CN110739411A - preparation method of perovskite light-emitting diode capable of improving performance - Google Patents
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Abstract
The invention provides preparation methods capable of improving the performance of perovskite light-emitting diodes, which have obvious advantages in improving the coverage of perovskite thin films and improving the light-emitting efficiency and stability of perovskite light-emitting diodes.
Description
Technical Field
The invention relates to the technical field of light emitting diodes, in particular to a preparation method of perovskite light emitting diodes with improved performance.
Background
The metal halogenated perovskite semiconductor material has attracted attention of researchers in the field of photoelectric energy sources by virtue of the advantages of high optical absorption coefficient, long carrier diffusion length, low defect state density, high carrier mobility, high fluorescence quantum efficiency and the like, and in recent years, the metal halogenated perovskite semiconductor material has been developed in a rapid manner in the field of electroluminescence.
Perovskite light emitting diodes (Pelens) capable of operating at room temperature, first reported by Richard H.friend and Zhi-Kuang Tan et al in 2014, as MAPbI3-XAnd MAPbBr3(MA＝CH3NH3 +) PeLEDs as the near-infrared and green light emitting layers achieve External Quantum Efficiency (EQE) of 0.76% and 0.1%, respectively (nat. nanotechnol.2014,9,687), then, PeLEDs have attracted more and more researchers to invest research, researchers have conducted extensive systematic research on PeLEDs through aspects of precursor material selection, precursor proportion regulation, luminescent layer defect suppression, luminescent layer interface engineering, etc., which also steadily improves the performance of PeLEDs, at present, PeLEDs based on near-infrared and green light have both broken through 20%, both research results are published on international top-level Nature, wherein the group of huangweishi and professor of wanqian professor have been led by simple low-temperature solution methods, a luminescent layer consisting of layers of discontinuous, irregularly distributed perovskite grains dense and low-refractive-index organic insulating layers embedded between the perovskite grains is realized by simple low-temperature solution methods, the light emitting layer consisting of perovskite layers dense and low-refractive-index organic insulating layers embedded between the perovskite grains is foreseen by pesmart perovskite luminous efficiency, which we have a balanced perovskite luminous efficiency of luminous efficiency, which is improved by the peweiqi and the future research of pekowsto show that the pekowste is achieved by pekowste research by pekowset 7, pekowsterics, and the pekowset 7, pekowsterical research shows that pekowsterics are excellent by the pekowsterical application of pekowsterical publication No. 36, and the pekowsteri, the pekows.
Although the performance of PeLEDs is greatly improved in short years, compared with the commercialized organic light emitting diode and inorganic quantum dot light emitting diode (EQE: 25% or more), the luminous efficiency and stability of PeLEDs have a large improvement space. At present, the main method for improving the luminous efficiency of the PelLEDs is to regulate and control the appearance of a luminous layer and inhibit defects. Since the perovskite material has very good crystallization property, larger crystal grains are easily formed in the film forming process, so that the coverage of a thinner light emitting layer is poorer, the defect density at the grain boundary is increased, and the light emitting performance of a device is influenced. Such discontinuous light emitting layers may also lead to increased device leakage current or increased risk of device shorting. Therefore, obtaining a perovskite light emitting layer that is uniform and dense and has high fluorescence quantum efficiency is crucial to achieving efficient PeLEDs.
Disclosure of Invention
The invention provides perovskite light-emitting diode preparation methods capable of improving performance, aiming at solving the technical problems that in the perovskite light-emitting diode preparation methods in the prior art, the inorganic perovskite light-emitting layer has limited solubility, and the thin film is easy to crystallize to form an uneven and discontinuous perovskite light-emitting layer.
The technical scheme of the preparation method of the perovskite light-emitting diode is as follows:
A method for preparing perovskite light emitting diode with improved performance, comprising the following steps:
i, preparing an anode interface layer on a substrate with a patterned transparent anode layer;
step ii, preparing an anode interface modification layer on the anode interface layer;
step iii, growing a perovskite luminous layer on the anode interface modification layer;
and iv, sequentially obtaining a cathode interface layer, a cathode interface modification layer and a cathode layer above the perovskite luminous layer through evaporation.
In the above technical scheme, in step ii, the anode interface modification layer is made of an alcohol amine compound.
In the above technical solution, step ii includes: uniformly coating the entire substrate with an alcamines compound solution by spin coating, controlling the spin coating speed to be 1000-;
the preparation method of the alcohol amine compound solution comprises the following steps: ethanol is used as a solvent, 5-40% alcohol amine solution is prepared, and the mixture is fully stirred at normal temperature.
In the technical scheme, the alcohol amine compound is ethanolamine, isopropanolamine, n-propanolamine or isobutanolamine.
In the above technical solution, in step i, the patterned transparent anode layer is an indium tin oxide electrode, and the thickness is 50-200 nm.
In the above technical scheme, in step i, the anode interface layer is poly thiophene derivative poly (3, 4-ethylenedioxythiophene) (PEDOT) doped polystyrene sulfonic acid (PSS), and the thickness is 10-50 nm.
In the above technical scheme, in step iii, the perovskite luminescent layer is a pure inorganic perovskite CsPbBr3Or CsPbCl3Or CsPbI3 kinds or more, the thickness is 10-50 nm.
In the above technical scheme, in the step iv, the cathode interface layer is TPBi, and the thickness is 5-50 nm.
In the above technical scheme, in the step iv, the cathode interface modification layer is LiF, and the thickness is 0.5-2 nm.
In the above technical solution, in the step iv, the cathode layer is aluminum or silver, and has a thickness of 20-100 nm.
The preparation method of the perovskite light-emitting diode capable of improving the performance has the following beneficial effects:
the preparation method of the perovskite light-emitting diode has obvious advantages in improving the coverage of the perovskite thin film and improving the light-emitting efficiency and stability of the perovskite light-emitting diode. Aiming at the problems that the solubility of an inorganic perovskite luminescent layer is limited, and the film is easy to crystallize to form an uneven and discontinuous perovskite luminescent layer, so that the performance of a device is influenced, the appearance of the perovskite film is effectively improved by adopting an alcohol amine compound as an anode interface modification layer, the coverage of the film is improved, the internal defects of the film and the leakage current of the device are reduced, and the performance and the stability of the luminescent device are further improved.
Drawings
FIG. 1 is a schematic diagram of a perovskite light emitting diode device fabricated using the method of the present invention.
FIG. 2 is a scanning electron micrograph of a perovskite thin film, wherein (a) is a scanning electron micrograph of a perovskite thin film in comparative example I, and (b) is a scanning electron micrograph of a perovskite thin film in example 1.
FIG. 3 is a photoluminescence spectrum of the perovskite thin film in comparative example I (curve 1) and example 1 (curve 2).
FIG. 4 is a graph of the perovskite light emitting device performance of comparative example I (curve 1) and example 1 (curve 2), wherein (a) is a current density-voltage relationship and (b) is a luminance-voltage relationship.
The reference numerals in the figures denote:
1-a substrate; 2-a patterned transparent anode layer; 3-anode interface layer; 4-anode interface modification layer;
a 5-perovskite light emitting layer; 6-a cathode interface layer; 7-cathode interface modification layer; 8-cathode layer.
Detailed Description
The invention provides a preparation method of perovskite light-emitting diodes with improved performance, and the structure of the perovskite light-emitting diode device is shown in figure 1:
the substrate 1 is made of transparent materials such as glass, quartz and the like, and the thickness is 1-5 mm;
the material of the patterned transparent anode layer 2 is an Indium Tin Oxide (ITO) transparent conductive film with high transmittance and high conductivity, and the thickness is 50-200 nanometers;
the anode interface layer 3 is PEDOT: PSS with a thickness of 10-50 nm;
the anode interface modification layer 4 is an alcohol amine compound, specifically ethanolamine, isopropanolamine, n-propanolamine or isobutanolamine.
The perovskite luminescent layer 5 is pure inorganic perovskite CsPbBr3Or CsPbCl3Or CsPbI3 or more kinds of them, the thickness is 10-50 nm;
the cathode interface layer 6 is TPBi, and the thickness is 5-50 nanometers;
the cathode interface modification layer 7 is LiF with the thickness of 0.5-2 nanometers
And the cathode layer 8 is made of metal aluminum or silver and has the thickness of 20-100 nanometers.
The preparation method of the perovskite light-emitting diode capable of improving the performance comprises the following process steps and conditions:
A method for preparing perovskite light emitting diode with improved performance, comprising the following steps:
step 1), preparing an anode interface layer 3 on a substrate 1 with a patterned transparent anode layer 2;
step 2), preparing an anode interface modification layer 4 on the substrate of the anode interface layer 3;
step 3), growing a perovskite light-emitting layer 5 on the anode modification layer 4;
and 4) evaporating above the perovskite luminescent layer 5 to obtain a cathode interface layer 6, a cathode interface modification layer 7 and a cathode layer 8.
Specifically, the method comprises the following steps:
1) placing a cleaned substrate 1 with a patterned transparent anode layer 2 with the thickness of 50-200 nanometers on a bracket of a spin coater, uniformly coating PEDOT (PSS) on the whole wafer through a 0.45-micrometer filter head, forming anode interface layers 3 with the thickness of 10-50 nanometers on the surfaces of transparent electrodes by adjusting the rotation speed of the spin coater to 1000-5000 revolutions per minute, and placing the transparent electrodes into an oven with the temperature of 120 ℃ to heat for 30 minutes;
2) the transparent anode substrate coated with PEDOT, PSS is placed on a bracket of a spin coater after being cooled, the entire wafer is uniformly coated with an alcohol amine solution, layers of monomolecular anode interface modification layers 4 are formed on the surface of the transparent electrode by adjusting the rotation speed of the spin coater to 1000-;
the preparation method of the alcohol amine solution comprises the following steps: ethanol is used as a solvent, an alcohol amine solution with the solution concentration of 5-40% is prepared, and the mixture is stirred for 1 hour at normal temperature;
3) transferring the substrate into a glove box, placing the glove box on a bracket of a spin coater, uniformly dripping the mixed perovskite precursor solution on the substrate 1, adjusting the rotation speed of the spin coater to 1000-;
the preparation method of the perovskite precursor solution comprises the following steps: uses dimethyl sulfoxide as solvent, inorganic perovskite CsPbBr3Or CsPbCl3Or CsPbI3 or more of them are solutes with the concentration of 10-40%, and the solution is heated and stirred for 3 hours at 60 ℃, and then the heating is stopped and the stirring is continued for 12 hours;
4) putting the product obtained in the step 3) into a vacuum coating machine for vacuumizing until the vacuum degree reaches 4 multiplied by 10-4And evaporating a cathode interface layer 6 with the thickness of 5-50 nanometers, a cathode interface modification layer 7 with the thickness of 0.5-2 nanometers and a cathode layer 8 with the thickness of 20-100 nanometers in sequence in pascal.
And then testing.
For purposes of making the objects, aspects and advantages of the present invention more apparent, the present invention will be described in detail in with reference to the following embodiments, which are to be construed as merely illustrative and not limitative of the remainder of the disclosure.
Comparative example i:
the method of manufacturing the perovskite light emitting diode of the present comparative example includes the steps of:
1) placing a cleaned glass substrate with 120-nanometer-thick patterned transparent anode ITO on a bracket of a spin coater, uniformly coating PEDOT (sodium dodecyl benzene sulfonate) PSS (sodium dodecyl benzene sulfonate) on the whole wafer through a 0.45-micrometer filter head, forming layers of 30-nanometer-thick anode interface layers on the surface of a transparent electrode by regulating the rotation speed of the spin coater to 2500 rpm, and placing the transparent electrode into a 120-DEG C oven to be heated for 30 minutes;
2) transferring the substrate into a glove box, placing the glove box on a bracket of a spin coater, uniformly dripping the mixed perovskite precursor solution on the substrate, adjusting the rotation speed of the spin coater to 2500 rpm, and performing spin coating for 1 minute to obtain a perovskite luminescent layer with the thickness of 30 nanometers;
the preparation method of the perovskite precursor solution comprises the following steps: uses dimethyl sulfoxide as solvent, inorganic perovskite CsPbBr3Heating and stirring at 60 deg.C for 3 hr, stopping heating, and stirring for 12 hr;
3) putting the product obtained in the step 2) into a vacuum coating machine for vacuumizing until the vacuum degree reaches 4 multiplied by 10-4And evaporating a TPBi cathode interface layer with the thickness of 20 nanometers, a LiF cathode interface modification layer with the thickness of 1 nanometer and an Al cathode layer with the thickness of 100 nanometers in sequence in pascal.
Comparative example ii:
the method of manufacturing the perovskite light emitting diode of the present comparative example includes the steps of:
1) placing a cleaned glass substrate with 50-nanometer patterned transparent anode ITO on a bracket of a spin coater, uniformly coating PEDOT (sodium dodecyl benzene sulfonate) PSS (sodium dodecyl benzene sulfonate) on the whole wafer through a 0.45-micrometer filter head, forming anode interface layers with the thickness of 50 nanometers on the surface of a transparent electrode by adjusting the rotation speed of the spin coater to 1000 rpm, and placing the transparent electrode in an oven at 120 ℃ for heating for 30 minutes;
2) transferring the substrate into a glove box, placing the glove box on a bracket of a spin coater, uniformly dripping the mixed perovskite precursor solution on the substrate, adjusting the rotation speed of the spin coater to 5000 rpm, and performing spin coating for 1 minute to obtain a perovskite luminescent layer with the thickness of 10 nanometers;
the preparation method of the perovskite precursor solution comprises the following steps: uses dimethyl sulfoxide as solvent, inorganic perovskite CsPbCl3Heating and stirring at 60 deg.C for 3 hr, stopping heating, and stirring for 12 hr;
3) putting the product obtained in the step 2) into a vacuum coating machine for vacuumizing until the vacuum degree reaches 4 multiplied by 10-4And evaporating a TPBi cathode interface layer with the thickness of 50 nanometers, a LiF cathode interface modification layer with the thickness of 2 nanometers and an Ag cathode layer with the thickness of 20 nanometers in sequence in pascal.
Comparative example iii:
the method of manufacturing the perovskite light emitting diode of the present comparative example includes the steps of:
1) placing a cleaned glass substrate with 200-nanometer patterned transparent anode ITO on a bracket of a spin coater, uniformly coating PEDOT (sodium dodecyl benzene sulfonate) PSS (sodium dodecyl benzene sulfonate) on the whole wafer through a 0.45-micrometer filter head, forming anode interface layers with the thickness of 10 nanometers on the surface of a transparent electrode by adjusting the rotation speed of the spin coater to 5000 rpm, and placing the transparent electrode into a 120-DEG C oven to be heated for 30 minutes;
2) transferring the substrate into a glove box, placing the glove box on a bracket of a spin coater, uniformly dripping the mixed perovskite precursor solution on the substrate, adjusting the rotation speed of the spin coater to 1000 revolutions per minute, and performing spin coating for 1 minute to obtain a 50-nanometer-thick perovskite luminescent layer;
the preparation method of the perovskite precursor solution comprises the following steps: uses dimethyl sulfoxide as solvent, inorganic perovskite CsPbI3Heating and stirring at 60 deg.C for 3 hr, stopping heating, and stirring for 12 hr;
3) putting the product obtained in the step 2) into a vacuum coating machine for vacuumizing until the vacuum degree reaches 4 multiplied by 10-4And evaporating a TPBi cathode interface layer with the thickness of 5 nanometers, a LiF cathode interface modification layer with the thickness of 0.5 nanometers and an Al cathode layer with the thickness of 80 nanometers in sequence in pascal.
Comparative example iv:
the method of manufacturing the perovskite light emitting diode of the present comparative example includes the steps of:
1) placing a cleaned quartz substrate with 50-nanometer patterned transparent anode ITO on a bracket of a spin coater, uniformly coating PEDOT (sodium dodecyl benzene sulfonate) PSS (sodium dodecyl benzene sulfonate) on the whole wafer through a 0.45-micrometer filter head, forming anode interface layers with the thickness of 50 nanometers on the surface of a transparent electrode by adjusting the rotation speed of the spin coater to 1000 rpm, and placing the transparent electrode in an oven at 120 ℃ for heating for 30 minutes;
2) transferring the substrate into a glove box, placing the glove box on a bracket of a spin coater, uniformly dripping the mixed perovskite precursor solution on the substrate, adjusting the rotation speed of the spin coater to 5000 rpm, and performing spin coating for 1 minute to obtain a perovskite luminescent layer with the thickness of 10 nanometers;
the preparation method of the perovskite precursor solution comprises the following steps: uses dimethyl sulfoxide as solvent, inorganic perovskite CsPbCl3And CsPbBr3Heating and stirring at 60 deg.C for 3 hr, stopping heating, and stirring for 12 hr;
3) putting the product obtained in the step 2) into a vacuum coating machine for vacuumizing until the vacuum degree reaches 4 multiplied by 10-4And evaporating a TPBi cathode interface layer with the thickness of 50 nanometers, a LiF cathode interface modification layer with the thickness of 2 nanometers and an Ag cathode layer with the thickness of 20 nanometers in sequence in pascal.
Example 1:
the preparation method of the perovskite light emitting diode comprises the following steps:
1) placing a cleaned glass substrate with 120-nanometer-thick patterned transparent anode ITO on a bracket of a spin coater, uniformly coating PEDOT (sodium dodecyl benzene sulfonate) PSS (sodium dodecyl benzene sulfonate) on the whole wafer through a 0.45-micrometer filter head, forming layers of 30-nanometer-thick anode interface layers on the surface of a transparent electrode by regulating the rotation speed of the spin coater to 2500 rpm, and placing the transparent electrode into a 120-DEG C oven to be heated for 30 minutes;
2) cooling the transparent anode substrate coated with PEDOT (PSS), placing the cooled transparent anode substrate on a bracket of a spin coater, uniformly coating the ethanolamine solution on the whole wafer, forming monomolecular anode interface modification layers on the surface of the transparent electrode by adjusting the rotating speed of the spin coater to 2500 rpm, and placing the transparent anode substrate on a hot table at 140 ℃ for heating for 15 minutes;
the preparation method of the ethanolamine solution comprises the following steps: ethanol is used as a solvent, ethanolamine solution with the concentration of 10% is prepared, and the mixture is stirred for 1 hour at normal temperature;
3) transferring the substrate into a glove box, placing the glove box on a bracket of a spin coater, uniformly dripping the mixed perovskite precursor solution on the substrate, adjusting the rotation speed of the spin coater to 2500 rpm, and performing spin coating for 1 minute to obtain a perovskite luminescent layer with the thickness of 30 nanometers;
as described aboveThe preparation method of the perovskite precursor solution comprises the following steps: uses dimethyl sulfoxide as solvent, inorganic perovskite CsPbBr3Heating and stirring at 60 deg.C for 3 hr, stopping heating, and stirring for 12 hr;
4) putting the product obtained in the step 3) into a vacuum coating machine for vacuumizing until the vacuum degree reaches 4 multiplied by 10-4And evaporating a TPBi cathode interface layer with the thickness of 20 nanometers, a LiF cathode interface modification layer with the thickness of 1 nanometer and an Al cathode layer with the thickness of 100 nanometers in sequence in pascal.
Example 2:
the preparation method of the perovskite light emitting diode comprises the following steps:
1) placing a cleaned glass substrate with a 50-nanometer-thick patterned transparent anode ITO on a bracket of a spin coater, uniformly coating PEDOT (sodium dodecyl benzene sulfonate) PSS (sodium dodecyl benzene sulfonate) on the whole wafer through a 0.45-micrometer filter head, forming anode interface layers with the thickness of 50 nanometers on the surface of a transparent electrode by adjusting the rotation speed of the spin coater to 1000 rpm, and placing the transparent electrode in an oven at 120 ℃ for heating for 30 minutes;
2) PSS is coated on the transparent anode substrate, the transparent anode substrate is placed on a bracket of a spin coater after being cooled, isopropanolamine solution is uniformly coated on the whole wafer, layers of monomolecular anode interface modification layers are formed on the surface of the transparent electrode by adjusting the rotating speed of the spin coater to 5000 revolutions per minute, and the transparent anode substrate is placed on a hot table at 140 ℃ for heating for 15 minutes;
the preparation method of the isopropanolamine solution comprises the following steps: preparing 5% isopropanolamine solution by using ethanol as a solvent, and stirring for 1 hour at normal temperature;
3) transferring the substrate into a glove box, placing the glove box on a bracket of a spin coater, uniformly dripping the mixed perovskite precursor solution on the substrate, adjusting the rotation speed of the spin coater to 5000 rpm, and performing spin coating for 1 minute to obtain a perovskite luminescent layer with the thickness of 10 nanometers;
the preparation method of the perovskite precursor solution comprises the following steps: uses dimethyl sulfoxide as solvent, inorganic perovskite CsPbCl3As solute, the concentration of the solution is 10 percent, and the solution is heated and stirred at 60 DEGStirring for 3 hours, stopping heating, and continuing stirring for 12 hours;
4) putting the product obtained in the step 3) into a vacuum coating machine for vacuumizing until the vacuum degree reaches 4 multiplied by 10-4And evaporating a TPBi cathode interface layer with the thickness of 50 nanometers, a LiF cathode interface modification layer with the thickness of 2 nanometers and an Ag cathode layer with the thickness of 20 nanometers in sequence in pascal.
Example 3:
the preparation method of the perovskite light emitting diode comprises the following steps:
1) placing a cleaned glass substrate with 200-nanometer-thick patterned transparent anode ITO on a bracket of a spin coater, uniformly coating PEDOT (sodium dodecyl benzene sulfonate) PSS (sodium dodecyl benzene sulfonate) on the whole wafer through a 0.45-micrometer filter head, forming layers of 10-nanometer-thick anode interface layers on the surface of a transparent electrode by adjusting the rotation speed of the spin coater to 5000 rpm, and placing the transparent electrode in a 120-DEG C oven for heating for 30 minutes;
2) PSS is coated on the transparent anode substrate, the transparent anode substrate is placed on a bracket of a spin coater after being cooled, n-propanolamine solution is uniformly coated on the whole wafer, layers of monomolecular anode interface modification layers are formed on the surface of the transparent electrode by adjusting the rotating speed of the spin coater to 1000 revolutions per minute, and the transparent anode substrate is placed on a hot table at 140 ℃ for heating for 15 minutes;
the preparation method of the n-propanolamine solution comprises the following steps: preparing a 40% n-propanolamine solution by using ethanol as a solvent, and stirring for 1 hour at normal temperature;
3) transferring the substrate into a glove box, placing the glove box on a bracket of a spin coater, uniformly dripping the mixed perovskite precursor solution on the substrate, adjusting the rotation speed of the spin coater to 1000 revolutions per minute, and performing spin coating for 1 minute to obtain a 50-nanometer-thick perovskite luminescent layer;
the preparation method of the perovskite precursor solution comprises the following steps: uses dimethyl sulfoxide as solvent, inorganic perovskite CsPbI3Heating and stirring at 60 deg.C for 3 hr, stopping heating, and stirring for 12 hr;
4) putting the product obtained in the step 3) into a vacuum coating machine for vacuumizing until the vacuum degree reaches4×10-4And evaporating a TPBi cathode interface layer with the thickness of 5 nanometers, a LiF cathode interface modification layer with the thickness of 0.5 nanometers and an Al cathode layer with the thickness of 80 nanometers in sequence in pascal.
Example 4:
the preparation method of the perovskite light emitting diode comprises the following steps:
1) placing a cleaned quartz substrate with a 50-nanometer-thick patterned transparent anode ITO on a bracket of a spin coater, uniformly coating PEDOT (sodium dodecyl benzene sulfonate) PSS (sodium dodecyl benzene sulfonate) on the whole wafer through a 0.45-micrometer filter head, forming anode interface layers with the thickness of 50 nanometers on the surface of a transparent electrode by adjusting the rotation speed of the spin coater to 1000 rpm, and placing the transparent electrode in an oven at 120 ℃ for heating for 30 minutes;
2) PSS, cooling the transparent anode substrate coated with PEDOT, placing the substrate on a bracket of a spin coater, uniformly coating the entire wafer with an isobutanol amine solution, forming layers of monomolecular anode interface modification layers on the surface of the transparent electrode by adjusting the rotating speed of the spin coater to 5000 rpm, and placing the transparent anode substrate on a hot table at 140 ℃ for heating for 15 minutes;
the preparation method of the isobutanolamine solution comprises the following steps: preparing an isobutanol amine solution with the concentration of 5% by using ethanol as a solvent, and stirring for 1 hour at normal temperature;
3) transferring the substrate into a glove box, placing the glove box on a bracket of a spin coater, uniformly dripping the mixed perovskite precursor solution on the substrate, adjusting the rotation speed of the spin coater to 5000 rpm, and performing spin coating for 1 minute to obtain a perovskite luminescent layer with the thickness of 10 nanometers;
the preparation method of the perovskite precursor solution comprises the following steps: uses dimethyl sulfoxide as solvent, inorganic perovskite CsPbCl3And CsPbBr3Heating and stirring at 60 deg.C for 3 hr, stopping heating, and stirring for 12 hr;
4) putting the product obtained in the step 3) into a vacuum coating machine for vacuumizing until the vacuum degree reaches 4 multiplied by 10-4Sequentially evaporating a TPBi cathode interface layer with the thickness of 50 nanometers, a LiF cathode interface modification layer with the thickness of 2 nanometers and an Ag cathode layer with the thickness of 20 nanometers in pascal。
As can be understood from the various examples and comparative examples above:
FIG. 2 is a scanning electron micrograph of the perovskite thin film in comparative example I and example 1. It can be seen from fig. 2 that in comparative example i, in which no anode interface modification layer ethanolamine was used, the perovskite thin film had a large crystal grain size and poor film coverage, whereas in example 1, in which ethanolamine was used as the anode interface modification layer, the perovskite thin film had a crystal grain size significantly reduced, and the thin film was uniform and continuous and had good coverage.
FIG. 3 is a photoluminescence spectrum of the perovskite thin films in comparative example I and example 1. Fig. 3 shows that the photoluminescence intensity of the perovskite thin film of example 1 treated by the ethanolamine as the anode interface modification layer is obviously improved compared with that of the perovskite thin film of comparative example i without treatment, which indicates that the ethanolamine can effectively inhibit the formation of the perovskite thin film defects at the anode interface layer, and further improve the luminescence performance of the thin film. The light intensity is given in candelas (cd) in fig. 3.
Fig. 4 is a comparison spectrum of the performance of the perovskite light emitting device of comparative example i and example 1, and it can be seen from the graph that, compared with comparative example i, example 1 has higher current density under the same voltage, which shows that it has smaller leakage current and higher brightness, thus showing that the ethanolamine anode interface modification layer effectively improves the light emitting performance of the device.
In another aspect, Table 1 below shows the luminescence performance parameters of comparative examples I, II, III, IV and examples 1, 2, 3, 4. similarly, example 1 has higher brightness, current efficiency and lifetime (21800 candela per square centimeter, 16.4 candela per ampere and 6 minutes) than comparative example I. similarly, examples 2, 3,4 also have higher brightness, current efficiency and lifetime, respectively, than comparative examples II, III, IV, thus demonstrating the superior luminescence and stability of the examples of the invention compared to their respective counterparts, thereby demonstrating the significant advantage of the method of the invention in improving the performance of perovskite light emitting diodes.
TABLE 1
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1, A method for preparing a perovskite light emitting diode with improved performance, comprising the steps of:
i, preparing an anode interface layer (3) on a substrate (1) with a patterned transparent anode layer (2);
step ii, preparing an anode interface modification layer (4) on the anode interface layer (3);
step iii, growing a perovskite luminous layer (5) on the anode interface modification layer (4);
and iv, sequentially obtaining a cathode interface layer (6), a cathode interface modification layer (7) and a cathode layer (8) above the perovskite luminescent layer (5) through evaporation.
2. The method according to claim 1, wherein in step ii, the anode interface modification layer (4) is made of an alcohol amine compound.
3. The method of claim 2, wherein step ii comprises:
uniformly coating the entire substrate (1) with an alcamines compound solution by spin coating, controlling the spin coating speed to be 1000-;
the preparation method of the alcohol amine compound solution comprises the following steps: ethanol is used as a solvent, 5-40% alcohol amine solution is prepared, and the mixture is fully stirred at normal temperature.
4. The method according to claim 2 or 3, wherein the alkanolamine compound is ethanolamine, isopropanolamine, n-propanolamine or isobutanolamine.
5. The method of claim 4, wherein in step i, the patterned transparent anode layer (2) is an indium tin oxide electrode having a thickness of 50-200 nm.
6. The preparation method according to claim 4, characterized in that in step i, the anode interface layer (3) is poly (3, 4-ethylenedioxythiophene) doped polystyrene sulfonic acid, a polythiophene derivative, and has a thickness of 10-50 nm.
7. A production method according to claim 4, characterized in that, in step iii, the perovskite light-emitting layer (5) is a pure inorganic perovskite CsPbBr3Or CsPbCl3Or CsPbI3 kinds or more, the thickness is 10-50 nm.
8. The method of claim 4, wherein in step iv, the cathode interfacial layer (6) is TPBi and has a thickness of 5 to 50 nm.
9. The method according to claim 4, wherein in step iv, the cathode interface modification layer (7) is LiF and has a thickness of 0.5-2 nm.
10. The method of claim 4, wherein in step iv, the cathode layer (8) is aluminum or silver and has a thickness of 20-100 nm.
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