CN110739411B - Preparation method of perovskite light-emitting diode capable of improving performance - Google Patents
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Abstract
The invention provides a preparation method capable of improving the performance of a perovskite light-emitting diode. 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 problem 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 as to influence the performance of a device, the alcohol amine compound is adopted as an anode interface modification layer to effectively improve the appearance of the perovskite film, improve the coverage of the film, reduce the internal defects of the film and the leakage current of the device, and further improve the performance and the stability of the luminescent device.
Description
Technical Field
The invention relates to the technical field of light emitting diodes, in particular to a preparation method of a perovskite light emitting diode capable of improving performance.
Background
The metal halogenated perovskite semiconductor material is widely focused by 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. In recent years, the field of electroluminescence has been developed dramatically.
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 +) Near-infrared and green pelds as the light emitting layer achieved External Quantum Efficiencies (EQE) of 0.76% and 0.1%, respectively (nat. nanotechnol.2014,9,687). Subsequently, pelds attract more and more researchers to be put into research, and researchers carry out a great deal of systematic research on pelds through aspects such as precursor material selection, precursor proportion regulation, luminescent layer defect inhibition, luminescent layer interface engineering and the like, so that the performance of pelds is stably improved. At present, the EQE of PeLEDs based on near-infrared light and green light has broken through 20%, and both research results are published in the international top-level journal Nature. The group led by the professor of huang wei hospital and wang jian pu realizes a light-emitting layer consisting of a layer of discontinuous and irregularly distributed perovskite crystal grains and a low-refractive-index organic insulating layer embedded between the perovskite crystal grains by a simple low-temperature solution method, so that the light extraction efficiency of the infrared PeLED is greatly improved, and the EQE of the PeLED prepared by the method reaches 20.7% (Nature 2018,562,249). In addition, the subject group of the professor of the weizhou dynasty of the university of the chinese qiao obtains a flat, dense and excellent perovskite thin film by utilizing the component distribution control strategy of perovskite, and improves the injection balance of electron holes by adding a barrier layer, so that the EQE of the green light emitting PeLED reaches 20.3% (Nature 2017,550, 92). Due to the rapid development of PeLEDs, we foresee that PeLEDs will have a wide application prospect in the future display field.
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 a preparation method of a perovskite light-emitting diode, which can improve the performance, and aims to solve the technical problems that in the preparation method of the perovskite light-emitting diode in the prior art, the solubility of an inorganic perovskite light-emitting layer is limited, and a 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 preparation method of a perovskite light-emitting diode capable of improving performance comprises 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 CsPbI3One or more of them, 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 idea of the invention is as follows: the perovskite light emitting diode device structure related to the preparation method of the perovskite light emitting diode capable of improving the performance is shown as the following 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 CsPbI3One or more 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 preparation method of a perovskite light-emitting diode capable of improving performance comprises 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) clean substrate 1 with a 50-200 nm thick patterned transparent anode layer 2 was placed on the spin coater tray and the PEDOT: PSS was evenly coated over the entire wafer, and the spin speed of the spin coater was adjusted to 1000-: PSS forms a layer of anode interface layer 3 with the thickness of 10-50 nanometers on the surface of the transparent electrode, and the anode interface layer is put into a drying oven with the temperature of 120 ℃ to be heated for 30 minutes;
2) coating the above-mentioned substrate with PEDOT: the PSS transparent anode substrate is placed on a bracket of a spin coater after being cooled, the entire wafer is uniformly coated with an alcohol amine solution, a monomolecular anode interface modification layer 4 is 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-;
as described aboveThe preparation method of the perovskite precursor solution comprises the following steps: uses dimethyl sulfoxide as solvent, inorganic perovskite CsPbBr3Or CsPbCl3Or CsPbI3One or more of the solute(s) is/are 10-40%, the solution is heated and stirred for 3 hours at 60 ℃, 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.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and it should be understood that the specific examples described herein are only for the purpose of explaining the present invention and are not intended to limit the present invention.
Comparative example i:
the method of manufacturing the perovskite light emitting diode of the present comparative example includes the steps of:
1) the cleaned glass substrate with the patterned transparent anode ITO 120 nm thick was placed on a cradle of a spin coater, and the PEDOT: PSS was evenly spread over the entire wafer and the spin speed of the spin coater was adjusted to 2500 rpm to allow the PEDOT: PSS forms a layer of anode interface layer with the thickness of 30 nanometers on the surface of the transparent electrode, and the anode interface layer is put into a 120 ℃ 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) intoVacuumizing in a vacuum coating machine, and when 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) the cleaned glass substrate with the 50 nm patterned transparent anode ITO was placed on a cradle of a spin coater, and the PEDOT: PSS was evenly spread over the entire wafer, and the spin speed of the spin coater was adjusted to 1000 rpm to maintain the PEDOT: PSS forms a 50 nm-thick anode interface layer on the surface of the transparent electrode, and the anode interface layer is placed in a 120 ℃ 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 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) the cleaned glass substrate with the 200 nm patterned transparent anode ITO was placed on a cradle of a spin coater, and the PEDOT: PSS was evenly spread over the entire wafer and the spin speed of the spin coater was adjusted to 5000 rpm to maintain the PEDOT: PSS forms a layer of anode interface layer with the thickness of 10 nanometers on the surface of the transparent electrode, and the anode interface layer is put into a 120 ℃ 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) the cleaned quartz substrate with the 50 nm patterned transparent anode ITO was placed on a cradle of a spin coater, and the PEDOT: PSS was evenly spread over the entire wafer, and the spin speed of the spin coater was adjusted to 1000 rpm to maintain the PEDOT: PSS forms a 50 nm-thick anode interface layer on the surface of the transparent electrode, and the anode interface layer is placed in a 120 ℃ 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 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 vacuum platingVacuumizing in a film machine, and when 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) the cleaned glass substrate with the patterned transparent anode ITO 120 nm thick was placed on a cradle of a spin coater, and the PEDOT: PSS was evenly spread over the entire wafer and the spin speed of the spin coater was adjusted to 2500 rpm to allow the PEDOT: PSS forms a layer of anode interface layer with the thickness of 30 nanometers on the surface of the transparent electrode, and the anode interface layer is put into a 120 ℃ oven to be heated for 30 minutes;
2) coating the above-mentioned substrate with PEDOT: the PSS transparent anode substrate is placed on a bracket of a spin coater after being cooled, ethanolamine solution is uniformly coated on the whole wafer, a monomolecular anode interface modification layer is formed on the surface of a transparent electrode by adjusting the rotating speed of the spin coater to 2500 rpm, and the transparent anode substrate is placed 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;
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;
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 20 nanometers, a LiF cathode interface modification layer with the thickness of 1 nanometer and an A with the thickness of 100 nanometers in pascall cathode layer.
Example 2:
the preparation method of the perovskite light emitting diode comprises the following steps:
1) the cleaned glass substrate with the 50 nm thick patterned transparent anode ITO was placed on a cradle of a spin coater, and the PEDOT: PSS was evenly spread over the entire wafer, and the spin speed of the spin coater was adjusted to 1000 rpm to maintain the PEDOT: PSS forms a 50 nm-thick anode interface layer on the surface of the transparent electrode, and the anode interface layer is placed in a 120 ℃ oven to be heated for 30 minutes;
2) coating the above-mentioned substrate with PEDOT: the PSS transparent anode substrate is placed on a bracket of a spin coater after being cooled, isopropanolamine solution is uniformly coated on the whole wafer, a monomolecular anode interface modification layer is formed on the surface of a transparent electrode by adjusting the rotating speed of the spin coater to 5000 rpm, 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 CsPbCl3Heating 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 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) the cleaned glass substrate with the 200 nm thick patterned transparent anode ITO was placed on a cradle of a spin coater, and the PEDOT: PSS was evenly spread over the entire wafer and the spin speed of the spin coater was adjusted to 5000 rpm to maintain the PEDOT: PSS forms a layer of anode interface layer with the thickness of 10 nanometers on the surface of the transparent electrode, and the anode interface layer is put into a 120 ℃ oven to be heated for 30 minutes;
2) coating the above-mentioned substrate with PEDOT: the PSS 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, a monomolecular anode interface modification layer is formed on the surface of a 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 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.
Example 4:
the preparation method of the perovskite light emitting diode comprises the following steps:
1) clean quartz substrates with 50 nm thick patterned transparent anode ITO were placed on a spin coater rack and the PEDOT: PSS was evenly spread over the entire wafer, and the spin speed of the spin coater was adjusted to 1000 rpm to maintain the PEDOT: PSS forms a 50 nm-thick anode interface layer on the surface of the transparent electrode, and the anode interface layer is placed in a 120 ℃ oven to be heated for 30 minutes;
2) coating the above-mentioned substrate with PEDOT: the PSS transparent anode substrate is placed on a bracket of a spin coater after being cooled, an isobutanol amine solution is uniformly coated on the whole wafer, a monomolecular anode interface modification layer is formed on the surface of a transparent electrode by adjusting the rotating speed of the spin coater to 5000 rpm, and the transparent anode substrate is placed on a hot table at the temperature of 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 10-4And 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.
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.
On the other hand, Table 1 shown below shows the parameters of luminescence properties of comparative examples I, II, III, IV and examples 1, 2, 3,4 in comparison. 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, and 4 also had higher brightness, current efficiency, and lifetime, respectively, than comparative examples ii, iii, and iv. Therefore, the embodiments of the invention have more excellent luminescence performance and stability than the corresponding comparative examples, so that the method of the invention has obvious advantages in improving the performance of the perovskite light emitting diode.
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 (9)
1. A preparation method of a perovskite light-emitting diode capable of improving performance comprises the following steps:
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);
step 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;
in the step ii, the anode interface modification layer (4) is made of an alcohol amine compound.
2. The method of claim 1, 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.
3. The method according to claim 1 or 2, wherein the alkanolamine compound is ethanolamine, isopropanolamine, n-propanolamine or isobutanolamine.
4. A method according to claim 3, wherein in step i, the patterned transparent anode layer (2) is an indium tin oxide electrode having a thickness of 50-200 nm.
5. The preparation method according to claim 3, 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.
6. A production method according to claim 3, characterized in that in step iii, the perovskite light-emitting layer (5) is a pure inorganic perovskite CsPbBr3Or CsPbCl3Or CsPbI3One or more of them, the thickness is 10-50 nm.
7. A method according to claim 3, wherein in step iv, the cathode interfacial layer (6) is TPBi with a thickness of 5-50 nm.
8. A method according to claim 3, wherein in step iv, the cathode interface modification layer (7) is LiF and has a thickness of 0.5-2 nm.
9. The method of claim 3, wherein in step iv, the cathode layer (8) is aluminum or silver and has a thickness of 20-100 nm.
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