CN110970579B - Zinc oxide nanocrystalline electron transport layer, preparation method thereof and electronic device - Google Patents
Zinc oxide nanocrystalline electron transport layer, preparation method thereof and electronic device Download PDFInfo
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- CN110970579B CN110970579B CN201811163003.1A CN201811163003A CN110970579B CN 110970579 B CN110970579 B CN 110970579B CN 201811163003 A CN201811163003 A CN 201811163003A CN 110970579 B CN110970579 B CN 110970579B
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Abstract
The invention discloses a zinc oxide nanocrystalline electron transport layer, a preparation method thereof and an electronic device. The preparation method of the zinc oxide electron transport layer comprises the following steps: and standing for a period of time in an environment with the humidity of more than 0 percent after the zinc oxide nanocrystalline solution is coated. In the invention, after the zinc oxide nanocrystalline solution is coated and before annealing treatment is carried out, the zinc oxide nanocrystalline coating is firstly kept stand for a period of time in an environment with certain humidity, and the zinc oxide nanocrystalline film is slowly crystallized under the action of water vapor, so that the electric conductivity of the film layer is favorably improved, the electron injection is strengthened, and the turn-on voltage of related electronic devices is favorably reduced; the zinc oxide nanocrystalline film is slowly crystallized under the action of water vapor, and is favorable for enhancing the interface bonding force between the electron transmission layer and the adjacent functional layer, thereby being favorable for prolonging the service life of related electronic devices.
Description
Technical Field
The invention relates to the field of electronic devices, in particular to a zinc oxide nanocrystalline electron transport layer, a preparation method thereof and an electronic device.
Background
Electronic transmitterThe arrangement of the transmission layer is related to the fields of solar cells or light emitting diodes and the like. The material of the electron transport layer is required to have good charge transport ability. The zinc oxide is a direct band gap semiconductor with the forbidden band width of 3.37eV, electrically represents an n-type semiconductor, and has the resistivity of as low as 10 -4 Omega/cm. Because the photoelectric material has excellent photoelectric characteristics, and the energy band position of the photoelectric material can be changed by doping different metal elements and ions, the effective injection of electrons is realized. The qianliei topic group utilizes a sol-gel method to synthesize nano zinc oxide with good crystallinity as an electron transport layer, and the nano zinc oxide shows excellent performance.
Although the turn-on voltage of the device using the zinc oxide electron transport layer is greatly reduced compared with the common organic electron transport layer (such as TPBi), the turn-on voltage is still not close to the theoretical value, and there is room for further reduction. In addition, the lifetime of the QLED device including the zinc oxide electron transport layer is greatly affected by zinc oxide, and thus it is also a current research direction to further improve the zinc oxide electron transport layer and the preparation process thereof to improve the lifetime of the electronic device.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of a zinc oxide nanocrystalline electron transport layer, and a device with the electron transport layer prepared by the method has lower turn-on voltage compared with the prior art and is closer to a theoretical value.
It is a further object of the invention to provide an electronic device having a longer lifetime compared to the prior art.
According to one aspect of the invention, a method for preparing a zinc oxide nanocrystalline electron transport layer is provided, after the zinc oxide nanocrystalline solution is coated, standing for a period of time in an environment with humidity greater than 0%, thereby preparing the electron transport layer.
Further, the method for coating the zinc oxide nanocrystalline solution is selected from one of the following methods: spin coating, ink jet printing, spray coating, screen printing, blade coating, drop coating, brush coating, transfer coating, dip coating, roll coating.
Further, the surface of the zinc oxide nanocrystal is modified with a ligand, and the ligand is selected from one or more of carboxylate, thiol, halide ions, alcohol amine and silane.
According to some preferred embodiments of the present invention, the surface of the zinc oxide nanocrystal is modified with a thiol ligand and/or a silane ligand, and after the zinc oxide nanocrystal is coated, the zinc oxide nanocrystal is allowed to stand for not less than 10 minutes in an environment with a humidity of greater than 0% and not greater than 100%.
Further, the zinc oxide nanocrystals are doped metal element zinc oxide nanocrystals, preferably, the doped metal element is selected from one or more of Mg, al, in, ga and Li.
According to some preferred embodiments of the present invention, after the coating of the Mg-doped zinc oxide nanocrystal solution is completed, it is left standing for not less than 10 minutes in an environment having a humidity of more than 0% and not more than 90%. The surface of the zinc oxide nanocrystal is modified with a carboxylate ligand.
According to other preferred embodiments of the present invention, after the coating of the zinc oxide nanocrystal solution doped with one or more of Al, in, ga, and Li is completed, the zinc oxide nanocrystal solution is left to stand In an environment having a humidity of not less than 20% and not more than 90% for not less than 10 minutes. The surface of the zinc oxide nanocrystal is modified with a carboxylate ligand.
According to another aspect of the invention, the zinc oxide nanocrystalline electron transport layer is prepared by the preparation method of the zinc oxide nanocrystalline electron transport layer.
According to another aspect of the present invention, there is provided an electronic device comprising the above-described zinc oxide nanocrystalline electron transport layer of the present invention.
Drawings
FIG. 1 shows a current-voltage diagram of example 1 and comparative example 1 of the present application;
FIG. 2 shows the EQE curves at different processing voltages for example 1 and comparative example 1 of the present application;
fig. 3 shows the luminance of the QLED of example 2 and comparative example 2 of the present application over time.
Detailed Description
The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.
In some documents or documents, the first electron transport layer adjacent to the cathode is referred to as an electron injection layer, and is not distinguished in the present application and is referred to as an electron transport layer.
The invention provides a preparation method of a zinc oxide nanocrystalline electron transport layer, which comprises the steps of standing for a period of time in an environment with the humidity more than 0% after a zinc oxide nanocrystalline solution is coated, so as to prepare the electron transport layer.
In the prior art, when a zinc oxide nanocrystal electron transport layer is prepared, a zinc oxide nanocrystal solution is generally coated and then is subjected to annealing treatment at a higher temperature. In the invention, after the zinc oxide nanocrystalline solution is coated, an annealing step is not needed, but the zinc oxide nanocrystalline coating is kept still for a period of time in an environment with certain humidity, and the zinc oxide nanocrystalline film is slowly crystallized under the action of water vapor, so that the conductivity of the film layer is favorably improved, the electron injection is strengthened, and the starting voltage of related electronic devices is favorably reduced; the zinc oxide nanocrystalline film is slowly crystallized under the action of water vapor, and is favorable for enhancing the interface bonding force between the electron transmission layer and the adjacent functional layer, thereby being favorable for prolonging the service life of related electronic devices. It should be noted that the environment with a certain humidity may be provided in air, and may be provided in an inert gas atmosphere, but is not limited thereto.
The preparation of zinc oxide nanocrystal solutions is well known in the art and will not be described in detail herein.
The coating of the zinc oxide nanocrystal solution can be performed in a variety of ways. In some embodiments, the method of zinc oxide nanocrystal solution coating is selected from one of the following methods: spin coating, ink jet printing, spray coating, screen printing, blade coating, drop coating, brush coating, transfer coating, dip coating, roll coating.
In some embodiments, the surface of the zinc oxide nanocrystals is modified with a ligand selected from one or more of carboxylates, thiols, halide ions, alcohol amines, and silanes.
In some embodiments, the ligand modified on the surface of the zinc oxide nanocrystal is a thiol ligand and/or a silane ligand, and after the zinc oxide nanocrystal is coated, the zinc oxide nanocrystal is kept still for not less than 10min in an environment with the humidity of more than 0% and the humidity of not more than 100%. When the ligand modified on the surface of the zinc oxide nanocrystal is a mercaptan ligand and/or a silane ligand, the water resistance is good, the stability is high, and therefore high humidity is needed to enable water vapor to act on the zinc oxide nanocrystal film. It should be noted that the zinc oxide nanocrystals may be doped with other metal elements, or may be undoped zinc oxide nanocrystals.
In addition, considering the manufacturing efficiency and the influence of water vapor on other functional layers of the electronic device, the standing time of the zinc oxide nanocrystalline solution with the surface modified thiol ligand and/or silane ligand in the environment with the humidity of 0-100% is not more than 72 hours after the coating is finished.
In some embodiments, the zinc oxide nanocrystals are doped metal element zinc oxide nanocrystals, preferably, the doped metal element is selected from one or more of Mg, al, in, ga, and Li.
In some embodiments, after the Mg-doped zinc oxide nanocrystalline solution is coated, it is left standing for not less than 10min in an environment with a humidity of more than 0% and not more than 90%. After the zinc oxide nanocrystals are doped with Mg, the zinc oxide nanocrystals are more sensitive to water vapor, can produce better effect even under the condition of lower humidity, and can be damaged by overhigh humidity. And the surface of the Mg-doped zinc oxide nanocrystal is modified with a carboxylate ligand.
Considering the manufacturing efficiency and the influence of water vapor on other functional layers, the time for standing the Mg-doped zinc oxide nanocrystalline solution in the environment with the humidity of more than 0% and not more than 90% is not more than 24 hours after the coating is finished.
In some embodiments, the zinc oxide nanocrystalline solution doped with one or more of Al, in, ga, and Li is left standing for not less than 10min In an environment having a humidity of not less than 20% and not more than 90% after coating is completed. And the surface of the zinc oxide nanocrystal doped with one or more of Al, in, ga and Li is modified with a carboxylate ligand.
Considering the manufacturing efficiency and the influence of water vapor on other functional layers, the time for standing In an environment with the humidity of not less than 20% and not more than 90% is not more than 48h after the coating of the zinc oxide nanocrystalline solution doped with one or more of Al, in, ga and Li is completed.
The zinc oxide nanocrystalline electron transport layer prepared by the above method can be applied to electronic devices such as QLED positive devices, QLED inversion devices, dye-sensitized solar cells, perovskite solar cells, and the like, and is not limited to the above-listed electronic devices. The working principle of the electron transport layer in different electronic devices is the prior art, and the invention is not described in detail.
[ example 1 ]
Preparation of a QLED positive device:
s1. Cleaning of ITO glass
Placing the ITO glass sheet with the back surface marked with the number into a glass dish filled with ethanol solution, cleaning the ITO surface with a cotton swab, sequentially performing ultrasonic treatment on the ITO glass sheet with acetone, deionized water and ethanol for 10min respectively, blow-drying the ITO glass sheet with a nitrogen gun, and finally placing the cleaned ITO glass sheet in oxygen plasma for continuous cleaning for 10min;
s2. Preparation of hole injection layer (Pedot: PSS)
PSS, rotating at 3000r/min for 45 seconds, annealing in air at 150 ℃ for 30 minutes, and quickly transferring the cleaned ITO glass sheet into a glove box in a nitrogen atmosphere;
s3. Preparation of Hole Transport Layer (HTL)
Continuously spin-coating the sheet obtained in the step S2 with a hole transport layer of TFB (8-10 mg/mL, chlorobenzene solution), wherein the rotation speed is 2000r/min, the spin-coating time is 45 seconds, annealing is carried out in a glove box after the spin-coating is finished, the annealing temperature is 150 ℃, and the annealing time is 30min;
s4. Preparation of Quantum dot light emitting layer (QDs)
Continuing to spin-coat the quantum dot solution (the quantum dots are CdZnSeS/ZnS core-shell quantum dots, the optical concentration of the quantum dots at 350nm is 30-40, the solvent is octaalkane) after annealing the wafer obtained in the step S3 is completed, wherein the spin-coating speed is 2000r/min, the spin-coating time is 45 seconds, and the next layer can be spin-coated without annealing after the spin-coating is completed;
s5. Preparation of electron transport layer
Spin-coating the wafer obtained in the step S4 with an undoped zinc oxide nanocrystal solution (30 mg/mL, ethanol as a solvent) with the surface modified with a carboxylate ligand at a rotating speed of 2000r/min for 45 seconds, and then standing the wafer in air with humidity of 60% for 30min;
s6. Electrode preparation
Putting the sheet obtained in the step S5 into a vacuum cavity, evaporating a top electrode, and controlling the evaporation rate at the first 10nm
In the range, the evaporation rate is improved to after 10nm
The thickness of the silver electrode was 100nm.
[ example 2 ] A method for producing a polycarbonate
Preparation of a QLED positive device:
s1, cleaning of ITO glass: same as in step S1 of example 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of example 1;
s3, preparing a Hole Transport Layer (HTL): same as step S3 of embodiment 1;
s4, preparing a quantum dot light emitting layer (QDs): same as step S4 of embodiment 1;
s5, preparing an electron transport layer: spin-coating the wafer obtained in the step S4 with a zinc oxide nanocrystalline solution (30 Mg/mL, ethanol is used as a solvent) doped with Mg and modified with a carboxylate ligand on the surface at a rotating speed of 2000r/min for 45 seconds, and then standing the wafer in air with the humidity of 90% for 10min;
s6, preparing an electrode: the same as in step S6 of embodiment 1.
[ example 3 ] A method for producing a polycarbonate
Preparing a QLED positive device:
s1, cleaning of ITO glass: same as in step S1 of example 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of example 1;
s3, preparing a Hole Transport Layer (HTL): same as step S3 of embodiment 1;
s4, preparing a quantum dot light emitting layer (QDs): same as step S4 of embodiment 1;
s5, preparing an electron transport layer: spin-coating the wafer obtained in the step S4 with a zinc oxide nanocrystalline solution (30 Mg/mL, ethanol is used as a solvent) doped with Mg and modified with a carboxylate ligand on the surface at a rotating speed of 2000r/min for 45 seconds, and then standing the wafer in air with the humidity of 10% for 3 hours;
s6, electrode preparation: the same as in step S6 of embodiment 1.
[ example 4 ]
Preparing a QLED positive device:
s1, cleaning of ITO glass: same as in step S1 of example 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of example 1;
s3, preparing a Hole Transport Layer (HTL): same as step S3 of embodiment 1;
s4, preparing a quantum dot light emitting layer (QDs): same as step S4 of embodiment 1;
s5, preparing an electron transport layer: spin-coating the wafer obtained in the step S4 with a zinc oxide nanocrystal solution (30 Mg/mL, ethanol as a solvent) doped with Mg and modified with a carboxylate ligand on the surface at a rotating speed of 2000r/min for 45 seconds, and then standing the wafer in air with humidity of 40% for 1.5 hours;
s6, electrode preparation: the same as in step S6 of embodiment 1.
[ example 5 ]
Preparation of a QLED positive device:
s1, cleaning of ITO glass: same as step S1 of example 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of example 1;
s3, preparing a Hole Transport Layer (HTL): same as step S3 of embodiment 1;
s4, preparing a quantum dot light emitting layer (QDs): same as step S4 of embodiment 1;
s5, preparing an electron transport layer: spin-coating the wafer obtained in the step S4 with a zinc oxide nanocrystalline solution (30 mg/mL, ethanol is used as a solvent) doped with Li and modified with a carboxylate ligand on the surface at a rotating speed of 2000r/min for 45 seconds, and then standing the wafer in air with the humidity of 90% for 10min;
s6, preparing an electrode: the same as in step S6 of embodiment 1.
[ example 6 ]
Preparation of a QLED positive device:
s1, cleaning of ITO glass: same as in step S1 of example 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of example 1;
s3, preparing a Hole Transport Layer (HTL): same as step S3 of embodiment 1;
s4, preparing a quantum dot light emitting layer (QDs): same as step S4 of embodiment 1;
s5, preparing an electron transport layer: spin-coating the wafer obtained in the step S4 with a zinc oxide nanocrystal solution (30 mg/mL, ethanol as a solvent) doped with Li and modified with a carboxylate ligand on the surface at a rotating speed of 2000r/min for 45 seconds, and then standing the wafer in air with humidity of 20% for 6 hours;
s6, electrode preparation: the same as in step S6 of embodiment 1.
[ example 7 ] A method for producing a polycarbonate
Preparation of a QLED positive device:
s1, cleaning of ITO glass: same as in step S1 of example 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of example 1;
s3, preparing a Hole Transport Layer (HTL): same as step S3 of embodiment 1;
s4, preparing a quantum dot light emitting layer (QDs): same as step S4 of embodiment 1;
s5, preparing an electron transport layer: spin-coating the wafer obtained in the step S4 with a zinc oxide nanocrystalline solution (30 mg/mL, ethanol is used as a solvent) doped with Li and modified with a carboxylate ligand on the surface at a rotating speed of 2000r/min for 45 seconds, and then standing the wafer in air with the humidity of 40% for 1h;
s6, electrode preparation: same as step S6 of embodiment 1.
[ example 8 ]
Preparing a QLED positive device:
s1, cleaning of ITO glass: same as step S1 of example 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of example 1;
s3, preparing a Hole Transport Layer (HTL): same as step S3 of embodiment 1;
s4, preparing a quantum dot light emitting layer (QDs): same as step S4 of embodiment 1;
s5, preparing an electron transport layer: spin-coating the wafer obtained In the step S4 with a zinc oxide nanocrystalline solution (30 mg/mL, ethanol is used as a solvent) which is doped with Li and In and is modified with a carboxylate radical ligand on the surface at a rotating speed of 2000r/min for 45 seconds, and then standing the wafer In air with humidity of 60% for 30min;
s6, preparing an electrode: same as step S6 of embodiment 1.
[ example 9 ]
Preparation of a QLED positive device:
s1, cleaning of ITO glass: same as in step S1 of example 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of example 1;
s3, preparing a Hole Transport Layer (HTL): same as step S3 of embodiment 1;
s4, preparing a quantum dot light emitting layer (QDs): same as step S4 of embodiment 1;
s5, preparing an electron transport layer: spin-coating the plate obtained in the step S4 with an undoped zinc oxide nanocrystal solution (30 mg/mL, ethanol as a solvent) with the surface coated with a thiol ligand at a rotation speed of 2000r/min for 45 seconds, and then standing the plate in air with the humidity of 100% for 30min;
s6, electrode preparation: the same as in step S6 of embodiment 1.
[ example 10 ] A method for producing a polycarbonate
Preparation of a QLED positive device:
s1, cleaning of ITO glass: same as in step S1 of example 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of example 1;
s3, preparing a Hole Transport Layer (HTL): same as step S3 of embodiment 1;
s4, preparing a quantum dot light emitting layer (QDs): same as step S4 of embodiment 1;
s5, preparing an electron transport layer: spin-coating the sheet obtained in the step S4 with a zinc oxide nanocrystalline solution (30 mg/mL, ethanol as a solvent) which is not doped and coated with a silane ligand at a rotating speed of 2000r/min for 45 seconds, and then standing the sheet in air with the humidity of 100% for 10min;
s6, electrode preparation: the same as in step S6 of embodiment 1.
[ example 11 ]
Preparation of a QLED positive device:
s1, cleaning of ITO glass: same as in step S1 of example 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of example 1;
s3, preparing a Hole Transport Layer (HTL): same as step S3 of embodiment 1;
s4, preparing a quantum dot light emitting layer (QDs): same as step S4 of embodiment 1;
s5, preparing an electron transport layer: spin-coating the plate obtained in the step S4 with an undoped zinc oxide nanocrystal solution (30 mg/mL, ethanol as a solvent) with the surface coated with a silane ligand at a rotating speed of 2000r/min for 45 seconds, and then standing the plate in air with the humidity of 90% for 24 hours;
s6, preparing an electrode: the same as in step S6 of embodiment 1.
Comparative example 1
Preparation of a QLED positive device:
s1, cleaning of ITO glass: same as in step S1 of example 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of example 1;
s3, preparing a Hole Transport Layer (HTL): same as step S3 of embodiment 1;
s4, preparing a quantum dot light emitting layer (QDs): same as step S4 of embodiment 1;
s5, preparing an electron transport layer: spin-coating the undoped zinc oxide nanocrystalline solution (30 mg/mL, ethanol as a solvent) with the surface modified with a carboxylate ligand on the wafer obtained in the step S4 at a rotating speed of 2000r/min for 45 seconds, and then standing the wafer in a glove box filled with nitrogen for 30min;
s6, electrode preparation: same as step S6 of embodiment 1.
Comparative example 2
S1, cleaning of ITO glass: same as in step S1 of example 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of example 1;
s3, preparing a Hole Transport Layer (HTL): same as step S3 of embodiment 1;
s4, preparing a quantum dot light emitting layer (QDs): same as step S4 of embodiment 1;
s5, preparing an electron transport layer: spin-coating the wafer obtained in the step S4 with a zinc oxide nanocrystal solution (30 Mg/mL, ethanol as a solvent) doped with Mg and modified with a carboxylate ligand on the surface at a rotating speed of 2000r/min for 45 seconds, and then standing the wafer in a glove box filled with nitrogen for 30 minutes;
s6, electrode preparation: same as step S6 of embodiment 1.
[ example 12 ]
Preparing a QLED inversion device:
s1. Cleaning of ITO glass substrate
Sequentially carrying out ultrasonic treatment on the ITO glass substrate by using deionized water and ethanol, wherein the ultrasonic treatment time is 15min each time, taking out the ITO glass substrate after the ultrasonic treatment is finished, and cleaning the ITO glass substrate for 15min under oxygen plasma after the surface of the ITO glass substrate is dried;
s2, preparation of electron injection and transmission layer
Spin-coating an undoped zinc oxide nanocrystalline solution (30 mg/mL, ethanol as a solvent) with a surface modified with a carboxylate ligand on a cleaned glass substrate at the rotating speed of 2500rpm for 45 seconds, and then standing the wafer in air with the humidity of 60% for 30min to form an electron injection and transmission layer;
s3. Preparation of quantum dot light-emitting layer
Dispersing quantum dots in n-octane to obtain a quantum dot solution with the solid content of 20mg/ml, spin-coating the quantum dot solution on an electron transmission layer at the rotating speed of 1500rpm for 60s, and drying to form a quantum dot light-emitting layer;
s4. Preparation of hole transport layer
A layer of 4,4' -bis (9-carbazole) biphenyl CBP (20 nm of film thickness) and a layer of molybdenum oxide MoO are evaporated on the quantum dot luminescent layer 3 Forming a hole transport layer (10 nm film thickness);
s5. Preparation of anode
And (5) putting the device obtained in the step (S4) into a vacuum evaporation cavity, and evaporating an anode electrode Al on the conductive particle layer of the device, wherein the thickness of the anode electrode Al is 200nm.
Comparative example 3
Preparing a QLED inversion device:
s1, cleaning an ITO glass substrate: same as in step S1 of example 12;
s2, preparing an electron injection and transmission layer: spin-coating an undoped zinc oxide nanocrystalline solution (30 mg/mL, ethanol is used as a solvent) with a surface modified with a carboxylate radical ligand on a cleaned glass substrate at the rotating speed of 2500rpm for 45 seconds, and then standing the wafer in a glove box filled with nitrogen for 30 minutes to form an electron injection and transmission layer;
s3, preparing a quantum dot light-emitting layer: same as step S3 of example 12;
s4, preparing a hole transport layer: same as step S4 of example 12;
s5, preparing an anode: the same as in step S5 of example 12.
Table 1 lists experimental data of the above examples and comparative external quantum dot efficiencies, and comparing examples 1-12 with comparative examples 1-3, it can be found that the external quantum efficiency of the electron transport layer can be improved to various degrees by selecting appropriate environmental humidity and standing time mainly according to the difference of the stability of the electron transport layer material.
TABLE 1
| Item | Kind of material of electron transport layer | Humidity (%) | Length of standing time (min) | External quantum efficiency (%) |
| Example 1 | |
60 | 30 | 14 |
| Example 2 | Mg-doped ZnO | 90 | 10 | 14 |
| Example 3 | Mg-doped |
10 | 180 | 12 |
| Example 4 | Doping with MgZnO of (2) | 40 | 90 | 16 |
| Example 5 | Li-doped ZnO | 90 | 10 | 11 |
| Example 6 | Li-doped ZnO | 20 | 360 | 13 |
| Example 7 | Li-doped ZnO | 40 | 60 | 14 |
| Example 8 | Li and In |
60 | 30 | 16 |
| Example 9 | Thiol-coated |
100 | 30 | 14 |
| Example 10 | Silane coated |
100 | 10 | 11 |
| Example 11 | Silane coated ZnO | 90 | 1440 | 16 |
| Comparative example 1 | |
0 | 30 | 11 |
| Comparative example 2 | Mg-doped |
0 | 30 | 12 |
| Example 12 | |
60 | 30 | 9 |
| Comparative example 3 | |
0 | 30 | 7 |
Note: znO not specifically stated in Table 1 all refer to ZnO nanocrystals with carboxylate ligands modified on the surface.
Fig. 1 shows current-voltage diagrams of example 1 and comparative example 1 of the present application, and it can be seen from the diagrams that the turn-on voltage of example 1 is lower, which illustrates that placing the electron transport layer in an environment with a certain humidity is beneficial to reduce the turn-on voltage of the electronic device.
Fig. 2 shows EQE curves at different processing voltages of example 1 and comparative example 1 of the present application, and it can be seen from the graph that the External Quantum Efficiency (EQE) of example 1 is higher than that of comparative example 1 under the same voltage, which illustrates that placing the electron transport layer in an environment with a certain humidity is beneficial to improve the external quantum efficiency of the electronic device.
Fig. 3 shows the luminance change curves of the QLEDs of example 2 and comparative example 2 according to the present application over time, and it can be seen from the graph that the luminance of the electronic device of example 2 decays more slowly with the time, i.e. the service life is longer, which illustrates that placing the electron transport layer in an environment with a certain humidity is beneficial to improving the service life of the electronic device.
In the invention, after the zinc oxide nanocrystalline solution is coated and before annealing treatment is carried out, the zinc oxide nanocrystalline coating is firstly kept stand for a period of time in an environment with certain humidity, and the zinc oxide nanocrystalline film is slowly crystallized under the action of water vapor, so that the conductivity of the film layer is favorably improved, the electron injection is strengthened, and the turn-on voltage of related electronic devices is favorably reduced; the zinc oxide nanocrystalline film slowly crystallizes under the action of water vapor, and is favorable for enhancing the interface bonding force between the electron transmission layer and the adjacent functional layer, thereby being favorable for prolonging the service life of related electronic devices.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention should not be limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Claims (5)
1. An electronic device is a QLED device and comprises a quantum dot light-emitting layer and an electron transport layer which are overlapped, wherein the electron transport layer is a zinc oxide nanocrystalline electron transport layer, and the preparation method of the zinc oxide nanocrystalline electron transport layer is as follows: and after the coating of the zinc oxide nanocrystalline solution doped with one or more of Al, in, ga and Li is finished, standing for not less than 10 minutes In an environment with the humidity of not less than 20% and not more than 90%, thereby preparing the electron transport layer.
2. The electronic device of claim 1, wherein the zinc oxide nanocrystal solution coating process is selected from one of the following processes: spin coating, ink jet printing, spray coating, screen printing, blade coating, drop coating, brush coating, transfer coating, dip coating, roll coating.
3. The electronic device of claim 1, wherein the surface of the zinc oxide nanocrystals is modified with a ligand selected from one or more of carboxylates, thiols, halides, alcohol amines, and silanes.
4. The electronic device of claim 3, wherein the surface of the zinc oxide nanocrystals is modified with a thiol ligand and/or a silane ligand.
5. The electronic device of claim 1, wherein the surface of the zinc oxide nanocrystals is modified with a carboxylate ligand.
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