WO2013035362A1 - Ensemble de nanoparticules semi-conductrices résistantes à l'élution d'ions - Google Patents

Ensemble de nanoparticules semi-conductrices résistantes à l'élution d'ions Download PDF

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Publication number
WO2013035362A1
WO2013035362A1 PCT/JP2012/056871 JP2012056871W WO2013035362A1 WO 2013035362 A1 WO2013035362 A1 WO 2013035362A1 JP 2012056871 W JP2012056871 W JP 2012056871W WO 2013035362 A1 WO2013035362 A1 WO 2013035362A1
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Prior art keywords
core
matrix
semiconductor
surfactant
semiconductor nanoparticles
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PCT/JP2012/056871
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English (en)
Japanese (ja)
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高橋 優
敬三 高野
中野 寧
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コニカミノルタエムジー株式会社
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Priority to JP2013532467A priority Critical patent/JP5880563B2/ja
Publication of WO2013035362A1 publication Critical patent/WO2013035362A1/fr

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881Chalcogenides
    • C09K11/883Chalcogenides with zinc or cadmium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures

Definitions

  • the present invention relates to a semiconductor nanoparticle assembly having high luminance and no ion elution in an aqueous solution. More specifically, the present invention relates to a matrix-coated assembly in which a semiconductor nanoparticle assembly containing semiconductor nanoparticles having a core / shell structure and a surfactant are coated with a silica matrix, and a method for producing the same.
  • III-V group semiconductor nanoparticles As semiconductor nanoparticles emitting fluorescence, II-VI group and III-V group semiconductor nanoparticles are widely known. However, when these semiconductor nanoparticles are used as a fluorescent diagnostic agent, the problem is that the brightness per particle is still insufficient, and that ions constituting the semiconductor nanoparticles leak out in an aqueous solution. Yes.
  • the brightness of the particles is extremely low with the core semiconductor nanoparticles alone, as compared with the semiconductor nanoparticles having a core / shell structure.
  • quantum wells are formed, and the luminance is significantly improved by the quantum confinement effect.
  • a method of increasing the brightness a method of increasing the brightness per particle by integrating the core / shell semiconductor nanoparticles can be considered.
  • Patent Document 1 discloses that a silica bead surface is converted to an amino group by silane coupling treatment, and a carboxyl group-terminated semiconductor nanoparticle is reacted to bond the silica bead and the semiconductor nanoparticle by an amide bond. Techniques for making them disclosed are disclosed. However, cadmium ion elution is observed even in the semiconductor nanoparticle assembly produced in this way. For example, when used for labeling a substance, elution of cadmium into cells causes a decrease in safety and further deterioration of the phosphor. It is done.
  • An object of the present invention is to provide a semiconductor nanoparticle assembly in which ions constituting the semiconductor nanoparticles are less likely to elute in an aqueous solvent.
  • the present inventors obtain the core / shell structure semiconductor nanoparticles thus precipitated by stirring with a higher amine as a surfactant and water and then hydrolyzing TEOS with ethanol and NH 3.
  • the present inventors have found that the matrix-covered aggregate (semiconductor nanoparticle-encapsulated particles) has less elution of ions forming the core portion, and has completed the present invention.
  • the present invention includes the following matters.
  • a semiconductor nanoparticle aggregate containing semiconductor nanoparticles having a core / shell structure, to which a surfactant is bound, and the semiconductor nanoparticle aggregate to which the surfactant is bound A matrix-coated assembly comprising a silica matrix.
  • the silica matrix is obtained by adding ethanol, ammonia [NH 3 ] and tetraethoxysilane [TEOS] in this order to the water-soluble semiconductor nanoparticle aggregate obtained in the step (X) [ 4] or the production method according to [5].
  • the elution of ions forming the core portion is 100 ppm or less, preferably 50 ppm or less, more preferably 10 ppm or less.
  • An integrated body and a manufacturing method thereof can be provided.
  • the present invention can provide a matrix-covered aggregate with high emission luminance and a method for producing the same without reducing the emission intensity even if the concentration of the semiconductor nanoparticle aggregate that emits fluorescence is below a certain level.
  • the matrix-covered aggregate of the present invention includes a semiconductor nanoparticle aggregate containing semiconductor nanoparticles having a core / shell structure, to which a surfactant is bound, and the semiconductor nanoparticle to which the surfactant is bound. And a silica matrix covering the particle aggregate.
  • a semiconductor nanoparticle aggregate by hydrolyzing semiconductor nanoparticles with TEOS in the presence of a surfactant such as amine.
  • the “semiconductor nanoparticle having a core / shell structure” used in the present invention is a particle having a nanosize (1 to 1000 nm) particle size containing a material (material) for forming a semiconductor, which will be described later, A particle having a multiple structure composed of a (core part) and a shell part (covering part) covering the core part.
  • Examples of the material for forming the core portion (also referred to as “core particle”) according to the present invention include silicon [Si], germanium [Ge], indium nitride [InN], indium phosphide [InP], and arsenic.
  • InP, CdTe or CdSe is particularly preferably used.
  • II-VI group, III-V group, and IV group inorganic semiconductors can be used as a material for forming the shell portion according to the present invention.
  • a semiconductor having a band gap larger than that of each core-forming inorganic material such as Si, Ge, InN, InP, GaAs, AlSe, CdSe, AlAs, GaP, ZnTe, CdTe, InAs, etc., or a non-toxic semiconductor is formed.
  • Raw materials are preferred.
  • ZnS is applied as a shell part to the core part of InP, CdTe or CdSe.
  • Method for producing semiconductor nanoparticles As a method for producing semiconductor nanoparticles according to the present invention, a liquid phase method can be employed.
  • liquid phase method examples include a precipitation method, a coprecipitation method, a sol-gel method, a uniform precipitation method, and a reduction method.
  • reverse micelle method and the supercritical hydrothermal synthesis method are also excellent methods for producing semiconductor nanoparticles (for example, Japanese Patent Application Laid-Open Nos. 2002-322468, 2005-239775, and Hei 10). No. -371070, JP 2000-104058, etc.).
  • the semiconductor precursor according to the present invention is a compound containing an element used as the semiconductor material, for example, when the semiconductor is Si, and the like SiCl 4 as semiconductor precursor.
  • Other semiconductor precursors include InCl 3 , P (SiMe 3 ) 3 , ZnMe 2 , CdMe 2 , GeCl 4 , tributylphosphine selenium and the like.
  • the reaction temperature of the reaction precursor is not particularly limited as long as it is not lower than the boiling point of the semiconductor precursor and not higher than the boiling point of the solvent, but is preferably in the range of 70 to 110 ° C.
  • Reducing agent that reduces the semiconductor precursor As such a reducing agent, various conventionally known reducing agents can be selected and used according to the reaction conditions.
  • lithium aluminum hydride [LiAlH 4 ] sodium borohydride [NaBH 4 ], bis (2-methoxyethoxy) aluminum hydride, tri (sec- Preferred are reducing agents such as lithium (butyl) boron [LiBH (sec-C 4 H 9 ) 3 ] and potassium tri (sec-butyl) borohydride, lithium triethylborohydride.
  • lithium aluminum hydride [LiAlH 4 ] is preferable because of its reducing power.
  • Surfactant used for reaction of semiconductor precursor various conventionally known surfactants can be used, and anionic, nonionic, cationic, and amphoteric surfactants are included. Of these, tetrabutylammonium chloride, bromide or hexafluorophosphate, tetraoctylammonium bromide [TOAB] or tributylhexadecylphosphonium bromide, which are quaternary ammonium salts, are preferred. Tetraoctyl ammonium bromide is particularly preferable.
  • the reaction by the liquid phase method varies greatly depending on the state of the compound containing the solvent in the liquid (* described later).
  • special care must be taken.
  • the size and state of the reverse micelle serving as a reaction field vary depending on the concentration and type of the surfactant, so that the conditions under which nanoparticles are formed are limited. Therefore, an appropriate combination of surfactant and solvent is required.
  • Solvent used in the liquid phase method Various known solvents can be used as the solvent for dispersing the semiconductor precursor.
  • Alcohols such as ethyl alcohol, sec-butyl alcohol, and t-butyl alcohol; hydrocarbon solvents such as toluene, decane, and hexane are used. It is preferable to use it.
  • a hydrophobic solvent such as toluene is particularly preferable as the dispersion solvent.
  • the semiconductor nanoparticle assembly used in the present invention is an assembly of semiconductor nanoparticles containing semiconductor nanoparticles having a core / shell structure.
  • the calculation of the number of semiconductor nanoparticles included in the aggregate is performed as follows. First, the element ratio of semiconductor nanoparticles is measured using ICP-AEC (ICPS-7500, Shimadzu Corporation), and the number of moles is calculated from the dry weight. Further, the molar extinction coefficient is obtained by measuring the absorbance. Thereafter, the dry weight of the semiconductor nanoparticle assembly is calculated and the absorbance is measured. Since the density of the semiconductor nanoparticle and the semiconductor nanoparticle assembly constituent compound is known, the concentration can be estimated together with the average particle size calculated by the dynamic light scattering method and the absorbance of the semiconductor nanoparticle assembly.
  • a liquid phase method may be used as described above, or another manufacturing method may be used.
  • other manufacturing methods include gas phase methods such as sputtering. Among these, from the viewpoint of particle size uniformity, a method for producing a semiconductor nanoparticle assembly by a liquid phase method is preferred.
  • surfactant examples include higher amines such as dodecylamine, hexadecylamine and octadecylamine, and organic phosphorus compounds such as trioctylphosphine and trioctylphosphine oxide. For this reason, higher amines are preferred.
  • the method for producing a matrix-covered aggregate of the present invention includes at least the following steps (X) and (Y).
  • the semiconductor nanoparticles are water-solubilized with a surfactant (step (X)).
  • a surfactant an amine compound can be used as the surfactant, and it is particularly preferable to use a higher amine such as dodecylamine.
  • the semiconductor nanoparticles solubilized with this surfactant are added with ethanol, ammonia [NH 3 ] and tetraethoxysilane [TEOS] in this order to hydrolyze TEOS, and the semiconductor nanoparticles are coated with a silica matrix.
  • a body, that is, a matrix-coated aggregate can be obtained (step (Y)). Note that the matrix-covered aggregate contains little or no water that acts as a catalyst for the TEOS reaction.
  • dodecylamine is added in an amount exceeding the limit amount that dissolves in water (for example, 78 mg / L at 25 ° C.).
  • an amount exceeding the limit amount for dissolving the surfactant in water is preferable in that the semiconductor nanoparticles having a core / shell structure are water-solubilized.
  • the semiconductor nanoparticles having a core / shell structure are water-solubilized.
  • a surfactant other than an amine compound or an organic phosphorus compound is added to water
  • the semiconductor nanoparticles having a core / shell structure are water-solubilized.
  • dodecylamine is used as the surfactant
  • the semiconductor nanoparticles do not become water-soluble unless a large amount of the surfactant exists because the water solubility of dodecylamine itself is extremely low.
  • dodecylamine is added in an amount that dissolves in water, the semiconductor nanoparticles are not mixed with water and completely separated from the aqueous phase.
  • dodecylamine when added in an amount exceeding 100 times that of the semiconductor nanoparticles by a molar ratio, it is separated into a dodecylamine phase and an aqueous phase in which the semiconductor nanoparticles are present.
  • the molar ratio is 100 times or less, the semiconductor nanoparticles are also present in the dodecylamine phase. This can be confirmed visually by irradiating with a UV lamp.
  • the surfactant used in the present invention with respect to semiconductor nanoparticles having a core / shell structure is preferably 10 to 400, more preferably in molar ratio [(surfactant) / (the semiconductor nanoparticles)]. Is added to water in an amount satisfying 50 to 200, most preferably about 100.
  • TEOS hydrolysis is represented by the following reaction formula.
  • Such a matrix-covered aggregate of the present invention is excellent in that in the ion elution test, elution of ions forming the core portion is extremely small, specifically 100 ppm or less, preferably 50 ppm or less, more preferably 10 ppm or less. It has the effect.
  • the matrix-coated aggregate is dispersed in an aqueous solvent at 0.1 ⁇ M, and is allowed to stand overnight (for example, 8 to 16 hours, to 24 hours, etc.), and then the core / shell that has oozed into the supernatant.
  • the amount of ions of constituent elements of the semiconductor nanoparticles having a structure is measured, and the degree of elution of ions of the matrix-covered aggregate is evaluated. The amount of ions was measured by using an inductively coupled plasma-atomic emission spectrometer (ICP-AES).
  • the outline of the matrix-coated aggregate, the method for producing the matrix-coated aggregate, and the outline of the ion elution test of the matrix-coated aggregate have been described above.
  • the matrix-coated assembly of the present invention can be applied to a biological material fluorescent labeling agent. Further, by adding the biological material labeling agent according to the present invention to a living cell or living body having a target (tracking) substance, the target substance is bound or adsorbed, and excitation light having a predetermined wavelength is applied to the conjugate or adsorbent. By irradiating and detecting fluorescence of a predetermined wavelength emitted from the semiconductor nanoparticles according to the excitation light, fluorescence dynamic imaging of the target (tracking) substance can be performed.
  • biomaterial labeling agent using the present invention can be used for bioimaging methods (technical means for visualizing biomolecules constituting the biomaterial and dynamic phenomena thereof).
  • the biological substance labeling agent using the present invention is obtained by binding the matrix-coated aggregate subjected to the hydrophilic treatment as described above and a molecular labeling substance (* described later) via an organic molecule (* described later). It is preferred that * Molecular labeling substance:
  • the biological substance labeling agent using the present invention can be labeled with a biological substance when the molecular labeling substance specifically binds and / or reacts with the target biological substance.
  • the molecular labeling substance examples include nucleotide chains, antibodies, antigens, cyclodextrins and the like.
  • Organic molecules In the biological material labeling agent using the present invention, the matrix-coated aggregate subjected to the hydrophilization treatment and the molecular labeling material are bound by organic molecules.
  • the organic molecule is not particularly limited as long as it is an organic molecule that can bind the matrix-covered aggregate and the molecular labeling substance.
  • proteins such as albumin, myoglobin, casein, or avidin that is a kind of protein. It is also suitable to use with biotin.
  • the form of the bond is not particularly limited, and examples thereof include a covalent bond, an ionic bond, a hydrogen bond, a coordinate bond, physical adsorption, and chemical adsorption.
  • a bond having a strong bonding force such as a covalent bond is preferable from the viewpoint of bond stability.
  • the matrix-coated aggregate is hydrophilized with mercaptoundecanoic acid
  • avidin and biotin can be used as organic molecules.
  • the carboxyl group of the matrix-coated assembly subjected to the hydrophilic treatment is preferably covalently bonded to avidin, the avidin is further selectively bonded to biotin, and biotin is further bonded to the biological material labeling agent to thereby bind the biological material labeling agent. It becomes.
  • the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
  • the ratio of the element in an Example and a comparative example shows molar ratio.
  • the InP / ZnS core / shell semiconductor nanoparticles thus obtained were particles having a maximum emission wavelength at 630 nm.
  • CdSe / ZnS core / shell semiconductor nanoparticles were synthesized by adding 15 g of TOPO to the obtained CdSe core particles and heating, followed by adding a solution of 1.1 g of zinc diethyldithiocarbamate in 10 mL of trioctylphosphine at 270 ° C. / ZnS core / shell semiconductor nanoparticles were obtained.
  • the CdTe core particles were synthesized according to the method according to Hemy, Volume 100, page 1772 (1996).
  • the CdTe core particles thus obtained were particles having a maximum emission wavelength at 640 nm.
  • AOT hydrophobic organic solvent
  • TEOS tetraethoxysilane
  • APS 3-aminopropyltrimethoxysilane
  • This dispersion was stirred for 2 days to obtain a semiconductor nanoparticle aggregate in which CdTe / ZnS was present in the silica matrix.
  • the CdTe / ZnS semiconductor nanoparticles were swollen in polystyrene by adding carboxyl group-terminated polystyrene particles (300 nm) of Invitrogen to this water-soluble semiconductor nanoparticle solution and stirring for 1 h.
  • Example 1 Acetone, which is a poor solvent, was added to the solution of InP / ZnS core / shell semiconductor nanoparticles synthesized in Comparative Example 1 to precipitate the semiconductor nanoparticles.
  • Example 2 In Example 1, the same procedure as in Example 1 was used except that the CdSe / ZnS core / shell semiconductor nanoparticles synthesized in Comparative Example 2 were used instead of the InP / ZnS core / shell semiconductor nanoparticles synthesized in Comparative Example 1. A matrix coating assembly was produced.
  • Example 3 In Example 1, the same procedure as in Example 1 was used except that the CdTe / ZnS core / shell semiconductor nanoparticles synthesized in Comparative Example 3 were used instead of the InP / ZnS core / shell semiconductor nanoparticles synthesized in Comparative Example 1. A matrix coating assembly was produced.
  • Example 4 In Example 1, the CdTe / ZnS core / shell semiconductor nanoparticles synthesized in Comparative Example 3 were used instead of the InP / ZnS core / shell semiconductor nanoparticles synthesized in Comparative Example 1, and instead of dodecylamine as a surfactant. A matrix-coated assembly was produced in the same manner as in Example 1 except that trioctylphosphine [TOP] was used.
  • TOP trioctylphosphine
  • the semiconductor nanoparticles synthesized in Comparative Examples 1 to 3 were precipitated with acetone as a poor solvent, the solvent was removed by centrifugation, 1 mL of ultrapure water and 1 ⁇ M mercaptopropionic acid were added, and the concentration of the semiconductor nanoparticles was 0. . Solubilized to 1 ⁇ M. After standing for 1 day, acetone was added again to precipitate water-soluble semiconductor nanoparticles, and the amount of ions eluted from the supernatant was calculated using ICP-AES.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
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Abstract

[Problème] Produire des nanoparticules de semi-conducteur qui ne subissent pas l'élution d'ions d'éléments constituant les nanoparticules de semi-conducteur à partir de celles-ci en solution aqueuse. [Solution] La présente invention concerne un ensemble de nanoparticules de semi-conducteur ayant une surface hydrosoluble, chaque nanoparticule de semi-conducteur ayant une structure noyau-enveloppe dans laquelle elle est encapsulée conjointement avec un tensioactif. L'ensemble de nanoparticules de semi-conducteur peut résoudre le problème mentionné ci-dessus.
PCT/JP2012/056871 2011-09-09 2012-03-16 Ensemble de nanoparticules semi-conductrices résistantes à l'élution d'ions WO2013035362A1 (fr)

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JP2013532467A JP5880563B2 (ja) 2011-09-09 2012-03-16 耐イオン溶出性半導体ナノ粒子集積体の製造方法

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JP2011197334 2011-09-09

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015190257A1 (fr) * 2014-06-11 2015-12-17 コニカミノルタ株式会社 Ensemble de nanoparticules semi-conductrices et leur procédé de production
WO2017012688A1 (fr) 2015-07-17 2017-01-26 Merck Patent Gmbh Particule luminescente, formulation d'encre, composition polymère, dispositif optique, fabrication de ceux-ci, et utilisation de la particule luminescente
WO2023182221A1 (fr) * 2022-03-25 2023-09-28 日本化学工業株式会社 Procédé de production de points quantiques

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JP2005281019A (ja) * 2004-03-29 2005-10-13 National Institute Of Advanced Industrial & Technology 半導体ナノ粒子を分散した蛍光性ガラスとその製造方法
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JP2010138367A (ja) * 2008-04-23 2010-06-24 National Institute Of Advanced Industrial Science & Technology 水分散性を有する高発光効率ナノ粒子及びその製造方法
WO2010128604A1 (fr) * 2009-05-08 2010-11-11 コニカミノルタエムジー株式会社 Nanoparticule de silice présentant des points quantiques encapsulés dans celle-ci, son procédé de production et agent de marquage biologique l'utilisant

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015190257A1 (fr) * 2014-06-11 2015-12-17 コニカミノルタ株式会社 Ensemble de nanoparticules semi-conductrices et leur procédé de production
JPWO2015190257A1 (ja) * 2014-06-11 2017-04-20 コニカミノルタ株式会社 半導体ナノ粒子集積体およびその製造方法
WO2017012688A1 (fr) 2015-07-17 2017-01-26 Merck Patent Gmbh Particule luminescente, formulation d'encre, composition polymère, dispositif optique, fabrication de ceux-ci, et utilisation de la particule luminescente
WO2023182221A1 (fr) * 2022-03-25 2023-09-28 日本化学工業株式会社 Procédé de production de points quantiques

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