CN116004224B - I-III-VI family quantum dot, synthesis method thereof and QD-LED device - Google Patents
I-III-VI family quantum dot, synthesis method thereof and QD-LED device Download PDFInfo
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- 238000001308 synthesis method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000002346 layers by function Substances 0.000 claims abstract description 10
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- 239000011593 sulfur Substances 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 239000004332 silver Substances 0.000 claims abstract description 5
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- 229910021476 group 6 element Inorganic materials 0.000 claims abstract description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
The invention provides a quantum dot of I-III-VI families, a synthesis method thereof and a QD-LED device. The method comprises the following steps: mixing the I-VI group quantum dots with a solution containing a precursor of III group elements and a surfactant for reaction, so that the I group elements and the III group elements are mutually diffused to realize partial replacement, and obtaining the I-III-VI group quantum dots; the group I element is selected from silver and/or copper, the group VI element is selected from one or two of sulfur and selenium, and the group III element is selected from one or more of indium, gallium and arsenic. The invention also provides the I-III-VI quantum dots synthesized by the method and the QD-LED device prepared from the same. The I-III-VI semiconductor quantum dot provided by the invention has the advantages of uniform size and high purity, and can be used for preparing a hole functional layer of a blue light QD-LED, so that the luminous performance of the blue light QD-LED can be improved.
Description
Technical Field
The invention relates to an I-III-VI family quantum dot, a synthesis method thereof and a QD-LED device, belonging to the technical field of electronics.
Background
Colloidal Quantum Dot (QD) materials have unique small size and quantum confinement effects compared to traditional macroscopic luminescent materials, and their advantages include: the method has the advantages of high luminous color purity, continuously adjustable luminous wavelength, narrow half-peak width of an emission spectrum and capability of being prepared by a solution method. QDs have been rapidly developed in recent years, and the fluorescence quantum yield is close to 100%, so that the QDs have a wide application prospect in the fields of illumination, flat panel display and the like.
The inorganic metal oxide semiconductor nano particles have the characteristics of higher carrier mobility, good stability and better conductivity, and are considered as an effective method for improving the stability of the electroluminescent device. In recent years, all-inorganic quantum dot light emitting diodes (QD-LEDs) prepared by using metal oxide semiconductor materials such as nickel oxide nanoparticles and molybdenum trioxide as hole function materials have become a research hotspot. However, when the prior art scheme is used for constructing an all-inorganic QD-LED device, the performance of the red light and green light QD-LED devices is obviously improved, for example, patent CN103840048A and patent CN102509756A, and the blue light performance is not obviously improved.
Therefore, the light emitting performance and the service life of the red light and green light QD-LEDs have reached commercial levels at present, but the brightness and the working stability of the blue light QD-LEDs, which are one of the three primary colors, are still greatly different from those of the red light and the green light, which seriously hinders the progress of the full color of the QD-LEDs and affects the commercial development of the QD-LEDs in the field of display panels.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide an I-III-VI family quantum dot and a synthesis method thereof, wherein the I-III-VI family quantum dot is a quantum dot material with uniform size and high purity, is used for preparing a hole functional layer of a blue light QD-LED, and can improve the luminous performance of the blue light QD-LED.
In order to achieve the above purpose, the present invention firstly provides a method for synthesizing I-III-VI family quantum dots, which comprises the following steps:
Mixing the I-VI group quantum dots with a solution containing a precursor of III group elements and a surfactant for reaction, so that the I group elements and the III group elements are mutually diffused to realize partial replacement, and obtaining the I-III-VI group quantum dots, wherein the molar ratio of the I group elements to the VI group elements to the III group elements is 1:1:2;
wherein the group I element is selected from silver and/or copper, the group VI element is selected from one or a combination of two of sulfur and selenium, and the group III element is selected from one or a combination of more than two of indium, gallium and arsenic.
In the above synthesis method, preferably, the precursor of the group III element is added in the form of a cationic salt of the group III element, which includes one or a combination of two or more of hydrochloride, acetylacetonate, and nitrate.
In the above synthetic method, preferably, the surfactant includes one or a combination of two or more of trioctylphosphine, diphenylphosphine, and triphenylphosphine.
In the above synthesis method, preferably, in the solution containing the precursor of the group III element and the surfactant, the molar ratio of the group III element to the surfactant is 1:1.
In the above synthesis method, the degree of substitution may be controlled by the reaction time and temperature, preferably, the reaction temperature is 180℃to 200℃and the reaction time is 5 minutes or more, preferably 5 to 15 minutes.
In the above synthesis method, preferably, the semiconductor quantum dot of mixed group I metal or mixed group III metal can be obtained by doping the group I-III-VI quantum dot.
In the above synthesis method, preferably, the group I-III-VI quantum dot is prepared by:
gallium acetylacetonate (preferably 0.4 mmole) is dissolved in a solution containing oleylamine (preferably 3 mmole) and tri-n-octylphosphorus (preferably 4-5 mL) to give solution D;
under inert atmosphere, raising the temperature of the solution D to a reaction temperature (preferably 180-200 ℃), and adding the cuprous sulfide quantum dot solution C into the solution D for reaction;
And (3) cooling the reacted mixed solution to room temperature in a water bath, cleaning, centrifuging, purifying, and finally dispersing in n-octane to prepare the solution containing the I-III-VI group quantum dots.
In the synthesis method of the I-III-VI group quantum dot, the original feeding ratio of the copper element and the gallium element is controlled between 1:1 and 2:1, so that the copper-gallium-sulfur quantum dot with uniform size and high purity can be obtained.
In the above synthesis method, preferably, the cuprous sulfide quantum dot is prepared by:
Cuprous acetate (preferably 0.4 mmol) and tri-n-octylphosphorus oxide (preferably 0.001-0.005 mol) are dissolved in 1-octadecene (preferably 20 ml) to give mixture a; heating the mixture A until the mixture A is clear and transparent to obtain a solution B, and keeping the temperature of the solution at 90-100 ℃;
The temperature of the solution B is raised to a reaction temperature (preferably 210-220 ℃) to carry out a reaction (the reaction time is preferably 15-20 minutes) under an inert atmosphere, and the ligand is added into the solution B when the temperature of the solution reaches 160 ℃ in the heating process;
the mixed solution after the reaction is cooled to room temperature in a water bath, and is finally dispersed in tri-n-octyl phosphorus (preferably 4ml-5 ml) through cleaning, centrifugation and purification, so as to prepare the cuprous sulfide quantum dot solution C.
In the above synthetic method, preferably, the ligand includes an organic ligand and/or an inorganic ligand. The amount of the ligand added can be controlled to 4 to 5 millimoles. According to a specific embodiment of the present invention, preferably, the organic ligand is short-chain 1-n-octyl mercaptan or 1-n-dodecyl mercaptan; the inorganic ligand is a halogen ion.
The method provided by the invention is a synthesis method of the group I-III-VI semiconductor quantum dot with high success rate and universality. The existing I-III-VI group quantum dot nano-particles are mainly synthesized directly by a one-pot method or a hot injection method. However, the Lewis acidity of the group I element and the group III element has large difference and large difference of reactivity, and the element components are difficult to accurately regulate and control in the fixed component range by a one-pot method. The quantum dot material synthesized by the hot injection method may introduce binary impurity phases and defect energy levels.
The invention adopts a cation exchange method to synthesize the I-III-VI semiconductor quantum dot material with uniform size and high purity, and adopts the material to prepare the hole functional layer of the blue light QD-LED, thereby improving the luminous performance and the service life of the blue light QD-LED.
The invention also provides the I-III-VI family quantum dot which is synthesized by the method.
According to a specific embodiment of the present invention, preferably, the spatial dimension of the I-III-VI quantum dots is 1-10nm, having a chalcopyrite structure.
The invention also provides a QD-LED device, which comprises a substrate, a transparent bottom electrode, a hole functional layer, a luminescent layer, an electron transport layer and a transparent top electrode;
Wherein the hole functional layer is made of the I-III-VI quantum dots.
According to a specific embodiment of the present invention, preferably, in the above QD-LED device, the substrate is a glass substrate.
According to a specific embodiment of the present invention, preferably, in the QD-LED device, the transparent bottom electrode is made of indium doped metal oxide (ITO), including one of zinc oxide doped with indium element and tin oxide doped with indium element.
According to a specific embodiment of the present invention, preferably, in the QD-LED device, the material of the light emitting layer contains one or a combination of two or more of blue light quantum dots, red light quantum dots, green light quantum dots, and other types of light emitting quantum dots (for example, inP or perovskite).
According to a specific embodiment of the present invention, in the QD-LED device, preferably, the electron transport layer is made of one or more of TiO 2 quantum dots, znO quantum dots, and doped derivatives thereof.
According to a specific embodiment of the present invention, in the QD-LED device, preferably, the transparent top electrode is made of silver or aluminum.
According to a specific embodiment of the present invention, preferably, in the QD-LED device described above:
The thickness of the transparent bottom electrode is 40-100nm;
The thickness of the hole functional layer is 50-200nm;
the thickness of the light-emitting layer is 30-100nm;
The thickness of the electron transport layer is 30-100nm;
the thickness of the transparent top electrode is 80-150nm.
According to the technical scheme, firstly, the I-III-VI semiconductor compound quantum dots are used as hole injection materials, and secondly, the hole conductivity of the quantum dot film can be regulated and controlled through the ligand, so that a hole transport layer with high hole mobility and hole concentration can be constructed, and the hole transport efficiency can be improved. The method for preparing the inorganic quantum dot hole functional material by the solution method has the advantages of simple process, short preparation period, strong repeatability and controllability, greatly reduced process cost and improved manufacturing yield of devices. The adoption of the hole functional material provided by the invention is beneficial to improving the luminous performance of the QD-LED.
Drawings
Fig. 1 is a schematic diagram of the synthesis of the cuprous sulfide quantum dots of example 1.
FIG. 2 is a schematic representation of the synthesis of group I-III-VI quantum dots of example 1.
Fig. 3 is a transmission electron microscope image of the copper gallium sulfide quantum dots synthesized in example 1.
Fig. 4 is an X-ray diffraction image of the copper gallium sulfide quantum dots synthesized in example 1.
Fig. 5 is a schematic overall cross-sectional structure of the blue QD-LED device prepared in example 1.
Fig. 6 is a graph of current density versus voltage for a blue QD-LED device.
The main reference numerals illustrate:
1-1 copper salt and 1-octadecene solution of tri-n-octyl phosphorus oxide, 1-2 n-dodecyl mercaptan, 1-3 gas washing device, 1-4 thermocouple, 1-5 three-neck flask and 1-6 injector;
2-1 of a mixed solution of oleylamine and tri-n-octyl phosphorus, 2-2 of a cuprous sulfide quantum dot solution, 2-3 of a gas washing device, 2-4 of a thermocouple, 2-5 of a three-neck flask and 2-6 of a syringe;
A 3-1 glass substrate, a 3-2 transparent bottom electrode, a 3-3 hole function layer, a 3-4 luminescent layer, a 3-5 electron transport layer and a 3-6 transparent top electrode.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1
The embodiment provides a synthesis method of I-III-VI family quantum dots, which comprises the following steps:
1. The preparation of the copper-gallium-sulfur quantum dot, the synthesis mode is shown in figures 1 and 2, wherein the first and second steps of the preparation process are carried out in a three-necked flask 1-5, the atmosphere in the flask is replaced by inert gas through a gas washing device 1-3, the temperature change is monitored through a thermocouple 1-4, and the liquid injection is carried out through a syringe 1-6;
Step three, four is carried out in a three-neck flask 2-5, the atmosphere in the flask is replaced by inert gas through a gas washing device 2-3, the temperature change is monitored through a thermocouple 2-4, and liquid injection is carried out through a syringe 2-6;
The specific process is as follows:
step one, cuprous acetate (0.4 mmol) and tri-n-octyl phosphorus oxide (0.001-0.005 mol) are taken and dissolved in 20mL of 1-Octadecyl (ODE) 1-1 to obtain a mixture A;
Heating the mixture A to obtain a solution B, maintaining the temperature of the solution at 90-100 ℃, and changing the atmosphere in the reaction system into an inert atmosphere by using a double-row tube through a vacuum pump and argon ventilation for three times.
Step two, heating the solution B, and adding 1ml of n-dodecyl mercaptan (purity 99%) 1-2 into the solution B to react when the temperature of the solution reaches 160 ℃, wherein the reaction temperature is 210-220 ℃ and the reaction time is 15-20 minutes;
and (3) cooling the reacted mixed solution to room temperature in a water bath, cleaning the mixed solution by ethanol and n-octane, centrifuging and purifying the mixed solution, and finally dispersing the mixed solution in tri-n-octyl phosphorus (4 ml-5 ml) by ultrasonic to prepare the cuprous sulfide quantum dot solution C.
Step three, gallium acetylacetonate (0.4 mmol) of group III element is dissolved in a mixed solution 2-1 of oleylamine (1 ml,3 mmol) and tri-n-octyl phosphorus (4 ml-5 ml), to obtain a solution D, and the atmosphere in the reaction system is changed into an inert atmosphere by three times of ventilation with a vacuum pump and argon gas by using double exhaust pipes.
Step four, raising the temperature of the solution D to a reaction temperature (180-200 ℃), adding the solution C (cuprous sulfide quantum dot solution 2-2) into the solution D completely, and reacting for 5-15 minutes;
And (3) cooling the reacted mixed solution to room temperature in a water bath, cleaning, centrifuging and purifying the mixed solution by using acetone/methanol (volume ratio is 1:1) and n-octane, and finally dispersing the mixed solution in the n-octane to prepare the copper-gallium-sulfur quantum dot solution.
The transmission electron microscope image of the copper gallium sulfide quantum dot obtained in the embodiment is shown in fig. 3, and the X-ray diffraction pattern of the copper gallium sulfide quantum dot is shown in fig. 4.
Quantum dots of different stoichiometric ratios can be obtained by varying the amount of the substance of gallium acetylacetonate.
2. Displacement of quantum dot ligands
Step one, taking 10-20 mu L of mercaptopropionic acid and 1ml of strong polar solution (such as formamide or polymethyl sulfoxide), uniformly mixing in an ampoule bottle, adding 1ml of copper-gallium-sulfur quantum dot solution, stirring, and standing for a period of time.
And step two, removing the transparent solution on the upper layer, continuously adding 1ml of n-octane, stirring, standing, and repeating for 2-3 times, wherein the solution on the lower layer is the I-III-VI family quantum dot solution after ligand replacement.
3. The preparation of the blue light QD-LED device comprises the following steps:
Step one, ITO with the thickness of about 40-100 nanometers is prepared on a glass substrate 3-1 by a magnetron sputtering method to serve as a transparent bottom electrode 3-2.
And secondly, treating the ITO by utilizing plasma, and transferring the treated glass into a glove box filled with nitrogen.
Step three, spin-coating the I-III-VI family quantum dots prepared in the example 1 layer by layer on ITO, wherein the rotating speed is 2000-3000 rpm, and spin-coating is performed for 30 seconds; and (3) placing the spin-coated film on a heating table, and annealing at 60-100 ℃ to prepare the hole functional layer 3-3 with the thickness of 20-50 nm.
Step four, spin coating a blue light emitting layer 3-4 with the thickness of 30-100nm on the hole functional layer, wherein the specific material is CdSe quantum dot spin coating parameters of 2000-3000 rpm, and 20-30 seconds; and (5) placing the coated glass on a heating table after spin coating, and annealing at 60-100 ℃.
And fifthly, spin-coating an electron transport layer 3-5 with the thickness of 30-100nm on the electron blocking layer, wherein the specific material is zinc oxide nano particles, spin-coating parameters are 2000-3000 rpm, 30-40 seconds, and annealing at 50-80 ℃ after spin-coating is finished.
Step six, uniformly evaporating a 100-150nm metal electrode serving as a transparent top electrode 3-6 on the electron transport layer through a covering mask plate by a high-vacuum thermal evaporation method, wherein the electrode material is silver or aluminum, the evaporation rate is about 10-30 angstroms/second, and a blue light QD-LED device is obtained, and the structure of the blue light QD-LED device is shown in figure 5. Fig. 6 is a graph showing the current density of the prepared blue QD-LED device as a function of voltage. As can be seen from fig. 6, compared with the QD-LED device of the conventional organic hole material poly (9, 9-dioctylfluorene-co-N- (4- (3-methylpropyl)) DIPHENYLAMINE) (TFB), the QD-LED device based on the copper-gallium-sulfur quantum dot has reduced leakage current at low voltage and improved current density at high voltage.
Claims (24)
1. The synthesis method of the I-III-VI family quantum dot comprises the following steps:
Mixing the I-VI group quantum dots with a solution containing a precursor of III group elements and a surfactant for reaction, so that the I group elements and the III group elements are mutually diffused to realize partial replacement, and obtaining the I-III-VI group quantum dots, wherein the molar ratio of the I group elements to the VI group elements to the III group elements is 1:1:2;
wherein the group I element is selected from copper, the group VI element is sulfur, and the group III element is gallium
The I-III-VI group quantum dot is prepared by the following steps:
dissolving gallium acetylacetonate in a solution containing oleylamine and tri-n-octyl phosphorus to obtain a solution D;
under inert atmosphere, raising the temperature of the solution D to a reaction temperature, and adding the cuprous sulfide quantum dot solution C into the solution D for reaction;
And (3) cooling the reacted mixed solution to room temperature in a water bath, cleaning, centrifuging, purifying, and finally dispersing in n-octane to prepare the solution containing the I-III-VI group quantum dots.
2. The synthesis method according to claim 1, wherein the group III element precursor is added in the form of a group III element cation salt including one or a combination of two or more of hydrochloride, acetylacetonate, nitrate.
3. The synthetic method of claim 1, wherein the molar ratio of group III element to surfactant is 1:1.
4. The synthesis method according to claim 1, wherein the reaction temperature is 180 ℃ to 200 ℃ and the reaction time is 5 minutes or more.
5. The synthetic method of claim 4, wherein the reaction time is 5-15 minutes.
6. The synthesis method according to claim 1, wherein the amount of gallium acetylacetonate is 0.4 millimoles, the amount of oleylamine is 3 millimoles, and the amount of tri-n-octylphosphorus is 4-5mL.
7. The synthesis method of claim 1, wherein the cuprous sulfide quantum dots are prepared by:
copper acetate and tri-n-octyl phosphorus oxide are dissolved in 1-octadecene to obtain a mixture A; heating the mixture A until the mixture A is clear and transparent to obtain a solution B, and keeping the temperature of the solution at 90-100 ℃;
In inert atmosphere, raising the temperature of the solution B to a reaction temperature for reaction, and adding a ligand into the solution B when the temperature of the solution reaches 160 ℃ in the process of raising the temperature;
And (3) cooling the reacted mixed solution to room temperature in a water bath, and finally dispersing the mixed solution in tri-n-octyl phosphorus to prepare the cuprous sulfide quantum dot solution C through cleaning, centrifuging and purifying.
8. The synthetic method of claim 7, wherein the ligand comprises an organic ligand and/or an inorganic ligand.
9. The synthetic method according to claim 7, wherein the ligand is added in an amount of 4 to 5 millimoles.
10. The synthetic method of claim 8, wherein the organic ligand is short-chain 1-n-octyl mercaptan or 1-n-dodecyl mercaptan.
11. The method of synthesis according to claim 8, wherein the inorganic ligand is a halogen ion.
12. The synthesis method according to claim 7, wherein the amount of cuprous acetate is 0.4 mmol, the amount of tri-n-octylphosphine oxide is 0.001-0.005 mol, and the amount of 1-octadecene is 20ml.
13. The synthetic method of claim 7, wherein the reaction temperature is 210 ℃ to 220 ℃ and the reaction time is 15 to 20 minutes.
14. The synthetic method of claim 7, wherein the tri-n-octyl phosphorus is used in an amount of 4ml to 5ml.
15. A group i-iii-vi quantum dot synthesized by the method of any one of claims 1-14.
16. The group I-III-VI quantum dot according to claim 15 wherein the group I-III-VI quantum dot has a spatial dimension of 1-10nm and has a chalcopyrite structure.
17. A QD-LED device comprising a substrate, a transparent bottom electrode, a hole function layer, a light emitting layer, an electron transport layer, a transparent top electrode;
wherein the hole functional layer is made of the I-III-VI quantum dot in claim 15 or 16.
18. The QD-LED device of claim 17, wherein the substrate is a glass substrate.
19. The QD-LED device of claim 17, wherein the transparent bottom electrode is ITO.
20. The QD-LED device of claim 17, wherein the luminescent layer comprises one or a combination of two or more blue, red, and green quantum dots.
21. The QD-LED device of claim 20, wherein the material of the light emitting layer comprises InP or perovskite.
22. The QD-LED device of claim 17, wherein the electron transport layer is made of one or more of TiO 2 quantum dots, znO quantum dots, and doped derivatives thereof.
23. The QD-LED device of claim 17, wherein the transparent top electrode is silver or aluminum.
24. The QD-LED device of claim 17, wherein:
the thickness of the transparent bottom electrode is 40-100 nm;
the thickness of the hole functional layer is 50-200 nm;
the thickness of the light-emitting layer is 30-100nm;
The thickness of the electron transport layer is 30-100nm;
the thickness of the transparent top electrode is 80-150nm.
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