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WO2018135434A1 - Point quantique colloïdal exempt de cd capable d'émettre une fluorescence visible, et son procédé de production - Google Patents

Point quantique colloïdal exempt de cd capable d'émettre une fluorescence visible, et son procédé de production Download PDF

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Publication number
WO2018135434A1
WO2018135434A1 PCT/JP2018/000807 JP2018000807W WO2018135434A1 WO 2018135434 A1 WO2018135434 A1 WO 2018135434A1 JP 2018000807 W JP2018000807 W JP 2018000807W WO 2018135434 A1 WO2018135434 A1 WO 2018135434A1
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colloidal quantum
liquid
raw material
temperature
quantum dots
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PCT/JP2018/000807
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Japanese (ja)
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孝久 小俣
宇野　貴博
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三菱マテリアル株式会社
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Priority claimed from JP2017248935A external-priority patent/JP2018115315A/ja
Application filed by 三菱マテリアル株式会社 filed Critical 三菱マテリアル株式会社
Priority to CN201880007299.XA priority Critical patent/CN110199006A/zh
Priority to KR1020197023225A priority patent/KR20190104583A/ko
Priority to US16/478,208 priority patent/US20190367810A1/en
Priority to EP18741280.4A priority patent/EP3572482A4/fr
Publication of WO2018135434A1 publication Critical patent/WO2018135434A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—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
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/56—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
    • C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
    • C09K11/621—Chalcogenides
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/851—Wavelength conversion means
    • H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
    • H10H20/8512—Wavelength conversion materials

Definitions

  • the present invention relates to a colloidal quantum dot that emits visible fluorescence, which is a kind of photoluminescent material, and a method for producing the same. More specifically, a colloidal quantum dot that does not contain Cd and emits visible fluorescence having emission wavelength controllability (particle size controllability), full width at half maximum (FWHM) of emission spectrum, and Stokes shift equivalent to that of a CdSe-based colloidal quantum dot, and its It relates to a manufacturing method. In particular, the present invention relates to a colloidal quantum dot not containing Cd that emits green or red visible fluorescence equivalent to a CdSe-based colloidal quantum dot and a method for producing the same.
  • This international application includes Japanese Patent Application No.
  • Japanese Patent Application No. 2017-6353 filed on January 18, 2017
  • Japanese Patent Application No. 248935 Japanese Patent Application No. 248935
  • December 26, 2017. No. 2017-248935 Japanese Patent Application No. 2017-248935
  • the optical filter is used to extract the light of the necessary wavelength from the light emission of the phosphor, to improve the color purity, and to achieve good chromaticity, but the optical filter reduces the light transmittance Therefore, the excitation energy must be increased, resulting in a significant reduction in efficiency.
  • One solution to this problem is to use a material that has a sharp emission spectrum, such as a colloidal quantum dot, and that can freely control the emission wavelength by particle size control using the quantum size effect. Can achieve chromaticity.
  • a material that has a sharp emission spectrum such as a colloidal quantum dot
  • a product using a blue LED as a backlight and a colloidal quantum dot phosphor that emits light when excited is commercially available.
  • Non-Patent Document 1 and Non-Patent Document 2 disclose colloidal quantum dots that do not contain Cd that emit green light or red light.
  • Non-Patent Document 1 discloses that a stable InP / ZnS core-shell colloidal quantum dot having high luminescence was developed by adding zinc acetate and dodecanethiol to an InP core solution step by step, and that zinc acetate is on the surface. It has been reported to play an important role in etching and ZnS shell formation.
  • Non-patent document 2 describes the origin of the photoluminescence (PL) particle size dependence of CuInS 2 —ZnS alloy / ZnS core-shell colloidal quantum dots (ternary compound semiconductors) and the effect of thin coating of ZnS on PL characteristics. Has been reported.
  • PL photoluminescence
  • the InP colloidal quantum dots shown in Non-Patent Document 1 have a light emission wavelength that varies greatly due to a slight difference in particle size, particularly in the region shorter than green, so that the particle size can be precisely controlled. Otherwise, it will not be a colloidal quantum dot with good chromaticity, and secondly, it has a large Stokes shift, so there is a large energy loss, and thirdly, the phosphide used as a synthetic raw material is very reactive and dangerous. There is a problem such as.
  • Non-Patent Document 2 the ternary compound semiconductor colloidal quantum dots represented by CuInS 2 shown in Non-Patent Document 2 have a wide solid solution region where a plurality of compounds exist, and synthesize compounds according to the chemical composition.
  • the technology is extremely difficult, and electron-hole recombination is via a defect level.
  • the emission spectrum is broad and the color purity is inferior.
  • a large Stokes shift There is a problem that energy loss is large and green light emission is difficult to realize.
  • the object of the present invention is to solve the above-mentioned problems and to emit Cd that emits visible fluorescence having emission wavelength controllability (particle size controllability), emission spectrum full width at half maximum (FWHM), and Stokes shift equivalent to those of CdSe-based colloidal quantum dots. It is providing the colloidal quantum dot which does not contain and its manufacturing method.
  • an object of the present invention is to provide a colloidal quantum dot not containing Cd that emits green or red visible fluorescence equivalent to that of a CdSe-based colloidal quantum dot and a method for producing the same.
  • the present inventors paid attention to ZnS, ZnSe, and ZnTe as II-VI compound semiconductors not containing Cd.
  • the band gaps in these bulk bodies are 3.83 eV, 2.72 eV, and 2.25 eV, respectively (both of zinc blende type crystals), and the colloidal quantum dots of ZnS and ZnSe emit light in the green or red region. While it is not possible to realize a possible band gap, ZnTe colloidal quantum dots can emit light in the blue-green region using the quantum size effect, but even if the particle size is greatly changed in the green region The change in the emission wavelength remains small, and the controllability of the emission wavelength in the green region is poor.
  • the band gap is as small as 2.03 eV.
  • the present inventors consider that such band gap bowing is realized also in colloidal quantum dots, and by combining the quantum size effect and band gap bowing, the band gap in the green or red region is realized, The invention has been reached.
  • a first aspect of the present invention is a core particle that is coated with a shell made of a compound semiconductor and forms the core of the shell, and emits visible fluorescence when irradiated with excitation light having a wavelength in the near ultraviolet region or blue region. It is a colloidal quantum dot that does not contain emitted Cd.
  • This colloidal quantum dot is represented by the chemical formula A (B1 1-x , B2 x ) (where 0 ⁇ x ⁇ 1), Zn as a group II element at the A site, and Te as a group VI element at the B1 site.
  • the B2 site has Se or S as a group VI element, and has an average particle size of 1 nm or more and 10 nm or less.
  • the second aspect of the present invention is a colloidal quantum dot that is based on the first aspect and does not include Cd in which the B2 site is Se and the visible fluorescence is green light.
  • a third aspect of the present invention is a colloidal quantum dot which is an invention based on the first aspect, wherein the B2 site is S and the visible fluorescence is red light and does not contain Cd.
  • a fourth aspect of the present invention is a first mixed liquid prepared by mixing a Zn raw material liquid, a Te raw material liquid, and a Se raw material liquid, or a second mixed liquid prepared by mixing a capping agent and a diluent. Any one of the above liquids is heated to a temperature of 200 ° C. to 350 ° C., a predetermined amount of the other liquid is injected into the heated one liquid in a non-oxidizing atmosphere, and the other liquid is injected into the one liquid.
  • This is a method for producing a colloidal quantum dot that does not contain Cd whose visible fluorescence is green light by adjusting the temperature of the liquid injected to 200 ° C. to 350 ° C. and holding it for 1 minute to 5 hours.
  • a fifth aspect of the present invention is a third mixed solution prepared by mixing a Zn raw material solution and a Te raw material solution or a fourth mixed solution prepared by mixing an S raw material solution, a capping agent, and a diluent. Any one of the above liquids is heated to a temperature of 200 ° C. to 350 ° C., a predetermined amount of the other liquid is injected into the heated one liquid in a non-oxidizing atmosphere, and the other liquid is injected into the one liquid.
  • This is a method for producing a colloidal quantum dot that does not contain Cd whose visible fluorescence is red light by adjusting the temperature of the solution injected at 200 ° C. to 350 ° C. and holding it for 1 minute to 5 hours.
  • the InP-based colloidal shown in Non-Patent Document 1 when irradiated with excitation light having a wavelength in the near-ultraviolet region or blue region, the InP-based colloidal shown in Non-Patent Document 1
  • the characteristics equivalent to those of the CdSe-based colloidal quantum dots can be realized, exceeding the characteristics of the quantum dots and the colloidal quantum dots of the ternary compound semiconductor shown in Non-Patent Document 2.
  • the influence of the difference in particle size on the change in the emission wavelength becomes small, the emission wavelength can be precisely controlled, and good chromaticity is realized.
  • the full width at half maximum (FWHM) of the emission spectrum is narrowed, and the color purity is improved.
  • the Stokes shift is reduced and energy loss is reduced. In all items, the characteristics are improved to the same level as the CdSe colloidal quantum dots.
  • the B2 site is changed to Se to form a Zn (Te 1-x , Se x ) colloidal quantum dot, whereby the visible fluorescence is changed to green.
  • the visible fluorescence is changed to red by changing the B2 site to S and forming a Zn (Te 1-x , S x ) colloidal quantum dot.
  • the first mixed liquid obtained by mixing the raw material liquids of Zn, Te, and Se and the second mixed liquid obtained by mixing the capping agent and the diluent are mixed together. Since the elements (Zn, Te, Se) are collectively prepared, the molar composition ratio of the colloidal quantum dots can be easily controlled by the molar charge ratio. In addition, since the lower temperature liquid is injected into one higher temperature liquid, the temperature after injection can be greatly changed (decreased), the separation between nucleation and growth is improved, and the colloidal is highly uniform. Since quantum dots are obtained and the grown nuclei are kept at a constant temperature, the particle size can be easily controlled with time, and as a result, colloidal quantum dots containing no Cd whose visible fluorescence is green light are obtained.
  • the third mixed solution obtained by mixing the respective raw material solutions of Zn and Te, and the fourth mixed solution obtained by mixing the S raw material solution, the capping agent, and the diluent are used. Since the lower temperature of the liquid is injected into the higher temperature of the liquid, the post-injection temperature can be greatly changed (decreased), the separation between nucleation and growth is improved, and colloidal quantum dots with high uniformity Furthermore, since the grown nuclei are kept at a constant temperature, the particle size can be easily controlled by time, and as a result, a colloidal quantum dot containing no Cd whose visible fluorescence is red light is obtained.
  • FIG. 4 is a diagram showing a simulation result of a band gap with respect to a Se molar composition ratio x Se in a Zn (Te 1-x , Se x ) colloidal quantum dot having a particle diameter of 2 to 10 nm.
  • Molar ratio x Se of Se is a diagram showing a simulation of the band gap results for the particle size in the Zn (Te 1-x, Se x) colloidal quantum dot when the 0.35.
  • FIG. 4 is a diagram showing a simulation result of a band gap with respect to a molar composition ratio x S of S in a Zn (Te 1-x , S x ) colloidal quantum dot having a particle diameter of 2 to 10 nm. It is a figure which shows the simulation result of the band gap with respect to the particle size in Zn (Te1 -x , Sx ) colloidal quantum dot when the molar composition ratio xS of S is 0.35.
  • Non-Patent Documents 4 and 5 report calculations for theoretically predicting the particle size dependence of the optical gap of colloidal quantum dots. Among them, effective mass approximation calculation that can obtain the same result as other methods by simple notation is convenient.
  • the Schrödinger equation for particles (mass: m) in potential: V (r) is expressed by the following equation (1).
  • a relational expression between the particle size and the optical gap is derived by a model assuming an effective mass approximation in a well-type potential of a finite depth.
  • the confinement potential is expressed as the following equation (2) as a central symmetry V (r) at a finite depth.
  • V (r) the radius of the spherical colloidal quantum dot is r 0 .
  • V 0 is defined as the following equation (3).
  • ⁇ E HOMO-LUMO is the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the surfactant coordinated as a capping agent on the surface of the colloidal quantum dot.
  • Energy difference ⁇ E HOMO-LUMO of oleic acid used as the surfactant is a value obtained by measuring the light absorption spectrum: 4.35 eV.
  • ZnTe, ZnSe, the band gap of the bulk of the ZnS: E g and electron-hole effective mass: m e * / m 0, m h * / m 0 is used the values shown in the following Table 1 .
  • the band gap: E is the band gap of the bulk body of ZnTe, ZnSe, ZnS: E g and the effective mass of electrons / holes: me * / m 0 , M h * / m 0 .
  • the band gap in the mixed crystal bulk body is calculated using the following equations (4) and (5) expressed using the bowing parameter (b).
  • the electron-hole effective mass m e * / m 0, m h * / the additive property assuming the m 0, calculating the relationship between the band gap and the particle size-molar ratio of the colloidal quantum dots is doing.
  • the additivity of the effective mass of electrons of Zn (Te 1-x , Se x ) is expressed by the following formula (6).
  • FIG. 2 shows a simulation result of the band gap with respect to the particle diameter in the Zn (Te 1-x , Se x ) colloidal quantum dot when the Se molar composition ratio x Se is 0.35.
  • the band portion indicates the green light emitting region.
  • FIG. 3 shows the simulation results of the band gap with respect to the molar composition ratio x S of S in Zn (Te 1-x , S x ) colloidal quantum dots having a particle diameter of 2 to 10 nm.
  • FIG. 4 shows a simulation result of the band gap with respect to the particle diameter in a Zn (Te 1-x , S x ) colloidal quantum dot when the molar composition ratio x S of S is 0.35.
  • a band portion indicates a red light emitting region. Taking into account the Stokes shift, which is typically 100 meV, red light is emitted from Zn (Te 1-x , S x ) colloidal quantum dots that do not contain Cd by adjusting the molar composition ratio x S of S and the particle size. Can be realized.
  • the colloidal quantum dot of this embodiment is a core particle that is coated with a shell made of a compound semiconductor and forms the core of the shell, and emits visible fluorescence when irradiated with excitation light having a wavelength in the near ultraviolet region or blue region. It is a colloidal quantum dot that does not contain emitted Cd.
  • This colloidal quantum dot is represented by the chemical formula A (B1 1-x , B2 x ) (where 0 ⁇ x ⁇ 1), Zn as a group II element at the A site, and Te as a group VI element at the B1 site.
  • the B2 site has Se or S as a group VI element, and has an average particle size of 1 nm or more and 10 nm or less.
  • the average particle size is less than 1 nm, it is difficult to control the particle size, and if it exceeds 10 nm, it takes a very long time for grain growth, resulting in poor production efficiency, widening the particle size distribution, and color. Purity deteriorates.
  • isoelectronic trap is obtained by adding a small amount of an element (Se) having the same electron configuration as an element constituting a compound semiconductor (for example, Zn and Te) and substituting a lattice point, This means that electrons or holes are attracted and become bound due to the difference in electron affinity.
  • the light emission mechanism by the isoelectronic trap can be explained by using a coordinate coordinate model indicating the relationship between the lattice displacement and the energy.
  • the excitons in the excited state are trapped in the pit of the excited state potential created by being bound. By entering the depression, the difference from the ground state potential is reduced. Therefore, the transition between the level of the dent and the ground state results in light emission with energy smaller than the band gap of the original compound semiconductor (ZnTe).
  • a method for producing a colloidal quantum dot of the present invention as a first embodiment, a method for producing a Zn (Te 1-x , Se x ) colloidal quantum dot whose visible fluorescence is green light is described as a second embodiment.
  • the manufacturing method of Zn (Te1 -x , Sx ) colloidal quantum dot whose visible fluorescence is red light is each explained in full detail.
  • the method for producing a colloidal quantum dot that emits green light is prepared by mixing a liquid prepared by mixing a Zn raw material liquid, a Te raw material liquid, and a Se raw material liquid, or a capping agent and a diluent.
  • One of the two liquids is heated to a temperature of 200 ° C. to 350 ° C., and a predetermined amount of the other liquid is injected into the heated one liquid in a non-oxidizing atmosphere.
  • the liquid into which the other liquid was injected was adjusted to a temperature of 200 ° C. to 350 ° C. and held for 1 minute to 5 hours, thereby producing a colloidal quantum dot containing no Cd whose visible fluorescence is green light. is there.
  • An example of the manufacturing method of the first embodiment is as follows: (a) a step of mixing a Zn raw material liquid, a Te raw material liquid, and a Se raw material liquid to prepare a first mixed liquid; and (b) sealing. (C) adjusting the temperature of the second mixed liquid to 200 ° C. to 350 ° C., and adding the capping agent and diluent to the container and mixing them; In a non-oxidizing atmosphere, a step of injecting a predetermined amount of the first mixture into the second mixture; and (d) a temperature of the solution obtained by injecting the first mixture into the second mixture is 200. And a step of adjusting to a temperature of from 350 to 350 ° C. and holding for 1 minute to 5 hours.
  • the reason why the temperature of the second mixed solution is adjusted to 200 ° C. to 350 ° C. is that if it is less than 200 ° C., rapid nucleation does not occur and the particle size distribution becomes wide, and if it exceeds 350 ° C., This is because volatilization of the organic solvent occurs preferentially and hinders the production of colloidal quantum dots.
  • the adjustment temperature of the second liquid mixture is preferably 250 ° C. to 310 ° C.
  • the temperature of the liquid obtained by injecting the first mixed liquid into the second mixed liquid is set to 200 ° C. to 350 ° C. If the temperature is lower than 200 ° C., the growth rate of the colloid becomes very slow, and the particle size can be controlled by time.
  • a preferred holding temperature is 230 ° C to 300 ° C.
  • the retention time of the liquid obtained by injecting the first mixed liquid into the second mixed liquid is set to 1 minute to 5 hours because the raw material is hardly consumed and the yield is greatly reduced if it is less than 1 minute. Yes, if it exceeds 5 hours, the productivity is poor, and the cost of power consumed during heating during growth greatly increases.
  • the preferred holding time is 10 minutes to 60 minutes.
  • Zn raw material solution liquid diethylzinc (DEZ) or powdered zinc stearate (Zn (St) 2 ) or the like as a Zn source is placed in a container substituted with an inert gas, and trioctylphosphine is added thereto.
  • Organic solvents such as (TOP), octadecene (ODE), acetic acid, oleic acid (OA), stearic acid, hexadecylamine (HDA), oleylamine (OLA), trioctylamine (TOA), tributylphosphonic acid (TBPA) It is prepared by adding a complexing agent) and heating.
  • the organic solvent is not limited to the organic solvents described above as long as the organic solvent forms a complex with Zn ions.
  • the container containing the mixed solution of Zn raw material is heated with an oil bath or the like.
  • the temperature heated in the oil bath is 20 ° C. to 350 ° C., and the holding time at the heated temperature is 5 minutes to 5 hours.
  • the heating temperature is less than 20 ° C. or the holding time is less than 5 minutes, the Zn source is not sufficiently dissolved in the organic solvent (complexing agent), and an undissolved portion of the Zn source is likely to be generated.
  • Te raw material liquid is filled with powdered metal tellurium (Te) as a Te source, powdered tellurium oxide or an available inexpensive and safe organic tellurium compound in a container substituted with an inert gas.
  • Te powdered metal tellurium
  • the same organic solvent (complex forming agent) as used for the preparation of the Zn raw material solution is added and heated.
  • the organic solvent is not limited to the organic solvents described above as long as the organic solvent forms a complex with Te ions.
  • the container containing the Te raw material mixture is heated in an oil bath or the like. The temperature at which the oil bath is heated is 100 ° C. to 350 ° C., and the holding time at the heated temperature is 5 minutes to 5 hours.
  • the Te source When the heating temperature is less than 100 ° C. or the holding time is less than 5 minutes, the Te source is not sufficiently dissolved in the organic solvent (complexing agent), and an undissolved portion of the Te source is likely to be generated. On the other hand, when the heating temperature exceeds 350 ° C., volatilization of the organic solvent (complex forming agent) occurs preferentially, which hinders dissolution of the Te source. When the holding time exceeds 5 hours, the Te source has sufficiently reached dissolution equilibrium, and wasteful power consumption due to heating occurs.
  • the Se raw material liquid is filled with powdered metal selenium (Se) as a Se source, powdered selenium oxide or an available inexpensive and safe organic selenium compound in a container substituted with an inert gas.
  • the same organic solvent (complex forming agent) as used for the preparation of the Zn raw material solution is added and heated. Note that the organic solvent is not limited to the organic solvents described above as long as the organic solvent forms a complex with Se ions.
  • the container containing the Se raw material mixture is heated in an oil bath or the like. The temperature heated in the oil bath is 20 ° C. to 350 ° C., and the holding time at the heated temperature is 5 minutes to 5 hours.
  • the Se source When the heating temperature is less than 20 ° C. or the holding time is less than 5 minutes, the Se source is not sufficiently dissolved in the organic solvent (complexing agent), and the Se source is not easily dissolved. On the other hand, if the heating temperature exceeds 350 ° C., the organic solvent (complexing agent) volatilizes preferentially, which hinders dissolution of the Se source. When the holding time exceeds 5 hours, the Se source has sufficiently reached dissolution equilibrium, and wasteful power consumption due to heating occurs. 1 to 10 mol of an organic solvent (complexing agent) is added to 1 mol of Se source. When the Se raw material is dissolved, the mixed solution becomes transparent.
  • preparation of Se raw material liquid is not limited to said preparation conditions, Conditions can be adjusted according to the combination with the solvent for complex formation to be used.
  • the first mixed liquid is a mixture of a Zn raw material liquid, a Te raw material liquid, and a Se raw material liquid in a container substituted with an inert gas so as to have a predetermined molar composition ratio. Prepared with stirring.
  • the second mixed liquid is a mixture of a capping agent and a diluent in a container, and after performing a degassing process of “120 ° C. ⁇ 30 minutes” in a vacuum while stirring, it is returned to atmospheric pressure with an inert gas, It is prepared by raising the temperature to 200 ° C. to 350 ° C. using a mantle heater or the like while ventilating an inert gas.
  • Examples of the capping agent include trioctylphosphine (TOP), oleic acid (OA), stearic acid, hexadecylamine (HDA), oleylamine (OLA), tributylphosphonic acid (TBPA), trioctylphosphine oxide (TOPO) and the like. It is done.
  • Examples of the diluent include trioctylphosphine (TOP), octadecene (ODE), oleylamine (OLA), hexadecylamine (HDA), and trioctylphosphine oxide (TOPO). Add 1-5 mol of diluent to 1 mol of capping agent.
  • the first mixed liquid room temperature
  • the injection is performed at a pushing speed of 1 to 20 mL / second using a syringe having an inner diameter of 10 mm.
  • the liquid mixture of Zn raw material liquid, Te raw material liquid, and Se raw material liquid is prepared.
  • a mixing method such as nozzle mixing or ejector mixing may be employed using an inert compressed gas depending on the scale of mixing.
  • the reason why the temperature of the second mixed solution is adjusted to 200 ° C. to 350 ° C. is that if it is less than 200 ° C., rapid nucleation does not occur and the particle size distribution becomes wide, and if it exceeds 350 ° C., This is because volatilization of the organic solvent occurs preferentially and hinders the nucleation of colloidal quantum dots.
  • the average particle size of the obtained colloidal quantum dots can be made constant.
  • the Se molar composition ratio x Se is fixed at around 0.30
  • the temperature of the second mixed solution, the temperature of the solution after the first mixed solution is injected into the second mixed solution, and the holding time are adjusted.
  • the average particle size of the colloidal quantum dots can be adjusted in the range of 3.0 to 7.0 nm.
  • the band gap of the colloidal quantum dots changes due to the quantum size effect, and green light emission (2.15 to 2.45 eV) is realized in the region where the average particle size is 3.0 to 7.0 nm.
  • the method for producing a colloidal quantum dot emitting red light according to the second embodiment is prepared by mixing a Zn raw material liquid and a Te raw material liquid or a S raw material liquid, a capping agent, and a diluent.
  • One of the two liquids is heated to a temperature of 200 ° C. to 350 ° C., and a predetermined amount of the other liquid is injected into the heated one liquid in a non-oxidizing atmosphere.
  • the liquid into which the other liquid was injected was adjusted to a temperature of 200 ° C. to 350 ° C. and held for 1 minute to 5 hours to produce a colloidal quantum dot containing no Cd whose visible fluorescence is red light. is there.
  • C) adjusting the temperature of the fourth mixture to 200 ° C. to 350 ° C., and non-oxidizing the inside of the sealed container A step of injecting a predetermined amount of the third mixed liquid into the fourth mixed liquid in a neutral atmosphere; and (d) the temperature of the liquid injected with the third mixed liquid into the fourth mixed liquid is 200 ° C. to Adjusting to 350 ° C. and holding for 1 minute to 5 hours.
  • the reason why the temperature of the fourth mixed liquid is adjusted to 200 ° C. to 350 ° C.
  • the adjustment temperature of the fourth mixed solution is preferably 260 ° C. to 320 ° C.
  • the temperature of the liquid obtained by injecting the third mixed liquid into the fourth mixed liquid is set to 200 ° C. to 350 ° C. If the temperature is lower than 200 ° C., the growth rate of the colloidal quantum dots becomes very slow.
  • a preferred holding temperature is 240 ° C to 310 ° C.
  • the retention time of the liquid obtained by injecting the third mixed liquid into the fourth mixed liquid is set to 1 minute to 5 hours because the raw material is hardly consumed and the yield is greatly reduced if it is less than 1 minute. Yes, if it exceeds 5 hours, the productivity is poor, and the cost of power consumed during heating during growth greatly increases.
  • the preferred holding time is 10 minutes to 3 hours.
  • the Zn raw material liquid is prepared in the same manner as the Zn raw material liquid used in the above-described method for producing Zn (Te 1-x , Se x ) colloidal quantum dots. 1 to 16 mol of an organic solvent (complexing agent) is added to 1 mol of Zn source. When the Zn raw material is dissolved, the mixed solution becomes transparent.
  • preparation of Zn raw material liquid is not limited to said preparation conditions, Conditions can be adjusted according to the combination with the solvent for complex formation to be used.
  • Te raw material liquid is prepared in the same manner as the Te raw material liquid used in the above-described method for producing Zn (Te 1-x , Se x ) colloidal quantum dots.
  • the S raw material liquid is filled with powdered sulfur (S) as an S source or an available inexpensive and safe organic sulfur compound in a container substituted with an inert gas. It is prepared by adding the same organic solvent (complexing agent) as used and heating. Note that the organic solvent is not limited to the organic solvents described above as long as the organic solvent forms a complex with S ions.
  • the container containing the mixed solution of the S raw material is heated with an oil bath or the like. The temperature heated in the oil bath is 20 ° C. to 350 ° C., and the holding time at the heated temperature is 5 minutes to 5 hours. When the heating temperature is less than 20 ° C.
  • the S source is not sufficiently dissolved in the organic solvent (complexing agent), and an undissolved portion of the S source is likely to be generated.
  • the heating temperature exceeds 350 ° C.
  • the volatilization of the organic solvent (complexing agent) occurs preferentially, which hinders dissolution of the S source.
  • the holding time exceeds 5 hours, the S source has sufficiently reached dissolution equilibrium, and wasteful power consumption due to heating occurs. 1 to 10 mol of an organic solvent (complexing agent) is added to 1 mol of the S source.
  • the mixed solution becomes transparent.
  • preparation of S raw material liquid is not limited to said preparation conditions, Conditions can be adjusted according to the combination with the solvent for complex formation to be used.
  • the third liquid mixture is prepared by mixing the Zn raw material liquid and the Te raw material liquid so as to have a predetermined molar composition ratio in a container substituted with an inert gas, and stirring the mixture while venting the inert gas at room temperature. Is done.
  • the fourth mixed liquid is a mixture of S raw material liquid, capping agent and diluent in a container, and after deaeration treatment at 120 ° C. for 30 minutes in vacuum with stirring, a large amount of inert gas is used.
  • the pressure is adjusted to 200 ° C. to 350 ° C. using a mantle heater or the like while returning to atmospheric pressure and passing an inert gas.
  • Examples of the capping agent include trioctylphosphine (TOP), oleic acid (OA), stearic acid, hexadecylamine (HDA), oleylamine (OLA), tributylphosphonic acid (TBPA), trioctylphosphine oxide (TOPO) and the like. It is done.
  • Examples of the diluent include trioctylphosphine (TOP), octadecene (ODE), oleylamine (OLA), hexadecylamine (HDA), and trioctylphosphine oxide (TOPO). Add 5-30 mol of capping agent and 1-30 mol of diluent to 1 mol of S source.
  • the 3rd liquid mixture (room temperature) is injected into the 4th liquid mixture at once using a syringe or the like, and colloidal quantum dots Generate nuclei.
  • the injection is performed at a pushing speed of 1 to 20 mL / second using a syringe having an inner diameter of 10 mm.
  • nuclei are formed over time, and the particle size distribution becomes wide. At high speeds above the upper limit, the injection operation becomes technically difficult.
  • a synthetic liquid is prepared by mixing the Zn raw material liquid, the Te raw material liquid, and the S raw material liquid.
  • a mixing method such as nozzle mixing or ejector mixing may be employed using an inert compressed gas depending on the scale of mixing.
  • the reason why the temperature of the fourth mixed liquid is adjusted to 200 ° C. to 350 ° C. is that if it is less than 200 ° C., rapid nucleation does not occur and the particle size distribution becomes wide, and if it exceeds 350 ° C., This is because volatilization of the organic solvent occurs preferentially and hinders the production of colloidal quantum dots.
  • the average particle diameter of the obtained colloidal quantum dot can be made constant.
  • the band gap of the colloidal quantum dots changes due to the quantum size effect, and red light emission (1.80 to 2.10 eV). ) Is realized.
  • the raw materials used in the examples and comparative examples of the present invention are as follows. ⁇ raw materials ⁇ The following reagents were prepared. All reagents were not purified and were used commercially. (1) Diethyl zinc (DEZ, ⁇ 52wt% Zn basis, Aldrich), (2) Selenium powder (Se, 100mesh, 99.99%, trace metal basis, Aldrich), (3) Tellurium powder (Te, 100mesh, 99.99% trace metal basis, Aldrich), (4) Tri-n-octylphosphine (TOP, ⁇ 96.0%, Wako Pure Chemical Industries), (5) oleylamine (OLA,> 98%, Aldrich), (6) Oleic acid (OA, 99%, Aldrich), (7) 1-octadecene (ODE,> 90%, Tokyo Kasei), (8) 1-dodecanethiol (DDT,> 95%, Tokyo Kasei), (9) Hexane (> 96%, Wako Pure Chemical) (
  • Example 1 [Synthesis of Zn (Te 1-x , Se x ) colloidal quantum dots]
  • a series of operations from the weighing of the reagent to the end of the synthesis were performed mainly in a glove box filled with nitrogen gas. Operation outside some glove boxes was performed in a sealed container filled with nitrogen gas so that the solution did not come into contact with the atmosphere.
  • Te powder 1.9142 g (15 mmol) and TOP: 50 mL were weighed into a three-necked flask and heated to 250 ° C. while bubbling argon gas, and stirred until the Te powder was completely dissolved and became a yellow transparent color. After dissolution, the mixture was allowed to cool to room temperature to obtain a Te raw material liquid. Further, Se powder: 1.1845 g (15 mmol) and TOP: 50 mL were weighed in a vial and put into an ultrasonic cleaner to completely dissolve Se powder to obtain a colorless and transparent Se raw material liquid.
  • Zn raw material liquid, Te raw material liquid, and Se raw material liquid can also be prepared separately
  • DEZ is in a liquid state, and here, TOP and DEZ are mixed and dissolved in Te raw material liquid and Se raw material liquid, It was set as the 1st liquid mixture.
  • the said 1st liquid mixture was rapidly inject
  • the colloidal quantum dots were grown at a temperature of 270 ° C. for 10 minutes, and then allowed to cool to room temperature.
  • the reaction solution was a clear solution without turbidity.
  • the temperature of the second liquid mixture is 290 ° C.
  • the growth temperature after the first liquid mixture is injected into the second liquid mixture is 270 ° C.
  • the growth time at that temperature is 10 minutes. This is a condition for adjusting the average particle diameter to 4.0 ⁇ 0.1 nm.
  • the particle size of the colloidal quantum dots can be adjusted. Table 2 below shows this condition.
  • Example 2 to 5 and Comparative Example 1 For Examples 2 to 5 and Comparative Example 1, the same Te raw material liquid, Se raw material liquid, TOP, DEZ and the like as in Example 1 were used. In Examples 2 to 5 and Comparative Example 1, these Te raw material liquid, Se raw material liquid, TOP, DEZ, and the like have a molar composition ratio x Se of colloidal quantum dots as shown in Table 2 above. And adjusting the particle size of the colloidal quantum dots by adjusting the temperature of the second mixed solution, the growth temperature after injecting the first mixed solution into the second mixed solution, and the growth time at that temperature. . Otherwise, in the same manner as in Example 1, Zn (Te 1-x , Se x ) / ZnS core-shell colloidal quantum dots were synthesized.
  • the Se raw material solution 1.5 mL was added to a 10 mL vial containing the Zn raw material solution, and after sufficient stirring, the mixture was immersed in an oil bath heated to 280 ° C. and held for 9 minutes while venting argon gas. Thereafter, the vial was taken out from the oil bath and allowed to cool to room temperature. The reaction solution was light yellow and transparent.
  • Example 2 shows the molar composition ratio x Se of the colloidal quantum dots of Comparative Example 2, the temperature of the second mixed liquid, the growth temperature after the first mixed liquid is injected into the second mixed liquid, and the growth at that temperature. Each time is shown.
  • the second mixed liquid which is the same mixed solution of OA and ODE as in Example 1, was heated to 310 ° C. while agitating and stirring argon gas. After confirming that the temperature of this 2nd liquid mixture was stabilized, the said 1st liquid mixture was rapidly inject
  • Example 7 to 12 For Examples 7 to 12, the same Te raw material liquid, Se raw material liquid, TOP, DEZ and the like as in Example 1 were used. In Examples 7 to 12, these Te raw material liquid, Se raw material liquid, TOP, DEZ, and the like were weighed so that the molar composition ratio of Se of colloidal quantum dots xSe as shown in Table 3 above. The particle size of the colloidal quantum dots was adjusted by adjusting the temperature of the second liquid mixture, the growth temperature after injecting the first liquid mixture into the second liquid mixture, and the growth time at that temperature. Otherwise, in the same manner as in Example 6, Zn (Te 1-x , Se x ) / ZnS core-shell colloidal quantum dots were synthesized.
  • tris (trimethylsilyl) phosphine (P (SiC 3 H 9 ) 3 ): 0.02 mmol was dissolved in ODE (C 18 H 36 ): 3 mL to prepare a P raw material solution.
  • the In raw material liquid was returned to atmospheric pressure with argon gas, and the temperature was raised to 300 ° C. while aerated and stirred with argon gas.
  • the P raw material solution weighed in a predetermined amount with a syringe was quickly injected into the heated In raw material solution, and then immediately cooled to room temperature to prepare an InP core colloidal quantum dot reaction solution.
  • the InP / ZnS core-shell colloidal quantum dot reaction liquid was cooled to room temperature, and isopropanol (C 3 H 8 O): 40 mL was added to the cooled liquid to aggregate the InP / ZnS core-shell colloidal quantum dots.
  • the precipitate recovered by centrifugation was redispersed with an appropriate amount of toluene (C 7 H 8 ), and a series of steps of aggregation with isopropanol, recovery by centrifugation, and redispersion with toluene were repeated several times.
  • the finally obtained precipitate by centrifugation was vacuum-dried at room temperature, and the remaining organic solvent was removed to obtain InP / ZnS core-shell colloidal quantum dots.
  • Zinc-sulfur solution: 2.5 mL, copper solution: 1.25 mL, and In solution: 1.25 mL were weighed and mixed, then heated to 200 ° C. while bubbling argon gas and maintained for 60 seconds.
  • a CuInS 2 —ZnS alloy core colloidal quantum dot reaction solution was prepared.
  • CuInS 2 —ZnS alloy core colloidal quantum dot 2.26 mg was taken out from 1.0 mL of the above CuInS 2 —ZnS alloy core colloidal quantum dot reaction solution.
  • this is used as a capping agent OA (C 18 H 34 O 2 ): 32 ⁇ L of zinc diethyldithiocarbamate concentration: 5.5 mM TOP and ODE mixed solution: Redispersed to 1.5 mL.
  • Se powder 94.8 mg (1.2 mmol) is weighed into a 12 mL screw cap bottle, TOP: 5.0 mL is added, and the powder is easily dissolved by stirring with a tube mixer and ultrasonic waves. A liquid was prepared. This Se raw material liquid was colorless and transparent.
  • the Cd raw material solution 2.0 mL and the Se raw material solution: 1.0 mL were collected and mixed in a 12 mL screw mouth bottle.
  • As a capping agent 150 ⁇ L of octylamine was added. After stirring well with a tube mixer, it was immersed in an oil bath at 280 ° C. and subjected to a heating reaction for a predetermined time until it grew to a particle size emitting green light.
  • Reaction solution About 3.0 mL was divided into test tubes, and 4-fold amount (12.0 mL) of butanol was added for dilution. Next, 2 times the amount of methanol (6.0 mL) was added to the diluted solution to aggregate the quantum dots. Centrifugation was carried out for 15 minutes to separate a colorless and transparent supernatant solution and a bright red precipitate, and the supernatant solution was removed.
  • Zn (st) 2 31.6 mg (0.05 mmol) was weighed into a 12 mL screw mouth bottle, and ODE: 2.0 mL was added. This solution was heated in an oil bath at 140 ° C. for about 10 minutes to melt the powder. When the screw cap bottle was pulled up and cooled to room temperature, the powder re-deposited but was used as it was. S used dodecanethiol as a solvent and S raw material.
  • Example 13 [Synthesis of Zn (Te 1-x , S x ) colloidal quantum dots]
  • a series of operations from the weighing of reagents to the end of synthesis were carried out in a glove box mainly filled with nitrogen gas, as in Example 1. I went there. The operation outside some glove boxes was performed in a sealed container filled with nitrogen gas in the same manner as in Example 1 so that the solution did not come into contact with the atmosphere.
  • Te raw material liquid Te powder: 114.8 mg (0.90 mmol) and TOP: 3.00 mL (6.72 mmol) were weighed into a 10 mL septum vial and heated to 200 ° C. while bubbling argon gas, and the Te powder was completely dissolved. The mixture was stirred until it became a yellow transparent color. After dissolution, the mixture was allowed to cool to room temperature to obtain a Te raw material liquid (0.3M).
  • Diethyl zinc (DEZ) as a raw material liquid 25 ⁇ L (0.25 mmol) was added, and the total volume was adjusted to 2 mL with TOP.
  • DEZ Diethyl zinc
  • the color of the solution changed from yellow transparent to colorless and transparent.
  • a mixed solution obtained by mixing the Zn raw material liquid and the Te raw material liquid was used as a third mixed liquid.
  • the reaction solution was a clear solution without turbidity.
  • the temperature of the fourth mixed solution is set to 300 ° C.
  • the growth temperature after the third mixed solution is injected into the fourth mixed solution is set to 290 ° C.
  • the growth time at that temperature is set to 15 minutes. This is a condition for adjusting the average particle diameter to 6.0 ⁇ 0.1 nm.
  • Example 14 to 17 and Comparative Example 6 For Examples 14 to 17 and Comparative Example 6, the same Te raw material liquid, S raw material liquid, TOP, DEZ and the like as in Example 13 were used. In Examples 14 to 17 and Comparative Example 6, these Te raw material liquid, S raw material liquid, TOP, DEZ, and the like have a molar composition ratio x S of S of colloidal quantum dots as shown in Table 4 above. And adjusting the temperature of the fourth mixed solution, the growth temperature after injecting the third mixed solution into the fourth mixed solution, and the growth time at that temperature to adjust the particle size of the colloidal quantum dots to 6. Adjusted to 0 ⁇ 0.1 nm. Otherwise, in the same manner as in Example 13, a Zn (Te 1-x , S x ) / ZnS core-shell colloidal quantum dot was synthesized.
  • the S powder was completely dissolved in an ultrasonic cleaner to prepare a colorless and transparent S raw material solution.
  • Example 19 to 24 In Examples 19 to 24, these Te raw material liquids, TOP, DEZ, and the like are weighed so that the molar composition ratio x S of S of colloidal quantum dots is as shown in Table 5 above, and the S raw material Is measured so as to have a molar composition ratio x S of S , and the temperature of the fourth mixed solution prepared by adding OA and ODE thereto, the growth temperature after injecting the third mixed solution into the fourth mixed solution, The particle size of the colloidal quantum dots was adjusted by adjusting the growth time at that temperature. Other than that was carried out similarly to Example 18, and the Zn (Te1 -x , Sx ) / ZnS core-shell colloidal quantum dot was synthesize
  • a CuInS 2 —ZnS alloy core colloidal quantum dot reaction liquid was prepared in the same manner as in Comparative Example 4 except that this was maintained for 3 minutes, and then a CuInS 2 —ZnS alloy / ZnS core shell colloidal quantum dot was obtained.
  • the average particle diameter of colloidal quantum dots was calculated by using a powder X-ray diffraction measurement method (XRD: X-ray diffraction). Using an X-ray diffractometer (RINT2500, Rigaku) equipped with a rotating cathode X-ray generation source and a curved monochromator, Cu-K ⁇ rays generated at an X-ray acceleration voltage of 40 kV and current of 375 mA (15 kW) It was measured by irradiating colloidal quantum dots on a reflective quartz plate.
  • XRD powder X-ray diffraction measurement method
  • the average particle diameter d XRD was calculated from the full width at half maximum (FWHM) of the diffraction pattern obtained by XRD using the Scherrer equation shown in the following equation (8).
  • B is the half width [rad] of the diffraction pattern
  • ⁇ is the diffraction angle [rad].
  • 0.9 was used for the Scherrer constant.
  • the average particle diameter d XRD was obtained from the linear approximation by the least square method of the cos ⁇ and 0.9 ⁇ / B plots of the diffraction patterns on the diffraction planes of the (111) plane, the (220) plane, and the (311) plane.
  • d XRD 0.9 ⁇ / Bcos ⁇ (8)
  • the molar feed ratio (x Se ) of Se was adjusted within the range of 0 ⁇ x Se ⁇ 1, Zn
  • the emission energy of the (Te 1-x , Se x ) colloidal quantum dots could be controlled to a desired value in the green region: 2.15 to 2.45 eV.
  • the Se molar charge ratio (x Se ) is in the range of 0.25 to 0.40
  • the Zn (Te 1-x , Se x ) colloidal quantum dot exhibits a minimum emission energy of about 2.3 eV. It was.
  • Table 3 above shows the synthesis conditions of colloidal quantum dots when the average particle size is adjusted by setting the Se molar charge ratio (x Se ) of Zn (Te 1-x , Se x ) to be constant at 0.30. .
  • the Se feed ratio (x Se ) is adjusted to 0.30
  • the temperature of the second mixed solution which is a mixed solution of OA and ODE
  • the first mixing which is a raw material solution
  • the average particle size is adjusted to 3.5 to 6.3 nm.
  • the emission energy of the Te 1-x , Se x ) colloidal quantum dots could be adjusted to the green region: 2.15 to 2.45 eV.
  • the green wavelength required for the color gamut expansion is about 530 nm (2.33 to 2.34 eV).
  • “Compliance” item “Yes” is indicated when conforming, and “None” when not conforming.
  • the colloidal quantum dots of Example 7 were made of InP / ZnS (Comparative Example 3), which is a representative example of colloidal quantum dots that do not contain Cd whose visible fluorescence is green, and ternary compound semiconductors ( When compared with Comparative Example 4), first, the average particle size can be increased, so the emission wavelength controllability is greatly improved, and second, the full width at half maximum (FWHM) of the emission spectrum is sharp. Therefore, the chromaticity better than that of the existing colloidal quantum dots not containing Cd can be realized, and the gamut expansion is expected. Third, the Stokes shift is greatly reduced, and the energy loss is greatly reduced.
  • FWHM full width at half maximum
  • the molar charge ratio (x S ) of S is adjusted in the range of 0 ⁇ x S ⁇ 1, Zn (Te).
  • the emission energy of the 1-x , S x ) colloidal quantum dots could be controlled to a desired value within the red region: 1.80 to 2.10 eV.
  • the Zn (Te 1-x , S x ) colloidal quantum dot exhibits a minimum emission energy of 1.96 eV. It was.
  • Table 5 shows the synthesis conditions for colloidal quantum dots when the average particle size is adjusted with the S molar charge ratio (x S ) of Zn (Te 1-x , S x ) kept constant at 0.35. .
  • the colloidal quantum dots emitting visible fluorescence of the present invention can be used in the fields of displays, illumination, medical images, biosensors, LEDs, and lasers.

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Abstract

L'invention concerne un point quantique colloïdal exempt de Cd qui constitue une particule noyau qui est revêtue d'une enveloppe constituée d'un semi-conducteur composite et qui sert de noyau à l'enveloppe, et qui peut émettre une fluorescence visible suite à son exposition à une lumière excitée présentant une longueur d'onde se situant dans l'ultraviolet proche ou le bleu. Le point quantique colloïdal est représenté par la formule chimique : A(B11-x, B2x) (dans laquelle 0 < x < 1), possède du Zn en tant qu'élément du groupe II dans le site A, du Te en tant qu'élément du groupe VI dans le site B1 et du Se ou du S en tant qu'élément du groupe VI dans le site B2, et présente un diamètre moyen de particule égal à 1 à 10 nm (bornes incluses).
PCT/JP2018/000807 2017-01-18 2018-01-15 Point quantique colloïdal exempt de cd capable d'émettre une fluorescence visible, et son procédé de production WO2018135434A1 (fr)

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CN201880007299.XA CN110199006A (zh) 2017-01-18 2018-01-15 发出可见荧光的不含Cd的胶体量子点及其制造方法
KR1020197023225A KR20190104583A (ko) 2017-01-18 2018-01-15 가시 형광을 발하는 Cd 를 포함하지 않는 콜로이달 양자 도트 및 그 제조 방법
US16/478,208 US20190367810A1 (en) 2017-01-18 2018-01-15 Cd-free colloidal quantum dot capable of emitting visible fluorescence, and method for producing same
EP18741280.4A EP3572482A4 (fr) 2017-01-18 2018-01-15 Point quantique colloïdal exempt de cd capable d'émettre une fluorescence visible, et son procédé de production

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