WO2012147429A1 - Glass particles containing enclosed semiconductor nanoparticles, and process for producing glass particles containing enclosed semiconductor nanoparticles - Google Patents

Glass particles containing enclosed semiconductor nanoparticles, and process for producing glass particles containing enclosed semiconductor nanoparticles Download PDF

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WO2012147429A1
WO2012147429A1 PCT/JP2012/056865 JP2012056865W WO2012147429A1 WO 2012147429 A1 WO2012147429 A1 WO 2012147429A1 JP 2012056865 W JP2012056865 W JP 2012056865W WO 2012147429 A1 WO2012147429 A1 WO 2012147429A1
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glass particles
semiconductor
semiconductor nanoparticles
semiconductor nanoparticle
core
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PCT/JP2012/056865
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French (fr)
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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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/58Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving labelled substances
    • G01N33/588Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving labelled substances with semiconductor nanocrystal label, e.g. quantum dots
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00Nanooptics, e.g. quantum optics or photonic crystals
    • 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
    • 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
    • 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
    • C09K11/70Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
    • 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
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using infra-red, visible or ultra-violet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6439Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks

Abstract

[Problem] To provide glass particles containing semiconductor nanoparticles enclosed therein, the glass particles giving high-sensitivity semiconductor nanoparticles (aggregates), and a process for producing the glass particles. [Solution] Glass particles containing enclosed semiconductor nanoparticles, the glass particles containing, enclosed therein, core/shell type semiconductor nanoparticles A that have a core/shell structure, characterized in that the core/shell type semiconductor nanoparticles A are semiconductor nanoparticles A having, on the surface, an amino compound having an amino group and a hydrophobic group.

Description

Semiconductor nanoparticle-encapsulated glass particles, method for producing semiconductor nanoparticle-encapsulated glass particles

The present invention relates to glass particles containing semiconductor nanoparticles used for fluorescent labeling members such as biological material fluorescent labeling agents.

In recent years, semiconductor nanoparticles have attracted attention in applications such as labeling agents and high-definition displays in the medical field.

In such applications, semiconductor nanoparticles are used as phosphors.

Semiconductors used as phosphors include II-VI group semiconductors (cadmium sulfide (CdS), zinc selenide (ZnSe), cadmium selenide (CdSe), zinc telluride (ZnTe), cadmium telluride (CdTe)) and Group III-V semiconductor nanoparticles are widely known.

Further, as semiconductor nanoparticles, it is known that semiconductor nanoparticles having a shell layer on a core layer are advantageously used particularly from the viewpoint of luminance (for example, see Patent Document 1).

As a method for producing such semiconductor nanoparticles, a method for synthesis in a solution has been developed.

However, semiconductor nanoparticles synthesized in solution have a deterioration in light emission characteristics over time, which is thought to be caused by particle aggregation, interaction with water, and so on. There was a problem that it was difficult to use.

Therefore, a method is known in which semiconductor nanoparticles are contained in transparent glass particles to prevent deterioration of light emission characteristics (see Patent Documents 2 and 3).

However, even in the method of using semiconductor nanoparticles contained in such glass particles, particularly when used as a biological material fluorescent labeling agent, when using at a low concentration to reduce the amount of labeling substance used In the low concentration region, it is difficult to maintain the linear relationship between the addition amount and the fluorescence property due to the deterioration of the fluorescence property. As a result, it is difficult to produce a highly sensitive biological substance fluorescent labeling agent.

No. 2007-86501 International Publication No. 04/000971 Pamphlet JP 2005-281019 A

An object of the present invention is to provide semiconductor nanoparticle-containing glass particles that provide highly sensitive semiconductor nanoparticles (nanoparticle aggregates), and a method for producing the same.

The above-mentioned problem according to the present invention can be solved by the following means.

1. Semiconductor nanoparticle-containing glass particles enclosing core-shell type semiconductor nanoparticles A having a core-shell structure, wherein the core-shell type semiconductor nanoparticles A have an amino compound having an amino group and a hydrophobic group on the surface. A semiconductor nanoparticle-containing glass particle, which is a nanoparticle A.

2. 2. The semiconductor nanoparticle inclusion according to 1, wherein the core portion of the core-shell type semiconductor nanoparticle A contains indium phosphide (InP), cadmium selenide (CdSe), or cadmium telluride (CdTe). Glass particles.

3. 3. The semiconductor nanoparticle-encapsulated glass particle according to 1 or 2, wherein the semiconductor nanoparticle-encapsulated glass particle includes a plurality of the semiconductor nanoparticles A.

4). A method for producing semiconductor nanoparticle-encapsulated glass particles, comprising producing the semiconductor nanoparticle-encapsulated glass particles according to any one of 1 to 3,
(1) a step of attaching an amino compound having an amino group and a hydrophobic group to the surface of a core-shell type semiconductor nanoparticle to form the semiconductor nanoparticle A having the amino compound on the surface;
(2) A glass particle forming step of producing glass particles using a glass precursor in the presence of the semiconductor nanoparticles A to produce semiconductor nanoparticle A-encapsulating glass particles containing the semiconductor,
The manufacturing method of the semiconductor nanoparticle inclusion | inner_cover glass particle characterized by having.

By the above means of the present invention, there are provided semiconductor nanoparticle-containing glass particles having high sensitivity by maintaining the linear relationship between the content and the emission intensity even in a region where the content of semiconductor nanoparticles is low, and a method for producing the same. There is to do.

It is an example of the graph (comparative example) which shows the relationship between a semiconductor nanoparticle density | concentration and emitted light intensity. It is another example of the graph (comparative example) which shows the relationship between a semiconductor nanoparticle density | concentration and emitted light intensity. It is another example of the graph (comparative example) which shows the relationship between a semiconductor nanoparticle density | concentration and emitted light intensity. It is another example of the graph (comparative example) which shows the relationship between a semiconductor nanoparticle density | concentration and emitted light intensity. It is an example of the graph (this invention) which shows the relationship between a semiconductor nanoparticle density | concentration and emitted light intensity. It is another example of the graph (this invention) which shows the relationship between a semiconductor nanoparticle density | concentration and emitted light intensity. It is another example of the graph (this invention) which shows the relationship between a semiconductor nanoparticle density | concentration and emitted light intensity.

The present invention relates to semiconductor nanoparticle-containing glass particles enclosing core-shell type semiconductor nanoparticles A having a core-shell structure, the core-shell type semiconductor nanoparticles A having amino groups and hydrophobic groups on the surface. It is the semiconductor nanoparticle A which has a compound, It is characterized by the above-mentioned.

In the present invention, in particular, by using the semiconductor nanoparticles that have been subjected to the specific treatment in advance, by producing glass particles that enclose the semiconductor nanoparticles, even in a region where the content of the semiconductor nanoparticles is low, the content and emission intensity By maintaining the linearity of the relationship, it is possible to provide semiconductor nanoparticle-containing glass particles having high sensitivity and a method for producing the same.

(Core-shell type semiconductor nanoparticles)
The core-shell type semiconductor nanoparticle is a particle containing a semiconductor forming material (raw material) to be described later and having a multiple structure composed of a core part (core part) and a shell part (covering part) covering it. And the particle diameter is 1000 nm or less.

(Core part forming material)
Examples of the material for forming the core portion (also referred to as “core particle”) according to the present invention 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.

In the present invention, InP, CdTe, and CdSe are particularly preferably used.

(Shell forming material)
As a material for forming the shell portion according to the present invention, II-VI group, III-V group inorganic semiconductors, group IV inorganic semiconductors and oxides can be used.

For example, it has a larger band gap and toxicity than each core-forming inorganic material such as Si, SiO 2 , Ge, GeO 2 , InN, InP, GaAs, AlSe, CdSe, AlAs, GaP, ZnS, ZnTe, CdTe, InAs. Semiconductors that do not, or the raw materials that form them are preferred.

More preferably, ZnS is applied as a shell to InP, CdTe, and CdSe.

(Method for producing semiconductor nanoparticle A)
As a method for producing semiconductor nanoparticles according to the present invention, a liquid phase method can be employed.

Examples of the liquid phase method include a precipitation method, a coprecipitation method, a sol-gel method, a uniform precipitation method, and a reduction method.

In addition, 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.).

In addition, when manufacturing the aggregate | assembly of a semiconductor nanoparticle by a liquid phase method, it is also preferable that it is a manufacturing method which has the process of reduce | restoring the said semiconductor precursor by a reductive reaction.

Moreover, the aspect which has the process performed in reaction of the said semiconductor precursor in presence of surfactant is preferable. 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, 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>
As the reducing agent for reducing the semiconductor precursor, various conventionally known reducing agents can be selected and used according to the reaction conditions. In the present invention, from the viewpoint of the strength of reducing power, lithium aluminum hydride (LiAlH 4 ), sodium borohydride (NaBH 4 ), sodium bis (2-methoxyethoxy) aluminum hydride, trihydride (sec- Preferred are reducing agents such as lithium (butyl) boron (LiBH (sec-C 4 H 9 ) 3 ), potassium tri (sec-butyl) borohydride, lithium triethylborohydride. In particular, lithium aluminum hydride (LiAlH 4 ) is preferable because of its reducing power.

<solvent>
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, and hydrocarbon solvents such as toluene, decane, and hexane are used. It is preferable to use it. In the present invention, a hydrophobic solvent such as toluene is particularly preferable as the dispersion solvent.

<Surfactant>
As the 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 preferable.

In particular, tetraoctyl ammonium bromide is preferable.

The reaction by the liquid phase method varies greatly depending on the state of the compound containing the solvent in the liquid. When producing nano-sized particles with excellent monodispersity, special care must be taken.

For example, in the reverse micelle reaction method, 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, a suitable surfactant needs to be combined with a solvent.

In addition, although the manufacturing method of the semiconductor nanoparticle aggregate, the semiconductor nanoparticle assembly, and the outline of the solvent resistance test have been described above, the specific method will be described in detail in the description of the examples.

(1) The process of forming the semiconductor nanoparticle A In the process of forming the semiconductor nanoparticle A, the compound having an amino group and a hydrophobic group is attached to the surface of the semiconductor nanoparticle to form the semiconductor nanoparticle A.

(Amino compound having amino group and hydrophobic group)
The hydrophobic group according to the present invention refers to a hydrocarbon group, and examples thereof include an alkyl group and an aromatic hydrocarbon group.

Examples of the alkyl group include an alkyl group having 6 to 30 carbon atoms, and an alkyl group having 8 to 20 carbon atoms can be particularly preferably used.

Examples of the aromatic group include a phenyl group and a naphthyl group.

Examples of the compound having an amino group and a hydrophobic group include n-heptylamine, nonylamine, dodecylamine, hexadecanamine and the like.

In order to attach the amino compound to the surface of the semiconductor nanoparticles, it can be obtained by mixing and stirring the solvent, the semiconductor nanoparticles, and the amino compound having an amino group and a hydrophobic group.

As the solvent, an organic solvent is used, and alcohols and ketones can be used, but alcohols are preferable, and lower alcohols having 1 to 4 carbon atoms are particularly preferable.

The amount of the semiconductor nanoparticles in the solvent is preferably 0.001% by mass to 1% by mass, and particularly preferably 0.01% by mass to 0.1% by mass with respect to the solvent.

The content of the compound having an amino group and a hydrophobic group in the solvent is preferably 0.01% by mass to 10% by mass, and particularly preferably 0.1% by mass to 1% by mass with respect to the solvent.

In the present invention, the semiconductor nanoparticles A are present in the above-mentioned solvent, but it is preferable to move to the following glass particle forming step in a solution state.

(2) Glass particle forming step In the glass particle forming step, glass particles are generated using a glass precursor in the presence of the semiconductor nanoparticles A, and a semiconductor nanoparticle-containing glass particle glass precursor containing a semiconductor is produced. .

The formation of glass particles can be obtained by hydrolyzing the glass precursor. Hydrolysis is obtained by hydrolyzing the glass precursor in an alkaline solvent. In the present invention, the semiconductor nanoparticles are contained in the alkaline solvent so that the semiconductor is contained. Semiconductor nanoparticle A-encapsulating glass particles can be produced.

Silicon alkoxide is used as the glass precursor.

Examples of the silicon alkoxide include tetraethoxysilane (TEOS) and tetramethoxysilane.

Examples of the solvent used include alcohols and ketones, but ethanol is preferably used.

Alkaline state can be obtained by adding ammonia or the like.

The temperature for the hydrolysis can be in the range of 5 ° C to 80 ° C, but the hydrolysis is preferably performed at 25 ° C.

The concentration of the glass precursor in the solvent can be in the range of 40 to 80% by mass.

By forming particles under such conditions, particles having a particle size of approximately 10 nm to 100 nm can be formed.

In the glass particles, there are a plurality of semiconductor nanoparticles A in a state where the semiconductor nanoparticles A are taken in and encapsulated.

The number of semiconductor nanoparticles A in the glass particles depends on the particle size of the semiconductor nanoparticles A used and the particle size of the glass particles to be formed, but those contained in the range of approximately 2 to 20 are preferably used. In particular, those containing 4 to 15 and glass particles having a particle size of 10 to 50 nm are preferably used.

Calculation of the number (inclusion number) contained in the glass of the semiconductor nanoparticles A can be performed as follows.

First, the element ratio of the semiconductor nanoparticles A 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.

Then, the dry weight of the semiconductor nanoparticle assembly is calculated and the absorbance is measured. Since the density of the semiconductor nanoparticle and the compound constituting the semiconductor nanoparticle assembly is known, it can be obtained by calculating the concentration together with the average particle diameter calculated by the dynamic light scattering method and the absorbance of the semiconductor nanoparticle assembly. Is possible.

The reason why the glass particles obtained by the production method of the present invention maintain a good linear relationship between the content and the fluorescence emission intensity in a low concentration region is not clear, but is specified as follows.

It is inferred that when the semiconductor nanoparticles are exposed to a solvent such as xylene at a low concentration, the solvent is adsorbed on the surface of the semiconductor nanoparticles and the surface state changes, resulting in a decrease in emission intensity. In addition, when the semiconductor nanoparticles dispersed in glass particles as described in the comparative example described below are exposed to a solvent such as xylene at a low concentration, the surface of the semiconductor nanoparticles and the —O—Si—O— matrix are chemically bonded. Since they are bonded at the base, it is presumed that the interaction between the semiconductor nanoparticle surface and —O—Si—O—matrix occurs and the emission intensity decreases. On the other hand, by using the semiconductor nanoparticles A according to the present invention, the semiconductor particles are more uniformly incorporated into the stitch structure formed of —O—Si—O— in the glass particles at the stage of producing the glass particles. This is presumably because the semiconductor particles are contained in a well dispersed state without agglomerating in the glass particles. Further, it is considered that amine is attached to the surface and dispersed in the glass particles, and it is presumed that the semiconductor nanoparticles are not dispersed on a chemical bond basis. Therefore, since it does not interact with the stitch structure formed of —O—Si—O—, it is assumed that the emission intensity does not decrease even when exposed to a solvent such as xylene at a low concentration.

(Use)
The semiconductor nanoparticle A-encapsulating glass particles obtained by the production method of the present invention can be used for the following uses.

(Biological substance labeling agents and bioimaging)
The glass particles (semiconductor nanoparticle assembly) according to 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.

That is, the biological material labeling agent can be used for a bioimaging method (technical means for visualizing a biological molecule constituting the biological material and its dynamic phenomenon).

[Hydrophilic treatment of semiconductor nanoparticle assembly]
The surface of the glass particle (semiconductor nanoparticle assembly) described above is generally hydrophilic, but when it is hydrophobic, for example, when used as a biological material labeling agent, the water dispersibility is poor as it is, Since there are problems such as aggregation of the semiconductor nanoparticle aggregate, it is preferable to subject the surface of the semiconductor nanoparticle aggregate to a hydrophilic treatment.

As a hydrophilic treatment method, for example, there is a method of chemically and / or physically binding a surface modifier to the surface of the semiconductor nanoparticle assembly after removing the lipophilic group on the surface with pyridine or the like.

As the surface modifier, 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. Specifically, for example, 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. By doing so, the surface of the shell of the inorganic nanoparticles can be modified with a carboxyl group.

[Biological substance labeling agent]
The biological substance labeling agent is obtained by bonding the above-described hydrophilic nanoparticle aggregate that has been subjected to the hydrophilic treatment, the molecular labeling substance, and the organic molecule.

<Molecular labeling substance>
The biological substance labeling agent can label the 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.

<Organic molecule>
A preferred embodiment of the biological material labeling agent is a mode in which the hydrophilically treated glass particles (semiconductor nanoparticle aggregates) and the molecular labeling substance are bound by organic molecules.

The organic molecule is not particularly limited as long as it is capable of binding the semiconductor nanoparticle aggregate and the molecular labeling substance. For example, among proteins, albumin, myoglobin, casein, etc. It is also preferably used together.

The form of the bond is not particularly limited, and examples thereof include covalent bond, ionic bond, hydrogen bond, coordination bond, physical adsorption and chemical adsorption.

A bond having a strong bonding force such as a covalent bond is preferable from the viewpoint of the stability of the bond.

Specifically, when the semiconductor nanoparticle aggregate is hydrophilized with mercaptoundecanoic acid, avidin and biotin can be used as organic molecules. In this case, 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. .

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

(Comparative Example 1)
(Synthesis of InP / ZnS, core / shell structure semiconductor nanoparticles)
InP core particles were synthesized by the following heated solution method.

6 ml of octadecene is placed in a three-necked flask, and the molar ratio of In (acac) 3 and tris (trimethylsilyl) phosphine dissolved in 1 ml of octadecene in the solvent is In / P = 1/1. In addition, the reaction was performed at 300 ° C. for 1 hour in an argon atmosphere to obtain InP core particles (dispersion).

InP / ZnS core / shell particles were synthesized by allowing the InP core particle dispersion after the reaction at 300 ° C. for 1 hour to cool to 80 ° C., and then adding zinc stearate + sulfur dissolved in 1 ml of octadecene to the dispersion. , P, Zn and S were added so that the molar ratio of In / P / Zn / S = 1/1/1/1 was increased from 80 ° C. to 230 ° C. and reacted for 30 minutes. The thus obtained InP / ZnS core / shell semiconductor nanoparticles (Comparative Particle 1) were particles having a maximum emission wavelength at 630 nm.

(Comparative Example 2)
(Synthesis of CdSe / ZnS, core / shell semiconductor nanoparticles)
CdSe / ZnS core / shell semiconductor nanoparticles were synthesized as follows.

In an Ar stream, 2.9 g of stearic acid, 620 mg of n-tetradecylphosphonic acid, and 250 mg of cadmium oxide were added to 7.5 g of tri-n-octylphosphine oxide (TOPO), and the mixture was heated and mixed at 370 ° C. After allowing to cool to 270 ° C., a solution of 200 mg of selenium dissolved in 2.5 ml of tributylphosphine was added and dried under reduced pressure to obtain CdSe core semiconductor nanoparticles coated with TOPO.

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 (Comparative Particle 2) were obtained.

(Comparative Example 3)
(Synthesis of CdTe / ZnS, core / shell semiconductor nanoparticles)
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).

That is, hydrogen telluride gas while vigorously stirring an aqueous cadmium perchlorate solution adjusted to 25 ° C. and pH = 11.4 in the presence of thioglycolic acid (HOOCCH 2 SH) as a surfactant under an argon gas atmosphere Was reacted. The aqueous solution was refluxed for 6 days in an air atmosphere to obtain CdTe core particles.

The CdTe core particles thus obtained were particles having a maximum emission wavelength at 640 nm.

The CdTe / ZnS core / shell particles were synthesized by heating this aqueous solution to 80 ° C., and then adding zinc stearate + sulfur dissolved in 1 ml of water to the molar ratio of Cd, Te, Zn, S to In / It was obtained by adding P / Zn / S = 1/1/1/1, raising the temperature from 80 ° C. to 230 ° C., and reacting for 30 minutes (Comparative Particle 3).

(Comparative Example 4)
According to Example 1 described in JP-A-2005-281019, semiconductor nanoparticle-containing glass particles (comparative particles 4) having CdTe / ZnS present in a silica matrix were prepared.

The CdTe / ZnS core / shell semiconductor nanoparticle dispersion was water-solubilized by adding thioglycolic acid as a surfactant under the conditions of 25 ° C. and pH = 10. Thereafter, 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 the solution was stirred and 0.74 ml of water was mixed with the above water-soluble CdTe / ZnS core / shell semiconductor nanoparticle solution 0. 3 ml was added and dissolved. Next, with stirring this solution, 0.399 ml of tetraethoxysilane (TEOS), which is an alkoxide, and 0.3 aminopropyltrimethoxysilane (APS), which is an organoalkoxysilane, are used as a sol-gel glass precursor. 079 ml was added.

The dispersion was stirred for 2 days to obtain semiconductor nanoparticles-containing glass particles (comparative particles 4) in which CdTe / ZnS was present in the silica matrix.

(Preparation of semiconductor nanoparticles containing glass particles 1 to 3)
Acetone, a poor solvent, was added to the InP, CdSe, and CdTe solutions in Comparative Examples 1 to 3 to cause precipitation. By adding 0.1 mg of dodecylamine and 1 ml of ethanol to 0.1 mg of the precipitate, a water-soluble semiconductor nanoparticle solution can be obtained by stirring for 1 hour. This water-soluble semiconductor nanoparticle solution is subjected to hydrolysis by adding 0.1 mg of TEOS, 0.01 ml of water, and 0.03 ml of NH 3 , so that glass particles 1 to 3 containing semiconductor nanoparticles containing InP, CdSe, and CdTe are obtained. I was able to get it.

(Sensitivity (low concentration linearity test))
A low concentration linearity test was performed as follows and used as an index of sensitivity.

Xylene / ethanol was used as the solvent for the low concentration linearity test. Comparative semiconductor nanoparticles 1 to 3 in Comparative Examples 1 to 3 are precipitated with acetone, which is a poor solvent, and the solvent is removed by centrifugation and replaced with xylene / ethanol to 0.001 to 1 μM (FIGS. 1 to 3). 3). For comparative particles 4 and semiconductor nanoparticles A-containing glass particles 1 to 3, the particles are centrifuged, and after removing the solvent, the solvent is replaced with xylene / ethanol to make 0.001 to 1 μM. (FIGS. 4-7, comparative particle 4 corresponds to FIG. 4). As an evaluation method, the sample of each concentration is replaced with xylene / ethanol and left to stand for 1 h, and then the emission intensity is measured. The emission intensity is measured using F-7000 manufactured by Hitachi High-Tech.

As is clear from the results shown in FIGS. 1 to 7, the emission intensity of the semiconductor nanoparticles A-containing glass particles 1 to 3 increases linearly with respect to the concentration (FIGS. 5 to 7). Even in a region where the content is low, the relationship between the content of the semiconductor nanoparticle aggregate and the light emission intensity remains linear. On the other hand, in the comparative example (FIGS. 1 to 4), it is clear that the relationship between the content of the semiconductor nanoparticle aggregate and the emission intensity does not maintain linearity in a low concentration region.

Claims (4)

  1. Semiconductor nanoparticle-containing glass particles enclosing core-shell type semiconductor nanoparticles A having a core-shell structure, wherein the core-shell type semiconductor nanoparticles A have an amino compound having an amino group and a hydrophobic group on the surface. A semiconductor nanoparticle-containing glass particle, which is a nanoparticle A.
  2. 2. The semiconductor nanoparticle according to claim 1, wherein the core portion of the core-shell type semiconductor nanoparticle A contains indium phosphide (InP), cadmium selenide (CdSe), or cadmium telluride (CdTe). Encapsulated glass particles.
  3. The semiconductor nanoparticle-encapsulated glass particles according to claim 1 or 2, wherein the semiconductor nanoparticle-encapsulated glass particles include a plurality of the semiconductor nanoparticles A.
  4. It is a manufacturing method of semiconductor nanoparticle inclusion glass particles which manufactures semiconductor nanoparticle inclusion glass particles given in any 1 paragraph of Claims 1-3,
    (1) a step of attaching an amino compound having an amino group and a hydrophobic group to the surface of a core-shell type semiconductor nanoparticle to form the semiconductor nanoparticle A having the amino compound on the surface;
    (2) A glass particle forming step of producing glass particles using a glass precursor in the presence of the semiconductor nanoparticles A to produce semiconductor nanoparticle A-containing glass particles containing the semiconductor,
    The manufacturing method of the semiconductor nanoparticle inclusion | inner_cover glass particle characterized by having.
PCT/JP2012/056865 2011-04-26 2012-03-16 Glass particles containing enclosed semiconductor nanoparticles, and process for producing glass particles containing enclosed semiconductor nanoparticles WO2012147429A1 (en)

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