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WO2020209579A1 - Points quantiques à base d'éléments des groupes iii-v et procédé de fabrication associé - Google Patents

Points quantiques à base d'éléments des groupes iii-v et procédé de fabrication associé Download PDF

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WO2020209579A1
WO2020209579A1 PCT/KR2020/004700 KR2020004700W WO2020209579A1 WO 2020209579 A1 WO2020209579 A1 WO 2020209579A1 KR 2020004700 W KR2020004700 W KR 2020004700W WO 2020209579 A1 WO2020209579 A1 WO 2020209579A1
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group
active metal
group iii
seed
quantum dot
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Korean (ko)
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방은별
김도언
박윤희
박종남
김강용
최용훈
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UNIST Academy Industry Research Corp
DukSan Neolux Co Ltd
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UNIST Academy Industry Research Corp
DukSan Neolux Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • 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
    • C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
    • 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
    • C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
    • 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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present invention relates to a III-V quantum dot and a method of manufacturing the same.
  • Quantum dots are semiconducting nano-sized particles having a three-dimensionally limited size, and exhibit excellent optical and electrical properties that semiconducting materials do not have in a bulk state. For example, even if a quantum dot is made of the same material, the color of light emitted may vary depending on the size of the particle. Due to such characteristics, quantum dots are attracting attention as next-generation high-brightness light emitting diodes (LEDs), bio sensors, lasers, and nanomaterials for solar cells.
  • LEDs next-generation high-brightness light emitting diodes
  • quantum dots have various advantages compared to fluorescent dyes of organic materials that are generally used. Through the quantum limiting effect by adjusting the size, it is possible to emit various spectra from quantum dots of the same composition, and it is possible to secure an emission spectrum with very high quantum efficiency and color purity of ⁇ 80% compared to dyes of organic materials. .
  • the quantum dot is a semiconductor composition of an inorganic material, it can have excellent light stability of about 100 to 1000 times compared to a fluorescent dye of an organic material.
  • Quantum dots using II-VI compound semiconductor composition composed of II and VI elements on the periodic table are materials capable of high luminous efficiency, light stability, and light in the visible region. come.
  • Patent Document 1 Korean Patent Registration No. 10-1462658 (Registration Date 2014.11.11)
  • Patent Document 2 Republic of Korea Patent Publication No. 10-2018-0095955 (published on August 28, 2018)
  • An aspect of the present invention is to provide an active nanocluster used in the synthesis of III-V-based quantum dots capable of improving the half-width (FWHM) and obtaining high quantum efficiency.
  • Another aspect of the present invention is to provide a method for preparing the above-described active nanoclusters.
  • Another aspect of the present invention is to provide a III-V quantum dot having an improved half-width (FWHM) and high quantum efficiency using active nanoclusters.
  • FWHM half-width
  • Another aspect of the present invention is to provide a III-V quantum dot capable of improving the half-width (FWHM) and obtaining high quantum efficiency.
  • Another aspect of the present invention is to provide a method of manufacturing the aforementioned group III-V quantum dots.
  • an active metal oxide-carboxylate-containing active nanocluster is provided.
  • it provides a quantum dot comprising the above-described active nanoclusters.
  • a seed comprising a Group III element, a Group V element, and an active metal capable of having various oxidation numbers, and wherein the molar ratio of the Group III element and the active metal is 1:3 to 1:30 Branches provide group III-V quantum dots.
  • an active metal oxide obtained by thermally decomposing an active metal-carboxylate-a precursor step of forming an active nanocluster comprising a carboxylate; And a seed forming step of forming a seed in which an active metal, a group III element, and a group V element are alloyed by injecting a group III element precursor and a group V element precursor solution into the precursor solution prepared in the precursor step. It provides a method of manufacturing foot-based quantum dots.
  • a seed comprising a group III element and a group V element; And a growth layer including a group III element and a group V element formed on an outer surface of the seed.
  • a group III-V quantum dot including an active metal capable of having various oxidation numbers in at least one of the seed or growth layer constituting the band gap control layer, having a band gap control layer comprising:
  • a group III element, a group V element, and an active metal capable of having various oxidation numbers are included, and selected from the group consisting of Al, Ga, Ti, Mg, Na, Li, and Cu.
  • the quantum dot has a seed doped with at least one additional element, and the quantum dot provides a III-V group quantum dot having an emission wavelength of 500 nm to 650 nm and a half width of 50 nm or less.
  • a group III element, a group V element, and an active metal capable of having various oxidation numbers are included, and selected from the group consisting of Al, Ga, Ti, Mg, Na, Li, and Cu.
  • the raw material of the active metal provides a group III-V quantum dot, which is an active nanocluster solution containing a compound represented by the following formula (1).
  • T is selected from the group consisting of Zn, Mn, Cu, Fe, Ni, Co, Cr, Ti, Zr, Nb, Mo, Ru, and combinations thereof, and x, y, z are natural numbers, x>y.
  • an active metal oxide obtained by thermally decomposing an active metal-carboxylate-a precursor step of forming an active nanocluster comprising a carboxylate; And a solution containing a group III element precursor, a group V element precursor, and at least one additional element selected from the group consisting of Al, Ga, Ti, Mg, Na, Li, and Cu to the precursor solution prepared in the precursor step. It provides a method of manufacturing a group III-V quantum dot comprising a seed forming step of alloying an active metal with a group III element and a group V element, and forming a seed containing the additional element.
  • the active nanocluster according to an aspect of the present invention has an effect of efficiently forming quantum dots and suppressing rapid saturation of the growth of quantum dots, thereby improving half-width and increasing quantum efficiency.
  • the active nanocluster according to another aspect of the present invention can be effectively prepared by heating an active metal-carboxylate and thermally decomposing it for a predetermined time.
  • III-V-based quantum dots according to another aspect of the present invention suppress rapid precursor depletion, thereby improving the half-width (FWHM) and having high quantum efficiency.
  • the method of manufacturing a III-V quantum dot according to another aspect of the present invention has an advantage that it is more suitable for mass production than a conventional method for synthesizing high-efficiency quantum dots by synthesizing a highly reactive reaction medium through simple pyrolysis.
  • a solution containing one or more additional elements selected from the group consisting of Al, Ga, Ti, Mg, Na, Li, Sn, and Cu is injected to prevent lattice mismatch.
  • FWHM half-width
  • FIG. 1 is a schematic diagram showing a method of manufacturing an active nanocluster according to an aspect of the present invention.
  • Example 2 is a graph showing MALDI-TOP (Matris Assisted Laser Desorption-Time of Flight) data obtained from the solution prepared in Example 1 in order to identify the active nanoclusters according to an aspect of the present invention.
  • MALDI-TOP Micros Assisted Laser Desorption-Time of Flight
  • Example 3 is a graph measuring UV and PL spectra of the seed of the quantum dots of Example 4 of the present invention and the seed of the quantum dots of Comparative Example 2.
  • Figure 4 is a graph of measuring UV and PL spectrum by preparing the quantum dot of Example 4 and the quantum dot of Comparative Example 2 of the present invention.
  • Example 5 is a graph of measuring a PL spectrum by preparing the quantum dots of Example 5 and Comparative Example 3 of the present invention.
  • Example 6 is a graph measuring a PL spectrum for each step of seed, growth, and shell formation in the quantum dot of Example 5 of the present invention.
  • a part such as a layer, film, region, plate, etc.
  • this includes not only “directly over” another part, but also a case where another part is in the middle.
  • another part when one part is “right above” another part, it means that there is no other part in the middle.
  • the reference part means that it is located above or below the reference part, and means that it is located “above” or “on” in the direction opposite to gravity. no.
  • the term "on a plane” means when the target part is viewed from above, and when “on a cross-sectional view”, it means when the target part is viewed from the side.
  • active metal precursor refers to a chemical substance prepared in advance to react an active metal, and refers to all compounds including an active metal.
  • the first aspect of the present invention is an active nanocluster including an active metal oxide-carboxylate.
  • the active metal refers to a metal that can be used as a metal in a metal oxide-carboxylate having an activity that is included in a seed, an active layer, a shell, etc. during the manufacture of a quantum dot to improve the half width and contribute to the improvement of quantum efficiency.
  • the active metal at least one selected from the group consisting of Zn, Mn, Cu, Fe, Ni, Co, Cr, Ti, Zr, Nb, Mo, Ru, and combinations thereof that may have various oxidation numbers may be used.
  • the active metal oxide is an oxide of an active metal selected from the group consisting of Zn, Mn, Cu, Fe, Ni, Co, Cr, Ti, Zr, Nb, Mo, Ru, and combinations thereof, and is active in the present invention.
  • the nanocluster may include the active metal oxide alone or in combination of two or more.
  • cluster refers to a particle in which a single atom, molecule, or other type of atom is agglomerated or bound within hundreds to thousands of atoms.
  • the particle average particle diameter of such a cluster is preferably 1.5 nm or less, for example, and the lower limit of the average particle diameter is 0.5 nm, which is more preferable because it can suppress rapid saturation of the growth of quantum dots.
  • the active nanocluster includes an active metal oxide-carboxylate.
  • the active metal oxide-carboxylate includes a compound represented by the following formula (1).
  • T is an active metal
  • carboxylate is a salt or ester of a carboxylic acid
  • the salt of a carboxylic acid has the general formula M(RCOO)n
  • the carboxylate ester is a general formula of RCOOR'.
  • M is a metal
  • n is a natural number
  • R and R' are organic groups other than hydrogen.
  • the active metal oxide-carboxylate may include two or more active metal oxides having different values of x.
  • the value of x of the two or more different active metal oxides may be 2 to 10.
  • it may include Zn 4 O (carboxylate) 5 , Zn 7 O 2 (carboxylate) 9 , and the like.
  • it may include Zn 4 O (carboxylate) 6 , Zn 7 O 2 (carboxylate) 10 and the like.
  • active nanocluster used in the present invention refers to an active metal oxide-carboxylate.
  • the active metal oxide reacts with an active metal precursor and a carboxylic acid to synthesize an active metal-carboxylate, and thermally decomposes the active metal oxide to convert all of the active metal oxide particles through the form of an active metal oxide-carboxylate. Therefore, such an active metal oxide is usually used.
  • an active nanocluster solution a solution containing an active metal oxide-carboxylate (hereinafter, referred to as an active nanocluster solution) is formed through multi-stage control of the thermal decomposition temperature, and the active nanocluster solution is used as a raw material of the active metal oxide. It can provide one technical feature for what you use.
  • a quantum dot having an alloy bond between a group III element and a group V element can be prepared, and as a result, the half width (FWHM) is improved and the quantum efficiency is increased, By suppressing the rapid saturation of the quantum dot growth, it is possible to provide an effect of efficiently growing the quantum dot.
  • the active nanocluster solution includes the active metal oxide-carboxylate and the active metal-carboxylate.
  • Zn oleate is first synthesized by the reaction of oleic acid as a carboxylate with Zn acetate, which is an active metal precursor.
  • active nanoclusters such as Zn 4 O (carboxylate) 5 , Zn 7 O 2 (carboxylate) 9 , Zn 4 O (carboxylate) 6 , and Zn 7 O 2 (carboxylate) 10 are synthesized.
  • ZnO nanoparticles are obtained as a final reactant.
  • active metal oxide-carboxylate as an active nanocluster exists in a solution in which unreacted Zn oleate (corresponding to the aforementioned active metal-carboxylate) is mixed. .
  • the content ratio of the active metal oxide-carboxylate and the active metal-carboxylate contained in the active nanocluster solution can be confirmed by measuring the weight change according to the activation of the active metal precursor.
  • Figure 2 which shows the measurement results using MALDI-TOP (Matris Assisted Laser Desorption-Time of Flight), when activated, 1683 m/z as well as 975 m/z appearing in the existing black graph as well as the red graph , Peak at 3020 m/z, and as a result of calculating the abundance ratio by integrating each peak and comparing the areas, 1683 m/ which represents Zn 4 O(carboxylate) 6 and Zn 7 O 2 (carboxylate) 10 , respectively, among all peaks. It was confirmed that the mass distribution occupied by the z and 3020m/z peaks was about 80%.
  • the active metal oxide-carboxylate has a higher mass distribution than the active metal-carboxylate, and is preferably included in a ratio of 60:40 to 99:1.
  • the active nanocluster improves the half-width (FWHM) and increases the quantum efficiency during quantum dot manufacturing.
  • quantum dots grow efficiently by suppressing rapid saturation of the growth of quantum dots. That is, the half width of the quantum dot is, for example, 50 nm or less, preferably 30 nm to 45 nm, more preferably 34 nm to 45 nm.
  • a second aspect of the present invention shows a method for producing an active nanocluster containing an active metal oxide-carboxylate obtained using an active metal-carboxylate.
  • the active nanocluster is prepared by reacting an active metal precursor with a carboxylic acid to prepare an active metal oxide-carboxylate and then thermally decomposing it.
  • the manufacturing method includes step 1-1, step 1-2, step 1-3, and step 1-4.
  • the name of each step is a name given to distinguish each step from other steps, and does not include all the technical meanings of each step.
  • Step 1-1 is a step of reducing pressure by mixing an active metal precursor and a carboxylic acid.
  • Active metal precursors include, for example, dimethyl zinc, diethyl zinc, zinc acetate, zinc acetate dihydrate, and zinc acetylacetonate when the active metal is zinc.
  • Zinc acetylacetonate Zinc acetylacetonate hydrate, Zinc iodide, Zinc bromide, Zinc chloride, Zinc fluoride, Zinc fluoride Zinc fluoride tetrahydrate, Zinc carbonate, Zinc cyanide, Zinc nitrate, Zinc nitrate hexahydrate, Zinc oxide, Zinc Zinc peroxide, Zinc perchlorate, Zinc perchlorate hexahydrate, Zinc sulfate, Diphenyl zinc, Zinc naphthenate, Zinc oleate (Zinc oleate) and zinc stearate (Zinc stearate) may be at least one selected from the group consisting of.
  • Carboxylic acid is required to react with the active metal precursor to make an active metal-carboxylate, and palmitic acid, myristate acid, oleic acid, stearic acid, and the like may be used.
  • the active metal precursor and the carboxylic acid are mixed in a molar ratio of 1:1 to 1:3 to prepare a mixed solution. If it is out of the above range, there is a problem in that unreacted excess salt or acid may unintentionally participate in the subsequent process.
  • the pressure to be reduced is preferably 100 torr to 0.001 torr, for example. If it is out of the above range, there occurs a problem that the removal of impurities or additionally generated products is not smooth.
  • Step 1-2 is a step of first reacting the mixed solution after raising the temperature of the mixed solution after step 1-1 to a first temperature.
  • the range of the first temperature varies depending on the type of carboxylic acid to be used, but is preferably room temperature (25°C) to 200°C as an example.
  • the pressure is maintained as it is.
  • the heating time is, for example, 10 minutes to 1 hour, and the reaction time is preferably 10 minutes to 3 hours, for example.
  • Step 1-3 is a step in which the mixed solution after step 1-2 is heated to a second temperature higher than the first temperature, and then the mixed solution is subjected to a secondary reaction.
  • the range of the second temperature may be in the range of 200°C to 500°C, for example, and is preferably a temperature higher than the first temperature.
  • the pressure is maintained as it is.
  • the heating time is, for example, 10 minutes to 1 hour, and the reaction time is preferably 10 minutes to 3 hours, for example.
  • Steps 1-4 are steps of injecting the mixed solution into the solvent in an inert atmosphere and then lowering the temperature to the third temperature (decreasing temperature).
  • the solvent is for controlling the concentration of the mixed solution, and both a coordinating solvent and a non-coordinating solvent may be used, and in general, octadecene may be used.
  • the range of the third temperature may be room temperature, and the pressure may maintain normal pressure.
  • the temperature reduction time is preferably 20 minutes to 2 hours.
  • an active nanocluster solution containing [Formula 1] T x O y (Carboxylate) z is prepared.
  • 1 is a schematic diagram in which an active nanocluster of the present embodiment is generated. According to this, it can be seen that the active metal-stearate in the solid state obtained by reacting the active metal precursor with the carboxylic acid was dissolved at 140°C, and then activated at 320°C to form an active nanocluster.
  • quantum dots can be prepared using active nanoclusters.
  • the quantum dot includes a seed and a shell, wherein the shell may be selectively included, and the seed is alloyed with an active metal derived from the above-described active nanocluster.
  • the present invention can prepare an active nanocluster using a method for producing an active nanocluster, through which quantum dots can be manufactured.
  • a third aspect of the present invention is a group III-V quantum dot synthesized using the active nanocluster according to the first aspect.
  • the quantum dot on the third side includes a seed and a shell.
  • the shell may be selectively included, and the active metal derived from the aforementioned active nanocluster is alloyed and included in the seed.
  • the active metal may be at least one selected from the group consisting of Zn, Mn, Cu, Fe, Ni, Co, Cr, Ti, Zr, Nb, Mo, Ru, and combinations thereof, which may have various oxidation numbers. have.
  • the molar ratio of the group III element: active metal in the present invention may be, for example, 1:3 to 1:30, preferably 1:3 to 1:20, more preferably 1:4 It may be from 1:15, and more preferably from 1:5 to 1:10.
  • concentration of the active metal exceeds the above range, there is a problem in that the growth of the quantum dots is limited.
  • the concentration of the active metal exceeds the above range, the growth of the quantum dots is rapidly saturated and the stability of the crystal lattice is deteriorated, thereby reducing the efficiency of the quantum dots.
  • the activated active metal precursor may be an active nanocluster including the active metal oxide-carboxylate of Formula 1 described in the first aspect of the present invention.
  • Seeds are Group III elements Al, Ga, In, Ti or a combination thereof and group V elements P, As, Sb, Bi, or a combination thereof, for example, GaN, GaP, GaAs, GaSb, AlN, AlP , AlAs, AlSb, InN, InP, InAs, InSb, and a binary compound selected from the group consisting of a mixture thereof;
  • the active metal When the active metal is alloyed with a group III element or a combination thereof, a group V element, or a combination thereof, the active metal appears to play a role in stabilizing the crystal lattice in the seed and complementing the defect.
  • the active metal is an active metal derived from an active nanocluster.
  • the molar ratio of the group III element and the group V element of the seed may be, for example, 1: 0.5 to 1: 1.2, and preferably 1: 0.7 to 1: 1.
  • the molar ratio of the group III element and the group V element exceeds the above range, there is a problem that it is difficult to obtain a quantum dot in a desired wavelength band, and if it is less than the above range, there is a problem that even growth is suppressed.
  • the seed may contain additional elements. Additional elements are included in the seed to change the properties of the quantum dot depending on the content. When additional elements such as Al, Ga, Ti, Mg, Na, Li, and Cu are included in the seed, there is an effect of increasing quantum efficiency by reducing surface defects by preventing lattice mismatch.
  • the molar ratio of the group III element of the seed: the additional element may be, for example, 1: 0.2 to 1: 0.8, and preferably 1: 0.3 to 1: 0.6.
  • the quantum efficiency may not be changed because the lattice mismatch cannot be effectively prevented.
  • the shell is formed by surrounding the outer surface of the seed.
  • the shell may be one selected from the group consisting of a II-VI semiconductor, a III-V semiconductor, and a IV-VI semiconductor material.
  • the shell can increase stability by coating the outer surface of the seed to prevent surface defects of the nanocrystals.
  • Group II element one selected from the group consisting of Zn, Cd, Hg, Mg, or a combination thereof
  • the Group III element one selected from the group consisting of Al, Ga, In, Ti or a combination thereof
  • a Group IV element one selected from the group consisting of Si, Ge, Sn, Pb, or a combination thereof
  • a Group VI element in the group consisting of O, S, Se, Te or a combination thereof Any one of your choice can be used.
  • the shell is preferably a group II-VI semiconductor.
  • the molar ratio of the group III element of the seed and the group VI element of the precursor used to form the shell may be, for example, 1: 3 to 1: 20, preferably 1: 5 to 1: 15, and , More preferably, it may be 1: 8 to 1: 10.
  • the molar ratio of the precursor used for shell coating is greater than or less than the above ratio, there is a problem in that uniform shell coating is not achieved.
  • CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnSeS, PbS, PbSe, PbSeS, PbTe, GaAs, GaP, InP, InGaP, InZnP, InAs, CuS, InN, GaN, InGaN, AlP, AlAs, InAs , GaAs, GaSb, InSb, AlSb, HgS, HgTe, HgCdTe, ZnCdS, ZnCdSe, CdSeTe, CuInSe2, CuInS2, AgInS2, SnTe, etc. can be used as shell materials.
  • the average diameter of the quantum dots is, for example, 1.5 nm to 5 nm, and the thickness of the shell alone is preferably 0.5 nm to 5 nm, or 0.5 nm to 1 nm, for example. If it is out of the above range, the emission wavelength does not match or the efficiency is deteriorated.
  • the quantum dot according to this aspect has a light emission wavelength of 500 nm to 650 nm, or 540 nm to 650 nm, for example, and a half width of 50 nm or less, 30 nm to 45 nm, or 34 to 45 nm, for example.
  • the manufacturing method of group III-V quantum dots includes a precursor step, a seed formation step, a shell formation step, and a purification step.
  • the name of each step is a name given to distinguish each step from other steps, and does not include all the technical meanings of each step.
  • the precursor step is a step of preparing an active nanocluster of Formula 1 defined in the second aspect of the present invention. Active nanoclusters are prepared by pyrolyzing an active metal-carboxylate.
  • the precursor step is the same as step 1-1, step 1-2, step 1-3, and step 1-4 as described in the second aspect of the present invention, and detailed descriptions are omitted.
  • the seed formation step is a step of injecting a group III element precursor and a group V element precursor solution into the precursor solution prepared in the precursor step to form a seed in which an active metal, a group III element, and a group V element are alloyed.
  • the seed formation step includes step 2-1, step 2-2, step 2-2, and step 2-4.
  • Step 2-1 is a step of mixing and stirring the active nanocluster solution, the group III element precursor solution, and the solvent.
  • the active nanocluster solution is as described above.
  • the Group III element precursor solution contains a Group III element precursor, a solvent, and a surfactant.
  • a Group III element precursor all precursors containing Group III elements, such as a halogen salt of a Group III element, may be used.
  • the indium precursor may be, for example, indium acetylacetonate, indium chloride, indium acetate, and trimethyl indium.
  • Alkyl Indium, Aryl Indium, Indium(III) Myristate, Indium(III) Myristate Acetate and Indium Myristate 2 acetate (Indium(III) Myristate) ) Myristate 2 Acetate) may be any one selected from the group consisting of, preferably indium acetylacetonate (Indium(III) acetylacetonate).
  • the solvent is 2,6,10,15,19,23-hexamethyltetrachoic acid (Squalane), 1-octadecene (ODE), trioctylamine (TOA), tributylphosphine oxide, octadecene, octadecylamine, It may be at least one selected from the group consisting of trioctylphosphine (TOP) and trioctylphosphine oxide (TOPO).
  • TOP trioctylphosphine
  • TOPO trioctylphosphine oxide
  • the surfactant may be selectively used, and may be a carboxylic acid-based compound, a phosphonic acid-based compound, or a mixture of these two compounds.
  • Carboxylic acid-based compounds include, for example, oleic acid, palmitic acid, stearic acid, linoleic acid, myristic acid, and lauric acid. It may be one or more selected from the group consisting of, and the phosphonic acid-based compound is for example hexylphosphonic acid, octadecylphosphonic acid, tetradecylphosphonic acid, hexadecylphosphonic acid ( It may be at least one selected from the group consisting of hexadecylphosphonic acid), decylphosphonic acid, octylphosphonic acid, and butylphosphonic acid.
  • Step 2-2 is a step of reacting for 50 to 100 minutes after raising the temperature to A temperature for 5 to 20 minutes while decompressing the solution of step 2-1.
  • a temperature is, for example, 100 °C to 150 °C.
  • impurities in the precursor may not be removed, and when the temperature is higher than the temperature range, the concentration of the solution changes, which may hinder efficient quantum dot growth.
  • Step 2-3 is a step of raising the temperature of the solution of step 2-2 to the B temperature for several seconds to 1 hour in an inert atmosphere, and injecting the group V element precursor solution.
  • the B temperature is higher than the A temperature and is preferably 200°C to 400°C. When the temperature is lower than the temperature range, quantum dot formation does not occur effectively, and when it is higher than the temperature, it is difficult to control the emission wavelength.
  • the Group V element precursor solution contains a Group V element precursor and a solvent.
  • Group V element precursors are, for example, tris(trimethylsilyl)phosphine ((Tris(trimethylsilyl)phosphine, TMSP), aminophosphine, white phosphorus, tris(pyrazolyl)phosphane), Organometallic phosphorus such as calcium phosphide may be used.
  • an alkylphosphine-based surfactant can be added to the group V element precursor solution, and when added together, the group V element and the alkylphosphine-based surfactant are combined to form a new organic complex. Stable reaction is possible, making it more suitable for mass production.
  • the size of the quantum dots may be adjusted according to the type of the alkylphosphine surfactant.
  • the alkylphosphine-based surfactant is not limited thereto, but triethyl phosphine, tributyl phosphine, trioctyl phosphine, triphenyl phosphine, and triphenyl phosphine. It may be one or more selected from the group consisting of cyclohexyl phosphine.
  • the solvent of the group V element precursor solution may include, for example, trioctylphosphine (TOP), tributylphosphine (TBP), octadecene (ODE), amines (primary amine, secondary amine, third amine), etc.
  • TOP trioctylphosphine
  • TBP tributylphosphine
  • ODE octadecene
  • amines primary amine, secondary amine, third amine
  • the molar concentration of the group V element precursor solution is preferably 0.001M to 2M, for example.
  • the molar ratio of the active metal and the group V element is, for example, 1: 0.02 to 1: 0.006, and 1: 0.03 to 1: 0.005. If it is out of the above range, a problem of forming non-uniform quantum dots may occur.
  • the shell formation step is a step of forming a shell on the seed surface after the seed formation step.
  • the shell forming step includes steps 4-1, 4-2, and 4-3.
  • the shell is formed by injecting one or both of a group III element precursor solution and a group V element precursor solution, or one or both of a group II element precursor solution and a group VI element precursor solution. That is, the shell is formed by injecting a group II element precursor or/and a group VI element precursor or a group III element precursor or/and a group V element precursor.
  • the shell is made of a II-VI group semiconductor.
  • the molar ratio of the group III element of the seed and the group VI element of the precursor used to form the shell may be, for example, 1: 3 to 1: 20, preferably 1: 5 to 1: 15, and , More preferably, it may be 1: 8 to 1: 10.
  • the molar ratio of the precursor used for shell coating is greater than or less than the above ratio, there is a problem in that uniform shell coating is not achieved.
  • the group II element when a shell is formed from a group II element and a group VI element, the group II element remains unreacted group II element involved in the formation of the active nanocluster, so that the group II element can be included without a separate injection.
  • Step 4-2 is a step of heating the solution in step 4-1 to X° C. for 10 to 30 minutes and reacting for 2 to 4 hours.
  • the range of X temperature is preferably 200°C to 400°C. If it is out of the above temperature range, there is a problem that effective shell coating is not performed.
  • Step 4-3 is a step of cooling to room temperature while blowing the solution in step 4-1 with an inert gas. If the inert gas is not blown, there is a problem that the surface of the quantum dot is oxidized due to the injection of air at a high temperature.
  • the purification step includes step 5-1, step 5-2, and step 5-3.
  • the solution after the shell formation step is placed in a container capable of centrifugation, and for example, an alcohol solvent and a polar solvent (eg, 2-propanol) are added and centrifuged to discard the supernatant to obtain a precipitate.
  • an alcohol solvent and a polar solvent eg, 2-propanol
  • the number of rotations during centrifugation is preferably 1000 rpm to 20000 rpm, for example.
  • Step 5-2 is a step of dissolving the precipitate in an organic solvent such as hexane, toluene, octadecane, and heptane.
  • Step 5-3 is a step of repeating steps 5-1 and 5-2 at least once, and then storing them in a dissolved state in a non-polar solvent.
  • the fifth aspect of the present invention is a group III-V quantum dot synthesized using the active nanocluster according to the first aspect.
  • the fifth side of the quantum dot is a seed containing a group III element and a group V element; And a growth layer including a group III element and a group V element formed on the outer surface of the seed, and a variety of oxidation numbers are applied to at least one of the seed and the growth layer constituting the bandgap control layer. It is a group III-V quantum dot containing an active metal that may have.
  • band gap control layer used in the present invention refers to a layer that has a seed and a growth layer and provides improved half width and light emission efficiency by controlling the band gap.
  • the growth layer is a semiconductor layer grown on the outer surface of the seed, and the growth layer is a III-V semiconductor layer composed of a group III element or a combination thereof and a group V element or a combination thereof, and the group III elements and group V included in the seed It may be made of the same type of semiconductor material as the element, and may contain an active metal. In addition, at least one of the seed and the growth layer should be included in the active metal.
  • the activated active metal precursor may be an active nanocluster including the active metal oxide-carboxylate of Formula 1 described in the first aspect of the present invention.
  • the description of the seed overlapping with the seed disclosed in the third aspect of the present invention will be omitted.
  • the seed may further include additional elements. Additional elements are included in the seed to change the properties of the quantum dot depending on the content. When additional elements such as Al, Ga, Ti, Mg, Na, Li, and Cu are included in the seed, there is an effect of increasing quantum efficiency by reducing surface defects by preventing lattice mismatch.
  • the molar ratio of the group III element of the seed: the additional element may be, for example, 1: 0.2 to 1: 0.8, and preferably 1: 0.3 to 1: 0.6.
  • the molar ratio of the group III element and the additional element of the seed exceeds or is less than the above range, it does not effectively prevent lattice mismatch, and thus there may be no change in quantum efficiency.
  • the growth layer is a semiconductor layer grown on the outer surface of the seed.
  • the growth layer is a group III-V semiconductor layer composed of a group III element or a combination thereof and a group V element or a combination thereof, and the group III element and group V element included in the seed It may be made of the same type of semiconductor material and contains an active metal. The active metal at this time may also be made of the same type as the active metal included in the seed.
  • the active metal When the active metal is alloyed with a group III element or a combination thereof and a group V element or a combination thereof, the active metal serves to stabilize the crystal lattice in the seed and compensate for defects.
  • the molar ratio of the group III element of the bandgap control layer and the active metal of the bandgap control layer may be, for example, 1: 0.2 to 1: 2, preferably 1: 0.2 to 1: 1, more Preferably, it may be 1:0.5 to 1:1.
  • concentration of the active metal exceeds the above range, growth of the growth layer is suppressed, and it is difficult to control the wavelength of the nanocrystal, and when the concentration is less than the above range, luminous efficiency may be lowered.
  • the molar ratio of the group III element of the band gap control layer and the group V element of the band gap control layer may be, for example, 1: 0.5 to 1: 2, preferably 1: 0.5 to 1: 1, More preferably, it may be 1:0.6 to 1:1.
  • concentration of the group V element in the bandgap control layer exceeds the above range, the stability of the synthesized quantum dots may be lowered.
  • the thickness of the growth layer included in the bend gap control layer may be, for example, 0.5 nm to 2.5 nm, and preferably 1 nm to 2 nm. If it exceeds the above range, there is a problem of red shifting than the desired wavelength band, and if it is less than the above range, there is a problem that the stability of the quantum dot is deteriorated.
  • the molar ratio of the group III element and the active metal of the bandgap control layer may be, for example, 1:0.2 to 1:2, and preferably 1:0.2. It may be from 1: 1, more preferably from 1: 0.3 to 1: 0.8.
  • concentration of the active metal exceeds the above range, growth of the growth layer is suppressed, and it is difficult to control the wavelength of the nanocrystal, and when the concentration is less than the above range, luminous efficiency may be lowered.
  • the growth layer included in the band gap control layer may further include an additional element. Additional elements are included in the growth layer to change the properties of the quantum dot depending on the content. When the growth layer contains additional elements other than the active metal, for example, Al, Ga, Ti, Mg, Na, Li, and Cu, the growth of the growth layer may be promoted and the emission wavelength may be changed.
  • the shell is formed by surrounding the outer surface of the seed and the growth layer, that is, the band gap control layer.
  • the shell is as described in the second aspect of the present invention.
  • the quantum dot according to this aspect has a light emission wavelength of 500 nm to 650 nm, or 540 nm to 650 nm, for example, and a half width of 50 nm or less, 30 nm to 45 nm, or 34 nm to 45 nm, for example.
  • the method of manufacturing an active metal alloy III-V quantum dot includes a precursor step, a seed formation step, a growth layer formation step, a shell formation step, and a refining step.
  • the step of forming the seed and the step of forming the growth layer may be referred to as a step of forming a band gap control layer.
  • the name of each step is a name given to distinguish each step from other steps, and does not include all the technical meanings of each step.
  • the precursor step is interpreted as a concept separate from the active metal precursor.
  • the precursor step may be a step of preparing an active nanocluster of Formula 1 defined in the second aspect of the present invention.
  • the precursor step is the same as step 1-1, step 1-2, step 1-3, and step 1-4 as described in the second aspect of the present invention, and a detailed description thereof will be omitted.
  • the seed formation step is a step of injecting a group III element precursor and a group V element precursor solution into the precursor solution prepared in the precursor step to form a seed in which an active metal, a group III element, and a group V element are alloyed.
  • the seed formation step may be the same as step 2-1, step 2-2, step 2-2, and step 2-4, and detailed descriptions will be omitted.
  • the growth layer formation step is a step of forming a growth layer on the outer surface of the seed after the seed formation step.
  • the growth layer is a semiconductor layer grown on the outer surface of the seed.
  • the growth layer is a group III-V semiconductor layer composed of a group III element or a combination thereof and a group V element or a combination thereof, and the group III and group V elements included in the seed It may be made of the same type of semiconductor material and contains an active metal. The active metal at this time may also be made of the same type as the active metal included in the seed.
  • the growth layer is formed by injecting a group III element-active metal-group V element (hereinafter referred to as 3-M-5) complex solution to the solution in the seed formation step.
  • 3-M-5 group III element-active metal-group V element
  • the molar ratio of the group III element and the active metal is preferably 1: 0.2 to 1: 0.8, and the molar ratio of the active metal and the group V element is, for example, 1: 1 to 1: 1.5 It is preferable to be.
  • a molar ratio outside the above range there is a problem in that non-uniform quantum dots are synthesized because the growth of the growth layer does not occur evenly.
  • the 3-M-5 complex solution is injected into the solution at temperature B after the seed formation step, and reacted, and the temperature is reduced to temperature C in an inert atmosphere.
  • the range of the C temperature is preferably 130°C to 170°C, for example.
  • the reason for reducing the temperature to the C temperature is to inject the shell precursor, and when the temperature is higher than the above temperature range, uniform shell coating is not formed, and the half width is widened.
  • the 3-M-5 complex solution is a solution in which a group III element, an active metal, and a group V element are mixed, and the preparation method of the 3-M-5 complex solution includes steps 3-1, 3-2, and It includes steps 3-3, 3-4 and 3-5.
  • Step 3-1 is a step of injecting and stirring a group III element precursor, an active metal precursor, and a solvent.
  • any precursor containing a Group III element such as a halogen salt of a Group III element may be used.
  • the group III element is indium
  • the indium precursor is, for example, indium acetylacetonate, indium chloride, indium acetate, trimethyl indium indium
  • Alkyl Indium, Aryl Indium, Indium(III) Myristate, Indium(III) Myristate Acetate and Indium(III) Myristate Acetate and Indium(III) ) Myristate 2 Acetate) may be any one selected from the group consisting of, preferably indium acetylacetonate (Indium(III) acetylacetonate).
  • a compound containing an active metal may be used without limitation, and the active metal is selected from the group consisting of Zn, Mn, Cu, Fe, Ni, Co, Cr, Ti, Zr, Nb, Mo, and Ru. At least one or more metals to be used may be used.
  • the active metal is Zn
  • zinc acetate, Zn (acac) (Zn (acetylacetonate)) or the like may be used. In this case, there is an advantage in that In-Zn carboxylate is easily synthesized when an acac-based precursor is used than zinc acetate (Zn acetate).
  • the solvent of step 3-1 is, for example, 2,6,10,15,19,23-hexamethyltetracoic acid (Squalane), 1-octadecene (ODE), trioctylamine (TOA), tributylphosphine It may be at least one selected from the group consisting of oxide, octadecene, octadecylamine, trioctylphosphine (TOP), and trioctylphosphine oxide (TOPO).
  • Squalane 2,6,10,15,19,23-hexamethyltetracoic acid
  • ODE 1-octadecene
  • TOA trioctylamine
  • tributylphosphine It may be at least one selected from the group consisting of oxide, octadecene, octadecylamine, trioctylphosphine (TOP), and trioctylphosphine oxide (TOPO
  • Step 3-2 is a step of reacting for 50 to 100 minutes after raising the temperature to ⁇ temperature for 5 to 20 minutes while decompressing the solution of step 3-1.
  • ⁇ temperature may be, for example, 100 °C to 150 °C, is preferably 110 °C to 130 °C.
  • the reason for raising the temperature and reducing the pressure in this step is to remove a small amount of impurities remaining in the precursor and simultaneously synthesize In-Zn carboxylate. If the temperature is higher than the above temperature range, the concentration of the solvent may change due to a different amount of the solvent. If the temperature is lower than the above temperature, impurities may not be properly removed.
  • Step 3-3 is a step of replacing the solution of step 3-2 with an inert atmosphere and then raising the temperature to ⁇ temperature.
  • the ⁇ temperature is preferably around 250°C to 300°C in consideration of the reactivity of the group V precursor to be added later for instant seed generation.
  • Step 3-4 is a step of injecting a group V element precursor solution into the solution of step 3-3 and reacting for 10 to 100 minutes at room temperature (25°C). This room temperature condition is to prevent In-Zn-P from becoming particles due to the high reactivity of the group V element precursor.
  • the Group V element precursor solution in Step 3-3 contains a Group V element precursor and a solvent.
  • Group V element precursors are, for example, organometallics such as tris(trimethylsilyl)phosphine (TMSP), amino phosphine, white phosphorus, tri(pyrazolyl)phosphane), and calcium phosphide. Organometallic phosphorus can be used.
  • an alkylphosphine-based surfactant can be added to the group V element precursor solution, and when used together, a new organic complex is formed by combining the group V element and the alkylphosphine-based surfactant.
  • the reaction is possible, making it more suitable for mass production.
  • the size of the quantum dots may be adjusted according to the type of the alkylphosphine surfactant.
  • An alkylphosphine surfactant can be added to the group V element precursor solution, and when used together, a new organic complex is formed by combining the group V element and the alkylphosphine surfactant, thereby enabling a more stable reaction and mass production. Becomes more suitable for The size of the quantum dots may be adjusted according to the type of the alkylphosphine surfactant.
  • the alkylphosphine-based surfactant is not limited thereto, but triethyl phosphine, tributyl phosphine, trioctyl phosphine, triphenyl phosphine, and triphenyl phosphine. It may be one or more selected from the group consisting of cyclohexyl phosphine.
  • the solvent for the group V element precursor solution may be, for example, TOP, TBP, ODE, amines (primary amine, secondary amine, third amine), etc., and the molar concentration of the group V element precursor solution is 0.001M to 2M Is preferred.
  • the molar ratio of the group III element and the active metal is 1:0.2 to 1:0.8. Preferably, it may be 1:0.3 to 1:0.6. If the molar ratio of the group III element and the active metal does not satisfy the above range, it may not be able to effectively prevent lattice mismatch and thus provide a change in quantum efficiency.
  • the molar ratio of the active metal to the group V element is preferably 1:1 to 1:1.5, for example. In the case of a molar ratio outside the above range, there may be a problem in that non-uniform quantum dots are synthesized because the growth of the growth layer does not occur evenly.
  • the additional elements included in the growth layer may be separately included, or additional elements in which the additional elements included during seed formation may be unreacted may be included.
  • additional elements when an additional element is to be injected into the growth layer, 1) a precursor containing the additional element is injected before the growth layer is injected, or 2) a seed is formed with a group V element.
  • An example of the latter is a method of forming a seed by mixing a GaCl3-toluene solution with a TOP-TMSP solution.
  • the shell formation step is a step of forming a shell on the surface of the growth layer after the growth layer formation step.
  • the shell forming step includes steps 4-1, 4-2, and 4-3.
  • the shell forming step may be the same as step 4-1, step 4-2, and step 4-3 as described in the fourth aspect of the present invention, and a detailed description thereof will be omitted.
  • the purification step includes step 5-1, step 5-2, and step 5-3.
  • the refining step may also be the same as step 5-1, step 5-2, and step 5-3, as described in the fourth aspect of the present invention, and a detailed description will be omitted.
  • Tris (trimethylsilyl) phosphine Tris (trimethylsilyl) phosphine, TMSP was injected into the solution, and the solution thus prepared is referred to as an In-Zn-P complex solution.
  • InZnP@ZnSeS quantum dots were prepared as follows using the Zn-OXO activated nanocluster solution synthesized in Example 1.
  • TMSP tris(trimethylsilyl)phosphine
  • the above InZnP seed was reacted by injecting a TOP-Se solution in which selenium was dissolved in trioctylphosphine as a shell material and a TOP-S solution in which sulfur was dissolved in trioctylphosphine.
  • the obtained quantum dots were put in acetone or ethanol and centrifuged.
  • InZnP/InZnP growth@ZnSeS quantum dots were prepared as follows using the Zn-OXO activated nanocluster solution synthesized in Example 1.
  • TMSP tris(trimethylsilyl)phosphine
  • the prepared InZnP/InZnP quantum dot solution was reacted by injecting a TOP-Se solution in which selenium was dissolved in trioctylphosphine as a shell material and a TOP-S solution in which sulfur was dissolved in trioctylphosphine.
  • InZnGaP@ZnSeS quantum dots were prepared as follows using the Zn-OXO activated nanocluster solution synthesized in Example 1.
  • the above InZnP seed was reacted by injecting a TOP-Se solution in which selenium was dissolved in trioctylphosphine as a shell material and a TOP-S solution in which sulfur was dissolved in trioctylphosphine.
  • the obtained quantum dots were put in acetone or ethanol and centrifuged.
  • Example 7 InZnGaP/InZnP growth@ZnSeS quantum dots using Zn-OXO>
  • InZnGaP/InZnP growth@ZnSeS quantum dots were prepared as follows.
  • the prepared InZnGaP/InZnP quantum dot solution was reacted by injecting a TOP-Se solution in which selenium was dissolved in trioctylphosphine as a shell material and a TOP-S solution in which sulfur was dissolved in trioctylphosphine.
  • InZnP@ZnSeS quantum dots were prepared in the same manner as in Example 4 using the active nanocluster solution synthesized in Example 1. At this time, the concentration of each precursor was all the same as in Example 1 except that the concentration of In: 0.1 mmol, Zn: 0.25 mmol.
  • InZnP@ZnSeS quantum dots were prepared in the same manner as in Example 4 using the active nanocluster solution synthesized in Example 1. At this time, the concentration of each precursor was the same as in Example 1, except that the concentration of In: 0.1 mmol, Zn: 6.25 mmol.
  • a quantum dot including a band gap control layer was prepared in the same manner as in Example 5, except that an In-P composite solution without Zn acetate was prepared and used in the In-Zn-P composite solution of Example 3.
  • Example 11 InZnP/InZnP growth@ZnSeS quantum dots using Zn-OXO>
  • a band gap control layer was included in the same manner as in Example 5, except that 2.5 mmol of Zn acetate was added to the In-Zn-P composite solution of Example 3 instead of 0.5 mmol to prepare an In-Zn-P composite solution. Quantum dots were prepared.
  • Quantum dots were prepared in the same manner as in Example 4, except that the active nanocluster solution of ⁇ Zn-OXO> in Example 4 was replaced with the zinc oleate solution synthesized in Comparative Example 1.
  • Quantum dots were prepared in the same manner as in Example 5, except that the active nanocluster solution of ⁇ Zn-OXO> in Example 5 was replaced with the zinc oleate solution synthesized in Comparative Example 1.
  • Quantum dots were prepared in the same manner as in Example 6, except that the active nanocluster solution of ⁇ Zn-OXO> in Example 6 was replaced with the zinc oleate solution synthesized in Comparative Example 1.
  • Quantum dots were prepared in the same manner as in Example 7, except that the active nanocluster solution of ⁇ Zn-OXO> in Example 7 was replaced with the zinc oleate solution synthesized in Comparative Example 1.
  • Figure 2 specifically shows the weight change according to the activation of the active metal precursor (Zn (oleate) 2 ), when activated, at 1683 m/z and 3020 m/z as in the red graph as well as 975 m/z shown in the existing black graph. Peaks are formed, and as a result of analyzing the 1683m/z and 3020m/z peaks at this time, it was found that they correspond to Zn 4 O (carboxylate) 6 and Zn 7 O 2 (carboxylate) 10 . From this, it was confirmed that active nanoclusters were synthesized by activating the active metal precursor.
  • the active metal precursor Zn (oleate) 2
  • Example 4 The quantum dots of Example 4 and the quantum dots of Comparative Example 2 were prepared, and UV and PL spectra were measured and shown in FIG. 4.
  • UV and PL spectra of the seed of the quantum dots of Example 4 of the present invention and the seed of the quantum dots of Comparative Example 2 were measured and shown in FIG. 3.
  • Figure 4 is a graph obtained by measuring the UV and PL spectrum by preparing the quantum dot of Example 4 and the quantum dot of Comparative Example 2 of the present invention.
  • Example 4 had quantum dots having a smaller size and uniformity and high quantum efficiency compared to Comparative Example 2 due to the use of active nanoclusters.
  • Example 5 The quantum dots of Example 5 and the quantum dots of Comparative Example 3 were prepared, and UV and PL spectra were measured and shown in FIG. 5.
  • FIG. 6 a graph measuring the PL spectrum of each step of seed, growth, and shell formation is shown in FIG. 6.
  • Example 5 due to the use of active nanoclusters, quantum dots including a bandgap control layer having a smaller size and uniformity and an improved half-value width compared to Comparative Example 3 were prepared.
  • the quantum dots obtained by Examples 4 to 7 and the quantum dots obtained by Comparative Examples 2 to 5 were dissolved in Toluene, respectively, and analyzed by light irradiation at a wavelength of 450 nm using Otsuka Electronics QE-2000 [luminescence Wavelength peak (Emission peak), quantum efficiency (Quantum Yield), full width at half maximum (FWHM)] was confirmed.
  • the measurement results are shown in Table 1 and FIGS. 4 to 6.
  • the quantum dots of Examples 4 to 7 using an active nanocluster have a narrow half width compared to the quantum dots of Comparative Examples 2 to 5 using zinc oleate instead of the active nanocluster, and have excellent luminous efficiency.
  • the half width was significantly improved compared to the quantum dots of Comparative Example 2, which did not contain additional elements and used zinc oleate instead of the active nanocluster. Has increased. That is, when the active nanocluster was used, it was confirmed that the half width was remarkably improved and the luminous efficiency was increased.
  • both the quantum dots of Example 4 and the quantum dots of Comparative Example 2 showed emission maximums of 500 nm to 550 nm, of which, in the case of Example 4, the emission maximum shifted to the right compared to the quantum dots of Comparative Example 2 It was confirmed that the half width and luminous efficiency were also improved.
  • the quantum dots of Example 6 containing an additional element and using an active nanocluster according to the present invention have a narrow half width compared to the quantum dots of Comparative Example 4 that contain the additional element and use zinc oleate instead of the active nanocluster, and have excellent light emission. Showed efficiency.
  • Example 7 contains an additional element, and looking at the measurement results, the luminous efficiency is slightly improved. Can be confirmed.
  • Example 7 contains an additional element, and the measurement results show that the luminous efficiency is slightly improved. I can confirm.
  • the measurement results are shown in Table 2.
  • Example 4 1:8 530 39 94
  • Example 8 1:1 545 45 20
  • Example 9 1:25 527 43 80

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Abstract

L'invention concerne des points quantiques à base d'éléments des groupes III-V et un procédé de fabrication associé, les points quantiques présentant une couche de régulation de largeur de bande interdite comprenant : un germe comprenant un élément du groupe III et un élément du groupe V ; et une couche de croissance formée sur la surface externe du germe et comprenant un élément du groupe III et un élément du groupe V. Les points quantiques selon l'invention comprennent un métal actif pouvant présenter divers nombres d'oxydation dans au moins le germe ou la couche de croissance formant la couche de régulation de largeur de bande interdite.
PCT/KR2020/004700 2019-04-11 2020-04-07 Points quantiques à base d'éléments des groupes iii-v et procédé de fabrication associé Ceased WO2020209579A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170018468A (ko) * 2013-03-15 2017-02-17 나노코 테크놀로지스 리미티드 Iii-v/아연 칼코겐 화합물로 합금된 반도체 양자점
WO2018146120A1 (fr) * 2017-02-10 2018-08-16 Merck Patent Gmbh Matériau nanométrique semi-conducteur

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170018468A (ko) * 2013-03-15 2017-02-17 나노코 테크놀로지스 리미티드 Iii-v/아연 칼코겐 화합물로 합금된 반도체 양자점
WO2018146120A1 (fr) * 2017-02-10 2018-08-16 Merck Patent Gmbh Matériau nanométrique semi-conducteur

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
KIM, M.: "Highly luminescent and stable green-emitting In(Zn,Ga)P/ZnSeS/ZnS small-core/thick-multishell quantum dots", JOURNAL OF LUMINESCENCE, January 2019 (2019-01-01), XP085532863 *
MOGHADDAM, E. O: "Investigation of Ultrasonic Effect on Morphology, Optical and Growth Properties of ZnO Quantum Dots", JOURNAL OF NANO RESEARCH, September 2017 (2017-09-01) *
R AMASAMY, P. O: "Two-Step ''Seed-Mediated'' Synthetic Approach to Colloidal Indium Phosphide Quantum Dots with High-Purity Photo- and Electroluminescence", CHEMISTRY OF MATERIALS, 2018, XP085532863 *

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