WO2021111777A1 - 量子ドット、波長変換材料、バックライトユニット、画像表示装置及び量子ドットの製造方法 - Google Patents

量子ドット、波長変換材料、バックライトユニット、画像表示装置及び量子ドットの製造方法 Download PDF

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WO2021111777A1
WO2021111777A1 PCT/JP2020/040566 JP2020040566W WO2021111777A1 WO 2021111777 A1 WO2021111777 A1 WO 2021111777A1 JP 2020040566 W JP2020040566 W JP 2020040566W WO 2021111777 A1 WO2021111777 A1 WO 2021111777A1
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quantum
quantum dot
quantum dots
solution
zns
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French (fr)
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義弘 野島
伸司 青木
一也 鳶島
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Shin Etsu Chemical Co Ltd
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Priority to CN202080083102.8A priority Critical patent/CN114746363B/zh
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Priority to KR1020227017572A priority patent/KR102799365B1/ko
Priority to US17/780,260 priority patent/US20220411695A1/en
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    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/88—Luminescent materials, e.g. electroluminescent or chemiluminescent 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
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    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
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    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/56—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing sulfur
    • C09K11/562—Chalcogenides
    • C09K11/565—Chalcogenides with zinc cadmium
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    • C09K11/88—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
    • F21S2/00—Systems of lighting devices, not provided for in main groups F21S4/00 - F21S10/00 or F21S19/00, e.g. of modular construction
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/1336—Illuminating devices
    • G02F1/133621—Illuminating devices providing coloured light
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/851—Wavelength conversion means
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    • 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
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21Y—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO THE FORM OR THE KIND OF THE LIGHT SOURCES OR OF THE COLOUR OF THE LIGHT EMITTED
    • F21Y2115/00—Light-generating elements of semiconductor light sources
    • F21Y2115/10—Light-emitting diodes [LED]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/851—Wavelength conversion means
    • H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
    • H10H20/8512—Wavelength conversion materials

Definitions

  • the present invention relates to quantum dots, wavelength conversion materials, backlight units, image display devices, and methods for manufacturing the quantum dots, which are crystalline nanoparticles.
  • Quantum dots Semiconductor crystal particles with nano-sized particles are called quantum dots, and excitons generated by light absorption are confined in the nano-sized region, so that the energy levels of the semiconductor crystal particles become discrete and their bands.
  • the gap changes depending on the particle size. Due to these effects, the fluorescence emission of quantum dots is higher in brightness and efficiency and the emission is sharper than that of a general phosphor.
  • the emission wavelength can be controlled due to the characteristic that the band gap changes depending on the particle size, and it is expected to be applied as a wavelength conversion material for solid-state lighting and displays.
  • the emission wavelength can be controlled due to the characteristic that the band gap changes depending on the particle size, and it is expected to be applied as a wavelength conversion material for solid-state lighting and displays.
  • quantum dots as a wavelength conversion material in a display, it is possible to realize a wider color gamut and lower power consumption than conventional phosphor materials.
  • Patent Document 1 As a mounting method in which quantum dots are used as a wavelength conversion material, a method in which quantum dots are dispersed in a resin material and a resin material containing the quantum dots is laminated with a transparent film is incorporated into a backlight unit as a wavelength conversion film. It has been proposed (Patent Document 1).
  • quantum dots that do not contain these harmful substances are required. ..
  • quantum dots that do not contain harmful substances such as Cd and Pb InP quantum dots (Patent Document 2), AgInS 2 , AgInSe 2 quantum dots (Patent Document 3), CuInS 2 , CuInSe 2 quantum dots (Patent Document 4). ) Etc. have been proposed. However, the emission half widths of these quantum dots are broader than those containing Cd and Pb, and those having the same or higher characteristics have not been obtained.
  • Zn-based quantum dots have been proposed as quantum dots that do not contain Cd or Pb, and characteristics equivalent to those of quantum dots containing Cd or Pb having a half-value width of 40 nm or less have been reported.
  • Patent Document 5 Such current ZnTe-based quantum dots have low quantum efficiency, and further improvement in quantum efficiency is required for use as a wavelength conversion material for displays and the like.
  • the present invention has been made to solve the above problems, and is a quantum dot having high quantum efficiency, which does not contain harmful substances such as Cd and Pb, has excellent light emission characteristics such as half width of light emission, and the quantum dot. It is an object of the present invention to provide a manufacturing method.
  • the present invention has been made to achieve the above object, and is a quantum dot which is a crystalline nanoparticle, and the quantum dot has a multi-layer structure including a core particle and a plurality of layers on the core particle.
  • quantum dots having Zn, S, Se and Te as constituent elements and having at least one quantum well structure in the radial direction from the center of the quantum dots.
  • quantum dot According to such a quantum dot, it is a quantum dot that does not contain harmful substances such as Cd and Pb, has excellent light emission characteristics such as half width of light emission, and has high quantum efficiency.
  • the quantum dot can be a quantum dot having a superlattice structure including two or more quantum well structures in the radial direction.
  • the quantum dots have better emission characteristics such as half-value width and higher quantum efficiency.
  • the quantum dots have better emission characteristics such as half-value width and higher quantum efficiency.
  • the quantum dots have better emission characteristics such as half-value width and higher quantum efficiency.
  • the method for producing quantum dots which are crystalline nanoparticles, includes a step of forming core particles and a step of forming a plurality of layers on the surface of the core particles, and the core particles and the above.
  • the plurality of layers are composed of Zn, S, Se and Te as constituent elements, and form at least one quantum well structure by the core particles and the plurality of layers or the plurality of layers in the radial direction from the center of the quantum dots. It is possible to provide a method for manufacturing quantum dots.
  • quantum dots that do not contain harmful substances such as Cd and Pb, have excellent light emission characteristics such as half width of light emission, and have high quantum efficiency.
  • the present invention it is possible to provide a quantum dot that does not contain harmful substances such as Cd and Pb, has excellent light emission characteristics such as half width of light emission, and has high quantum efficiency, and a method for producing the quantum dot. Is possible. Further, by using such a wavelength conversion material and an image display device using quantum dots, it is possible to provide a wavelength conversion material and an image display device having high luminous efficiency and good color reproducibility.
  • quantum dots that do not contain harmful substances such as Cd and Pb, have excellent light emission characteristics such as half width of light emission, and have high quantum efficiency, and a method for producing the quantum dots.
  • the present inventors have obtained quantum dots which are crystalline nanoparticles, and the quantum dots have a multi-layer structure including core particles and a plurality of layers on the core particles.
  • harmful substances such as Cd and Pb are formed by the quantum dots which are composed of Zn, S, Se and Te and have at least one quantum well structure in the radial direction from the center of the quantum dots.
  • the present invention has been completed by finding that the quantum dots are excellent in emission characteristics such as half-price range and have high quantum efficiency.
  • quantum dots which are crystalline nanoparticles, and includes a step of forming core particles and a step of forming a plurality of layers on the surface of the core particles, and the core particles and the plurality of layers.
  • the layer is composed of Zn, S, Se and Te as constituent elements, and forms at least one quantum well structure by the core particles and the plurality of layers or the plurality of layers in the radial direction from the center of the quantum dots.
  • the present invention has been completed by finding that a quantum dot can be produced by a method for producing quantum dots, which does not contain harmful substances such as Cd and Pb, has excellent emission characteristics such as half-value width, and has high quantum efficiency.
  • FIG. 1 shows an example of quantum dots according to the present invention.
  • the quantum dot 10 according to the present invention has a core-shell structure having a multi-layer structure including a core particle 1 and a plurality of layers on the core particle 1, and has Zn, S, Se, and Te as constituent elements. Further, it has a quantum well structure in which a layer 2 having a small bandgap in the radial direction from the center of a quantum dot (particle) is sandwiched between layers 3 having a large bandgap.
  • Zn, S, Se and Te are constituent elements" means that unavoidable impurities may be contained.
  • composition ratio of Zn, Te, Se, and S of the core of the quantum dot and a plurality of layers (sometimes referred to as “shell” or “shell layer”) on the core and core particles is in the radial direction from the center of the quantum dot (particle).
  • it is not particularly limited as long as it forms a quantum well structure in which a layer having a small bandgap is sandwiched between layers having a large bandgap, and it can be appropriately selected according to the emission characteristics such as the target emission wavelength. It is possible.
  • the quantum well structure and composition of quantum dots include ZnS x Se 1-x / ZnTe / ZnS y Se 1-y (0 ⁇ x ⁇ 1,0 ⁇ y ⁇ 1) and ZnS x Se 1-x / ZnS ⁇ Se.
  • the composition ratio is determined so that the band gap of the ZnTe layer and the ZnS ⁇ Se ⁇ Te ⁇ layer is smaller than that of the ZnS x Se 1-x layer and the ZnS y Se 1-y layer.
  • Such a quantum dot is excellent in light emission characteristics such as a half width of light emission, and becomes a quantum dot having higher quantum efficiency.
  • the ratio of Zn, Te, Se, and S of the core and shell layers is adjusted to band a layer having a small band gap in the radial direction from the center of the quantum dots (particles). It is preferable that the structure and composition are such that two or more quantum well structures sandwiched between layers having a large gap are formed.
  • the quantum well structure and composition of such quantum dots include ZnS x Se 1-x / (ZnTe / ZnSe / ZnTe) n / ZnS y Se 1-y (0 ⁇ x ⁇ 1,0 ⁇ y ⁇ 1, n). It is preferable that it is represented by (an integer of 1 or more).
  • the quantum well structure and composition of the quantum dots according to the present invention is a repeating structure consisting of a quantum well structure in which a layer having a small bandgap is sandwiched between layers having a large bandgap in the radial direction from the center of the quantum dots (particles). It is preferable to have a superlattice structure having a plurality of.
  • An integer represented by y ⁇ 1,0 ⁇ z ⁇ 1, n: 1 or more) can be exemplified.
  • the thickness of the quantum well layer in the quantum dots can be appropriately selected according to the target emission wavelength and characteristics, and in order to further improve the quantum efficiency, it is preferably 3 nm or less, preferably 1 nm or less. Is particularly preferable.
  • the quantum well structure is not particularly limited, and may be a structure having a rectangular bandgap or a structure having a stepped shape.
  • the presence of a thin film layer such as a quantum well layer causes mismatch shifts caused by lattice mismatch. It is expected to suppress the production. For this reason, it is considered that the quantum efficiency can be improved.
  • the size and shape of the core particles and the shell layer of the quantum dots are not particularly limited, and can be appropriately selected according to the target emission wavelength and characteristics.
  • the average particle size of the quantum dots is preferably 20 nm or less. When the average particle size is in such a range, the quantum size effect can be obtained more stably, high luminous efficiency can be stably maintained, and bandgap control based on the particle size becomes easier.
  • a coating layer such as an organic molecule, an inorganic molecule, or a polymer may be further provided on the surface of the quantum dot, and the thickness of the coating layer can be appropriately selected according to the purpose.
  • the thickness of the coating layer is not particularly limited, but if the total particle size of the quantum dots and the coating layer is 100 nm or less, the dispersibility is more stable and the reduction of light transmittance and the aggregation are more effective. It is preferable because it can be prevented.
  • the coating layer includes organic molecules such as stearic acid, oleic acid, palmitic acid, dimercaptosuccinic acid, oleylamine, hexadecylamine, octadecylamine, 1-dodecanethiol, trioctylphosphine oxide, and triphenylphosphine oxide, and polyvinyl alcohol.
  • organic molecules such as stearic acid, oleic acid, palmitic acid, dimercaptosuccinic acid, oleylamine, hexadecylamine, octadecylamine, 1-dodecanethiol, trioctylphosphine oxide, and triphenylphosphine oxide, and polyvinyl alcohol.
  • Polyvinylpyrrolidone polysilsesquioxane
  • poly (methyl methacrylate) polyacrylonitrile
  • polymers such as polyethylene glycol
  • inorganic molecules such as si
  • the particle diameter and shell layer thickness of the quantum dots are measured by measuring a particle image obtained by a transmission electron microscope (TEM), and the average diameter of the major axis and the minor axis of 20 or more particles, that is, 2 It can be calculated from the average value of the shaft average diameter.
  • the shell layer thickness can be calculated as the difference between the average value of the particle sizes before and after the shell layer formation reaction.
  • the method for measuring the average particle size is not limited to this, and other methods can be used for the measurement.
  • the method for producing quantum dots includes a step of forming core particles and a step of forming a plurality of layers on the surface of the core particles. Then, the core particles and the plurality of layers form Zn, S, Se and Te as constituent elements, and at least one quantum well composed of the core particles and the plurality of layers or the plurality of layers in the radial direction from the center of the quantum dots. Form a structure.
  • the method for forming the quantum well structure is not particularly limited, but for example, SILAR (Successive) in which Zn precursors and chalcogenide precursors are alternately dropped into a heated solution in which already formed core particles or core shell particles are present.
  • Quantum dots having a quantum well structure can be obtained by forming layers in which the bandgap is changed one by one by using the Ion Layer Addition and Reaction method (Non-Patent Document 1).
  • ZnTe / ZnSeTe / ZnSe can be formed by diffusing adjacent chalcogenide elements in a quantum dot having a core-shell structure of ZnTe / ZnSe.
  • the band gap can be controlled by forming ZnSe / ZnTeSeS / ZnS in a quantum dot having a core-shell structure composed of ZnSe / ZnTe / ZnS.
  • the heating method, the heating temperature and the treatment time can be appropriately selected according to the desired characteristics.
  • a heat treatment method a method of heating quantum dots dispersed in a high boiling point solvent with a mantle heater can be exemplified.
  • wavelength conversion material can be obtained from the quantum dots according to the present invention.
  • the wavelength conversion material include, but are not limited to, uses such as wavelength conversion films and color filters.
  • a wavelength conversion material having a desired emission wavelength, good color reproducibility, and good luminous efficiency can be obtained.
  • the method for producing the wavelength conversion material according to the present invention is not particularly limited, and can be appropriately selected depending on the intended purpose.
  • the quantum dots according to the present invention can be dispersed in the resin by mixing them with the resin.
  • the quantum dots dispersed in the solvent can be added and mixed with the resin and dispersed in the resin.
  • the quantum dots can be dispersed in the resin.
  • the method for dispersing the quantum dots in the resin is not particularly limited, and can be appropriately selected depending on the intended purpose.
  • the solvent for dispersing the quantum dots is not particularly limited as long as it is compatible with the resin used.
  • the resin material is not particularly limited, and a silicone resin, an acrylic resin, an epoxy resin, a urethane resin, or the like can be appropriately selected according to desired characteristics. It is desirable that these resins have a high transmittance in order to increase the efficiency as a wavelength conversion material, and it is particularly desirable that the transmittance is 80% or more.
  • a substance other than quantum dots may be contained, fine particles such as silica, zirconia, alumina, and titania may be contained as a light scatterer, and an inorganic phosphor or an organic phosphor may be contained.
  • Inorganic phosphors include YAG, LSN, LYSN, CASN, SCASN, KSF, CSO, ⁇ -SIALON, GYAG, LuAG, SBCA, and organic phosphors include perylene derivatives, anthraquinone derivatives, anthracene derivatives, phthalocyanine derivatives, and cyanine. Examples thereof include derivatives, dioxazine derivatives, benzooxadinone derivatives, coumarin derivatives, quinophthalone derivatives, benzoxazole derivatives, pyrarizone derivatives and the like.
  • a wavelength conversion material can also be obtained by applying a resin composition in which quantum dots are dispersed in a resin to a transparent film such as PET or polyimide, curing the resin composition to form a resin layer, and laminating the resin composition.
  • a spray method such as spray or inkjet, a spin coating, a bar coater, a doctor blade method, a gravure printing method or an offset printing method can be used.
  • the thickness of the resin layer and the transparent film is not particularly limited and can be appropriately selected depending on the intended use.
  • the present invention provides a backlight unit in which a wavelength conversion material such as the wavelength conversion film is installed on a light guide panel surface to which a blue LED is coupled, and an image display device including the backlight unit. Further, the wavelength conversion material such as the wavelength conversion film provides an image display device in which, for example, a light guide panel surface to which a blue LED is coupled and a liquid crystal display panel are arranged. In such a backlight unit or an image display device, the wavelength conversion film absorbs at least a part of the blue light of the primary light which is the light source and emits the secondary light having a wavelength longer than that of the primary light. , It can be converted into light having an arbitrary wavelength distribution depending on the emission wavelength of the quantum dot.
  • the fluorescence emission characteristics of the quantum dots produced in the examples and comparative examples shown below were evaluated using a quantum efficiency measurement system (QE-2100 manufactured by Otsuka Electronics Co., Ltd.) with an excitation wavelength of 450 nm.
  • the core particle size was calculated by the average value of the biaxial average diameters of 20 particles obtained by TEM observation.
  • the shell layer thickness was calculated as the difference between the average values of the biaxial average diameters of 20 particles before and after the reaction.
  • Example 1 (ZnSe core particle synthesis) 20 mL of 1-octadecene and 1.2 mL of oleic acid were put into a 100 mL three-necked flask as a solvent, and degassing treatment was performed at 120 ° C. for 60 minutes. After degassing, the inside of the flask was filled with nitrogen gas, and the reaction was carried out in a state where oxygen was blocked. Next, under a nitrogen atmosphere, 10 mL of the above selenium solution and 0.6 mL of a hexane solution of 1.0 mol / L diethylzinc were mixed, and this mixed solution was quickly added dropwise to a flask heated and stirred at 250 ° C. to 250 ° C. Then, the reaction was carried out for 30 minutes to synthesize ZnSe core particles, and a solution containing ZnSe core particles was obtained.
  • ZnTe quantum well layer formation A solution containing ZnSe core particles was heated and stirred at 250 ° C., and 0.5 mL of the prepared zinc solution was slowly added dropwise and heated for 40 minutes. Further, 0.5 mL of tellurium solution was slowly added dropwise, the solution temperature was heated to 280 ° C., and the reaction was carried out at 280 ° C. for 45 minutes to obtain a solution containing ZnSe / ZnTe.
  • the emission wavelength was 503 nm
  • the half width of emission was 25 nm
  • the internal quantum efficiency was 31%.
  • ZnSe / ZnTe / ZnS had a core particle diameter of 2.8 nm and a shell layer thickness of 0.6 nm / 1.8 nm, respectively.
  • Example 2 ZnSeS core particle synthesis 20 mL of 1-octadecene and 1.2 mL of oleic acid were put into a 100 mL three-necked flask as a solvent, and degassing treatment was performed at 120 ° C. for 60 minutes. After degassing, the inside of the flask was filled with nitrogen gas, and the reaction was carried out in a state where oxygen was blocked.
  • ZnSeTe quantum well layer formation A solution containing ZnSe 0.7 S 0.3 core particles was heated and stirred at 250 ° C., and 0.5 mL of the prepared zinc solution was slowly added dropwise and heated for 40 minutes. Further, 0.3 mL of tellurium solution and 0.1 mL of selenium solution were mixed, and this mixed solution was slowly added dropwise, the solution temperature was heated to 280 ° C., and the reaction was carried out at 280 ° C. for 45 minutes, and ZnSe 0.7 S 0.3 /. A solution containing ZnSe 0.25 Te 0.75 was obtained.
  • the emission wavelength was 531 nm
  • the half width of emission was 28 nm
  • the internal quantum efficiency was 38%.
  • ZnSe 0.7 S 0.3 / ZnSe 0.25 Te 0.75 / ZnSe 0.5 S 0.5 had a core particle diameter of 2.2 nm and a shell layer thickness of 0.5 nm, respectively. It had /1.6 nm.
  • Example 3 (ZnSe core particle synthesis) 20 mL of 1-octadecene and 1.2 mL of oleic acid were put into a 100 mL three-necked flask as a solvent, and degassing treatment was performed at 120 ° C. for 60 minutes. After degassing, the inside of the flask was filled with nitrogen gas, and the reaction was carried out in a state where oxygen was blocked. Under a nitrogen atmosphere, 10 mL of the selenium solution and 0.6 mL of a hexane solution of 1.0 mol / L diethylzinc are mixed, and this mixed solution is quickly added dropwise to a flask heated and stirred at 250 ° C. and reacted at 250 ° C. for 30 minutes. , ZnSe core particles were synthesized to obtain a solution containing ZnSe core particles.
  • ZnTe quantum well layer formation A solution containing ZnSe core particles was heated and stirred at 250 ° C., and 0.5 mL of the prepared zinc solution was slowly added dropwise and heated for 30 minutes. Further, 0.5 mL of tellurium solution was slowly added dropwise, the solution temperature was heated to 260 ° C., and the reaction was carried out at 260 ° C. for 45 minutes. In this way, a solution containing ZnSe / ZnTe core-shell quantum dots was obtained.
  • ZnTe quantum well layer formation A solution containing quantum dots having a ZnSe / ZnTe / ZnSe structure was heated and stirred at 270 ° C., and 0.5 mL of the adjusted zinc solution was slowly added dropwise and heated for 40 minutes. Further, 0.4 mL of tellurium solution was slowly added dropwise, the solution temperature was heated to 280 ° C., and the reaction was carried out at 280 ° C. for 30 minutes. In this way, a solution containing quantum dots having a structure of ZnSe / ZnTe / ZnSe / ZnTe was obtained.
  • ZnS shell layer formation A solution containing ZnSe / ZnTe / ZnSe / ZnTe core-shell particles was heated and stirred at 280 ° C., and 5.5 mL of the prepared zinc solution was slowly added dropwise and reacted at 280 ° C. for 30 minutes. 0.2 mL of 1-dodecanethiol was slowly added dropwise and reacted for an additional 45 minutes. In this way, a solution (quantum dot solution) containing quantum dots having two quantum well structures of ZnSe / ZnTe / ZnSe / ZnTe / ZnS was obtained.
  • the emission wavelength was 520 nm
  • the half width of emission was 30 nm
  • the internal quantum efficiency was 49%.
  • ZnSe / ZnTe / ZnSe / ZnTe / ZnS had a core particle diameter of 2.5 nm and a shell layer thickness of 0.5 nm / 0.7 nm / 0.4 nm / 1.4 nm, respectively. ..
  • Example 4 ZnSeS core particle synthesis 20 mL of 1-octadecene and 1.2 mL of oleic acid were put into a 100 mL three-necked flask as a solvent, and degassing treatment was performed at 120 ° C. for 60 minutes. After degassing, the flask was filled with nitrogen gas, and the reaction was carried out with oxygen blocked.
  • ZnSSeTe quantum well layer formation A solution containing ZnSe 0.67 S 0.33 core particles was heated and stirred at 250 ° C., and 0.5 mL of the prepared zinc solution was slowly added dropwise and heated for 40 minutes. Further, 0.28 mL of tellurium solution, 0.14 mL of selenium solution and 0.05 mL of sulfur solution were mixed, and this mixed solution was slowly added dropwise, the solution temperature was heated to 280 ° C., and the reaction was carried out at 280 ° C. for 45 minutes. In this way, a solution containing ZnSe 0.67 S 0.33 / ZnS 0.1 Se 0.3 Te 0.6 was obtained.
  • the emission wavelength was 592 nm
  • the half width of emission was 38 nm
  • the internal quantum efficiency was 52%.
  • ZnSe 0.67 S 0.33 / ZnS 0.1 Se 0.3 Te 0.6 / ZnSe 0.5 S 0.5 had a core particle diameter of 2.2 nm and a shell layer thickness, respectively. It had a value of 0.5 nm / 1.6 nm.
  • Example 5 (ZnSeS core particle synthesis) 20 mL of 1-octadecene and 1.2 mL of oleic acid were put into a 100 mL three-necked flask as a solvent, and degassing treatment was performed at 120 ° C. for 60 minutes. After degassing, the reaction was carried out in a state where the inside of the flask was filled with nitrogen gas and oxygen was blocked.
  • ZnSeTe quantum well layer formation A solution containing ZnSe 0.67 S 0.33 core particles was heated and stirred at 250 ° C., and 0.4 mL of the prepared zinc solution was slowly added dropwise and heated for 40 minutes. Further, 0.3 mL of the tellurium solution and 0.1 mL of the selenium solution were mixed, and the mixed solution was slowly added dropwise, the solution temperature was heated to 280 ° C., and the reaction was carried out at 280 ° C. for 45 minutes. In this way, a solution containing ZnSe 0.67 S 0.33 / ZnSe 0.25 Te 0.75 core-shell quantum dots was obtained.
  • ZnSeTe quantum well layer formation Prepared in a place where a solution containing quantum dots having a quantum well structure of ZnSe 0.67 S 0.33 / ZnSe 0.25 Te 0.75 / ZnSe 0.6 S 0.4 is heated and stirred at 250 ° C. 0.4 mL of the zinc solution was slowly added dropwise and heated for 40 minutes. Further, 0.3 mL of the tellurium solution and 0.1 mL of the selenium solution were mixed, and the mixed solution was slowly added dropwise, the solution temperature was heated to 280 ° C., and the reaction was carried out at 280 ° C. for 45 minutes. In this way, a solution containing ZnSe 0.67 S 0.33 / ZnSe 0.25 Te 0.75 / ZnSe 0.6 S 0.4 / ZnSe 0.25 Te 0.75 was obtained.
  • ZnSeS shell layer formation A solution containing ZnSe 0.67 S 0.33 / ZnSe 0.25 Te 0.75 / ZnSe 0.6 S 0.4 / ZnSe 0.25 Te 0.75 is heated and stirred at 280 ° C. 6.2 mL of the prepared zinc solution was slowly added dropwise, and the reaction was carried out at 280 ° C. for 30 minutes. Further, 3.3 mL of the selenium solution and 0.04 mL of 1-dodecanethiol were mixed, and the mixed solution was slowly added dropwise and reacted for another 45 minutes.
  • the emission wavelength was 538 nm
  • the half width of emission was 35 nm
  • the internal quantum efficiency was 56%.
  • the emission wavelength was 501 nm
  • the half width of emission was 30 nm
  • the internal quantum efficiency was 11%.
  • ZnTe / ZnS each had a core particle diameter of 2.1 nm and a shell layer thickness of 1.8 nm.
  • the emission wavelength was 538 nm
  • the half width of emission was 36 nm
  • the internal quantum efficiency was 8%.
  • ZnSe 0.7 S 0.3 / ZnS / ZnSe 0.5 S 0.5 have a core particle diameter of 2.3 nm and a shell layer thickness of 1.0 nm / 1.6 nm, respectively.
  • the quantum dots according to the present invention have excellent light emission characteristics such as the half width of light emission, have high quantum efficiency, and improve the light emission efficiency.
  • the present invention is not limited to the above embodiment.
  • the above-described embodiment is an example, and any object having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect and effect is the present invention. Is included in the technical scope of.

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