JP2002153738A - Method for controlling particle position, method for manufacturing particle film by using the method, and particle film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for controlling apparent gravity and buoyancy of a particle by acting a magnetic field vertically and changing the strength and direction of the magnetic field, and to provide a method for manufacturing a particle film, which can manufacture a particle film where particles in the nanometer range are accumulated two-dimensionally, and a particle film manufactured by the method. SOLUTION: In this method for controlling the positions of particles, a magnetic field is added to a solvent in which particles are dispersed, and the positions of the particles in the solvent are controlled by the strength and direction of the magnetic field. In this method for manufacturing a particle film, a solvent in which particles are dispersed is applied to a substrate, and the solvent is evaporated by using the method for controlling the positions of the particles with respect to the liquid level of the solvent by the strength and direction of the magnetic field, thereby accumulating the particles two- dimensionally.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for controlling a particle position, a method for producing a particle film using the control method, and a particle film. More particularly, the present invention relates to a method for controlling a particle position dispersed in a solvent depending on the strength and direction of a magnetic field. The present invention relates to a method for controlling particle size, a method for manufacturing a particle film in which particles are two-dimensionally integrated by controlling the position of particles by the intensity and direction of a magnetic field, and a particle film.

[0002]

2. Description of the Related Art Hitherto, advection accumulation has been used as a method for producing a particle film by accumulating particles two-dimensionally.
A method for producing a particle film by the advection accumulation method will be described with reference to FIG. FIG. 1A is a diagram showing a state where a solvent 3 applied on a substrate 1 is evaporated. Solvent 2 such as an organic solvent or a mixed solution of an organic solvent and an inorganic solvent
The solution in which the particles 3 are dispersed is applied to the substrate 1 by dropping. Further, the substrate 1 is placed in a heating device or a decompression device (not shown) to evaporate the solvent 2 applied on the substrate 1. The evaporation rate of the solvent 2 is adjusted by adjusting the temperature of a heating device (not shown) or the pressure of a pressure reducing device. Further, the solvent 2 can be evaporated by natural evaporation without using a heating device or a decompression device (not shown), or the evaporation can be performed by reducing the evaporation speed of the solvent 2 by covering the container.

FIG. 1B is a view showing a state in which the evaporation of the solvent 2 has progressed and the particles 3 have emerged from the interface 4 of the solvent 1. The interface 4 between the solvent 2 and the gas 5 surrounding the atmosphere is deformed by the presence of the particles 3, and the particles 3 are advected so that the interfacial energy increased by the deformation is minimized. As the solvent 2 evaporates, the particles 3 break off from the solvent 2 and protrude from the interface 4 as shown in FIG. 1B, and act on the interface 4 formed by the solvent 2 and the gas 5 surrounding the atmosphere. It is considered that the particles 3 are advected by the lateral capillary force so as to accumulate.

FIG. 1C shows a particle film in which particles 3 are two-dimensionally integrated. When the evaporation rate of the solvent 2 shown in FIG. 1B is controlled by controlling the evaporation rate of the solvent 2, a horizontal capillary force acts on the interface 4 between the solvent 2 and the gas 5 surrounding the atmosphere, and the particles 3 are advected. And two-dimensionally integrated. Accumulated particles 3
When all of the solvent 2 evaporates, a particle film shown in FIG. 1C is formed.

[0005] The particle position in the above-mentioned advection accumulation method is as follows.
By controlling the evaporation rate of the solvent, horizontal control of particles such as horizontal capillary force is performed. In the advection accumulation method, by controlling the evaporation rate of the solvent, a particle film in which particles having a particle diameter up to the micrometer range are two-dimensionally accumulated is manufactured.

[0006] The force acting on the particles in the vertical direction includes gravity and buoyancy acting to reduce the apparent weight by the volume excluded by the particles in the solvent.
However, gravity and buoyancy are uniquely determined by the mass and density of the particles, so the advection and accumulation method cannot control the forces acting in the vertical direction, and therefore control the position of the particles in the vertical direction relative to the liquid surface. Could not. In addition, since the position of the particles in the vertical direction cannot be controlled, it has not been possible to manufacture a particle film by two-dimensionally accumulating particles having a particle diameter of a micrometer range or less, for example, a nanometer range.

[0007] A so-called magnetic Archimedes levitation in which an object is levitated by applying a strong magnetic field to a diamagnetic object is known (for example, Kitazawa et al., Faculty of Engineering, The University of Tokyo;・ Magnetic levitation of paramagnetic substances ”, SNMS'98 (Symposiu
mon New Magneto-Science '
98) Proceeding of The Seco
nd MeetingNov. 25-27 '98 J
ap. p27-31). However, magnetic Archimedes levitation so far is currently applied only to observing phenomena such as floating of wood pieces and living things in water or in the air.

[0008]

SUMMARY OF THE INVENTION Accordingly, the present invention has been made in view of the above-mentioned problems, and provides a method of controlling a particle position in a solvent by applying a magnetic field in a vertical direction and controlling the strength and direction of the magnetic field. An object of the present invention is to provide a method for producing a particle film capable of producing a particle film in which particles in the nanometer range are two-dimensionally integrated using the method, and a particle film produced by the method.

[0009]

SUMMARY OF THE INVENTION The present invention is based on the finding that it is possible to control the position of particles, particularly at the gas-liquid interface, by applying a strong magnetic field to the particles dispersed in a solution. It was done. At the interface between the gas and the liquid, there are a surface tension acting to minimize the surface area by the surface free energy of the liquid, and a horizontal capillary force generated between the particles. This transverse capillary force is
It depends on the particle position with respect to the liquid surface, that is, the distance between the particles. The present invention has been made by finding that it is possible to control the transverse capillary force applied to a particle by controlling the position of the particle at the gas-liquid interface using the magnetic Archimedes levitation described above. That is,
The above object of the present invention is solved by providing a method for controlling a particle position according to the present invention, a method for producing a particle film using the control method, and a particle film.

According to the first aspect of the present invention, there is provided a method for controlling a particle position in which a magnetic field is applied to a solvent in which particles are dispersed, and the particle position in the solvent is controlled by the strength and direction of the magnetic field.

According to the invention of claim 2 of the present invention, there is provided a method for controlling the position of particles, wherein the particles are diamagnetic particles, paramagnetic particles or ferromagnetic particles.

According to the third aspect of the present invention, there is provided a method for controlling the position of a particle in which the magnetic field has a magnetic flux density of 0.5 to 20T.

According to a fourth aspect of the present invention, there is provided a method for controlling a position of a particle, wherein the particle has a particle diameter of 1 to 100 nm.

According to a fifth aspect of the present invention, there is provided a method for controlling the position of a particle, wherein the particle is a colloid particle protected by an organic compound containing sulfur.

According to the invention of claim 6 of the present invention, the particles are dispersed in a solvent, the solvent in which the particles are dispersed is applied on a substrate, and the position of the particles relative to the liquid surface of the solvent is controlled by the strength and direction of the magnetic field. And evaporating the solvent to accumulate the particles two-dimensionally.

According to a seventh aspect of the present invention, there is provided a method for producing a particle film, wherein the particles are diamagnetic particles, paramagnetic particles or ferromagnetic particles.

According to an eighth aspect of the present invention, there is provided a method for producing a particle film, wherein the magnetic field has a magnetic flux density of 0.5 to 20 T.

According to the ninth aspect of the present invention, there is provided a method for producing a particle film, wherein the particles have a particle diameter of 1 to 100 nm.

According to a tenth aspect of the present invention, there is provided a method for producing a particle membrane, wherein the particles are colloidal particles protected by an organic compound containing sulfur.

According to the eleventh aspect of the present invention, there is provided a method for producing a particle membrane in which the organic compound containing sulfur is an alkylthiol having 2 to 20 carbon atoms.

According to the twelfth aspect of the present invention, the particles are made of Ag, Au, Cu, Pb, Zn, Sn, Bi,
Pt, Ti, Pd, Cr, Mn, Al, Fe, Co, N
A method for producing a particle film, which is a colloidal particle of a metal selected from the group including i.

According to the thirteenth aspect of the present invention, the particles are dispersed in a solvent, the solvent in which the particles are dispersed is applied onto a substrate, and the position of the particles with respect to the liquid surface of the solvent is controlled by the strength and direction of the magnetic field. Then, the solvent is evaporated to provide a particle film in which the particles are two-dimensionally accumulated.

According to a fourteenth aspect of the present invention, there is provided a particle film, wherein the particles are diamagnetic particles, paramagnetic particles, or ferromagnetic particles.

According to the fifteenth aspect of the present invention, there is provided a particle film having a thickness of 1 to 100 nm.

According to the sixteenth aspect of the present invention, there is provided a particle membrane, wherein the particles are colloidal particles protected by an organic compound containing sulfur.

According to the seventeenth aspect of the present invention, there is provided a particle membrane in which the organic compound containing sulfur is an alkylthiol having 2 to 20 carbon atoms.

According to the eighteenth aspect of the present invention, the particles are made of Ag, Au, Cu, Pb, Zn, Sn, Bi,
Pt, Ti, Pd, Cr, Mn, Al, Fe, Co, N
There is provided a particle membrane which is a colloidal particle of a metal selected from the group comprising i.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail,
The present invention is not limited to the embodiments described below. The method for controlling the particle position in the solvent by the magnetic field according to the present invention will be described with reference to FIGS.

FIG. 2 shows the structure of an apparatus used in the method for controlling the position of a particle according to the present invention and particles 6 whose position is controlled by a magnetic field.
It is the figure which showed a and 6b. In the present invention, any magnetic field generating means can be used to generate a magnetic field. As such a magnetic field generating means, an electromagnet,
Any material such as a superconducting magnet and a permanent magnet can be used. Further, in the embodiment of the present invention, description will be made assuming that the superconducting magnet 7 is used as the magnetic field generating means.

As shown in FIG. 2, a magnetic field center 9 is formed inside a cylindrical superconducting magnet 7 having a bore 8 at the center. Here, the magnetic field center 9 refers to a position where the magnetic field gradient dBz / dz becomes zero. Bz indicates a magnetic flux density, z
Indicates the distance in the direction indicated by z in FIG. In the bore 8 of the superconducting magnet 7, a container containing a solvent (not shown) in which the particles 6a and 6b are dispersed is disposed, and the particles 6a and 6b dispersed in the solvent are disposed.
Is applied to the magnetic field. In FIG. 2, the particle 6a is above the magnetic field center 9 and the particle 6b is below.
, And the direction of the force applied by the magnetic field acting on the particles 6a, 6b.

When the particles 6a and 6b are diamagnetic particles, when a magnetic field is applied in the z direction in FIG.
A magnetic field such that the magnetic flux density Bz decreases in the z direction is applied to the particles 6a existing above the magnetic field center 9 of the magnetic field.
In addition, particles 6 b existing below the magnetic field center 9 include:
A magnetic field that increases the magnetic flux density Bz in the z direction is applied. Since the diamagnetic material is magnetized in the opposite direction to the external magnetic field, it receives a force in the direction in which the magnetic field decreases. Such diamagnetic materials include Ag, Au, Cu,
Examples thereof include Pb, Zn, Sn, and Bi. In the present invention, particles formed from these metals can be used.

In the present invention, particles formed from a paramagnetic or ferromagnetic material can also be used.
Paramagnetic or ferromagnetic materials are materials that are magnetized in the same direction as the magnetic field, such as Pt, Ti, Pd,
Examples thereof include Cr, Mn, Al, Fe, Co, and Ni. In the present invention, when a paramagnetic substance or a ferromagnetic substance is used as the particles 6a and 6b, z shown in FIG.
When a magnetic field is formed in the direction, a force is applied to the particles 6a and 6b in the direction shown by the broken line.

The above-mentioned metal particles, ceramic particles, and polymer particles which can be used in the present invention are prepared by a gas phase method, a sedimentation method, a solvent evaporation method, a sol-gel method, a decomposition method from an organic metal, a resistance heating method, a plasma method. Heating method, molten pool evaporation method, powder evaporation method, active plasma arc evaporation method, high frequency induction heating method, electron beam heating method, laser beam heating method,
It can be manufactured by a sputtering method or the like. Examples of the method for producing such ultrafine particles or particles include, for example, Chemical Review, “Ultrafine Particles-Chemistry and Applications”, 4
8, 1985, Gakkai Shuppan Center and "Wet Process Handbook", March 1996, first edition published by New Generation Research Institute, published by Nikkan Kogyo Shimbun. In the present invention, as the particles 3, those produced in a solution can be used as they are as a dispersion solution, or those in which the particles 3 are separately dispersed in a solvent described later can be used as a dispersion solution. The particles 3 used in the present invention may be present at any concentration as a dispersion.

A force F shown below is applied to the particles 3 disposed inside the superconducting magnet 7 in accordance with magnetic properties such as diamagnetism, paramagnetism and ferromagnetism.

[0035]

(Equation 1)

In the equation (1), F is the force of the magnetic field acting in the z direction, C is a coefficient including the magnetic moment of the material forming the particles 3, Bz is the magnetic flux density in the z direction, and dBz / dz is the magnetic field. Shows the gradient. C is a coefficient that is negative for diamagnetic particles and positive for paramagnetic and ferromagnetic particles.
As described above, in the embodiment of the present invention using the diamagnetic particles, the magnetic field gradient dBz / dz is negative and C is negative on the upper side in the z direction with the magnetic field center 9 as a boundary. The force F is generated. On the other hand, since C is negative below the magnetic field center 9 in the z direction and the magnetic field gradient dBz / dz is positive, a force F in the direction opposite to the z direction is applied.

FIG. 3 shows a solvent 11a and 10b in which particles 6a and 6b formed of diamagnetic particles are dispersed above and below a magnetic field center 9 in a bore 8 of the superconducting magnet 7 shown in FIG. 11b show the positions of the particles 6a and 6b with respect to the liquid surface of the solvents 10a and 10b when a magnetic field is applied in the z direction. FIG. 3A shows the substrate 11a.
FIG. 3 is a diagram showing a position of a particle 6a with respect to a liquid surface in a case where is disposed above a magnetic field center 9 shown in FIG. FIG.
As shown in (a), when the force F acts upward, the particles 6a are caused by the magnetic Archimedes floating effect,
It receives an apparent buoyancy upward so as to float on the liquid surface of the solvent 10a.

Further, since the relative distance between the particles 6a and 6a 'is reduced by applying the upward force F to the particles 6a, the horizontal capillary force applied to the particles 6a and 6a' is increased, and 6a and 6a 'are attracted to each other. Since this transverse capillary force also depends on the evaporation rate of the solvent 10a, it has been found that it can be controlled by controlling the evaporation rate of the solvent 10a. In the present invention, the particle 6a is given an apparent buoyancy by the force F due to the magnetic field,
It has been found that the particles 6a can be more densely accumulated by accumulating them by the transverse capillary force.

FIG. 3B is a diagram showing the position of the particles 6b with respect to the liquid surface when the substrate 11b is arranged below the magnetic field center 9 shown in FIG. By the action of the downward force F shown in FIG. 3B, the particles 6b
, A downward force F is applied.
Further, the particles 6b receive the transverse capillary force, and the particles 6b and 6b '
Are attracted to each other, but the particles 6b are pressed against the substrate 11b by the force F applied by the magnetic field, so that the relative distance between the particles 6b and 6b 'becomes coarse, the horizontal capillary force becomes small, and the particles 6b, 6b' Are coarsely integrated. Therefore, by changing the position where the substrates 11a and 11b are arranged, the intensity and direction of the magnetic field can be changed, and the integration density of the particles 6a and 6b can be controlled.

Assuming that the particles 6a and 6b are paramagnetic particles or ferromagnetic particles, a downward force F acts on the particles 6a above the center 9 of the magnetic field.
As shown in (b), a downward force F is applied so as to be pressed against the substrate 11a. Also, the particles 6b are applied with an upward force F below the center of the magnetic field, so that apparent buoyancy is applied so that the particles 6b float on the surface of the solvent 10b as shown in FIG. 3A. .

Next, a method for producing a particle film by using the above-described method of controlling the position of particles with respect to the liquid surface of the solvent by the magnetic field according to the present invention will be described. FIG. 4 shows a sectional view of an apparatus for producing the particle membrane of the present invention. The solvent 2 in which the particles 3 are dispersed can be applied to the substrate 1 by an appropriate method such as dropping, spin coating, wire bar coating, spray coating, or the like. In the embodiment shown in FIG. 4, the substrate 1 on which the solvent 2 has been
The container 12 is placed on a table 14 provided in the bore 8 of the cylindrical superconducting magnet 7 having the bore 8 in the vertical direction. In the present invention, in order to adjust the evaporation rate of the solvent 2, the
The temperature in the inside can be controlled, and the temperature can be controlled by putting the entire apparatus shown in FIG. 4 into a heating device. Further, by providing a pressure adjusting device in the container 12 to adjust the pressure in the container 12, the evaporation rate of the solvent 2 can be controlled, or the pressure can be controlled by putting the entire device shown in FIG. May be controlled.

As the substrate 1 in the present invention, it is preferable to use a smooth flat plate in order to produce a particle film in which the particles 3 are two-dimensionally integrated. However, as the substrate 1 used in the present invention, a substrate having a spherical surface, a cylindrical surface, a hyperboloid, or any other complicated curved surface other than these can be used as long as it can appropriately hold the solvent 2. Further, as the substrate 1 used in the present invention, a substrate coated with an organic or inorganic substance may be used.

In the embodiment shown in FIG. 4 of the present invention, the container 12 used in the present invention has any shape as long as it can accommodate the substrate 1 and can be arranged in the bore 8 of the superconducting magnet 7. However, it can be used. Further, the lid 13 can be disposed in the bore 8 of the superconducting magnet 7,
Any material can be used as long as it can suppress the vapor of the solvent 2 evaporating from the upper part of the container 12. The table 14 may be a horizontal table or a basket such as a car that can be hung from the top as long as it can keep the substrate 1 horizontal to the vertical magnetic field. Further, as the container 12 and the lid 13 used in the present invention, those capable of accommodating the entire apparatus shown in FIG. 4 may be used. The substrate 1, the container 12, the lid 13, and the base 14 used in the present invention may be made of glass, aluminum, polymer resin, or the like.

When diamagnetic particles are used as the particles 3 that can be used in the present invention, A
g, Au, Cu, Pb, Zn, Sn, Mg, Bi and other metal particles, vinyl polymers, polyolefins, polydienes, polyamide polyesters, polyurethanes, addition condensation polymers, ring-opening polymerization polymers, polypeptides And ceramic particles such as GeO ₂ and PbO. Similarly, as the paramagnetic particles, Pt, Ti, Pd, Cr, Al,
As ferromagnetic particles such as Mn, Fe, Co, Ni,
Iron oxide and the like can be mentioned.

In the present invention, the solvent 2 in which the particles 3 are dispersed
Can be used various organic solvents, and specific examples of such organic solvents include, for example, amylbenzene, isopropylbenzene, ethylbenzene, octane, gasoline, xylene, diethylbenzene, cyclohexane, cyclohexylbenzene, cyclohexene, Cyclopentane, dipentene, dimethylnaphthalene, cymes, camphor oil, styrene, petroleum ether, petroleum benzine, solvent naphtha, decalin, decane, tetralin, turpentine, kerosene, dodecane, dodecylbenzene,
Examples thereof include hydrocarbon solvents such as toluene, naphthalene, nonane, pine oil, pinene, hexane, heptane, benzene, pentane, methylcyclohexane, methylcyclopentane, p-menthane, and igloin.

The above organic solvents further include allyl chloride, 2-ethylhexyl chloride, amyl chloride, isopropyl chloride, ethyl chloride, butyl chloride, naphthalene chloride, hexyl chloride, methylene chloride, o-chlorotoluene, p-chlorotoluene, chlorobenzene. , Chloroform, carbon tetrachloride, dichloroethane, dichloroethylene,
Dichlorotoluene, dichlorobutane, dichloropropane, dichlorobenzene, dibromoethane, dibromobutane, dibromopropane, dibromobenzene, dibromopentane, allyl bromide, isopropyl bromide, ethyl bromide,
Octyl bromide, butyl bromide, methyl bromide, lauryl bromide, tetrachloroethane, tetrachloroethylene, tetrabromoethane, tetramethylenechlorobromide, trichloroethane, trichlorobenzene, bromochloroethane, 1-bromo-3-chloropropane, bromonaphthalene, bromo Halogenated hydrocarbon solvents such as benzene, hexachloroethane and pentamethylenechlorobromide can be used.

Examples of the organic solvent include amyl alcohol, allyl alcohol, isoamyl alcohol, isobutyl alcohol, isopropyl alcohol, undecanol, ethanol, 2-ethylbutanol, 2-ethylhexanol, 2-octanol, n-octanol, glycidol, Cyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, n-decanol, tetrahydrofurfuryl alcohol, α-terpineol, neopentyl alcohol, nonanol, fusel oil, butanol, furfuryl alcohol, propargyl alcohol, propanol , Hexanol, heptanol, benzyl alcohol, pentanol, methanol,
Methylcyclohexanol, 2-methyl-1-butanol, 3-methyl-2-butanol, 3-methyl-1-butyn-3-ol, 4-methyl-2-pentanol, 3
Alcohols such as -methyl-1-pentyn-3-ol can also be mentioned.

Examples of the organic solvent include anisole, ethyl isoamyl ether, ethyl t-butyl ether, ethyl benzyl ether, epichlorohydrin, 1,2-epoxybutane, crown ethers, cresyl methyl ether, and diisoamyl ether. , Propylene oxide, diisoamyl ether, diisopropyl ether, diethyl acetal, diethyl ether, dioxane, diglycidyl ether, 1,8-cineole, diphenyl ether, dibutyl ether, dipropyl ether, dibenzyl ether, dimethyl ether, tetrahydropyran, trioxane, bis (2-chloroethyl) ether, vinyl ethyl ether, vinyl methyl ether, phenetole, butyl phenyl ether, furan, furfural, methyl Lumpur, methyl -t- butyl ether, 2-methylfuran, ether acetal solvents such monochloro diethyl ether can be exemplified.

As the above-mentioned organic solvent, acrolein,
Acetylacetone, acetophenone, acetaldehyde, acetone, isophorone, ethyl-n-butyl ketone, diacetone alcohol, diisobutyl ketone, diisopropyl ketone, diethyl ketone, cyclohexanone, di-n-propyl ketone, holone, mesityl oxide, methyl-n-amyl ketone, Ethyl methyl ketone,
Ketone / aldehyde solvents such as methyl isobutyl ketone, methyl cyclohexanone, methyl-n-butyl ketone, methyl-n-propyl ketone, methyl-n-hexyl ketone, and methyl-n-heptyl ketone can also be used.

Solvents that can be used in the present invention include diethyl adipate, dioctyl adipate, triethyl acetyl citrate, tributyl acetyl citrate, ethyl acetoacetate, allyl acetoacetate, methyl acetoacetate, methyl abietate, and benzoate. Isoamyl acid, ethyl benzoate, butyl benzoate, propyl benzoate, benzyl benzoate, methyl benzoate, isoamyl isovalerate, ethyl isovalerate, isoamyl formate, isobutyl formate, ethyl formate, butyl formate, propyl formate, hexyl formate , Benzyl formate, tributyl citrate, tetraethoxysilane, tetramethoxysilane, cinnamate, methyl cinnamate, ethyl cinnamate, amyl acetate, allyl acetate, isoamyl acetate, isobutyl acetate, isopropyl acetate, ethyl acetate Le, acetate-2-ethylhexyl, cyclohexyl acetate, butyl acetate, propyl acetate,
Benzyl acetate, methyl acetate, methyl cyclohexyl acetate, isoamyl salicylate, benzyl salicylate, methyl salicylate, ethyl salicylate, diamyl oxalate, diethyl oxalate, dibutyl oxalate, diethyl tartrate, dibutyl tartrate, amyl stearate, ethyl stearate, ethyl stearate, butyl stearate, sepacin Dioctyl acid, dibutyl sebacate, diphenyl carbonate, dimethyl carbonate, isoamyl lactate, ethyl lactate, methyl lactate, diethyl phthalate, dioctyl phthalate, dibutyl phthalate, dimethyl phthalate, γ-butyrolactone, isoamyl propionate, ethyl propionate, Butyl propionate, Benzyl propionate, Methyl propionate, Borates, Dioctyl maleate, Dibutyl maleate, Diisopropyl malonate, Malon Diethyl, dimethyl malonate,
Ester solvents such as isoamyl butyrate, isopropyl butyrate, ethyl butyrate, butyl butyrate, and phosphoric esters can also be mentioned.

As the above-mentioned solvent, ethylene carbonate, ethylene glycol, ethylene glycol diethyl ether, ethylene glycol diacetate, ethylene glycol dibutyl ether, ethylene glycol diglycidyl ether, ethylene glycol monoacetate, ethylene glycol dimethyl ether, ethylene glycol Monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monophenyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol Monomethyl ether acetate , Ethylene glycol monomethyl methoxymethyl ether, ethylene chlorohydrin, 1,3
Octylene glycol, glycerin, glycerin 1,3
-Diacetate, glycerin dialkyl ether, glycerin fatty acid ester, glycerin triacetate, glycerin trilaurate, glycerin monoacetate,
2-chloro-1,3-propanediol, 3-chloro-
Examples include polyhydric alcohols such as 1,2-propanediol, diethylene glycol, diethylene glycol ethyl methyl ether, and polypropylene glycol, and derivatives thereof.

Further, as the above-mentioned solvent, isovaleric acid,
Carboxylic acid derivatives such as isobutyric acid, itaconic acid, 2-ethylhexanoic acid, 2-ethylacetic acid, oleic acid, caprylic acid, caproic acid, valeric acid, acetic acid, lactic acid, pivalic acid, propionic acid, ethylphenol, octylphenol, and guaiacol , Xylenol, p-cumylphenol, cresol, dodecylphenol, naphthol,
Nonylphenol, phenol, benzylphenol,
phenols such as p-methoxyethylphenol,
Acetamide, acetonitrile, acetone cyanohydrin, aniline, allylamine, isoquinoline, isobutylamine, isopropanolamines, imidazole,
N-ethylethanolamine, 2-ethylhexylamine, N-ethylmorpholine, ethylenediamine, caprolactam, quinoline, chloroaniline, ethyl cyanoacetate, diamylamine, isobutylamine, diaethanolamine, N, N-diethylaniline, diethylbenzylamine, diethylenetriamine , Dioctylamine,
Cyclohexylamine, triethylamine, triamylamine, trioctylamine, triethanolamine,
Trioctylamine, tri-n-butylamine, tripropylamine, toluidine, nitroanisole, picoline, piperazine, pyrazine, pyridine, pyrrolidine, N
-Nitrogen-containing compounds such as phenylmorpholine, morpholine, butylamine, heptylamine, and lutidine; in addition to these solvents, sulfur-containing compound-based solvents, fluorine-based solvents and the like can also be mentioned.

Further, a mixed solvent of the above-mentioned organic solvents can be used. In addition to the organic solvent, water and the like can be used as the inorganic solvent.

FIG. 5 shows colloid particles in which the particles 3 are protected by an organic compound 15 containing sulfur. In FIG. 5, the particles 3
Are Ag particles, and the particles 3 are organic compounds 15 containing sulfur.
As protected around with dodecanethiol. In the present invention, any organic compound 15 containing sulfur can be used. However, in the present invention, when a metal colloid such as Au or Ag is used for the particles 3, it is preferable to use an alkylthiol having 2 to 20 carbon atoms such as dodecanethiol.
In addition, as the particles 3 that can be used in the present invention, those having a particle diameter in the range of 1 to 100 nm can be used. As such particles 3, in addition to the above-described metal particles, polymer particles, and ceramic particles, a mixture of the above-described metal particles, polymer particles, and colloid particles that protect the ceramic particles with an organic compound containing sulfur may be used. it can. By applying the present invention to a particle mixture system in which diamagnetic particles and paramagnetic particles are mixed, it is also possible to control the structure of a particle film. Also,
The method for controlling the position of the particles 3 of the present invention can also be applied to separation of diamagnetic particles, paramagnetic particles, and ferromagnetic particles.

Particles 3 usable in the present invention
In the method for producing a compound, any method known so far can be used. The particle size of the particles 3 or colloids that can be used in the present invention can be measured by using a laser light scattering method, an electron microscope method, a sedimentation method, or the like.

In order to improve the stability of the particles 3 or colloid in a solution, any of the compounds having a combination of a hydrophobic group and a hydrophilic group, a surfactant, Agents and dispersants can also be used. The above-mentioned compounds, surfactants and dispersants which can be used in the present invention include, for example, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, butyl stearate, oleic acid, linoleic acid, linolenic acid, Elaidic acid, octyl stearate, amyl stearate, isooctyl stearate, octyl myristate, butoxyethyl stearate, anhydrosorbitan monostearate, anhydrosorbitan distearate, anhydrosorbitan tristearate, oleyl alcohol, lauryl alcohol Is raised.

The compounds, surfactants and dispersants mentioned above include alkylene oxides, glycerins, glycidols, alkylphenol ethylene oxide adducts, and more specifically, Nippon Oil & Fats Co., Ltd.
AA-102, NAA-415, NAA-312, NA
A-160, NAA-180, NAA-174, NAA
-175, NAA-222, NAA-34, NAA-3
5, NAA-171, NAA-122, NAA-14
2, NAA-160, NAA-173K, castor hardened fatty acid, NAA-42, NAA-44, cation SA, cation MA, cation AB, cation BB, Nymin L-201, Nymin L-202, Nymin S-2
02, Nonion E-208, Nonion P-208, Nonion S-207, Nonion K-204, Nonion NS-
202, Nonion NS-210, Nonion HS-20
6, Nonion L-2, Nonion S-2, Nonion S-
4, Nonion O-2, Nonion LP-20R, Nonion PP-40R, Nonion SP-60R, Nonion OP-
80R, Nonion OP-85R, Nonion LT-22
1, Nonionic ST-221, Nonionic OT-221, Monogly MB, Nonionic DS-60, Anone BF, Anone LG, Butyl stearate, Butyl laurate, Erucic acid, Kanto Chemical, Oleic acid, Takemoto Yushi, FAL
-205, FAL-123, manufactured by Nippon Rika Co., Ltd., Njerbu LO, Njolbu IPM, Sansocizer E40
30, Shin-Etsu Chemical Co., Ltd., TA-3, KF-96, KF-9
6L, KF96H, KF410, KF420, KF96
5, KF54, KF50, KF56, KF907, KF
851, X-22-819, X-22-822, KF9
05, KF700, KF393, KF-857, KF-
860, KF-865, X-22-980, KF-10
1, KF-102, KF-103, X-22-371
0, X-22-3715, KF-910, KF-393
5. Lion Armor, Armide P, Armide C, Armoslip CP, Lion Yushi, Duomin TDO, Nisshin Oil, BA-41G, Sanyo Kasei, Profan 2012E, New Pole PE61, Ionnet MS Nonionic surfactants, cyclic amines, ester amides, quaternary ammonium salts, hydantoin derivatives, heterocycles, such as -400, Ionnet MO-200, Ionnet DL-200, Ionnet DS-300, and Ionnet DS-1000 Ionnet DO-200 , A cationic surfactant such as a phosphonium or a sulfonium, an anionic surfactant containing an acidic group such as a carboxylic acid, a sulfonic acid, a phosphoric acid, a sulfate group, a phosphate group, an amino acid, an aminosulfonic acid, and an amino alcohol. Sulfuric acid or phosphorus Esters, alkyl betaine type amphoteric surfactants and the like.

The manufacturing method of the particle film of the present invention will be further described with reference to FIG. 4 again. The diamagnetic particles are used as the particles 3 and the substrate 1 accommodated in the container 12 is arranged above the center 9 of the magnetic field. I do. The container 12 is formed by using a superconducting magnet 7 capable of applying 20 T with a magnetic flux density at a magnetic field center 9.
Is moved above the magnetic field center 9, the magnetic flux density, which is the strength of the magnetic field applied to the particles 3 in the container 12, can be changed from 0.5 to 20T. When magnetic particles or ferromagnetic particles are used for the particles 3,
By disposing the substrate 1 accommodated in the container 12 below the magnetic field center 9 and moving the position of the container 12 below the magnetic field center 9, the magnetic flux density applied to the particles 3 in the container 12 is reduced by 0.5. Can be changed up to 20T. As the superconducting magnet 7, other than those having a bore 8 in the vertical direction, for example, those having a plate shape, a columnar shape, or the like can be used as long as a magnetic field can be applied in the vertical direction. In addition to the superconducting magnet 7, in the present invention, other than those capable of applying a magnetic flux density of 20T at the magnetic field center 9, any other magnetic flux density of 0.5 to 20 T may be applied at the magnetic field center 9. Anything can be used.

In the method for producing a particle membrane according to the present invention,
In order to produce a particle film having a particle diameter of 100 nm, control may be performed by increasing the vapor pressure of the solvent 2 to suppress the evaporation rate of the solvent 2. In the embodiment of the present invention, as shown in FIG.
In step 3, the evaporation rate of the solvent 2 can be suppressed by increasing the vapor pressure of the solvent 2. Solvent 2 in container 12
Is evaporated through the gap of the lid 13. After all of the solvent 2 evaporates, only the particles 3 are left on the substrate 1 to produce a particle film.

The vapor pressure of the solvent 2 can be further increased by providing a separate container such as a beaker with an open top inside the container 12 and filling the solvent 2, thereby suppressing the evaporation rate of the solvent 2. . It is also possible to control the evaporation rate of the solvent 2 in the container 12 by using a container that can be hermetically sealed and providing a valve or the like. In addition, it is also possible to control the evaporation rate of the solvent 2 by providing a heating device to control the temperature as described above, or by providing a pressure reducing device to control the pressure.

FIG. 6 is a schematic view of a particle film produced by the method for producing a particle film of the present invention. By controlling the position of the particles 3 with respect to the liquid surface of the solvent 2 by using the intensity and direction of the magnetic field using the apparatus shown in FIG. 4, and further suppressing the evaporation rate of the solvent 2 by storing the particles 3 in the container 12 as shown in FIG.
As shown in (1), a particle film in which the particles 3 are two-dimensionally integrated on the substrate 1 can be manufactured. According to the present invention, not only a particle film in which the particles 3 form a single layer on the substrate 1 but also a laminated film in which a plurality of layers are superposed can be formed.

[0062]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples. (Example 1) The particle membrane of the present invention was produced using the apparatus shown in FIG. The diameter of the bore 8 is 150 m in the superconducting magnet 7.
m, a superconducting magnet (10T 150 diameter, manufactured by Kobe Steel Co., Ltd.) capable of applying a magnetic field of 10T to the magnetic field center 9 was used. Ag particles having a particle diameter of 10 nm protected by dodecanethiol were used as the particles 3. Further, toluene was used as the solvent 2 in which the particles 3 were dispersed.
Further, as the container 12, a glass petri dish with a lid 13 having an outer diameter of 120 mm was used. As the substrate 1, a carbon vapor-deposited film obtained by vapor-depositing carbon on a collodion film adhered to a slide glass, having a width of 26 mm, a length of 76 mm, and a thickness of 1 mm was used. The container 12 was placed on a table 14 which can be placed horizontally, and was placed in the bore 8 of the superconducting magnet 7.

Next, a drop of a liquid in which Ag particles were dispersed in toluene was dropped on a smooth substrate 1 and developed in a circular shape. The substrate 1 was housed in a petri dish and covered with a lid 13. The table 14 was placed in the bore 8 of the superconducting magnet 7 and the petri dish was arranged at a position 0.15 m above the magnetic field center 9. Thereafter, a current was passed through the super-electric magnet 7 to generate a magnetic field of 10 T vertically upward at the magnetic field center 9 to produce a particle film.

(Example 2) In the same manner as in Example 1 except that a petri dish was arranged at the center of the magnetic field 9 by changing the height of the base 14 in the bore 8 of the superconducting magnet 7, a 10 T A magnetic field was generated vertically upward to produce a particle film.

(Example 3) Except that the height of the base 14 was changed in the bore 8 of the superconducting magnet 7 and the petri dish of the container 12 was arranged at 0.15 m below the center 9 of the magnetic field. Similarly to 1, a 10 T magnetic field was generated vertically upward at the magnetic field center 9 to produce a particle film.

(Magnetic field gradient in bore of superconducting magnet) When a magnetic field of 10 T was applied vertically to the magnetic field center 9 of the superconducting magnet 7 shown in FIG. 4, a magnetic field gradient was generated as shown in FIG. The vertical axis z in FIG. 7 indicates the distance in the vertical direction from the magnetic field center 9 with the magnetic field center 9 as 0, and the horizontal axis Bz shown at the bottom of FIG. 7 indicates the magnetic flux density which is the strength of the magnetic field. FIG.
The horizontal axis BzdBz / dz shown in the upper part of the figure is a value of the force applied by the magnetic field, which is caused by the magnetic field, and indicates the value of the product of the magnetic field and the magnetic field gradient. The solid line in FIG. 7 shows the relationship between the distance z in the vertical direction and the magnetic flux density Bz. The broken line indicates the product BzdBz / dz of the distance z in the vertical direction and the magnetic field gradient.
The relationship is shown below. In the magnetic field shown in FIG. 7, the magnetic field gradient becomes 0 at the magnetic field center 9 and is 0.15 m above and below the magnetic field center 9.
In the examples described in the present invention, the Ag particles protected by dodecanethiol are diamagnetic particles, so that the Ag particles are above the magnetic field center 9 in Example 1 and 0 in FIG. At the position of .15 m, the product of the magnetic field and the magnetic field gradient was the minimum value -300 T ² / m, and the force applied by the magnetic field was maximum upward (in the direction acting as buoyancy). The lower side of the magnetic field center 9 of the third embodiment, in FIG.
At a position of 0.15 m, the product of the magnetic field and the magnetic field gradient had a maximum value of 300 T ² / m, and the force applied by the magnetic field was maximum downward (in the direction of gravity). In the present invention, the positive / negative force applied by the magnetic field defines the direction of gravity as positive and the direction acting as buoyancy, that is, the direction opposite to gravity as negative. Further, at the magnetic field center 9 in Example 2, the force applied by the magnetic field was zero.

(Magnetic Field Effect of Particle Film) FIG.
(B) and (c) show the particle membranes manufactured in Examples 1, 2, and 3 using a transmission electron microscope (HITA, manufactured by Hitachi, Ltd.).
CHI H-7500). FIG.
As shown in (a), it is found that a particle film in which Ag particles are densely accumulated is manufactured by disposing the container 12 containing the substrate 1 at a position where the force applied by the magnetic field is maximized. Was. 8 (a), 8 (b) and 8
It was found that as the force applied by the magnetic field decreases so as to give buoyancy to the particles 3 in the order of (c), the Ag particles are coarsely accumulated to produce a particle film. Therefore, it has been found that by using the method for producing a particle film using the method for controlling the position of particles of the present invention, the horizontal capillary force for accumulating particles is effectively used, and the arrangement regularity of particles is significantly improved. Was done.

[0068]

As described above, the present invention can provide a method for controlling a particle position in which a magnetic field is applied to a solvent in which particles are dispersed, and the particle position with respect to the liquid surface of the solvent is controlled by the strength and direction of the magnetic field. Applying a solvent in which particles are dispersed on a substrate, evaporating the solvent using a particle position control method that controls the particle position with respect to the liquid surface of the solvent according to the strength and direction of a magnetic field, and accumulating the particles in two dimensions. Can be provided.

Therefore, by using the method for controlling the position of particles and the method for producing a particle film using the control method of the present invention, the arrangement regularity of particles can be significantly improved by effectively utilizing the lateral capillary force for accumulating particles. It is possible to manufacture a particle film by two-dimensionally accumulating particles having a particle diameter of a nanometer range or less, which is smaller than a micrometer range.

Further, the particle membrane produced according to the present invention comprises:
A single-electron device, an optical device, a catalyst, a magnetic recording medium, an electrode or a sensor, as well as anything used magnetically, electrically and optically, can be used. , Semiconductor, catalyst, analysis, separation, chemistry, storage, and recording.

[Brief description of the drawings]

FIG. 1 is a view showing a stage of manufacturing a particle film by an advection accumulation method.

FIG. 2 is a diagram showing directions of magnetic field forces acting on particles in a bore of a superconducting magnet.

FIG. 3 is a diagram illustrating a position of a particle with respect to a liquid surface of a solvent according to a direction of force by a magnetic field according to the present invention.

FIG. 4 is a cross-sectional view of an apparatus for producing the particle membrane of the present invention.

FIG. 5 is a view showing colloid particles protected by an organic compound containing sulfur used in the present invention.

FIG. 6 is a view showing a particle membrane produced by the method for producing a particle membrane of the present invention.

FIG. 7 is a diagram showing a magnetic field gradient of a superconducting magnet used in an example of the present invention.

FIG. 8 is a view showing a particle membrane manufactured in Examples 1, 2, and 3 of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Substrate 2 ... Solvent 3 ... Particle 4 ... Interface 5 ... Gas 6a, 6a ', 6b, 6b' ... Particle 7 ... Superconducting magnet 8 ... Bore 9 ... Center of magnetic field 10a, 10b ... Solvent 11a, 11b ... Substrate 12 ... Container 13: lid 14: table 15: organic compound containing sulfur

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01F 41/16 H01F 41/16 5E049 // B22F 1/02 B22F 1/02 CF term (Reference) 4D006 GA41 HA41 MA03 MC02X NA46 NA50 NA51 NA64 4G065 AA04 AB21X BA07 BB01 BB06 CA01 DA02 DA06 DA09 DA10 EA03 FA03 4G075 AA24 AA35 AA61 BB02 BB05 BD16 BD17 CA42 CA51 FB02 4K018 BA01 BA02 BA04 BA08 BA10 BA13 BA20 BA23 BA02 A03A BA17 BA21 BA25 BA27 BA28 BA31 DA09 DB12 DB19 EA01 EA04 5E049 AC08 BA06 EB01 FC10

Claims (18)

[Claims] 1. A method for controlling a particle position, wherein a magnetic field is applied to a solvent in which particles are dispersed, and a particle position in the solvent is controlled by an intensity and a direction of the magnetic field. 2. The method according to claim 1, wherein the particles are diamagnetic particles, paramagnetic particles, or ferromagnetic particles. 3. The magnetic field has a magnetic flux density of 0.5 to 20T.
The method for controlling a particle position according to claim 1 or 2, wherein 4. The method according to claim 1, wherein said particles have a particle diameter of 1 to 100 nm. 5. The method according to claim 1, wherein the particles are colloidal particles protected by an organic compound containing sulfur. 6. dispersing particles in a solvent, applying the solvent in which the particles are dispersed on a substrate, evaporating the solvent by controlling the position of the particles with respect to the liquid surface of the solvent by the intensity and direction of a magnetic field, A method for producing a particle film, wherein the particles are two-dimensionally integrated. 7. The method according to claim 6, wherein the particles are diamagnetic particles, paramagnetic particles, or ferromagnetic particles. 8. The magnetic field has a magnetic flux density of 0.5 to 20T.
The method for producing a particle membrane according to claim 6, wherein: 9. The method according to claim 6, wherein the particles have a particle diameter of 1 to 100 nm. 10. The method according to claim 6, wherein the particles are colloid particles protected by an organic compound containing sulfur. 11. The method according to claim 10, wherein the organic compound containing sulfur is an alkylthiol having 2 to 20 carbon atoms. 12. The particles are made of Ag, Au, Cu, P.
b, Zn, Sn, Bi, Pt, Ti, Pd, Cr, M
The method for producing a particle film according to any one of claims 6 to 9, wherein the method is a colloidal particle of a metal selected from the group including n, Al, Fe, Co, and Ni. 13. dispersing particles in a solvent, applying the solvent in which the particles are dispersed on a substrate, evaporating the solvent by controlling the position of the particles with respect to the liquid surface of the solvent by the intensity and direction of a magnetic field, A particle film in which the particles are two-dimensionally integrated. 14. The particle film according to claim 13, wherein the particles are diamagnetic particles, paramagnetic particles, or ferromagnetic particles. 15. The film thickness of the particle film is 1 to 100 nm.
The particle membrane according to claim 13, wherein 16. The particles according to claim 13, wherein the particles are colloid particles protected by an organic compound containing sulfur.
The particle membrane according to any one of the above. 17. The particle membrane according to claim 16, wherein the organic compound containing sulfur is an alkylthiol having 2 to 20 carbon atoms. 18. The method of claim 18, wherein the particles are Ag, Au, Cu, P
b, Zn, Sn, Bi, Pt, Ti, Pd, Cr, M
The particle membrane according to any one of claims 13 to 15, wherein the particle membrane is a colloidal particle of a metal selected from the group including n, Al, Fe, Co, and Ni.