JP3360751B2 - Molecules having ultrafine particles and structures thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to electronic materials and sensor materials such as optical materials, nonlinear optical materials, and superlattice elements, magnetic materials, pharmaceuticals, agricultural chemicals, catalyst materials, inorganic materials, paint / coating materials, and cosmetic materials. .

[0002]

[Prior art]

(General Properties of Ultrafine Particles) 10
Small particles having a particle size of 0 nm or less are used for electronic component materials, optoelectronic materials, medical materials, catalyst materials,
Applications are being made in a wide range of fields such as sensor materials, paint and coating materials, and cosmetics. The advantages of using such small particles include the fact that they can be easily dispersed in a medium or a solvent or can be mixed more uniformly. Furthermore, since the proportion of constituent atoms and molecules existing at the interface increases, the properties of surface atoms and surface molecular layers appear, and the appearance of specific reactivity is expected.

Further, in semiconductor ultrafine particles or metal ultrafine particles, since they are ultrafine particles, the space in which electrons and holes can move is restricted, and a behavior which cannot be seen in a bulk material or a particle size of about micrometers is present. And its application is planned. In particular, the emergence of nonlinear optical characteristics utilizing electronic peculiarity caused by such a small crystal space is expected. The form of the small crystal space in which such quantization characteristics appear is in the form of a thin film, rod, disk, etc., but in the case of ultrafine particles, the isotropic nature of performance emerges compared to these forms. There is an excellent point. (Conventional method for producing ultrafine particles) As a method for producing ultrafine particles, generally, a production method by mechanical pulverization, a production method in a gas phase utilizing evaporation using heat or plasma, a precipitation method, or the like. And a production method in a liquid phase utilizing hydrolysis or the like. These production methods are described in, for example, "Particle Handbook" (edited by Motoji Jimbo, Asakura Shoten, 19
1991). (Conventional technology of ultrafine particle composite) There are known several technologies for complexing ultrafine particles, imparting an additional function by surface modification, and stabilizing the ultrafine particles. One of the major issues when using ultrafine particles in the past was the technology to prevent and stabilize the ultrafine particles from agglomeration and coagulation. As a method for solving this problem, for example, an example in which the surface of cadmium selenide ultrafine particles is covered with a phenyl group and stabilized is described in the journal of the American Chemical Society (J. Am. Chem. Soc. 1988, 110, 304).
6).

Further, a technique for fixing ultrafine particles on a carrier has been reported for the purpose of enhancing the catalytic activity. For example, an example in which rhodium ultrafine particles are immobilized on a polymer carrier crosslinked by an amide bond is described in Macromolecule, 2
4 (20), 5567-5572). Examples of composites in which ultrafine particles are organized include, for example, an example in which a monomolecular layer of alkanethiol having a bifunctional group is formed on the surface of gold or aluminum and a cadmium sulfide ultrafine particle layer is formed. Am. Chem. Soc. 1992, 114, 5221-5230). In these examples, the technique of compounding ultrafine particles has been considered from the idea of surface modification of ultrafine particles and immobilization of ultrafine particles. Such an idea is applied to conventional micrometer-sized particles. It was not an extension of this.

On the other hand, as a composite of ultrafine particles, for example, a reactive microgel (cross-linked reactive polymer latex) is used for the purpose of combining an organic compound and an inorganic compound to produce a material having intermediate properties. Report on the binding complexation of tetraethoxysilane with tetraethoxysilane, Proceedings of the Society of Polymer Science of Japan, 38, 7
No. 2319-2321. This is also an attempt to directly combine organic fine particles and inorganic fine particles to form a mixed material, and has not exceeded the conventional concept of particles. (Ultra-fine particle dispersion technology) On the other hand, ultra-fine particle dispersion technology is important in forming ultra-fine particle materials.
For example, there is a description of dispersion technology on page 340 of "Particle Handbook" (edited by Motoji Jimbo et al., Asakura Shoten, 1991) cited earlier. Methods such as adding an additive called a dispersant and performing surface treatment are known.
It is not a technique for controlling the spatial distance between ultrafine particles. In order to develop highly functional materials that take advantage of the properties of ultrafine particles, advanced nanometer-scale dispersion technology is expected.

[0006]

An object of the present invention is to provide a novel substance comprising ultrafine particles and a molecular chain. Another object of the present invention is to provide a novel ultrafine particle structure based on this.

[0007]

Means for Solving the Problems The present inventors diligently developed an ultrafine particle composite, and discovered and created an entirely new ultrafine particle substance. That is, a feature of the present invention is a molecule having an ultrafine particle in which a plurality of ultrafine particles are bonded by a molecular chain, and a molecule in which a plurality of ultrafine particles or a molecule having an ultrafine particle are continuously bonded by a molecular chain. A structure composed of ultrafine particles having a one-dimensional, two-dimensional, or three-dimensional multidimensional structure and a molecular chain.

That is, the present invention relates to a molecule having ultrafine particles in which a plurality of ultrafine particles are bonded by a molecular chain,
In addition, a structure in which a plurality of ultrafine particles or molecules having the above ultrafine particles are continuously bonded in a molecular chain to form a structure having a one-dimensional, two-dimensional, or three-dimensional multidimensional structure and a molecular chain. The ultrafine particles are semiconductors, and the ultrafine particles are semiconductors, and the ultrafine particles are metals or metal oxides. And a structure in which the ultrafine particles are a metal or a metal oxide, a molecule in which the ultrafine particles are an organic compound, and a structure in which the ultrafine particles are an organic compound, A molecule formed from a compound having two functional groups capable of bonding to the ultrafine particles, and a structure formed from a compound having two functional groups capable of bonding the molecular chain to the ultrafine particles;
Further, a molecule formed from a compound or a polymer compound having three or more functional groups whose molecular chains bind to ultrafine particles, and a compound having three or more functional groups whose molecular chains bind to ultrafine particles or A structure formed from a polymer compound, and a molecular dispersion obtained by dispersing the molecule in a medium; and a structure dispersion obtained by dispersing the structure in a medium; It is.

(Concept of the Invention) (Typical Example) FIG. 1 shows a typical example of a molecule having a plurality of ultrafine particles according to the present invention. It goes without saying that the present invention belongs to a new material concept and is not limited to this material example. FIG. 1 shows an example in which ultrafine cadmium sulfide particles having a diameter of nanometers are combined with benzenedithiol. Benzenedithiol, which is a bond, is about 0.7 nanometers long, and can be regarded as a basic unit of a new nanometer-sized substance that combines ultrafine particles and molecules. For example, cadmium sulfide ultrafine particles can be bonded to a plurality of benzenethiol molecular chains, and a bonded higher-order structure composed of cadmium sulfide ultrafine particles and benzenethiol can be produced. The molecules and structures having these ultrafine particles provide a new substance group different from conventional inorganic molecules, organic molecules, and crystals. Hereinafter, the concept of the present invention will be described in detail using a model.

(Model of the Invention) FIG. 2 shows the simplest model of the substance of the present invention in which two ultrafine particles are combined. In FIG. 2, circles indicate ultrafine particles, and lines connecting them represent molecular chains. That is, the most basic components of the present invention can be regarded as a bonding part composed of ultrafine particles and a bond composed of molecular chains, and the present invention refers to a structure formed by these elements. The length of a bond composed of a molecular chain, that is, the distance between ultrafine particles can be controlled depending on the type of the molecular chain. Further, since the ultrafine particles have a plurality of binding sites, the ultrafine particles may have a bond having a plurality of molecular chains. In addition, the size of the bonding portion made of ultrafine particles, that is, the particle diameter, and the type, that is, the type of ultrafine particles, can be changed. FIG.
FIG. 3 shows various molecular model diagrams in which two ultrafine particles are bonded.

The present invention, as exemplified in FIGS. 2 and 3, has a nanometer-sized structure in which a joint made of ultrafine particles is a bowl (ball) and a bond made of molecular chains is a stick (rod). It is a body, which goes beyond the concept of particles and opens up a new field like macromolecules or clusters. The present invention can be regarded as an ultrafine particle instead of an atom in a molecule, and as a kind of a molecule or a molecular analog having a nanometer size which is one rank larger in which a molecular chain is replaced instead of a chemical bond. Larger than. That is, since the joining portion made of ultrafine particles is an ultrafine particle, it has a large number of joining points and can form various high-order structures. In addition, these structures can form a structure in which the space between the ultrafine particles and the ultrafine particles is controlled.

For example, FIG. 4 shows an example of a one-dimensional model such as a chain or a branched chain; FIG. 5 shows an example of a two-dimensional model such as a ring, a ring, a ladder or a mesh; Shape, spiral,
An example of a three-dimensional model such as a multilayer is given. FIG.
As shown in (1), a bond composed of a molecular chain may be branched, and examples thereof include a tuft-like structure and a pendant structure. Furthermore, a molecular chain that is not a bond may be bonded to a bonding portion composed of ultrafine particles, as conventionally performed by surface modification of ultrafine particles. FIG. 8 shows an example of a model thereof. Further, as illustrated in FIG. 9, the structure of the present invention may be a so-called polymer having a large number of repeating structures, which may have a multilayer structure, a crystal structure, and various structures. Or an amorphous body. Thus, the cross-linking aggregation in which the structure of the present invention is such that a polymer chain as known in a colloid dispersion system is simultaneously adsorbed and aggregated on several particle surfaces,
It goes without saying that it is a completely different concept. In the present invention, another component may be contained in the structure, or conversely, a material in which the component comprising the structure is dispersed and dissolved in another matrix, a solvent, or the like may be used.

(Comparison with Conventional Technique) FIG. 10 shows, for comparison, a conventional molecular modification of ultrafine particles and a fixed body of ultrafine particles on a carrier similar to the models shown in FIGS. 2 to 10. Shown in notation. As is clear from the comparison with these model diagrams, the present invention goes beyond the conventional concept of particle processing in which ultrafine particles are fixed or modified, and has a nanometer-size structure composed of ultrafine particles and molecular chains. It provides a new substance. Hereinafter, the present invention will be described in detail.

(Ultrafine particles and measuring method thereof) The ultrafine particles referred to herein are 100 nanometers or less, preferably 20 nanometers or less, and more preferably 10 nanometers or less.
A particle having an average diameter of nanometers or less. Means for measuring the particle size and composition of such ultra-fine particles, which are very small, include commonly known methods, such as observation and analysis with a transmission electron microscope, powder X-ray diffraction, and light absorption spectrum. Measurement or the like can be used. In particular, by measuring the light absorption spectrum of the ultrafine particles, information on the particle size distribution can be easily obtained. In other words, as the particles become smaller, the electrons and holes in the semiconductor space are confined and a quantum box-like phenomenon occurs. Since the interstitial division increases and a light absorption peak appears, the particle size and the particle size distribution can be estimated.

(Material of Ultrafine Particle) The material of the ultrafine particle in the present invention is not particularly limited as long as it can bind to a molecular chain. And organic compounds. Alternatively, these components may be mixed, and further, ultrafine particles of different materials may be mixed and bound. Further, the surface of the ultrafine particles may be covered with a component different from the internal component, and the covering portion may be bonded to a molecular chain which is a bond.

(Semiconductor) The semiconductor used for the ultrafine particles in the present invention includes a group IV element such as silicon and germanium, an oxide semiconductor such as TiO ₂ and ZnO,
III-V compound semiconductors such as GaAs, InP and InSb, or II-VI compound semiconductors such as CdS, CdSe, ZnSe and CdTe, and further CuCl and CuB
and r-I-VII compound semiconductors.

(Metal and Metal Oxide) The metal used in the ultrafine particles in the present invention includes a group I (alkali metal and copper group) such as copper, silver and gold excluding hydrogen, and a group II such as zinc and cadmium. (Alkaline earth metals and zinc group), Group III such as aluminum except boron, Group IV such as tin and lead except carbon and silicon, and VI such as iron, cobalt and nickel
Group V (iron and platinum groups), vanadium, chromium, manganese and other V, VI and VII a subgroup elements, antimony,
It refers to bismuth, polonium, and the like. The metal oxide in the present invention refers to these oxides.

(Organic compound) The organic compound used for the ultrafine particles in the present invention is not particularly limited as long as it forms ultrafine particles. Preferred examples thereof include aromatic compounds such as naphthalene and pyrene, and porphyrins. And macrocyclic azaannulene such as phthalocyanines, and metal complexes, and polymers such as polystyrene and polyethylene.

(Molecular Chain) The term "molecular chain" as used in the present invention refers to a molecule that has a precursor having a plurality of functional groups involved in bonding in order to bond a plurality of ultrafine particles. Any functional group may be used as long as it reacts with ultrafine particles to form a bond, such as boron, carbon, nitrogen, oxygen, silicon, phosphorus, sulfur, germanium, arsenic, selenium, antimony, tin, tellurium, and bismuth. That form a bond through an atom of More preferred specific examples include, for example, a hydroxyl group, a mercapto group, an amino group, a bismasino group, a boryl group, a germyl group, a phosphino group, a plumbyl (Plumbyl) group, a siloxyl group, a stibino (Stibino) group, Examples thereof include halogenated carbon terminals such as a carboxyl group and a carbonyl halide group.

(Method for Producing Molecules and Molecular Structures Having Ultrafine Particles) In the method for producing molecules and molecular structures having ultrafine particles, a compound that becomes a molecular chain is added after the ultrafine particles are produced. And a method in which ultrafine particles are formed and produced in the presence of a compound that will become a molecular chain, and a method in which the molecular chains are modified on the surface and then the molecular chains react with each other.

(Method for Measuring Molecules and Molecular Structures Having Ultrafine Particles) Methods for measuring molecules or structures having ultrafine particles include infrared absorption spectrum, nuclear magnetic resonance, elemental analysis, mass spectrometry, and X-ray diffraction. This can be observed by a commonly known method such as observation with an electron microscope or a combination with a separation method such as a chromatograph or a centrifugal separation method.

(Typical Example 1 of Production Method) Examples of a method of producing ultrafine particles after forming them, or a method of producing ultrafine particles in the presence of a compound to be a molecular chain and producing them are as follows. The method is taken.

(Method for Producing Fine Particles) Superparticles of semiconductors, metals, metal oxides, and organic substances include generally known production methods in a gas phase and a liquid phase, and also include a gas phase and a liquid phase. It is manufactured by a manufacturing method in a solid. For example, in the gaseous phase, a vapor condensation method such as a vapor deposition method in a gas or a laser evaporation method, or a CV such as a plasma CVD method or a laser CVD method.
Ultrafine particles can be produced by the D method or the like, or in the liquid phase by a coprecipitation method, a metal alkoxide method, a protective colloid method, or the like. From the viewpoint of easy control of the reaction and the viewpoint of mass productivity, a preferable example is a production method in a liquid phase such as a coprecipitation method, a metal alkoxide method, a protective colloid method, and an organosol method.

(Production Example of Molecule / Structure Having Ultrafine Particles) The ultrafine particles produced by these methods are redispersed in a gas phase or a solution, and reacted with a compound to be a molecular chain to obtain a desired ultrafine particle. Molecules and structures having fine particles can be obtained. Further, when producing ultrafine particles by these methods, a compound to be a molecular chain is allowed to coexist to obtain a molecule and a structure having desired ultrafine particles.

(Specific Example of Manufacturing Molecule or Structure Having Ultrafine Particles) As a method of manufacturing a molecule or a structure having ultrafine particles, for example, when manufacturing a structure having semiconductor ultrafine particles, the following method is used. An example of a manufacturing method is given. First, a semiconductor raw material is dissolved in a solvent. The solvent used is water or a non-aqueous solvent, preferably a relatively polar non-aqueous solvent, specifically, for example, acetone, acetonitrile, benzonitrile, dimethylformamide, dimethylsulfoxide, chloroform, methanol, ethanol , Dioxane, tetrahydrofuran, methyl ethyl ketone, or a mixed solvent containing these.

In the synthesis of semiconductor particles in such a liquid phase, a metal compound soluble in a solvent to be used is used as a semiconductor raw material. These metal compounds are preferably 1
Mol / liter or less, more preferably to a solution of a concentration of 10 ^{@ 6} to 10 ^-1 mole / liter. When the compound to be a molecular chain is allowed to react in the coexistence in advance, the concentration of the compound to be a molecular chain in the reaction solution is preferably from 0.0001 to 100 times the molar concentration of the metal compound used. Can be These compounds may be mixed in advance, may be gradually added during the reaction, or the kind of the compound to be added may be sequentially changed as the reaction proceeds.

As the metal compound, for example, organic acid salts such as acetate, metal nitrates, perchlorates, alkoxides, acetylaceronates, halides and the like are used. Preferably, metal halides, metal nitrates, metal perchlorates, and metal acetates are used. These may contain water of crystallization. Examples of the metal species include Al and G that form a III-V compound semiconductor.
a, a group III element such as In, a group II element such as Zn, Cd, and Hg for forming a group II-VI compound semiconductor;
Group I elements such as Cu that generate Group VII compound semiconductors, IV
-Groups of Pb, Ti, Sn, etc. that generate Group VI compound semiconductors
Group IV elements are examples.

When a metal compound is used for the semiconductor, for example, II such as CdS, CdSe, ZnSe and CdTe
For example, in the case of producing ultrafine particles of a Group VI compound semiconductor, a suitable chalcogenizing agent such as a hydride such as hydrogen sulfide gas or hydrogen selenide gas, or an organic chalcogenide such as bistrimethylsilyl sulfur is used as a raw material solution. , Semiconductor particles can be generated and grown to obtain desired semiconductor ultrafine particles. These reagents can be diluted with an inert gas such as helium or nitrogen or a solvent to control the reaction for producing semiconductor particles. The concentration of the reaction gas is preferably 100% to 0.0001% by volume, and the flow rate may be an amount sufficient to allow the reaction to proceed steadily. When the reaction solution is 100 ml or less, the reaction can be preferably performed at a flow rate of usually 1 ml / min to 500 ml / min. The progress of the reaction can be monitored by a method such as light absorption spectrum observation. The reaction is terminated when the formation reaction of the semiconductor ultrafine particles is saturated by these observations.

A compound that will become a molecular chain may be added to the obtained dispersion liquid of semiconductor ultrafine particles as it is, or it may be concentrated, or the solvent may be removed to obtain a solid, and then reacted with the compound that becomes a molecular chain. You may. More preferably,
A compound that becomes a molecular chain as it is is added to the obtained semiconductor ultrafine particle dispersion. When a compound to be a molecular chain is allowed to coexist in advance and reacted, the solvent can be removed by a method such as evaporation or distillation under reduced pressure and used as it is as a material.

More specifically, preferred examples of the compound which becomes a molecular chain include benzenedithiol, 4,4′-biphenyldithiol, and 1,3-disiloxanedithiol in the case of II-VI group semiconductor ultrafine particles. And dithiols such as bis (4-mercaptophenyl) sulfide, trithiols, diselenols such as benzenediselenol, and the like. Orthosilicate acid derivatives such as diphenyldihydrogen orthosilicate can also be preferably used. After the production of the ultrafine particles, the compounds to be these molecular chains are preferably added in a molar ratio of 0.0001 to 100 with respect to the raw material compounds,
Heat or reflux as needed. Also, when a compound to be a molecular chain is added in advance, post-treatment such as heating may be performed. The respective structures may be separated from the solution or the precipitate obtained in this way by a usual separation and purification method such as a chromatography such as gel chromatography, a centrifugation method, a recrystallization method, and a reprecipitation method, Also,
The solvent may be removed by a method such as evaporation or distillation under reduced pressure and used directly as a material. In addition, the polymer component may be dissolved in the obtained solution to form a desired dispersion material.

(Typical Example 2 of Production Method) Further, for example, there is a production method in which ultrafine particles are modified with a compound that becomes a molecular chain, and then the molecular chains are bonded to each other. According to this method, a molecule or a structure having ultrafine particles of different types can be selectively produced using a compound that becomes a molecular chain having a plurality of different types of functional groups. For example, a compound that becomes a molecular chain having both a mercapto group and a carboxyl group,
Modification on cadmium sulfide ultrafine particles. On the other hand, cadmium selenide ultrafine particles modified with a compound that forms a molecular chain having both a selenol group and a hydroxyl group are prepared, and after mixing these, an esterification reaction is performed to bind the molecular chains.

(Usage Form) The molecule or structure having the ultrafine particles according to the present invention can be used as it is as a material. The obtained molecule or structure having ultrafine particles is used in the form of a thin film, a multilayer film thereof, a block, a lens, a fiber, a waveguide, or the like. That is,
It can be appropriately cut, compressed or stretched, melted, or formed into a desired form by a method such as screen printing, dip coating, spin coating or injection molding in a solution state, or injection molding. .
Further, the formed thin film or the like can be further processed by a generally known method such as dry etching to obtain an element having a desired form.

(Dispersion) The molecule or the structure having the produced ultrafine particles can be used by dispersing it in an appropriate medium. Even when a molecule or a structure having ultrafine particles is dispersed in a vacuum or a gas phase, or remains dispersed in a liquid phase, an optical material or an optoelectronic material can be formed by light passing through a dispersion space. It is preferable to disperse in a solid medium from the viewpoint of practicality, but it can also be provided in the form of a coating solution in a dispersed solution state. As a medium for dispersing a molecule or a structure having ultrafine particles in a solid, an inorganic medium such as glass or an organic medium material such as a polymer can be suitably used. This dispersion
It is used in the form of a thin film, a multilayer film thereof, a block, a lens, a fiber, a waveguide, or the like.

(Method for Producing a Dispersion of a Molecule or Structure Having Ultrafine Particles) As a method of forming a dispersion of a molecule or structure having ultrafine particles, for example, an inorganic medium such as glass is prepared by mixing SiO 2 in oxygen. Methods such as formation of a SiO ₂ medium by evaporation, impregnation of porous glass with a molecule or structure dispersion liquid having manufactured ultrafine particles, and formation of a glass medium by a sol-gel method can be used. Examples of a method for forming an organic medium such as a polymer include a method of mixing a molecule or a structure having ultrafine particles extracted as a powder with a polymer component, and a method of mixing a molecule or a structure dispersion having ultrafine particles manufactured in a liquid phase. A method of adding a polymer component and curing it by a polymerization reaction or the like, or forming a solid medium by removing a solvent can be employed. These dispersion materials can be further compressed, melted, or formed into a desired form in a solution state by a method such as screen printing, dip coating, or spin coating, or a molding method such as injection molding. Further, the formed thin film of dispersed semiconductor ultrafine particles can be further processed by a generally known method such as dry etching to obtain an element having a desired form. When a polymer is used as the medium of the dispersion material, the polymer may be selected according to the use of the device, and is not particularly limited. Specific preferable examples include polymethyl methacrylate, polyethyl methacrylate, and poly (2- (meth) acrylate). Hydroxyethyl) methacrylate, polycarbonate, polystyrene, polyester,
Examples include polyethylene terephthalate, polyvinyl chloride, polyether sulfone, polyacrylonitrile, a copolymer of vinyl chloride and vinyl acetate, a copolymer of styrene and acrylonitrile, or a mixture thereof. Further, a light-curing resin or a thermosetting resin can also be used. As another component, a surfactant or the like may be mixed. Hereinafter, an example of an embodiment of the present invention will be described with reference to examples.

[0035]

The present invention will be described below in more detail with reference to examples. Example 1 cadmium perchlorate hexahydrate _{(Cd (ClO 4) 2 ·} 6
The H ₂ O) to 2.0 × 10 ^over 3 mol / l in acetonitrile 300ml were dissolved in a concentration of, placed in a three-necked flask equipped with a Dimroth and gas inlet tube with a cock, to which benzene dithiol (HSC ₆ H ₄ SH) is 2.3 ×
It was added dropwise an acetonitrile solution 2.0ml dissolved at a concentration of 10 ^@ 3 mol / l, stirring with a magnetic stirrer 1
Performed for 0 minutes. Next, after introducing 10 ml of hydrogen sulfide gas into the flask with a syringe, the cock was closed, and the solution was stirred in a hydrogen sulfide gas atmosphere for 10 minutes. A hydrogen sulfide trap was set in front of the Dimroth, and the reaction was performed in a fume hood. After the reaction, nitrogen was flowed into the system from a gas inlet tube to remove residual hydrogen sulfide gas. The solution thus obtained was yellow and transparent.

When the particle size distribution of the obtained solution was examined by the dynamic light scattering method from light scattering, a particle size distribution of 15 nm or more was observed. From this, it can be seen that a compound which is a compound obtained by modifying ultrafine cadmium sulfide particles, which is regarded as a large particle body as compared with the product in Comparative Example 1 below, is formed in the solution. The solvent was removed from this solution by an evaporator to obtain a yellow solid residue.
This solid does not redissolve in the solvent acetonitrile,
It did not dissolve in dimethylformamide (DMF). That is, it was shown that a large structure that could not be solvated was formed. This was measured infrared absorption spectrum of the solid, SH stretching from benzene dithiol appearing at 2400cm ^{-1 ～2600Cm-1} was not observed at all. That is, it can be seen that the SH structure has disappeared and has been bonded to the cadmium sulfide particles. From these facts, it was identified that a molecule or a structure having cadmium sulfide ultrafine particles having -SC ₆ H ₄ S- as a molecular chain was produced.

Comparative Example 1 In Example 1, a molecule or structure having ultrafine particles was used.
In order to make it more clear that
1, benzenedithiol (HSC₆H _FourSH)
Benzenethiol (C instead of solution)₆H_FiveSH)
7.0 × 10^{ー 3}mol / l acetonitrile solution
The operation was carried out under the same conditions except that was used. The resulting solution
From the light scattering of the liquid, we investigated the particle size distribution by the dynamic light scattering method.
At this time, a particle size distribution was observed around 8 nm. That is,
Cadmium sulfide ultrafine particles modified by reaction with monofunctional group
Alone cannot achieve the particle size distribution as in Example 1.
I understand. The solvent is removed from this solution by an evaporator.
A yellow residue solid was obtained upon removal.
This solid is redissolved in the solvent acetonitrile and
Also dissolved in dimethylformamide (DMF). Sa
The particle size distribution in the solution dissolved in
It was consistent with the value for the liquid. That is, higher-order structures are not
You can see that it is not. The infrared absorption spectrum of this powder
When measured, it was 2400 cm as in Example 1.^{ー 1}~ 2
600cm^{ー 1}Of benzenethiol induced SH stretching
Was not observed at all. That is, the SH structure reacts
You can see that it is gone. From these, the ratio
In Comparative Example 1, ultrafine particles and molecular chain-SC₆H_FiveUltra-fine
Modified forms of the particles are produced, but of course,
The molecule or structure having ultrafine particles as in Example 1
It turns out that it does not work. That is, it has a plurality of functional groups
From the compound that becomes a molecular chain and the ultrafine particles, the ultrafine particles of Example 1
Comparison of the fact that a molecule or a structure having a child is generated
It is clear from the example.

Example 2 Cadmium Sulfide Ultrafine Particles Obtained in Comparative Example 1 and Molecular Chain
1. A solution in which a modified product of ultra-fine particles composed of SC ₆ H ₅ is dispersed, and benzenedithiol (HSC ₆ H ₄ SH).
2.0 ml of an acetonitrile solution having a concentration of 3 × 10 ⁻³ mol / l was added, and stirring was further continued for 10 minutes. When the particle size distribution by dynamic light scattering was examined from the light scattering of the obtained solution, a particle size distribution of 18 nm or more was observed. From this, it can be seen that a compound which is regarded as a large particle body as compared with the product of Comparative Example 1, which is a compound obtained by modifying cadmium sulfide ultrafine particles, is generated in the solution.

The solvent was removed from this solution by an evaporator to obtain a yellow solid residue.
This powder did not redissolve in acetonitrile as a solvent and did not dissolve in dimethylformamide (DMF).
That is, it was shown that a large structure that could not be solvated was formed. This was measured infrared absorption spectrum of the solid, SH stretching from benzene dithiol appearing at 2400cm ^{-1 ～2600Cm-1} was not observed at all. That is, it is understood that the SH structure has disappeared and the newly added benzenedithiol is also bonded to the cadmium sulfide particles. from these things,
-SC bound with -SC ₆ H ₄ S- as a molecular chain
It has been identified that a molecule or structure having cadmium sulfide ultrafine particles modified with ₆ H ₅ has been produced.

Example 3 Cadmium Sulfide Ultrafine Particles Obtained in Comparative Example 1 and Molecular Chain
2.3 × ¹⁰⁻² mol / l of benzenedithiol (HSC ₆ H ₄ SH), which was added in Example 2, to the solution in which the modified ultrafine particle composed of SC ₆ H ₅ was dispersed in a concentration of 10 times, was added.
When 2.0 ml of acetonitrile-dimethylformamide (DMF) solution was added, a precipitate was instantaneously formed.
When the precipitated solid was filtered out, it did not dissolve in dimethylformamide (DMF). That is, having cadmium sulfide ultrafine particles, -SC ₆ H ₄
It was shown that a large structure in which S- was continuously bonded as a molecular chain was formed.

[0041]

According to the present invention, a new substance group comprising ultrafine particles and molecular chains based on a novel concept can be provided. This structure is also provided as an ultrafine particle dispersion in which ultrafine particles are dispersed in a nanometer size. Substances composed of ultrafine particles and molecular chains obtained by the present invention include optical materials, nonlinear optical materials, electronic materials and sensor materials such as superlattice elements, magnetic materials, pharmaceuticals, agricultural chemicals, catalyst materials, inorganic materials, paints and coatings. It can be used for materials and cosmetic materials.

[Brief description of the drawings]

FIG. 1 is an explanatory view of a typical example of a molecule having ultrafine particles according to the present invention.

FIG. 2 is a diagram illustrating a basic model of a molecule having ultrafine particles of the present invention.

FIG. 3 is a model explanatory diagram of a relationship between ultrafine particles of a molecule having ultrafine particles and a molecular chain.

FIG. 4 is a diagram illustrating a model example of a one-dimensional structure based on a molecule having ultrafine particles.

FIG. 5 is an explanatory diagram of a model example of a two-dimensional structure composed of ultrafine particles and molecular chains.

FIG. 6 is a diagram illustrating a model example of a three-dimensional structure composed of ultrafine particles and molecular chains.

FIG. 7 is an explanatory diagram of a model example of a structure in which a molecular chain composed of ultrafine particles and a molecular chain is branched.

FIG. 8 is an explanatory diagram of a model example of a structure composed of ultrafine particles modified with ultrafine particles and molecular chains.

FIG. 9 is a diagram illustrating an example of a model of a continuous structure composed of ultrafine particles and molecular chains.

FIG. 10 is a diagram illustrating an example of a model according to the related art.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI // C09K 3/00 C09K 3/00 C H01L 21/52 H01L 21/52 E (58) Fields surveyed (Int. Cl. ⁷ , DB name) B01J 19/00-19/32

Claims (13)

(57) [Claims] 1. A structure having ultrafine particles in which a plurality of ultrafine particles are bonded by a molecular chain. 2. A one-dimensional, two-dimensional, or three-dimensional multidimensional structure, which is a structure in which a plurality of ultrafine particles or a structure having the ultrafine particles according to claim 1 are continuously bonded by molecular chains. Comprising ultrafine particles having a molecular chain and a molecular chain. 3. The method according to claim 1, wherein the ultrafine particles are semiconductors.
Structure . 4. The structure according to claim 2, wherein the ultrafine particles are semiconductors. 5. The structure according to claim 1, wherein the ultrafine particles are a metal or a metal oxide. 6. The structure according to claim 2, wherein the ultrafine particles are a metal or a metal oxide. 7. The structure according to claim 1, wherein the ultrafine particles are an organic compound. 8. The structure according to claim 2, wherein the ultrafine particles are an organic compound. 9. The functional group whose molecular chain binds to ultrafine particles has two functional groups.
The structure according to claim 1, wherein the structure is formed from a compound having two components. 10. The structure according to claim 2, wherein the molecular chain is formed from a compound having two functional groups that bind to the ultrafine particles. 11. structures of the molecular chain according to claim 1, formed from a compound or a polymer compound having three or more functional groups that bind the ultrafine particles. 12. The structure according to claim 2, wherein the molecular chain is formed from a compound or a polymer having three or more functional groups capable of binding to the ultrafine particles. 13. A structure dispersion obtained by dispersing the structure according to claim 1 in a medium.