CN110970579A - 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
- Publication number
- CN110970579A CN110970579A CN201811163003.1A CN201811163003A CN110970579A CN 110970579 A CN110970579 A CN 110970579A CN 201811163003 A CN201811163003 A CN 201811163003A CN 110970579 A CN110970579 A CN 110970579A
- Authority
- CN
- China
- Prior art keywords
- zinc oxide
- transport layer
- electron transport
- coating
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Electroluminescent Light Sources (AREA)
- Luminescent Compositions (AREA)
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 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.
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
The arrangement of the electron transport 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 10-4Omega/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 Qianlilai task group utilizes a sol-gel method to synthesize nano zinc oxide with good crystallinity as an electron transport layer, and 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 a 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, the solution is left to stand in an environment having a humidity of more than 0% 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 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 treatment 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 also referred to as an electron injection layer, and is not distinguished in the present application and is collectively 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 of 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, and the stability is high, so that higher 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 time for standing the zinc oxide nanocrystalline solution with the surface modified with the thiol ligand and/or the silane ligand in the environment with the humidity of 0-100% is not longer than 72 hours.
In some embodiments, the zinc oxide nanocrystals are metal element doped 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 coating of the Mg-doped zinc oxide nanocrystal solution is completed, the solution is allowed to stand 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, after the coating of the zinc oxide nanocrystal solution doped with one or more of Al, In, Ga, and Li is completed, the solution is left standing for not less than 10min In an environment having a humidity of not less than 20% and not more than 90%. 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, after the coating of the zinc oxide nanocrystalline solution doped with one or more of Al, In, Ga and Li is finished, the zinc oxide nanocrystalline solution is kept still for no more than 48 hours In an environment with the humidity of no less than 20% and no more than 90%.
The zinc oxide nanocrystalline electron transport layer prepared by the above method can be applied to electronic devices such as QLED positive devices, QLED negative 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 10 min;
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 wafer obtained in the step S2 with a hole transport layer of TFB (8-10 mg/mL, chlorobenzene solution) at a rotation speed of 2000r/min for 45 seconds, and annealing in a glove box at an annealing temperature of 150 ℃ for 30min after the spin-coating is finished;
s4. preparation of Quantum dot light emitting layers (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, 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 finished;
s5. preparation of electron transport layer
Spin-coating the undoped zinc oxide nanocrystalline solution (30mg/mL, solvent is ethanol) with the surface modified with the carboxylate ligands on the wafer obtained in the step S4 at the rotating speed of 2000r/min for 45 seconds, and then standing the wafer in air with the humidity of 60% for 30 min;
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 about 100 nm.
[ example 2 ]
Preparation of a QLED positive device:
s1, cleaning of ITO glass: same as step S1 of embodiment 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of embodiment 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 (30Mg/mL, solvent is ethanol) 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 90% for 10 min;
s6, electrode preparation: the same as step S6 of embodiment 1.
[ example 3 ]
Preparation of a QLED positive device:
s1, cleaning of ITO glass: same as step S1 of embodiment 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of embodiment 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 (30Mg/mL, solvent is ethanol) 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 10% for 3 hours;
s6, electrode preparation: the same as step S6 of embodiment 1.
[ example 4 ]
Preparation of a QLED positive device:
s1, cleaning of ITO glass: same as step S1 of embodiment 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of embodiment 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 (30Mg/mL, solvent is ethanol) 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 step S6 of embodiment 1.
[ example 5 ]
Preparation of a QLED positive device:
s1, cleaning of ITO glass: same as step S1 of embodiment 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of embodiment 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 (30mg/mL, solvent is ethanol) 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 90% for 10 min;
s6, electrode preparation: the same as step S6 of embodiment 1.
[ example 6 ]
Preparation of a QLED positive device:
s1, cleaning of ITO glass: same as step S1 of embodiment 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of embodiment 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 (30mg/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 step S6 of embodiment 1.
[ example 7 ]
Preparation of a QLED positive device:
s1, cleaning of ITO glass: same as step S1 of embodiment 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of embodiment 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 (30mg/mL, solvent is ethanol) 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 40% for 1 h;
s6, electrode preparation: the same as step S6 of embodiment 1.
[ example 8 ]
Preparation of a QLED positive device:
s1, cleaning of ITO glass: same as step S1 of embodiment 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of embodiment 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 (30mg/mL, ethanol as a solvent) doped with Li and In 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 60% for 30 min;
s6, electrode preparation: the same as step S6 of embodiment 1.
[ example 9 ]
Preparation of a QLED positive device:
s1, cleaning of ITO glass: same as step S1 of embodiment 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of embodiment 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 a zinc oxide nanocrystal solution (30mg/mL, ethanol as a solvent) which is not doped and is 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 30 min;
s6, electrode preparation: the same as step S6 of embodiment 1.
[ example 10 ]
Preparation of a QLED positive device:
s1, cleaning of ITO glass: same as step S1 of embodiment 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of embodiment 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 a zinc oxide nanocrystal solution (30mg/mL, ethanol as a solvent) which is not doped and is coated with a silane ligand on the surface at a rotating speed of 2000r/min for 45 seconds, and then standing the plate in air with the humidity of 100% for 10 min;
s6, electrode preparation: the same as step S6 of embodiment 1.
[ example 11 ]
Preparation of a QLED positive device:
s1, cleaning of ITO glass: same as step S1 of embodiment 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of embodiment 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 (30mg/mL, ethanol as a solvent) with the surface coated with a silane ligand at a rotation speed of 2000r/min for 45 seconds, and then standing the plate in air with the humidity of 90% for 24 hours;
s6, electrode preparation: the same as step S6 of embodiment 1.
Comparative example 1
Preparation of a QLED positive device:
s1, cleaning of ITO glass: same as step S1 of embodiment 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of embodiment 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 (30mg/mL, ethanol as solvent) with the surface modified with carboxylate ligands on the wafer obtained in the step S4 at the rotating speed of 2000r/min for 45 seconds, and then standing the wafer in a glove box filled with nitrogen for 30 min;
s6, electrode preparation: the same as step S6 of embodiment 1.
Comparative example 2
S1, cleaning of ITO glass: same as step S1 of embodiment 1;
s2, preparing a hole injection layer (Pedot: PSS): same as step S2 of embodiment 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 (30Mg/mL, solvent is ethanol) 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: the 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 (30mg/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 (20nm of film thickness) and a layer of molybdenum oxide MoO are evaporated on the quantum dot luminescent layer3Forming a hole transport layer (10nm 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 200 nm.
Comparative example 3
Preparing a QLED inversion device:
s1, cleaning an ITO glass substrate: same as step S1 of embodiment 12;
s2, preparing an electron injection and transmission layer: spin-coating an undoped zinc oxide nanocrystalline solution (30mg/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 a glove box filled with nitrogen for 30min to form an electron injection and transmission layer;
s3, preparing a quantum dot light-emitting layer: same as step S3 of embodiment 12;
s4, preparing a hole transport layer: same as step S4 of embodiment 12;
s5, preparing an anode: same as step S5 of embodiment 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 | Mg-doped ZnO | 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 shown in Table 1 refers to ZnO nanocrystals having carboxylate ligands 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.
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 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.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (10)
1. A preparation method of a zinc oxide nanocrystalline electron transport layer is characterized in that after a zinc oxide nanocrystalline solution is coated, the zinc oxide nanocrystalline solution is placed for a period of time in an environment with the humidity of more than 0%, so that the electron transport layer is prepared.
2. The method for preparing a zinc oxide nanocrystalline electron transport layer according to claim 1, wherein the method for applying 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.
3. The method for preparing the electron transport layer of zinc oxide nanocrystals, as claimed in claim 1, wherein the surface of the zinc oxide nanocrystals is modified with a ligand selected from one or more of carboxylate, thiol, halide, alcohol amine and silane.
4. The method for preparing the electron transport layer of zinc oxide nanocrystals, as claimed in claim 3, wherein the surface of the zinc oxide nanocrystals is modified with thiol ligands and/or silane ligands, and the zinc oxide nanocrystals, after being coated, are allowed to stand in an environment with a humidity of greater than 0% and not greater than 100% for at least 10 minutes.
5. The method for preparing the electron transport layer of zinc oxide nanocrystals according to claim 1, wherein the zinc oxide nanocrystals are doped with metal elements, preferably the doped metal elements are selected from one or more of Mg, Al, In, Ga and Li.
6. The method for producing the zinc oxide nanocrystalline electron-transporting layer according to claim 5, wherein the Mg-doped zinc oxide nanocrystalline solution is left to stand in an environment with a humidity of more than 0% and not more than 90% for not less than 10 minutes after the coating.
7. The method for producing a zinc oxide nanocrystalline electron transport layer according to claim 5, characterized In that 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 solution is left to stand In an environment with a humidity of not less than 20% and not more than 90% for not less than 10 minutes.
8. The method for preparing the electron transport layer of zinc oxide nanocrystals according to claim 6 or 7, wherein the surface of the zinc oxide nanocrystals is modified with a carboxylate ligand.
9. A zinc oxide nanocrystalline electron transport layer produced by the method of any one of claims 1-8.
10. An electronic device comprising an electron transport layer, wherein the electron transport layer is the zinc oxide electron transport layer of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811163003.1A CN110970579B (en) | 2018-09-30 | 2018-09-30 | Zinc oxide nanocrystalline electron transport layer, preparation method thereof and electronic device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811163003.1A CN110970579B (en) | 2018-09-30 | 2018-09-30 | Zinc oxide nanocrystalline electron transport layer, preparation method thereof and electronic device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110970579A true CN110970579A (en) | 2020-04-07 |
| CN110970579B CN110970579B (en) | 2022-12-02 |
Family
ID=70029288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811163003.1A Active CN110970579B (en) | 2018-09-30 | 2018-09-30 | Zinc oxide nanocrystalline electron transport layer, preparation method thereof and electronic device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110970579B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113809248A (en) * | 2020-06-15 | 2021-12-17 | Tcl科技集团股份有限公司 | Composite material, preparation method thereof and quantum dot light-emitting diode |
| WO2021253786A1 (en) * | 2020-06-15 | 2021-12-23 | Tcl科技集团股份有限公司 | Composite material and preparation method therefor and quantum dot light-emitting diode |
| CN113948647A (en) * | 2020-07-17 | 2022-01-18 | Tcl科技集团股份有限公司 | Nano material, preparation method thereof and quantum dot light-emitting diode |
| WO2022091373A1 (en) * | 2020-10-30 | 2022-05-05 | シャープ株式会社 | Light emitting element, display device, lighting device, and method for producing light emitting element |
Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009096713A (en) * | 2007-09-27 | 2009-05-07 | Mitsubishi Materials Corp | Zno vapor deposition material, its production method, and zno film and the like formed therefrom |
| CN101661994A (en) * | 2009-09-29 | 2010-03-03 | 吉林大学 | Method needing no vacuum process to prepare organic polymer solar cell |
| CN103137868A (en) * | 2013-01-18 | 2013-06-05 | 中国科学院等离子体物理研究所 | Organic/ inorganic hybridization solar battery based on ternary nanometer array and preparation method thereof |
| CN103311440A (en) * | 2013-06-08 | 2013-09-18 | 苏州方昇光电装备技术有限公司 | Layered semiconductor material used for organic solar cell hole transport layer and preparation method of layered semiconductor material |
| US20130277669A1 (en) * | 2010-09-27 | 2013-10-24 | The Technical University Of Denmark | Electron transport layer |
| CN103474574A (en) * | 2013-09-26 | 2013-12-25 | 天津理工大学 | Hybrid solar cell with aluminum-doped zinc oxide nanorod as electron transfer layer |
| CN103904217A (en) * | 2014-01-10 | 2014-07-02 | 中国科学院等离子体物理研究所 | Multi-element organic/ inorganic hybridization solar cell and preparation method thereof |
| US20150028305A1 (en) * | 2012-01-06 | 2015-01-29 | Qd Vision, Inc. | Light emitting device including blue emitting quantum dots and method |
| CN104549209A (en) * | 2014-12-26 | 2015-04-29 | 哈尔滨工业大学 | Double-faced zinc oxide nanoarray photocatalytic material and preparation method thereof |
| JP2015134703A (en) * | 2013-11-29 | 2015-07-27 | 三菱化学株式会社 | Composition for forming metal oxide-containing layer, and method for producing electronic device |
| CN105679858A (en) * | 2016-01-20 | 2016-06-15 | 苏州大学 | Nanocrystalline composite center-based stacked solar cell and preparation method thereof |
| CN105720205A (en) * | 2016-03-03 | 2016-06-29 | 吉林大学 | PEI (polyethyleneimine) based high-efficiency perovskite quantum dot light-emitting thin film and preparation method thereof |
| CN105765753A (en) * | 2013-11-05 | 2016-07-13 | 艾尼股份公司 | Inverted polymer solar cells and process for producing the same |
| CN105977393A (en) * | 2016-05-27 | 2016-09-28 | 纳晶科技股份有限公司 | Electroluminescent device and manufacturing method thereof |
| CN105981190A (en) * | 2013-12-12 | 2016-09-28 | 纳米格拉德股份公司 | Electronic Devices Comprising Solution-Processable Metal Oxide Buffer Layers |
| US20160285022A1 (en) * | 2015-03-25 | 2016-09-29 | Kabushiki Kaisha Toshiba | Photoelectric conversion element and method for manufacturing the same |
| US20180033984A1 (en) * | 2015-02-12 | 2018-02-01 | Avantama Ag | Optoelectronic devices comprising solution-processable metal oxide buffer layers |
| CN107732014A (en) * | 2017-10-23 | 2018-02-23 | 中国科学院合肥物质科学研究院 | A kind of solar cell based on the inorganic build hetero-junction thin-film of ternary and preparation method thereof |
-
2018
- 2018-09-30 CN CN201811163003.1A patent/CN110970579B/en active Active
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009096713A (en) * | 2007-09-27 | 2009-05-07 | Mitsubishi Materials Corp | Zno vapor deposition material, its production method, and zno film and the like formed therefrom |
| CN101661994A (en) * | 2009-09-29 | 2010-03-03 | 吉林大学 | Method needing no vacuum process to prepare organic polymer solar cell |
| US20130277669A1 (en) * | 2010-09-27 | 2013-10-24 | The Technical University Of Denmark | Electron transport layer |
| US20150028305A1 (en) * | 2012-01-06 | 2015-01-29 | Qd Vision, Inc. | Light emitting device including blue emitting quantum dots and method |
| CN103137868A (en) * | 2013-01-18 | 2013-06-05 | 中国科学院等离子体物理研究所 | Organic/ inorganic hybridization solar battery based on ternary nanometer array and preparation method thereof |
| CN103311440A (en) * | 2013-06-08 | 2013-09-18 | 苏州方昇光电装备技术有限公司 | Layered semiconductor material used for organic solar cell hole transport layer and preparation method of layered semiconductor material |
| CN103474574A (en) * | 2013-09-26 | 2013-12-25 | 天津理工大学 | Hybrid solar cell with aluminum-doped zinc oxide nanorod as electron transfer layer |
| CN105765753A (en) * | 2013-11-05 | 2016-07-13 | 艾尼股份公司 | Inverted polymer solar cells and process for producing the same |
| JP2015134703A (en) * | 2013-11-29 | 2015-07-27 | 三菱化学株式会社 | Composition for forming metal oxide-containing layer, and method for producing electronic device |
| CN105981190A (en) * | 2013-12-12 | 2016-09-28 | 纳米格拉德股份公司 | Electronic Devices Comprising Solution-Processable Metal Oxide Buffer Layers |
| CN103904217A (en) * | 2014-01-10 | 2014-07-02 | 中国科学院等离子体物理研究所 | Multi-element organic/ inorganic hybridization solar cell and preparation method thereof |
| CN104549209A (en) * | 2014-12-26 | 2015-04-29 | 哈尔滨工业大学 | Double-faced zinc oxide nanoarray photocatalytic material and preparation method thereof |
| US20180033984A1 (en) * | 2015-02-12 | 2018-02-01 | Avantama Ag | Optoelectronic devices comprising solution-processable metal oxide buffer layers |
| US20160285022A1 (en) * | 2015-03-25 | 2016-09-29 | Kabushiki Kaisha Toshiba | Photoelectric conversion element and method for manufacturing the same |
| CN105679858A (en) * | 2016-01-20 | 2016-06-15 | 苏州大学 | Nanocrystalline composite center-based stacked solar cell and preparation method thereof |
| CN105720205A (en) * | 2016-03-03 | 2016-06-29 | 吉林大学 | PEI (polyethyleneimine) based high-efficiency perovskite quantum dot light-emitting thin film and preparation method thereof |
| CN105977393A (en) * | 2016-05-27 | 2016-09-28 | 纳晶科技股份有限公司 | Electroluminescent device and manufacturing method thereof |
| CN107732014A (en) * | 2017-10-23 | 2018-02-23 | 中国科学院合肥物质科学研究院 | A kind of solar cell based on the inorganic build hetero-junction thin-film of ternary and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| M.N.KAMALASANAN等: ""Sol-gel synthesis of ZnO thin films"", 《THIN SOLID FILM》 * |
| MOAZZAM ALI等: ""ZnO Nanocrystals: Surprisingly ‘Alive’"", 《CHEMISTRY OF MATERIALS》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113809248A (en) * | 2020-06-15 | 2021-12-17 | Tcl科技集团股份有限公司 | Composite material, preparation method thereof and quantum dot light-emitting diode |
| WO2021253786A1 (en) * | 2020-06-15 | 2021-12-23 | Tcl科技集团股份有限公司 | Composite material and preparation method therefor and quantum dot light-emitting diode |
| CN113809248B (en) * | 2020-06-15 | 2024-01-02 | Tcl科技集团股份有限公司 | Composite material, preparation method thereof and quantum dot light emitting diode |
| CN113948647A (en) * | 2020-07-17 | 2022-01-18 | Tcl科技集团股份有限公司 | Nano material, preparation method thereof and quantum dot light-emitting diode |
| WO2022091373A1 (en) * | 2020-10-30 | 2022-05-05 | シャープ株式会社 | Light emitting element, display device, lighting device, and method for producing light emitting element |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110970579B (en) | 2022-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110970579B (en) | Zinc oxide nanocrystalline electron transport layer, preparation method thereof and electronic device | |
| US9859515B2 (en) | Methods for producing thin film charge selective transport layers | |
| CN108807724B (en) | Preparation method and application of perovskite luminescent layer, perovskite luminescent device and preparation method thereof | |
| WO2021253923A1 (en) | Quantum dot light-emitting diode component, preparation method therefor, and display panel | |
| US10270055B2 (en) | Flexible display device and method of manufacturing the same | |
| CN111244298B (en) | Light-emitting device and display | |
| KR102077534B1 (en) | Manufacturing method for transparent top electrode of optical device based on solution process and transparent top electrode of optical device manufactured by the same | |
| CN111384247B (en) | Quantum dot light-emitting diode and preparation method thereof | |
| CN108933201B (en) | Light emitting device and method of manufacturing the same | |
| KR102085670B1 (en) | Quantum-dot light emitting diodes and method of manufacturing the same | |
| CN114267814B (en) | Quantum dot light emitting diode and preparation method thereof | |
| CN110943171A (en) | Quantum dot light-emitting diode and preparation method thereof | |
| US20230105743A1 (en) | Preparation method of charge transport layer and light-emitting diode | |
| CN114267799B (en) | Quantum dot light emitting diode and preparation method thereof | |
| CN110970534A (en) | Nickel oxide film, preparation method thereof and quantum dot light-emitting diode | |
| CN112397673B (en) | Quantum dot light-emitting diode and preparation method thereof | |
| CN114685811B (en) | PEDOT material, quantum dot light emitting diode and preparation method | |
| CN113130776B (en) | Quantum dot light-emitting diode and preparation method thereof | |
| KR20130063165A (en) | Manufacturing method of solution-processed semiconductor buffer layer and solar cells using it | |
| CN111384259B (en) | Quantum dot light-emitting diode and preparation method thereof | |
| CN114023911A (en) | ITO anode and preparation method thereof, QLED device and display device | |
| WO2023078233A1 (en) | Light-emitting device preparation method, light-emitting device, and display apparatus | |
| Yamada et al. | Improved NiO x surface using phosphonic acid-based self-assembled monolayer treatment toward printed light-emitting diodes | |
| CN116615044A (en) | Doped material, preparation method thereof, light emitting diode and display device | |
| CN116648082A (en) | Composite material, preparation method thereof, photoelectric device and display device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |