WO2023155605A1 - Nanoparticule, diode électroluminescente et dispositif d'affichage - Google Patents

Nanoparticule, diode électroluminescente et dispositif d'affichage Download PDF

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WO2023155605A1
WO2023155605A1 PCT/CN2022/142616 CN2022142616W WO2023155605A1 WO 2023155605 A1 WO2023155605 A1 WO 2023155605A1 CN 2022142616 W CN2022142616 W CN 2022142616W WO 2023155605 A1 WO2023155605 A1 WO 2023155605A1
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shell
core
cdzns
lattice mismatch
layer
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PCT/CN2022/142616
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Chinese (zh)
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周礼宽
杨一行
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Tcl科技集团股份有限公司
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Priority claimed from CN202210163356.1A external-priority patent/CN116656338A/zh
Priority claimed from CN202210153051.2A external-priority patent/CN116656337A/zh
Application filed by Tcl科技集团股份有限公司 filed Critical Tcl科技集团股份有限公司
Publication of WO2023155605A1 publication Critical patent/WO2023155605A1/fr

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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
    • C09K11/02—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

Definitions

  • the present application relates to the field of display technology, in particular to a nano particle, a light emitting diode and a display device.
  • Quantum dot materials are widely used in light-emitting fields due to their unique optical properties, such as light-emitting layer materials for quantum dot light-emitting diodes (QLEDs). Compared with organic electroluminescent diodes (OLEDs), quantum dot light-emitting diodes have the advantages of narrow emission spectrum, wide color gamut, good stability, and low production cost.
  • QLEDs quantum dot light-emitting diodes
  • quantum dot light-emitting diodes there is a problem of unbalanced electron and hole injection in the light-emitting layer, such as more electron injection than hole injection (ie, excess electrons), and the imbalance of electrons and holes will cause the quantum dots to be in a charged state. And charged quantum dots will produce non-radiative Auger recombination, which eventually leads to short lifetime of quantum dot light-emitting diodes.
  • the present application provides a nano particle, a light emitting diode and a display device.
  • the embodiment of the present application provides a nanoparticle, wherein the structure of the nanoparticle includes core/first shell/.../nth shell, and the crystal between the core and the first shell
  • the lattice mismatch is less than or equal to 5%.
  • the lattice mismatch degrees between adjacent shell layers are all less than or equal to 5%.
  • the n is an integer greater than or equal to 2
  • the material of the second shell layer of the nanoparticles is CdZnS.
  • the molar weight of Cd is 10-50% of the total molar weight of Cd and Zn.
  • the luminescence wavelength of the nanoparticles is 647-760 nm
  • the molar weight of Cd is 25-50% of the total molar weight of Cd and Zn.
  • the luminescence wavelength of the nanoparticles is 492-550nm
  • the molar amount of Cd is 15-25% of the total molar weight of Cd and Zn.
  • the luminescence wavelength of the nanoparticles is 430-455 nm
  • the molar weight of Cd is 10-25% of the total molar weight of Cd and Zn.
  • the core and the shell layers other than the second shell layer independently contain one or more of Zn and Cd, and each independently contain one or more of Te, Se and S .
  • the xth shell layer and the x+1th shell layer of the nanoparticles contain both Cd and Zn, wherein, 1 ⁇ x ⁇ n, the molar amount of Cd in the x+1th shell layer is relative to Cd and Zn
  • the proportion of the total molar weight of Zn is less than the proportion of the molar weight of Cd in the xth shell relative to the total molar weight of Cd and Zn, and the band gap Eg of the core and each shell layer satisfies Eg core ⁇ Eg 1 shell ⁇ Eg the nth shell .
  • the n is greater than 2
  • the third shell of the nanoparticles contains Cd and Zn
  • the molar ratio of Cd in the third shell to the total molar mass of Cd and Zn is smaller than that of the second shell
  • the ratio of the molar amount of Cd in the layer to the total molar amount of Cd and Zn, and the forbidden band width of the second shell layer and the third shell layer satisfy Eg second shell layer ⁇ Eg third shell layer .
  • the n is greater than 2
  • the material of the third shell of the nanoparticle is ZnS
  • the band gap of the second shell and the third shell satisfies Eg second shell ⁇ Eg third shell .
  • the material of the first shell layer is ZnSe.
  • the cations in the core include both Zn and Cd, and the anions in the core are selected from one or more of Te, Se and S.
  • the core contains both Zn and Cd, and the molar weight of Cd is 10-60% of the total molar weight of Cd and Zn.
  • the core contains both Se and S, and the molar weight of Se is 50-95% of the total molar weight of Se and S.
  • the shell layers other than the first shell layer independently contain one or more of Zn and Cd, and each independently contain one or more of Te, Se and S .
  • the forbidden band of the core is in the range of 1.9-2.75eV.
  • the band gap Eg of the core and each shell layer satisfies: Eg core ⁇ Eg first shell ⁇ Eg nth shell .
  • n 1 ⁇ n ⁇ 5; preferably, n is 3.
  • the nanoparticles are selected from CdSe/CdS/CdZnS/ZnS, CdSe/CdS/CdZnS, CdZnSe/ZnSe/CdZnS/ZnS, CdZnSe/ZnSe/CdZnS/ZnS, CdZnS/ZnSe/CdZnS/ZnS, CdZnS/ZnSe/CdZnS/ZnS, CdZnSe/ZnSe/ZnS/ZnS, CdZnSe/ZnSeS/ZnS, CdZnSe/ZnSe, or CdZnSe/ZnSe/CdZnSeS/CdZnS/ZnS.
  • the molar weight of Cd is 22-27% of the total molar weight of Cd and Zn, and the lattice mismatch between the core and the first shell layer
  • the lattice mismatch between the first shell and the second shell is 1.8-2.2%, and the lattice mismatch between the second shell and the third shell is 2.4-2.8%;
  • the molar weight of Cd is 18-22% of the total molar weight of Cd and Zn, and the lattice mismatch between the core and the first shell layer is 1.9-2.3 %, the lattice mismatch between the first shell and the second shell is 2.8-3.2%, and the lattice mismatch between the second shell and the third shell is 2.4-2.7%;
  • the molar weight of Cd is 8-12% of the total molar weight of Cd and Zn, and the lattice mismatch between the core and the first shell layer is 3.3-3.8 %, the lattice mismatch between the first shell and the second shell is 1.8-2.2%, and the lattice mismatch between the second shell and the third shell is 1.4-1.8%;
  • the molar weight of Cd is 55% to 65% of the total molar weight of Cd and Zn; 45-55%; the lattice mismatch between the core and the first shell is 2-3%, the lattice mismatch between the first shell and the second shell is 2.5-3.5%, the second shell and the second shell
  • the lattice mismatch degree of the 3 shell layer is 3-4%;
  • the molar weight of Cd is 30-40% of the total molar weight of Cd and Zn; the molar weight of Cd in the second shell CdZnS is 18% of the total molar weight of Cd and Zn. ⁇ 22%; the lattice mismatch between the core and the first shell is 1.2 ⁇ 1.8%, the lattice mismatch between the first shell and the second shell is 3.2 ⁇ 3.8%, the second shell and the third The lattice mismatch degree of the shell layer is 1.5-2.3%;
  • the molar weight of Cd is 12-18% of the total molar weight of Cd and Zn, and the molar weight of Se is 80-88% of the total molar weight of Se and S;
  • the molar mass of Se in the shell ZnSeS is 45-55% of the total molar mass of Se and S;
  • the lattice mismatch between the core and the first shell is 3.2-3.7%, and the crystal lattice between the first shell and the second shell
  • the lattice mismatch is 2.3-2.8%, and the lattice mismatch between the second shell and the third shell is 1.8-2.2%;
  • the molar mass of Cd is 48-53% of the total molar mass of Cd and Zn, and the lattice mismatch between the core and the first shell is 1.6-2.2%;
  • the molar weight of Cd is 38-43% of the total molar weight of Cd and Zn; the molar weight of Cd in the second shell CdZnSeS is the total molar weight of Cd and Zn
  • the molar mass of Se is 48-52% of the total molar mass of Se and S; the molar mass of Cd in the third shell is 28-32% of the total molar mass of Cd and Zn; the core and the first shell
  • the lattice mismatch degree of the layer is 0.8-1.2%, the lattice mismatch degree of the first shell layer and the second shell layer is 2.3-2.8%, and the lattice mismatch degree of the second shell layer and the third shell layer is 1.3-1.7%, and the lattice mismatch between the third shell and the fourth shell is 1.8-2.3%.
  • the size of the nanoparticles ranges from 10 to 20 nm.
  • the application also provides a light-emitting diode, including an anode, a light-emitting layer, and a cathode stacked in sequence, wherein the light-emitting layer includes the above-mentioned nanoparticles.
  • the anode and the cathode are independently selected from a doped metal oxide electrode, a composite electrode, a graphene electrode, a carbon nanotube electrode, a metal element electrode or an alloy electrode, and the doped metal oxide electrode Materials selected from indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide and aluminum-doped magnesium oxide One or more of them, the composite electrode is selected from AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO 2 /Ag/TiO 2 , TiO 2 /Al/TiO 2 , ZnS/Ag/ZnS or ZnS/A
  • the application also provides a display device, wherein the display device includes the above light emitting diode.
  • the lattice mismatch between the core and the first shell of the nanoparticle of the present application is less than or equal to 5%, which can make the interface defects between the core and the first shell in the nanoparticle less, thereby reducing the crystal lattice.
  • the formation of non-radiative recombination centers at the interface defects caused by the stress improves the stability and fluorescence quantum efficiency of the nanoparticles, thereby improving the luminous efficiency and lifespan of light-emitting diodes prepared using the nanoparticles.
  • the light-emitting diode prepared by using the nano-particles has a high degree of charge carrier injection balance, so it has high luminous efficiency and long life.
  • Fig. 1 is a schematic structural diagram of a light emitting diode provided in an embodiment of the present application
  • Fig. 2 is a schematic structural diagram of another light-emitting diode provided in the embodiment of the present application.
  • Fig. 3 is a schematic structural diagram of another light-emitting diode provided in the embodiment of the present application.
  • Fig. 4 is a schematic structural diagram of another light-emitting diode provided in the embodiment of the present application.
  • Fig. 5 is a schematic structural diagram of another light emitting diode provided by the embodiment of the present application.
  • Embodiments of the present application provide a molybdenum oxide nanomaterial, a preparation method, and a photoelectric device. Each will be described in detail below. It should be noted that the description sequence of the following embodiments is not intended to limit the preferred sequence of the embodiments. In addition, in the description of the present application, the term “including” means “including but not limited to”.
  • expressions such as “one or more” refer to one or more of the listed items, and “multiple” refers to any combination of two or more of these items, including single items (species) ) or any combination of plural items (species), for example, "at least one (species) of a, b, or c" or "at least one (species) of a, b, and c" can mean: a ,b,c,a-b (that is, a and b),a-c,b-c, or a-b-c, where a,b,c can be single or multiple.
  • An embodiment of the present application provides a nanoparticle based on group II-VI elements, including a core and at least one shell layer coated on the surface of the core.
  • the nanoparticle includes a core and layers coated on the surface of the core Stacked n shells, in other words, the nanoparticle structure includes core/first shell/ ⁇ /nth shell, wherein n is an integer greater than or equal to 1.
  • the lattice mismatch between the core and the first shell, and between adjacent shells are all less than or equal to 5%.
  • the degree of lattice mismatch between the core of the nanoparticle and the first shell, and between the adjacent shell and the shell is less than or equal to 5%, which can make the core and the first shell in the nanoparticle
  • the light-emitting diode prepared by using the nano-particles based on II-VI group elements is beneficial to the balance of carrier injection, so it has higher luminous efficiency and longer life.
  • the material of the first shell layer is ZnSe.
  • the first shell layer is conducive to the injection of holes into the core and restricts (impedes) the injection of electrons into the core, so that the carriers injected into the core for radiative recombination light tend to balance, and avoid excessive electrons from making the nanoparticles in a charged state , resulting in non-radiative Auger recombination and quenching, thereby improving the luminous efficiency and lifespan of the light-emitting diode prepared by using the nanoparticle.
  • the cations in the core of the nanoparticles contain both Zn and Cd, and the anions in the core can be selected from but not limited to one or more of Te, Se and S.
  • the core composed of the elements is a core based on II-VI group elements, and the carrier injection of the light-emitting diode prepared from the nanoparticles comprising the core tends to be balanced, thereby having higher luminous efficiency and longer lifetime. life.
  • the core includes two metal elements, Zn and Cd, to form an alloy core
  • the nanoparticles of the core-shell structure comprising the alloy core have a nanoparticle core-shell interface of an alloying and transition interface, and the nanoparticle core
  • the lattice mismatch ratio of the shell interface and the energy band deviation between the core and the shell are small, which is conducive to obtaining high fluorescence quantum efficiency, and the alloy core is more conducive to obtaining larger nanoparticles, which can inhibit the energy resonance transfer effect to a certain extent effect.
  • the core contains Zn, so that when the material of the first shell is ZnS, the lattice between the core and the first shell can be more matched, ensuring that the core and the first shell are The lattice mismatch between them is less than or equal to 5%.
  • the ratio of Cd to Zn is not limited.
  • the molar weight of Cd is 10% to 60% of the total molar weight of Cd and Zn.
  • the core and the first shell can be The lattice of the layers is more closely matched.
  • both Se and S are included in the core. It can be understood that the ratio of Se to S is not limited. In at least some embodiments, the molar weight of Se is 50% to 95% of the total molar weight of Se and S. Within the range, when the material of the first shell is ZnS, the core and the first shell can be The lattice of the layer ZnSe is more closely matched.
  • the material of the core may be CdZnSe or CdZnSeS.
  • the shell layers ie, the second shell layer to the nth shell layer
  • the shell layers can independently include but not limited to Zn, Cd One or more, and independently include but not limited to one or more of Te, Se and S.
  • the core when matched with the core, the core can be made of nanoparticles based on II-VI group elements, and the carrier injection of the light-emitting diode prepared by the nanoparticles tends to be balanced, thereby having higher luminous efficiency and higher efficiency. long life.
  • the material of the shell layers other than the first shell layer can be selected from but not limited to CdZnSe, CdZnSeS, CdZnS, CdSeTe, CdSeS, ZnSeS, CdSe, CdS, CdTe, ZnTe, ZnSe or ZnS.
  • n is an integer greater than or equal to 2
  • the material of the second shell layer of the nanoparticle is CdZnS, which is conducive to hole injection into the core and limits (impedes) electron injection into the core, so that the injection into the core
  • the radiative recombination and light-emitting carriers in the core tend to be balanced, avoiding excessive electrons entering the nucleus and making the nanoparticles in a charged state, resulting in non-radiative Auger recombination and quenching, thereby further improving the stability and fluorescence quantum efficiency of nanoparticles , and further improve the luminous efficiency and lifespan of the light emitting diode prepared by using the nano particles.
  • the nanoparticle when the nanoparticle satisfies that the degree of lattice mismatch between adjacent shells is less than or equal to 5%, and the degree of lattice mismatch between the core and the first shell is less than or equal to 5%.
  • the material of the second shell layer is a combination of any two conditions in CdZnS, the improvement effect on the stability of nanoparticles and the fluorescence quantum efficiency is better than that when only one condition is satisfied.
  • the molar weight of Cd is 10-50% of the total molar weight of Cd and Zn.
  • the forbidden band width of the second shell layer CdZnS can be 2-3eV, so that the energy level difference between the energy level of the valence band top of the second shell layer and the energy level of the core valence band top is relatively large, so that the second shell layer It has a strong binding effect on the excitons in the nucleus.
  • the bandgap width of the second shell CdZnS will be significantly narrowed, the binding effect on the exciton in the core will be weakened, and the fluorescence stability of the nanoparticle material will be reduced; if the Cd content is lower than the stated range, the first The large lattice mismatch between the 2-shell CdZnS and the 1st shell leads to an increase in the number of interface defect states, resulting in poor fluorescence performance of the nanoparticle material.
  • the luminescence wavelength of the nanoparticles is 647-760nm, in other words, the nanoparticles are red nanoparticles, and the molar amount of Cd in the second shell CdZnS is the total molar amount of Cd and Zn 25-50% of that.
  • the defect states on the surface of the red nanoparticles can be more effectively passivated and the excitons in the core can be bound, preventing the excitons from being delocalized to the surface of the shell layer and being captured and quenched by the defect states on the surface of the shell layer.
  • the luminescence wavelength of the nanoparticles is 492-550nm, in other words, the nanoparticles are green nanoparticles, and the molar amount of Cd in the second shell CdZnS is the total molar amount of Cd and Zn 15-25% of that.
  • the defect states on the surface of the green nanoparticles can be more effectively passivated and the excitons in the core can be bound, preventing the excitons from being delocalized to the surface of the shell layer and being captured and quenched by the defect states on the surface of the shell layer.
  • the luminescent wavelength of the nanoparticles is 430-455nm, in other words, the nanoparticles are blue nanoparticles, and the molar amount of Cd in the second shell CdZnS is the total molar amount of Cd and Zn 10-25% of the amount.
  • the defect states on the surface of the blue nanoparticles can be more effectively passivated and the excitons in the core can be bound, so that the excitons can be prevented from being delocalized to the surface of the shell layer and being captured and quenched by the defect states on the surface of the shell layer.
  • the xth shell and the x+1th shell of the nanoparticle when the xth shell and the x+1th shell of the nanoparticle contain both Cd and Zn, wherein, 1 ⁇ x ⁇ n, then the mole of Cd in the x+1th shell
  • the ratio of the molar amount of Cd to the total molar amount of Cd and Zn is smaller than the ratio of the molar amount of Cd in the xth shell layer to the total molar amount of Cd and Zn.
  • the forbidden band width of the x+1 shell layer can be made larger than the forbidden band width of the x shell layer, the conduction band bottom energy level of the x+1 shell layer is greater than the conduction band bottom energy level of the x shell layer, and Making the top energy level of the valence band of the x+1 shell layer greater than the top energy level of the valence band of the x shell layer can further bind the electrons and holes injected into the core in the core, effectively inhibiting the flow of carriers from the core Internal tunneling to the surface of the x+1th shell reduces the possibility of excitons being captured and quenched by defect states on the surface of nanoparticles, and also enables The higher degree of lattice matching between them is conducive to eliminating the generation of interface defect states, so that the surface defect states of nanoparticles are less, thereby improving the luminous efficiency of nanoparticles, and then improving the light-emitting diodes prepared using the nanoparticles. Luminous efficiency.
  • the band gap Eg of the core and each shell of the nanoparticle satisfies Eg core ⁇ Eg first shell ⁇ Eg nth shell , in other words, the nanoparticle is a Type I nanoparticle , in other words, the bottom energy level of the conduction band and the top energy level of the valence band of the core of the nanoparticle and each shell layer meet the Type I type, and in other words, the bottom energy level of the conduction band of the core of the nanoparticle and each shell layer
  • the energy level of the valence band top of the core and each shell of the nanoparticle gradually increases along the direction from the core to the outermost nth shell, and gradually decreases along the direction from the core to the outermost nth shell.
  • the electrons and holes injected into the core can be effectively confined in the core, effectively suppressing the tunneling of carriers from the core to the surface of the shell, and reducing the chance of excitons being captured and quenched by defect states on the surface of nanoparticles. It is possible to improve the luminous efficiency of the nanoparticles, and further improve the luminous efficiency of the light-emitting diodes prepared using the nanoparticles.
  • the lattice matching between adjacent cores and shells and between adjacent shells and shells can be made higher, which is beneficial to eliminate the generation of interface defect states, and make the surface defect states of nanoparticles less, thereby improving the luminous efficiency and lifespan of the light-emitting diode prepared by using the nanoparticle.
  • the band gap of the core is in the range of 1.9-2.75 eV, so that the nanoparticles can emit red, green or blue light with high color purity.
  • the n is greater than 2
  • Cd and Zn are included in the third shell of the nanoparticle, and the molar amount of Cd in the third shell is relative to the total molar weight of Cd and Zn.
  • the ratio is less than the ratio of the molar mass of Cd in the second shell to the total molar mass of Cd and Zn, and the bandgap width of the second shell and the third shell satisfies Eg second shell ⁇ Eg third shell .
  • the n is greater than 2
  • the material of the third shell of the nanoparticle is ZnS
  • the band gaps of the second shell and the third shell meet the requirement of Eg second shell ⁇ Eg second shell 3 shells .
  • the core and the shells other than the second shell may independently include but not limited to one or more of Zn and Cd, and independently include but not limited to one of Te, Se and S or more.
  • the nanoparticles composed of the elements are the cores based on II-VI group elements, and the carrier injection of the light-emitting diode prepared from the nanoparticles tends to be balanced, so that it has higher luminous efficiency and longer life.
  • the material of the core and the material of the shell except the second shell can be selected from but not limited to CdSe, CdZnSe, CdS, CdTe, CdSeTe, CdZnS, CdZnSeS, ZnTe, CdSeS, ZnSe, ZnS or ZnSeS.
  • the nanoparticles include a third shell, and the material of the third shell is selected from CdZnS, ZnSe, ZnSeS or ZnS.
  • the band gaps of the materials are larger than the band gaps of the second shell layer CdZnS.
  • the core of the nanoparticles and the materials of the shells can be the same or different, as long as the nanoparticles are Type I nanoparticles, that is, as long as the forbidden band width of each shell satisfies Eg 1 Shell ⁇ Eg nth shell is sufficient.
  • the nanoparticle can satisfy Type I by adjusting the ratio of elements in the materials.
  • n 1 ⁇ n ⁇ 5.
  • the number of shells of nanoparticles is too much, the preparation process is complicated, and with the increase of the number of shells, more interfaces will be generated.
  • the interlattice stress between different shells will cause the interface between the core and the shell to The number of defects generated at the shell-to-shell interface increases, resulting in increased non-radiative recombination energy loss of nanoparticles.
  • the number of shell layers of the nanoparticles is 3, that is, the nanoparticles include 3 shell layers. In this way, it can ensure that the nanoparticles have a good water-oxygen barrier effect, and can make the nanoparticles The nanoparticles have fewer interface defects, so that the nanoparticles have high stability and fluorescence quantum efficiency at the same time, so that the light-emitting diodes prepared using the nanoparticles have high luminous efficiency and long life .
  • the nanoparticles may be selected from red nanoparticles CdSe/CdS/CdZnS/ZnS, red nanoparticles CdSe/CdS/CdZnS, red nanoparticles CdZnSe/ZnSe/CdZnS/ZnS, green nanoparticles CdZnSe/ZnSe/ CdZnS/ZnS, blue nanoparticles CdZnS/ZnSe/CdZnS/ZnS, red nanoparticles CdZnSe/ZnSeS/ZnS, green nanoparticles CdZnSe/ZnSe/CdZnS/ZnS, blue nanoparticles CdZnSeS/ZnSe/ZnS/ZnS/ZnS, Red nanoparticles CdZnSe/ZnSe, or red nanoparticles CdZnSe/
  • the molar amount of Cd is 22-27% of the total molar weight of Cd and Zn
  • the molar amount of the core and the first shell layer is The degree of lattice mismatch is 3.7-4.3%
  • the degree of lattice mismatch between the first shell and the second shell is 1.8-2.2%
  • the degree of lattice mismatch between the second shell and the third shell is 2.4- 2.8%.
  • the molar amount of Cd in the second shell layer CdZnS is 25% of the total molar weight of Cd and Zn, and the crystals of the core and the first shell layer
  • the degree of lattice mismatch is 3.9%, the degree of lattice mismatch between the first shell and the second shell is 2%, and the degree of lattice mismatch between the second shell and the third shell is 2.5%.
  • the molar amount of Cd is 18-22% of the total molar weight of Cd and Zn, and the molar amount of the core and the first shell layer
  • the degree of lattice mismatch is 1.9-2.3%
  • the degree of lattice mismatch between the first shell and the second shell is 2.8-3.2%
  • the degree of lattice mismatch between the second shell and the third shell is 2.4- 2.7%.
  • the molar amount of Cd is 20% of the total molar weight of Cd and Zn, and the core and the first shell layer
  • the lattice mismatch degree is 2%
  • the lattice mismatch degree between the first shell layer and the second shell layer is 3%
  • the lattice mismatch degree between the second shell layer and the third shell layer is 2.5%.
  • the molar amount of Cd is 8-12% of the total molar weight of Cd and Zn, and the core and the first shell layer
  • the lattice mismatch degree is 3.3-3.8%
  • the lattice mismatch degree of the first shell layer and the second shell layer is 1.8-2.2%
  • the lattice mismatch degree of the second shell layer and the third shell layer is 1.4 ⁇ 1.8%.
  • the molar amount of Cd is 10% of the total molar weight of Cd and Zn, and the core and the first shell
  • the degree of lattice mismatch between the layers was 3.5%
  • the degree of lattice mismatch between the first shell and the second shell was 2%
  • the degree of lattice mismatch between the second and third shell was 1.5%.
  • the molar amount of Cd is 55-65% of the total molar weight of Cd and Zn; in the second shell CdZnSeS, the molar amount of Se is The amount is 45-55% of the total molar weight of Se and S; the lattice mismatch between the core and the first shell is 2-3%, and the lattice mismatch between the first shell and the second shell is 2.5- 3.5%, and the lattice mismatch between the second shell and the third shell is 3-4%.
  • the molar amount of Cd is 60% of the total molar weight of Cd and Zn; in the second shell CdZnSeS, the molar amount of Se The amount is 50% of the total molar amount of Se and S; the band gap of the core CdZnSe is 1.95eV; the lattice mismatch between the core and the first shell is 2.5%, and the lattice of the first shell and the second shell The degree of mismatch is 3%, and the degree of lattice mismatch between the second shell and the third shell is 3.5%.
  • the molar weight of Cd is 30-40% of the total molar weight of Cd and Zn; the molar weight of Cd in the second shell CdZnS is It is 18-22% of the total molar weight of Cd and Zn; the lattice mismatch between the core and the first shell is 1.2-1.8%, and the lattice mismatch between the first shell and the second shell is 3.2-3.8 %, the lattice mismatch between the second shell and the third shell is 1.5-2.3%.
  • the molar weight of Cd in the green nanoparticles CdZnSe/ZnSe/CdZnS/ZnS, in the core CdZnSe, is 35% of the total molar weight of Cd and Zn; the molar weight of Cd in the second shell layer CdZnS It is 20% of the total molar weight of Cd and Zn; the band gap of the core CdZnSe is 2.33eV; the lattice mismatch between the core and the first shell is 1.5%, and the lattice mismatch between the first shell and the second shell The ratio is 3.5%, and the lattice mismatch between the second shell and the third shell is 2%.
  • the molar weight of Cd is 12% to 18% of the total molar weight of Cd and Zn
  • the molar weight of Se is the total molar weight of Se and S. 80-88% of the molar mass
  • the molar mass of Se in the second shell ZnSeS is 45-55% of the total molar mass of Se and S
  • the lattice mismatch between the core and the first shell is 3.2-3.7%.
  • the degree of lattice mismatch between the first shell and the second shell is 2.3-2.8%, and the degree of lattice mismatch between the second shell and the third shell is 1.8-2.2%.
  • the molar weight of Cd is 15% of the total molar weight of Cd and Zn
  • the molar weight of Se is the total molar weight of Se and S
  • the molar mass of Se in the second shell ZnSeS is 50% of the total molar mass of Se and S
  • the band gap of the core CdZnSeS is 2.64eV
  • the lattice mismatch between the core and the first shell is 3.5 %
  • the lattice mismatch degree between the first shell layer and the second shell layer is 2.5%
  • the lattice mismatch degree between the second shell layer and the third shell layer is 2%.
  • the molar weight of Cd is 48-53% of the total molar weight of Cd and Zn, and the lattice mismatch between the core and the first shell layer is 1.6 ⁇ 2.2%.
  • the molar amount of Cd is 50% of the total molar weight of Cd and Zn
  • the band gap of the core CdZnSe is 2eV
  • the core and the first shell layer The lattice mismatch is 2%.
  • the molar weight of Cd is 38% to 43% of the total molar weight of Cd and Zn;
  • the molar weight is 28-33% of the total molar weight of Cd and Zn, and the molar weight of Se is 48-52% of the total molar weight of Se and S;
  • the molar weight of Cd in the third shell is 28% of the total molar weight of Cd and Zn.
  • the lattice mismatch between the core and the first shell is 0.8 ⁇ 1.2%
  • the lattice mismatch between the first shell and the second shell is 2.3 ⁇ 2.8%
  • the second shell and the third The lattice mismatch degree of the shell layer is 1.3-1.7%
  • the lattice mismatch degree of the third shell layer and the fourth shell layer is 1.8-2.3%.
  • the molar amount of Cd is 40% of the total molar weight of Cd and Zn; the molar amount of Cd in the second shell layer CdZnSeS The molar weight of Cd and Zn is 30% of the total molar weight of Cd and Zn, and the molar weight of Se is 50% of the total molar weight of Se and S; the molar weight of Cd in the third shell is 30% of the total molar weight of Cd and Zn; the core CdZnSe
  • the band gap is 1.98eV; the lattice mismatch between the core and the first shell is 1%, the lattice mismatch between the first shell and the second shell is 2.5%, the second shell and the third shell The degree of lattice mismatch of the layers was 1.5%, and the degree of lat
  • the nanoparticles are quantum dots.
  • the lattice mismatch between adjacent cores and shells and between adjacent shells and shells of the nanoparticles described in the present application is relatively low. Therefore, it is possible to prepare a particle with a larger particle size by controlling the thickness of the shell. And the nanoparticles with the same number of interface defect states or even fewer interface defect states.
  • the size of the nanoparticles ranges from 10 to 20 nm. Within the particle size range, it can effectively weaken the energy loss caused by the energy resonance transfer effect caused by the too small distance between the nanoparticles arranged and stacked after the nanoparticle film is formed, resulting in the problem of reduced energy conversion efficiency of the nanoparticles.
  • the size of the nanoparticles can be made uniform and have a suitable half-peak width, thereby improving the fluorescence quantum efficiency of the nanoparticles, and further improving the luminous efficiency of a light-emitting diode prepared by using the nanoparticles.
  • the embodiment of the present application also provides a nanoparticle composition, including the nanoparticle and a solvent.
  • the solvent is a solvent known in the art for dispersing nanoparticles, such as n-octane and the like.
  • the concentration of the nanoparticles is in the range of 8-50 mg/ml. If the concentration is too low, it is easy to cause problems such as lack of compactness of the light-emitting layer after film formation and leakage; if the concentration is too high, there will be problems such as easy agglomeration of the composition and excessive thickness of the formed film layer.
  • the embodiment of the present application also provides a light emitting diode 100 , which includes an anode 10 , a light emitting layer 20 and a cathode 30 stacked in sequence.
  • the light-emitting layer 20 includes the nanoparticles described above.
  • the light emitting diode 100 further includes a hole transport layer 40 located between the anode 10 and the light emitting layer 20 .
  • the LED 100 includes an anode 10 , a hole transport layer 40 , a light emitting layer 20 and a cathode 30 stacked in sequence.
  • the light emitting diode 100 further includes an electron transport layer 50 located between the light emitting layer 20 and the cathode 30 .
  • the LED 100 includes an anode 10 , a light emitting layer 20 , an electron transport layer 50 and a cathode 30 stacked in sequence.
  • the light emitting diode 100 includes an anode 10 , a hole transport layer 40 , a light emitting layer 20 , an electron transport layer 50 and a cathode 30 stacked in sequence.
  • the LED 100 further includes a hole injection layer 60 located between the anode 10 and the hole transport layer 40 .
  • the LED 100 includes an anode 10 , a hole injection layer 60 , a hole transport layer 40 , a light emitting layer 20 , an electron transport layer 50 and a cathode 30 stacked in sequence.
  • the anode 10 and the cathode 30 are anodes and cathodes known in the art for light-emitting diodes, for example, can be independently selected from but not limited to doped metal oxide electrodes, composite electrodes, graphene electrodes, carbon nanotubes Electrode, single metal electrode or alloy electrode.
  • the material of the doped metal oxide electrode can be selected from but not limited to indium doped tin oxide (ITO), fluorine doped tin oxide (FTO), antimony doped tin oxide (ATO), aluminum doped zinc oxide (AZO ), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), magnesium-doped zinc oxide (MZO) and aluminum-doped magnesium oxide (AMO).
  • the composite electrode is a composite electrode with a metal sandwiched between doped or non-doped transparent metal oxides, such as AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO 2 /Ag/TiO 2 , TiO 2 /Al/TiO 2 , ZnS/Ag/ZnS, ZnS/Al/ZnS, etc.
  • the material of the single metal electrode may be selected from but not limited to one or more of Ag, Al, Au, Pt, Ca and Ba. Wherein, "/" indicates a laminated structure, for example, AZO/Ag/AZO indicates a composite electrode with a laminated structure formed by sequentially laminating an AZO layer, an Ag layer and an AZO layer.
  • the material of the hole transport layer 40 can also be a material known in the art for the hole transport layer, for example, can be selected from but not limited to poly[bis(4-phenyl)(2,4,6-tri Methylphenyl)amine] (PTAA), 2,2',7,7'-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene (spiro -omeTAD), 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline](TAPC), N,N'-bis(1-naphthyl)-N,N'- Diphenyl-1,1'-diphenyl-4,4'-diamine (NPB), 4,4'-bis(N-carbazole)-1,1'-biphenyl (CBP), poly[ (9,9-dioctylfluorenyl-2,7-diyl
  • the material of the electron transport layer 50 is a material known in the art for the electron transport layer, for example, can be selected from but not limited to metal oxides, doped metal oxides, 2-6 group semiconductor materials, 3-5 group One or more of semiconductor materials and Group 1-3-6 semiconductor materials.
  • the metal oxide can be selected from but not limited to one or more of ZnO, TiO 2 , SnO 2 , Al2O3; the metal oxide in the doped metal oxide can be selected from but not limited to ZnO One or more of , TiO2, SnO2, doping elements can be selected from but not limited to one or more of Al, Mg, Li, In, Ga, as an example, the doped metal oxide can be Aluminum zinc oxide (AZO), lithium-doped zinc oxide (LZO) and magnesium-doped zinc oxide (MZO), etc.; the 2-6 semiconductor group materials can be selected from but not limited to one or more of ZnS, ZnSe, and CdS The 3-5 semiconductor group material can be selected from but not limited to one or more of InP, GaP; the 1-3-6 group semiconductor material can be selected from but not limited to one or more of CuInS, CuGaS Various.
  • the material of the hole injection layer 60 can also be a material known in the art for the hole injection layer, such as can be selected from but not limited to 2,3,6,7,10,11-hexacyano-1, 4,5,8,9,12-hexaazatriphenylene (HAT-CN), PEDOT:PSS, PEDOT:PSS derivatives doped with s-MoO3 (PEDOT:PSS:s-MoO3), nickel oxide, One or more of molybdenum oxide, tungsten oxide, vanadium oxide, molybdenum sulfide, tungsten sulfide and copper oxide.
  • the light-emitting diode 100 can also add some functional layers commonly used in light-emitting diodes to help improve the performance of light-emitting diodes, such as electron blocking layers, hole blocking layers, electron injection layers, interface modification layers, and the like.
  • each layer of the light emitting diode 100 can be adjusted according to the light emitting requirement of the light emitting diode 100 .
  • the light emitting diode 100 may be an upright light emitting diode or an inverted light emitting diode.
  • the light-emitting layer 20 of the light-emitting diode 100 includes the nano-particles described in this application, so it has higher luminous efficiency and longer life.
  • the present application also relates to a display device, which includes the light emitting diode 100 .
  • the core CdSe Synthesize the core CdSe, grow the first shell layer CdS on the surface of the core, grow the second shell layer CdZnS on the surface of the first shell layer, the molar amount of Cd in the second shell layer is 40% of the total molar weight of Cd and Zn,
  • the third shell ZnS is grown on the surface of the second shell to obtain red nanoparticles CdSe/CdS/CdZnS/ZnS.
  • the wavelength of the core is 632nm
  • the core and the first The lattice mismatch degree of the shell is 3.9%
  • the lattice mismatch degree of the first shell layer and the second shell layer is 2%
  • the lattice mismatch degree of the second shell layer and the third shell layer is 2.5%
  • the band gaps of the core, the first shell, the second shell, and the third shell are 2.2eV, 2.49eV, 2.93eV, and 3.61eV, respectively;
  • the red nanoparticles CdSe/CdS/CdZnS/ZnS are dispersed in n-octane solvent to obtain a nanoparticle composition, and the nanoparticle composition is spin-coated on the hole transport layer 40 to obtain a thickness of 15nm
  • This embodiment is basically the same as Embodiment 1, the difference is that the preparation method of the light-emitting layer 20 of this embodiment is:
  • the wavelength of the core is 535nm
  • the core and the first The lattice mismatch degree of the shell is 2%, the lattice mismatch degree of the first shell layer and the second shell layer is 3%, the lattice mismatch degree of the second shell layer and the third shell layer is 2.5%
  • the band gaps of the core, the first shell, the second shell and the third shell are 2.32eV, 2.69eV, 3.2eV and 3.61eV respectively;
  • the green nanoparticle CdZnSe/ZnSe/CdZnS/ZnS is dispersed in n-octane solvent to obtain a nanoparticle composition, and the nanoparticle composition is spin-coated on the hole transport layer 40 to obtain a thickness of 20nm.
  • the luminescent layer 20 is dispersed in n-octane solvent to obtain a nanoparticle composition, and the nanoparticle composition is spin-coated on the hole transport layer 40 to obtain a thickness of 20nm.
  • the luminescent layer 20 is dispersed in n-octane solvent to obtain a nanoparticle composition, and the nanoparticle composition is spin-coated on the hole transport layer 40 to obtain a thickness of 20nm.
  • This embodiment is basically the same as Embodiment 1, the difference is that the preparation method of the light-emitting layer 20 of this embodiment is:
  • the blue nanoparticles CdZnS/ZnSe/CdZnS/ZnS are dispersed in n-octane solvent to obtain a nanoparticle composition, and the nanoparticle composition is spin-coated on the hole transport layer 40 to obtain a thickness of 25 nm light emitting layer 20 .
  • This embodiment is basically the same as Embodiment 1, the difference is that the preparation method of the light-emitting layer 20 of this embodiment is:
  • the red nanoparticle CdSe/CdS/CdZnS is dispersed in n-octane solvent to obtain a nanoparticle composition, and the nanoparticle composition is spin-coated on the hole transport layer 40 to obtain a luminescence with a thickness of 10 nm. Layer 20.
  • This embodiment is basically the same as Embodiment 1, the difference is that the preparation method of the light-emitting layer 20 of this embodiment is:
  • the core CdZnSe grow the first shell layer ZnSe on the surface of the core, grow the second shell layer CdZnS on the surface of the first shell layer, the molar amount of Cd in the second shell layer is 30% of the total molar weight of Cd and Zn
  • the third shell layer ZnSeS is grown on the surface of the second shell layer, the molar mass of Se in the third shell layer is 20% of the total molar mass of Se and S
  • the fourth shell layer ZnS is grown on the surface of the third shell layer to obtain Red nanoparticles CdZnSe/ZnSe/CdZnS/ZnSeS/ZnS, in the red nanoparticles CdZnSe/ZnSe/CdZnS/ZnSeS/ZnS, the wavelength of the core is 625nm, and the lattice mismatch between the core and the first shell is 2.5% , the lattice mismatch between the first shell and the second
  • This embodiment is basically the same as Embodiment 1, the difference is that the molar weight of Cd in the second shell layer of the red nanoparticles CdSe/CdS/CdZnS/ZnS in this embodiment is 25% of the total molar weight of Cd and Zn, the second The band gap of the 2 shell is 3.15eV.
  • Embodiment 2 is basically the same as Embodiment 1, the difference is that the molar weight of Cd in the second shell layer of the red nanoparticles CdSe/CdS/CdZnS/ZnS in this embodiment is 50% of the total molar weight of Cd and Zn, the second The bandgap of the 2 shell is 2.85eV.
  • This embodiment is basically the same as Embodiment 1, the difference is that the molar weight of Cd in the second shell layer of the red nanoparticles CdSe/CdS/CdZnS/ZnS in this embodiment is 20% of the total molar weight of Cd and Zn, the second The band gap of the 2 shell is 3.2eV.
  • This embodiment is basically the same as Embodiment 1, the difference is that the molar weight of Cd in the second shell layer of the red nanoparticles CdSe/CdS/CdZnS/ZnS in this embodiment is 60% of the total molar weight of Cd and Zn, the second The bandgap of the 2 shell is 2.75eV.
  • This embodiment is basically the same as Embodiment 2, the difference is that the molar weight of Cd in the second shell layer of the green nanoparticles CdZnSe/ZnSe/CdZnS/ZnS in this embodiment is 15% of the total molar weight of Cd and Zn, the second The band gap of the 2 shell is 3.3eV.
  • This embodiment is basically the same as Embodiment 2, the difference is that the molar weight of Cd in the second shell layer of the green nanoparticles CdZnSe/ZnSe/CdZnS/ZnS in this embodiment is 25% of the total molar weight of Cd and Zn, the second The band gap of the 2 shell is 3.15eV.
  • This embodiment is basically the same as Embodiment 2, the difference is that the molar weight of Cd in the second shell layer of the green nanoparticles CdZnSe/ZnSe/CdZnS/ZnS in this embodiment is 10% of the total molar weight of Cd and Zn, the second The bandgap of the 2 shell is 3.4eV.
  • This embodiment is basically the same as Embodiment 2, the difference is that the molar weight of Cd in the second shell layer of the green nanoparticles CdZnSe/ZnSe/CdZnS/ZnS in this embodiment is 35% of the total molar weight of Cd and Zn, the second The band gap of the 2-shell is 2.98eV.
  • This embodiment is basically the same as Embodiment 3, the difference is that the molar weight of Cd in the second shell of the blue nanoparticles CdZnS/ZnSe/CdZnS/ZnS in this embodiment is 25% of the total molar weight of Cd and Zn,
  • the band gap of the second shell layer is 3.5 eV.
  • This embodiment is basically the same as Embodiment 3, the difference is that the molar weight of Cd in the second shell of the blue nanoparticles CdZnS/ZnSe/CdZnS/ZnS in this embodiment is 15% of the total molar weight of Cd and Zn,
  • the band gap of the second shell layer is 3.3eV.
  • This embodiment is basically the same as Embodiment 3, the difference is that the molar weight of Cd in the second shell of the blue nanoparticles CdZnS/ZnSe/CdZnS/ZnS in this embodiment is 3% of the total molar weight of Cd and Zn,
  • the band gap of the second shell layer is 3.58eV.
  • This embodiment is basically the same as Embodiment 3, the difference is that the molar weight of Cd in the second shell of the blue nanoparticles CdZnS/ZnSe/CdZnS/ZnS in this embodiment is 30% of the total molar weight of Cd and Zn,
  • the band gap of the second shell layer is 3.2eV.
  • the wavelength of the core is 635nm
  • the molar weight of Cd is 60% of the total molar weight of Cd and Zn
  • the first shell layer ZnSe is grown on the surface of the core
  • the second shell layer ZnSeS is grown on the surface of the first shell layer
  • the molar weight of Se in the second shell is 50% of the total molar weight of Se and S
  • the third shell ZnS is grown on the surface of the second shell
  • the red nanoparticle material CdZnSe/ZnSe/ZnSeS/ZnS is obtained, and the In the red nanoparticle material CdZnSe/ZnSe/ZnSeS/ZnS, the lattice mismatch between the core and the first shell is 2.5%, and the lattice mismatch between the first shell and the second shell is 3%.
  • the lattice mismatch between the 2nd shell and the 3rd shell is 3.5%, and the band gaps of the core, 1st shell, 2nd shell and 3rd shell are 1.95eV, 2.69eV, 3.2eV and 3.61 eV;
  • the red nanoparticle material CdZnSe/ZnSe/ZnSeS/ZnS is dispersed in n-octane solvent to obtain a nanoparticle composition, and the nanoparticle composition is spin-coated on the hole transport layer 40 to obtain a thickness of 15nm.
  • This embodiment is basically the same as Embodiment 18, the difference is that the preparation method of the light-emitting layer 20 of this embodiment is:
  • the wavelength of the core is 532nm
  • the molar weight of Cd is 35% of the total molar weight of Cd and Zn
  • the first shell layer ZnSe is grown on the surface of the core
  • the second shell layer CdZnS is grown on the surface of the first shell layer
  • the molar weight of Cd in the second shell is 20% of the total molar weight of Cd and Zn
  • the third shell ZnS is grown on the surface of the second shell
  • green nanoparticles CdZnSe/ZnSe/CdZnS/ZnS are obtained, said In green nanoparticles CdZnSe/ZnSe/CdZnS/ZnS, the lattice mismatch between the core and the first shell is 1.5%
  • the lattice mismatch between the first shell and the second shell is 3.5%
  • the second shell The lattice mismatch between the layer and the third shell is 2%, and the band gaps of the core
  • This embodiment is basically the same as Embodiment 18, the difference is that the preparation method of the light-emitting layer 20 of this embodiment is:
  • the wavelength of the core is 470nm
  • the molar weight of Cd is 15% of the total molar weight of Cd and Zn
  • the molar weight of Se is 85% of the total molar weight of Se and S
  • the second shell layer ZnSeS is grown on the surface of the first shell layer
  • the molar amount of Se in the second shell layer is 50% of the total molar weight of Se and S
  • the third shell layer ZnS is grown on the surface of the second shell layer ;
  • This embodiment is basically the same as Embodiment 18, the difference is that the preparation method of the light-emitting layer 20 of this embodiment is:
  • the core CdZnSe is synthesized, the wavelength of the core is 630nm, the molar weight of Cd is 50% of the total molar weight of Cd and Zn, and the first shell layer ZnSe is grown on the surface of the core to obtain red nanoparticle CdZnSe/ZnSe, the red nanoparticle In CdZnSe/ZnSe, the lattice mismatch between the core and the first shell is 2%, and the band gaps of the core and the first shell are 2eV and 2.69eV, respectively;
  • Red nanoparticles CdZnSe/ZnSe were dispersed in n-octane solvent to obtain a nanoparticle composition, and the nanoparticle composition was spin-coated on the hole transport layer 40 to obtain a light emitting layer 20 with a thickness of 15 nm.
  • This embodiment is basically the same as Embodiment 18, the difference is that the preparation method of the light-emitting layer 20 of this embodiment is:
  • the wavelength of the core is 625nm
  • the molar weight of Cd is 40% of the total molar weight of Cd and Zn
  • the first shell layer ZnSe is grown on the surface of the core
  • the first shell layer ZnSe is grown on the surface of the core
  • the surface of the first shell layer grows the second shell layer CdZnSeS
  • the molar weight of Cd in the second shell layer is 30% of the total molar weight of Cd and Zn
  • the molar weight of Se is 50% of the total molar weight of Se and S
  • the third shell layer CdZnS is grown on the surface of the second shell layer, and the molar mass of Cd in the third shell layer is 30% of the total molar mass of Cd and Zn
  • the fourth shell layer ZnS is grown on the surface of the third shell layer; red nano Particle CdZnSe/ZnSe/CdZnSeS/CdZnS/ZnS, in
  • This comparative example is basically the same as Example 1, except that the material of the light-emitting layer 20 in this comparative example is red nanoparticle CdSe/CdS, wherein the lattice mismatch between the core and the first shell layer is 3.6%, and the core, The bandgap widths of the first shell layer are 1.99eV and 2.49eV, respectively.
  • This comparative example is basically the same as Example 2, except that the material of the light-emitting layer 20 in this comparative example is green nanoparticles CdZnSe/CdZnS/ZnS, wherein the lattice mismatch between the core and the first shell layer is 3.6%, The lattice mismatch between the first shell and the second shell is 2.5%, and the band gaps of the core, the first shell, and the second shell are 2.45eV, 2.8eV, and 3.61eV, respectively.
  • the material of the light-emitting layer 20 in this comparative example is green nanoparticles CdZnSe/CdZnS/ZnS, wherein the lattice mismatch between the core and the first shell layer is 3.6%, The lattice mismatch between the first shell and the second shell is 2.5%, and the band gaps of the core, the first shell, and the second shell are 2.45eV, 2.8eV, and 3.61eV, respectively.
  • This comparative example is basically the same as Example 3, except that the material of the light-emitting layer 20 in this comparative example is blue nanoparticle CdZnSe/CdZnS/ZnS, wherein the lattice mismatch between the core and the first shell layer is 2%. , the lattice mismatch between the first shell and the second shell is 1.8%, and the band gaps of the core, the first shell, and the second shell are 2.75eV, 3.3eV, and 3.61eV, respectively.
  • the material of the light-emitting layer 20 in this comparative example is blue nanoparticle CdZnSe/CdZnS/ZnS, wherein the lattice mismatch between the core and the first shell layer is 2%. , the lattice mismatch between the first shell and the second shell is 1.8%, and the band gaps of the core, the first shell, and the second shell are 2.75eV, 3.3eV, and 3.61eV, respectively.
  • This comparative example is basically the same as Example 1, except that the material of the light-emitting layer 20 in this comparative example is red nanoparticle CdSe/ZnS, wherein the lattice mismatch between the core and the first shell layer is 10.6%, and the core, The bandgap widths of the first shell layer are 1.95eV and 3.61eV, respectively.
  • This comparative example is basically the same as Example 2, except that the material of the light-emitting layer 20 in this comparative example is green nanoparticles CdZnSeS/ZnSe/ZnS, wherein the lattice mismatch between the core and the first shell layer is 6.3%, The lattice mismatch between the first shell and the second shell is 4%, and the band gaps of the core, the first shell, and the second shell are 2.32eV, 2.7eV, and 3.61eV, respectively.
  • the material of the light-emitting layer 20 in this comparative example is green nanoparticles CdZnSeS/ZnSe/ZnS, wherein the lattice mismatch between the core and the first shell layer is 6.3%, The lattice mismatch between the first shell and the second shell is 4%, and the band gaps of the core, the first shell, and the second shell are 2.32eV, 2.7eV, and 3.61eV, respectively.
  • This comparative example is basically the same as Example 3, except that the material of the light-emitting layer 20 in this comparative example is blue nanoparticle CdZnS/ZnSeS/ZnS, wherein the lattice mismatch between the core and the first shell layer is 5.5%. , the lattice mismatch between the first shell and the second shell is 2.5%, and the band gaps of the core, the first shell, and the second shell are 2.63eV, 2.9eV, and 3.61eV, respectively.
  • the material of the light-emitting layer 20 in this comparative example is blue nanoparticle CdZnS/ZnSeS/ZnS, wherein the lattice mismatch between the core and the first shell layer is 5.5%. , the lattice mismatch between the first shell and the second shell is 2.5%, and the band gaps of the core, the first shell, and the second shell are 2.63eV, 2.9eV, and 3.61eV, respectively.
  • This comparative example is basically the same as Example 18, except that the material of the light-emitting layer 20 in this comparative example is red nanoparticle CdSe/CdS/ZnS, wherein the lattice mismatch between the core and the first shell layer is 4.1%, The lattice mismatch between the first shell and the second shell is 7.2%, and the band gaps of the core, the first shell, and the second shell are 1.97eV, 2.49eV, and 3.61eV, respectively.
  • the material of the light-emitting layer 20 in this comparative example is red nanoparticle CdSe/CdS/ZnS, wherein the lattice mismatch between the core and the first shell layer is 4.1%, The lattice mismatch between the first shell and the second shell is 7.2%, and the band gaps of the core, the first shell, and the second shell are 1.97eV, 2.49eV, and 3.61eV, respectively.
  • This comparative example is basically the same as Example 19, except that the material of the light-emitting layer 20 in this comparative example is green nanoparticles CdZnSe/CdZnS/ZnS, wherein the lattice mismatch between the core and the first shell layer is 6.5%, The lattice mismatch between the first shell and the second shell is 3%, and the band gaps of the core, the first shell, and the second shell are 2.32eV, 2.88eV, and 3.61eV, respectively.
  • the material of the light-emitting layer 20 in this comparative example is green nanoparticles CdZnSe/CdZnS/ZnS, wherein the lattice mismatch between the core and the first shell layer is 6.5%, The lattice mismatch between the first shell and the second shell is 3%, and the band gaps of the core, the first shell, and the second shell are 2.32eV, 2.88eV, and 3.61eV, respectively.
  • This comparative example is basically the same as Example 20, except that the material of the light-emitting layer 20 in this comparative example is blue nanoparticle CdZnS/ZnSe/ZnS, wherein the lattice mismatch between the core and the first shell layer is 3.5%. , the lattice mismatch between the first shell and the second shell is 4.6%, and the band gaps of the core, the first shell, and the second shell are 2.65eV, 2.69eV, and 3.61eV, respectively.
  • the material of the light-emitting layer 20 in this comparative example is blue nanoparticle CdZnS/ZnSe/ZnS, wherein the lattice mismatch between the core and the first shell layer is 3.5%. , the lattice mismatch between the first shell and the second shell is 4.6%, and the band gaps of the core, the first shell, and the second shell are 2.65eV, 2.69eV, and 3.61eV, respectively.
  • the fluorescence quantum efficiency PLQY and particle size of the nanoparticles of Examples 1-12 and Comparative Examples 1-9 were detected respectively.
  • the efficiency of fluorescent nanoparticles is tested by Edinburgh FS5SC-30 fluorescence spectrophotometer; the particle size is measured by transmission electron microscope (TEM). Refer to Table 1 for test results.
  • Electron injection performance, hole injection performance, luminescent emission peak (EL paek), full width at half maximum (FWHM), external quantum efficiency (EQE) and Life T95@1knit is tested.
  • the electron injection performance and the hole injection performance are measured by the conventional carrier injection performance test method: through the semi-device of the light-emitting diode (single carrier transport thin film device HOD) of the embodiment 1-22 and the comparative example 1-9 /EOD) to test the difference between electron and hole injection performance, select the current density in the trap-limited space charge limited current region in the curve of the complete single-carrier device as a comparison parameter, and obtain the electron injection performance and hole injection performance of the half-device Performance;
  • the emission peak, half-peak width and external quantum efficiency EQE of light-emitting diodes are calculated by Keithley 2400 high-precision digital source meter, Ocean Optic USB2000+ spectrometer and LS-160 luminance meter; the test method of life T95@1knit is at 2mA
  • the nanoparticles of Examples 1-2 and 4-13 Compared with the nanoparticles of Comparative Examples 1-2 and 4-5, the nanoparticles of Examples 1-2 and 4-13 have larger particle diameters and higher fluorescence quantum efficiency; The nanoparticles of ratio 6, the nanoparticles of Examples 3, 14-17 have larger particle diameters and higher fluorescence quantum efficiencies.
  • the material of the 2nd shell layer of the present application is CdZnS and between the nucleus and the 1st shell layer, and between the adjacent shell layer and the nanoparticle that the lattice mismatch degree between the shell layer is all less than or equal to 5% has more Large particle size and higher fluorescence quantum efficiency.
  • the injection of electrons and holes in the light-emitting diodes of Examples 1-2 and 4-13 is more balanced, and has higher luminous efficiency and longer life;
  • the injection of electrons and holes in the light-emitting diodes of Examples 3 and 14-17 is more balanced, and has higher luminous efficiency and longer life.
  • the material of the second shell layer of the present application is CdZnS, and the crystal lattice mismatch between the core and the first shell layer, and between the adjacent shell layers and the shell layers is all less than or equal to 5%. Light-emitting diodes have higher luminous efficiency and longer life.
  • the light-emitting diodes in Example 1 Compared with the light-emitting diodes in Examples 4-5, the light-emitting diodes in Example 1 have higher luminous efficiency and longer lifespan. It can be seen that the light-emitting diode with three shell layers has higher luminous efficiency and longer life.
  • the light-emitting diodes in Examples 1, 6, and 7 have higher luminous efficiency and longer lifespan. It can be seen that when the molar mass of Cd in the second shell layer of the red nanoparticles is 25-50% of the total molar mass of Cd and Zn, the light-emitting diode produced has higher luminous efficiency and longer lifetime.
  • the light-emitting diodes in Examples 2, 10, and 11 have higher luminous efficiency and longer lifespan. It can be seen that when the molar amount of Cd in the second shell layer of the green nanoparticle is 15-25% of the total molar weight of Cd and Zn, it has higher luminous efficiency and longer lifetime.
  • the light-emitting diodes of Examples 3, 14, and 15 have higher luminous efficiency and longer lifetime. It can be seen that when the molar amount of Cd in the second shell layer of the blue nanoparticle is 10-25% of the total molar amount of Cd and Zn, it has higher luminous efficiency and longer lifetime.
  • the nanoparticles of Examples 18-22 Compared with the nanoparticles of Comparative Examples 7-9, the nanoparticles of Examples 18-22 have larger particle diameters and higher fluorescence quantum efficiencies.
  • the light-emitting diodes of Examples 18-19 and 21-22 have higher luminous efficiency and longer life; compared with the blue light-emitting diodes of Comparative Example 9, Example 20 Blue light-emitting diodes have higher luminous efficiency and longer life. It can be seen that the use of the nanoparticles of the present application can effectively improve the luminous efficiency and lifespan of the light-emitting diode.
  • the light-emitting diodes of Examples 18-19 have higher luminous efficiency and longer life. It can be seen that the nanoparticles with three shells can more effectively improve the efficiency of light-emitting diodes. Luminous efficiency and lifespan.

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  • Luminescent Compositions (AREA)

Abstract

L'invention concerne une nanoparticule, une diode électroluminescente et un dispositif d'affichage, la nanoparticule comprenant un noyau/une première couche d'enveloppe /.../une nième couche d'enveloppe ; le mésappariement de réseau entre le noyau et la première couche d'enveloppe est inférieur ou égal à 5 %, ce qui peut réduire les défauts d'interface, améliorer la stabilité et l'efficacité quantique de fluorescence de la nanoparticule, et améliorer en outre l'efficacité lumineuse et la durée de vie d'une diode électroluminescente préparée à l'aide de la nanoparticule décrite.
PCT/CN2022/142616 2022-02-18 2022-12-28 Nanoparticule, diode électroluminescente et dispositif d'affichage WO2023155605A1 (fr)

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CN202210163356.1A CN116656338A (zh) 2022-02-18 2022-02-18 量子点、量子点组合物、发光二极管及显示装置
CN202210163356.1 2022-02-18
CN202210153051.2A CN116656337A (zh) 2022-02-18 2022-02-18 纳米颗粒、纳米颗粒组合物、发光二极管及显示装置
CN202210153051.2 2022-02-18

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090001349A1 (en) * 2007-06-29 2009-01-01 Kahen Keith B Light-emitting nanocomposite particles
CN110055051A (zh) * 2019-04-28 2019-07-26 南昌航空大学 一种应用于发光二极管的多壳层量子点的制备方法
CN111139060A (zh) * 2019-12-30 2020-05-12 上海大学 具有周期核壳结构的超大尺寸磷化铟量子点的制备方法
CN113122231A (zh) * 2019-12-31 2021-07-16 Tcl集团股份有限公司 一种量子点及其制备方法与量子点发光二极管
CN113948647A (zh) * 2020-07-17 2022-01-18 Tcl科技集团股份有限公司 一种纳米材料及其制备方法与量子点发光二极管

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090001349A1 (en) * 2007-06-29 2009-01-01 Kahen Keith B Light-emitting nanocomposite particles
CN110055051A (zh) * 2019-04-28 2019-07-26 南昌航空大学 一种应用于发光二极管的多壳层量子点的制备方法
CN111139060A (zh) * 2019-12-30 2020-05-12 上海大学 具有周期核壳结构的超大尺寸磷化铟量子点的制备方法
CN113122231A (zh) * 2019-12-31 2021-07-16 Tcl集团股份有限公司 一种量子点及其制备方法与量子点发光二极管
CN113948647A (zh) * 2020-07-17 2022-01-18 Tcl科技集团股份有限公司 一种纳米材料及其制备方法与量子点发光二极管

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