CN113823751A - Perovskite light emitting diode and preparation method thereof - Google Patents
Perovskite light emitting diode and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
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Abstract
The invention discloses a perovskite light-emitting diode and a preparation method thereof, the structure of the perovskite light-emitting diode sequentially comprises a substrate, an anode, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode from bottom to top, wherein the light-emitting layer is a perovskite light-emitting layer; when the perovskite luminescent layer is prepared, a perovskite precursor solution is coated on the hole transport layer in a rotating mode, critical time is determined by monitoring photoluminescence, an anti-solvent is introduced by selecting anti-solvent introduction time according to the critical time, and then the perovskite luminescent layer is obtained through annealing treatment. The invention can easily determine the dropping time of the introduced anti-solvent by monitoring the phenomenon of fluorescence in photoluminescence, and realizes the accurate control of the dropping time of the anti-solvent.
Description
Technical Field
The invention relates to the technical field of preparation of optoelectronic devices, in particular to a perovskite light-emitting diode and a preparation method thereof.
Background
Metal halide perovskite light emitting diodes (PeLEDs) are receiving attention due to their characteristics of high color purity, adjustable light emitting wavelength, high photoluminescence quantum efficiency, low cost solution process preparation, and the like. Since room-temperature near-infrared metal halide Pelens were first reported in 2014, the maximum External Quantum Efficiencies (EQE) of green, red and near-infrared Pelens all exceed 20%, and the photoelectric properties of the Pelens are comparable to those of organic light-emitting diodes and inorganic quantum dot light-emitting diodes. The proliferation of PeLEDs benefits from fundamental understanding of perovskite formation mechanisms and optoelectronic properties, as well as mature experience in the processing of perovskite optoelectronic devices.
Although researchers have repeatedly demonstrated how to use different methods to fabricate high efficiency PeLEDs, the highest device performance perovskite light emitting diodes reported to date have been prepared by a simple spin-on process. During the spin coating process, the controllable and uniform crystallization is a prerequisite for ensuring the formation of a high-quality perovskite light-emitting layer. So far, the antisolvent assisted spin-coating process has proven to be an effective strategy to rationally control the crystallization kinetics. In principle, an anti-solvent process is used before the end of the spin-coating process to remove the bulk solvent, initiate rapid and extensive nucleation, and subsequently accelerate crystallization. A smooth and dense perovskite thin film having uniform nanocrystals of small size can be formed by the anti-solvent treatment. The uniformly distributed small nanocrystals greatly enhance radiative recombination by spatially confining carriers/excitons. Precise control of the antisolvent process is crucial in view of its role in nucleation and crystallization kinetics. However, the practical operation of the anti-solvent step is difficult and the process window is narrow, and researchers have investigated how variables such as anti-solvent volume, process temperature, doping additives, spin-coating conditions, and solvent atmosphere affect the formation of perovskite thin films and the quality of the resulting thin films.
Basically, these variables are closely related to the antisolvent drip time, and one can find different drip times in different reports. It is well known that although previous work has provided a procedure for the anti-solvent process, researchers from different laboratories have had to waste time searching themselves for the best application of the anti-solvent step. Worse still, the anti-solvent drop time may vary over time, for example, due to variations in the solvent atmosphere and process temperature of the glove box. These significant differences and variations in drop time can be attributed to compositional-dependent liquid crystal kinetics and complex crystallization pathways, making it difficult to determine the drop time of the anti-solvent step, and therefore, rational control of the anti-solvent step is a key requirement for technological development to achieve highly reproducible fabrication of perovskite light emitting diodes with superior performance.
The above is only for the purpose of assisting understanding of the technical aspects of the present invention, and does not represent an admission that the above is prior art.
Disclosure of Invention
The invention mainly aims to provide a perovskite light-emitting diode and a preparation method thereof, and aims to solve the technical problem that the dropping time of an anti-solvent step is difficult to determine.
In order to achieve the above object, the present invention provides a perovskite light emitting diode, which comprises a substrate, an anode, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode in sequence from bottom to top, wherein the light emitting layer is a perovskite light emitting layer;
when the perovskite luminescent layer is prepared, a perovskite precursor solution is coated on the hole transport layer in a rotating mode, critical time is determined by monitoring photoluminescence, an anti-solvent is introduced by selecting anti-solvent introduction time according to the critical time, and then the perovskite luminescent layer is obtained through annealing treatment.
Optionally, the anti-solvent introduction time comprises before the critical time, at the critical time, and after the critical time;
the antisolvent comprises a chlorobenzene-trioctylphosphine oxide solution.
Optionally, the perovskite precursor solution is prepared by the following steps: and dissolving the perovskite, the large-group organic halide and other additives into a dimethyl sulfoxide or dimethyl formamide solvent to obtain a perovskite precursor solution.
Optionally, when the perovskite light emitting diode is a green perovskite light emitting diode, the perovskite precursor solution is prepared by: and (3) dissolving cesium bromide, lead bromide, phenethyl amine bromide and cyclotetradecane in a dimethyl sulfoxide solvent to obtain the perovskite precursor solution.
Optionally, when the perovskite light emitting diode is a blue light perovskite light emitting diode, the preparation method of the perovskite precursor solution is as follows: and (3) dissolving cesium bromide, lead bromide, phenethyl amine chloride, guanidine bromide and guanidine thiocyanate in a dimethyl sulfoxide solvent to obtain the perovskite precursor solution.
Optionally, the anode is indium tin oxide transparent conductive glass or a flexible transparent electrode, and the thickness of the anode is 10-300 nm;
the hole transport layer is one or more of PEDOT (Poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid), PVK (polyvinyl carbazole) and Poly-TPD (Poly [ bis (4-phenyl) (4-butylphenyl) amine ]), and the thickness of the hole transport layer is 20-100 nm;
the light-emitting layer comprises one or more of perovskite, large-group organic halide and other additives, and the thickness of the light-emitting layer is 20-100 nm;
the electron transport layer is one or more of TPBi (1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene), POT2T (2,4, 6-tri [3- (diphenylphosphine oxy) phenyl ] -1,3, 5-triazole) and TmPyPB (4, 6-bis (3, 5-di (3-pyridine) phenyl) -2-methylpyrimidine), and the thickness of the electron transport layer is 20-100 nm;
the electron injection layer is Liq (8-hydroxyquinoline-lithium) or LiF (lithium fluoride), and the thickness of the electron injection layer is 0.5-3 nm;
the cathode is one or more of aluminum (Al) or silver (Ag), and the thickness of the cathode is 50-200 nm.
The invention also provides a preparation method of the perovskite light-emitting diode, which is used for preparing any one of the perovskite light-emitting diodes and comprises the following steps:
designing a pattern of the anode substrate by using a laser etching process;
sequentially using deionized water, alkali liquor, isopropanol solution and ethanol solution to ultrasonically clean the anode substrate with the designed pattern, drying after ultrasonic cleaning, and drying in a drying oven;
carrying out UV ozone pretreatment on the dried anode substrate;
spin-coating the precursor solution of the hole transport layer on an anode substrate pretreated by UV ozone, and then annealing to obtain the hole transport layer;
spin-coating a perovskite precursor solution on the hole transport layer, determining critical time by monitoring photoluminescence, selecting introduction time of an anti-solvent by referring to the critical time, introducing the anti-solvent, and annealing to obtain a perovskite luminescent layer;
and sequentially evaporating an electron transport layer, an electron injection layer and a cathode on the perovskite luminescent layer by a vacuum thermal evaporation method to obtain the perovskite luminescent diode.
Optionally, the preparation method of the cavity layer precursor solution is as follows: and mixing the PEDOT/PSS (4083) solution and the ethanolamine solution according to a preset volume ratio to obtain the cavity layer precursor solution.
Optionally, the cleaning time period corresponding to ultrasonic cleaning of the anode substrate with the designed pattern is 15-30min, and the treatment time period corresponding to UV ozone pretreatment of the dried anode substrate is 10-20 min.
Optionally, the rotation speed corresponding to spin-coating the hole transport layer precursor solution is 3000-7000rpm and the corresponding spin-coating time length is 30-100s, the corresponding annealing temperature of the hole transport layer is 0-200 ℃ and the corresponding annealing time length is 0-30 minutes;
the corresponding rotating speed of the perovskite precursor solution is 3000-7000rpm, the corresponding spin-coating time length is 30-100s, the corresponding annealing temperature of the perovskite luminescent layer is 0-200 ℃, and the corresponding annealing time length is 0-30 minutes.
The invention provides a perovskite light-emitting diode, which structurally comprises a substrate, an anode, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode from bottom to top in sequence, wherein the light-emitting layer is a perovskite light-emitting layer; when the perovskite luminescent layer is prepared, a perovskite precursor solution is coated on the hole transport layer in a rotating mode, critical time is determined by monitoring photoluminescence, an anti-solvent is introduced by selecting anti-solvent introduction time according to the critical time, and then the perovskite luminescent layer is obtained through annealing treatment. In the invention, in the spin coating process of the perovskite precursor solution, the perovskite is crystallized and the photoluminescence phenomenon can be observed under the irradiation of an ultraviolet lamp. By the occurrence of fluorescence in the photoluminescence of the perovskite thin film, the dropping time of the introduced anti-solvent can be easily determined, and the accurate control of the dropping time of the anti-solvent is realized. Accurate control of the anti-solvent drop time not only effectively improves PeLEDs performance, but also ensures highly reproducible manufacturing of PeLEDs. Moreover, the present invention determines that proper drop times are independent of environmental conditions, such as process temperature, solvent atmosphere, and spin-coating speed, and can be extended to the fabrication of other types of high-efficiency pelds, thereby providing a versatile method for fabricating pelds with high performance and high reproducibility.
Drawings
FIG. 1 is a schematic diagram of the device structure of a perovskite light emitting diode of the present invention;
FIG. 2 is a schematic flow chart of a first embodiment of a method of making a perovskite light emitting diode of the present invention;
FIG. 3 is a schematic representation of a pipette for introducing an anti-solvent according to the present invention;
FIG. 4 is a schematic representation of the distance between a sample and a pipette according to the present invention;
FIG. 5 is a schematic illustration of a process for preparing a perovskite light emitting layer of the present invention;
FIG. 6 is a schematic illustration of the antisolvent introduction process of the present invention;
FIG. 7 is an atomic force microscope image (AFM) of a perovskite thin film of the present invention;
FIG. 8 is a Scanning Electron Microscope (SEM) image of a perovskite thin film of the present invention;
FIG. 9 is a Fluorescent Lifetime Imaging Micrograph (FLIM) of a perovskite thin film of the present invention;
FIG. 10 is a confocal fluorescence micrograph of a perovskite thin film of the present invention;
FIG. 11 is an electroluminescence spectrum of a perovskite light emitting diode of the present invention under different conditions;
FIG. 12 is a graph of the luminance and voltage of a perovskite light emitting diode of the present invention;
FIG. 13 is a graph of the external quantum efficiency and current density of a perovskite light emitting diode of the present invention;
FIG. 14 is a graph of the fluorescence quantum yield of perovskite thin films under various conditions of the present invention;
FIG. 15 is a CIE color coordinate diagram of a green perovskite light emitting diode of the present invention;
FIG. 16 is the External Quantum Efficiency (EQE) statistics for the green perovskite light emitting diode of the present invention under different conditions;
FIG. 17 is a CIE color coordinate diagram of a blue perovskite light emitting diode of the present invention;
fig. 18 is an External Quantum Efficiency (EQE) statistic for the blue perovskite light emitting diode of the present invention under different conditions.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a perovskite light-emitting diode, which refers to a schematic device structure diagram of the perovskite light-emitting diode shown in figure 1, and the perovskite light-emitting diode sequentially comprises a substrate, an anode, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode from bottom to top, wherein the light-emitting layer is a perovskite light-emitting layer;
when the perovskite luminescent layer is prepared, a perovskite precursor solution is coated on the hole transport layer in a rotating mode, critical time is determined by monitoring photoluminescence, an anti-solvent is introduced by selecting anti-solvent introduction time according to the critical time, and then the perovskite luminescent layer is obtained through annealing treatment.
In this embodiment, after the hole transport layer is prepared, a perovskite precursor solution prepared in advance is spin-coated on the hole transport layer, critical time is determined by monitoring photoluminescence, an anti-solvent is dropped into the hole transport layer for a time selected by referring to the critical time, and then an annealing treatment is performed to obtain a perovskite light emitting layer, and the obtained perovskite light emitting layer is on the hole transport layer. After obtaining the perovskite luminescent layer, an electron transport layer, an electron injection layer and a cathode are sequentially evaporated on the perovskite luminescent layer by a vacuum thermal evaporation method, and finally the perovskite luminescent diode is obtained. That is, on the perovskite light emitting layer, an electron transport layer, an electron injection layer, and a cathode are in this order. The perovskite precursor solution is prepared before the perovskite luminescent layer is prepared, and the preparation process of the perovskite precursor solution is as follows: and dissolving the perovskite, the large-group organic halide and other additives into a dimethyl sulfoxide or dimethyl formamide solvent to obtain a perovskite precursor solution.
Further, the anti-solvent may be introduced before the critical time, at the critical time, and after the critical time; the anti-solvent dropped includes chlorobenzene-trioctylphosphine oxide solution.
Further, when the perovskite light emitting diode is a green perovskite light emitting diode, the preparation method of the perovskite precursor solution comprises the following steps: and (3) dissolving cesium bromide, lead bromide, phenethyl amine bromide and cyclotetradecane in a dimethyl sulfoxide solvent to obtain a perovskite precursor solution.
Further, when the perovskite light emitting diode is a blue light perovskite light emitting diode, the preparation method of the perovskite precursor solution comprises the following steps: and (3) dissolving cesium bromide, lead bromide, phenethyl amine chloride, guanidine bromide and guanidine thiocyanate in a dimethyl sulfoxide solvent to obtain a perovskite precursor solution.
Furthermore, the anode is indium tin oxide transparent conductive glass or a flexible transparent electrode, and the thickness of the anode is 10-300 nm;
the hole transport layer is one or more of PEDOT (Poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid), PVK (polyvinyl carbazole) and Poly-TPD (Poly [ bis (4-phenyl) (4-butylphenyl) amine ]), and the thickness of the hole transport layer is 20-100 nm;
the luminescent layer comprises one or more of perovskite, large-group organic halide and other additives, and the thickness of the luminescent layer is 20-100 nm;
the electron transport layer is one or more of TPBi (1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene), POT2T (2,4, 6-tri [3- (diphenylphosphine oxy) phenyl ] -1,3, 5-triazole) and TmPyPB (4, 6-bis (3, 5-di (3-pyridine) phenyl) -2-methylpyrimidine), and the thickness of the electron transport layer is 20-100 nm;
the electron injection layer is Liq (8-hydroxyquinoline-lithium) or LiF (lithium fluoride), and the thickness of the electron injection layer is 0.5-3 nm;
the cathode is one or more of aluminum (Al) or silver (Ag), and the thickness of the cathode is 50-200 nm.
The hole transport layer functions to transport holes, the electron transport layer functions to transport electrons, and the electron injection layer functions to inject electrons into the electron transport layer. The luminescent layer provides a region for electron and hole recombination luminescence, and an anti-solvent process is adopted to improve the film form in the process of spin coating the perovskite luminescent layer. The introduction of the anti-solvent can effectively inhibit non-radiative recombination, improve the appearance of the perovskite and form a compact and smooth film.
To eliminate the effect of the anti-solvent extrusion time and achieve a faster anti-solvent dropping speed, the tip of a 1000. mu.l pipette was cut 1cm during the anti-solvent process (as shown in FIG. 3), while keeping the distance between the sample and the pipette fixed at 10mm (as shown in FIG. 4).
FIG. 5 is a schematic illustration of a process for preparing a perovskite light emitting layer of the present invention, in which a 365nm UV lamp is placed over a spin coater. The temporal and spatial nucleation and crystallization kinetics of perovskites can be readily identified by observing the photoluminescence of spin-coated thin films under excitation by ultraviolet light.
At the beginning of the spin coating process, the liquid perovskite thin film contains a large amount of dimethyl sulfoxide (DMSO) solvent, which does not reach a supersaturated state, and no photoluminescence occurs (steps 1 and 2). After evaporation and removal of the excess solvent, the formation of supersaturation leads to nucleation,and a certain degree of crystallization of the film occurs at the edge of the substrate, at which point it can be monitored that photoluminescence starts to occur at the edge of the substrate (steps 3 and 4). When nucleation and crystallization occur over the entire substrate (step 5), it is defined as the critical time (t) of the antisolvent process0) The entire substrate can now be monitored for complete and uniform photoluminescence. Obviously, the critical time t0It is related to the state of the substrate exhibiting uniform photoluminescence, which is a function of the solvent atmosphere, glove box temperature, spin coating speed, and the like. The influence of other process conditions can be avoided by the occurrence of the photoluminescence phenomenon as a critical time determination condition. Achieving a critical time (t) from monitoring of photoluminescence0) Can then be determined at the critical time t0、t0Front, t0An anti-solvent dropping process was then introduced (as shown in figure six).
In order to reveal the effect of the different antisolvent dropping times of the present invention on the properties of the perovskite thin film, i.e., the perovskite light-emitting layer, further explanation is provided below.
The invention realizes the highly reproducible preparation of perovskite light emitting diodes (PelLEDs) based on an in-situ photoluminescence monitoring technology. In order to reveal the influence of different anti-solvent dropping times on the properties of the perovskite thin film under the in-situ photoluminescence monitoring technology, the preparation process of a green perovskite light emitting diode is taken as an example. Reference critical time t0Two seconds (t) before the critical time is selected0-2s), critical time (t)0) Two seconds after the critical time (t)0) Respectively introducing an anti-solvent (chlorobenzene-trioctylphosphine oxide solution CB-TOPO), and annealing to obtain the perovskite luminescent layer. By Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM) tests, it was found that perovskite nanocrystals tend to form a uniform and smooth morphology due to rapid uniform growth after the incubation period. Root mean square roughness as measured by Atomic Force Microscope (AFM) (as shown in FIG. 7) was from 4.16nm (t)0-2s) down to 4.07nm (t)0) And 3.58nm (t)0+2 s). A smooth interface will help reduce the likelihood of carrier leakage. Furthermore, from the Scanning Electron Microscope (SEM) (as shown in FIG. 8), at t0+2s stripsUnder conditions, the size of the film grains is smaller than that of other films. The antisolvent process does not affect nucleation, avoiding the heterogeneous defect that affects charge-carrier recombination. The enhancement of the film radiative recombination is seen from the Fluorescence Lifetime Imaging Micrograph (FLIM) of the film (see fig. 9) and the confocal fluorescence micrograph (see fig. 10). T in FLIM0The film under-2 s conditions was darker and showed local variation in fluorescence lifetime due to the non-uniform distribution of surface traps showing variation in non-radiative recombination rate. When at a later time (t)0And t0+2s) the inhomogeneity of fluorescence lifetime is mitigated when antisolvent drops are introduced. The extension of the fluorescence lifetime indicates that non-radiative recombination caused by the non-uniform growth of the perovskite nanocrystals is suppressed. The result of the confocal fluorescence microscopic image shows the same trend as the fluorescence lifetime imaging microscopic image FLIM of the film, and the condition of introducing the anti-solvent is t0The +2s perovskite thin film shows the highest brightness and photoluminescence intensity.
Taking the preparation process of the green perovskite light emitting diode as an example, fig. 11 is a device light emitting performance diagram of green PeLEDs prepared based on the in-situ photoluminescence monitoring technology. Devices with different antisolvent introduction times showed the same emission peak at 512nm, 20nm full width at half maximum (FWHM) (fig. 12). The antisolvent introduction time is the critical time t0The device of (2) showed the highest luminance of 33057cd/m2 (FIG. 12). The antisolvent introduction time is t0The device of +2s showed the highest External Quantum Efficiency (EQE) (fig. 13), with the device maximum EQE from 11.2% (t)02s) to 13.9% (t)0+2 s). From t0+2s antisolvent conditions produced a maximum EQE of 15.5%. The corresponding perovskite thin film fluorescence quantum yield (PLQY) has the same trend (fig. 14), from 35% (t)02s) to 43% (t)0+2 s). The change in PLQY indicates that the antisolvent dropping time has a large influence on the crystal recombination kinetics of the perovskite light-emitting layer. The increase in PLQY indicates suppression of non-radiative recombination due to the reduction of bulk/surface trap defects, which is the key reason for the efficiency improvement described earlier. The CIE diagram in fig. 15 shows the corresponding color coordinates (0.08, 0.74) for green PeLEDs. To evaluate the reproducibility of PeLEDs, in different solventsTens of devices were fabricated under the conditions and glove box temperature. These devices have high reproducibility, although the fabrication of the devices has no intentional control of process conditions (fig. 16). The antisolvent introduction time is t0-2s device with a medium EQE of 11.4% and a standard deviation of 0.24%; the antisolvent introduction time is t0The apparatus of (a) shows a medium EQE of 12.2% and a standard deviation of 0.3%, the anti-solvent introduction time being t0The +2s device showed a medium EQE of 14.1% and a standard deviation of 0.8%. These results indicate that reasonable control of the antisolvent process can be achieved by the in situ photoluminescence monitoring techniques proposed by the present invention. The standard deviation was less than 1% in all cases, which represents a highly reproducible manufacture of PeLEDs.
To assess the versatility of the invention for other types of PeLEDs, the invention can also be used to fabricate blue perovskite light emitting diodes (fig. 17). The performance trends under anti-solvent conditions for blue PeLEDs are similar to those for green PeLEDs, highlighting the importance of reasonable control over the anti-solvent process. Fig. 18 shows that EQE of blue PeLEDs prepared under different anti-solvent application conditions exhibited less than 1% standard deviation, indicating the universality of the invention.
In conclusion, the in-situ photoluminescence monitoring technology of the invention can realize highly reproducible manufacturing of high-efficiency perovskite light emitting diodes, and the introduction process of the anti-solvent can be accurately determined and controlled by in-situ monitoring of the photoluminescence phenomenon, so that the nucleation and crystallization of the perovskite light emitting layer can be reasonably controlled. The method used by the invention is independent of the process conditions such as temperature, solvent atmosphere, spin coating speed and the like. By reasonably controlling the anti-solvent time, the highly reproducible high-efficiency perovskite light-emitting diode can be prepared. Furthermore, it was found that the introduction of anti-solvent drop times after the nucleation phase would suppress non-radiative recombination caused by heterogeneous growth of the perovskite nanocrystals, which leads to an improvement in device performance. From the point of view of PeLEDs fabrication, the present invention will take an important step forward in highly reproducible perovskite display technology and illumination technology.
The invention provides a perovskite light-emitting diode, which structurally comprises a substrate, an anode, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode from bottom to top in sequence, wherein the light-emitting layer is a perovskite light-emitting layer; when the perovskite luminescent layer is prepared, a perovskite precursor solution is coated on the hole transport layer in a rotating mode, critical time is determined by monitoring photoluminescence, an anti-solvent is introduced by selecting anti-solvent introduction time according to the critical time, and then the perovskite luminescent layer is obtained through annealing treatment. In the invention, in the spin coating process of the perovskite precursor solution, the perovskite is crystallized and the photoluminescence phenomenon can be observed under the irradiation of an ultraviolet lamp. By the occurrence of fluorescence in the photoluminescence of the perovskite thin film, the dropping time of the introduced anti-solvent can be easily determined, and the accurate control of the dropping time of the anti-solvent is realized. Accurate control of the anti-solvent drop time not only effectively improves PeLEDs performance, but also ensures highly reproducible manufacturing of PeLEDs. Moreover, the present invention determines that proper drop times are independent of environmental conditions, such as process temperature, solvent atmosphere, and spin-coating speed, and can be extended to the fabrication of other types of high-efficiency pelds, thereby providing a versatile method for fabricating pelds with high performance and high reproducibility.
The invention also provides a preparation method of the perovskite light emitting diode, and referring to fig. 2, fig. 2 is a schematic flow chart of a first embodiment of the preparation method of the perovskite light emitting diode.
In this embodiment, the method for manufacturing the perovskite light emitting diode includes the following steps:
step S10, designing the pattern of the anode substrate by using the laser etching process;
in this embodiment, starting with the preparation of the perovskite light emitting diode, an anode substrate is provided to perform the preparation of the perovskite light emitting diode based on the anode substrate; and designing the pattern of the anode substrate by using a laser etching process. The anode substrate may be an ITO glass substrate, the ITO is indium tin oxide, the ITO glass substrate is a glass substrate covered with ITO (indium tin oxide), that is, the glass substrate is covered with ITO, the glass substrate serves as a substrate of the perovskite light emitting diode, and the ITO serves as an anode of the blue perovskite light emitting diode.
Step S20, ultrasonic cleaning is carried out on the anode substrate with the designed pattern by using deionized water, alkali liquor, isopropanol solution and ethanol solution in sequence, and the anode substrate is dried after ultrasonic cleaning and then is placed in a drying oven for drying;
step S30, carrying out UV ozone pretreatment on the dried anode substrate;
in this embodiment, after the anode substrate is subjected to pattern design, the anode substrate after the pattern design is sequentially subjected to ultrasonic cleaning by using deionized water, alkali solution, isopropanol solution and ethanol solution, respectively. After the ultrasonic cleaning, the anode substrate after the ultrasonic cleaning is dried. Wherein, the step of drying the cleaned anode substrate comprises the following steps: drying the fabric firstly and then putting the fabric into a drying box for drying. And then, carrying out UV ozone pretreatment on the dried anode substrate.
Further, the cleaning time period corresponding to ultrasonic cleaning of the anode substrate with the designed pattern is 15-30min, and the treatment time period corresponding to UV ozone pretreatment of the dried anode substrate is 10-20 min.
Step S40, spin-coating the hole transport layer precursor solution on an anode substrate pretreated by UV ozone, and then annealing to obtain a hole transport layer;
in this embodiment, the hole transport layer precursor solution is spin-coated on the anode substrate processed in step S30, and then the anode substrate spin-coated with the hole transport layer precursor solution is annealed to obtain the hole transport layer, so as to prepare the hole transport layer on the anode substrate, that is, the hole transport layer is on the anode substrate.
Further, spin-coating the hole transport layer precursor solution on the anode substrate pretreated by the UV ozone at a first preset rotation speed for a first spin-coating time, and annealing at a first preset temperature for a first preset time to obtain the hole transport layer on the anode substrate. Wherein the first preset rotating speed is the rotating speed corresponding to the spin coating of the cavity transport layer precursor solution, and the first preset rotating speed is 3000-7000 rpm; the first spin coating time is the time corresponding to the spin coating of the cavity transport layer precursor solution, and the first spin coating time is 30-100 s; the first preset time is the annealing time corresponding to the hole transport layer, and the annealing time is 5-30 min; the first preset temperature is the annealing temperature corresponding to the hole transport layer, and the first preset temperature is 0-200 ℃.
Further, before the hole transport layer is prepared, a hole transport layer precursor solution needs to be prepared, and the preparation process of the hole transport layer precursor solution is as follows: and mixing the PEDOT/PSS (4083) solution and the ethanolamine solution according to a preset volume ratio to obtain a cavity layer precursor solution. Further, a preparation process of the hole transport layer precursor solution may be: and mixing a PEDOT/PSS (4083) solution and an ethanolamine solution according to a volume ratio of 1000:4 to obtain a hole transport layer precursor solution, wherein the PEDOT/PSS (4083) is poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid).
Step S50, spin-coating a perovskite precursor solution on the hole transport layer, determining critical time by monitoring photoluminescence, selecting anti-solvent introduction time by referring to the critical time, introducing anti-solvent, and annealing to obtain a perovskite light-emitting layer;
and step S60, sequentially evaporating an electron transport layer, an electron injection layer and a cathode on the perovskite light-emitting layer by a vacuum thermal evaporation method to obtain the perovskite light-emitting diode.
In this embodiment, after the hole transport layer is prepared, a perovskite precursor solution prepared in advance is spin-coated on the hole transport layer, critical time is determined by monitoring photoluminescence, an anti-solvent is dropped into the hole transport layer for a time selected by referring to the critical time, and then an annealing treatment is performed to obtain a perovskite light emitting layer, and the obtained perovskite light emitting layer is on the hole transport layer. After obtaining the perovskite luminescent layer, an electron transport layer, an electron injection layer and a cathode are sequentially evaporated on the perovskite luminescent layer by a vacuum thermal evaporation method, and finally the perovskite luminescent diode is obtained. That is, on the perovskite light emitting layer, an electron transport layer, an electron injection layer, and a cathode are in this order. The perovskite precursor solution is prepared before the perovskite luminescent layer is prepared, and the preparation process of the perovskite precursor solution is as follows: and dissolving the perovskite, the large-group organic halide and other additives into a dimethyl sulfoxide or dimethyl formamide solvent to obtain a perovskite precursor solution.
Further, the anti-solvent may be introduced before the critical time, at the critical time, and after the critical time; the anti-solvent dropped includes chlorobenzene-trioctylphosphine oxide solution.
And further, spin-coating the perovskite precursor solution on the hole transport layer at a second preset rotation speed for a second spin-coating time, and annealing at a second preset temperature for a second preset time after the anti-solvent is dropped for the introduction time to obtain the light-emitting layer. Wherein the second preset rotating speed is the rotating speed corresponding to the spin-coating perovskite precursor solution, and the second preset rotating speed is 3000-7000 rpm; the second spin-coating time is the spin-coating time corresponding to the spin-coating perovskite precursor solution, and is 30-100 s; the second preset temperature is the annealing temperature corresponding to the perovskite luminescent layer, and the second preset temperature is 0-200 ℃; the second preset time is the annealing time corresponding to the perovskite luminescent layer, and the second preset time is 0-30 min.
In the preparation method of the perovskite light emitting diode provided by the embodiment, the pattern design is carried out on the anode substrate by utilizing the laser etching process; sequentially using deionized water, alkali liquor, isopropanol solution and ethanol solution to ultrasonically clean the anode substrate with the designed pattern, drying after ultrasonic cleaning, and drying in a drying oven; carrying out UV ozone pretreatment on the dried anode substrate; spin-coating the precursor solution of the hole transport layer on an anode substrate pretreated by UV ozone, and then annealing to obtain the hole transport layer; spin-coating a perovskite precursor solution on the hole transport layer, determining critical time by monitoring photoluminescence, selecting introduction time of an anti-solvent by referring to the critical time, introducing the anti-solvent, and annealing to obtain a perovskite luminescent layer; and sequentially evaporating an electron transport layer, an electron injection layer and a cathode on the perovskite luminescent layer by a vacuum thermal evaporation method to obtain the perovskite luminescent diode. Through the steps, in the spin coating process of the perovskite precursor solution, the perovskite is crystallized, and the photoluminescence phenomenon can be observed under the irradiation of an ultraviolet lamp. By the occurrence of fluorescence in the photoluminescence of the perovskite thin film, the dropping time of the introduced anti-solvent can be easily determined, and the accurate control of the dropping time of the anti-solvent is realized. Accurate control of the anti-solvent drop time not only effectively improves PeLEDs performance, but also ensures highly reproducible manufacturing of PeLEDs. Moreover, the present invention determines that proper drop times are independent of environmental conditions, such as process temperature, solvent atmosphere, and spin-coating speed, and can be extended to the fabrication of other types of high-efficiency pelds, thereby providing a versatile method for fabricating pelds with high performance and high reproducibility.
Based on the first embodiment, a second embodiment of the method for manufacturing a perovskite light emitting diode of the present invention is provided, in which the following provides a process for manufacturing a green perovskite light emitting diode, specifically including:
(1) firstly, designing patterns on an ITO substrate by utilizing a laser etching process;
(2) sequentially using deionized water, alkali liquor, isopropanol solution and ethanol solution to respectively perform ultrasonic cleaning on the ITO substrate layer for 15-30min, then drying by blowing, and putting into a drying oven for drying;
(3) carrying out UV ozone pretreatment on the dried ITO glass substrate;
(4) mixing a PEDOT (4083) solution and a ethanolamine solution according to a volume ratio to obtain a cavity layer precursor solution;
(5) spin-coating the hole transport layer precursor solution on the ITO glass substrate treated in the step (3) for 30-100s at the rotating speed of 3000-7000rpm, and annealing at 0-200 ℃ for 0-30 minutes to obtain a hole transport layer;
(6) dissolving cesium bromide (CsBr), lead bromide (PbBr2), phenethyl amine bromide (PEABr) and cyclotetradecane (cyclam) in a dimethyl sulfoxide (DMSO) solvent to obtain a perovskite precursor solution;
(7) putting a 365nm ultraviolet lamp above a spin coater in advance, spin-coating the perovskite precursor solution prepared in the step (6) on the hole transport layer for 30-100s at the rotating speed of 3000-7000rpm, and determining the critical time t by monitoring the photoluminescence phenomenon0Reference critical time t0Is selected atTwo seconds before critical time (t)0-2s), critical time (t)0) Two seconds after the critical time (t)0+2s) respectively introducing an anti-solvent (chlorobenzene-trioctylphosphine oxide solution CB-TOPO), and annealing at 0-200 ℃ for 0-30 minutes to obtain a perovskite luminescent layer;
(8) sequentially evaporating the perovskite luminescent layer prepared in the step (7) by a vacuum thermal evaporation method to form a 20-100nm electron transport layer (TPBi), a 0.5-3nm electron injection Layer (LiF) and a 50-200nm cathode (Al);
(9) finally, the green perovskite light emitting diode is obtained, and the device structure of the green perovskite light emitting diode is as follows from bottom to top: ITO/PEDOT PSS/Perovskite/TPBi/LiF/Al.
Based on the first embodiment, a third embodiment of the method for manufacturing a perovskite light emitting diode of the present invention is provided, in which the following provides a manufacturing process of a blue perovskite light emitting diode, specifically including:
(1) designing patterns on the ITO substrate by using a laser etching process;
(2) sequentially using deionized water, alkali liquor, isopropanol solution and ethanol solution to respectively perform ultrasonic cleaning on the ITO substrate layer for 15-30min, then drying by blowing, and putting into a drying oven for drying;
(3) carrying out UV ozone pretreatment on the dried ITO glass substrate;
(4) mixing a PEDOT (4083) solution and a ethanolamine solution according to a volume ratio to obtain a cavity layer precursor solution;
(5) spin-coating the hole transport layer precursor solution on the ITO glass substrate treated in the step (3) for 30-100s at the rotating speed of 3000-7000rpm, and annealing at 0-200 ℃ for 0-30 minutes to obtain a hole transport layer;
(6) dissolving cesium bromide (CsBr), lead bromide (PbBr2), phenethyl ammonium chloride (PEACl), guanidine bromide (GDBr) and guanidine thiocyanate (GuSCN) in a dimethyl sulfoxide (DMSO) solvent to obtain a perovskite precursor solution;
(7) putting a 365nm ultraviolet lamp above a spin coater in advance, spin-coating the perovskite precursor solution prepared in the step (6) on the hole transport layer for 30-100s at the rotating speed of 3000-7000rpm, and monitoring photoluminescencePhenomenon determination critical time t0Reference critical time t0Two seconds (t) before the critical time is selected0-2s), critical time (t)0) Two seconds after the critical time (t)0+2s) respectively introducing an anti-solvent (chlorobenzene-trioctylphosphine oxide solution CB-TOPO), and annealing at 0-200 ℃ for 0-30 minutes to obtain a perovskite luminescent layer;
(8) sequentially evaporating the perovskite luminescent layer prepared in the step (7) by a vacuum thermal evaporation method to form a 20-100nm electron transport layer (TPBi), a 0.5-3nm electron injection Layer (LiF) and a 50-200nm cathode (Al);
(9) finally obtaining the blue perovskite light emitting diode, wherein the device structure of the blue perovskite light emitting diode is as follows from bottom to top: ITO/PEDOT PSS/Perovskite/TPBi/LiF/Al.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or system. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a process, method, article, or system that comprises the element.
The above-mentioned serial numbers of the embodiments of the present invention are merely for description and do not represent the merits of the embodiments.
Through the above description of the embodiments, those skilled in the art will clearly understand that the method of the above embodiments can be implemented by software plus a necessary general hardware platform, and certainly can also be implemented by hardware, but in many cases, the former is a better implementation manner. Based on such understanding, the technical solution of the present invention may be embodied in the form of a software product, which is stored in a storage medium (e.g., ROM/RAM, magnetic disk, optical disk) as described above and includes instructions for enabling a terminal device (e.g., a mobile phone, a computer, a server, an air conditioner, or a network device) to execute the method according to the embodiments of the present invention.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by using the contents of the present specification and the accompanying drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. The perovskite light emitting diode is characterized by comprising a substrate, an anode, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode from bottom to top in sequence, wherein the light emitting layer is a perovskite light emitting layer;
when the perovskite luminescent layer is prepared, a perovskite precursor solution is coated on the hole transport layer in a rotating mode, critical time is determined by monitoring photoluminescence, an anti-solvent is introduced by selecting anti-solvent introduction time according to the critical time, and then the perovskite luminescent layer is obtained through annealing treatment.
2. The perovskite light emitting diode of claim 1, wherein the anti-solvent introduction time comprises before the critical time, at the critical time, and after the critical time;
the antisolvent comprises a chlorobenzene-trioctylphosphine oxide solution.
3. The perovskite light emitting diode of claim 1, wherein the perovskite precursor solution is prepared by a method comprising: and dissolving the perovskite, the large-group organic halide and other additives into a dimethyl sulfoxide or dimethyl formamide solvent to obtain a perovskite precursor solution.
4. The perovskite light emitting diode of claim 1, wherein when the perovskite light emitting diode is a green perovskite light emitting diode, the perovskite precursor solution is prepared by: and (3) dissolving cesium bromide, lead bromide, phenethyl amine bromide and cyclotetradecane in a dimethyl sulfoxide solvent to obtain the perovskite precursor solution.
5. The perovskite light-emitting diode according to claim 1, wherein when the perovskite light-emitting diode is a blue light optical perovskite light-emitting diode, the perovskite precursor solution is prepared by: and (3) dissolving cesium bromide, lead bromide, phenethyl amine chloride, guanidine bromide and guanidine thiocyanate in a dimethyl sulfoxide solvent to obtain the perovskite precursor solution.
6. The perovskite light emitting diode of claim 1, wherein the anode is indium tin oxide transparent conductive glass or a flexible transparent electrode, the anode having a thickness of 10-300 nm;
the hole transport layer is one or more of PEDOT (Poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid), PVK (polyvinyl carbazole) and Poly-TPD (Poly [ bis (4-phenyl) (4-butylphenyl) amine ]), and the thickness of the hole transport layer is 20-100 nm;
the light-emitting layer comprises one or more of perovskite, large-group organic halide and other additives, and the thickness of the light-emitting layer is 20-100 nm;
the electron transport layer is one or more of TPBi (1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene), POT2T (2,4, 6-tri [3- (diphenylphosphine oxy) phenyl ] -1,3, 5-triazole) and TmPyPB (4, 6-bis (3, 5-di (3-pyridine) phenyl) -2-methylpyrimidine), and the thickness of the electron transport layer is 20-100 nm;
the electron injection layer is Liq (8-hydroxyquinoline-lithium) or LiF (lithium fluoride), and the thickness of the electron injection layer is 0.5-3 nm;
the cathode is one or more of aluminum (Al) or silver (Ag), and the thickness of the cathode is 50-200 nm.
7. A method of manufacturing a perovskite light emitting diode, for manufacturing a perovskite light emitting diode according to any one of claims 1 to 6, the method comprising the steps of:
designing a pattern of the anode substrate by using a laser etching process;
sequentially using deionized water, alkali liquor, isopropanol solution and ethanol solution to ultrasonically clean the anode substrate with the designed pattern, drying after ultrasonic cleaning, and drying in a drying oven;
carrying out UV ozone pretreatment on the dried anode substrate;
spin-coating the precursor solution of the hole transport layer on an anode substrate pretreated by UV ozone, and then annealing to obtain the hole transport layer;
spin-coating a perovskite precursor solution on the hole transport layer, determining critical time by monitoring photoluminescence, selecting introduction time of an anti-solvent by referring to the critical time, introducing the anti-solvent, and annealing to obtain a perovskite luminescent layer;
and sequentially evaporating an electron transport layer, an electron injection layer and a cathode on the perovskite luminescent layer by a vacuum thermal evaporation method to obtain the perovskite luminescent diode.
8. The method of making the perovskite light emitting diode of claim 7, wherein the hole layer precursor solution is prepared by: and mixing the PEDOT/PSS (4083) solution and the ethanolamine solution according to a preset volume ratio to obtain the cavity layer precursor solution.
9. The method of making a perovskite light emitting diode as claimed in claim 7 wherein the ultrasonic cleaning of the patterned anode substrate corresponds to a cleaning time period of 15-30min and the UV ozone pre-treatment of the dried anode substrate corresponds to a treatment time period of 10-20 min.
10. The method of any of claims 7 to 9, wherein the spin coating of the hole transport layer precursor solution corresponds to a rotation speed of 3000-7000rpm and a spin coating time of 30-100s, the hole transport layer corresponding to an annealing temperature of 0-200 ℃ and an annealing time of 0-30 min;
the corresponding rotating speed of the perovskite precursor solution is 3000-7000rpm, the corresponding spin-coating time length is 30-100s, the corresponding annealing temperature of the perovskite luminescent layer is 0-200 ℃, and the corresponding annealing time length is 0-30 minutes.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111785846A (en) * | 2020-06-05 | 2020-10-16 | 北京化工大学 | Green-light perovskite light-emitting diode based on surface post-treatment process and preparation |
| CN111916571A (en) * | 2020-06-24 | 2020-11-10 | 华南理工大学 | Red perovskite light emitting diode based on mixed halogen and preparation method thereof |
| US20210166885A1 (en) * | 2018-08-09 | 2021-06-03 | Soochow University | Method for preparing inorganic perovskite battery based on synergistic effect of gradient annealing and antisolvent, and prepared inorganic perovskite battery |
-
2021
- 2021-09-02 CN CN202111029460.3A patent/CN113823751A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210166885A1 (en) * | 2018-08-09 | 2021-06-03 | Soochow University | Method for preparing inorganic perovskite battery based on synergistic effect of gradient annealing and antisolvent, and prepared inorganic perovskite battery |
| CN111785846A (en) * | 2020-06-05 | 2020-10-16 | 北京化工大学 | Green-light perovskite light-emitting diode based on surface post-treatment process and preparation |
| CN111916571A (en) * | 2020-06-24 | 2020-11-10 | 华南理工大学 | Red perovskite light emitting diode based on mixed halogen and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 夏鹏飞: "准二维钙钛矿发光二极管的制备及性能研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
| 宋博: "基于准二维钙钛矿薄膜与电致发光器件的研究", 《基于准二维钙钛矿薄膜与电致发光器件的研究》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114751933A (en) * | 2022-03-16 | 2022-07-15 | 武汉大学深圳研究院 | Far-red light perovskite luminescent material, device and preparation method |
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