CN110729406A - Mixed hole injection layer QLED device and preparation method thereof - Google Patents
Mixed hole injection layer QLED device and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of light emitting diodes, and particularly relates to a mixed hole injection layer QLED device and a preparation method thereof. The invention is realized by mixing V2O5The precursor solution of (A) and PEDOT and PSS are mixed to prepare V2O5PSS solution is coated on an aluminum-doped zinc oxide AZO transparent electrode in a spin mode to form a film serving as a mixed hole injection layer, a mixed hole injection layer QLED device is prepared, and the performance of the prepared QLED device is detected. Through test determination, the repeatability of the construction process of the QLED device is good, the average value of the maximum current efficiency is 55.51 cd/A, the standard deviation is 2.59 cd/A, the service life of the QLED device is 9051 h, and V is not introduced2O5，I.e. a QLED device with only the PEDOT: PSS hole injection layer, by a factor of 3.15.
Description
Technical Field
The invention belongs to the technical field of light emitting diodes, and particularly relates to a mixed hole injection layer QLED device and a preparation method thereof.
Background
Quantum dot light emitting diodes (QLEDs) are greatly limited by their advantages of tunable emission wavelength, narrow half-peak width, high brightness, solution-soluble preparation, etc. in the visible rangeNote that it shows great application potential in the fields of next-generation flat panel display and solid-state lighting. At present, based on literature (Yizhe Sun, WeiChen, Yinghui Wu, Zhubin He, Shengdong Zhuang and Shuming Chen. A low-temperature-associated and UV-ozone-modified chemical organic emission layer for flexible inorganic lighting diodes [ J ] J]Nanoscale, 2019, 11, 1021) reports that the most commonly used hole injection material for construction of QLED devices is poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonate (poly (3,4-ethylenedioxythiophene): poly (styrene-sulfonate), PEDOT: PSS. However, PEDOT and PSS are weakly acidic and hygroscopic, and corrode electrodes to a certain extent, thereby affecting the stability of devices and reducing the service life of the devices. In order to solve the problem and prolong the service life of the QLED device, researchers introduce inorganic transition metal oxides with good chemical stability and simple synthesis process into the QLED device, such as: NiO and MoO3、WOxAnd V2O5And the stability of the device is successfully improved. Chen et al (Chen S M, Wang S T, SunX W, et al, Solution-processed vanadium oxide as an effective hole injectionlayer for quality-dot light-emitting diodes [ J]Journal of materials chemistry C, 2017, 5(4): 817-823) preparation of V by solution method2O5And the QLED device is constructed by taking the QLED as a hole injection layer, and the service life of the QLED device is prolonged by 4.5 times compared with that of a standard device. In 2018, Qian et al (Q. Zeng, Z. Xu, C. Zheng, Y. Liu, W. Chen, T. Guo, F. Li, C. Xiang, Y. Yang, W. Cao, X. Xie, X.Yan, L. Qian and P. Holloway, Improving Charge Injection via Blade-coating Molybdenum Layer: heated High-Performance Large-Area Quantum-Dot Light-Emitting Diodes [ J. Zeng, Z. Xu, C. Zheng, T. Guo, F. Li, C. Xiang, Y. Yang, W. Cao, X. Xie, X.Yan, L. Qian and P. Holloway, Improving Charge Injection via Blade-coating Molybdenum Layer: heated High-Performance Large-Area Quantum-Dot Light-Emitting Diodes [ J].ACS Appl. Mater. Interface,2018, 10, 8258-8264) MoO prepared by solution methodxThe device lifetime of the QLED device, which is a hole injection layer, is increased by a factor of 2 compared to the standard device. In the same year, Chen et al (Chen L, Wang S J, Fang Y, et al, Simultaneous improvement of efficacy and lifetime of quality dot light-emitting diodes with a bilayer halogen layer regulating of PEDOT: PSS and solution-processed WO3[J]. ACSApplied Materials&Interfaces, 2018, 10(28): 24232-24241) constructed by a solution method based on WO3PSS double hole injection layer QLED device with about 2 times of standard device lifetime. In addition, Kwon research group (Kwon Y, Kim Y, Lee H, et al, Composite film of poly (3, 4-ethylenedioxythiopene): poly (styrene sulfonate) and MoO3as an efficient holeinjection layer for polymer light-emitting diodes[J]Organic Electronics,2014, 15(6): 1083-3And PEDOT PSS mixed hole injection layer PLED device with 2.5 times of standard device lifetime. Obviously, the introduction of these metal oxides has great research value for the research of long-life QLEDs due to their inherent air environment stability. However, the luminance and efficiency of light emission are still different from those of QLEDs mainly constructed with PEDOT (PSS) as a hole injection layer.
Disclosure of Invention
The invention aims to provide a mixed hole injection layer QLED device and a preparation method thereof, aims to prolong the service life of the device and solve the problems of insufficient brightness and efficiency of light emission of the conventional QLED device.
Based on the purpose, the invention adopts the following technical scheme:
a mixed hole injection layer QLED device and a preparation method thereof comprise the following steps:
(1) preparing an aluminum-doped zinc oxide AZO transparent electrode;
(2) spin-coating a mixed hole injection layer on the aluminum-doped zinc oxide AZO transparent electrode, wherein the material of the mixed hole injection layer is V2O5-PEDOT:PSS；
(3) Spin coating a hole transport layer on the mixed hole injection layer;
(4) a quantum dot light-emitting layer is spin-coated on the hole transport layer, and the material of the quantum dot light-emitting layer is ZnCdSeS/ZnS quantum dots;
(5) spin-coating an electron transport layer ZnO on the quantum dot light-emitting layer;
(6) and (4) evaporating and plating a top electrode on the ZnO electron transport layer, and packaging the device after evaporation of the device is finished.
Further, the thickness of the mixed hole injection layer is 40 nm, the thickness of the hole transport layer is 35 nm, the thickness of the quantum dot light emitting layer is 30 nm, the thickness of the electron transport layer ZnO is 35 nm, and the thickness of the top electrode is 100 nm.
Further, the step (2) of mixing the hole injection layer is carried out by mixing V2O5PSS solution is coated on an aluminum-doped zinc oxide AZO transparent electrode to prepare the V2O5PSS solution from V2O5The precursor solution is mixed with PEDOT and PSS to prepare the compound.
Further, V2O5The volume ratio of the mixed precursor solution and PEDOT to PSS is 1 (5-25), specifically 1:5, 1:10, 1:15, 1:20 and 1: 25.
Further, V2O5The preparation steps of the precursor solution are as follows: mixing a vanadium precursor (triisopropoxytriantium) and isopropanol according to a volume ratio of 1 (60-80) to obtain the vanadium catalyst.
Further, the hole transport layer in the step (3) is one or more of PVK, TFB, poly-TPD, TCTA and CBP, before the TFB is used, TFB powder is dissolved in chlorobenzene to prepare a solution with the concentration of 8 mg/mL, and then a TFB film is prepared by a spin coating method for later use.
Further, before the QLED device is prepared in the step (4), ZnCdSeS/ZnS green quantum dots with the particle size of 8 nm are dissolved in n-octane to prepare a solution with the concentration of 18 mg/mL, and then the quantum dot light-emitting film is prepared by a spin coating method for later use.
Further, in the step (5), before the preparation of the QLED device, ZnO with the grain diameter of 3-4 nm is dissolved in ethanol to prepare a ZnO solution with the concentration of 30 mg/mL, and a ZnO film is prepared by a spin coating method for later use.
Further, the top electrode in the step (6) is an Al, Ag, Cu, Au or alloy electrode; and during packaging, curing the obtained substrate by adopting ultraviolet curing resin.
Further, the aluminum-doped zinc oxide AZO transparent electrode is prepared by a radio frequency magnetron sputtering method, and the specific preparation process is as follows:
and placing the cleaned glass substrate in a cavity of a magnetron sputtering coating machine, placing a patterned mask plate on the surface of the glass substrate, and preparing the AZO transparent electrode by using a magnetron sputtering method.
Further, during preparation, the target base distance is 75 mm, the vacuum degree of the magnetron sputtering background is 5.00 multiplied by 10-6Setting the sputtering power to 125W, the sputtering pressure to 1.0 mTorr, the sputtering time to 40 min, the sputtering temperature to normal temperature, cooling the system for 30 min after the sputtering process is finished, and taking out the AZO substrate for later use; and pre-sputtering for 2 min before formal film deposition to avoid impurity pollution on the surface of the target.
The preparation method comprises mixing V2O5And the mixed hole injection layer QLED device is prepared by using the mixed hole injection layer QLED device and PEDOT and PSS together as a hole injection layer.
The invention has the following beneficial effects:
the invention synthesizes V by a solution method2O5The precursor solution has the advantages of high transmittance, good chemical stability and the like, so that the service life of the device can be effectively prolonged by introducing the precursor solution into a QLED device. Determined by tests, and finally based on AZO electrodes and V2O5PSS QLED device with mixed hole injection layer having maximum luminance, maximum current efficiency, and maximum EQE of 98300cd/m255.53 cd/A, 13.85%. The QLED device has good repeatability in the construction process, the average value of the maximum current efficiency is 55.51 cd/A, the standard deviation is 2.59 cd/A, the service life of the QLED device is 9051 h, and V is not introduced2O5，I.e. a QLED device with only the PEDOT: PSS hole injection layer, by a factor of 3.15.
Drawings
FIG. 1 shows V in example 22O5V prepared by different mixing ratios of PEDOT to PSS2O5PSS solution contact angle test pattern;
FIG. 2 shows V in example 22O5V prepared by different mixing ratios of PEDOT to PSS2O5PSS solution of PEDOTA sub-force scanning probe (AFM) profile;
FIG. 3 shows V in example 22O5V prepared by different mixing ratios of PEDOT to PSS2O5PSS solution formed film transmittance profile;
FIG. 4 shows V in example 22O5V prepared by different mixing ratios of PEDOT to PSS2O5Characterization of thin-film conductive atomic force scanning probes (C-AFM) formed from a PSS solution;
FIG. 5 is a schematic diagram of a mixed hole injection layer QLED device prepared in example 2;
FIG. 6 is a schematic diagram of the energy level structure of a mixed hole injection layer QLED device prepared in example 2;
FIG. 7 is V prepared in example 22O5V prepared by different mixing ratios of PEDOT to PSS2O5A QLED device performance diagram constructed by a PSS hole injection layer;
FIG. 8 is V prepared in example 22O5V prepared by different mixing ratios of PEDOT to PSS2O5PSS hole injection layer to construct a single-hole device current-voltage (J-V) test;
FIG. 9 is V prepared in example 22O5V prepared by different mixing ratios of PEDOT to PSS2O5PSS hole injection layer to construct a QLED device repeatability histogram;
FIG. 10 shows the respective PEDOT, PSS and V preparations of example 22O5PSS is used as a hole injection layer to construct a QLED device life characterization.
Detailed Description
In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The glass substrates in the following examples were purchased from Luoyang gulo glass Co., Ltd, China, and were 25.00 mm by 25.00 mm in size and 1.0 mm to 1.2 mm in thickness. The magnetron sputtering system is a three-target sputtering systemModel PVD75, purchased in ketlesco, usa; the AZO target is Al2O3The mass fraction is 2.00 percent, the aluminum-doped zinc oxide ceramic target has high purity (99.99 percent), the diameter of the target material is about 75.00 mm, the thickness of the target material is about 4.00 mm, and the target material is purchased from Xinnuo material in Beijing of China; the detergent is purchased from Liquinox, acetone and isopropanol are purchased from Scientific, and chlorobenzene and toluene are purchased from Sigma-Aldrich; vanadium triisopropoxide was purchased from carbofuran reagent, Inc. (3,4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT: PSS) under the trade designation CLEVOS P VP AI 4083, purchased from Heraeus.
The hole transport layer in the examples below was (poly [9, 9-dioctylfluorene-co-N- (4-butylphenyl) -diphenylamine]) (TFB) purchased from American Dye Source; the Quantum Dots (QDs) are ZnCdSeS/ZnS green light quantum dots, which are made by laboratories; zinc oxide (ZnO) solution is prepared by laboratories; the aluminum electrode is composed of a material with a density of 2.702 g/cm3The aluminum particles with the boiling point of 2467 ℃, the melting point of 660.4 ℃ and the purity of 99.99 percent are prepared by vapor deposition, and the aluminum particles are purchased from Kurt J.Lesker; an ultraviolet-ozone cleaner, purchased from Shanghai Bingun trade company Limited; UV curable resins were purchased from Norland, USA with NOA63 specification.
The model of the conductive atomic force scanning probe microscope is Dimension Icon, purchased from Bruker corporation, usa; the four-probe tester is model ST2253, and is purchased from Suzhou lattice electronics, China; the variable temperature hall effect tester model is HMS-5300, purchased from Ecopia, korea; the model of the digital measurement source meter is Keithley 2400; the spectral radiometer model is PR-735, M-75 Lens, standard SD card, power adapter (AC-730-6). The spin coater model was WS-650MZ-23NPP/LITE, available from Mycro corporation, USA.
Example 1
The preparation method of the aluminum-doped zinc oxide AZO transparent electrode by using a radio frequency magnetron sputtering method comprises the following steps:
a. washing and preparing the glass substrate: cleaning the surface of a substrate by using a detergent (brand: Alconox, USA; model: Liquinox), then putting the substrate into ultrapure water, acetone and isopropanol reagents in sequence for ultrasonic treatment for 15 min, and finally, quickly drying the surface of the substrate by using a high-purity nitrogen gun for later use;
b. placing the cleaned glass substrate in a cavity of a magnetron sputtering coating machine, placing a patterned mask plate on the surface of the glass substrate, preparing an AZO transparent electrode by using a magnetron sputtering method, and pre-sputtering for 2 min before formally depositing a film to avoid impurity pollution on the surface of a target material, wherein the target base distance is set to be 75 mm, and the vacuum degree of the magnetron sputtering background is 5.00 multiplied by 10-6And (3) setting the Torr, the sputtering power to be 125W, the sputtering pressure to be 1.0 mTorr, sputtering for 40 min at room temperature, cooling the system for 30 min after the sputtering process is finished, and taking out the AZO substrate for later use.
Example 2
A preparation method of a QLED device with a mixed hole injection layer comprises the following steps:
the structure of the QLED device is shown in fig. 5, and the structure thereof is: AZO/V2O5PEDOT PSS/TFB/QDs/ZnO/Al. AZO as the anode of the QLED device, Al as the cathode of the QLED device, V2O5PSS, TFB, QDs and ZnO are respectively used as a hole injection layer HIL, a hole transport layer HTL, a quantum dot light emitting layer EML and an electron transport layer ETL of the QLED device; the thickness of the mixed hole injection layer is 40 nm, the thickness of the hole transport layer is 35 nm, the thickness of the quantum dot light emitting layer is 30 nm, the thickness of the electron transport layer ZnO is 35 nm, and the thickness of the top electrode is 100 nm. The device construction process is as follows:
(1) quickly putting the cleaned AZO substrate into an ultraviolet-ozone cleaning instrument for ultraviolet-ozone treatment for 15 min, wherein the ultraviolet-ozone treatment can improve the hydrophilicity of the surface of the substrate;
(2) applying V by spin coating2O5PSS solution is spin-coated on an AZO substrate to form a hole injection layer, and the specific steps are as follows:
a. preparation of V by sol-gel method2O5The precursor solution of (a): 100 mu L of vanadium precursor (triisopropoxytrianisum) is put into a 25 mL sample bottle, then a liquid-transferring gun is used for adding 7 mL of isopropanol solution into the sample bottle, finally the sample bottle is placed on a stirring table to be stirred for 2 h and is uniformly dissolved to obtain V2O5And 0.45 μm ofFiltering by a filter head for later use;
b. will V2O5The precursor solution and PEDOT PSS are mixed according to different volume ratios to prepare V2O5PSS solution of PEDOT, V2O5The volume ratio of the precursor solution to PEDOT to PSS is 1:5, 1:10, 1:15, 1:20, 1:25 and 1:30 respectively, a filter head with the diameter of 0.45 mu m is used for filtering, a pipette is used for sucking 150 mu L of filtered solution to be dripped in the center of an AZO substrate, the substrate is kept to spin-coat for 60 s under the condition of 4000rpm, and the AZO/V is obtained2O5PSS substrate, taking off the substrate, wiping the edge of the substrate with ultrapure water to expose the electrode, and annealing at 130 ℃ for 15 min on a heating table;
(3) the TFB solution (8 mg/mL) dissolved in chlorobenzene was filtered through a 0.20 μm filter tip, and 60 μ L of the filtered solution was pipetted onto the above AZO/V2O5PSS substrate, spin-coating at 2500 rpm for 45 s to obtain AZO/V2O5PSS/TFB substrate, taking down the substrate, placing the substrate on a heating table, carrying out annealing treatment for 30 min at 150 ℃, and taking down the substrate after the annealing is finished;
(4) the ZnCdSeS/ZnS green quantum dot solution (18 mg/mL) dissolved in n-octane was filtered with a 0.20 μm filter head, 60 μ L of the filtered solution was sucked with a pipette and dropped on the above AZO/V2O5PSS/TFB substrate, spin-coating at 3000 rpm for 45 s while maintaining the substrate to obtain AZO/V2O5PSS/TFB/QDs substrates;
(5) the ZnO solution (30 mg/mL) dissolved in ethanol was filtered through a 0.20 μm filter, 60 μ L of the filtered solution was aspirated through a pipette and dropped on the above AZO/V2O5PSS/TFB/QDs substrate, spin-coating the substrate at 2500 rpm for 45 s to obtain AZO/V2O5PSS/TFB/QDs/ZnO substrate, wiping the edge of the substrate with toluene solution to expose the electrode, and placing the substrate on a heating table to carry out annealing treatment for 30 min at 60 ℃;
(6) the AZO/V after the spin coating is carried out2O5Placing a PEDOT: PSS/TFB/QDs/ZnO substrate in a thermal evaporation platingIn the film coating machine, when the vacuum degree of the film coating machine is lower than 5.00 multiplied by 10-7Carrying out evaporation under the mbar condition, keeping the evaporation rate at 4 Å/s, keeping the electrode thickness at 100 nm, breaking vacuum after the evaporation is finished, and taking out the substrate;
(7) packaging of the device: the constructed device AZO/V2O5And (4) PEDOT, namely PSS/TFB/QDs/ZnO/Al, packaging by using ultraviolet curing resin NOA63, covering a cover glass, and curing under the irradiation of an ultraviolet lamp.
For the AZO/V obtained in the step (2)2O5PSS substrate assay:
as indicated by V in FIG. 12O5V prepared at a different mixing volume ratio to PEDOT to PSS2O5PSS solution contact Angle test results show that V is dependent on2O5Reduction of the ratio V2O5PSS droplets increase the static contact angle from around 53 to around 67. Due to V2O5The PEDOT PSS droplets were all sharp at the AZO film surface, from which it was concluded that different mixing ratios V were obtained2O5The PEDOT PSS solution can form a film with good quality on the surface of AZO. FIG. 2 shows V at different mixing ratio ranges2O5PSS films are relatively similar in appearance; and V is within the range of 2.00 mu m multiplied by 2.00 mu m scanning area under different mixing ratios2O5The roughness of the PEDOT PSS film is about 3.00 nm. Different volume ratio V2O5Characterization of the transmittance of the PEDOT PSS film shows V2O5The PEDOT PSS film can maintain the transmittance of more than 88% in the visible light range, as shown in figure 3, which is beneficial to improving the brightness of the device.
FIG. 4 is V2O5Micro-area current image of the film, as can be seen from FIG. 4, V2O5The current of the film in the micro area is in the pA magnitude, and the current of the other film in the micro area is in the nA magnitude, so that V2O5The conductivity of the film is relatively poor. (b) The micro-area current image of the PEDOT PSS film shows that the micro-area current of the PEDOT PSS film almost reaches 15 nA, so that the conductivity of the PEDOT PSS film is the best. (c) FIG. D and FIG. D show the mixing ratioExamples are V of 1:5 and 1:102O5Micro-area current image of PSS film, with the magnitude of the micro-area current of the film between 0 and 2.5 nA, and V2O5When the mixing ratio of the PEDOT to the PSS film is 1:10, the conductivity of the film is relatively better. (e) FIG. 1, (f) and (g) are V at a mixing ratio of 1:15, 1:20, 1:252O5The micro-area current of the PEDOT PSS film is between 3 nA and 15 nA, and the conductivity of the film is gradually enhanced when the volume ratio of the film is changed from 1:15 to 1: 25.
For the QLED device constructed by the above method, FIG. 6 shows that AZO is used as the anode and V is used as the cathode2O5PSS as hole injection layer, wherein the work function of AZO electrode and V are2O5PSS, the HOMO level is relatively close, so that holes are shifted from V2O5PSS layer HOMO level transport to the HOMO level of the TFB hole transport layer HTL the barrier height to overcome is 0.36 eV. Corresponding V2O5The performance of QLED devices with different volume ratios of PEDOT to PSS is shown in FIG. 7. it can be seen from FIG. 7 that when V is2O5The mixing ratio of PEDOT to PSS varies from 1:5 to 1:30 with V2O5The decrease of the occupied ratio gradually increases the device performance when V2O5When the mixing ratio of PEDOT to PSS is 1:15, the performance of the device is optimal; with V2O5The proportion is continuously reduced, and the performance of the device is gradually reduced.
Table 1 example 1 based on V2O5Summary table of performance of QLED devices with a mixture of hole injection layers of PEDOT: PSS.
At the same time, the device performance is changed with V2O5The variation of the PEDOT: PSS mixing ratio is summarized in Table 1. When V is found by combining the figures and tables2O5When the mixing ratio of PEDOT to PSS is 1:15, the device performance is best: maximum luminance of 98300cd/m2The maximum current efficiency was 55.53 cd/A, EQEmaxThe content was 13.85%. As can be seen from Table 1, with V2O5Increase in volume ratio of PEDOT to PSS, Lmax、ηA、ηP、EQEmaxIncrease first and decrease later, when V2O5L when the volume ratio of PEDOT to PSS is 1:10maxMaximum, when V2O5Eta. PEDOT: PSS volume ratio of 1:15A、ηP、EQEmaxAnd max.
Based on the above discussion, a single-hole device and a single-electron device based on the hole injection layer HIL with different mixing ratios are constructed, and J-V characteristic curves of the devices are shown in fig. 8. The single-electron device structure is as follows: Al/QDs/ZnO/Al, and the structure of the single-hole device is as follows: AZO/(PEDOT: PSS) V2O5PEDOT PSS/TFB/QDs/Au. As can be seen from the figure, when V is2O5The results of the experiment match the above conclusion that the conductivity of the thin film gradually decreases as the current density of the hole-only device gradually decreases as the mixing ratio of PEDOT to PSS gradually changes from 1:25 to 1: 5. When V is2O5The current density of the single-hole device is larger than that of the single-electron device when the mixing ratio of PEDOT to PSS is 1:25, 1:20 and 1: 15; when V is2O5When the mixing ratio of PEDOT to PSS is 1:10 and 1:5, the current density of the corresponding single hole device is smaller than that of the single electron device. Due to V2O5Introduction of (a) V2O5PSS films are gradually reduced in conductivity and reduced in hole transport efficiency, so that carrier injection in QLED devices based on AZO electrodes is relatively balanced. As can be seen from the figure, when V is2O5The J-V curves of the single-hole device and the single-carrier device are closer when the mixing ratio of PEDOT to PSS is 1:15, and the electron-hole injection in the QLED device is relatively balanced. This conclusion also illustrates that when V2O5When the mixing ratio of the QLED and the PEDOT/PSS is 1:15, the QLED device has better performance.
For examination of the electrode based on AZO, V2O5Reproducibility of the hybrid hole injection layer devices PEDOT PSS 30 devices (V of 30 devices) from different batches2O51:15 in the mixing ratio with PEDOT: PSS, respectively)The maximum current efficiency was counted as shown in fig. 9. The average value of the maximum current efficiency was 55.51 cd/A and the standard deviation was 2.59 cd/A, which sufficiently indicates that the reproducibility of the device was good. FIG. 10 shows the results of the analysis of PEDOT, PSS and V, respectively2O5PSS is used as a hole injection layer to construct a life characterization curve of the QLED device. As can be seen, the device is at an initial luminance L0= 5000 cd/m2Under the condition of continuous DC driving, by the formula L0 n×T0.5= K (where K is a constant, 1)<n<2) Assuming that the acceleration factor n = 1.5, both devices are converted to an initial luminance of 100 cd/m2The service lives of the two are 2180 h and 9051 h respectively, V2O5The service life is improved by 3.15 times.
The invention adopts AZO as the anode of the QLED device, when V is2O5When the mixing ratio of the material to PEDOT to PSS is 1:15, the device performance is optimal, the work function is about 5.0 eV, the hole injection barrier can be effectively reduced, and the hole injection efficiency is improved; by using V2O5PSS is used as a mixed hole injection layer of the QLED device, and the service life of the device can be effectively prolonged.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a mixed hole injection layer QLED device is characterized by comprising the following steps:
(1) preparing an aluminum-doped zinc oxide AZO transparent electrode;
(2) spin-coating a mixed hole injection layer on the aluminum-doped zinc oxide AZO transparent electrode, wherein the material of the mixed hole injection layer is V2O5-PEDOT:PSS；
(3) Spin coating a hole transport layer on the mixed hole injection layer;
(4) a quantum dot light-emitting layer is spin-coated on the hole transport layer, and the material of the quantum dot light-emitting layer is ZnCdSeS/ZnS quantum dots;
(5) spin-coating an electron transport layer ZnO on the quantum dot light-emitting layer;
(6) and (4) evaporating and plating a top electrode on the ZnO electron transport layer, and packaging the device after evaporation of the device is finished.
2. The method according to claim 1, wherein the hole injection layer is mixed in the step (2) by mixing V2O5PSS solution is coated on an aluminum-doped zinc oxide AZO transparent electrode to prepare the V2O5PSS solution from V2O5The precursor solution is mixed with PEDOT and PSS to prepare the compound.
3. The method of claim 2, wherein V is2O5The volume ratio of the mixed precursor solution of the (1) to the PEDOT to PSS is 1 (5-25).
4. The method of claim 2, wherein V is2O5The preparation steps of the precursor solution are as follows: mixing a vanadium precursor and isopropanol according to a volume ratio of 1 (60-80) to obtain the vanadium-containing composite material; the precursor of the vanadium is triisopropoxytrianisum.
5. The preparation method according to claim 1, wherein the hole transport layer in step (3) is one or more of PVK, TFB, poly-TPD, TCTA and CBP, and before use, TFB is prepared into a solution with a concentration of 8 mg/mL by dissolving TFB powder in chlorobenzene and then is prepared into a TFB film by a spin coating method for later use.
6. The preparation method according to claim 1, wherein in step (4), before the preparation of the QLED device, ZnCdSeS/ZnS green quantum dots with a particle size of 8 nm are dissolved in n-octane to prepare a solution with a concentration of 18 mg/mL, and then the solution is spin-coated to prepare the quantum dot light-emitting film for later use.
7. The preparation method according to claim 1, wherein in the step (5), before the QLED device is prepared, ZnO with the particle size of 3-4 nm is dissolved in ethanol to prepare a ZnO solution with the concentration of 30 mg/mL, and the ZnO film is prepared by a spin coating method and is ready for use.
8. The production method according to claim 1, wherein the top electrode of step (6) is an Al, Ag, Cu, Au or alloy electrode; and during packaging, curing the obtained substrate by adopting ultraviolet curing resin.
9. The preparation method according to claim 1, wherein the aluminum-doped zinc oxide AZO transparent electrode is prepared by a radio frequency magnetron sputtering method.
10. A mixed hole injection layer QLED device prepared by the method of any one of claims 1 to 9.
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