JP2010082776A - Nano-particle synthetic method by organic solvent sono-chemistry - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To develop technology synthesizing not only a metal oxide-based nanoparticle but also a non-metal oxide nanoparticle as a nano-particle having a uniform particle diameter by a simple method by sono-chemistry. <P>SOLUTION: An organic solvent having a lower boiling point is made to coexist in a reaction field for forming a particle of nanometer size from liquid mixture containing a nano-particle precursor and a stabilizer by the sono-chemistry, and formation of the particle of nanometer size is performed in the presence of the organic solvent. Thereby, the nano-particle having a uniform shape and a relatively uniform particle diameter can be easily synthesized. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

    The present invention relates to a method for synthesizing nanoparticles by organic solvent sonochemistry.

  Nanometer-sized particles (nanoparticles) exhibit various unique and excellent properties, characteristics, and functions, so they are more accurate, smaller, and lighter than all current materials and products. It is expected to realize a technology that satisfies the above requirements. In this way, nanoparticles are made from ceramic nanostructure modifiers, optical functional coating materials, electromagnetic shielding materials, secondary battery materials, fluorescent materials, electronic component materials, magnetic recording materials, polishing materials, and other industrial and industrial materials, It is attracting attention as a material for the 21st century because it enables high-performance, high-performance, high-density, and high-precision products such as pharmaceuticals and cosmetics. From the recent basic research on nanoparticles, the discovery of ultra-high functionality, new physical properties, and the synthesis of new materials by the quantum size effect of nanoparticles has attracted a great deal of interest from industry.

Various methods have been proposed for the nanoparticle synthesis method. However, in many cases, since the surface energy of the nanoparticles is extremely high, the nanoparticles are likely to aggregate, and the original function of the nanoparticles is often not expressed. Once agglomerated nanoparticles cannot be redispersed, even if a surfactant or the like is used at that stage, the nanoparticles cannot be dispersed.
As a method for solving this, there is a method in which a surfactant is allowed to coexist in a nanoparticle synthesis field, and at the same time as a nanoparticle is generated, the surfactant is adsorbed on the surface to be stabilized and dispersed in a solvent. In the reverse micelle method, one or two kinds of reactive raw material aqueous solutions are injected together with a surfactant into an organic solvent to form reverse micelles, and thermal micelles or reverse micelles composed of different reaction solutions are combined. This is a method of stabilizing the nanoparticles produced by the reaction and at the same time. In the hot soap method, a surfactant is used as a solvent, a metal aqueous solution is injected and stirred vigorously to form minute water droplet micelles, and nanoparticles synthesized by thermal decomposition or reaction between two types of reactive raw materials are produced. The surrounding surfactant protects the coating.

None

  Conventionally, synthesis of nanoparticles by sonochemistry using ultrasonic waves has been performed, but it is generally performed in a surfactant to suppress aggregation of the generated nanoparticles, and stable with a surfactant at the same time as nanoparticle generation. It was to become. The principle of sonochemistry is to generate microbubbles and use the energy of the microreaction field in the process of generation and extinction. The boiling point of the surfactant is high, and bubbles cannot be generated sufficiently uniformly. It was. In addition, there is a need for the development of technology that can be applied not only to metal oxide nanoparticles but also to nanoparticles other than metal oxides, and to synthesize nanoparticles with a uniform particle diameter using a simple method. Yes.

  As a result of diligent research, the present inventor succeeded in synthesizing various nanoparticles by sonochemistry using ultrasonic waves by using a lower boiling point organic solvent. It was found that the uniform shape and its particle size were relatively uniform. Based on these findings, the present invention has been completed.

In representative aspects, the present invention provides the following.
[1] A low boiling point organic solvent is allowed to coexist in a reaction field in which nanometer-sized particles are formed by sonochemistry from a liquid mixed system containing a nanoparticle precursor and a nanoparticle stabilizer. A method for producing nanometer-size particles, comprising applying ultrasonic irradiation to the nanometer-size particles.
[2] The nanometer size according to [1], wherein the nanoparticle stabilizer is selected from the group consisting of organic carboxylic acids, organic nitrogen compounds, organic sulfur compounds, and organic phosphorus compounds. Of particle production.
[3] The method for producing nanometer-sized particles according to the above [1] or [2], wherein the organic solvent is a low-boiling solvent having a boiling point of 200 ° C. or lower.
[4] The method for producing nanometer-sized particles according to any one of [1] to [3], wherein the organic solvent is methanol, ethanol, or dimethylformamide (DMF).

According to the technology of the present invention, nanoparticles having various shapes such as spherical nanoparticles having a size of 3 to 40 nm or rod-shaped nanoparticles having a length of 4 to 300 nm and a width of 1 to 5 nm have a relatively uniform particle size. Can be obtained as Further, by using a precursor composed of two or more kinds of metals as a raw material, multi-component metal-containing nanoparticles including a two- and three-component composite metal oxide can be synthesized.
Other objects, features, excellence and aspects of the present invention will be apparent to those skilled in the art from the following description. However, it is understood that the description of the present specification, including the following description and the description of specific examples and the like, show preferred embodiments of the present invention and are presented only for explanation. I want. Various changes and / or modifications (or modifications) within the spirit and scope of the present invention disclosed herein will occur to those skilled in the art based on the following description and knowledge from other parts of the present specification. Will be readily apparent. All patent documents and references cited herein are cited for illustrative purposes and are not to be construed as a part of this specification. is there.

  The present invention provides a technique for synthesizing nanoparticles by sonochemistry as well as the nanoparticles obtained by this technique. Bubbles are generated when external heat or force overcomes the force required to maintain the liquid. Similarly, when ultrasonic waves are applied to the liquid or solution, bubbles are generated due to local pressure fluctuations. Will occur. It is considered that bubbles generated by ultrasonic waves concentrate energy in a short time during the adiabatic compression process and form a high-temperature and high-pressure local field of 5,000 to tens of thousands of degrees and 1,000 to several hundred atm when they collapse. In other words, cavitation occurs when a liquid or solution is irradiated with powerful ultrasonic waves having a frequency of 20 kHz to several MHz. Cavitation is a physical phenomenon in which bubbles are generated and disappeared in a short time due to a pressure difference in a liquid flow. It is known that when a bubble collapses by cavitation, a short-lived high-temperature, high-pressure local field (hot spot) is formed. This reaction field functions as a kind of extreme reaction field and can be used in various application fields. Sonochemistry refers to the field dealing with chemical action using cavitation derived from ultrasound, and refers to chemistry in the reaction field around the hot spot caused by ultrasonic cavitation. And since the sonochemistry as a whole is normal temperature normal pressure, it can be performed with a simple apparatus. Cavitation is likely to occur, that is, the pressure at which cavitation occurs is called a cavitation threshold, and depends on physicochemical properties such as liquid viscosity, vapor pressure, surface tension, and ultrasonic irradiation conditions. In general, cavitation is more likely to occur at lower frequencies.

  The method for forming nanoparticles by sonochemistry of the present invention is suitable for forming high-quality nanoparticles with low defects and impurity concentrations. This sonochemistry nanoparticle formation method is a general term for the method of obtaining particles from raw materials (nanoparticle precursors) in a container holding a predetermined liquid medium in a local high temperature and high pressure environment at a hot spot. However, the present invention particularly refers to a technique for forming nanoparticles in the presence of a substantial amount of a low-boiling organic solvent as a liquid medium.

In sonochemistry, particles can be formed using an oscillator, a vibrator, and a reaction vessel. The transducer for transmitting ultrasonic waves is a Langevin transducer in which a ceramic resonator such as barium titanate or lead zirconate titanate or an electrostrictive resonator such as barium titanate is sandwiched between two thick metal cylinders. Etc. may be used. There is also a method of directly introducing ultrasonic waves into the sample solution from the outside using an ultrasonic horn attached to the tip of the vibrator. A cone-type vibrator can be used, or a flow reactor can be used. As the ultrasonic irradiation apparatus, an apparatus known in the art can be used, and such an ultrasonic irradiation apparatus is also known as a sonicator or an ultrasonic homogenizer and is commercially available. For example, BRANSON Ultrasonic Homogenizer from Central Science Trading Co., Ltd. High intensity ultrasonic irradiation device with horn type probe (tap type horn, solid type horn), for example, BRANSON Model 250D , BRANSON Model 450D etc. can be used.

  In the present invention, nanoparticles are formed from the nanoparticle precursor in an environment where the surfactant used in the hot soap method is present as a stabilizer for the formed nanoparticles. In particular, the present invention is characterized in that a low-boiling solvent having a high affinity for both the stabilizer and the raw material nanoparticle precursor is selected and coexisted. Thereby, it is possible to satisfactorily synthesize nanoparticles by controlling the generation of cavitation while forming a uniform phase. In the present invention, the term “nanoparticle” refers to a nanometer-sized particle, for example, a nanoparticle in which the particle is a metal oxide, a nanoparticle that is a composite oxide composed of at least two kinds of metal elements, a metal Nanoparticles that are composite metals composed of at least two kinds of metals, nanoparticles that are semiconductor compounds containing Group 5 elements of the periodic table, and nanoparticles that are semiconductor compounds containing Group 6 elements of the periodic table Particles, those in which the above nanoparticles are crystalline nanoparticles, and the like. The nanoparticles can typically include nanoparticles containing a metal element. In the method of the present invention, metal oxide crystal nanoparticles can be produced.

The stabilizer present in the reaction field for nanoparticle formation of the present invention provides a reaction field capable of forming desired nanoparticles and / or formed in a reaction field capable of forming desired nanoparticles. There are no particular limitations as long as the nanoparticles can be stabilized, and for example, those known in the art can be used. Preferably, as the stabilizer, a surfactant used in the hot soap method as described above can be used. As the stabilizer, those capable of stabilizing the formed nanoparticles can be suitably used, and function as an organic modifier in a liquid phase in which a local high-temperature and high-pressure spot is present under ultrasonic irradiation conditions. What can be used can also be used suitably. Examples of the stabilizer include organic carboxylic acids, organic nitrogen compounds, organic sulfur compounds, and organic phosphorus compounds. The stabilizer can be arbitrarily selected as long as the objective effect of the present invention is not significantly impaired, and can be used in combination of one or more kinds as appropriate. The organic carboxylic acids are not particularly limited as long as the object and effects of the present invention are not significantly impaired. Examples thereof include aliphatic carboxylic acids, alicyclic carboxylic acids, aromatic carboxylic acids, and the like, and preferably aliphatic carboxylic acids. Can be selected and used. The number of carbon atoms of the carboxylic acids is arbitrary as long as the objective effect of the present invention is not significantly impaired, but is usually 5 or more, in some cases 6 or more, preferably 14 or more, more preferably 16 or more, and usually 24 or less, Preferably it may be 20 or less, more preferably 18 or less. In a preferred embodiment, the carboxylic acids include, for example, long-chain alkyl carboxylic acids, and typically C ₆ -C ₁₈ long-chain alkyl carboxylic acids are preferred. Examples of carboxylic acids include oleic acid, linoleic acid, linolenic acid, caprylic acid, capric acid, lauric acid, behenic acid, stearic acid, myristic acid, palmitic acid, myristoleic acid, palmitoleic acid, vaccenic acid, eicosenoic acid, etc. Is mentioned. Particularly preferred is oleic acid.

Examples of organic nitrogen compounds include organic amines, organic amide compounds, nitrogen-containing heterocyclic compounds, and the like. The organic amines may be any of primary amines, secondary amines, and tertiary amines, and preferably primary amines and secondary amines. Examples of the organic amines include aliphatic amines, and examples thereof include primary aliphatic amines and secondary aliphatic amines. The number of carbon atoms of the amines is not particularly limited as long as the objective effects of the present invention are not significantly impaired. For example, the number of carbons is usually 8 or more, preferably 14 or more, more preferably 16 or more, and usually 24 or less, preferably 20 Below, more preferably 18 or less. In a preferred embodiment, organic nitrogen compounds include, for example, long chain alkyl amines, and typically C ₆ -C ₁₈ long chain alkyl amines are preferred. Typical aliphatic amines include, for example, oleylamine, laurylamine, myristylamine, palmitylamine, stearylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, dioctylamine and the like. Examples thereof include alkylamines, aromatic amines such as aniline, hydroxyl group-containing amines such as methylethanolamine and diethanolamine, and derivatives thereof. Particularly preferred is oleylamine. In one embodiment of the present invention, a mixture comprising a mixture selected from the above carboxylic acids and one selected from the above organic amines is also preferably used. For example, the use of oleic acid and oleylamine is also preferred in some cases. Examples of the nitrogen-containing heterocyclic compounds include heterocyclic compounds having a saturated or unsaturated 3- to 7-membered ring containing 1 to 4 nitrogen atoms. It may contain a sulfur atom, an oxygen atom or the like as an atom. Representative nitrogen-containing heterocyclic compounds include pyridine, lutidine, collidine, quinolines, and the like.

  Examples of organic sulfur compounds include organic sulfides, organic sulfoxides, sulfur-containing heterocyclic compounds, and the like. Representative organic sulfur compounds include, for example, dialkyl sulfides such as dibutyl sulfide, dialkyl sulfoxides such as dimethyl sulfoxide and dibutyl sulfoxide, and sulfur-containing heterocyclic compounds such as thiophene, thiolane, and thiomorpholine. .

Examples of the organic phosphorus compounds include phosphate esters, phosphine, phosphine oxides, trialkylphosphine, phosphite esters, phosphonate esters, phosphinate esters, phosphinate esters And phosphinic acid esters. Typical organic phosphorus compounds include, for example, trialkylphosphine such as tributylphosphine, trihexylphosphine, trioctylphosphine, tributylphosphine oxide, trihexylphosphine oxide, trioctylphosphine oxide ( TOPO), and trialkylphosphine oxides such as tridecylphosphine oxide. As the organophosphorus compounds, compounds having a carbon-phosphorus single bond in the molecule are suitable, and trialkylphosphine oxides such as TOPO are most suitable.
In general, the stabilizer is preferably determined in consideration of the solubility between the raw material and the solvent. For example, it is preferable to select to constitute a homogeneous phase, and if possible, it is possible to use a molecular species having a shorter carbon chain. The stabilizer may function as an organic modifier. In that case, preferably, the stabilizer contains the organic molecule residue as a substituent so as to provide the organic molecule residue described below. You can use what you have.

Such a stabilizer may be used alone to constitute a liquid phase medium, or may be used in combination with a plurality of kinds as required. Further, an appropriate organic solvent (for example, benzene, toluene, xylene, naphthalene, etc.) may be used. Cyclic carbonization of alkanes including long-chain alkanes such as aromatic hydrocarbons, n-hexane, n-heptane, n-octane, isooctane, nonane, decane, dodecane, octadecane, cyclopentane, cyclohexane, methylcyclohexane, etc. You may dilute and use with hydrogen etc.). Moreover, you may dilute and use with the organic solvent made to coexist in the reaction field which forms the nanometer size particle | grain from the liquid mixed system containing the nanoparticle precursor and stabilizer mentioned below.

As an organic solvent used in the present invention to coexist in a reaction field for forming nanometer-sized particles from a liquid mixed system containing a nanoparticle precursor and a stabilizer, good nanoparticles under ultrasonic irradiation conditions Although it is not particularly limited as long as it has a property that provides a formation field, in particular, it has a low boiling point, for example, it has a high affinity for the stabilizer and the raw material aqueous solution, and its decomposability is low. Those having good cavitation generation and capable of forming nanoparticles by reaction are preferred. The organic solvent is preferably one that dissolves the raw material and the stabilizer. As the solvent, those having affinity for both polar solvents and organic solvents are generally preferred, and any solvent having such properties can be used without any particular limitation. Examples of the organic solvent include low-boiling solvents having a boiling point of 200 ° C. or less, such as alcohols having a hydroxyl group, ketones or aldehydes having a carbonyl group, nitriles having a cyano group, lactam compounds, oxime compounds, amides. Examples thereof include amides or ureas having a group, amines having an amino group, sulfides, sulfoxides, phosphate esters, carboxylic acids or esters which are carboxylic acid derivatives, carbonic acid or carbonic acid esters, ethers and the like.

Examples of alcohols having a hydroxyl group include methanol, ethanol, propanol, isopropanol, n-butanol, t-butyl alcohol, 1,4-butanediol, 1,3-butanediol, pentanol, cyclopentanol, hexanol, 2- Ethylhexanol, cyclohexanol, heptanol, cycloheptanol, octanol, cyclooctanol, nonanol, decanol, dodecanol, tridecanol, tetradecanol, heptadecanol, cycloheptanol, methoxyethanol, chloroethanol, trifluoroethanol, hexafluoropropanol Phenol, benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and the like. Examples of ketones or aldehydes having a carbonyl group include acetone, 2-butanone, 3-pentanone, diethyl ketone, methyl ethyl ketone, methyl propyl ketone, butyl methyl ketone, cyclohexanone, acetophenone, and the like. Examples of nitriles having a cyano group include acetonitrile and benzonitrile. Examples of the lactam compound include ε-caprolactam. Examples of the oxime compound include cyclohexanone oxime.

Examples of amides or ureas having an amide group include formamide, N-methylformamide, N, N-dimethylformamide (DMF), N, N′-dimethylacetamide, pyrrolidone, N-methyl-2-pyrrolidone, N, N′-dimethylethyleneurea, N, N′-dimethylpropyleneurea, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoramide and the like can be mentioned. Examples of amines having an amino group include quinoline, triethylamine, tributylamine and the like. Examples of the sulfoxides include sulfolane and dimethyl sulfoxide (DMSO). Examples of phosphate esters include hexamethylene phosphonic acid. Examples of the carboxylic acid and esters include ethyl acetate, methyl acetate, amyl acetate, ethyl lactate, formic acid, acetic acid, dimethyl carbonate, diethyl carbonate, propylene carbonate, ethyl 3-ethoxypropionate and the like. Examples of ethers include diglyme, diethyl ether, t-butyl methyl ether (MTBE), 1,2-dimethoxyethane, methoxymethyl butanol, butyl carbitol, cellosolve, methyl cellosolve, britsellosolve, anisole, tetrahydrofuran (THF ), 1,4-dioxane, 1,3-dioxane, 1,3-dioxolane and the like. Among these, DMF can be preferably used. The organic solvent may be arbitrarily an aqueous solvent as long as the objective effects of the present invention are not significantly impaired, and may be used in combination of one or more kinds as appropriate. As the organic solvent, one having a boiling point lower than that of the stabilizer can be used, and DMF has a boiling point of 153 ° C., and those having a boiling point in the vicinity thereof or lower can be preferably used.

  The nanoparticle precursor as a raw material can be preferably used as a stabilizer to be used and / or one that dissolves in a mixture of a stabilizer and an organic solvent, but is in a liquid state for the convenience of production operation Can also be suitably used. The raw material may be a solution of an appropriate organic solvent, water, or a mixture thereof as required, but may be used as it is if the raw material itself is liquid at room temperature. In the present invention, a nanoparticle precursor that can form a homogeneous system in a reaction field can be suitably used. In the present invention, a homogeneous system can be formed in the reaction field, and a water-soluble raw material precursor can be used.

  As the nanoparticle precursor, those giving desired nanoparticles can be suitably used, and any substance can be used as long as the desired nanoparticles can be obtained. Therefore, it is possible to arbitrarily select and use an appropriate one from simple substances or compounds containing elements contained in the nanoparticles to be produced. Preferably, those which are commercially available and can be easily obtained, or those which can be easily derived therefrom are used. For example, in the case of nanoparticles containing a metal element, examples of metal nanoparticle (metal compound nanoparticle) precursors include metal halides, metal carbonates, metal carboxylates, metal alkoxides, and metal alkylxanthogenic acids. Examples thereof include salts, metal complex compounds such as metal carbonyl compounds, and metal hydroxides. As typical metal nanoparticle precursors, for example, metal alkoxide, metal hydroxide, metal acetate, metal citrate, metal amine complex, metal acetone complex, metal acetylacetonate and the like are preferably used. Furthermore, it can be used as a constituent element donor of a desired nanoparticle so that a compound containing the constituent element coexists. As such a constituent element donor, those known in the art can be used, and examples thereof include, but are not limited to, thiourea and selenourea.

  As the nanoparticle precursor, those giving desired metal oxide crystal nanoparticles can also be suitably used, and any substance can be used as long as the desired metal oxide crystal nanoparticles can be obtained. Therefore, it is possible to arbitrarily select and use an appropriate metal element or metal compound containing the metal element contained in the metal oxide crystal nanoparticles to be produced. Examples of the metal oxide precursor include metal chloride, metal acetate, metal acetylacetonate, metal alkoxide, metal hydroxide, and the like. Among these, metal alkoxides, metal acetates, metal citrates, metal acetylacetonates, and metal hydroxides are preferably used from the viewpoint of by-produced impurities (such as chlorides). The precursors may be used alone or in combination of two or more in any combination and ratio. The precursor may exist in any state in the reaction solution, but usually the precursor exists in a dissolved state in the reaction system.

The “metal” constituting the nanoparticles of the present invention is not particularly limited as long as it can typically produce nanoparticles, and can be selected and used from those known to those skilled in the art. Typical metals include the group IIIB boron (B)-group IVB silicon (Si)-group VB arsenic (As)-group VIB tellurium (Te) lines in the long-period periodic table. The elements on the line with the boundary as well as those on the left or lower side of the long-period periodic table from the boundary, such as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, etc., Group IB elements such as Cu, Ag, Au, etc., Group IIB elements such as Zn, Cd, Hg, etc., Group IIIB elements such as B, Al, Ga, In, Tl, etc.
Group IVB elements include Si, Ge, Sn, Pb, Group VB elements such as As, Sb, Bi, Group VIB elements include Te, Po, and Groups IA to VIIA. It is done. Mn, Tc, Re, etc. for Group VIIA elements, Cr, Mo, W, etc. for Group VIA elements, V, Nb, Ta for Group VA elements, etc.
For Group IVA elements, Ti, Zr, Hf, etc. For Group IIIA elements, Sc, Y, Lanthanoids (eg, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho , Er, Yb, Lu, etc.), actinoids (Ac, Th, etc.), misch metal, etc., Group IIA elements, such as Be, Mg, Ca, Sr, Ba, etc., Group IA elements, Li, Na, K, Rb, Cs etc. are mentioned.

The nanoparticles of the present invention include (a) a metal oxide nanoparticle, (b) at least a composite oxide composed of two or more metals, (c) a metal nanoparticle, (d) at least Nanoparticles that are composite metals composed of two or more metals, (e) Nanoparticles that are semiconductor compounds containing Group 5 elements of the periodic table, (f) Nanoparticles (a) to (e) above are crystalline nano Includes particles. The nanoparticles of the present invention also include nanoparticles in which the particles are semiconductor compounds containing Group 6 elements of the periodic table. Suitable examples include nanoparticles in which the particles are sulfur compounds, for example, those in which the nanoparticles are ZnS.

In the present invention, ultrasonic irradiation is performed in the system by immersing an ultrasonic irradiation probe of a device capable of irradiating high-intensity ultrasonic waves in a liquid mixed system containing a nanoparticle precursor and a nanoparticle stabilizer. Thus, nanometer-sized particles are formed by sonochemistry through the use of energy in the micro-reaction field during the generation of microbubbles and the generation and extinction process, and a low-boiling organic solvent is allowed to coexist in the reaction field. Meter size particle formation is performed. The chemical reaction in this sonochemistry does not improve the reactivity due to the temperature rise, but proceeds at a low temperature mainly related to the properties of the solvent system. Therefore, the apparatus can be simplified, and nanoparticles having a uniform particle size can be synthesized by an inexpensive and simple operation. In the case of performing ultrasonic irradiation, since the ultrasonic wave itself has a dispersing ability, stirring by a stirrer or a stirrer is not particularly required. The ultrasonic generation source may be any apparatus that generates ultrasonic waves as described above, such as an ultrasonic cleaning machine used for cleaning, an ultrasonic homogenizer used for crushing or emulsifying particles, and is particularly limited. It can be selected according to the purpose and used appropriately. The frequency of the ultrasonic wave is designated as an ultrasonic wave, and a range of 16 to 10,000 kHz can be used. Typical examples include 20 kHz and 40 kHz. The ultrasonic irradiation intensity can be 0.5 to ²⁰ W / cm ² . As the output of the ultrasonic irradiation apparatus, for example, 200 W, 400 W, 800 W, 1100 W and the like are commercially available, but not limited thereto.

Although the time of ultrasonic irradiation can be selected so that a desired nanoparticle may be obtained, it can be 5 to 60 minutes, for example. The reaction time depends in particular on the reactivity of the raw materials and the numerical values of the thermodynamic parameters of the stabilizer and the added organic solvent. The temperature range can be selected according to the type and composition of the target nanoparticles. The ultrasonic irradiation can be carried out after appropriately heating the solution system to 50 to 90 ° C, preferably 55 to 80 ° C, more preferably 60 to 75 ° C, more preferably 65 to 70 ° C. Ultrasonic irradiation can be performed from the side surface, bottom surface, top surface, or central part of the inside of the reaction container, or from all of them. Typically, a probe is inserted into the liquid. It is preferable to start from the center. The ultrasonic wave irradiation means may be disposed at one place on each of the side surface and the bottom surface, or may be disposed uniformly dispersed at a plurality of places. Nanoparticle formation may be performed continuously using a flow reactor, or may be performed in batch using a batch reactor. The reaction vessel or the reaction apparatus is not limited to a rectangular parallelepiped or a cylindrical body, but may be of another form.
There are various conditions for ultrasonic irradiation, such as the type and amount of nanoparticle precursors used, nanoparticle stabilizers, organic solvents with lower boiling points, the shape of the reaction vessel, the type and number of ultrasonic irradiation devices, etc. The optimum value can be determined by experiment, taking into account the parameters.

The ratio of the nanoparticle precursor to the stabilizer in the starting mixture for reaction can be determined by performing experiments or the like as appropriate so that the desired nanoparticle product can be obtained. The ratio of nanoparticle precursor: stabilizer in molar ratio is from about 1: 10,000 to about 1: 1, preferably from about 1: 2,500 to about 1: 2, more preferably from about 1: 250 to about 1: 4. In some cases, about 1: 150 to about 1: 5,
More preferably, it can be about 1: 100 to about 1: 6, more preferably about 1:70 to about 1: 8, more preferably about 1:50 to about 1:10. The ratio of nanoparticle precursor: stabilizer in the starting mixture for reaction to a molar ratio of about 1:60 to about 1:40, about 1:35 to about 1:15, or about 1:30 To about 1:20, about 1:35 to about 1:20, or about 1:25 to about 1:15. The ratio of the stabilizer to the organic solvent in the starting mixture for the reaction can be determined by performing experiments or the like as appropriate to obtain the desired nanoparticle product, and is not particularly limited. For example, the stabilizer The ratio of organic solvent in volume ratio (v / v) is about 1,000: 1 to about 1: 1,000, preferably about 100: 1 to about 1: 100, more preferably about 20: 1 to about 1:20. In some cases from about 10: 1 to about 1:10, more preferably from about 5: 1 to about 1: 5, more preferably from about 5: 1 to about 2: 1, more preferably about 4.5: It can be 1 to about 2.5: 1.

  About reaction time, although it changes also with the kind of target nanoparticle, the raw material to be used, the kind of stabilizer, and the magnitude | size and quantity of the nanoparticle to manufacture, it can usually be made from several minutes to several hours. During the reaction, the reaction temperature may be constant, or the temperature may be gradually raised or lowered. After a reaction time for producing desired nanoparticles, the temperature is lowered. The temperature lowering method is not particularly limited, but it may be left as it is or may be air-cooled. If necessary, it can be rapidly cooled using a refrigerant. In the method of the present invention, by changing parameters such as reaction time, ratio of precursor: stabilizer, carbon chain length of long-chain fatty amine or long-chain fatty acid, reaction temperature, etc., particle size of 2-22 nm Each of the nanoparticles can be obtained. Rod-shaped nanoparticles and wire-shaped nanoparticles having a width of 5 nm can be obtained, and cube-shaped nanoparticles having a uniform size can be obtained.

In one exemplary synthesis process of the invention, a 50 mL glass beaker is charged with the required amount of dimethylformamide (DMF) and 30 mL of ligand-forming solvent and then warmed to 65-70 ° C. in an oil bath. To do. A required amount of precursor (precursor) is added to the solution with stirring to obtain a clear solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn-type probe is directly immersed in the solution, and ultrasonic irradiation (USI) is started. After several minutes of irradiation, the clear solution becomes cloudy. The turbidity indicates that fine particles are formed. Continue USI for desired time. Fine particles synthesized after USI are treated with ethanol to form a flocculent mass. After centrifugation, it is suspended again in a hydrophobic solvent such as toluene. This process is repeated 2-3 times to remove almost all of the free ligand. In this way, desired nanoparticles can be easily obtained by a simple method.

In the present specification, the term “nanoparticle” refers to a nanometer-sized particle as described above, for example, an average particle diameter of 1 μm (1,000 nm) or less.
Preferably, the average particle diameter refers to a size of 200 nm or less, and preferably a size of 150 nm or less. In some cases, the nanoparticles may have an average particle size of 100 nm or less, and in other cases the average particle size may be 50 nm or less. In a preferred case, the nanoparticles have an average particle size of 20 nm or less, and in other cases, the average particle size is 10 nm or less, or 5 nm or less. It may be a thing. The nanoparticles are 0.1-50 nm particles, 1-50 nm particles, preferably 1-25 nm particles, more preferably 1-20 nm particles, more preferably 5-20 nm particles, even more preferably 5-10 nm. Particles. In a preferred case, the nanoparticles preferably have a uniform particle size, but may have a mixture of particles having different particle sizes at a certain ratio.

In the technology of the present invention, those having a particle size of 5 nm, those having a particle size of 2 to 7 nm, particles having a particle size of 2 to 2.5 nm, and even 70% or more, 80% or more of the nanoparticle population 90% or more, 95% or more of 5 nm particle size, 2 to 7 nm particle size, or 2 to 2.5 nm particle size is obtained . Nanoparticle populations obtained by the technique of the present invention include 1-5 nm particles, 5-10 nm particles, 10-15 nm particles, 15
~ 20nm particles, 20-30nm particles, 30-50nm particles, 1-3nm particles, 3-5nm particles, 5-7nm particles, 7-10nm particles, 10-13nm particles, 13-16nm Particles, 16-20 nm particles, or 20
˜25 nm particles and 70% or more, 80% or more of the nanoparticle population, 90
% Or more, 95% or more is included as that size.

When the nanoparticle shape is a rod, cylinder, cuboid, elliptic cylinder, etc., the size of the short axis is a small value of the particle size, and the size of the long axis is smaller than the size of the short axis. It may be a large value. Nanoparticles are spheres, cubes, polygonal cubes, rods, cylinders, oval shapes, tetragonal, hexagonal, trigonal, orthorhombic, monoclinic, triclinic, wurtzite crystals, single It may be in the shape of a wall or multi-wall nanotube, or other nanoscale shape. They exhibit very interesting electrical and optical properties.
The particle size can be measured by methods known in the art, such as TEM,
It can be measured by adsorption method, light scattering method, SAXS, etc. In TEM, observation is performed with an electron microscope. When the particle size distribution is wide, it is necessary to pay attention to whether or not the particles entering the field of view represent all particles. In the adsorption method, the BET surface area is evaluated by N ₂ adsorption or the like.

  In the sonochemistry nanoparticle formation method of the present invention, nanoparticles composed of simple metals, alloy nanoparticles composed of two or more metal elements (for example, binary alloy nanoparticles, ternary alloy nanoparticles, quaternary alloys) Nanoparticles, multi-component alloy nanoparticles, etc.), semiconductor nanoparticles, magnetic nanoparticles, phosphor nanoparticles, conductor nanoparticles, pigment nanoparticles, etc. in a simple manner, advantageously in large quantities and / or High quality products can be manufactured at low cost and uniformly dispersed or homogeneous. Thus, the nanoparticles can be used to produce products with high performance.

The metal nanoparticles and alloy nanoparticles produced by this sonochemistry nanoparticle formation method are those selected from the above metals, for example, elements of Group IB of the long-period periodic table such as Cu, Ag, Au, etc. (Copper group elements), Group VIII elements (iron group elements and / or platinum group elements) such as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Zn, Cd, Hg, etc. Periodic Table Group IIB Elements (Zinc Group Elements), Mn, Tc, Re, etc. Periodic Table Group VIIA Elements (Manganese Group Elements), Cr, Mo, W, etc. Periodic Table Group VIA Elements (Chromium) Group elements), V, Nb, Ta and other periodic table group VA elements (earth metal elements), Ti, Zr, Hf and other periodic table group IVA elements (titanium group elements), Sc, Y, lanthanoids (For example, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, etc.), actinides (Ac, Th, etc.), Misch metal, etc. (Including rare earth elements), B,
Periodic table group IIIB elements (aluminum group elements) such as Al, Ga, In, Tl, Si, Ge, Sn, Pb
Periodic Table Group IVB elements (carbon group elements), such as As, Sb, Bi Periodic Table Group VB elements, Te,
Examples include elements selected from Group VIB elements such as Po and Group IIA elements such as Mg, Ca, Sr and Ba. The nanoparticles may be used alone or may contain a plurality of elements. Moreover, in an alloy, what contains 2 or more types selected from said element may be mentioned.

The semiconductor nanoparticles produced by the sonochemistry nanoparticle formation method of the present invention include simple elements of Group 4B elements of the periodic table (referred to as Group IV semiconductors in the present invention), such as carbon (C) [for example, diamond, etc. ], Silicon (Si), germanium (Ge), tin (Sn) [for example, α-Sn, etc.]
Lead (Pb) and other periodic group 5B elements, for example, phosphorus (black phosphorus), arsenic (As), antimony (Sb) and other periodic group 6B elements, for example, selenium (Se) and tellurium (Te), the compound comprising a plurality of periodic table group 4B elements such, SiC, etc. Si _1-x Ge _x, the periodic table compounds of the group 4B elements and periodic table group 5B elements, for example, Compounds of Group 4B elements of Periodic Table and Group 6B elements of Periodic Table, such as Si ₃ N ₄ , for example, SiO ₂ , tin (IV) oxide (SnO ₂ ), tin sulfide (II) (SnS), tin sulfide ( IV) (SnS ₂ ), tin sulfide (II, IV) (Sn (II) Sn (IV) S ₃ ), tin selenide (II) (SnSe), tin telluride (II) (SnTe), lead sulfide ( PbS), lead selenide (PbSe), lead telluride (PbTe), etc., compounds of Group 3B elements of the periodic table and Group 5B elements of the periodic table (referred to as III-V group compound semiconductors in the present invention), for example, Boron nitride (BN)
Boron phosphide (BP), Boron arsenide (BAs), Aluminum nitride (AlN), Al _x Ga _1-x N, Al _x Ga _1-x A
s, aluminum phosphide (AlP), aluminum arsenide (AlAs), aluminum antimonide (AlSb), gallium nitride (GaN), gallium phosphide (GaP), GaInP _2, gallium arsenide (GaAs), gallium antimonide (GaSb) Indium nitride (InN), indium phosphide (InP), indium arsenide (InAs), In _x Ga _1-x As, indium antimonide (InSb), Ga-Al-In-As, etc. And compounds of Group 6B elements of the periodic table, for example, Al ₂ O ₃ , aluminum sulfide (Al ₂ S ₃ ), aluminum selenide (Al ₂ Se ₃ ), gallium sulfide (Ga ₂ S ₃ ), gallium selenide ( Ga ₂ Se ₃ ), gallium telluride (Ga ₂ Te ₃ ), indium oxide (In ₂ O ₃ ), indium sulfide (In ₂ S ₃ ), indium selenide (In ₂ Se ₃ ), indium telluride (In ₂ Te _3), such as the periodic table compounds of the group 2B elements and periodic table group 5B elements, such as Cd ₃ P _2, periodic table group 2B elements and periodic table 6B Compounds with elements (referred to as II-VI group compound semiconductors in the present invention), for example, zinc oxide (ZnO), zinc sulfide (ZnS), zinc selenide (ZnSe), zinc telluride (ZnTe), cadmium oxide ( CdO), cadmium sulfide (CdS), cadmium selenide (CdSe), cadmium telluride (CdTe), mercury sulfide (HgS), mercury selenide (HgSe), mercury telluride (HgTe), etc. And compounds of Group 6B elements of the periodic table, for example, antimony (III) sulfide (Sb ₂ S ₃ ), antimony selenide (III) (Sb ₂ Se ₃ ), antimony telluride (III) (Sb ₂ Te ₃ ) Bismuth (III) sulfide (Bi ₂ S ₃ ), bismuth selenide (III) (Bi ₂ Se ₃ ), bismuth telluride (III) (Bi ₂ Te ₃ ), etc. Compounds with Group 6B elements, for example, copper (I) (Cu ₂ O), Cu ₂ S, Ag ₂ S, Periodic Table Group 4A elements, Periodic Table Group 5A elements, Periodic Table Group 6A elements, Periodic Table Group 7A elements and Periodic Table Group 8 Arsenide (including the iron group elements and platinum group elements)
Compound with selected ones and the Periodic Table Group 6B elements from the group consisting of, for example, titanium oxide (such as _{TiO 2, Ti 2 O 5,} Ti 2 O 3, Ti 5 O 9), zirconium oxide (ZrO _2, Zr ₂ O ₃ etc.), such as vanadium oxide (II) (VO), vanadium oxide (IV) (VO ₂ ), tantalum oxide (V) (Ta ₂ O ₅ ), molybdenum sulfide (IV) (MoS ₂ ), Tungsten oxide (IV) (WO ₂ ), manganese oxide (II) (MnO), etc., cobalt oxide (II) (CoO), cobalt sulfide (II) (CoS), nickel oxide (II) (NiO), tetraoxide Compounds of Group 2A elements of the periodic table and Group 6B elements of the periodic table, such as triiron (Fe ₃ O ₄ ), iron (II) sulfide (FeS), Fe ₂ S, Fe ₂ O _3, such as magnesium sulfide ( MgS) and magnesium selenide (MgSe), furthermore, chalcogen spinels, such as _{CdCr 2 O 4, CdCr 2 Se} 4, CuCr 2 S 4, CuIn 2 S 2, CuIn 2 Se 2, HgCr 2 Se 4 , YSi ₂ , BaTiO _{3 and the} like.
Among these, as important semiconductors, for example, Si, Ge, SnS ₂ , SnS, SnSe, SnTe, PbS, PbSe, PbTe, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb , Al ₂ S ₃ , Al ₂ Se ₃ , Ga ₂ S ₃ , Ga ₂ Se ₃ , Ga ₂ Te ₃ , In ₂ S ₃ , In ₂ Se ₃ , In ₂ Te ₃ , ZnS, ZnSe, ZnTe, CdS, CdSe CdTe, HgS, HgSe, HgTe, Sb ₂ S ₃ , Sb ₂ Se ₃ , Sb ₂ Te ₃ , Bi ₂ S ₃ , Bi ₂ Se ₃ , Bi ₂ Te ₃ , MgS, MgSe, and the like.

In one aspect of the present invention, semiconductor nanoparticle synthesis methods using the sonochemistry nanoparticle formation method of the present invention as well as semiconductor nanoparticles exhibiting very useful properties are provided. In a typical embodiment, the semiconductor nanoparticle synthesis method includes a long-period periodic table group IIB element such as Zn, Cd, Hg, and a periodic table group IIIB element such as Al, Ga, In, and Tl. And nanoparticle precursors containing one selected from the group consisting of Group IVB elements of the same periodic table such as Si, Ge, Sn, Pb, for example, xanthates, acetates or acetyls of these elements Provided is a method for producing nanometer-size particles, characterized in that acetonate is subjected to sonochemistry nanoparticle formation conditions in a mixture of a stabilizer and an organic solvent to form nanometer-size particles. Thus, nanoparticles and / or nanoparticle dispersions or nanoparticle compositions having a uniform particle size and capable of maintaining a good dispersion state can be obtained. In this method, if necessary, for example, a constituent element donor of desired nanoparticles such as thiourea and selenourea can be added to the mixture. ZnS nanoparticles, one of the nanoparticles obtained in this way, are, for example, organic molecular residues on the particle surface,
For example, a hydrocarbon group such as an alkyl group and / or an alkenyl group is bonded by a chemical bond. These materials have excellent dispersibility in the medium of nanoparticles due to repulsion between the organic molecular residues.

The semiconductor nanoparticles obtained by the production method of the present invention are the main nanoparticle constituents,
Any activator may be doped (meaning that it is intentionally added). Examples of such active materials include alkaline earth metals such as magnesium, aluminum group elements such as manganese, boron, aluminum, gallium, indium and thallium, carbon group elements such as carbon, tin and germanium, phosphorus, arsenic and antimony , Nitrogen group elements such as bismuth, copper group elements such as copper and silver, rare earth elements including lanthanoids such as yttrium, cerium, europium, terbium, erbium and thulium, and halogen elements such as chlorine and fluorine, etc. However, the present invention is not limited thereto and is selected from those used in the field.

The magnetic nanoparticles produced by the sonochemistry of the present invention include metals or alloys having iron group or manganese group elements as essential components, or nano-sized particles containing iron group element oxides. Can be mentioned. Typical magnetic materials include Fe, Co, Ni metals, FePt, CoPt, FePd, M ¹ nAl, FePtM ¹ , CoPtM ¹ , FePdM ¹ , alloys selected from the group consisting of M ¹ nAlM ¹ ( In the chemical formula, M ¹ represents a metal element, and as M ¹ , for example, Li, Mg, Al, Si, P, S, Mn, Ni, Cu, Zn, Ga, Ge, As, Se, Ag, Cd, In, Sn, Sb, Te, I, Au, Tl, Bi, Po, and At are included), or a metal oxide containing iron oxide Fe ₂ O ₃ . Typical ones include FeNi, FePd, FePt, FeRh, CoNi, CoPt, CoPd, CoRh, CoAu, Ni ₃ Fe, FePd ₃ , Fe ₃ Pt, FePt ₃ , CoPt ₃ , Ni ₃ Pt, CrPt ₃ , Ni ₃ Mn, FeNiPt, FeCoPt, CoNiPt, FeCoPd, FeNiPd, FePtCu, FePtIn, FePtPb, FePtBi, FePtAg, CoPtCu, FePdCu, FeCoPtCu, FeNiPtCu, FePtCuAg, FeNiPdCu, etc. may be included. Examples of the metal oxide include a general formula: (M ² O) m · Fe ₂ O ₃ (wherein M ² represents a divalent metal atom, and M ² includes, for example, Mn, Ni, Co, Mg, Ca, Sr, Ba, Cu, Zn, Pb, etc. are included, and m is a number represented by 0 ≦ m ≦ 1, and Y-Fe garnet (YIG) may be included. More representative examples include spinel crystals containing as a main component Fe ₂ O ₃ , magnetoplumbite type hexagonal crystals, Mn ferrite, Ni ferrite, Zn ferrite, Mn- Zn ferrite, Ni-Zn ferrite and the like may be included.

Important examples include magnetic iron oxide (eg, magnetite (Fe ₃ O ₄ ), γ-Fe ₂ O _3, etc.). Magnetic materials include Ni-Fe alloys (Permalloy), Fe or Fe-Co alloys, Fe-Cr-Co alloys, Alnico magnet alloys, rare earth cobalt intermetallic compounds, Nd-Fe-B intermetallic compounds, etc. Good. Further, as the magnetic nanoparticles, the general formula, A _x B _3-x M ³ _y Fe _5-y O ₁₂ (where 0 ≦ x <3, 0 ≦ y <5, A is Bi, Ca , Ce, Pb, Pt, one or more elements selected from B, and B is one or more elements selected from rare earth elements including Y (yttrium), specifically, Ce, Dy, eu, Er, Gd, and in Ho, La, Lu, Nd, Pm, Pr, Sm, Tb, Tm, Y, Yb , etc., M ³ is, Al, Co, Cr, Cu , Fe (II), Ga, Represents one or more elements selected from Ge, Hf, In, Li, Mn, Mo, Nd, Ni, Pb, Rh, Ru, Sc, Si, Sn, Ti, V, Zn, Zr) It may be a magnetic material such as a garnet-type magnetic material. Here, when x = 0, B is Y, and y = 0, yttrium-iron garnet (YIG) represented by the composition formula Y ₃ Fe ₅ O ₁₂ which is a typical oxide magnetic material is obtained. Further, in this composition, a part of Y can be substituted with Bi, Gd, etc., and a part of Fe can be substituted with Ga, In, Al, etc. The YIG thus substituted is referred to as a substitution type YIG. When the substitution type YIG is used, the Curie temperature, the magnetic anisotropy, the magnetostriction coefficient, and the like can be changed.

By using the technique of the present invention, highly crystalline nanoparticles can be obtained.
High crystallinity includes electron diffraction, transmission electron microscope (TEM), field emission transmission electron microscope (FE-TEM), scanning electron microscope (SEM), scanning transmission electron microscope. This can be confirmed by analysis of an electron micrograph such as (Scanning Transmission Electron Microscope: STEM), X-ray diffraction (XRD), or thermogravimetric analysis. For example, in electron diffraction, a dot is obtained as a diffraction interference image for a single crystal, a ring for a polycrystal, and a halo for an amorphous. In the electron micrograph, the crystal plane is solid if it is a single crystal, and it is polycrystalline if it has such a shape that crystals further appear from above the particles. When polycrystalline primary particles are small and many particles aggregate to form secondary particles, they become spherical. If it is amorphous, it must be spherical. In X-ray diffraction, a sharp peak is obtained if it is a single crystal. The crystallite size can be evaluated from the width of 1/2 height of the X-ray peak using the Sherre equation. If the crystallite size obtained by the evaluation is the same as the particle diameter evaluated from the electron microscope image, it is evaluated as a single crystal. In thermogravimetric analysis, when heated in a dry inert gas with a thermobalance, weight loss due to evaporation of moisture adsorbed at around 100 ° C
In addition, weight reduction due to dehydration from inside the particles is observed up to about 250 ° C. When organic materials are included, even greater weight loss is observed at 250-400 ° C. In the case of particles obtained by the technique of the present invention, even when the temperature is raised to 400 ° C., the weight loss due to dehydration from the inside of the crystal is 10% or less at maximum, which is greatly different from the case of nanoparticles synthesized at low temperature. Thus, the characteristics of the metal oxide fine particles obtained according to the present invention are characterized by high crystallinity, for example, a sharp peak in X-ray diffraction, dots or rings observed in electron diffraction, For example, dehydration of crystal water is 10% or less per dry particle by thermogravimetric analysis, and / or primary particles have a crystal plane in an electron micrograph.

Nanoparticles are, for example, SiO ₂ for pigments, catalyst carriers, high temperature materials, honeycombs, corrosion resistant materials, etc., Fe ₂ O ₃ for pigments, magnetic materials, etc., CeO ₂ for abrasives, catalyst carriers, ions, etc. For applications such as conductors and solid electrolytes, TiO ₂ is used for applications such as photocatalysts, pigments and cosmetics, Y ₂ O ₃ is used for applications such as pigments and catalyst carriers, InO is used for applications such as transparent conductors, and ZnO is Light material, conductive material,
For applications such as pigments and electronic materials, SiO ₂ is used for catalyst carriers, zeolites, fillers, beads, etc., SnO ₂ is used for conductive materials, conductors, sensors, etc., Nb ₂ O ₃ is used for magnetic materials, etc. Cu, Ag and Al are used for applications such as electrodes and catalyst materials, Ni is used for applications such as electrodes, magnetic materials and catalyst materials, Co and Fe are used for applications such as magnetic materials and catalyst materials, and Ag / Cu is used B ₄ C, AlN, TiB ₂ etc. are used for applications such as high temperature materials and high strength materials for applications such as electrodes and catalyst materials.
Nanoparticles and thin films having nanoparticles in a specific arrangement are recognized to exhibit unique and excellent characteristics. For example, a single-layered array of nanoparticles is known to be capable of being densely packed like magnetic nanoparticles and exhibit excellent functions as a near-field memory element, and is applied to magnetic tapes and the like. It exhibits excellent properties and is useful. In addition, since the quantum size effect can be obtained, for example, in the case of nano phosphors arranged in a dispersion pattern, products such as quantum effect phosphors, quantum effect light emitters, and LSI high-density mounting bases can be provided. . A multi-layered arrangement of nanoparticles such as titania exhibits excellent functions such as low light scattering and a photocatalytic effect, such as a wet photoelectric conversion element and a high-performance photocatalytic coating. A particle-dispersed film can be provided with excellent functions such as a reinforcing effect and a flame-retardant effect, and can be used as a semiconductor sealing agent.
The nanoparticles obtained by the present invention function as particles that meet user needs. For example, it is useful as a high-concentration barium titanate-dispersed resin for semiconductor packaging, a nanoparticle-dispersed ink for inkjet, a battery material, a catalyst material, a lubricant, and the like, which can be prepared as follows.

Electronic components such as semiconductors must be packaged with a high dielectric constant resin in order to eliminate electrical disturbance from outside the package. For this purpose, a barium titanate particle-dispersed thermosetting resin is used. In high-concentration barium titanate-dispersed resins for packaging such as this semiconductor, it has been required to disperse barium titanate particles at a high concentration. Although it is possible to disperse the titanium dioxide in the resin using a surfactant, there is a problem that dielectric loss occurs at the interface. By using the nanoparticle production technology of the present invention, it is possible to synthesize particles that have been surface-modified with chemical bonds, and ultimately, by introducing the same monomer as the resin, a material in which the resin and the inorganic material are integrated is obtained. Can be synthesized.
Since nanoparticles exhibit excellent physical properties such as hue, color development, and durability, they are used in inks for high-tech equipment, for example, nanoparticle-dispersed inks for inkjet. An ink jet printer using ink in which nanoparticles are dispersed is expected to be used for manufacturing wiring, circuit diagrams, and the like by ink jet. However, for that purpose, it is necessary to synthesize nanoparticles suitable for it and disperse them in a solvent at a high concentration. The nanoparticle production technology of the present invention makes it possible to synthesize particles having the same polymer as the ink solvent.
Battery materials, for example, electrode materials such as Li-ion batteries and capacitor materials, are mixed with carbon materials to make materials for products. The battery material needs to be well dispersed with carbon and solvent. In general, a treatment using a dispersant is required, but the nanoparticle production technique of the present invention can synthesize a material that is homogeneously dispersed with a solvent without using any dispersant.

The supported metal catalyst is activated when the electron orbit of the metal interacts with the oxide catalyst to cause charge transfer. Therefore, by using the nanoparticle particle manufacturing technology of the present invention that can mix different kinds of materials on the order of nanometers, it becomes possible to prepare a catalyst having a high density of active sites where metals and oxides come into contact with each other. Become.
In addition, the lubricant is used to reduce the friction acting between the solids, but it can be expected that the lubricant acts as a nano-bearing because the lubricant is contained in the lubricant. Specifically, the shear force is converted into the rotational kinetic energy of the bearing to prevent it from being transmitted as a shear force to the other surface. Conventionally, an organic polymer has been used as the lubricant, but the nanoparticle production technology of the present invention makes it possible to disperse nanoparticles having a strong structure.
The present invention will be described in detail with reference to the following examples, which are provided merely for the purpose of illustrating the present invention and for reference to specific embodiments thereof. These exemplifications are for explaining specific specific embodiments of the present invention, but are not intended to limit or limit the scope of the invention disclosed in the present application. In the present invention, it should be understood that various embodiments based on the idea of the present specification are possible.
All examples were performed or can be performed using standard techniques, except as otherwise described in detail, and are well known and routine to those skilled in the art. .

[Synthesis of gold nanoparticles]
(a) Oleylamine: HAuCl ₄ (precursor) = 30: 1 was sonicated in oleylamine and DMF for 5 minutes to produce Au nanoparticles. That is, a typical synthesis method was as follows. A 50 mL glass beaker was charged with 8 mL of DMF and 30 mL of oleylamine, and then heated to 65-70 ° C. on an oil bath. 0.003 mol HAuCl ₄ was added to the solution with stirring to obtain a clear solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was directly immersed in the solution, and ultrasonic irradiation (USI) was started. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. The USI was continued for 5 minutes. The microparticles synthesized after the USI were treated with ethanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free oleylamine, the resulting sample was stored. As a result, 4-5 nm spherical gold particles were obtained. The result of observing the gold nanoparticle sample obtained in Example 1 (a) with TEM is shown in FIG. Moreover, the result of having measured the particle size distribution of this sample is shown in FIG.

(b) The process of Example 1 (a) was repeated except that the ultrasonic irradiation treatment was performed for 10 minutes instead of the ultrasonic irradiation for 5 minutes. As a result, spherical gold fine particles of approximately 5 nm were obtained. The results of observing the gold nanoparticle sample obtained in Example 1 (b) with TEM and XRD are shown in FIGS. 3 and 5, respectively. Moreover, the result of having measured the particle size distribution of this sample is shown in FIG.

(c) Decylamine: HAnCl ₄ = 30: 1 was sonicated in decylamine and DMF for 10 minutes to produce Au nanoparticles. That is, a typical synthesis method was as follows: a 50 mL glass beaker was charged with 6 mL of DMF and 25 mL of decylamine, and then heated to 65-70 ° C. on an oil bath. 0.003 mol HAuCl ₄ was added to the solution with stirring to obtain a clear solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was directly immersed in the solution, and ultrasonic irradiation (USI) was started. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. The USI was continued for 10 minutes. The fine particles synthesized after the USI were treated with methanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free decylamine, the resulting sample was stored. As a result, 20 nm spherical gold fine particles were obtained. The result of observing the gold nanoparticle sample obtained in Example 1 (c) with TEM is shown in FIG. Moreover, the result of having measured the particle size distribution of this sample is shown in FIG.

(d) The process of Example 1 (b) above was repeated, except that 30 mL oleylamine was used instead of a mixture of 8 mL DMF and 30 mL oleylamine and the microparticles synthesized after USI were treated with methanol. . As a result, spherical gold fine particles of approximately 12 nm were obtained as having a relatively wide particle size distribution. The result of observing the gold nanoparticle sample obtained in Example 1 (d) with TEM is shown in FIG.

(e) Oleylamine: HAuCl ₄ = 10: 1 instead of oleylamine: HAuCl ₄ = 30: 1
Using the criteria, instead of 0.003 mol HAuCl _4, but using 0.009 mol HAuCl _4, repeated process steps of Example 1 (b). As a result, spherical gold fine particles of approximately 15 nm were obtained.
The result of observing the gold nanoparticle sample obtained in Example 1 (e) with TEM is shown in FIG.

(f) Instead of a mixture of 8 mL DMF and 30 mL oleylamine, use a mixture of 8 mL DMF, 22 mL oleylamine and 8 mL oleic acid, and instead of oleylamine: HAuCl ₄ = 30: 1, oleylamine: The treatment step of Example 1 (b) was repeated except that the conditions of oleic acid: HAuCl ₄ = 22.5: 7.5: 1 were used. As a result, spherical gold fine particles of approximately 5 to 6 nm were obtained.

[Synthesis of silver nanoparticles]
Oleylamine: Silver acetate (precursor) = 30: 1 was sonicated in oleylamine and DMF for 15 minutes to produce Ag nanoparticles. That is, a typical synthesis method was as follows: a 50 mL glass beaker was charged with 8 mL of DMF and 30 mL of oleylamine, and then heated to 65-70 ° C. on an oil bath. 0.003 mol of silver acetate was added to the solution with stirring to obtain a clear solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was immersed directly in the solution to initiate USI. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. The USI was continued for 15 minutes. The microparticles synthesized after the USI were treated with ethanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free oleylamine, the resulting sample was stored. As a result, 5 nm spherical silver particles were obtained. The results of observing the silver nanoparticle sample obtained in Example 2 with TEM and XRD are shown in FIGS. 10 and 12, respectively. In addition, the result of measuring the particle size distribution of the sample is shown in FIG.

[Synthesis of platinum nanoparticles]
Oleylamine: Platinum acetylacetonate (precursor) = 30: 1 was sonicated in oleylamine and DMF for 20 minutes to produce Pt nanoparticles. That is, a typical synthesis method was as follows: a 50 mL glass beaker was charged with 8 mL of DMF and 30 mL of oleylamine, and then heated to 65-70 ° C. on an oil bath. 0.003 mol of platinum acetylacetonate was added to the solution with stirring to obtain a clear solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was immersed directly in the solution to initiate USI. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. The USI was continued for 20 minutes. The microparticles synthesized after the USI were treated with ethanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free oleylamine, the resulting sample was stored. As a result, 3-4 nm spherical platinum fine particles (sperical platinum fine particles)
particles). The results obtained by observing the platinum nanoparticle sample obtained in Example 3 with TEM and XRD are shown in FIGS. 13 and 14, respectively.

[Synthesis of palladium nanoparticles]
Oleylamine: Pd nanoparticles were produced by sonicating in oleylamine and DMF for 30 minutes under the condition of palladium acetate (precursor) = 30: 1. That is, a typical synthesis method was as follows: a 50 mL glass beaker was charged with 8 mL of DMF and 30 mL of oleylamine, and then heated to 65-70 ° C. on an oil bath. 0.003 mol palladium acetate was added to the solution with stirring to obtain a clear solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was immersed directly in the solution to initiate USI. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. The USI was continued for 30 minutes. The microparticles synthesized after the USI were treated with ethanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free oleylamine, the resulting sample was stored. As a result, 8 nm plate-like palladium particles were obtained. The results obtained by observing the palladium nanoparticle sample obtained in Example 4 with TEM and XRD are shown in FIGS. 15 and 16, respectively.

[Synthesis of nickel nanoparticles]
Oleylamine: Nickel acetate (precursor) = 30: 1 was sonicated in oleylamine and DMF for 10 minutes to produce Ni nanoparticles. That is, a typical synthesis method was as follows: a 50 mL glass beaker was charged with 8 mL of DMF and 30 mL of oleylamine, and then heated to 65-70 ° C. on an oil bath. 0.003 mol of nickel acetate was added to the solution with stirring to obtain a clear solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was immersed directly in the solution to initiate USI. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. The USI was continued for 10 minutes. The microparticles synthesized after the USI were treated with ethanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free oleylamine, the resulting sample was stored. As a result, facetted nickel particles of 30 nm were obtained. FIG. 17 shows the result of observation of the nickel nanoparticle sample obtained in Example 5 with TEM.

[Synthesis of cobalt nanoparticles]
Oleylamine: Cobalt acetate (precursor) = 30: 1, oleylamine and DMF
Co nanoparticles were produced by sonication treatment for 20 minutes. That is, a typical synthesis method was as follows: a 50 mL glass beaker was charged with 8 mL of DMF and 30 mL of oleylamine, and then heated to 65-70 ° C. on an oil bath. 0.003 mol cobalt acetate was added to the solution with stirring to obtain a clear solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was immersed directly in the solution to initiate USI. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. The USI was continued for 20 minutes. The microparticles synthesized after the USI were treated with ethanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free oleylamine, the resulting sample was stored. As a result, 35-40 nm facetted cobalt particles were obtained.

[Zinc sulfide nanoparticles]
(a) Oleylamine: zinc ethyl xanthate (precursor) = 20: 1 was sonicated in oleylamine and DMF for 7-8 minutes to produce ZnS nanoparticles. That is, in a typical synthesis method, a 50 mL glass beaker was charged with 6 mL of DMF and 30 mL of oleylamine, and then heated to 65-70 ° C. on an oil bath. 0.0045 mol of zinc ethylxanthate was added to the solution with stirring to obtain a clear solution. Next, the clear solution is applied to a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20KHz)
Set. A horn type probe was immersed directly in the solution to initiate USI. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. The USI was continued for 7-8 minutes. The microparticles synthesized after the USI were treated with ethanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free oleylamine, the resulting sample was stored. As a result, zinc sulfide rods (ZnS rods) having a length of 4.5 to 5 nm and a width of 1 nm were obtained. FIG. 18 shows the result of TEM observation of the zinc sulfide nanoparticle sample obtained in Example 7 (a).

  (b) The treatment process of Example 7 (a) was repeated except that the ultrasonic irradiation treatment was performed for 30 minutes instead of the ultrasonic irradiation for 7 to 8 minutes. As a result, zinc sulfide wires (ZnS wires) having a length of approximately 200 nm and a width of 1 nm were obtained. The results obtained by observing the zinc sulfide nanoparticle sample obtained in Example 7 (b) with TEM and XRD are shown in FIGS. 19 and 20, respectively.

(c) Oleylamine: Oleic acid = 3: 1 and total amount of stabilizer: Ethyl xanthate zinc (precursor) = 40: 1 Ultrasonic irradiation treatment in a mixture of DMF, oleylamine and oleic acid for 30 minutes ZnS nanoparticles were manufactured. That is, a typical synthesis method is as follows. A 50 mL glass beaker is charged with 6 mL of DMF and 30 mL of a mixture of oleylamine and oleic acid (oleylamine: oleic acid = 3: 1, molar ratio), and then an oil bath. Warmed to 65-70 ° C above. 0.00225 mol of zinc ethylxanthate was added to the solution with stirring to obtain a clear solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was immersed directly in the solution to initiate USI. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. The USI was continued for 30 minutes. The microparticles synthesized after the USI were treated with ethanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free oleylamine and oleic acid, the resulting sample was stored. As a result, spherical zinc sulfide particles having a diameter of 5 to 6 nm were obtained. The results obtained by observing the zinc sulfide nanoparticle sample obtained in Example 7 (c) with TEM and XRD are shown in FIGS. 21 and 23, respectively. In addition, the result of measuring the particle size distribution of the sample is shown in FIG.

[Cadmium sulfide nanoparticles]
(a) Oleylamine: CdS nanoparticles were produced by sonication treatment in oleylamine and DMF for 30 minutes under conditions of cadmium ethylxanthate (precursor) = 20: 1. That is, in a typical synthesis method, a 50 mL glass beaker was charged with 6 mL of DMF and 30 mL of oleylamine, and then heated to 65-70 ° C. on an oil bath. 0.0045 mol of cadmium ethyl xanthate was added to the solution with stirring to obtain a clear solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was immersed directly in the solution to initiate USI. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. The USI was continued for 30 minutes. The microparticles synthesized after the USI were treated with ethanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free oleylamine, the resulting sample was stored. This results in a length of approximately 20-30 nm and 5 nm
Cadmium sulfide rods, dipods and tripods with a width of cadmium were obtained. The results of observing the cadmium sulfide nanoparticle sample obtained in Example 8 (a) with TEM and XRD are shown in FIGS. 24 and 25, respectively.

(b) Oleylamine: Oleic acid = 3: 1 and total amount of stabilizer: Ethylxanthate cadmium (precursor) = 40: 1. Ultrasonic irradiation treatment in a mixture of DMF, oleylamine and oleic acid for 30 minutes. CdS nanoparticles were manufactured. That is, a typical synthesis method is as follows. A 50 mL glass beaker is charged with 6 mL of DMF and 30 mL of a mixture of oleylamine and oleic acid (oleylamine: oleic acid = 3: 1, molar ratio), and then an oil bath. Warmed to 65-70 ° C above. 0.00225 mol of cadmium ethyl xanthate was added to the solution with stirring to obtain a clear solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was immersed directly in the solution to initiate USI. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. The USI was continued for 30 minutes. Fine particles synthesized after the USI are treated with ethanol to form a flocculent mass,
Next, after centrifugation, it was again suspended in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free oleylamine and oleic acid, the resulting sample was stored. As a result, 5 nm spherical cadmium sulfide particles were obtained. FIG. 26 shows the result of TEM observation of the cadmium sulfide nanoparticle sample obtained in Example 8 (b). In addition, the result of measuring the particle size distribution of the sample is shown in FIG.

[Zinc selenide nanoparticles]
(a) Oleylamine: oleylamine and DMF under the condition of zinc acetate (precursor) = 20: 1
The ZnSe nanoparticles were produced by ultrasonic irradiation treatment for 10 minutes. That is, a typical synthesis method was as follows: a 50 mL glass beaker was charged with 30 mL oleylamine and then heated to 65-70 ° C. on an oil bath. 0.0045 mol of zinc acetate was added to the solution with stirring to obtain a clear solution. A separately prepared solution of 6 mL of DMF and 0.004 mol of selenourea was added to the obtained solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was immersed directly in the solution to initiate USI. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. The USI was continued for 10 minutes. The microparticles synthesized after the USI were treated with ethanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free oleylamine, the resulting sample was stored. As a result, zinc selenide rods (ZnSe rods) having a length of 5 nm and a width of 1 nm were obtained.

(b) Oleylamine: oleylamine and DMF under the condition of zinc acetate (precursor) = 20: 1
The ZnSe nanoparticles were produced by ultrasonic irradiation for 30 minutes. That is, a typical synthesis method was as follows: a 50 mL glass beaker was charged with 30 mL oleylamine and then heated to 65-70 ° C. on an oil bath. 0.0045 mol of zinc acetate was added to the solution with stirring to obtain a clear solution. A separately prepared solution of 6 mL of DMF and 0.004 mol of selenourea was added to the obtained solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was immersed directly in the solution to initiate USI. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. The USI was continued for 30 minutes. The microparticles synthesized after the USI were treated with ethanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free oleylamine, the resulting sample was stored. As a result, zinc selenide wires having a length of approximately 300 nm and a width of 1 nm were obtained. Example 9 (b)
28 and 29 show the results of observation of the zinc selenide nanoparticle sample obtained in TEM by TEM and XRD, respectively.

(c) Oleylamine: Oleic acid = 3: 1 and total amount of stabilizer: Zinc acetate (precursor) = 40: 1 was sonicated in a mixture of DMF, oleylamine and oleic acid for 30 minutes, ZnSe nanoparticles were produced. That is, a typical synthesis method is as follows. A 50 mL glass beaker is charged with 14 mL of DMF and 30 mL of a mixture of oleylamine and oleic acid (oleylamine: oleic acid = 3: 1, molar ratio), and then an oil bath. Warmed to 65-70 ° C above. 0.00225 mol of zinc acetate was added to the solution with stirring to obtain a clear solution. A separately prepared solution of 6 mL of DMF and 0.002 mol of selenourea was added to the obtained solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was immersed directly in the solution to initiate USI. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. The USI was continued for 30 minutes. The microparticles synthesized after the USI were treated with ethanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free oleylamine and oleic acid, the resulting sample was stored. As a result, 6 nm spherical zinc selenide fine particles (zinc selenide spherical particles) were obtained. The results of observation of the zinc selenide nanoparticle sample obtained in Example 9 (c) by XRD and TEM are shown in FIGS. 30 and 31, respectively.

[Lead sulfide nanoparticles]
Oleylamine: Lead ethyl xanthate (precursor) = 30: 1 was subjected to ultrasonic irradiation treatment in oleylamine for 4 to 5 minutes to produce PbS nanoparticles. That is, a typical synthesis method was as follows: a 50 mL glass beaker was charged with 30 mL oleylamine and then heated to 65-70 ° C. on an oil bath. 0.003 mol of lead ethyl xanthate was added to the solution with stirring to obtain a clear solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was immersed directly in the solution to initiate USI. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. That USI 4-5
Continued for a minute. The microparticles synthesized after the USI were treated with ethanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process is 2
After ˜3 repetitions to remove almost all of the free oleylamine, the resulting sample was stored. As a result, lead sulfide cubes (PbS cubes) having an edge length of 30 nm were obtained. The results of observation of the lead sulfide nanoparticle sample obtained in Example 10 by TEM and XRD are shown in FIGS. 32 and 33, respectively.

[Copper sulfide nanoparticles]
CuS nanoparticles were prepared by sonication treatment in oleylamine for 4-5 minutes under the conditions of oleylamine: copper ethylxanthate (precursor) = 30: 1. That is, a typical synthesis method was as follows: a 50 mL glass beaker was charged with 30 mL oleylamine and then heated to 65-70 ° C. on an oil bath. 0.003 mol of copper ethyl xanthate was added to the solution with stirring to obtain a clear solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was immersed directly in the solution to initiate USI. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. That USI 4-5
Continued for a minute. The microparticles synthesized after the USI were treated with ethanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free oleylamine, the resulting sample was stored. This results in a copper sulfide hexagonal plate (CuS hexagonal plate) with an edge length of 30 nm.
plates). FIG. 34 shows the result of observation of the copper sulfide nanoparticle sample obtained in Example 11 by XRD.

[Zinc oxide nanoparticles]
Oleylamine: zinc acetylacetonate (precursor) = 20: 1 was sonicated in oleylamine and DMF for 30 minutes to produce ZnO nanoparticles. That is, a typical synthesis method was as follows: a 50 mL glass beaker was charged with 8 mL of DMF and 30 mL of oleylamine, and then heated to 65-70 ° C. on an oil bath. 0.0045 mol of zinc acetylacetonate was added to the solution with stirring to obtain a clear solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was immersed directly in the solution to initiate USI. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. The USI was continued for 30 minutes. The microparticles synthesized after the USI were treated with ethanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free oleylamine, the resulting sample was stored. As a result, a zinc oxide flower having a beautiful appearance was obtained. The results of observation of the zinc oxide nanoparticle sample obtained in Example 12 by TEM and XRD are shown in FIGS. 35 and 36, respectively.

[In ₂ O ₃ nanoparticles]
Oleylamine: Indium acetylacetonate (precursor) = 20: 1
In ₂ O ₃ nanoparticles were produced by sonication in oleylamine and DMF for 45 minutes. That is, in a typical synthesis method, a 50 mL glass beaker was charged with 6 mL of DMF and 30 mL of oleylamine, and then heated to 65-70 ° C. on an oil bath. 0.0045 mol of indium acetylacetonate was added into the solution with stirring to obtain a clear solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was immersed directly in the solution to initiate USI. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. The USI was continued for 45 minutes. The microparticles synthesized after the USI were treated with ethanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free oleylamine, the resulting sample was stored. As a result, spherical fine particles of 10 nm indium oxide were obtained. The results of observation of the indium oxide nanoparticle sample obtained in Example 13 with TEM and XRD are shown in FIGS. 37 and 38, respectively.

[Ga ₂ O ₃ nanoparticles]
Oleylamine: gallium acetylacetonate (precursor) = 20: 1 was sonicated in oleylamine and DMF for 45 minutes to produce Ga ₂ O ₃ nanoparticles. That is, in a typical synthesis method, a 50 mL glass beaker was charged with 6 mL of DMF and 30 mL of oleylamine, and then heated to 65-70 ° C. on an oil bath. 0.0045 mol of gallium acetylacetonate was added to the solution with stirring to obtain a clear solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was immersed directly in the solution to initiate USI. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. The USI was continued for 45 minutes. The microparticles synthesized after the USI were treated with ethanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free oleylamine, the resulting sample was stored. As a result, spherical fine particles of gallium oxide of about 8 nm were obtained. The results obtained by observing the gallium oxide nanoparticle sample obtained in Example 14 with TEM and XRD are shown in FIGS. 40 and 41, respectively.

[Mn ₃ O ₄ nanoparticles]
Oleylamine: Manganese acetylacetonate (precursor) = 20: 1 was sonicated in oleylamine and DMF for 45 minutes to produce Mn ₃ O ₄ nanoparticles. That is, in a typical synthesis method, a 50 mL glass beaker was charged with 6 mL of DMF and 30 mL of oleylamine, and then heated to 65-70 ° C. on an oil bath. 0.0045 mol of manganese acetylacetonate was added to the solution with stirring to obtain a clear solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was immersed directly in the solution to initiate USI. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. The USI was continued for 45 minutes. The microparticles synthesized after the USI were treated with ethanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free oleylamine, the resulting sample was stored. As a result, spherical fine particles of trimanganese tetraoxide of approximately 6 nm were obtained. The results of observation of the trimanganese tetraoxide nanoparticle sample obtained in Example 15 with TEM and XRD are shown in FIGS. 42 and 43, respectively.

[Eu ₂ O ₃ nanoparticles]
Eu ₂ O ₃ nanoparticles were produced by sonication for 45 minutes in oleylamine and DMF under the conditions of oleylamine: europium acetylacetonate (precursor) = 20: 1. That is, in a typical synthesis method, a 50 mL glass beaker was charged with 6 mL of DMF and 30 mL of oleylamine, and then heated to 65-70 ° C. on an oil bath. 0.0045 mol of europium acetylacetonate was added into the solution with stirring to obtain a clear solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was immersed directly in the solution to initiate USI. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. The USI was continued for 45 minutes. The microparticles synthesized after the USI were treated with ethanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free oleylamine, the resulting sample was stored. As a result, spherical fine particles of approximately 5 nm of europium oxide were obtained. The Eu ₂ O ₃ nanoparticle sample obtained in Example 16 was subjected to TEM and XRD.
The results observed in FIG. 44 are shown in FIGS. 44 and 45, respectively.

[Triiron tetraoxide nanoparticles]
(a) oleylamine: iron (III) acetylacetonate (precursor) = 30: 1,
Ultrasonic irradiation treatment in oleylamine and DMF for 45 minutes produced Fe ₃ O ₄ nanoparticles. That is, in a typical synthesis method, a 50 mL glass beaker was charged with 6 mL of DMF and 30 mL of oleylamine, and then heated to 65-70 ° C. on an oil bath. 0.003 mol of iron (III) acetylacetonate was added to the solution with stirring to obtain a clear solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was immersed directly in the solution to initiate USI. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. The USI was continued for 45 minutes. The microparticles synthesized after the USI were treated with ethanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free oleylamine, the resulting sample was stored. As a result, spherical fine particles of 5 nm were obtained. The results of observing the Fe ₃ O ₄ nanoparticle sample obtained in Example 17 (a) with TEM and XRD are shown in FIGS. 46 and 47, respectively. In addition, FIG. 48 shows the result of measuring the particle size distribution of the sample.

(b) oleylamine: iron (III) acetylacetonate (precursor) = 10: 1 instead of 30: 1, 0.009 mol iron (III) acetylacetonate instead of 0.003 mol, The processing step of Example 17 (a) was repeated except that the ultrasonic irradiation treatment was performed for 60 minutes instead of the ultrasonic irradiation for 45 minutes. As a result, 10 nm spherical fine particles were obtained.

[CoFe ₂ O ₄ nanoparticles]
Oleylamine: Iron (III) acetylacetonate (precursor) = 30: 1 was sonicated in oleylamine and DMF for 45 minutes to produce CoFe ₂ O ₄ nanoparticles. That is, in a typical synthesis method, a 50 mL glass beaker was charged with 6 mL of DMF and 30 mL of oleylamine, and then heated to 65-70 ° C. on an oil bath. 0.002 mol of iron (III) acetylacetonate and 0.001 mol of cobalt (II) acetylacetonate were added into the solution with stirring to obtain a clear solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was immersed directly in the solution to initiate USI. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. The USI was continued for 45 minutes. The microparticles synthesized after the USI were treated with ethanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free oleylamine, the resulting sample was stored. As a result, 12 nm spherical fine particles were obtained. The results of observing the CoFe ₂ O ₄ nanoparticle sample obtained in Example 18 with TEM and XRD are shown in FIGS. 49 and 51, respectively. Further, FIG. 50 shows the result of measuring the particle size distribution of the sample.

[NiFe ₂ O ₄ nanoparticles]
Oleylamine: Iron (III) acetylacetonate (precursor) = Nitro ₂ O ₄ nanoparticles were produced by sonication for 45 minutes in oleylamine and DMF under the condition of 30: 1. That is, in a typical synthesis method, a 50 mL glass beaker was charged with 6 mL of DMF and 30 mL of oleylamine, and then heated to 65-70 ° C. on an oil bath. 0.002 mol of iron (III) acetylacetonate and 0.001 mol of nickel (II) acetylacetonate were added into the solution with stirring to obtain a clear solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was immersed directly in the solution to initiate USI. After several minutes of irradiation, the clear solution became cloudy. The turbidity indicates that fine particles are formed. The USI was continued for 45 minutes. The microparticles synthesized after the USI were treated with ethanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free oleylamine, the resulting sample was stored. As a result, 10 nm spherical fine particles were obtained. FIG. 52 shows the result of observation of the NiFe ₂ O ₄ nanoparticle sample obtained in Example 19 with TEM. In addition, FIG. 53 shows the result of measuring the particle size distribution of the sample.

[CoTiO ₃ nanoparticles]
Oleylamine: Cobalt (II) acetylacetonate (precursor) = 20: 1 was sonicated in oleylamine and DMF for 45 minutes to produce CoTiO ₃ nanoparticles. That is, in a typical synthesis method, a 50 mL glass beaker was charged with 6 mL of DMF and 30 mL of oleylamine, and then heated to 65-70 ° C. on an oil bath. 0.00225 mol of cobalt (II) acetylacetonate was added to the solution with stirring to obtain a clear solution. Next, the clear solution was set in a high-intensity ultrasonic irradiation device (homogenizer with horn type probe, Branson 450D, frequency: 20 KHz). A horn type probe was immersed directly in the solution to initiate USI. After 1 minute of irradiation, 0.00225 mol of titanium isopropoxide was injected and USI was continued for 45 minutes. The microparticles synthesized after the USI were treated with ethanol to form a flocculent lump, then centrifuged and then suspended again in a hydrophobic solvent such as toluene. This process was repeated 2-3 times and after removing almost all of the free oleylamine, the resulting sample was stored. As a result, spherical fine particles of approximately 3 nm were obtained. FIG. 54 shows the result of observation of the CoTiO ₃ nanoparticle sample obtained in Example 20 by TEM.

By applying the technology of the present invention, nanoparticles exhibiting various unique and excellent properties, characteristics and functions can be produced. In particular, metal nanoparticles, metal sulfide nanoparticles, metal selenide nanoparticles, multi-component metal nanoparticles can be obtained by a simple method, and the particle size of the nanoparticles can be controlled, and the product has a uniform particle size. And is also excellent as a semiconductor material and a crystalline material. Nanoparticles obtained in the present invention are used in industries such as ceramic nanostructure modifiers, optical functional coating materials, electromagnetic wave shielding materials, secondary battery materials, fluorescent materials, electronic component materials, magnetic recording materials, and polishing materials. Excellent for use as industrial material, pharmaceutical and cosmetic material.
It will be apparent that the invention may be practiced otherwise than as particularly described in the foregoing description and examples. Many modifications and variations of the present invention are possible in light of the above teachings, and thus are within the scope of the claims appended hereto.

It is a photograph which shows the result of TEM observation of the gold nanoparticle obtained by this invention. It is a graph which shows the result of having measured the particle size distribution of the gold nanoparticle sample shown by FIG. It is a photograph which shows the result of TEM observation of the gold nanoparticle obtained by this invention. It is a graph which shows the result of having measured the particle size distribution of the gold nanoparticle sample shown by FIG. The result of the XRD observation of the gold nanoparticle sample shown in FIG. 3 is shown. It is a photograph which shows the result of TEM observation of the gold nanoparticle obtained by this invention. It is a graph which shows the result of having measured the particle size distribution of the gold nanoparticle sample shown by FIG. It is a photograph which shows the result of TEM observation of the gold nanoparticle obtained by this invention. It is a photograph which shows the result of TEM observation of the gold nanoparticle obtained by this invention. It is a photograph which shows the result of TEM observation of the silver nanoparticle obtained by this invention. 11 is a graph showing the result of measuring the particle size distribution of the silver nanoparticle sample shown in FIG. The result of the XRD observation of the silver nanoparticle sample shown in FIG. 10 is shown. It is a photograph which shows the result of TEM observation of the platinum nanoparticle obtained by this invention. The result of the XRD observation of the platinum nanoparticle sample shown in FIG. 13 is shown. It is a photograph which shows the result of TEM observation of the palladium nanoparticle obtained by this invention. FIG. 16 shows the result of XRD observation of the palladium nanoparticle sample shown in FIG. It is a photograph which shows the result of TEM observation of the nickel nanoparticle obtained by this invention. It is a photograph which shows the result of TEM observation of the zinc sulfide nanoparticle obtained by this invention. It is a photograph which shows the result of TEM observation of the zinc sulfide nanoparticle obtained by this invention. FIG. 19 shows the result of XRD observation of the zinc sulfide nanoparticle sample shown in FIG. It is a photograph which shows the result of TEM observation of the zinc sulfide nanoparticle obtained by this invention. FIG. 22 is a graph showing the results of measuring the particle size distribution of the zinc sulfide nanoparticle sample shown in FIG. FIG. 22 shows the result of XRD observation of the zinc sulfide nanoparticle sample shown in FIG. It is a photograph which shows the result of TEM observation of the cadmium sulfide nanoparticle obtained by this invention. FIG. 25 shows the results of XRD observation of the cadmium sulfide nanoparticle sample shown in FIG. It is a photograph which shows the result of TEM observation of the cadmium sulfide nanoparticle obtained by this invention. FIG. 27 is a graph showing the results of measuring the particle size distribution of the cadmium sulfide nanoparticle sample shown in FIG. It is a photograph which shows the result of TEM observation of the zinc selenide nanoparticle obtained by this invention. FIG. 29 shows the results of XRD observation of the zinc selenide nanoparticle sample shown in FIG. The result of the XRD observation of the zinc selenide nanoparticle obtained by this invention is shown. FIG. 31 is a photograph showing the result of TEM observation of the zinc selenide nanoparticles shown in FIG. It is a photograph which shows the result of TEM observation of the lead sulfide nanoparticle obtained by this invention. FIG. 33 shows the result of XRD observation of the lead sulfide nanoparticle sample shown in FIG. The result of the XRD observation of the copper sulfide nanoparticle sample obtained by the present invention is shown. It is a photograph which shows the result of TEM observation of the zinc oxide nanoparticle obtained by this invention. The result of the XRD observation of the zinc oxide nanoparticle sample shown in FIG. 35 is shown. Is a photograph showing the results of TEM observation of the resulting In ₂ O ₃ nanoparticles in the present invention. FIG. 37 shows the result of XRD observation of the In ₂ O ₃ nanoparticle sample shown in FIG. FIG. 38 is a graph showing the results of measuring the particle size distribution of the In ₂ O ₃ nanoparticle sample shown in FIG. 37. Is a photograph showing the results of TEM observation of the obtained Ga ₂ O ₃ nanoparticles in the present invention. 40 shows the results of XRD observation of the Ga ₂ O ₃ nanoparticle sample shown in FIG. Is a photograph showing the results of TEM observation of the obtained Mn ₃ O ₄ nanoparticles present invention. The result of the XRD observation of the Mn ₃ O ₄ nanoparticle sample shown in FIG. 42 is shown. Is a photograph showing the results of TEM observation of the resulting Eu ₂ O ₃ nanoparticles in the present invention. 44 shows the result of XRD observation of the Eu ₂ O ₃ nanoparticle sample shown in FIG. Is a photograph showing the results of TEM observation of the obtained Fe ₃ O ₄ nanoparticles present invention. 46 shows the result of XRD observation of the Fe ₃ O ₄ nanoparticle sample shown in FIG. 47 is a graph showing the results of measuring the particle size distribution of the Fe ₃ O ₄ nanoparticle sample shown in FIG. 46. FIG. Is a photograph showing the results of TEM observation of the resultant CoFe ₂ O ₄ nanoparticles present invention. FIG. 50 is a graph showing the results of measuring the particle size distribution of the CoFe ₂ O ₄ nanoparticle sample shown in FIG. 49. The result of the XRD observation of the CoFe ₂ O ₄ nanoparticle sample shown in FIG. 49 is shown. Is a photograph showing the results of TEM observation of the obtained NiFe ₂ O ₄ nanoparticles present invention. FIG. 53 is a graph showing the results of measuring the particle size distribution of the NiFe ₂ O ₄ nanoparticle sample shown in FIG. 52. It is a photograph which shows the result of TEM observation of the CoTiO ₃ nanoparticle obtained by this invention.

Claims (4)

A low boiling point organic solvent is allowed to coexist in a reaction field where nanometer-sized particles are formed by sonochemistry from a liquid mixed system containing a nanoparticle precursor and a nanoparticle stabilizer, and ultrasonic waves are present in the presence of the organic solvent. A method for producing nanometer-size particles, wherein irradiation is performed to form the nanometer-size particles. The nanometer-sized particles according to claim 1, wherein the nanoparticle stabilizer is selected from the group consisting of organic carboxylic acids, organic nitrogen compounds, organic sulfur compounds, and organic phosphorus compounds. Law. The method for producing nanometer-sized particles according to claim 1 or 2, wherein the organic solvent is a low-boiling solvent having a boiling point of 200 ° C or lower. The organic solvent is methanol, ethanol or dimethylformamide (DMF).
4. A method for producing nanometer-sized particles according to any one of 3 above.