WO2020029780A1 - Point quantique vert, son procédé de fabrication et son utilisation - Google Patents

Point quantique vert, son procédé de fabrication et son utilisation Download PDF

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WO2020029780A1
WO2020029780A1 PCT/CN2019/097048 CN2019097048W WO2020029780A1 WO 2020029780 A1 WO2020029780 A1 WO 2020029780A1 CN 2019097048 W CN2019097048 W CN 2019097048W WO 2020029780 A1 WO2020029780 A1 WO 2020029780A1
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quantum dot
cdse
znse
source
green
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PCT/CN2019/097048
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Chinese (zh)
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陈小朋
赵海洋
谢阳腊
苏叶华
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纳晶科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C09K11/883—Chalcogenides with zinc or cadmium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • 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]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots

Definitions

  • the invention relates to the technical field of functional materials, in particular to a green quantum dot, a preparation method thereof and an application thereof.
  • Quantum dots that is, semiconductor nanocrystals that are usually between 1 and 100 nm in size and have quantum confinement effects. Due to its special optical and optoelectronic properties, such as extremely wide absorption spectrum, very narrow emission spectrum, and high luminous efficiency, by adjusting the size of the quantum dot to adjust the corresponding band gap of the quantum dot, its electrical properties can be significantly adjusted. , Optical characteristics, etc. Quantum dots have a wide range of application prospects in a variety of elements such as light-emitting elements or photoelectric conversion elements. At present, they have been used in many fields such as display, lighting, solar energy, anti-counterfeiting, and biological fluorescent labeling.
  • Quantum dot-based light-emitting diodes have the advantages of low lighting voltage, good light-emitting monochromaticity, low energy consumption, and light-emitting colors that can be prepared by quantum dot size adjustment and low-cost solution methods.
  • the display field and solid-state lighting field have huge application potential.
  • quantum dots for green QLED there are two main synthesis methods of quantum dots for green QLED:
  • Green core-shell structure quantum dots synthesized by traditional methods such as CdSe / ZnSe, CdSe / CdS, CdSe / ZnS and other core-shell structure quantum dots. Although their fluorescence quantum efficiency can reach 50-80%, this structure exists Many disadvantages. Taking the most commonly used CdSe core quantum dots as an example, the more suitable shell materials are ZnS, ZnSe, and CdS. However, the inventor found the following problems:
  • the thickness of the ZnS layer required for its shell layer is usually 3 to 5 nm or even thicker, and such a thickness of ZnS will greatly increase the startup voltage of QLEDs, thereby accelerating QLED
  • the aging process of the device cannot obtain the ideal device life.
  • large-sized green quantum dots have poor solubility in high-viscosity inks used for printing, which will further limit the CdSe @ ZnS / ZnS green quantum dots of such alloy structures. Application prospects in QLED.
  • the main purpose of the present invention is to provide a green quantum dot, a preparation method thereof, and an application thereof, in order to solve the problems of stability, quantum efficiency, device life, and solubility in high-viscosity inks used for printing of green quantum dots in the prior art. There are problems with lower levels.
  • a green quantum dot has a CdSe / ZnSe X S 1-X / ZnS structure, including a CdSe core; a ZnSe X S 1-X shell layer, CdSe core is coated on the periphery, where 0 ⁇ X ⁇ 1; ZnS shell is coated on the periphery of ZnSe X S 1-X shell.
  • the particle size of the CdSe / ZnSe X S 1-X quantum dot composed of the CdSe core and the ZnSe X S 1-X shell layer is 5-9 nm, and the particle size of the green quantum dot is 8-14 nm.
  • the UV wavelength corresponding to the first exciton peak of the CdSe core is 495-545 nm.
  • the emission wavelength PL of the CdSe / ZnSe X S 1-X quantum dot is 496 to 556 nm, and the half-width of the peak is 19 to 25 nm.
  • the half-width of the CdSe / ZnSe X S 1-X quantum dot is 19 to 22 nm.
  • the emission wavelength PL of the green quantum dots is 490 to 550 nm, and the half-peak width is 20 to 26 nm.
  • the half-width width of the green quantum dots is preferably 20 to 23 nm.
  • a method for preparing green quantum dots including the following steps: S1, preparing CdSe quantum dots as a CdSe core; S2, forming a ZnSe X S 1-X shell layer on the periphery of the CdSe core, CdSe / ZnSe X S 1-X quantum dots are obtained, where 0 ⁇ X ⁇ 1; S3, a ZnS shell is formed on the periphery of the CdSe / ZnSe X S 1-X quantum dots, and the green quantum dots are obtained.
  • step S2 further includes: S21, mixing the Zn source with the first ligand and the first organic solvent, and heating up to 150-200 ° C to obtain a mixed solution C; S22, mixing the Se source with the second organic solvent, A mixed solution D is obtained; S23, the S source is mixed with a third organic solvent to obtain a mixed solution E; S24, the mixed solution C is heated to 280-310 ° C, and then a CdSe quantum dot solution containing CdSe quantum dots is added thereto, and mixed The solution D and the mixed solution E were incubated for 10 to 60 minutes to obtain a CdSe / ZnSe X S 1-X quantum dot solution containing CdSe / ZnSe X S 1-X quantum dots.
  • step S3 further includes: S31, mixing the Zn source with the second ligand and the fourth organic solvent, and heating up to 150-200 ° C to obtain a mixed solution F; S32, mixing the S source with the fifth organic solvent, A mixed solution G is obtained; S33. Under the protection of an inert gas, the mixed solution F is heated to 280-310 ° C, and then a CdSe / ZnSe X S 1-X quantum dot solution and a mixed solution G are added thereto, and the reaction is held for 10 to 60 minutes. A green quantum dot solution containing green quantum dots was obtained.
  • step S2 in the process of preparing the ZnSe X S 1-X shell layer, the molar ratio of Zn in the Zn source, Se in the Se source, and S in the S source is 1: 0.1 to 1: 0 to 0.9.
  • step S3 the molar ratio of Zn in the Zn source to S in the S source during the preparation of the ZnS shell is 1: 0.1 to 1.
  • the molar ratio of the CdSe quantum dot core, the Zn in the Zn source in step S2 and the Zn in the Zn source in step S3 is 1: 1 ⁇ 10 4 to 5 ⁇ 10 5 : 1 ⁇ 10 4 to 5 ⁇ 10 5 .
  • a quantum dot light emitting diode is provided, using any one of the above-mentioned green quantum dots.
  • the external quantum efficiency of the quantum dot light emitting diode is greater than 10%, and the T50 lifetime of the quantum dot light emitting diode at a brightness of 100 cd ⁇ m -2 is greater than or equal to 10,000 hours.
  • a quantum dot composition includes any one of the green quantum dots described above.
  • the present application provides a green quantum dot having a CdSe / ZnSe X S 1-X / ZnS structure, which includes a CdSe core, and a ZnSe X S 1-X shell layer and a ZnS shell layer sequentially covering the periphery of the CdSe core.
  • ZnSe X S 1-X the lattice matching between ZnSe and CdSe is high, and it can form a good alloyed structure with the outer layer of ZnS, and the outer layer of ZnS can improve the stability of the coating.
  • the present invention provides a green quantum dot, which has a CdSe / ZnSe X S 1-X / ZnS structure, and specifically includes: a CdSe core; and a ZnSe X S 1 covering a periphery of the CdSe core.
  • An X shell layer where 0 ⁇ X ⁇ 1; and a ZnS shell layer covering the periphery of the ZnSe X S 1-X shell layer.
  • the green quantum dots provided in the present application are coated with ZnSe X S 1-X with a certain thickness on the CdSe core as a shell, and then coated with ZnS.
  • CdSe quantum dots have a wider absorption wavelength band, higher emission intensity, and better light stability.
  • the emission and absorption wavelengths can be controlled by adjusting their size; the lattices of ZnSe and CdSe in ZnSe X S 1-X
  • the degree of matching is high, and it can form a good alloyed structure with the outer layer of ZnS. Therefore, it can ensure that the quantum dots form a perfect core-shell structure during the entire synthesis process, which improves the stability of the core and the monodispersity of the quantum dots.
  • ZnS can provide a range of energy levels for the doping of various metals and transition metal ions, and at the same time epitaxially grow a shell on the quantum dot core to passivate the surface, thereby greatly improving the luminous efficiency and optical stability.
  • the toxic ZnS shell is coated on the outermost layer and is environmentally friendly. With CdSe as the nucleus, and by adjusting the reactivity of the precursors of Se and S and the amount of coating, the position of its emission wavelength can be adjusted relatively easily, and finally high optical quality (efficiency above 90%, half-width at 25nm) Below) green quantum dots with CdSe / ZnSe X S 1-X / ZnS structure.
  • the above-mentioned ZnSe X S 1-X In the shell layer, 0.2 ⁇ X ⁇ 1; more preferably 0.2 ⁇ X ⁇ 1.
  • the average particle size of the CdSe / ZnSe X S 1-X quantum dots composed of the CdSe core and the ZnSe X S 1-X shell is 5-9 nm, and the average particle size of the green quantum dots is 8-14 nm.
  • the particle size of the quantum dot can achieve a more ideal quantum confinement effect, suppress the Auger effect of the quantum dot under the action of the electric field, thereby reducing the startup voltage of the QLED device made by the quantum dot, slowing the aging process of the QLED device, and obtaining the life. Longer QLED devices.
  • the UV wavelength corresponding to the first exciton peak of the CdSe core is 495-545 nm.
  • the half-peak width represents the particle size distribution of the quantum dots and affects the purity of the quantum dots' emission color.
  • CdSe / ZnSe X S 1 The emission wavelength PL of the -X quantum dot is 496 to 556 nm, and the half-peak width is 19 to 25 nm.
  • the half-peak width of the CdSe / ZnSe X S 1-X quantum dot is 19-22 nm.
  • the emission wavelength PL (maximum emission peak position) of the green quantum dot is 490 to 550 nm, and the half-peak width is 20 to 26 nm. In a preferred embodiment, the half-peak width of the green quantum dot is 20 to 23 nm.
  • the present application provides a method for preparing green quantum dots, including the following steps: S1, preparing CdSe quantum dots as CdSe cores; S2, forming ZnSe X S 1- The X- shell layer is obtained to obtain CdSe / ZnSe X S 1-X quantum dots, where 0 ⁇ X ⁇ 1; S3, a ZnS shell layer is formed on the periphery of the CdSe / ZnSe X S 1-X quantum dots to obtain the green quantum dots described above.
  • the green quantum dot preparation method firstly prepares a CdSe quantum dot by a two-step coating method, and uses the CdSe quantum dot as a CdSe core, and sequentially coats a ZnSe X S 1-X shell (0 ⁇ X ⁇ 1) and ZnS shell. This makes the prepared green quantum dots have different absorption wavelength characteristics from that of CdSe cores, and then adjusts the reactivity and coating amount of the precursors of Se and S in the ZnSe X S 1-X shell to regulate its emission. The position of the wavelength finally results in green quantum dots with high optical quality, high brightness lifetime and high quantum efficiency in QLED devices.
  • the green quantum dots obtained by this preparation method have high controllability of the emission wavelength and can achieve kilogram level.
  • the production scale of quantum dots, and its photobleaching resistance and high air stability can meet the requirements for the preparation of QLED devices in the air, which greatly reduces the equipment requirements and preparation costs when preparing green QLEDs.
  • the preparation method has simple and reliable operation, good controllability, is suitable for large-scale production, and has great value for the development of quantum dot applications.
  • the above-mentioned step S1 includes: S11, mixing the Cd source with the third ligand and the sixth organic solvent, and raising the temperature to 160-180 ° C under the protection of an inert gas to obtain a mixed solution A; S12 S13 is mixed with a seventh organic solvent to obtain a mixed solution B; S13, under the protection of an inert gas, the mixed solution A is heated to 220-240 ° C, and then the mixture B is added thereto, and the reaction is held for 10-20 minutes to obtain CdSe quantum dot solution of CdSe quantum dots.
  • the mixed solution A is obtained by magnetic stirring, wherein the stirring speed is 60 rpm / min;
  • mixed solution C was obtained by dispersing Se powder in a seventh organic solvent by ultrasonic vibration for 2 min.
  • the process of purifying the CdSe quantum dot solution is further included as follows: the CdSe quantum dot solution and n-hexane are placed in a first liquid separation In the device, wash with methanol 2 to 3 times, move the upper solution to a centrifugal device, add acetone, remove the solid precipitate after centrifugation, and dissolve it in a non-polar solvent such as octadecene (ODE). After purification, CdSe quantum dot solution.
  • the specific purification method is not limited to this, and other purification methods may also be adopted.
  • the above step S2 includes: S21, mixing the Zn source with the first ligand and the first organic solvent, and heating up to 150-200 ° C under the protection of an inert gas to obtain a mixed solution C; S22 S source is mixed with a second organic solvent to obtain a mixed solution D; S23, S source is mixed with a third organic solvent to obtain a mixed solution E; S24, under the protection of an inert gas, the mixed solution C is heated to 280-310 CdSe, and then add CdSe quantum dot solution, mixed solution D and mixed solution E, and hold the reaction for 10-60 minutes to obtain a CdSe / ZnSe X S 1-X quantum dot solution containing CdSe / ZnSe X S 1-X quantum dots.
  • the mixed solution C is passed through a magnetic force. Obtained by stirring, the stirring speed is 60 rpm / min; the Se powder and the S powder are dispersed in their corresponding organic solvents by ultrasonic vibration for 2 min to obtain mixed solutions D and E.
  • step S2 and before step S3 a process of purifying the CdSe / ZnSe X S 1-X quantum dot solution is further included as follows: CdSe / ZnSe X S 1-X quantum The spot solution and acetone were placed in a centrifugal device. After centrifugation, the solid precipitate was taken out and dissolved in an ODE solution to obtain a purified CdSe / ZnSe X S 1-X quantum dot solution.
  • the above-mentioned step S3 includes: S31, mixing the Zn source with the second ligand and the fourth organic solvent, and heating up to 150-200 ° C under the protection of an inert gas to obtain a mixed solution F; S32 S source is mixed with a fifth organic solvent to obtain a mixed solution G; S33, under the protection of an inert gas, the mixed solution F is heated to 280-310 ° C, and then a CdSe / ZnSe X S 1-X quantum dot solution is added thereto It is mixed with the solution G and incubated for 10 to 60 minutes to obtain a green quantum dot solution containing green quantum dots.
  • the mixed solution F is obtained by magnetic stirring, and the stirring speed is 60 rpm / min. ;
  • the mixed solution G was obtained by dispersing S powder in its corresponding organic solvent by ultrasonic shaking for 2 min.
  • the purity of the CdSe / ZnSe X S 1-X quantum dot solution was improved to realize the improvement of green quantum dots.
  • the purpose of dot optical performance in a preferred embodiment, after step S3, the purification process of the green quantum dot solution is further included as follows: the green quantum dot solution and acetone are placed in a centrifugal device, and after centrifugation The solid precipitate was taken out, and the precipitate was dissolved in a toluene solution to obtain a purified green quantum dot solution.
  • the Cd source includes, but is not limited to, cadmium acetate dihydrate, cadmium oxide, or dimethyl cadmium, preferably cadmium acetate dihydrate;
  • the Zn source includes, but is not limited to, zinc acetate;
  • the source of Se is selected from Se powder ;
  • S source is selected from S powder;
  • the first ligand, the second ligand and the third ligand are independently selected from olive oil or oleic acid, preferably oleic acid;
  • the six organic solvents and the seventh organic solvent are each independently selected from one or more of liquid paraffin, oleylamine, and octadecene, and preferably all are octadecene;
  • the solvent is selected from one or more of tributyl phosphate, tributylphosphine, triphenylphosphine
  • the ligand can adjust the dynamic rate of the adsorption and shedding of the quantum dot crystal plane and the coordination solvent, so that one crystal plane of the quantum dot can grow faster than other crystal planes, change the shape of the quantum dot, control the crystal form, and make the energy level of the quantum dot.
  • the forbidden band width can be matched with the forbidden band width of the energy level of zinc oxide nanocrystals (as electron transport material) in the QLED device, that is, an orderly stepped structure is formed.
  • step S2 during the preparation of the ZnSe X S 1-X shell layer, the molar ratio of Zn in the Zn source, Se in the Se source, and S in the S source is 1: 0.1 to 1: 0 to 0.9.
  • This can further improve the stability of the CdSe core and the ZnS shell, reduce the overall lattice mismatch of the green quantum dots, and further improve the quantum efficiency of the green quantum dots.
  • the half-peak width of the green quantum dots is prevented from being affected by an excessively thick shell layer, thereby further ensuring the lifetime of the quantum dots.
  • step S3 the ZnS shell layer is prepared.
  • the molar ratio of Zn in the Zn source to S in the S source is 1: 0.1 to 1.
  • the molar ratio of the CdSe quantum dot core, the Zn in the Zn source in step S2 and the Zn in the Zn source in step S3 is 1: 1 ⁇ 10 4 to 5 ⁇ 10 5 : 1 ⁇ 10 4 to 5 ⁇ 10 5 .
  • the present application provides a quantum dot light emitting diode, which adopts any one of the above-mentioned green quantum dots or a green quantum dot prepared by any of the above methods.
  • the quantum dot light emitting diode includes an anode, a light emitting layer, and a cathode.
  • the light emitting layer includes any of the green quantum dots described above, and optionally further includes an electron or hole functional layer.
  • the quantum dot light emitting diode provided in the present application the external quantum efficiency of the quantum dot light emitting diode is greater than 10%, and the T50 of the quantum dot light emitting diode at a brightness of 100 cd ⁇ m -2 (the device brightness is reduced to an initial 50% Time) life is greater than or equal to 10,000 hours, which can meet the needs of commercial applications.
  • a display device including at least one quantum dot light emitting diode.
  • the present application provides a quantum dot composition including any one of the above-mentioned green quantum dots.
  • the quantum dot composition may be a quantum dot ink for making a QLED device.
  • step (2) the amount of ZnAc 2 is increased to 2 mmol, the amount of OA is increased to 8 mmol, the amount of S powder is increased to 1 mmol, dissolved in 2 ml of TBP, and the temperature of preparing the precursor solution (mixed solution F) of Zn source is 150 ° C.
  • the synthesis temperature of the synthesized CdSe / ZnSe 0.8 S 0.2 / ZnS quantum dots is 280 ° C, and the reaction is held for 10 min.
  • the final CdSe / ZnSe 0.8 S 0.2 / ZnS PL is 550 nm, the half-value width is 23 nm, the QY is 91.8%, and the average size of the electron microscope It is 12.0nm. Up to 83 mg of quantum dots can be dissolved in the corresponding 1 mL of printing ink.
  • step (2) the amount of ZnAc 2 was increased to 1.5 mmol, the amount of OA was increased to 6 mmol, the amount of S powder was increased to 0.5 mmol, dissolved in 1 ml of TBP, and the temperature of preparing a precursor solution of Zn source (mixed solution F) was 200 ° C.
  • the reaction temperature for the synthesis of CdSe / ZnSe 0.8 S 0.2 / ZnS quantum dots was 310 ° C, and the reaction was held for 60 minutes.
  • the final PL of CdSe / ZnSe 0.2 S 0.8 / ZnS was 529 nm, the half-value width was 23 nm, and the QY was 96.7%.
  • the size is 10.2 nm.
  • a maximum of 156 mg of quantum dots can be dissolved in the corresponding 1 mL of printing ink.
  • step (3) the amount of ZnAc 2 was increased to 1.2 mmol, the amount of OA was increased to 4.8 mmol, the amount of S powder was increased to 0.4 mmol, dissolved in 0.8 ml of TBP, and the final CdSe / ZnSe 0.4 S 0.6 / ZnS PL was 520 nm.
  • the peak width was 22 nm, QY was 94.8%, and the average size of the electron microscope was 9.3 nm.
  • a maximum of 178 mg of quantum dots can be dissolved in the corresponding 1 mL of printing ink.
  • step (2) the amount of ZnAc 2 was increased to 1.2 mmol, the amount of OA was increased to 4.8 mmol, the amount of S powder was 1 mmol, dissolved in 2 ml of TBP, and the temperature was maintained for 60 min.
  • the PL of CdSe / ZnSe / ZnS was 524 nm and the half-peak width It was 23 nm, QY was 93.6%, and the average size of the electron microscope was 10.8 nm.
  • a maximum of 138 mg of quantum dots can be dissolved in the corresponding 1 mL of printing ink.
  • Example 2 The difference from Example 1 is that the amount of Se powder is 0.5 mmol, dissolved in 1 mL of TBP solution, and no S-TBP solution is added; the reaction is maintained for 60 minutes, and the PL of CdSe / ZnSe quantum dots is measured to be 501 nm and the half-width It is 24nm, the average size of the electron microscope is 5.4nm; the PL of the final CdSe / ZnSe / ZnS quantum dot is 496nm, the half-value width is 25nm, and the QY is 90.6%.
  • Example 2 It differs from Example 1 only in that the amount of Se powder was reduced to 0.1 mmol and dissolved in 0.2 mL of TOP solution; the amount of S powder was reduced to 0.4 mmol and dissolved in 0.8 mL of TBP; the reaction was held for 60 min, and CdSe / ZnSe 0.2 was measured.
  • the PL of the S 0.8 quantum dots is 499 nm, the half-value width is 23 nm, and the average size of the electron microscope is 5.7 nm.
  • the PL of the CdSe / ZnSe 0.2 S 0.8 / ZnS quantum dots is 496 nm, the half-width is 23 nm, and QY is 92.4%.
  • Example 8 QLED based on 520nm CdSe / ZnSe 0.4 S 0.6 / ZnS quantum dot
  • CdSe @ ZnS / ZnS quantum dots The average size of CdSe @ ZnS electron microscope is 9.5nm, and the average size of CdSe @ ZnS / ZnS electron microscope is 12.7nm. Up to 43 mg of quantum dots can be dissolved in the corresponding 1 ml of printing ink.
  • step (2) Different from Example 1, only S-TBP (0.5mmolS in 1mL TBP) was injected in step (2).
  • the final PL of CdSe / ZnS was 526nm, the half-width of the peak was 38nm, the QY was 56.8%, and the average size of the electron microscope It is 6.8nm.
  • Comparative Example 4 QLED based on 520nm CdSe @ ZnS / ZnS quantum dots of Comparative Example 1
  • a QLED prepared in the air based on the 520nmCdSe @ ZnS / ZnS quantum dots of Comparative Example 1 (the preparation process is the same as in Example 6), and its external quantum efficiency (EQE) can reach 12%, and the brightness is 100 cd ⁇ m -2
  • the T50 life is about 1000 hours.
  • Comparative Example 5 QLED based on 535nm CdSe @ ZnS quantum dots of Comparative Example 2
  • the QLED prepared in the air based on 535nmCdSe @ ZnS / ZnS quantum dots of Comparative Example 2 has an external quantum efficiency (EQE) of 8%, and a T50 life of 100cd ⁇ m -2 brightness is about 8000 hours.
  • the above embodiments of the present invention achieve the following technical effects: using the green quantum dots provided in the present application, firstly preparing CdSe quantum dots through a two-step coating method, and using this as a CdSe core A ZnSe X S 1-X shell layer (0 ⁇ X ⁇ 1) and a ZnS shell layer are formed by coating on the periphery in order.
  • green quantum dots with high optical quality (more than 90% quantum efficiency and half-peak width below 26nm) and high quantum efficiency (more than 80%) are obtained.
  • the size of the electron microscope of the particles is between 8-12nm.
  • the green quantum dots obtained by the preparation method have high controllability of the emission wavelength, can realize the production scale of kilogram-level quantum dots, and have high photobleaching resistance and high air stability, which can meet the requirements for preparing devices in the air, greatly reducing The requirements and equipment cost of green QLED preparation are also discussed.
  • the preparation method has simple and reliable operation, good controllability, is suitable for large-scale production, and has great value for the development of quantum dot applications.
  • QLEDs prepared using this kind of green quantum dots have ideal device lifetime (100cd ⁇ m -2 brightness T50 lifetime greater than 10,000 hours) and quantum efficiency (greater than 10%), meeting the needs of commercial applications.

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Abstract

La présente invention concerne un point quantique vert, son procédé de préparation et son utilisation. Le point quantique vert présente une structure CdSe/ZnSe XS 1-X/ZnS, comprenant : un noyau de CdSe; une enveloppe de ZnSe XS 1-X revêtue sur la périphérie du noyau de CdSe, où 0<X≤1; et une enveloppe de ZnS revêtue sur la périphérie de l'enveloppe de ZnSe ZnSe XS 1-X. Le point quantique vert présente des caractéristiques d'un rendement quantique supérieur à 90 %, une largeur de demi-pic comprise entre 20 et 26 nm, une monodispersité, et analogues. Un dispositif QLED utilisant le point quantique vert présente les avantages d'un rendement quantique externe élevé et d'une longue durée de vie de dispositif.
PCT/CN2019/097048 2018-08-09 2019-07-22 Point quantique vert, son procédé de fabrication et son utilisation WO2020029780A1 (fr)

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CN201810904568.4A CN110819348B (zh) 2018-08-09 2018-08-09 绿色量子点、其制备方法及其应用
CN201810904568.4 2018-08-09

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