CN113130834A - Light emitting diode and preparation method thereof - Google Patents
Light emitting diode and preparation method thereof Download PDFInfo
- Publication number
- CN113130834A CN113130834A CN201911417228.XA CN201911417228A CN113130834A CN 113130834 A CN113130834 A CN 113130834A CN 201911417228 A CN201911417228 A CN 201911417228A CN 113130834 A CN113130834 A CN 113130834A
- Authority
- CN
- China
- Prior art keywords
- zinc oxide
- indium zinc
- oxide precursor
- film
- light
- 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
-
- 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
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
- H10K71/421—Thermal treatment, e.g. annealing in the presence of a solvent vapour using coherent electromagnetic radiation, e.g. laser annealing
-
- 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
- H10K2102/10—Transparent electrodes, e.g. using graphene
- H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
- H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electromagnetism (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention belongs to the technical field of display, and particularly relates to a light-emitting diode and a preparation method thereof. The preparation method provided by the invention comprises the following steps: depositing an indium zinc oxide precursor on a substrate to form an indium zinc oxide precursor film; irradiating the indium zinc oxide precursor film by adopting infrared laser, and annealing to form an indium zinc oxide film; and irradiating the indium zinc oxide film by adopting ultraviolet laser to carry out post-annealing treatment. The problem that the annealing process of the conventional electron transport layer easily causes damage to the inside of a device is solved.
Description
Technical Field
The invention belongs to the technical field of display, and particularly relates to a light-emitting diode and a preparation method thereof.
Background
In recent years, Indium Zinc Oxide (IZO) has been widely used in the preparation of solar cells, thin film transistors, light emitting diodes, and the like, due to its excellent electrical characteristics and good visible light transmittance, and has a wide development prospect. The method for preparing Indium Zinc Oxide (IZO) by adopting the sol-gel method can meet most research and development requirements and is widely used due to the advantages of short manufacturing period, controllable components, simple process, low cost and the like.
Quantum Dot Light Emitting Diodes (QLEDs) are mainly composed of functional film layers such as a hole injection layer, a hole transport layer, a Light Emitting layer, an electron transport layer, and an electron injection layer to form a p-i-n junction-like structure. The balance of electrons and holes is an important factor influencing the performance of the device, so how to optimize the transmission efficiency of the electrons and the holes directly influences the service life and the performance improvement of the QLED device. In the existing process for preparing the electron transport layer, Indium Zinc Oxide (IZO) is often used as an electron transport layer material to be coated on the quantum dot light emitting layer, and then annealing treatment is performed. The annealing temperature and the annealing time influence the performance and the service life of the device, the annealing temperature of the indium zinc oxide film prepared by adopting the sol-gel method can reach as high as 600 ℃, and the annealing temperature is too high, so that the internal damage of the device is easily caused, and the fluorescence quenching is caused.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a light-emitting diode, and aims to solve the problem that the annealing process of the conventional electron transport layer is easy to cause damage to the inside of a device.
Another object of the present invention is to provide a light emitting diode prepared by the above preparation method.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a light-emitting diode comprises the following steps:
providing a substrate and an indium zinc oxide precursor, and depositing the indium zinc oxide precursor on the substrate to form an indium zinc oxide precursor film;
irradiating the indium zinc oxide precursor film by adopting infrared laser, and carrying out annealing treatment to form an indium zinc oxide film;
and irradiating the indium zinc oxide film by adopting ultraviolet laser to carry out post-annealing treatment.
According to the preparation method of the light-emitting diode, on one hand, the indium zinc oxide precursor film is irradiated by infrared laser, so that the temperature of the surface of the material is instantly increased to generate a heat effect, and the indium zinc oxide film is formed, so that the purpose of annealing is achieved, the method is short and effective, the annealing time is greatly reduced, the risk of contact between the device and water and oxygen is reduced, and the service life of the device is prolonged; meanwhile, the roughness of the film is reduced by the short-time and effective laser annealing, and the crystallinity of the film is improved, so that the resistivity is improved; in addition, the infrared laser directly irradiates the indium zinc oxide precursor film, so that the high temperature generated by the infrared laser mainly acts on the indium zinc oxide precursor film, the damage of the high temperature to the internal structure of the device is avoided, and the luminous performance of the device is integrally improved. On the other hand, after the infrared laser is annealed, the ultraviolet laser is adopted for post-annealing treatment, the ultraviolet laser has high photon energy, can directly destroy covalent bonds of organic matters, promotes the organic matters which are difficult to volatilize and remain in the film layer to be decomposed into gaseous molecules and volatilize to the outside, eliminates the influence of the remaining organic matters on the electrical properties of the film layer, and avoids the problem of damage to the inside of the device caused by adopting a method of decomposing the remaining organic matters in the film layer at high temperature for a long time. Therefore, when the electronic transmission layer is prepared, the method of annealing by using the infrared laser and the ultraviolet laser in sequence is adopted, so that the influence of annealing on the interior of the device is considered while effective annealing is realized, the annealing time is greatly shortened, the performance of the film layer is improved, and the performance and the service life of the device can be integrally improved.
Correspondingly, the light-emitting diode is prepared by the preparation method.
The light-emitting diode provided by the invention is prepared by the preparation method, and has good light-emitting performance and long service life.
Drawings
Fig. 1 is a flowchart of a method for manufacturing a light emitting diode according to an embodiment of the present invention;
fig. 2 is a schematic diagram of a light emitting diode according to an embodiment of the present invention;
FIG. 3 is an AFM image of the electron transport layer prepared in example 1;
fig. 4 is an AFM image of the electron transport layer prepared in comparative example 1.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
A method for manufacturing a light emitting diode, as shown in fig. 1, includes the following steps:
s01, providing a substrate and an indium zinc oxide precursor, and depositing the indium zinc oxide precursor on the substrate to form an indium zinc oxide precursor film;
s02, irradiating the indium zinc oxide precursor film by using infrared laser, and carrying out annealing treatment to form an indium zinc oxide film;
and S03, irradiating the indium zinc oxide film by adopting ultraviolet laser, and carrying out post-annealing treatment.
According to the preparation method of the light-emitting diode provided by the embodiment of the invention, on one hand, the indium zinc oxide precursor film is irradiated by infrared laser, so that the temperature of the surface of the material is instantly increased to generate a heat effect, and the indium zinc oxide film is formed, thereby achieving the purpose of annealing, being short and effective, greatly reducing the annealing time, reducing the risk of contact between the device and water and oxygen, and being beneficial to prolonging the service life of the device; meanwhile, the roughness of the film is reduced by the short-time and effective laser annealing, and the crystallinity of the film is improved, so that the resistivity is improved; in addition, the infrared laser directly irradiates the indium zinc oxide precursor film, so that the high temperature generated by the infrared laser mainly acts on the indium zinc oxide precursor film, the damage of the high temperature to the internal structure of the device is avoided, and the luminous performance of the device is integrally improved. On the other hand, after the infrared laser is annealed, the ultraviolet laser is adopted for post-annealing treatment, the ultraviolet laser has high photon energy, can directly destroy covalent bonds of organic matters, promotes the organic matters which are difficult to volatilize and remain in the film layer to be decomposed into gaseous molecules and volatilize to the outside, eliminates the influence of the remaining organic matters on the electrical properties of the film layer, and avoids the problem of damage to the inside of the device caused by adopting a method of decomposing the remaining organic matters in the film layer at high temperature for a long time. Therefore, when the electronic transmission layer is prepared, the method of annealing by using the infrared laser and the ultraviolet laser in sequence is adopted, so that the influence of annealing on the interior of the device is considered while effective annealing is realized, the annealing time is greatly shortened, the performance of the film layer is improved, and the performance and the service life of the device can be integrally improved.
Specifically, in step S01, the indium zinc oxide precursor is deposited on the substrate to obtain an indium zinc oxide precursor thin film.
The substrate is used as a carrier for depositing the indium zinc oxide precursor, the specific structure can refer to the conventional technology in the field, and the indium zinc oxide precursor film can be formed on the substrate.
As an embodiment, the substrate has formed thereon: a light emitting layer;
the step of depositing the indium zinc oxide precursor on the substrate comprises: and depositing the indium zinc oxide precursor on the light-emitting layer.
And depositing an indium zinc oxide precursor on the light emitting layer to form an indium zinc oxide film on the light emitting layer. Because the embodiment of the invention adopts the method of successively adopting the infrared laser and the ultraviolet laser for annealing, the annealing time is greatly shortened, the performance of the film layer is improved, the influence of the annealing on the luminescent layer material such as quantum dots and the like is also considered, and the performance and the service life of the device are integrally improved.
In some embodiments, the matrix comprises: an anode on which the light emitting layer is formed.
The material of the anode can refer to the conventional anode in the art, and in some embodiments, the material of the anode is selected from at least one of indium tin oxide, indium antimony oxide and arsenic trioxide.
The material of the light emitting layer can be inorganic semiconductor nanoparticles, including blue quantum dots, red quantum dots, green quantum dots, or the like. In some embodiments, the material of the light emitting layer is a blue quantum dot, including CdZnS/ZnS, CdZnSe/ZnS, CuXIn1-XS/ZnS and ZnXCd1-XAt least one of Te/ZnS. According to the embodiment of the invention, by adopting the method of annealing by adopting the infrared laser and the ultraviolet laser in sequence, the high temperature is prevented from being transferred to the light-emitting layer, the influence of the annealing process on the blue quantum dots can be reduced to a certain extent, the device is prevented from carrying out fluorescence quenching, and the performance of the blue quantum dot light-emitting device is favorably improved. In a further embodiment, the surface of the quantum dot is also combined with a ligand, wherein the ligand is one or more of acid ligand, thiol ligand, amine ligand, phosphine oxide ligand, phospholipid, lecithin, polyvinyl pyridine and the like.
In addition to the anode and the light-emitting layer, the substrate may further include other functional film layers. In some embodiments, the matrix further comprises: hole injection layer and hole transport layer, hole injection layer set up between positive pole and quantum dot luminescent layer, and hole transport layer sets up between hole injection layer and quantum dot luminescent layer to promote the hole transport efficiency of device, thereby improve the luminous performance of device. In some embodiments, the material of the hole injection layer is selected from at least one of poly-PEDOT: PSS (Chinese name: 3, 4-ethylenedioxythiophene: poly (styrenesulfonic acid)), 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanoquinodimethane, and 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene. In some embodiments, the material of the hole transport layer is selected from at least one of poly (3-alkylthiophene) (P3AT), 1,2,4, 5-tetrakis (trifluoromethyl) benzene, polysilanes, triphenylmethanes, and triarylamines.
Specifically, in step S01, an indium zinc oxide precursor is used as a precursor material for preparing the electron transport layer. Compared with the traditional zinc oxide material, the electron transport layer made of materials such as indium zinc oxide has more excellent electrical and optical properties, such as better electron transport efficiency and transmittance, and can further improve the light emitting performance of a QLED device, especially a blue light QLED.
In one embodiment, the indium zinc oxide precursor is an indium zinc oxide precursor solution prepared by a sol-gel method. The sol-gel method has the advantages of short manufacturing period, large-area preparation, simple process, low cost and the like, and is a conventional method for preparing indium zinc oxide. However, the indium zinc oxide thin film prepared by the traditional sol-gel method requires a higher heat treatment temperature, such as 300 ℃ to 600 ℃, to obtain the ideal effect, however, high-temperature annealing easily causes damage to the quantum dot light emitting layer, which limits the application of the method in preparing the QLED device. The applicant proposes to use a method of annealing by successively using an infrared laser and an ultraviolet laser, which can effectively solve this problem.
In some embodiments, the method for preparing the indium zinc oxide precursor solution comprises the following steps:
s011, mixing an indium source, ethylene glycol monomethyl ether, acetylacetone and ammonia water, and stirring at the rotating speed of 600-800rpm at the temperature of 55-65 ℃ for 1-1.5 hours to obtain a first mixture;
s012, mixing a zinc source, ethylene glycol monomethyl ether and acetylacetone, and stirring at the rotating speed of 600-800rpm at 55-65 ℃ for 1-1.5 hours to obtain a second mixture;
s013, mixing the first mixture and the second mixture, and stirring at the rotation speed of 450-550rpm for 2.5-3.5 hours to obtain the indium zinc oxide precursor solution; wherein the molar ratio of indium atoms to zinc atoms in the mixed solution of the first mixture and the second mixture is (2-4): (6-8).
In the method, glycol methyl ether and acetylacetone are used as solvents, ammonia water is used as a stabilizer, and the indium zinc oxide precursor solution is prepared by firstly preparing the silver oxide gel solution and then adding the zinc source solution for mixed reaction. The indium zinc oxide precursor solution prepared by the method has the advantages of good dispersibility, uniform subsequent film forming and the like, and is beneficial to forming a stable indium zinc oxide precursor film by coating the indium zinc oxide precursor solution on the quantum dot light emitting layer in a spinning way, and the molar ratio of indium atoms to zinc atoms in the formed indium zinc oxide film is (2-4) to (6-8).
Specifically, the step of depositing the indium zinc oxide precursor on the light emitting layer may refer to the conventional operation in the art, and the deposition may employ spin coating, inkjet printing, magnetron sputtering, or the like. In some embodiments, the indium zinc oxide precursor is spin coated on the light emitting layer using a spin coating process to form an indium zinc oxide precursor thin film.
Specifically, in step S02, the indium zinc oxide precursor film is irradiated with infrared laser light and annealed, thereby forming an indium zinc oxide film.
The infrared laser has wavelength longer than that of visible light, such as 800 nm, and has high energy and high collimation, so that the energy is released instantaneously in the radiation interface to produce instantaneous heat effect. According to the embodiment of the invention, the annealing treatment method is adopted by irradiating the indium zinc oxide precursor film with infrared laser, so that the temperature of the surface of the material is instantly increased to generate thermal effect laser evaporation, the rapid annealing of the indium zinc oxide precursor film can be realized, the time consumption is only within 10 seconds, and the annealing treatment method is short and effective. The infrared laser radiation in a short time can obviously reduce the roughness of the surface of the film and improve the crystallinity of the film, thereby reducing the resistivity of the film and further improving the luminous performance of the QLED device. Due to the fact that annealing time is greatly shortened, the risk that the device is invaded by water and oxygen before being packaged is reduced, and the service life of the device is prolonged. The short-time and effective infrared laser annealing can also reduce the damage degree of the film structure inside the device, such as avoiding the damage to the quantum dot structure caused by long-time high-temperature annealing, and effectively improving the electron mobility. Therefore, under the same current, the brightness of the device subjected to light treatment can be obviously improved, and the heat accumulation of the device can be reduced, thereby having a positive effect on the service life of the device.
The step of irradiating the indium zinc oxide precursor film by using infrared laser refers to the step of conventional infrared laser irradiation in the field, so that infrared laser spots are directly irradiated on the indium zinc oxide precursor film.
As one embodiment, the wavelength of the infrared laser is 950-1050 nanometers. When the quantum dot light-emitting layer is made of blue quantum dots, the wavelength of infrared laser is larger than the excitation wavelength of the blue quantum dots, and the blue quantum dots are slightly affected by the method of annealing treatment by irradiating the indium zinc oxide precursor film with the infrared laser, so that the quantum dot light-emitting layer is effectively protected, and the device is ensured to have good light-emitting performance.
In one embodiment, the annealing step is performed by irradiating the indium zinc oxide precursor thin film with infrared laser light for 0.1 to 0.2 microseconds.
As an implementation mode, the pulse width of the infrared laser is 115-125fs, the frequency is 0.8-1.2kHz, and the beam quality factor is 1-1.2. The infrared laser beam is adopted to anneal the film, and three-dimensional localized annealing is carried out on an electron transmission layer of the device with high focusing and high collimation through a physical heat effect, so that the influence on other film layers of the QLED device is reduced to the greatest extent. Meanwhile, the laser annealing period is short, generally 0.1-0.2 microseconds, and uncontrollable impurity pollution cannot be introduced, so that the performance of the device is improved.
Specifically, in step S03, the indium zinc oxide thin film is irradiated with ultraviolet laser light and post-annealing treatment is performed, thereby forming an electron transport layer.
And after the infrared laser is annealed, continuously irradiating the indium zinc oxide precursor film by adopting ultraviolet laser to carry out post-annealing treatment. The ultraviolet laser has high photon energy, can directly destroy covalent bonds of organic matters, promotes the organic matters which are difficult to volatilize and remain in the film layer to be decomposed into gaseous molecules and volatilize to the outside, eliminates the influence of the remaining organic matters on the electrical property of the film layer, and avoids the problem of quantum dot damage caused by adopting a method of decomposing the remaining organic matters in the film layer at high temperature for a long time.
The step of irradiating the indium zinc oxide film by adopting ultraviolet laser refers to the step of conventional ultraviolet laser radiation in the field, so that ultraviolet laser spots are directly radiated on the indium zinc oxide film.
In one embodiment, the wavelength of the uv laser is 240-260 nm. When the quantum dot light-emitting layer is made of the blue quantum dot, the wavelength of ultraviolet laser is within the range of the excitation wavelength of the blue quantum dot, and the ultraviolet laser has a certain excitation effect on the blue quantum dot, so that the luminous intensity of the quantum dot can be enhanced to a certain extent, and the luminous performance of a device is favorably improved.
In one embodiment, the post annealing step is performed by irradiating the indium zinc oxide thin film with an ultraviolet laser for 30 to 45 seconds.
As an embodiment, the pulse width of the ultraviolet laser is 18-22ns, the power is 2.2-2.8W, the frequency is 0.8-1.2Hz, and the laser energy is 4.5-6 ev. Under the condition, residual organic matters in the film layer can be completely eliminated.
The indium zinc oxide precursor film is annealed to form an electron transport layer, which, as an embodiment, has a thickness of 50 to 60 nanometers. The electron transport layer with the thickness has the best influence on the overall electrical performance of the device, and particularly in the preparation process of the top emission device, the electron transport layer with the thickness not only has relatively good electron mobility, but also has excellent optical performance.
In the method for manufacturing a light emitting diode provided by the embodiment of the present invention, after the step of manufacturing the electron transport layer, the method further includes: depositing a cathode on the electron transport layer. The step of depositing the cathode on the electron transport layer can be performed by means of a conventional technique in the art, such as spin coating, ink jet printing, magnetron sputtering, and the like. The cathode material can be referred to the cathode conventional in the art.
In summary, compared with the conventional method of annealing at a high temperature for a long time, the embodiment of the invention uses the method of annealing by irradiating the indium zinc oxide precursor film with the infrared laser and the ultraviolet laser in sequence, thereby achieving the purpose of annealing transiently and effectively, improving the performance of the film layer and the service life of the device, and removing the persistent organic matters remained in the film layer effectively, thereby improving the performance and the service life of the device as a whole.
Based on the technical scheme, the embodiment of the invention also provides the light-emitting diode.
Correspondingly, the light-emitting diode is prepared by the preparation method.
The light-emitting diode provided by the invention is prepared by the preparation method, and has good light-emitting performance and long service life.
As an embodiment, as shown in fig. 2, the light emitting diode sequentially includes: anode L01, hole injection layer L02, hole transport layer L03, quantum dot light emitting layer L04, electron transport layer L05, and cathode L06. In some embodiments, the electron transport layer has a thickness of 50-60 nanometers. In some embodiments, the quantum dot light emitting layer has a thickness of 20-60 nm. In some embodiments, the cathode has a thickness of 15-30 nm.
In order that the above details of the practice and operation of the present invention will be clearly understood by those skilled in the art, and the advanced nature of the light emitting diode and the method of making the same according to the embodiments of the present invention will be apparent, the practice of the present invention will be illustrated by the following examples.
Example 1
The embodiment prepares the light emitting diode, and specifically comprises the following steps:
1. preparing IZO precursor solution
Firstly, 0.1M of [ In (NO)3)3·xH2O]The powder was placed in a reagent bottle, and 2.5ml of ethylene glycol methyl ether, 50ml of acetone, and 22.5ml of ammonia water were added to the bottle. Thereafter, another reagent bottle was prepared, to which 0.1M of [ Zn (CH) was added3COO)2·2H2O]Powder, 1.5ml of ethylene glycol methyl ether and 30ml of acetone. Two reagent bottles were placed in a magnetic stirrer and stirred at 700rpm for one hour in an environment of 60 ℃. The two solutions obtained were mixed in a one-to-one ratio, and then sufficiently stirred at 500rpm in an environment of 27 ℃ for three hours to obtain an IZO precursor solution.
2. Preparation of light emitting diodes
(1) On an ITO glass substrate, PEDOT: PSS, the spin coating time is 30 seconds, the spin coating is carried out, then the heating is carried out for 15 minutes, the temperature is 150 ℃, and a hole injection layer is formed.
(2) On the hole injection layer, TFB of 8mg/ml was spin-coated at 3000rpm for 30 seconds, and then heated at 150 ℃ for 30 minutes to form a hole transport layer.
(3) And spin-coating CdZnS/ZnS blue quantum dots with the concentration of 20mg/mL on the hole transport layer at the rotating speed of 2000rpm for 30 seconds to form a quantum dot light-emitting layer.
(4) Spin-coating an IZO precursor solution on the quantum dot light-emitting layer at the rotating speed of 3000rpm for 30 seconds to form an IZO precursor film;
(5) irradiating the IZO precursor film by adopting infrared laser for 0.2 second to form the IZO film; wherein, the light-emitting diameter of the infrared laser is 3mm, the wavelength is 1053nm, the pulse width is 120fs, the repetition frequency is 1kHz, and the beam quality factor is 1.2.
(6) The IZO film was irradiated with ultraviolet laser light for 45 seconds to form an electron transporting layer. Wherein the power of the ultraviolet laser is 2.5W, the irradiation frequency is 1Hz, the irradiation time is 50s, the laser pulse width is 20nm, and the laser energy is 5 eV.
(7) And evaporating an Al electrode on the electron transport layer. The vacuum degree is not higher than 3 x 10 by adopting the metal thermal evaporation process to plate aluminum- 4Pa, speed of
The time was 800 seconds and the thickness was 80 nm.
Example 2
This example prepared a light emitting diode which differed from example 1 in that: the quantum dot light-emitting layer is made of CdZnSe/ZnS blue quantum dots; in the step of depositing an Al electrode on the electron transport layer, the deposition time was 150 seconds, and the thickness of the aluminum electrode was 12 nm.
The rest of the process is substantially the same as that of embodiment 1, and the description thereof is omitted here.
Comparative example 1
This comparative example prepared a light emitting diode which differed from example 1 in that: in the step of preparing the light-emitting diode, the original steps (5) to (6) are replaced by: and (3) placing the device prepared in the step (4) on a heating plate in an inert gas environment, connecting the ITO glass substrate with the heating plate, and then carrying out annealing treatment at 300 ℃.
The rest of the process is substantially the same as that of embodiment 1, and the description thereof is omitted here.
Comparative example 2
This comparative example prepared a light emitting diode which was different from comparative example 1 in that: replacing the IZO precursor solution with a ZnO precursor solution; after a ZnO precursor film is formed on the quantum dot light-emitting layer by spin coating, the device is placed on a heating plate in an inert gas environment, the ITO glass substrate is connected with the heating plate, and then annealing treatment is carried out at 80 ℃.
The rest of the process is substantially the same as that of embodiment 1, and the description thereof is omitted here.
1. Morphology observation is carried out on the electron transport layers prepared in the example 1 and the comparative example 1, and FIG. 3 is an AFM image of the electron transport layer prepared in the example 1, wherein the Rq value is 1.2; fig. 4 is an AFM image of the electron transport layer prepared in comparative example 1, which shows that the Rq value of the electron transport layer prepared in example 1 is 3.1, and the electron transport layer prepared in example 1 has good film properties, and is flat and dense in surface.
2. The light emitting diodes prepared in example 1 and comparative examples 1 to 2 were subjected to performance tests, and table 1 shows the test results. In table 1, L is the luminous intensity per unit area, and is used to indicate the brightness intensity of the light emitting device; j is the current density, which represents the amount of electricity passing through a certain unit area in unit time; EOE is external quantum efficiency, and the overall luminous performance of the reaction device; eta a is the current efficiency of the device.
As shown in table 1, L, J, EQE and η a of example 1 are both larger than those of comparative examples 1-2, which illustrate that the light emitting performance of the device can be improved by the method provided by the embodiment of the present invention.
TABLE 1
| L(cd/m2) | J(mA/cm2) | EQE(％) | ηA(Cd/A) | |
| Example 1 | 4077.9 | 63.1 | 10.8 | 6.5 |
| Comparative example 1 | 2.9 | 10.6 | 0.02 | 0.03 |
| Comparative example 2 | 3047.8 | 38.7 | 9.8 | 5.9 |
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A preparation method of a light-emitting diode is characterized by comprising the following steps of preparing an electron transport layer:
providing a substrate and an indium zinc oxide precursor, and depositing the indium zinc oxide precursor on the substrate to form an indium zinc oxide precursor film;
irradiating the indium zinc oxide precursor film by adopting infrared laser, and carrying out annealing treatment to form an indium zinc oxide film;
and irradiating the indium zinc oxide film by adopting ultraviolet laser to carry out post-annealing treatment.
2. The production method according to claim 1, wherein a light-emitting layer is formed on the substrate;
the step of depositing the indium zinc oxide precursor on the substrate comprises: and depositing the indium zinc oxide precursor on the light-emitting layer.
3. The production method according to claim 1, wherein the indium zinc oxide precursor is an indium zinc oxide precursor solution prepared by a sol-gel method.
4. A method of making as claimed in claim 3 wherein the method of making the indium zinc oxide precursor solution comprises the steps of:
mixing an indium source, ethylene glycol monomethyl ether, acetylacetone and ammonia water, and stirring at the rotating speed of 600-800rpm at the temperature of 55-65 ℃ for 1-1.5 hours to obtain a first mixture;
mixing a zinc source, ethylene glycol monomethyl ether and acetylacetone, and stirring at the rotation speed of 600-800rpm at the temperature of 55-65 ℃ for 1-1.5 hours to obtain a second mixture;
mixing the first mixture and the second mixture, and stirring at the rotation speed of 450-550rpm for 2.5-3.5 hours to obtain the indium zinc oxide precursor solution; wherein the molar ratio of indium atoms to zinc atoms in the mixed solution of the first mixture and the second mixture is (2-4): (6-8).
5. The method according to any one of claims 1 to 4, wherein the wavelength of the infrared laser is 950-1050 nm; and/or
The wavelength of the ultraviolet laser is 240-260 nm.
6. The production method according to any one of claims 1 to 4, wherein in the step of performing annealing treatment, irradiation of the indium zinc oxide precursor thin film with infrared laser light is performed for 0.1 to 0.2 microseconds; and/or
And in the step of post-annealing treatment, ultraviolet laser is adopted to irradiate the indium zinc oxide film for 30-45 seconds.
7. The method as claimed in any one of claims 1 to 4, wherein the infrared laser has a pulse width of 115-125fs, a frequency of 0.8-1.2kHz, and a beam quality factor of 1-1.2.
8. The production method according to any one of claims 1 to 4, wherein the ultraviolet laser has a pulse width of 18 to 22ns, a power of 2.2 to 2.8W, a frequency of 0.8 to 1.2Hz, and a laser energy of 4.5 to 6 ev.
9. The production method according to any one of claims 2 to 4, wherein a material of the light-emitting layer is a blue quantum dot; and/or
The material of the luminescent layer comprises CdZnS/ZnS, CdZnSe/ZnS and CuXIn1-XS/ZnS and ZnXCd1-XAt least one of Te/ZnS.
10. A light-emitting diode produced by the production method according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911417228.XA CN113130834B (en) | 2019-12-31 | 2019-12-31 | Light emitting diode and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911417228.XA CN113130834B (en) | 2019-12-31 | 2019-12-31 | Light emitting diode and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113130834A true CN113130834A (en) | 2021-07-16 |
| CN113130834B CN113130834B (en) | 2022-08-09 |
Family
ID=76769773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911417228.XA Active CN113130834B (en) | 2019-12-31 | 2019-12-31 | Light emitting diode and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113130834B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103828018A (en) * | 2011-01-28 | 2014-05-28 | 西北大学 | Low-temperature fabrication of metal oxide thin films and nanomaterial-derived metal composite thin films |
| US20160086802A1 (en) * | 2014-09-24 | 2016-03-24 | Qualcomm Mems Technologies, Inc. | Laser annealing technique for metal oxide tft |
| US20160126505A1 (en) * | 2014-10-30 | 2016-05-05 | Nano And Advanced Materials Institute Limited | Solution Process Electron Transporting Layer for Polymer Light Emitting Diode |
| CN110534652A (en) * | 2019-09-10 | 2019-12-03 | 西北工业大学 | A kind of perovskite solar battery and preparation method thereof |
-
2019
- 2019-12-31 CN CN201911417228.XA patent/CN113130834B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103828018A (en) * | 2011-01-28 | 2014-05-28 | 西北大学 | Low-temperature fabrication of metal oxide thin films and nanomaterial-derived metal composite thin films |
| US20160086802A1 (en) * | 2014-09-24 | 2016-03-24 | Qualcomm Mems Technologies, Inc. | Laser annealing technique for metal oxide tft |
| US20160126505A1 (en) * | 2014-10-30 | 2016-05-05 | Nano And Advanced Materials Institute Limited | Solution Process Electron Transporting Layer for Polymer Light Emitting Diode |
| CN110534652A (en) * | 2019-09-10 | 2019-12-03 | 西北工业大学 | A kind of perovskite solar battery and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| HARIBABU PALNEEDI等: "Laser Irradiation of Metal Oxide Films and Nanostructures", 《ADVANCED MATERIALS》 * |
| SEUNGNAM CHA等: "Ultrafast and low temperature laser annealing for crystalline TiO2 nanostructures patterned by electro-hydrodynamic lithography", 《APPLIED PHYSICS LETTERS》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113130834B (en) | 2022-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106816545B (en) | Quantum dot light-emitting diode, manufacturing method thereof, array substrate and display device | |
| CN102610725B (en) | Semiconductor quantum dot light-emitting diode and preparing method thereof | |
| CN106784191B (en) | QLED device and preparation method thereof | |
| CN109888109B (en) | Quantum dot modified double-body heterojunction organic solar cell and preparation method thereof | |
| CN103972416A (en) | Semiconductor quantum dot LED based on reverse structure and preparation method thereof | |
| CN114566598A (en) | Light-emitting device, display device and manufacturing method | |
| CN112538163A (en) | Composite material, preparation method thereof and quantum dot light-emitting diode | |
| CN111952471B (en) | Based on Au@SiO 2 Preparation method of plasmon enhanced quantum dot light-emitting diode | |
| CN113130834B (en) | Light emitting diode and preparation method thereof | |
| CN111384247B (en) | Quantum dot light-emitting diode and preparation method thereof | |
| CN112687820A (en) | QLED device, preparation method of QLED device and display device | |
| CN110416420B (en) | Quantum dot light-emitting diode and preparation method thereof | |
| CN113130786A (en) | Light emitting diode and preparation method thereof | |
| CN108695411B (en) | Quantum dot light-emitting diode and preparation method thereof | |
| WO2022227661A1 (en) | Quantum dot film and preparation method therefor, and preparation method for quantum dot light-emitting diode | |
| CN114203941B (en) | Method for preparing film and light-emitting diode | |
| CN114695819A (en) | Quantum dot light-emitting diode and preparation method thereof | |
| CN113972344A (en) | Light emitting diode and preparation method thereof | |
| CN114695736A (en) | Preparation method of quantum dot light-emitting diode | |
| CN113659088A (en) | Quantum dot light-emitting diode, preparation method thereof and display device | |
| CN109713152B (en) | Thin film, preparation method thereof and QLED device | |
| CN111952474A (en) | Quantum dot light-emitting diode based on organic matter polymerization and preparation method thereof | |
| CN113130809B (en) | Composite electrode and preparation method thereof, and quantum dot light-emitting diode | |
| CN110963535A (en) | Composite material, preparation method thereof and quantum dot light-emitting diode | |
| CN110970566A (en) | Core-shell nano material, preparation method thereof and quantum dot light-emitting diode |
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 | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 516006 TCL science and technology building, No. 17, Huifeng Third Road, Zhongkai high tech Zone, Huizhou City, Guangdong Province Applicant after: TCL Technology Group Co.,Ltd. Address before: 516006 Guangdong province Huizhou Zhongkai hi tech Development Zone No. nineteen District Applicant before: TCL Corp. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |