JP2000096236A - Metal oxide structure having network structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a latticed structure comprising plural combinations of flat platy bodies of a metal oxide having central faces parallel to each other and specified dimensions at a specified density and having a large surface area per unit volume by blowing a metal compound on a substrate of a metal oxide or the like to torm a metal oxide. SOLUTION: Two or more combinations of flat platy bodies having central faces parallel to each other are allowed to exist to obtain the objective metal oxide structure having a latticed structure. The flat platy bodies preferably have 0.005-10,000 μm width, 0.05-10,000 μm length, a height to width ratio of >=1 and >=0.1 μm weighted average height and preferably comprise metal oxide single crystals formed on a metal oxide substrate. The flat platy bodies are optionally fixed by filling the gaps with an organic or inorganic material, metal or the like. The metal oxide structure is formed by blowing a metal compound as gas or fine particles on a substrate kept at a prescribed temperature and allowing the compound to react with oxygen, water, ammonia or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a metal oxide structure having a lattice structure.

[0002]

2. Description of the Related Art Metal oxides are used for electronic materials such as ceramic capacitors, actuators, light wavelength conversion devices, laser oscillation devices, cold cathode devices, etc., surface modifiers for antibacterial and antifouling effects, gas phase and the like. It is used as a catalyst in the liquid phase or both phases, its carrier, and the like. For use in these materials, a large surface area per volume is desired. To increase the surface area per volume,
For example, a lamination technique has been conventionally developed. However, this method has a limitation in increasing the surface area per volume.

There is also a method of forming a large number of needle-like crystals as a method of increasing the surface area. Conventionally, a needle-like crystal made of at least one of a group III-V compound semiconductor, a group IV-VI compound semiconductor, and an elemental semiconductor is formed by MOCVD using an organometallic thermal decomposition method (hereinafter referred to as "MOCVD method"). There is a method of forming the substrate by using the method. However, the acicular crystals obtained by this method are III-
It was made of at least one of a group V compound semiconductor, a group IV-VI compound semiconductor, and an elemental semiconductor, and was oriented in one direction. Furthermore, there is no teaching or suggestion in the known literature regarding the formation of a flat body composed of a number of oriented metal oxides.

Further, as a method of forming a metal oxide by MOCVD under normal pressure, for example, Journal of the Ceramic Society of Japan, 105 (1997), pp. 551-554 (Jou)
rnal of the Ceramic Society
ty of Japan, 105 (1997) pp. L
551 to R554). However, the method described in the article only forms a titanium oxide thin film and does not disclose a method for increasing the surface area.

[0005]

The present invention relates to a metal oxide structure having a peculiar structure such as a large surface area due to the presence of a flat plate at a specific density.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies on a structure having a large surface area per volume, and as a result, have found a structure in which a large number of metal oxide plate-like bodies are present in a small area. The present invention has been completed.

That is, the present invention provides (1) a metal oxide structure having a lattice-like structure composed of a plate-like body and having two or more combinations in which the center plane of the plate-like body is parallel to each other; The width of the plate is 0.005 to 10000μ
m, a metal oxide structure according to (1), wherein the length is 0.05 to 10000 μm and the ratio of height to width is 1 or more;
(3) The flat body is 10 μm × 10 μm on the plane of the structure
(1) The metal oxide structure of (2), which exists at a density of 0.01 to 10,000 per area of the metal oxide, and (4) the flat body exists on a plate made of metal oxide (1). ~ (3)
(5) The metal oxide structure of (1) to (4), wherein the flat body is a metal oxide single crystal, and (6) the center plane of the flat body is parallel to each other. Two or more combinations exist and the crystal axes exist in the same direction (1) to
(5) The metal oxide structure according to (1) to (6), wherein the weighted average of the ratio of the height to the width of the plate is less than 5; The metal oxide structure according to any one of (1) to (6), wherein the weighted average of the ratio of the height to the width of the body is 5 or more. (9) The weighted average height of the flat body is 0.1 μm
m or more, (1) to (8),
0) The metal oxide structure according to any one of (1) to (9), wherein the plate-like body is fixed with an organic substance, an inorganic substance, or a metal.

Hereinafter, the present invention will be described in detail. The plate-like body in the present invention refers to a plate-like body whose central axis is formed of one straight line when the structure is observed from a plane direction. The direction of the central axis in this case is the major axis direction. When the central axis of the plate-like body is composed of two or more straight lines, for example, like the letter L of the alphabet, one plate-like body is regarded as one central axis. The direction of the central axis and the central plane of the flat body is determined by a conventionally known method such as ordinary X-ray diffraction method, visual observation from a scanning electron microscope (hereinafter referred to as “SEM”) photograph and image analysis. Can be measured and determined.

The structure according to the present invention comprises a plate-like metal oxide having a lattice structure, in which there are two or more combinations whose central planes are parallel to each other. The number of combinations in which the center planes of the plate-like objects are parallel to each other may be any number as long as there are two or more, but preferably six or less. 1 of plate-like objects whose central planes are parallel to each other with respect to the number of all plate-like objects
Although the ratio of the number per set is not limited, this ratio is preferably 1 / (5 × n) or more when n sets of combinations in which the central surfaces of the plate-like objects are parallel to each other. For example, the combination in which the center planes of the plate-like objects are parallel to each other is 2
In the case of a set, 1/10 or more is a preferable range of the ratio of the number of one plate-like object whose center plane is parallel to the number of all plate-like objects. More preferably, it is 1 / (3 × n) or more. Here, the number of plate-like objects refers to the number of plate-like objects existing per 10 μm × 10 μm area when the structure is observed from a planar direction.

Although the size of the flat plate is not particularly limited,
Preferably, the width is 0.005 to 10000 μm. More preferably, it is 0.01 to 100 μm, most preferably 0.05 to 10 μm. In addition, the length is 0.
It is preferably from 0.05 to 10000 μm. More preferably 0.1 to 500 μm, even more preferably 0.1 to 500 μm
100 μm. Here, the length of the flat body refers to the length of the long axis of the flat body which is substantially recognized as one rod when observing the plane portion of the structure in the present invention. In addition, the width of the flat body referred to here is a half of the length of the flat body which is substantially recognized as one rod when the flat portion of the structure in the present invention is observed. Indicates the width.

When the width is less than 0.005 μm, it is difficult to obtain a grown flat plate, and when it exceeds 10,000 μm, the effect of increasing the surface area by the flat plate is poor, which is not preferable. The ratio of the length to the width of the flat plate is not particularly limited, but is preferably 1 or more. If the ratio of the length to the width of the flat body is too small, the effect of increasing the surface area by the flat body does not appear. The higher the ratio of the length to the width of the flat body is, the more the effect of the flat body appears, but if the ratio of the length to the width of the flat body is too high, it becomes difficult to maintain the strength of the structure.

As the three-dimensional shape of the flat plate, the ratio of the height to the width of the flat plate is preferably 1 or more.
When the ratio of the height to the width of the flat body is less than 1, the effect of increasing the surface area by the flat body does not appear, which is not preferable. The higher the ratio of the height to the width of the flat body is, the more the effect of the flat body appears. However, if the ratio of the height to the width of the flat body is too high, it is difficult to maintain the strength of the structure. Here, the height refers to the height from the position where the flat plate is substantially projected to the top of the flat plate. The height is different depending on the application to be used and is not limited, but is usually preferably 0.1 to 10000 μm, more preferably 1 to 10000 μm from a practical point of view.
１０００1000 μm, more preferably 10-500 μm. When the length of the flat body is less than 0.1 μm, the effect of increasing the surface area by the flat body is poor, and when it exceeds 10,000 μm, it becomes difficult to maintain the strength of the structure.

The ratio of the height to the width and the average value of the heights of the plurality of flat plates are not particularly limited depending on the type of the metal oxide. The average value of the height to width ratio in the present invention refers to the weighted average value of the ratio of the height to the width of the flat plate in the range of a cross section having a length of 200 μm in the center of the structure. The structures of the present invention are classified into squat low sidewall structures having an average height to width ratio of less than 5, and high wall structures having an average height to width ratio of 5 or more. Is done. These can be used properly depending on the application. The average height value in the present invention refers to a weighted average height of the protrusions in a range of 10 μm × 10 μm on the metal oxide surface. The average height is preferably 0,1.
1 μm or more. Both the average value of the ratio of the height to the width and the average value of the height may have any distribution width.

The three-dimensional shape of the flat body is not particularly limited. Specifically, when the cross section of the flat body is observed from the plane direction while changing the height of the flat body, the width and / or the length of the flat body are from the top to the bottom regardless of the height of the flat body. The width and / or length of the flat body at the root portion in the height direction of the flat body were small, and the width and / or length of the flat body once increased upward. Later, the width and / or length of the flat body gradually decreases again toward the top, and the width and / or length of the flat body at the base of the flat body is small and goes to the center. The width and / or length of the flat body is reduced toward the top while repeating the increase and decrease of the width and / or length of the flat body twice or more, and the flat body is reduced. The width and / or length of the plate gradually decrease from the root to the top And it shall, up to a distance close to the top portion is the same width and / or length of the plate-like body,
Or, it becomes larger or smaller, from which a shape like a pyramid or a truncated pyramid, a cone or a truncated cone, a hemisphere, or the like, or a combination thereof can be given. More preferably, it is prismatic. Although it depends on the crystal structure, for example, in the case of titanium oxide, it is often a square pillar. Further, it may be a prism having a cross section of another polygon.

The flat body may be present on a substrate made of a metal oxide. Further, it may be present on a substrate other than the metal oxide. The shape of the substrate may be any shape as long as it has a substantially flat and / or curved surface, but a shape having a large surface area with respect to the thickness is more preferable. Further, in the case of a plate, it is preferable that the area of the surface on which the flat body exists is the largest as compared with the other surfaces. The size of the surface on which the flat body is present is not particularly limited, but in the case of a plate, the thickness is preferably from 0.01 mm to 100 mm, more preferably from 0.02 mm to 50 m, for practical purposes.
m, most preferably 0.05 mm to 10 mm. The ratio of the flat body on the surface is 10 μm × 10
The number is preferably 0.01 to 10000, more preferably 0.01 to 1000, and still more preferably 1 to 500 per μm area. When the value is less than 0.01, the effect of increasing the surface area by the plate is poor, and when it exceeds 10,000, it is difficult to obtain a grown plate, which is not preferable.

The structure according to the present invention comprises a metal oxide. The metal oxide in the present invention means that the metal species in the periodic table is Group 1 other than hydrogen, Group 2 or 13 excluding boron.
Group, 14 excluding carbon, 15 excluding nitrogen, phosphorus and arsenic
Tribe, Po and 3, 4, 5, 6, 7, 8, 9, 10, 1
It is an oxide that is an element belonging to Groups 1 and 12. As the metal species, for example, Li, Na, K, Rb, Cs, B
e, Mg, Ca, Sr, Ba, Al, Ga, In, T
1, Si, Ge, Sn, Pb, Sb, Bi, Po, S
c, Y, La, Th, Ce, Pr, Nd, Pm, Sm,
Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, L
u, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo,
W, Mn, Tc, Re, Fe, Ru, Os, Co, R
h, Ir, Ni, Pd, Pt, Cu, Ag, Au, Z
n, Cd, Hg and the like, and among these, Li, Na, K, Rb, Cs, Be, Mg, Ca, S
r, Ba, Al, Ga, In, Tl, Si, Ge, S
n, Pb, Sb, Bi, Sc, Y, La, Ce, Th,
Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn,
Re, Fe, Ru, Os, Co, Rh, Ir, Ni, P
d, Pt, Cu, Ag, Au, Zn, Cd, and Hg, and more preferably Li, K, Mg, Ca, Sr,
Ba, Al, In, Si, Sn, Pb, Th, Y, C
e, Ti, Zr, V, Nb, Ta, Cr, Mo, W, M
n, Fe, Co, Ni, Pd, Pt, Cu, Ag, Z
n and Cd.

These metals can be used alone or in combination of two or more. For example,
MgO, Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , Sn
O ₂ , TiO ₂ , ZnO, barium titanate, SrTi
O ₃ , LiNiO ₃ , PZT, YBCO, YSZ, YA
G, ITO (In ₂ O ₃ / SnO ₂ ) and the like.
Further, an alkali metal and another metal can be used in combination. For example, Ta, Nb and or KTaO ₃ in combination alkali metal or the like, to form a composite oxide such as NbLiO _3, can be a metal oxide.

The metal oxide may be basically crystalline or amorphous, but is more preferably crystalline. Even if the crystalline material is one or more single crystals, even if it is polycrystalline,
One or more semi-crystalline materials having both an amorphous part and a crystalline part may be used, or a mixture thereof. Particularly preferably, it is a single crystal. In the case of using two or more types of metal oxides, the metal oxides may be mixed to form a single layer, or layers of metal oxides having different compositions may be stacked.

Next, a preferred method of forming a metal oxide in the present invention will be described. The metal oxide in the present invention can be produced, for example, by converting a metal compound, which is a raw material of the metal oxide, into a gas and / or fine particles and reacting it with oxygen, water, ammonia, or the like. At this time, the metal compound is not particularly limited as long as it has a metal in the metal oxide of the target structure and reacts with oxygen, water, ammonia or the like to form an oxide.

Examples of such a metal compound include alkoxides in which the hydrogen of the hydroxyl group of an alcohol is replaced with a metal at the atom of the metal or metal-like element, and acetylacetone, ethylenediamine, bipiperidine, bipyrazine at the atom of the metal or metal-like element. , Cyclohexanediamine, tetraazacyclotetradecane, ethylenediaminetetraacetic acid, ethylenebis (guanide), ethylenebis (salicylamine), tetraethylene glycol, aminoethanol, glycine, triglycine, naphthyridine, phenanthroline, pentanediamine, pyridine,
One or two ligands selected from salicylaldehyde, salicylideneamine, porphyrin, thiourea, etc.
Fe, Cr, Mn, Co, Ni, Mo, V, W, having various kinds of complexes having a carbonyl group as a ligand
Various metal carbonyls such as Ru, carbonyl group, alkyl group, alkenyl group, phenyl or alkylphenyl group, olefin group, aryl group, conjugated diene group including cyclobutadiene group, and cyclopentadienyl group. Various metal compounds and metal halide compounds having one or more ligands selected from trienyl groups such as a dienyl group, a triene group, an arene group, a cycloheptatrienyl group and the like can be used. . Also, metal complexes can be used. Among them, complexes such as acetylacetone and alkoxides are more preferably used.

The complex according to the present invention includes β-
Distribution of diketones, ketoesters, hydroxycarboxylic acids or salts thereof, various Schiff bases, ketoalcohols, polyvalent amines, alkanolamines, enol active hydrogen compounds, dicarboxylic acids, glycols, ferrocenes, etc. Compounds in which one or two or more ligands are bonded are exemplified.

Specific examples of the compound serving as a ligand of the complex used in the present invention include, for example, acetylacetone, ethylenediamine, triethylenediamine, ethylenetetramine, bipiperidine, cyclohexanediamine, tetraazacyclotetradecane, ethylenediaminetetraacetic acid, ethylenebis (Guanide), ethylenebis (salicylamine), tetraethyleneglycol, diethanolamine, triethanolamine, tartaric acid, glycine, triglycine, naphthyridine, phenanthroline, pentanediamine, salicylaldehyde, catechol, porphyrin, thiourea, 8-hydroxyquinoline, 8-hydroxyquinaldine, β-aminoethyl mercaptan, bisacetylacetone ethylenediimine, eriochrome black T, oxy , Quinaldine acid salicylaldoxime, picolinic acid, glycine,

Dimethylglyoximat, dimethylglyoxime, α-benzoinoxime, N, N'-bis (1
-Methyl-3-oxobutylidene) ethylenediamine,
3-{(2-aminoethyl) amino} -1-propanol, 3- (aminoethylimino) -2-butaneoxime, alanine, N, N′-bis (2-aminobenzylidene) ethylenediamine, α-amino-α -Methylmalonic acid, 2-{(3-aminopropyl) amino} ethanol, aspartic acid, 1-phenyl-1,3,5-hexanetrione, 5,5 ′-(1,2-ethanediyldinitrilo) bis (1-phenyl-1,3-hexanedione), 1,3-bis {bis [2- (1-ethylbenzimidazolyl) methyl] amino} -2-propanol,
1,2-bis (pyridine-α-aldimino) ethane,
1,3-bis {bis (2-pyridylethyl) aminomethyl} benzene, 1,3-bis {bis (2-pyridylethyl) aminomethyl} phenol, 2,2′-bipiperidine,

2,6-bis {bis (2-pyridylmethyl) aminomethyl} -4-methylphenol, 2,2 ′
-Bipyridine, 2,2'-bipyrazine, hydrotris (1-pyrazolyl) borate ion, catechol, 1,2
-Cyclohexanediamine, 1,4,8,11-tetraazacyclododecane, 3,4: 9,10-dibenzo-
1,5,8,12-tetraazacyclotetradecane-
1,11-diene, 2,6-diacetylpyridine dioxime, dibenzyl sulfide, N- {2- (diethylamino) ethyl} -3-amino-1-propanol, o-
Phenylenebis (dimethylphosphine), 2- {2-
(Dimethylamino) ethylthiodiethanol, 4,4 '
-Dimethyl-2,2'-bipyridine, N, N'-dimethyl-1,2-cyclohexanediamine, dimethylglyoxime, 1,2-bis (dimethylphosphino) ethane,
1,3-bis (diacetylmonooximino) propane,

3,3'-trimethylene dinitrobis (2
-Butane oxime) 1,5-diamino-3-pentanol dipivaloylmethane, 1,2-bis (diphenylphosphino) ethane, diethyldithiocarbamate ion,
N, N'-bis {2- (N, N'-diethylaminoethyl) aminoethyl} oxamide, ethylenediaminetetraacetic acid, 7-hydroxy-4-methyl-5-azahept-4-en-2-one, 2-amino Ethanol, N,
N'-ethylenebis (3-carboxysalicylideneamine), 1,3-bis (3-formyl-5-methylsalicylideneamino) propane, 3-glycylamino-1-propanol, glycylglycine, N'- (2-hydroxyethyl) ethylenediaminetriacetic acid, hexafluoroacetylacetone, histidine, 5,26: 13,18
-Diimino-7,11: 20,24-dinitrodibenzo [c, n] -1,6,12,17-tetraazacyclodocosin, 2,6-bis {N- (2-hydroxyphenyl) iminomethyl}- 4-methylphenol, 5,5
7,12,12,14-hexamethyl-1,4,8,1
1-tetraazacyclotetradecane-N, N ″ -diacetate,

1,2-dimethylimidazole, 3,3 '
-Ethylenebis (iminomethylidene) -di-2,4-pentanedione, N, N'-bis (5-amino-3-hydroxypentyl) malonamide, methionine, 2-hydroxy-6-methylpyridine, methyliminodiacetic acid,
1,1-dicyanoethylene-2,2-dithiol, 1,
8-naphthyridine, 3- (2-hydroxyethylimino) -2-butanone oxime, 2,3,7,8,12,
13,17,18-octaethylporphyrin, 2,
3,7,8,12,13,17,18-octamethylporphyrin, oxalic acid, oxamide, 2-pyridylaldoxime, 3- {2- (2-pyridyl) ethylamino}
-1-propanol, 3- (2-pyridylethylimino) -2-butanone oxime, 2-picolylamine, 3
-(2-pyridylmethylimino) -2-butanone oxime, dihydrogen diphosphite, 3-n-propylimino-2-butanone oxime, proline, 2,4-pentanediamine, pyridine,

N, N'-dipyridoxylideneethylenediamine, N-pyridoxylideneglycine, pyridine-2
-Thiol, 1,5-bis (salicylideneamino) -3
-Pentanol, salicylaldehyde, N-salicylidenemethylamine, salicylic acid, N- (salicylidene)-
N '-(1-methyl-3-oxobutylidene) ethylenediamine, salicylideneamine, N, N'-disalicylidene-2,2'-biphenylylenediamine, N, N'-
Disalicylidene-2-methyl-2- (2-benzylthioethyl) ethylenediamine, N, N'-disalicylidene-4-aza-1,7-heptanediamine, N, N'-disalicylideneethylenediamine, N-salicylide Denglycine, salicylaldoxime, N, N'-disalicylidene-o-phenylenediamine, N, N'-disalicylidene trimethylenediamine,

3-salicylideneamino-1-propanol, tetrabenzo [b, f, j, n] -1,5,9,1
3-tetraazacyclohexadecine, 1,4,7-triazacyclononane, 5,14-dihydrodibenzo [b,
i] -1,4,8,11-Tetraazacyclotetradecine, tris (2-benzimidazolylmethyl) amine,
6,7,8,9,16,17,18,19-octahydrodicyclohepta [b, j] -1,4,8,11-tetraazacyclotetradecene, 4,6,6-trimethyl-
3,7-diazanone-3-ene-1,9-diol, tris (3,5-dimethyl-1-pyrazolylmethyl) amine, 2,2 ′: 6 ′, 2 ″ -terpyridine, 5,7,
7,12,14,14-hexamethyl-1,4,8,1
1-tetraazacyclotetradecane, tetrahydrofuran,

Tris (2-pyridylmethyl) amine,
N, N, N ', N'-tetramethylurea, N, N'-bis (3-aminopropyl) oxamide, N, N, N',
N'-tetrakis (2-pyridylmethyl) ethylenediamine, all-cis-5,10,15,20-tetrakis {2- (2,2'-dimethylpropionamido) phenyl} porphyrin, 5,10,15,20- Tetraphenylporphyrin, 1,4,7-tris (2-pyridylmethyl) -1,4,7-triazacyclononane, hydrotris (1-pyrazolyl) borate, 3,3′4-
Trimethyldipyrromethene, trimethylenediaminetetraacetic acid, 3,3′5,5′-tetramethyldipyrromethene,
5,10,15,20-tetrakis (p-triporphyrin) and the like.

In forming the metal oxide, it is more preferable to form the metal oxide using a specific substrate. As a method for forming a metal oxide, a gas of a metal compound and / or
Or a method of reacting the fine particles with the metal oxide on the substrate surface,
Depositing metal oxides in the form of gas and / or fine particles;
Alternatively, any method such as a method of laminating may be used. In addition, both of these methods can be used in combination.

The specific substrate referred to herein is, for example, a metal oxide single crystal plate such as aluminum oxide, a semiconductor single crystal, ordinary ceramic, a metal containing silicon, glass, or the like.
It refers to plastic and the like. When using glass or plastic, it is preferable that the surface is subjected to an orientation treatment. Of these, metals containing silicon, metal oxides, and ZnTe, GaP, and GaAs are preferably used.
s, semiconductor single crystal such as InP. One factor in selecting a single crystal seed preferably used as the substrate is that the lattice constant of the formed metal oxide crystal seed is close to the lattice constant of the single crystal seed used as the substrate. The lattice constant can be measured by a conventionally known method such as a wide-angle X-ray diffraction method.

This value is a ratio expressed by the lattice constant of the surface of the metal oxide crystal seed to be in contact with the substrate / the lattice constant of the surface of the single crystal seed used as the substrate that is in contact with the metal oxide crystal. Is preferably 0.8 to 1.2,
0.9 to 1.1, more preferably 0.95
It is particularly preferable that the number is 1.05 to 1.05. Particularly preferably used are metal oxide single crystals such as silicon, aluminum oxide, magnesium oxide and SrTiO3. The crystals in this case may be one or more single crystals, polycrystals, one or more semi-crystalline materials having both an amorphous part and a crystalline part, or a mixture thereof. You may.

Most preferably, it is a single crystal. in this case,
The surface of the substrate is preferably a specific surface of a single crystal. Specifically, for example, when a metal oxide forming titanium oxide is selected, a (100) plane is used for a magnesium oxide substrate, and when a metal oxide forming a zinc oxide is selected, (111) is used for a silicon substrate. ) Plane, the (0001) plane for an aluminum oxide substrate, and the (001) plane for an SrTiO ₃ substrate. The substrate may or may not be included in the structure.

The procedure for actually forming the metal oxide is as follows. First, the metal compound is converted into gas and / or fine particles.
In order to obtain a metal oxide having a flat body, it is important to control the temperature conditions at this time. The temperature at this time depends on the metal compound used. The temperature is preferably a temperature at which the metal compound is vaporized, or a temperature at which it is heated to a higher temperature, particularly preferably 30 to 600 ° C, and most preferably 50 to 300 ° C.

The metal oxide may be formed as it is by using the gas and / or the metal compound which has become fine particles, or the metal oxide may be formed by spraying another gas as a medium. A preferred method is to spray metal gas as another medium to form a metal oxide. In this case, the flow rate of the gas is related to the temperature at which the metal compound is converted into gas and / or fine particles and the atmosphere in which the metal oxide is formed. In particular, the flow rate of this gas is preferably 20 / min or less, which is a space volume value represented by a value obtained by dividing the flow rate by the volume of the metal compound heating tank under ordinary room temperature and normal pressure atmosphere. More preferably, 5
/ Min or less.

The amount of the gas and / or the fine metal compound is controlled by the degree of supersaturation. The degree of supersaturation in the present invention is defined by [(actual vapor pressure) − (equilibrium vapor pressure) / equilibrium vapor pressure] × 100 (%). In order to obtain the metal oxide in the present invention, the degree of supersaturation is preferably 1% or more. It is more preferably at least 10%, particularly preferably at least 20%. The gas used as a medium for spraying the gas and / or the fine metal compound is not particularly limited as long as it does not react with the metal compound used. Specific examples include nitrogen gas, helium, neon, inert gas such as argon, carbon dioxide,
Organic fluorine gas, or an organic substance such as heptane or hexane is exemplified. Among these, an inert gas is preferable from the viewpoint of safety and economy. In particular, nitrogen gas is the most preferable in terms of economy.

In the case where a metal oxide formed on a substrate by spraying a gas and / or a metal compound which has been turned into fine particles with a gas, the distance between the outlet of the metal compound and the surface of the metal oxide is as large as possible. The distance is preferably determined by the ratio of the distance between the outlet and the surface of the metal oxide / the length of the long axis of the opening. This value is preferably 0.01 to 1, more preferably 0.05 to 0.7, particularly preferably 0.1 to 0.
5 Although this ratio varies depending on the shape of the outlet, a ratio of 1 or more is not preferable because the metal compound is not effectively converted to a metal oxide and the efficiency is poor.

The temperature of the substrate itself when the metal oxide is formed is not particularly limited as long as the solid metal oxide is formed near and on the surface of the substrate. Affects shape. Preferably 0-8
00 ° C, more preferably 20 to 800 ° C, particularly preferably 100 to 700 ° C. When the substrate is a metal oxide, the metal oxide is more preferably grown epitaxially on the substrate. Whether or not the metal oxide is epitaxially grown on the substrate can be confirmed by a usual X-ray diffraction method. In particular, a method of confirming by observing the in-plane orientation relationship between the substrate and the metal oxide by the φ scan method is preferably used.

When the flat body on the metal oxide is a metal oxide crystal, the direction of the crystal plane in the case where there are two or more combinations in which the central planes of the metal oxide crystal are parallel to each other exists. There is no problem. This direction depends on the type of the metal oxide and the crystal structure in the case of a crystal. For example, when the titanium oxide structure according to the present invention is formed on the (100) plane of MgO, (010), (10)
0) is a combination of two directions. When the flat body on the metal oxide is a metal oxide crystal, it is preferable that the crystal axes are in the same direction (the crystal axis directions are aligned). For example, the fluctuation of the crystal axis orientation measured by the X-ray rocking curve method is preferably within 10 degrees, more preferably within 5 degrees.

If oxygen, water, ammonia or the like is present in the system, a metal oxide may be formed in the apparatus before release, and clogging or the like may occur, and a metal oxide having a desired form may be formed. It is not preferable because it cannot be obtained. However, when the reaction rate of the metal compound with oxygen, water, ammonia or the like is extremely low, oxygen, water, ammonia or the like may be coexisted in the system in advance. The atmosphere in which the gas and / or the metal compound in the form of fine particles and the substrate are present may be under reduced pressure, under normal pressure, or under pressure. However, when the process is performed under a high degree of reduced pressure, for example, under an ultra-vacuum, the growth rate of the metal oxide is low, and the productivity is poor.
When the process is performed under pressure, there is no problem with the growth rate of the metal oxide, but equipment for pressurization is required. Usually 0.
It is preferably carried out at 001 to 20 atm, more preferably 0.1 to 10 atm, and most preferably normal pressure.

The reaction time required to form a metal oxide is not particularly limited. It differs depending on the reaction conditions and the type of the raw material. For example, when zinc acetylacetonate is used as the raw material, it is preferably 10 minutes or more at normal room temperature and normal pressure. It is more preferably at least 30 minutes, particularly preferably at least 1 hour. When tetraisopropoxytitanate is used as a raw material, it is preferable that the temperature be 3 minutes or less at normal room temperature and normal pressure. More preferably, it is 90 seconds or less. When forming the metal oxide, the metal compound may be mixed to form gas and / or fine particles, or the gas and / or fine metal compound may be mixed. In addition, both of these methods can be used in combination.

FIG. 1 shows a schematic view of an example of a reaction apparatus preferably used in the present invention. N ₂ is dehydrated by a liquid nitrogen trap. Metal compound metal compound in the heating tank is heated by the heater becomes a gas and / or particulate, N ₂
Is sprayed on the substrate through the nozzle and the slit. The line after the heating tank is heated by the ribbon heater. MgO with (100) face to slit on substrate
A single crystal plate is used. On the substrate heated by the heater, the metal compound forms the metal oxide described in the present invention. The metal oxide in the present invention usually has voids between the plate-like bodies. Deformation during use may occur depending on the use situation. That is, there is a possibility that many rod-shaped bodies may be knocked down due to physical stress. In order to prevent this, for example, the flat body can be fixed with an organic substance such as a thermoplastic resin, a thermosetting resin, an elastomer, and an instant adhesive such as cyanoacrylate, an inorganic substance such as glass and ceramic, or a metal. .

The thermoplastic resin used for fixing the plate-like body includes low, medium and high density polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polystyrene, acrylonitrile-styrene copolymer (hereinafter referred to as "S
AN resin), acrylonitrile-butadiene-styrene copolymer (hereinafter abbreviated as “ABS resin”), polyamide, polyacetal, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyphenylene ether, polymethyl methacrylate, polyether Imides, polysulfones, polyetherimides, polyarylates, polyphenylene sulfites, styrene-butadiene copolymers and hydrogenated compositions thereof, and polymer blends and copolymers of combinations of two or more of these, for example, polycarbonate and acrylonitrile- Butadiene-styrene copolymer, polyphenylene ether and polystyrene can be exemplified.

Examples of the thermosetting resin used for fixing the flat body include epoxy resin, DFK resin, xylene resin, guanamine resin, diallyl phthalate resin, vinyl ester resin, phenol resin, unsaturated polyester resin, and furan resin. , Polyimide, poly (p-hydroxybenzoic acid), polyurethane, maleic acid resin, melamine resin, urea resin and the like.

Examples of the elastomer used for fixing the flat body include natural rubber, butadiene rubber, silicone rubber, polyisoprene rubber, chloroprene rubber, ethylene propylene rubber, butyl rubber, isobutylene rubber,
Synthetic rubbers such as styrene / butadiene rubber, styrene / isoprene / styrene block copolymer rubber, acrylic rubber, acrylonitrile / butadiene rubber, hydrochloric acid rubber, chlorosulfonated polyethylene rubber, and polysulfide rubber. In addition, polytetrafluoroethylene, petroleum resin, alkyd resin and the like can also be used. further,
The metal oxide of the present invention fixed between the flat plates can be used even when only the flat plates parallel to each other are taken out.

When the metal oxide in the present invention is used, for example, for a capacitor or the like, it can be used by coating a conductive substance. The conductive substance in the present invention refers to a substance having a specific resistivity of 10 Ω / m or less. Preferably it is 1 Ω / m or less. Specifically, metal and / or metal paste, ITO (In ₂ O ₃ / Sn)
O ₂ ), conductive resin, carbon thin film, diamond thin film and the like. The type of metal is not particularly limited, but specific examples include copper, nickel, chromium, iron, gold, silver, palladium,
Aluminum, zinc, tin, silicon, titanium and alloys thereof.

The metal oxide in the present invention includes an insulator, a conductor, a solid electrolyte, a fluorescent display tube, an EL device, a ceramic capacitor, an actuator, a laser oscillator, a cold cathode device, a ferroelectric memory, a piezoelectric, Mr,
Electronic materials such as varistors and superconductors, electromagnetic wave shielding materials,
Photodielectrics, optical switches, optical sensors, solar cells, optical wavelength conversion elements, optical elements such as light absorption filters, sensor materials such as temperature sensors and gas sensors, surface modifiers, surface protective agents, antireflective agents, antibacterial, It can be used as a surface modifier for the purpose of antifouling effect or the like, a catalyst in a gas phase, a liquid phase or both phases, a carrier thereof and the like.

[0048]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described more specifically with reference to examples and the like, but the present invention is not limited to these examples and the like.

Example 1 The apparatus schematically shown in FIG. 1 was used. He was charged with _{Ti (O-isoC 3 H 7} ) 4 to the metal compound heated tank. The metal compound heating tank was heated to an internal temperature of 120 ° C. 350 ° C of MgO single crystal just below the blowing slit
And set. Dry nitrogen gas was introduced into the metal compound heating tank at a flow rate of 2 dm ³ / min, and Ti (O-isoC ₃
H ₇ ) ₄ was sprayed on the MgO single crystal. Thirty seconds after the start of spraying, the obtained metal oxide was removed together with the MgO single crystal. The obtained metal oxide was subjected to observation by SEM after gold was deposited as a conductive substance on the entire metal oxide by sputtering. The obtained SEM images are shown in FIG. 2 and FIG.

[0049]

Example 2 The temperature of the metal compound heating tank in Example 1 was set to 130.
C. and a metal oxide was obtained under the same conditions as in Example 1 except that the spraying time was 90 seconds. The resulting metal oxide is
After depositing gold as a conductive substance on the entire metal oxide by sputtering, observation was performed by SEM. The obtained SEM image is shown in FIG.

[0050]

The structure according to the present invention has a large number of flat bodies in a small area, and has a large surface area with a small volume. The metal oxide of the present invention includes an insulator, a conductor, a solid electrolyte, a fluorescent display tube, an EL device, a ceramic capacitor, an actuator, a laser oscillation device, a cold cathode device, a ferroelectric memory, a piezoelectric material, a thermistor,
Electronic materials such as varistors and superconductors, electromagnetic wave shielding materials,
Photodielectrics, optical switches, optical sensors, solar cells, optical wavelength conversion elements, optical elements such as light absorption filters, sensor materials such as temperature sensors and gas sensors, surface modifiers, surface protective agents, antireflective agents, antibacterial, It can be used as a surface modifier for the purpose of antifouling effect or the like, a catalyst in a gas phase, a liquid phase or both phases, a carrier thereof and the like.

[Brief description of the drawings]

FIG. 1 is a schematic view of an example of a metal oxide reactor preferably used in the present invention.

FIG. 2 is an SEM photograph of the structure obtained in Example 1. However, this structure is entirely covered with a conductive material for SEM observation.

FIG. 3 is an SEM photograph of the structure obtained in Example 1 observed obliquely from above. However, this structure is entirely covered with a conductive material for SEM observation.

FIG. 4 is an SEM photograph of the structure obtained in Example 2. However, this structure is entirely covered with a conductive material for SEM observation.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Keiichi Nakazawa, Inventor 1-3-1, Yoko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Asahi Kasei Kogyo Co., Ltd. (72) Hideo Kinoshita 1-3-3, Yakko, Kawasaki-ku, Kawasaki-shi, Kanagawa No. 1 Asahi Kasei Kogyo Co., Ltd.

Claims (10)

[Claims] 1. A metal oxide structure having a lattice-like structure, comprising a plate-like body, wherein two or more combinations in which the center planes of the plate-like body are parallel to each other are present. 2. The flat body has a width of 0.005 to 10,000.
2. The metal oxide structure according to claim 1, wherein the metal oxide structure has a height of 0.05 μm, a length of 0.05 to 10000 μm, and a height to width of 1 or more. 3. A plate-like body having a size of 10 μm × 10 μm on a plane of a structure.
The metal oxide structure according to claim 1, wherein the metal oxide structure is present at a density of 0.01 to 10,000 per 10 μm area. 4. The metal oxide structure according to claim 1, wherein the flat body is present on a metal oxide plate. 5. The metal oxide structure according to claim 1, wherein the flat body is a metal oxide single crystal. 6. The metal oxide structure according to claim 1, wherein there are two or more combinations in which the center planes of the plate-like bodies are parallel to each other, and the crystal axes are in the same direction. . 7. The metal oxide structure according to claim 1, wherein a weighted average of a ratio of a height to a width of the flat body is less than 5. 8. The metal oxide structure according to claim 1, wherein a weighted average of a ratio of a height to a width of the flat body is 5 or more. 9. The weighted average of the height of the flat plate is 0.1 μm.
The metal oxide structure according to any one of claims 1 to 8, which is as described above. 10. The metal oxide structure according to claim 1, wherein the space between the plate-like bodies is fixed with an organic substance, an inorganic substance, or a metal.