum, and the thickness is 1 nanometer;
(8) Preparation of the cathode
And preparing a layer of Al cathode with the thickness of 100nm by adopting a vacuum evaporation method, a sputtering method or ink-jet printing method.
The test results of the quasi-two-dimensional perovskite light emitting diode with the synergistic enhancement of plasmon polaritons in the embodiment are similar to those of embodiment 1, and are not repeated herein.
Example 4
The preparation method of the surface plasmon polariton synergistically enhanced quasi-two-dimensional perovskite light-emitting diode comprises the following steps:
(1) Cleaning an anode substrate:
further, the anode substrate in the step (1) is an ITO substrate. The method comprises the following specific steps of sequentially placing an anode substrate into tetrahydrofuran, isopropanol, washing liquor and deionized water for ultrasonic cleaning, and then placing the anode substrate into the isopropanol for ultrasonic cleaning, wherein the ultrasonic time is 10min each time; after the ultrasonic treatment is finished, the substrate is placed in an oven to be dried for more than 4 hoursThen subjecting the substrate to O for 10min 2 -Plasma surface treatment.
(2) Preparation of hole injection layer:
further, the method for preparing the hole injection layer in the step (2) comprises the following steps: PSS water solution is filtered by a 0.22-micron water-based filter head, and then is dripped on an anode substrate to form a hole injection layer film by a spin coating process, wherein the spin coating speed is 3000 r/min, the spin coating time is 30s, and the hole injection layer film is annealed at 120 ℃ for 15min at room temperature.
(3) Deposition of a two-dimensional atomic crystal matching layer:
the two-dimensional atomic crystal dispersion liquid in the step (3) adopts MoS 2 The method comprises the steps of preparing a quantum dot solution, wherein a solvent of the solution is water, the concentration of the solution is 2mg/ml, spin coating is needed in a glove box in the preparation process, the spin coating rotating speed is 4000 revolutions per minute, the using amount of the solution is 50 mu l, the spin coating time is 80 seconds, and annealing is carried out for 10 minutes at 80 ℃ after the spin coating is completed.
(4) Preparation of perovskite luminescent layer:
in the preparation process, a certain amount of perovskite solution is dripped on the two-dimensional atomic crystal film by adopting a liquid-transferring gun in a glove box, and annealing treatment is carried out after the preparation is finished so as to improve the film-forming quality of the perovskite film;
further, the novel quasi-two-dimensional perovskite precursor mixed solution in the step (4) is prepared from PEABr, csBr and PbBr 2 Preparation, wherein PEABr: csBr: pbBr 2 2, solutes PEABr, csBr and PbBr 2 Is 8wt.%, and the solvent is anhydrous dimethyl sulfoxide (DMSO).
When the perovskite precursor mixed solution is spin-coated in a glove box, the content of water and oxygen in the glove box is not more than 0.1ppm, and the spin-coating speed of the perovskite precursor mixed solution in the preparation process is 4000 revolutions per minute. The spin coating time was 80s. After the spin coating preparation is finished, annealing is carried out on a hot table under the nitrogen environment of a glove box, the annealing temperature is 60 ℃, and the annealing time is 10min.
(5) Preparation of metal nano-particle core-shell structure layer
The silver @ silicon dioxide nanoparticle core-shell structure is prepared by a template method (reference example 1), the average size of the nanoparticle core-shell structure in the preparation process is 8nm, the average size of a surface polystyrene ligand is 20 nm, the nanoparticle core-shell structure layer is prepared in a glove box by a spin coating method, the concentration of a solution in the spin coating process is 5mg/ml, the rotating speed is 3000 revolutions per minute, and the time is 30s.
(6) Preparation of an electron transport layer:
under high vacuum, evaporating a TPBi layer on the surface of the perovskite luminous layer by adopting a vacuum evaporation method to obtain an electron transmission layer, wherein the thickness of the electron transmission layer is 50 nanometers;
(7) Preparation of an electron injection layer:
under high vacuum, an electron injection layer LiF is thermally evaporated on the electron transport layer in vacuum, and the thickness is 1 nanometer;
(8) Preparation of the cathode
And preparing a layer of Al cathode with the thickness of 100nm by adopting a vacuum evaporation method, a sputtering method or ink-jet printing method.
The test results of the quasi-two-dimensional perovskite light emitting diode with the synergistic enhancement of plasmon polaritons in the embodiment are similar to those of embodiment 1, and are not repeated herein.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (9)

1. A quasi-two-dimensional perovskite light emitting diode with synergistically enhanced surface plasmons is characterized in that the perovskite light emitting device sequentially comprises an anode substrate, a hole injection layer, a two-dimensional atomic crystal material layer, a perovskite light emitting layer, a metal nanoparticle core-shell structure layer, an electron transmission layer, an electron injection layer and a cathode from bottom to top; the two-dimensional atomic crystal material comprises a transition metal sulfide two-dimensional crystal, the perovskite luminescent layer is a quasi two-dimensional perovskite, and the quasi two-dimensional perovskite is realized by adding organic halide ammonium salt into a precursor;
the metal nanoThe particle core-shell structure layer comprises a metal nanoparticle core layer and a shell layer; the metal nano-particle core layer is one of Au and Ag or AlAg alloy, and the shell layer is SiO 2 (ii) a The surface of the metal nano particle core-shell structure layer is provided with a surface ligand, and the surface ligand is polystyrene;
the two-dimensional crystal of the transition metal sulfide comprises MoS 2 、WS 2 。
2. A surface plasmon synergistic enhanced quasi-two dimensional perovskite light emitting diode as claimed in claim 1 wherein said metal nanoparticles are 5-30 nanometers in size;
the size of the surface ligand of the metal nano particle core-shell structure layer is 10-100 nanometers.
3. The surface plasmon polariton synergistically enhanced quasi-two-dimensional perovskite light-emitting diode according to claim 1, wherein said quasi-two-dimensional perovskite material has the formula L 2 M x Pb 3 Br 10 L is monovalent organic ammonium ion and comprises PPA + 、PEA + 、PBA + 、i-BA + M is MA + , FA + , Cs + X =2~3.
4. The surface plasmon polariton synergistically enhanced quasi-two-dimensional perovskite light-emitting diode according to claim 1, wherein the thickness of the two-dimensional crystal is 0.5 to 10 nm;
the hole injection layer comprises PEDOT PSS, PVK, TPD or TFB.
5. The surface plasmon polariton synergistically enhanced quasi-two-dimensional perovskite light-emitting diode according to claim 1, wherein the electron injection layer is made of LiF material, and the thickness of the electron injection layer is 2-10 nm; the material of the electron transport layer comprises TPBi, BCP and PCBM, and the thickness of the electron transport layer is 50-200 nanometers.
6. The surface plasmon polariton synergistically enhanced quasi-two-dimensional perovskite light emitting diode according to claim 1, wherein the anode substrate is an ITO substrate, an IZO substrate or an FTO substrate; the cathode is metal or metal oxide, and the thickness of the cathode is 80-200nm.
7. The method for preparing a surface plasmon polariton synergistically enhanced quasi-two-dimensional perovskite light-emitting diode as claimed in any one of claims 1 to 6, comprising the steps of:
(1) Cleaning an anode substrate;
(2) Preparation of hole injection layer:
forming a hole injection layer film on the anode substrate by a spin coating process, and annealing to obtain a hole injection layer;
(3) Deposition of a two-dimensional atomic crystal material layer:
spin-coating two-dimensional atomic crystal dispersion liquid on the hole injection layer, and annealing to obtain a two-dimensional atomic crystal material layer;
(4) Preparing a perovskite luminescent layer:
dripping a quasi-two-dimensional perovskite precursor mixed solution on the two-dimensional atomic crystal material layer, spin-coating to form a film, and annealing to obtain a perovskite light-emitting layer;
(5) Preparing a metal nano particle core-shell structure layer:
preparing a metal nanoparticle core-shell structure by adopting a template method, wherein the metal nanoparticle core-shell structure layer is prepared by adopting a spin-coating method;
(6) Preparation of an electron transport layer:
evaporating an electronic transmission layer on the surface of the metal nanoparticle core-shell structure layer by adopting a vacuum evaporation method;
(7) Preparation of an electron injection layer:
vacuum thermal evaporation of an electron injection layer on the electron transport layer;
(8) Preparing a cathode:
the cathode is prepared by adopting a vacuum evaporation method, a sputtering method or ink-jet printing.
8. The production method according to claim 7,
the anode substrate in the step (1) is one of an ITO substrate, an IZO substrate or an FTO substrate; the anode substrate cleaning method comprises the following specific steps: sequentially putting the anode substrate into tetrahydrofuran, isopropanol, washing liquor and deionized water for ultrasonic cleaning, and then putting the anode substrate into isopropanol for ultrasonic cleaning, wherein the ultrasonic time is 15-30 min each time; after the ultrasonic treatment is finished, the substrate is placed in an oven to be dried for more than 4 hours, and then the substrate is subjected to UV or O treatment for 15-20 min 2 -Plasma surface treatment;
the spin coating speed of the step (2) is 3000-4000 rpm, and the spin coating time is 30-40 s; the annealing temperature is 130-170 ℃, and the annealing time is 10-20min.
9. The production method according to claim 7,
the two-dimensional atomic crystal dispersion liquid in the step (3) is MoS 2 Dispersion liquid and MoS 2 Quantum dot solution, WS 2 Dispersion liquid, WS 2 A quantum dot solution; the solvent of the two-dimensional atomic crystal dispersion liquid is water, ethanol, DMF, IPA and NMP; the concentration of the two-dimensional atomic crystal dispersion liquid is 1-10mg/ml; spin coating is needed in a glove box in the preparation process, the rotating speed of the spin coating is 2000-5000 r/min, and the spin coating time is 30-100 seconds; the temperature of the annealing treatment is 50-150 DEG C o C, annealing for 10-30 minutes;
the quasi-two-dimensional perovskite precursor mixed solution in the step (4) comprises PBABR, MABr and PbBr 2 Wherein PBABR, MABr, pbBr 2 In a molar ratio of (1~2): (2~3): 3,PBABR, MABr and PbBr 2 The total mass fraction of (1) is 3-10wt.%, and the solvent is anhydrous N, N-dimethylformamide or dimethyl sulfoxide; the spin coating speed is 2000-8000 rpm; the spin coating time is 30-100s; the temperature of the annealing is 30-80 DEG C o C, annealing for 10-40 min;
the size of the metal nano particles of the metal nano particle core-shell structure in the step (5) is 5-30 nanometers, and the size of the surface polystyrene ligand is 10-100nm; the spin coating is carried out in a glove box; the concentration of the spin-coating solution is 5-20mg/ml, the rotating speed is 1000-3000 r/min, and the time is 30-200s.
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