WO2011158531A1 - Agrégat de nanoparticules semi-conductrices - Google Patents

Agrégat de nanoparticules semi-conductrices Download PDF

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WO2011158531A1
WO2011158531A1 PCT/JP2011/054296 JP2011054296W WO2011158531A1 WO 2011158531 A1 WO2011158531 A1 WO 2011158531A1 JP 2011054296 W JP2011054296 W JP 2011054296W WO 2011158531 A1 WO2011158531 A1 WO 2011158531A1
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semiconductor
core
aggregate
semiconductor nanoparticle
shell
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Japanese (ja)
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優 高橋
秀樹 星野
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コニカミノルタエムジー株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/08—Other phosphides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/007—Tellurides or selenides of metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G11/00—Compounds of cadmium
    • C01G11/02—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00—Compounds of gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/08—Sulfides
    • 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
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • 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
    • C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
    • C09K11/592—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
    • C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties

Definitions

  • the present invention relates to a semiconductor nanoparticle assembly with high emission luminance.
  • III-V group semiconductor nanoparticles As semiconductor nanoparticles emitting fluorescence, II-VI group and III-V group semiconductor nanoparticles are widely known. If these semiconductor nanoparticles are used as a fluorescent diagnostic agent, the brightness per particle is still insufficient.
  • the brightness of the particles is much lower with the core semiconductor nanoparticles alone than with the semiconductor nanoparticles having a core / shell structure.
  • a semiconductor material having a wider band gap than the core particle as the shell 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.
  • concentration quenching is considered to be caused by the fact that electron transfer occurs when the core / shell particles come into contact with each other and the quantum confinement effect is lowered.
  • Patent Document 1 discloses a reverse micelle method and a sol-gel method using a mixture of an organoalkoxysilane and an alkoxide having an organic functional group having a good adsorptivity to semiconductor nanoparticles at the end of a molecule as a glass precursor.
  • a glass phosphor having semiconductor nanoparticles dispersed and fixed therein is disclosed.
  • a decrease in luminous efficiency is observed due to the influence of the reaction in the sol-gel method.
  • the hydrolysis product of an organic alkoxysilane and an alkoxide is included, there exists a problem that the distance between semiconductor nanoparticles becomes long and a semiconductor particle cannot be collected so much concentration.
  • the present invention has been made in view of the above-described problems and situations, and a solution to the problem is a semiconductor nanoparticle aggregate having high emission luminance that does not quench the concentration even when semiconductor nanoparticles emitting fluorescence are densely integrated. Is to provide.
  • a semiconductor nanoparticle aggregate comprising a semiconductor nanoparticle having a core / shell structure, wherein the semiconductor nanoparticle aggregate is formed by re-shelling an aggregate of semiconductor nanoparticles.
  • the material constituting the core part of the semiconductor nanoparticles having the core / shell structure is selected from the group consisting of indium phosphide (InP), silicon (Si), cadmium selenide (CdSe), and cadmium telluride (CdTe). 4.
  • a poor solvent is added to form an aggregate of core / shell semiconductor nanoparticles.
  • the aggregate does not have the brightness corresponding to the number of core / shell semiconductor nanoparticles due to the concentration quenching as it is.
  • the light emission luminance is about 40% of the original light emission luminance of each core / shell semiconductor nanoparticle constituting the aggregate.
  • the semiconductor nanoparticle assembly of the present invention is a semiconductor nanoparticle assembly containing semiconductor nanoparticles having a core / shell structure, and is formed by re-shelling an aggregate of the semiconductor nanoparticles. And This feature is a technical feature common to the inventions according to claims 1 to 5.
  • the material constituting the shell part of the semiconductor nanoparticles having the core / shell structure and the material for re-shelling are the same compound, or It is preferable to contain the same compound.
  • material which constitutes the shell portion of the semiconductor nanoparticles having the core / shell structure is preferably a zinc sulfide (ZnS) or silicon dioxide (SiO 2).
  • the material which comprises the core part of the semiconductor nanoparticle which has the said core / shell structure consists of indium phosphide (InP), silicon (Si), cadmium selenide (CdSe), and cadmium telluride (CdTe). It is preferably a simple substance or a compound selected from
  • the average particle diameter of the semiconductor nanoparticle aggregate is in the range of 50 to 500 nm.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the semiconductor nanoparticle assembly of the present invention is a semiconductor nanoparticle assembly containing semiconductor nanoparticles having a core / shell structure, and is formed by re-shelling an aggregate of the semiconductor nanoparticles.
  • the “semiconductor nanoparticle having a core / shell structure” is a particle having a nanosize (1 to 1000 nm) particle size containing a semiconductor forming material (material) described later, ) And a shell part (covering part) covering the same.
  • aggregate refers to an aggregate in which a plurality of semiconductor nanoparticles are in contact with each other.
  • Aggregate refers to particles obtained by shelling the aggregate.
  • Re-shelling refers to shelling a core / shell structure semiconductor nanoparticle aggregate.
  • the peak of pores derived between the particles of the semiconductor nanoparticles is within the range of 5 to 50 nm in the aggregate.
  • the aggregate is characterized in that no pore peak is observed at 5 to 50 nm, but only a pore peak (100 nm or more) derived between the aggregates.
  • pores are found in the aggregate and it is very porous.
  • pores such as micropores and mesopores are not seen, and the aggregate surface is coated. it is conceivable that.
  • the pore size distribution measurement using N 2 molecules can be performed using BELSORP-mini gas adsorption instrument of BEL.
  • the adsorption / desorption curve is measured at 77 k, and the pore size distribution can be calculated by the BJH (Barrett, Joyner, and Halenda) method using the adsorption curve.
  • the TEM image can be observed using, for example, Hitachi H-9000NA (300 kV).
  • the aggregate of semiconductor nanoparticles according to the present invention can be formed by using a poor solvent that hardly dissolves the semiconductor nanoparticles and their materials in the semiconductor nanoparticle formation process or the dispersion process after the formation.
  • the poor solvent for example, alcohols (methanol, ethanol, propanol, etc.) and ketones (acetone, methyl ethyl ketone, etc.) can be used.
  • the average particle size of the semiconductor nanoparticle aggregate is preferably within the range of 5 to 1000 nm, and more preferably within the range of 50 to 500 nm.
  • the particle size (volume average particle size) of the semiconductor nanoparticles having a core / shell structure and the semiconductor nanoparticle aggregate is measured by a particle size measuring device by a dynamic light scattering method (Malvern Instruments, Zetasizer Nano S). It was determined by measuring the particle size distribution immediately after the production of semiconductor nanoparticles or aggregates (before aggregation). The average particle size (volume average particle size) was the particle size at the peak (center) position of the particle size distribution.
  • the elemental ratio of semiconductor nanoparticles is measured using a sequential high-frequency plasma emission analyzer (ICPS-7500, manufactured by Shimadzu Corporation). Thereafter, the element ratio of the re-shelled semiconductor nanoparticle assembly is measured by the high-frequency plasma emission analyzer (ICP-AES) to calculate the concentration used for the re-shelling. Since the densities of the semiconductor nanoparticles and the re-shelling compound are known, it is possible to estimate the number of inclusions together with the average particle diameter calculated by the dynamic light scattering method.
  • ICPS-7500 sequential high-frequency plasma emission analyzer
  • ICP-AES high-frequency plasma emission analyzer
  • the number of semiconductor nanoparticles having a core / shell structure contained in the semiconductor nanoparticle aggregate is preferably as large as possible.
  • the number of inclusions is preferably 800 or more.
  • Core part forming material examples include semiconductors such as Si, Ge, InN, InP, GaAs, AlSe, CdSe, AlAs, GaP, ZnTe, CdTe, and InAs. Or the raw material which forms these can be used.
  • InP, Si, CdTe, and CdSe are particularly preferably used.
  • the average particle size of the core portion (“core particle”) according to the present invention is preferably 0.5 to 15 nm.
  • 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 larger band gap than each core-forming inorganic material such as Si, Ge, InN, InP, GaAs, AlSe, CdSe, AlAs, GaP, ZnTe, CdTe, InAs, etc. Is preferred.
  • ZnS is applied to InP, CdTe, and CdSe, and SiO 2 is applied to Si as a shell.
  • the shell portion according to the present invention may not completely cover the entire surface of the core particle as long as the core particle is not partially exposed to cause a harmful effect.
  • the average particle size of the core / shell structure semiconductor nanoparticle according to the present invention is preferably 1 to 20 nm.
  • Re-shelling material As a material used for reselling the aggregate of semiconductor nanoparticles, the same material as the shell portion forming material can be used.
  • Si, Ge, InN, InP, GaAs, AlSe, CdSe, AlAs, GaP, ZnTe, CdTe, and InAs are preferable.
  • a shell having the same composition as the shell part of the core / shell structure semiconductor nanoparticles is applied (if the core / shell structure semiconductor nanoparticles are InP / ZnS, CdTe / ZnS, and CdSe / ZnS, ZnS In the case of Si / SiO 2 , SiO 2 ).
  • the shell thickness at the time of re-shelling can be easily controlled by changing the amount added at the time of re-shelling.
  • the shell thickness at the time of re-shelling is a value obtained by subtracting the average particle size of the semiconductor nanoparticle aggregate from the average particle size of the semiconductor nanoparticle aggregate, and the thickness is preferably 2 to 200 nm.
  • the thickness is preferably in the range of ⁇ 20 nm.
  • Method for producing semiconductor nanoparticles As a method for producing semiconductor nanoparticles according to the present invention, a liquid phase method or a gas 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.
  • the reverse micelle method, the supercritical hydrothermal synthesis method, and the like are also excellent methods for producing nanoparticles (for example, JP 2002-322468, JP 2005-239775, JP 10-310770 A). No., JP 2000-104058 A, etc.).
  • the semiconductor precursor according to the present invention is a compound containing an element used as the semiconductor material.
  • the semiconductor precursor includes SiCl 4 .
  • 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 for reducing the semiconductor precursor various conventionally known reducing agents can be selected and used according to the reaction conditions.
  • lithium aluminum hydride (LiAlH 4 ) is preferable because of its reducing power.
  • solvents can be used as the solvent for dispersing the semiconductor precursor.
  • Alcohols such as ethyl alcohol, sec-butyl alcohol and t-butyl alcohol, and 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.
  • ⁇ Surfactant> 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.
  • 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.
  • the opposing raw material semiconductor is evaporated by the first high temperature plasma generated between the electrodes, and in the second high temperature plasma generated by electrodeless discharge in a reduced pressure atmosphere.
  • a method of separating and removing nanoparticles from an anode made of a raw material semiconductor by electrochemical etching for example, see Japanese Patent Application Laid-Open No. 2003-515459).
  • laser ablation for example, see JP-A-2004-356163
  • high-speed sputtering method for example, see JP-A-2004-296781
  • a method of synthesizing a powder containing particles by reacting a raw material gas in a gas phase in a low pressure state is also preferably used.
  • the semiconductor nanoparticle 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 generated from the fluorescent semiconductor fine particles according to the excitation light, fluorescence dynamic imaging of the target (tracking) substance can be performed.
  • the biological material labeling agent according to the present invention can be used for a bioimaging method (technical means for visualizing biological molecules constituting the biological material and dynamic phenomena thereof).
  • hydrophilic treatment method for example, there is a method in which a surface modifying agent is chemically and / or physically bonded to the surface of the semiconductor nanoparticle assembly after removing the lipophilic group on the surface with pyridine or the like.
  • a surface modifying agent for example, those having a carboxyl group / amino group as a hydrophilic group are preferably used, and specific examples include mercaptopropionic acid, mercaptoundecanoic acid, aminopropanethiol and the like.
  • 10 ⁇ 5 g of Ge / GeO 2 type nanoparticles are dispersed in 10 ml of pure water in which 0.2 g of mercaptoundecanoic acid is dissolved, and stirred at 40 ° C. for 10 minutes to treat the surface of the shell.
  • the surface of the shell of the inorganic nanoparticles can be modified with a carboxyl group.
  • the biological material labeling agent according to the present invention is obtained by binding the above-described hydrophilic nanoparticle aggregate, the molecular labeling material, and an organic molecule.
  • the biological substance labeling agent according to the present invention can label a biological substance by specifically binding and / or reacting with the target biological substance.
  • Examples of the molecular labeling substance include nucleotide chains, antibodies, antigens, and cyclodextrins.
  • a hydrophilic semiconductor nanoparticle aggregate and a molecular labeling substance are bound by an organic molecule.
  • the organic molecule is not particularly limited as long as it is an organic molecule that can bind the semiconductor nanoparticle aggregate and the molecular labeling substance.
  • the form of the bond is not particularly limited, and examples thereof include covalent bond, ionic bond, hydrogen bond, 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 semiconductor nanoparticle aggregate is hydrophilized with mercaptoundecanoic acid
  • avidin and biotin can be used as organic molecules.
  • the carboxyl group of the nanoparticles subjected to hydrophilic treatment is preferably covalently bonded to avidin, and avidin further selectively binds to biotin, and biotin further binds to the biological material labeling agent to become a biological material labeling agent.
  • InP core particles were synthesized by the following heated solution method.
  • the InP core particles thus obtained were particles having a maximum emission wavelength at 630 nm.
  • the InP / ZnS core / shell semiconductor nanoparticles thus obtained were particles having a maximum emission wavelength at 630 nm, similar to the InP core particles.
  • the semiconductor nanoparticle aggregate-containing dispersion is centrifuged and washed several times with ethanol. Octadecene was added to the washed precipitate, and the solvent was replaced with octadecene. At that time, re-dispersion of the aggregate did not occur and the particle size of the aggregate was maintained.
  • the temperature was raised from 80 ° C. to 230 ° C. and reacted for 30 minutes to re-shell, thereby obtaining a semiconductor nanoparticle aggregate.
  • ZnS was added in an amount 10 times the amount of InP or InP / ZnS core particles.
  • Si / SiO 2 core / shell semiconductor nanoparticles were obtained by treating amorphous Si (manufactured by Sigma-Aldrich) with an HNO 3 / HF solution.
  • Si core particles were particles having a maximum emission wavelength at 630 nm.
  • Si or Si / SiO 2 aggregate is crystallized as HF as CaF by adding CaCO 3 to the Si / SiO 2 core / shell or Si core semiconductor nanoparticle dispersion, the CaF is removed by filtration. It is obtained by adding acetone, which is a poor solvent.
  • TEOS tetraethoxysilane
  • CdSe / ZnS core / shell semiconductor nanoparticle synthesis was performed 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 semiconductor nanoparticle aggregate-containing dispersion is centrifuged and washed several times with ethanol. Octadecene was added to the washed precipitate, and the solvent was replaced with octadecene. At that time, re-dispersion of the aggregate did not occur and the particle size of the aggregate was maintained.
  • This octadecene-substituted aggregate solution is transferred to a three-necked flask, heated to 80 ° C., zinc stearate + sulfur is added, the temperature is raised from 80 ° C. to 230 ° C., and reacted for 30 minutes to re-shell. A nanoparticle assembly was obtained. The re-shelling when the aggregates were aggregated added ZnS in a 10-fold molar amount of CdSe or CdSe / ZnS core particles.
  • Example 12 (Examples 12, 13, and 14) (Synthesis of CdTe core particles and CdTe / ZnS core / shell semiconductor nanoparticles) CdTe core particles and CdTe / ZnS core / shell semiconductor nanoparticles were synthesized according to Example 1 of JP-A-2005-281019.
  • 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.
  • the semiconductor nanoparticle aggregate-containing dispersion is centrifuged and washed several times with ethanol. Octadecene was added to the washed precipitate, and the solvent was replaced with octadecene. At that time, re-dispersion of the aggregate did not occur and the particle size of the aggregate was maintained.
  • Zn / S 1 and 10 times the molar amount of ZnS as CdTe or CdTe / ZnS core particles.
  • ZnS is added in an amount 10 times the amount of CdTe or CdTe / ZnS core particles.
  • Example 4 According to Example 1 described in Japanese Patent Application Laid-Open No. 2005-281019, a semiconductor nanoparticle aggregate in which InP / ZnS, CdSe / ZnS, and CdTe / ZnS exist in the silica matrix was produced.
  • the surfactant bis (2-ethylhexyl) sulfosuccinate sodium (required for forming reverse micelle (reverse microemulsion) in 25 ml of isooctane (2,2,4-trimethylpentane) as a hydrophobic organic solvent ( (Aerosol OT) (also referred to as “AOT”) 1.1115 g was dissolved and then 0.74 ml of water and the above water-soluble InP / ZnS, CdSe / ZnS, CdTe / ZnS were mixed while stirring the solution. 0.3 ml of the core / shell semiconductor nanoparticle solution was added and dissolved.
  • AOT hydrophobic organic solvent
  • TEOS tetraethoxysilane
  • APS aminopropyltrimethoxysilane
  • the dispersion was stirred for 2 days to obtain a semiconductor nanoparticle aggregate in which InP / ZnS, CdSe / ZnS, and CdTe / ZnS were present in the silica matrix, respectively.
  • Table 1 summarizes the contents of the various semiconductor nanoparticle assemblies obtained above and the results of luminance measurement.
  • the luminance measurement uses a 146 nm vacuum ultraviolet lamp (USHIO Inc.) as a light source, sets a sample in a vacuum chamber, and irradiates excitation light from a certain distance at a vacuum degree of 1.33 ⁇ 10 Pa. Measured with The luminance value is shown as a relative value when the luminance of the InP particle assembly of Example 1 is 1000.
  • USHIO Inc. 146 nm vacuum ultraviolet lamp
  • the particle size (volume average particle size) of the semiconductor nanoparticles and the semiconductor nanoparticle aggregate is determined by using a particle size measuring device (Malvern Instruments, Zetasizer Nano S) by dynamic light scattering method. It was determined by measuring the particle size distribution immediately after production (before aggregation). The average particle size (volume average particle size) was the particle size at the peak (center) position of the particle size distribution.
  • a particle size measuring device Malvern Instruments, Zetasizer Nano S
  • the elemental ratio of the semiconductor nanoparticles was measured using a sequential type high frequency plasma emission analyzer (ICPS-7500, manufactured by Shimadzu Corporation). Thereafter, the element ratio of the re-shelled semiconductor nanoparticle assembly was measured with the high-frequency plasma emission analyzer (ICP-AES) to calculate the concentration used for re-shelling. Since the densities of the semiconductor nanoparticles and the re-shelling compound are known, the inclusion number was estimated together with the average particle diameter calculated by the dynamic light scattering method.
  • ICPS-7500 sequential type high frequency plasma emission analyzer
  • ICP-AES high-frequency plasma emission analyzer
  • the emission luminance of the semiconductor nanoparticle aggregate formed by re-shelling the aggregate of semiconductor nanoparticles of the present invention is superior to that of the comparative example. I understand.

Abstract

L'invention concerne un agrégat de nanoparticules semi-conductrices avec une luminance élevée en émission et sans extinction par concentration, même quand les nanoparticules semi-conductrices qui émettent une lumière fluorescente sont accumulées de façon dense. Ledit agrégat contient des nanoparticules semi-conductrices avec une structure cœur/coquille et est formé en réenrobant des agglomérats de nanoparticules semi-conductrices.
PCT/JP2011/054296 2010-06-16 2011-02-25 Agrégat de nanoparticules semi-conductrices WO2011158531A1 (fr)

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WO2009014588A2 (fr) * 2007-06-29 2009-01-29 Eastman Kodak Company Particules nanocomposites électroluminescentes
JP2009281760A (ja) * 2008-05-20 2009-12-03 Konica Minolta Medical & Graphic Inc ナノ粒子内包シリカ、それを用いた生体物質の標識物質および生体物質の標識方法

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