WO2017034228A1 - Procédé de traitement de surface des boîtes quantiques pour leur conférer une résistance chimique, et boîtes quantiques ainsi produites - Google Patents

Procédé de traitement de surface des boîtes quantiques pour leur conférer une résistance chimique, et boîtes quantiques ainsi produites Download PDF

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WO2017034228A1
WO2017034228A1 PCT/KR2016/009160 KR2016009160W WO2017034228A1 WO 2017034228 A1 WO2017034228 A1 WO 2017034228A1 KR 2016009160 W KR2016009160 W KR 2016009160W WO 2017034228 A1 WO2017034228 A1 WO 2017034228A1
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quantum dots
quantum
quantum dot
chemical resistance
metal ions
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PCT/KR2016/009160
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English (en)
Korean (ko)
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김재일
임태윤
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주식회사 두하누리
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials

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  • the present invention relates to a method for imparting chemical resistance to quantum dots and a quantum dot manufactured by the method, and more particularly, to impart chemical resistance to quantum dots so as not to be affected by the external environment, thereby having excellent chemical resistance and heat resistance. A surface treatment method and a quantum dot produced thereby.
  • quantum dot which is a semiconductor material corresponding to a nano size of about 2 to 10 nm in diameter, and when it is smaller than a certain size, electron motion characteristics in the bulk semiconductor material are further restricted. It is a material that gives a quantum confinement effect that the emission wavelength is different from the bulk state.
  • the quantum dot receives light from an excitation source and reaches an energy excited state, the quantum dot emits energy according to a corresponding energy band gap. Therefore, by adjusting the size of the quantum dot it is possible to adjust the band gap, the energy of various wavelength bands can be obtained, thereby showing optical, electrical and magnetic properties that are completely different from the original physical properties.
  • quantum dots have recently been studied for use in various fields, including a wide range of applications, such as displays, solar energy conversion, molecular and cellular imaging, and the like.
  • quantum dot-matrix thin film of Korea Patent Publication No. 10-2013-0067137, which includes a plurality of quantum dots; An inorganic matrix embedded with a plurality of said quantum dots; And an interface layer positioned between the quantum dots and the inorganic matrix and surrounding the surface of the quantum dots.
  • the quantum dot is sensitive to the external chemical environment due to the nano-sized small particles and metal ions, together with the above-described characteristics, thereby causing a sudden change in luminescence and poor chemical resistance, and reaction with oxygen in the atmosphere at a high temperature of 100 ° C. or higher.
  • the surface was damaged, resulting in a problem of poor heat resistance in which the luminescence dropped sharply.
  • Poor chemical resistance of quantum dots is evidence that the luminescence deteriorates during the quantum dot surface ligand substitution experiment, and the quantum dots are not completely protected from the external environment except for a very thick CdS shell, and an inorganic shell coating The coating is not complete and the external environment is affected. Therefore, there was a need to improve these disadvantages.
  • the present invention allows the inorganic shell coating to be simply and stably formed on the surface of the quantum dots so as not to be influenced by the external environment, thereby providing excellent resistance to It is intended to have chemical and heat resistance, and to have a thickness that does not affect the luminescence of the buffer-type inorganic layer formed on the outermost quantum dots.
  • the metal ions present on the surface of the quantum dots by a cation exchange reaction (cation exchange reaction)
  • the heterogeneous metal ions existing outside the quantum dots Provided is a method for treating a chemically imparted surface of a quantum dot to allow for site exchange.
  • the material exchanged with the heterogeneous metal ions has a larger atom or ion than the metal ions on the surface of the quantum dot, and thus has a lower band gap when the metal ions on the surface of the quantum dot are replaced. It may be a forming material.
  • the material exchanged with the heterogeneous metal ions may include some of Cd, Al, Ga (Gallium), and In (Indium) when the outermost metal atom of the quantum dot is Zn.
  • CdO, ligand, and 1-octadecene are added to the container, and based on 10 mmol of the CdO, the ligand is 5-100 mmol, and the 1-octadecene (ODE) is 10 Bringing to 2000 mL; Dissolving the CdO by bringing the vessel to a temperature of 100 to 300 ° C. in a vacuum state; Adding a quantum dot to the solution in which the CdO is dissolved so that the metal ion of the surface of the quantum dot is exchanged at a temperature of 100 to 300 ° C .; And cooling the solution to purify the quantum dots with an organic solvent.
  • ODE 1-octadecene
  • the ligand may be an alkyl acid, an alkyl phosphonic acid, an alkyl phosphinic acid, an aryl acid, or an aryl phosph that may react with a metal to form a metal salt. It may include any one of arylphosphonic acid and aryl phosphinic acid.
  • a quantum dot produced by the method for imparting chemical resistance of the quantum dot according to one aspect of the present invention.
  • an inorganic shell coating is simply and stably performed on the surface of the quantum dots, thereby preventing them from being affected by the external environment. Therefore, it is possible to have excellent chemical resistance and heat resistance, and to have a thickness that does not affect the luminescence of a buffer-type inorganic layer formed on the outermost quantum dots.
  • FIG. 3 is a flowchart illustrating a chemical treatment-resistant surface treatment method of a quantum dot according to an embodiment of the present invention.
  • FIG. 4 is a view comparing before and after chemical resistance imparting surface treatment according to the present invention.
  • FIG. 1 is a view for explaining a chemical treatment-resistant surface treatment method of a quantum dot according to the present invention, which shows that the CdSe / ZnS quantum dots are surface-treated with Cd ions.
  • metal ions existing on the surface of the quantum dot are present outside the quantum dot by a cation exchange reaction.
  • the temperature for causing the metal ions present on the surface of the quantum dot to be exchanged with the different metal ions is less than the temperature at which the core and the shell of the quantum dot form an alloy, and the metal ions of the surface and the hetero ions are cations as described above. It may be a temperature range to allow a cation exchange reaction.
  • Substances exchanged with heterogeneous metal ions have a larger atom or ion than metal ions on the surface of the quantum dots, thereby forming a layer having a lower band gap when the metal ions on the surface of the quantum dots are replaced.
  • the outermost metal atom of the quantum dot when the outermost metal atom of the quantum dot is Zn, it may include some of Cd, Al, Ga (Gallium) and In (Indium), for example, the outermost portion of the quantum dot.
  • the material that is exchanged with heterogeneous metal ions may be, for example, CdS, in addition to ZnSe.
  • the quantum dots may be selected from any one of Si-based nanocrystals, II-VI compound semiconductor nanocrystals, III-V compound semiconductors, and IV-VI compound semiconductor nanocrystals and compounds thereof. Nanocrystals.
  • group II-VI compound semiconductor nanocrystals are CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, PbSe, PbS, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeS, HgSeS, HgSeS Among CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HggZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgZTSe, HdHgZTT, In addition, group III-V compound semiconductor nanocrystals are GaN, GaP,
  • the quantum dot may be a Cd compound such as CdS, CdSe, CdTe, CdTe, or the like, or an In compound such as InP, InN, InAs, etc.
  • the shell surrounding the core may be a Zn compound such as a quantum dot core and a lattice parameter. May be similar ZnS or ZnSe, and thus may include nanocrystals made of CdSe / ZnS as shown in FIG. 1 or nanocrystals made of InP / ZnS as another example.
  • an inorganic shell coating simply and reliably and not to affect the internal size of the particles, It has a buffer characteristic at the outermost part of the quantum dot but does not affect the luminescence by forming a very thin inorganic film due to the thickness of less than 1 monolayer.
  • the change in the luminescence when the quantum dot is CdSe / ZnS as shown in Fig. 2 (a), the ZnS crystal lattice grows on the CdSe crystal lattice, at a predetermined thickness, for example 1.7 mL or more Crack is generated, as shown in (b) of FIG. 2, in the case of the quantum dot manufactured by the chemical resistance surface treatment method of the quantum dot according to the present invention, for example, CdSe / ZnS / CdS is formed on the CdSe crystal lattice. As the ZnS crystal lattice grows and Cd larger than Zn enters the outermost quantum dot, cracks caused by the increase in ZnS thickness are prevented.
  • Cd enters the position where the crack occurs, and as a result, the crack disappears on the crystal lattice, thereby suppressing lattice mismatch, minimizing energy loss and improving luminescence.
  • the phenomenon that chemicals penetrate into the space formed when the crack is generated to reduce the luminescence is prevented by suppressing the occurrence of the crack as described above. This also improves the high temperature heat resistance in the presence of oxygen and reduces the likelihood of attacking foreign chemicals due to high density ligand binding. Since CdS is not a shell of sufficient thickness, it does not affect the quantum dot emission wavelength.
  • the quantum dots are mixed with a solution containing heterogeneous metal ions, and the quantum dots are mixed at a temperature of 100 to 300 ° C.
  • a method for treating chemical resistance of a quantum dot is prepared by adding CdO, a ligand, and 1-octadecene (ODE) to a container, based on 10 mmol of CdO, wherein the ligand is 5 to 100 to 1 mmol of octadecene (ODE) to 10 to 2000 mL, to dissolve the CdO by bringing the vessel to a temperature of 100 to 300 ° C.
  • the ligand is an alkyl acid, alkyl phosphonic acid, alkyl phosphinic acid, aryl which can react with metals such as Cd, Al, Ga, In and the like to form metal salts
  • Acid (aryl acid), aryl phosphonic acid (aryl phosphonic acid) and aryl phosphinic acid (aryl phosphinic acid) may include any one, and the structure and molecular weight of the material is not limited.
  • the quantum dot according to an embodiment of the present invention is a quantum dot manufactured by the chemical resistance imparting surface treatment method of the quantum dots according to the embodiments of the present invention as described above, the chemical resistance imparting surface treatment method of the quantum dots has already been described in detail. Since the description thereof will be omitted, more specific embodiments will be described below.
  • TOP-Se 1M selenium solution
  • TOP-S 1M sulfur
  • Se and S were dissolved in tri-n-octylphosphine, respectively, to prepare a 1M selenium solution (TOPSe) and 1M sulfur (TOPS) solution, which is a chalcogenide standard solution for red quantum dot synthesis.
  • TOPSe 1M selenium solution
  • TOPS 1M sulfur
  • a 100 mL two neck round bottom flask 0.128 g (1.0 mmol) of cadmium oxide, 0.634 mL (2.0 mmol) of oleic acid, and 10 mL of octadecine were added until the solution became clear. It heated to C, and obtained the cadmium oleate metal precursor. The resulting water was then removed by heating in vacuo to 150 ° C. and degassing for 20 minutes.
  • the temperature of the mixed solution was raised to 300 ° C. and 2 mL of 1 M selenium solution (TOPSe) was injected. After the growth step to adjust the temperature to 280 °C and proceeded for 12 minutes to obtain a CdSe core quantum dot.
  • TOPSe 1 M selenium solution
  • 0.1 g of the CdSe Core QD obtained above is dissolved in 10 mL of ODE. After raising the temperature of the reaction vessel to 200 ° C. under vacuum, the temperature is increased to 280 ° C. after N2 purging. Mix 1 mmol of zinc stearate with 1 mL of the prepared TOP-S and dilute by adding 5 mL of TOP (referred to as Zn-S precursor solution). The Zn-S precursor solution is slowly dropped into the CdSe core QD / ODE solution using a syringe pump. After the reaction for 3 hours to lower the temperature of the reaction vessel to room temperature, EtOH is added to the container in excess, the quantum dots are precipitated, and the particles are recovered at 15,000rpm using a centrifuge.
  • Se and S were dissolved in tri-n-octylphosphine, respectively, to prepare a 1M selenium solution (TOP-Se) and 1M sulfur (TOP-S) solution, which is a chalcogenide standard solution for red quantum dot synthesis.
  • TOP-Se 1M selenium solution
  • TOP-S 1M sulfur
  • 0.128 g (1.0 mmol) of cadmium oxide, 0.878 g (4.0 mmol) of zinc acetate, 5.7 g (20.0 mmol) of stearic acid, 10 ml of 2.7 g (10 mmol) oleylamine octadecine was added and heated to 180 ° C.
  • the surface-treated quantum dots show low luminescence, but as shown in (b) it can be observed that the surface-treated quantum dots maintained a high luminescence properties.
  • surface treatment refers to a quantum dot stock solution obtained by synthesis
  • after surface treatment refers to a case of quantum dots substituted with surface metal by Cd obtained through Cd-alkyl acid.
  • the luminescence is increased by more than 10% after the surface treatment, while under room light means that the camera was photographed under a fluorescent lamp.
  • the inorganic shell coating (simple and stable) to the surface of the quantum dot is made to be affected by the external environment Therefore, it is possible to have excellent chemical resistance and heat resistance, and to have a thickness that does not affect the luminescence of a buffer-type inorganic layer formed on the outermost of the quantum dots.

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

Abstract

La présente invention concerne : un procédé de traitement de surface de boîtes quantiques pour leur conférer une résistance chimique par soumission des ions métalliques présents sur la surface des boîtes quantiques à une réaction d'échange de cations et les soumettre ainsi à un échange d'emplacement avec des ions métalliques d'un autre type qui étaient précédemment présents à l'extérieur des boîtes quantiques ; et des boîtes quantiques produites par ledit procédé. La présente invention est conçue de façon qu'un revêtement de coque inorganique soit constitué sur la surface des boîtes quantiques de manière simple mais également stable, et de façon que les effets de l'environnement extérieur ne soient pas subis, et, par conséquent, que l'invention présente une excellente résistance chimique et résistance à la chaleur, et qu'une couche inorganique, ayant la nature d'un tampon, formée sur la coque la plus extérieure de la boîte quantique, puisse avoir une épaisseur qui n'affecte pas les propriétés électroluminescentes.
PCT/KR2016/009160 2015-08-21 2016-08-19 Procédé de traitement de surface des boîtes quantiques pour leur conférer une résistance chimique, et boîtes quantiques ainsi produites WO2017034228A1 (fr)

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Cited By (2)

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US20190157517A1 (en) * 2017-11-20 2019-05-23 eLux Inc. METHOD FOR FABRICATING QUANTUM DOT LIGHT EMITTING DIODES (LEDs) WITH SUPPRESSED PHOTOBRIGHTING
WO2022206873A1 (fr) * 2021-04-02 2022-10-06 纳晶科技股份有限公司 Composition nanocristalline, procédé de préparation associé et application correspondante

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KR102711311B1 (ko) 2019-04-18 2024-09-26 삼성전자주식회사 리튬 함유 무카드뮴 양자점, 그 제조 방법, 및 이를 포함하는 전자 소자
CN112680211A (zh) 2019-10-17 2021-04-20 三星电子株式会社 芯壳量子点、其制造方法、量子点群、量子点复合物、量子点组合物和显示器件
CN112680210A (zh) 2019-10-17 2021-04-20 三星电子株式会社 芯壳量子点、其制造方法、包括其的量子点复合物、量子点组合物、显示器件和电子器件
WO2021216941A2 (fr) * 2020-04-24 2021-10-28 The Government Of The United States Of America, As Represented By The Secretary Of The Navy Nanocristaux noyau/enveloppe de cu2-xs/pbs

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190157517A1 (en) * 2017-11-20 2019-05-23 eLux Inc. METHOD FOR FABRICATING QUANTUM DOT LIGHT EMITTING DIODES (LEDs) WITH SUPPRESSED PHOTOBRIGHTING
US10403798B2 (en) * 2017-11-20 2019-09-03 eLux, Inc. Method for fabricating quantum dot light emitting diodes (LEDs) with suppressed photobrighting
WO2022206873A1 (fr) * 2021-04-02 2022-10-06 纳晶科技股份有限公司 Composition nanocristalline, procédé de préparation associé et application correspondante
CN115181561A (zh) * 2021-04-02 2022-10-14 纳晶科技股份有限公司 纳米晶组合物及其制备方法和应用

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