WO2021054650A2 - Procédé de fabrication de points quantiques et points quantiques fabriqués par celui-ci - Google Patents

Procédé de fabrication de points quantiques et points quantiques fabriqués par celui-ci Download PDF

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WO2021054650A2
WO2021054650A2 PCT/KR2020/011741 KR2020011741W WO2021054650A2 WO 2021054650 A2 WO2021054650 A2 WO 2021054650A2 KR 2020011741 W KR2020011741 W KR 2020011741W WO 2021054650 A2 WO2021054650 A2 WO 2021054650A2
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solution
precursor
organic solvent
znsete core
halide
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WO2021054650A3 (fr
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강현진
길경훈
박지솔
김경남
하성민
남춘래
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주식회사 한솔케미칼
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C09K11/883—Chalcogenides with zinc or cadmium
    • 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
    • C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
    • C09K11/562—Chalcogenides
    • C09K11/565—Chalcogenides with zinc cadmium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements

Definitions

  • the present invention relates to a method of manufacturing a quantum dot and a quantum dot manufactured thereby.
  • Quantum dot is a material having a crystal structure of several nano to tens of nanometers, and it is easy to adjust the band gap by controlling the size and composition of nanoparticles, and can realize light of various wavelengths. It can have electrical, magnetic, optical, chemical, and mechanical properties. These quantum dots can be applied to various devices such as light-emitting diodes (LEDs), organic-inorganic hybrid electroluminescent devices, inorganic electroluminescent devices, solar cells, and transistors.
  • LEDs light-emitting diodes
  • organic-inorganic hybrid electroluminescent devices organic-inorganic hybrid electroluminescent devices
  • inorganic electroluminescent devices solar cells, and transistors.
  • an LED display to which a quantum dot is applied such as a quantum dot TV, uses a blue-emitting LED as a light source, and the quantum dot absorbs light having a predetermined wavelength and emits light having a different wavelength-a quantum dot-polymer composite sheet (QD It is included in the form of a sheet).
  • QD quantum dot-polymer composite sheet
  • OLED displays to which quantum dots are applied like OLED TVs, are in the spotlight as next-generation light emitting displays because, unlike conventional OLEDs, they have excellent color reproduction and color purity.
  • An object of the present invention is to provide a method for manufacturing quantum dots having a light emission wavelength of 445 nm or more and having high quantum efficiency by uniformly controlling the particle diameter of a ZnSeTe core in synthesizing quantum dots.
  • another object of the present invention is to provide a quantum dot having a light emission wavelength of 445 nm or more and high quantum efficiency.
  • the present invention includes heating a first solution including a first zinc precursor, a first carboxylic acid compound, and a first organic solvent; Forming a second solution by injecting a first mixture of a first selenium (Se) precursor and a telenium (Te) precursor into a second organic solvent; Mixing the heated first solution and the second solution to form a ZnSeTe core; And forming a shell of at least one layer on the ZnSeTe core, wherein the second organic solvent has a difference in polarity index with the first organic solvent in the range of 0 to 0.4.
  • the present invention provides a quantum dot having an emission wavelength of 445 nm or more, including a ZnSeTe core, and at least one layer of a shell, manufactured by the above-described method.
  • quantum dots having a light emission wavelength of 445 nm or more and high quantum efficiency can be manufactured.
  • Example 1 is a graph showing emission spectra of quantum dots prepared in Example 1 and Comparative Example 2, respectively.
  • an organic solvent having the same or similar polarity as the organic solvent used in the zinc precursor-containing solution is added to the zinc precursor-containing solution together with the selenium precursor and the telenium precursor and reacted to form a ZnSeTe core.
  • a quantum dot having a light emission wavelength of 445 nm or more and having high quantum efficiency can be manufactured.
  • a method of manufacturing a quantum dot includes heating a first solution including a first zinc precursor, a first carboxylic acid compound, and a first organic solvent; Forming a second solution by injecting a first mixture of a first selenium (Se) precursor and a telenium (Te) precursor into a second organic solvent; Mixing the heated first solution and the second solution to form a ZnSeTe core; And forming a shell of at least one layer on the ZnSeTe core, wherein the second organic solvent has a difference in polarity index with the first organic solvent in the range of 0 to 0.4.
  • step S100' After preparing a first solution including a first zinc (Zn) precursor, a first carboxylic acid compound, and a first organic solvent, the first solution is heated (hereinafter referred to as'step S100').
  • the step S100 includes (S110) preparing a first solution by introducing a first zinc precursor and a first carboxylic acid-based compound into a first organic solvent; And (S120) heating the first solution under vacuum and then raising the temperature to a higher temperature under a nitrogen gas atmosphere, but is not limited thereto.
  • the first zinc precursor usable in the present invention is not particularly limited as long as it is a zinc metal itself or a compound containing zinc (Zn), as long as it is commonly known in the art.
  • Zn zinc
  • the zinc precursor may be zinc acetate.
  • the first carboxylic acid-based compound usable in the present invention is a material capable of uniformly dispersing the first zinc precursor in the first organic solvent, such as oleic acid, myristoleic acid, palmitolein C 6 ⁇ C 30 unsaturated fatty acids such as Palmitoleic acid, Linoleic acid, Eicosapentaenoic acid (EPA), Docosapentaenoic acid (DPA), and the like; Lauric acid, palmitic acid, stearic acid, myristic acid, elaidic acid, eicosanoic acid, Heneicos Heneicosanoic acid, tricosanoic acid, docosanoic acid, tetracosanoic acid, hexacosanoic acid, heptacosanoic acid, octacosanoic acid There are saturated fatty acids of C 3 to C 30 such as (octacosanoic acid) and
  • the first organic solvent usable in the present invention may be used without limitation, as long as it is an organic solvent used in the synthesis of ZnSeTe core in the art, for example, C 6 ⁇ C 22 primary alkylamines such as hexadecylamine, dioctylamine Amine-based organic solvents such as C 6 to C 22 secondary alkylamines and C 6 to C 40 tertiary alkylamines such as trioctylamine; Nitrogen (N)-containing heterocyclic compounds such as pyridine; Pentene, hexine, heptene, octadecene, nonene, decene, undecene, dodecene, tridecene, tetra Aliphatic hydrocarbons of C 5 to C 40 such as tetradecene, pentadecene, octane, hexadecane, octadecane, octadecen
  • the content of the first zinc precursor, the first carboxylic acid compound, and the first organic solvent is not particularly limited.
  • the content of the first carboxylic acid-based compound may be about 1 to 5 mol per 1 mol of the first zinc precursor.
  • the content of the first organic solvent may be about 100 to 50,000 ml per 1 mol of the first zinc precursor.
  • This first solution may be heated under vacuum and then heated to a higher temperature under a nitrogen atmosphere.
  • the heating temperature and time under vacuum are not particularly limited, and may be heated at, for example, about 100° C. or higher, specifically about 100 to 160° C. for about 0.5 to 24 hours.
  • heating temperature and time are not particularly limited, and for example, the temperature may be raised to about 200° C. or more, specifically about 250 to 350° C.
  • This step is a step of forming a second solution containing a selenium precursor and a telenium precursor by injecting a first mixture of a first selenium (Se) precursor and a telenium precursor into a second organic solvent (hereinafter referred to as'step S200'). Is).
  • the second organic solvent a solvent having the same or similar polarity index as the first organic solvent used in step S100, specifically the same or similar polarity, and the same or similar boiling point (Boiling Point, BP), more specifically the same solvent is used.
  • the polarity index of the solvent generally indicates the polarity of the solvent, and when the polarity of water is 1.000, it means a relative polarity.
  • the second organic solvent is a solvent having a difference in polarity with the first organic solvent of about 0 to 0.4.
  • the second organic solvent may be a solvent having a difference in polarity with the first organic solvent of about 0 to 0.4 and a difference in boiling point with the first organic solvent of about 0 to 100°C.
  • the second organic solvent may be the same solvent as the first organic solvent.
  • This second organic solvent prevents aggregation of the first selenium precursors and telenium precursors when storing and injecting the second solution, while mixing the second solution with the first solution to react the second solution and the first solution.
  • it also induces a uniform reaction by preventing a difference in boiling point (BP) between the second solution and the first solution. Therefore, in the present invention, a ZnSeTe core having a uniform particle diameter can be synthesized.
  • This step S200 has no temporal precedence relationship with the step S100. For example, it may be performed after step S100, but may be performed before step S100 or may be performed separately at the same time as step S100.
  • the first mixture in this step includes a first selenium precursor and a telenium precursor.
  • the first selenium precursor is not particularly limited as long as it is known in the art as a compound containing selenium (Se), and for example, selenium-diphenylphosphine selenide, selenium-trioctylphosphine, selenium-tri It may be butylphosphine, selenium-triphenylphosphine, diethyl diselenide, dimethyl selenide, bis(trimethylsilyl)selenide [bis(trimethylsilyl)selenide], and the like. These may be used alone or in combination of two or more.
  • the telenium precursor is not particularly limited as long as it is known as a compound containing telenium (Te) in the art, for example, tellurium-trioctylphosphine, tellurium-tributylphosphine, or tellurium-triphenylphosphine. There are, and these may be used alone or in combination of two or more.
  • Te telenium
  • the content of the first mixture in which the first selenium precursor and the telenium precursor are mixed is not particularly limited, for example, the total content of selenium and telenium in the first mixture is about 0.05 to 2 with respect to 1 mol of zinc in the first zinc precursor. mol range.
  • the mixing ratio of the first selenium precursor and the telenium precursor is not particularly limited, and may be, for example, a molar ratio of 1: 0.0001 to 0.029, specifically a molar ratio of 1: 0.001 to 0.01. If the content ratio of the telenium precursor to the content of the first selenium precursor exceeds 0.029 molar ratio, the tail in the long wavelength region of the emission wavelength may increase, and thus the color purity of blue may decrease.
  • the second organic solvent used in this step is the same as those described for the first organic solvent, and thus are omitted.
  • the second organic solvent of the present invention is a solvent having a difference in polarity with the first organic solvent used in step S100 in the range of 0 to 0.4, and specifically, the difference in polarity with the first organic solvent. It is a solvent in the range of 0 to 0.4 and a boiling point difference of 0 to 100°C with the first organic solvent, and more specifically, the same solvent as the first organic solvent.
  • the second organic solvent when the first organic solvent is an amine-based organic solvent, specifically a tertiary alkylamine, in consideration of the difference in polarity with the first organic solvent and further, the difference in boiling point with the first organic solvent, the second organic solvent It may also be an amine-based organic solvent, specifically a tertiary alkylamine. According to an example, both the first organic solvent and the second organic solvent may be a tertiary amine containing a C 6 ⁇ C 40 alkyl group, specifically trioctylamine.
  • the content of the second organic solvent is adjusted according to the content of the first mixture, and may be, for example, about 1 to 100 parts by volume based on 100 parts by volume of the first mixture.
  • This step is a step of mixing and reacting the first solution heated in step (S100) with the second solution formed in step (S200) to form a ZnSeTe core (hereinafter referred to as'step S300').
  • the second solution is added to the heated first solution, or the heated first solution is added to the second solution to mix the heated first solution and the second solution.
  • the use ratio (mixing ratio) of the first solution and the second solution is not particularly limited, and may be 1: 0.001 to 1 volume ratio.
  • the temperature, speed, and time are not particularly limited, and vary depending on the amount of the second solution.
  • the second solution may be added to the first solution for about 6 hours or less at room temperature or higher, specifically, about 15 to 30°C. At this time, the injection rate can be adjusted according to the content of the second solution.
  • a halide solution may be additionally added.
  • the halide solution is a solution in which halide is dispersed or dissolved in a solvent, and by etching and coating the surface of the ZnSeTe core with the halide in the halide solution, the growth and surface of the ZnSeTe core are stabilized, leading to high quantum efficiency of the ZnSeTe core.
  • the organic material layer e.g., organic ligand layer
  • a material constituting the halide such as a metal cation-halide anion or a hydrocarbon group-halogen
  • a material constituting the halide such as a metal cation-halide anion or a hydrocarbon group-halogen
  • the occurrence of defects on the surface of the ZnSeTe core due to the removal of the organic ligand layer is suppressed by the coating layer formed of halide, the growth of the ZnSeTe core and stability of the surface are improved, thereby obtaining quantum dots having high quantum efficiency.
  • the manufactured quantum dot has a halide layer interposed in some or all of the interface between the ZnSeTe core and the shell.
  • the halide usable in the present invention is not particularly limited as long as it is a halide known in the art, and not only inorganic halide such as fluoride, chloride, bromide, iodide, etc., but also halogenated hydrocarbons (eg, C 1 ⁇ C 12 alkyl halide) It may be an organic halide such as. Specific examples include, but are not limited to, NH 4 Cl, NH 4 Br, NH 4 I, ZnCl 2 , ZnBr 2 , ZnI 2 , CH 3 Cl, CH 3 Br, CH 3 I, and the like.
  • the solvent in the halide solution is not particularly limited as long as it is a polar solvent or non-polar solvent known in the art capable of dissolving or dispersing the halide.
  • the content of the halide solution is not particularly limited, and may be, for example, in the range of about 0.01 to 100 parts by volume based on 100 parts by volume of the second solution.
  • the concentration of the halide solution is not particularly limited, and may be, for example, about 1 to 30% by weight, specifically about 5 to 20% by weight, and more specifically about 8 to 15% by weight based on the total amount of the halide solution. .
  • the concentration of the halide solution may be about 10% by weight.
  • the ZnSeTe core particles formed in the above-described step (S300) are dissolved together with impurities in a solvent.
  • the ZnSeTe core particles may be separated.
  • a halide may be added together with an anti-solvent. This purification process may be repeatedly performed one or more times.
  • Non-limiting examples of the anti-solvent include acetone, ethanol, methanol, butanol, propanol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, and the like, and these may be used alone or in combination of two or more. have.
  • the method of separating the ZnSeTe core particles is not particularly limited as long as it is known as a liquid-solid separation method in the art, and includes, for example, a centrifugal separation method.
  • the halide not only prevents defects on the surface of the ZnSeTe core from occurring when the ZnSeTe core particles are separated and purified, but also improves the reaction between the ZnSeTe core and the shell precursor so that a shell is formed and grown on the ZnSeTe core. have.
  • halogen F, Cl, Br, I, etc.
  • metal fluoride metal chloride, metal bromide, metal iodide, etc. It may be the same metal halide salt.
  • ZnCl 2 , ZnBr 2 , ZnI 2 NH 4 Cl, NH 4 Br, NH 4 I, and the like.
  • the organic halide may be a halogenated hydrocarbon or the like, specifically, a C 1 ⁇ C 12 alkyl halide, and the like, such as CH 3 Cl, CH 3 Br, CH 3 I, and the like. These may be used alone or in combination of two or more.
  • the halide may be ZnCl 2.
  • the content of halide is not particularly limited, for example, the ratio of the volume (V 2 ) of the solution in which the halide is dissolved (hereinafter,'halide solution') to the volume (V 1 ) of the ZnSeTe core dispersion (V 2 /V 1 ) may be about 0.1 to 5, and the halide content in the halide solution is about 0.1 wt% or more, and the halide can be dissolved up to the solubility limit.
  • the ZnSeTe core particles separated above may be redispersed in a non-polar solvent.
  • the ZnSeTe core particles are colloidally dispersed and present in a non-polar solvent, they can be stably stored.
  • non-polar solvents examples include hexane, benzene, xylene, toluene, octane, chloroform, chlorobenzene, tetrahydrofuran (THF), methylene chloride, 1,4 -Dioxane (1,4-dioxane), diethyl ether (diethyl ether), cyclohexane, dichlorobenzene, and the like, but are not limited thereto.
  • This step is a step of forming and growing a shell of at least one layer on the ZnSeTe core formed in step (S300) (hereinafter referred to as'step S400'), in which a shell is formed and grown on the core of quantum dots in the industry. If it is a method, it is not particularly limited. In this case, the shell formation process may be appropriately selected according to the component, thickness, and number of layers of each shell.
  • step S400 may include forming a third solution by mixing the ZnSeTe core formed in step S410 with a solution containing a second zinc precursor; (S420) adding a second selenium precursor to the third solution and reacting to form a solution containing first particles having a ZnSeTe core/ZnSe shell structure; And (S430) adding a sulfur precursor to the solution containing the first particles and reacting to form a solution containing particles having a ZnSeTe core/ZnSe shell/ZnS shell structure, but is not limited thereto.
  • step (S410) is a step of forming a third solution by mixing the ZnSeTe core formed in step (S300) with a solution containing a second zinc precursor.
  • the solution containing the second zinc precursor may contain a second zinc precursor and a second carboxylic acid-based compound, and may optionally further contain a third organic solvent.
  • the solution containing the second zinc precursor may be heated under vacuum and then heated to a higher temperature under a nitrogen gas atmosphere. Accordingly, it is possible to increase the reaction rate between the ZnSeTe core, the second zinc precursor, and the second selenium precursor.
  • the second zinc precursor, the second carboxylic acid compound, and the third organic solvent that can be used in this step are the same as or different from the first zinc precursor, the first carboxylic acid compound, and the first organic solvent used in step S100, respectively, Each of these examples is as already described in step S100.
  • the contents of the second zinc precursor, the second carboxylic acid-based compound, and the third organic solvent are not particularly limited.
  • the content of the second carboxylic acid-based compound may be about 1 to 5 mol per 1 mol of the second zinc precursor.
  • the content of the third organic solvent may be about 0 to 50,000 ml per 1 mol of the second zinc precursor.
  • the solution containing this second zinc precursor is heated under vacuum and then heated to a higher temperature under a nitrogen atmosphere.
  • the heating temperature and time under vacuum are not particularly limited, and may be heated at, for example, about 100° C. or higher, specifically about 100 to 160° C. for about 0.5 to 24 hours.
  • the temperature and time of raising the temperature in a nitrogen atmosphere are not particularly limited, and the temperature may be raised to, for example, about 200° C. or more, and specifically, about 250 to 350° C.
  • the content of the solution containing the second zinc precursor is not particularly limited, and may be, for example, about 50 to 100,000 parts by weight based on 100 parts by weight of the ZnSeTe core.
  • step (S420) is a step of injecting and reacting a second selenium precursor into a third solution containing a ZnSeTe core and a second zinc precursor prepared in step (S410), and a ZnSe shell is formed on the surface of the ZnSeTe core.
  • a solution containing the first particles having a ZnSeTe core/ZnSe shell structure can be obtained.
  • the second selenium precursor may be added dropwise into the third solution.
  • the second selenium precursor by slowly adding the second selenium precursor, it is possible to form and grow a strong, stable and uniform ZnSe shell on the surface of the ZnSeTe core without being affected by temperature.
  • the second selenium precursor usable in step (S420) is a compound containing selenium, and may be the same as or different from the first selenium precursor used in step S200.
  • it may be selenium-diphenylphosphine selenide, selenium-trioctylphosphine, selenium-tributylphosphine, selenium-triphenylphosphine, and the like, but is not limited thereto. These may be used alone or in combination of two or more.
  • the content of the second selenium precursor may be adjusted according to the thickness and composition of the ZnSe shell.
  • the second selenium precursor and the second zinc precursor in the third solution may be used in a molar ratio of 1:1 to 1:100.
  • the temperature, speed, and time are not particularly limited, and may vary depending on the amount of the second selenium precursor.
  • the second selenium precursor may be added to the third solution for about 6 hours or less at room temperature or higher, specifically, about 15 to 30°C. At this time, the input rate is adjusted according to the content of the second selenium precursor.
  • step (S430) a sulfur precursor is additionally added and reacted to the solution containing the first particles of the ZnSeTe core/ZnSe shell structure formed in the step (S420), thereby forming a ZnS shell on the surface of the ZnSe shell.
  • a solution containing quantum dots having a ZnSeTe core/ZnSe shell/ZnS shell structure can be obtained.
  • the content of Zn and Se in the quantum dot has a concentration gradient that gradually decreases from the center toward the surface (outermost layer), and the content of S has a concentration gradient that gradually increases from the center toward the surface (outermost layer).
  • the introduction rate of the sulfur precursor is not limited, and may be the same, similar to, or faster than the introduction rate of the Se precursor in consideration of the reaction process.
  • the sulfur precursor is added to a solution containing the first particles having a ZnSeTe core/ZnSe shell structure and reacted, a ZnS shell can be formed and grown on the surface of the ZnSe shell.
  • the sulfur precursor usable in the present invention is not particularly limited as long as it is known as a compound containing sulfur in the art, such as sulfur-diphenylphosphine sulfide, sulfur-trioctylphosphine, sulfur-tpibutylphosphine , Sulfur-triphenylphosphine, sulfur-trioctylamine, trimethylsilyl sulfur, ammonium sulfide, sodium sulfide, hexane thiol, octane thiol, decane thiol, dodecane thiol, hexadecane thiol, and the like, but are not limited thereto. These may be used alone or in combination of two or more.
  • the content of the sulfur precursor can be adjusted according to the thickness of the ZnS shell.
  • the sulfur precursor may be mixed with particles of a ZnSeTe core/ZnSe shell structure in the solution of the step (S420) in a molar ratio of 1:0.01 to 10.
  • the thickness of the ZnS shell may be 0.1 to 5 nm.
  • the temperature, speed, and time are not particularly limited, and may vary depending on the amount of the sulfur precursor added.
  • the sulfur precursor may be added to the solution obtained in step (S420) for about 6 hours or less at room temperature or higher, specifically, about 15 to 30 °C. At this time, the input rate is adjusted according to the content of the sulfur precursor.
  • the quantum dots formed through the step (S400) may be purified.
  • an anti-solvent is added to the quantum dots formed in step (S400) to precipitate the quantum dots, and then the ZnSeTe core particles may be separated. This purification process may be repeatedly performed one or more times.
  • the quantum dots are cooled to room temperature, specifically about 23 to 28° C., thereby preventing the quantum dots from becoming excessively large. Accordingly, the particle diameter of the quantum dot particles may be uniform.
  • anti-solvents examples include acetone, ethanol, methanol, butanol, propanol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, and the like, and these are used alone or in combination of two or more. I can.
  • the method of separating the quantum dots is not particularly limited as long as it is known as a liquid-solid separation method in the art, and includes, for example, a centrifugal separation method.
  • the quantum dots may be redispersed in a non-polar solvent and stored.
  • the quantum dots since they are colloidally dispersed in a non-polar solvent, they can be stably stored.
  • non-polar solvents that can be used at this time include hexane, benzene, xylene, toluene, octane, chloroform, chlorobenzene, tetrahydrofuran (THF), methylene chloride, 1,4 -Dioxane (1,4-dioxane), diethyl ether (diethyl ether), cyclohexane, dichlorobenzene, and the like, but are not limited thereto.
  • the quantum dots of the present invention manufactured according to the above-described method include a ZnSeTe core, and at least one layer of a shell, and, unlike conventional ZnSeTe-based quantum dots, have an emission wavelength of about 445 nm or more, specifically about 445 to 500 nm. . Further, the quantum dot according to the present invention may have a full width at half maximum (FWHM) of about 30 nm or less, an average particle diameter of about 5 to 20 nm, and a quantum efficiency of about 75% or more.
  • FWHM full width at half maximum
  • the quantum dot of the present invention is a ZnSeTe core; And a ZnSe shell and a ZnS shell continuously formed on the ZnSeTe core.
  • each shell has a layered gradient composition. That is, Zn, Se, and S in each shell may have different contents.
  • the Zn and Se content has a concentration gradient that gradually decreases from the center of the quantum dot to the surface (outermost layer) side
  • the content of S is a concentration gradient that gradually increases from the center to the surface (outermost layer) side.
  • the ZnSeTe core may have a Te content of more than about 0.1 part by weight and 1 part by weight or less based on 100 parts by weight of Se. Accordingly, the quantum dots of the present invention may have an emission wavelength of about 445 nm or more.
  • Such quantum dots can be variously applied to various electronic devices such as light emitting diode (LED) displays, organic light emitting diode (OLED) displays, sensors, imaging sensors, solar cells, and the like.
  • LED light emitting diode
  • OLED organic light emitting diode
  • a first solution was formed by adding 20 mmol of Zn acetate[Zn(CH 3 COO) 2 ] to a solution of 100 ml of oleic acid 60 mmol and trioctylamine(TOA) (boiling point at 1 atm: about 365 ⁇ 367 °C). After that, the first solution was heated at 120° C. for 120 minutes under vacuum, and then heated to a temperature of about 300° C. in a nitrogen gas atmosphere.
  • TOA trioctylamine
  • Se precursor is formed by dissolving 2 mmol of selenium (Se) powder in 2 ml of diphenylphosphine, and 0.1 mmol of telenium (Te) powder is dissolved in 0.5 ml of Trioctylphosphine to form a Te precursor, and then the Se precursor and the Te precursor are 1: The mixture was mixed at 0.01 molar ratio to obtain a first mixture. Thereafter, TOA was mixed with the first mixture in a volume ratio of 1:1 to obtain a second solution. The second solution was slowly injected into the heated first solution using an injection pump and reacted at 300° C.
  • Zn precursor-containing solution 20 mmol of Zn acetate was added to a solution in which 60 mmol of oleic acid and 100 ml of trioctylamine (TOA) were mixed to form a Zn precursor-containing solution, and the Zn precursor-containing solution was heated at 120° C. for 120 minutes under vacuum, and then, The temperature was raised to a temperature of about 280 °C in a nitrogen atmosphere. Thereafter, the ZnSeTe core synthesized in Example 1-1 was added to the 280° C. Zn precursor-containing solution to obtain a third solution. Subsequently, 0.13 M Se precursor was injected (injected) into the third solution for 4 hours using an injection pump to form a ZnSe shell on the surface of the ZnSeTe core.
  • TOA trioctylamine
  • Example 1-1 when the second solution was slowly injected into the first solution, a ZnSeTe core was performed in the same manner as in Example 1-1, except that 0.3 ml of a halide solution (containing HF) was added at regular intervals. Was synthesized.
  • Quantum dots were manufactured in the same manner as in Example 1-2, except that the ZnSeTe core synthesized in Example 2-1 was used instead of the ZnSeTe core of Example 1-1 used in Example 1-2. .
  • Quantum dots were manufactured in the same manner as in Example 1-2, except that the ZnSeTe core synthesized in Comparative Example 1-1 was used instead of the ZnSeTe core of Example 1-1 used in Example 1-2. .
  • a ZnSeTe core was synthesized.
  • Quantum dots were manufactured in the same manner as in Example 1-2, except that the ZnSeTe core synthesized in Comparative Example 2-1 was used instead of the ZnSeTe core of Example 1-1 used in Example 1-2. .
  • Example 1-1 instead of the second solution, a mixture of the first mixture and water (polarity: 1, boiling point at 1 atm: 100° C.) (1:1 volume ratio) was used. In the same manner as in 1-1, the ZnSeTe core was synthesized. However, the mixed solution was not mixed with the first solution and phase-separated, and some components (Se precursor) in the mixed solution were solidified and could not be injected, so that the ZnSeTe core could not be synthesized.
  • polarity 1, boiling point at 1 atm: 100° C.
  • Example 1-1 Except for using a mixture (1:1 volume ratio) of the first mixture and Toluene (polarity: 0.099, boiling point at 1 atm: about 110 to 111 °C) in Example 1-1 instead of the second solution in Example 1-1 , To synthesize a ZnSeTe core by performing the same as in Example 1-1. However, when the mixed solution was injected into the first solution, the reactor was exploded due to the vapor of Toluene, so that the ZnSeTe core could not be synthesized.
  • polarity 0.099, boiling point at 1 atm: about 110 to 111 °C
  • the emission peak (PL peak), half width (FWHM), and quantum efficiency (QE) were measured at an excitation wavelength of 370 nm using a wavelength equipment of Otsuka QE2100. And the results are shown in Table 1 and FIG. 1 below. At this time, each quantum dot was measured while being dispersed in octane.
  • Both of the quantum dots of Examples 1 and 2 had emission peaks of 445 nm or more, whereas the emission peaks of Comparative Examples 1 and 2 were less than 445 nm.
  • both of the quantum dots of Examples 1 and 2 had a half width as small as 17 nm or less, and a quantum efficiency as high as 75% or more.
  • the quantum dots synthesized according to the present invention had an emission wavelength of 445 nm or more while having a uniform particle diameter of the core.
  • the quantum dots synthesized using the halide solution according to the present invention can further improve the quantum efficiency compared to the quantum dots without the halide solution.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

La présente invention concerne un procédé de fabrication de points quantiques et des points quantiques fabriqués par celui-ci. Le procédé de fabrication de points quantiques comprend les étapes consistant à : chauffer une première solution contenant un premier précurseur de zinc, un premier composé à base d'acide carboxylique et un premier solvant organique ; ajouter un premier mélange d'un premier précurseur de sélénium (Se) et d'un précurseur de télénium (Te) à un second solvant organique pour former une seconde solution ; mélanger la première solution chauffée et la seconde solution pour former un noyau de ZnSeTe ; et former au moins une coque en couches sur le noyau de ZnSeTe, la différence d'indice de polarité du second solvant organique par rapport au premier solvant organique étant dans la plage de 0 à 0,4.
PCT/KR2020/011741 2019-09-18 2020-09-02 Procédé de fabrication de points quantiques et points quantiques fabriqués par celui-ci WO2021054650A2 (fr)

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CN117126669A (zh) * 2022-05-18 2023-11-28 苏州星烁纳米科技有限公司 一种ZnSe(Te)量子点及其制备方法、电致发光器件

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EP3536762B1 (fr) * 2018-03-09 2021-05-05 Samsung Electronics Co., Ltd. Points quantiques et dispositifs les comprenant

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* Cited by examiner, † Cited by third party
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CN117126669A (zh) * 2022-05-18 2023-11-28 苏州星烁纳米科技有限公司 一种ZnSe(Te)量子点及其制备方法、电致发光器件

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