WO1999057345A1 - Element fonctionnel pour dispositif electrique, electronique ou optique, et son procede de production - Google Patents

Element fonctionnel pour dispositif electrique, electronique ou optique, et son procede de production Download PDF

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Publication number
WO1999057345A1
WO1999057345A1 PCT/JP1999/001477 JP9901477W WO9957345A1 WO 1999057345 A1 WO1999057345 A1 WO 1999057345A1 JP 9901477 W JP9901477 W JP 9901477W WO 9957345 A1 WO9957345 A1 WO 9957345A1
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WO
WIPO (PCT)
Prior art keywords
functional element
metal oxide
substrate
needle
oxide
Prior art date
Application number
PCT/JP1999/001477
Other languages
English (en)
Japanese (ja)
Inventor
Hidetoshi Saito
Minoru Sato
Yoshikazu Ueda
Hideo Kinoshita
Original Assignee
Asahi Kasei Kogyo Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Kasei Kogyo Kabushiki Kaisha filed Critical Asahi Kasei Kogyo Kabushiki Kaisha
Priority to US09/647,489 priority Critical patent/US6810575B1/en
Priority to DE19983159T priority patent/DE19983159B4/de
Priority to GB0023716A priority patent/GB2352562B/en
Publication of WO1999057345A1 publication Critical patent/WO1999057345A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
    • H01L29/06—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions
    • H01L29/0657—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions characterised by the shape of the body
    • H01L29/0665—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions characterised by the shape of the body the shape of the body defining a nanostructure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/005—Growth of whiskers or needles
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/62—Whiskers or needles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02—Manufacture of electrodes or electrode systems
    • H01J9/022—Manufacture of electrodes or electrode systems of cold cathodes
    • H01J9/025—Manufacture of electrodes or electrode systems of cold cathodes of field emission cathodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
    • H01L29/06—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions
    • H01L29/0657—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions characterised by the shape of the body
    • H01L29/0665—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions characterised by the shape of the body the shape of the body defining a nanostructure
    • H01L29/0669—Nanowires or nanotubes
    • H01L29/0673—Nanowires or nanotubes oriented parallel to a substrate

Definitions

  • the present invention relates to a functional element for an electric, electronic or optical device.
  • the present invention relates to a functional element for an electric, electronic or optical device, which comprises a substrate and a plurality of needle-shaped metal elements extending on an upper surface thereof.
  • the needle-shaped metal oxide wherein the needle-shaped metal oxide extends upward from the upper surface of the substrate, and the respective central axes thereof are arranged substantially parallel to each other.
  • the object has a specific weighted average circle-converted diameter and a specific weighted average aspect ratio, and the acicular metal oxide is present at a specific density on the upper surface of the substrate. It relates to a functional element to be described.
  • the present invention also relates to a method for manufacturing this functional element.
  • the functional element for an electric, electronic or optical device of the present invention has an excellent feature that the thickness can be reduced despite the very large surface area of the metal oxide on the substrate. It has excellent performance as a component for various electric, electronic or optical devices.
  • Prior Art Metal oxides are used for various purposes by taking advantage of the various functions of metal oxides.
  • a ceramic capacitor using a ferroelectric function and a gas sensor using a resistance function First, it is used as a variety of electric and electronic components, such as magnetic tapes or magnetic heads, utilizing its magnetic material function.
  • optical components such as an optical switch utilizing an optical waveguide function and an ultraviolet laser single oscillation element utilizing an optical oscillation function is being studied.
  • the metal oxide When used for these applications, the metal oxide generally has a flat surface.
  • a metal oxide having a ferroelectric function for example, titanium titanate
  • a metal oxide having a ferroelectric function for example, titanium titanate
  • magnetic tapes are used in the form of a metal oxide (eg, chromium oxide) film formed on a polymer film.
  • the performance can be significantly improved by increasing the surface area of the metal oxide depending on the application. For example, in the case of the above capacitor, its most important performance is capacitance. The higher the capacitance, the better the performance, but the capacitance is proportional to the surface area of the metal oxide and inversely proportional to the thickness.
  • the current mainstream capacitor is one in which electrodes and metal oxides are laminated close to about 100 layers. That is, by increasing the number of layers, the surface area of the metal oxide is increased, and the thickness of the electrode and the metal oxide is reduced as much as possible. This makes it a high-capacitance capacitor.
  • multi-layering by laminating electrodes and metal oxides in many layers is very disadvantageous in terms of productivity and economy.
  • a metal oxide consisting of only one layer can be made to have a surface area equal to or greater than that of a multilayer capacitor that is currently used with the same thickness, that is, if a high capacitance can be obtained, Multi-layer soldering not only improves productivity and economy, but also makes it possible to use a capacitor with a higher capacitance.
  • the metal oxide has a structure that can be reduced in thickness even if the surface area is increased, so that it can be used in various applications currently used, such as the above-mentioned capacitor example.
  • it can be an improved electrical / electronic component or optical component, and can also be a component that allows for new product development.
  • Japanese Patent Application Laid-Open No. 50-65797 discloses that zinc and a zinc alloy composed of a metal having a higher boiling point than zinc or a mixture thereof are heated in an oxygen-containing atmosphere, and are heated on a substrate.
  • a method for producing a zinc oxide whisker characterized in that a needle-shaped zinc oxide whisker is produced.
  • the purpose of producing this zinc oxide whisker is to separate the generated whiskers from the substrate and to separate the whiskers themselves from resin or ceramic. It is used as a reinforcing agent or a semiconductor to increase the strength of a box or the like. It is a structure consisting of a substrate and a sheet of power formed on its surface. It is not disclosed for use as a part.
  • the nanocrystal of ⁇ formed on the substrate has a height of 5 nm and a circle-equivalent diameter of 100 nm, that is, the ratio of the length of the cross-section to the circle-equivalent diameter (the length of the cross-section).
  • the diameter is extremely small (0.05 in circle), and there is a limit to increasing the surface area with a small thickness.
  • the present inventors have aimed for use as an electric, electronic or optical component, and have been made up of a substrate and a metal oxide formed on the surface thereof, and a surface area of the metal oxide.
  • a functional device with the advantageous structure of large and small thickness.
  • it comprises a substrate and a plurality of needle-shaped metal oxides extending to an upper surface thereof, wherein the needle-shaped metal oxides extend upward from an upper surface of the substrate, and each of the needle-shaped metal oxides extends upward.
  • the central axes are arranged substantially parallel to each other, and the needle-shaped metal oxide has a weight-average circle-converted diameter of 0.01 to 100, 000; and a weight of 0.1 or more.
  • the conductive element has an excellent feature that the surface area is extremely large despite the extremely small thickness of the metal oxide.
  • functional elements having such characteristics include, for example, energy-saving electron-emitting elements capable of emitting electrons at a low voltage, high-capacitance capacitor elements, and high-density memories.
  • devices for electric or electronic devices such as devices, high-sensitivity sensor devices, etc., and for laser devices, especially devices for optical devices such as lasers with low wavelengths such as ultraviolet light, and highly integrated optical switch devices. We found that it could be applied. Based on this finding, the present invention has been completed.
  • one object of the present invention is to provide an excellent feature that the metal oxide formed on the substrate and the surface thereof has a small thickness despite its very large surface area. It is an object of the present invention to provide a functional element for an electric, electronic or optical device which has excellent performance as a component for various electric, electronic or optical devices.
  • Another object of the present invention is to provide a manufacturing method for effectively and efficiently manufacturing the above-described functional element for electric, electronic, or optical devices.
  • FIG. 1 is a schematic diagram showing an example of a production facility preferably used for producing the functional element of the present invention
  • FIGS. 2 (a) and 2 (b) are scanning electron microscope (SEM) photographs of the functional device obtained in Example 1 obliquely observed from above, and FIG. 2 (a) and FIG. Fig. 2 (b) shows different magnifications;
  • FIG. 3 is an SEM photograph of the functional device obtained in Example 2 observed from directly above;
  • FIG. 4 is an SEM photograph of the functional element obtained in Example 3 observed from directly above;
  • FIG. 5 is a SEM photograph of the functional device obtained in Example 4 observed obliquely from above;
  • FIG. 6 is a SEM photograph of the functional device obtained in Example 5 observed obliquely from above;
  • FIG. 7 is a SEM photograph of the functional device obtained in Example 6 observed obliquely from above;
  • FIG. 8 is a vertical sectional view of a circuit device including the functional element (shown in FIG. 7) obtained in Example 6.
  • Nickel (Ni) electrode formed by sputtering
  • the needle-shaped metal oxide is 0.0 :! ⁇ 100,000 ⁇ m, which is the weighted average diameter of a circle having an area equal to the area of the cross section of the needle-shaped metal oxide.
  • the cross section is a cross section taken along a plane perpendicular to the central axis of the acicular metal oxide at a central portion located at 12 of the length of the acicular metal oxide.
  • the acicular metal oxide has a weighted average aspect ratio of 0.1 or more, and the weighted average aspect ratio is determined by the weight of the acicular metal oxide with respect to the above-mentioned weighted average circle-converted diameter.
  • the needle-like metal oxide is 1 ⁇ m ⁇ ⁇ 10 ⁇ m on the upper surface of the substrate.
  • a functional element characterized by being present at a density of 0.01 to 100,000 per unit area having m
  • a method for producing a functional element for electric, electronic or optical devices comprising:
  • At least one kind of metal compound having volatility or sublimability which reacts with at least one kind of oxide-forming substance to form a metal oxide corresponding to the metal compound.
  • a functional element for an electric, electronic or optical device 1.
  • the needle-shaped metal oxide has a weight-average circle-equivalent diameter of 0.01 to 100,000 m, and the central axes thereof are arranged substantially parallel to each other.
  • the weighted average circle-converted diameter is defined as the weighted average diameter of a circle having an area equal to the area of the cross section of the acicular metal oxide, and the cross section is 2 of the length of the acicular metal oxide.
  • the acicular metal oxide has a weighted average aspect ratio of 0.1 or more, and the weighted average aspect ratio is determined by the weight of the acicular metal oxide with respect to the above-mentioned weighted average circle-converted diameter. Defined as the ratio of the average lengths, the needle-shaped metal oxides are in a unit area of 10 mx 10 ⁇ m on the upper surface of the substrate. A functional element that exists at a density of individual pieces.
  • the functional element as described in 1 above which is a memory element for an electric or electronic device.
  • the functional element as described in 1 above which is a sensor element for an electric or electronic device.
  • the functional element as described in 1 above which is a laser oscillation element for an optical device.
  • a method for producing a functional element for an electric, electronic or optical device comprising:
  • the metal component of the metal compound is at least one selected from the group consisting of elements from Groups 1 to 15 of the periodic table, excluding hydrogen, boron, carbon, nitrogen, phosphorus, and arsenic. 10.
  • the metal component of the metal compound comprises at least one element selected from the group consisting of zinc, silicon, aluminum, tin, titanium, zirconium and lead.
  • the functional element for an electric, electronic or optical device of the present invention comprises: a substrate; A plurality of needle-like metal oxides (i.e., metal oxide whiskers) extending to the upper surface thereof, wherein the needle-like metal oxides extend upward from the upper surface of the substrate, and each of the centers thereof. It has a structure in which the axes are arranged substantially parallel to each other.
  • the needle-shaped metal oxide may be a metal oxide having a shape such as a mountain-shaped raised shape, a rod shape or a prism shape.
  • the thickness of the needle-shaped metal oxide is preferably such that the weighted average circle-converted diameter of the cross section is from 0.01 to ⁇ ,, ⁇ ⁇ ⁇ m.
  • the weighted average circle-equivalent diameter is the square root of the square area obtained by calculating the cross-sectional area by a conventionally known method such as image analysis and dividing the obtained area by the pi. It is expressed as a double value and is defined as the weighted average diameter of a circle having an area equal to the area of the cross section of the acicular metal oxide.
  • the above-mentioned cross section is a cross section obtained along a plane facing the central axis of the needle-shaped metal oxide at a central portion located at 1 Z 2 of the length of the needle-shaped metal oxide.
  • the weighted average circle-equivalent diameter is less than 0.0 Olym, it is difficult to stably obtain the grown needle-shaped metal oxide, and when it exceeds 100000 ⁇ m, the needle-shaped metal oxide becomes needle-shaped.
  • the effect of increasing the surface area by the metal oxide is poor and not preferred.
  • the ratio of the weighted average length to the weighted average circle-converted diameter is 0. 1 or more, preferably Is greater than 0.5, more preferably greater than 1.0. If the aspect ratio is smaller than 0.1, the effect of increasing the surface area by the acicular metal oxide does not appear.
  • the aspect ratio is preferably 100,000 or less, more preferably 100,000 or less, and particularly preferably 1,000 or less.
  • the weighted average length of the needle-shaped metal oxide varies depending on the intended use, but is not particularly limited. In general, it is preferably from 0.1 to 100,000 m, and from 1 to 1,0 m. 0 0 m is preferred. If the length of the needle-shaped metal oxide is less than 0.1 m, the effect of increasing the surface area of the needle-shaped metal oxide is poor, and if it exceeds 1 1, ⁇ ⁇ ⁇ , it is difficult to maintain the strength of the functional element. Becomes However, even when the length exceeds 100,000 ⁇ , as described later, sufficient strength can be maintained by holding the acicular metal oxides with each other with an organic substance, an inorganic substance, or the like. It is possible.
  • the weighted average circle-converted diameter, the weighted average length, and the weighted average aspect ratio of the needle-shaped metal oxide are determined by SEM observation according to the following method. First, the sample of the functional element is cut along a plane extending through the center of the upper surface and extending parallel to the longitudinal direction of the acicular metal oxide.
  • the shape of the acicular metal oxide is not particularly limited as long as the aspect ratio is 0.1 or more.
  • the shape does not change from the root to the tip, the diameter does not change from the root to a distance from the root to the tip, and the diameter of the root is small.
  • the diameter increases once at the tip, then gradually decreases again, and gradually decreases from the root to the tip, but near the tip.
  • Some have shapes such as pyramids, truncated pyramids, cones, truncated cones, and hemispheres, depending on the distance.
  • the specific shape differs depending on the crystal structure. In many cases, it is a square prism. There are also prisms with other polygons in cross-sectional shape.
  • the shape of the tip of the needle-shaped metal oxide is not particularly limited, but when the shape of the tip is a plane, the shape of the tip is, for example, a truncated cone or a truncated pyramid. If the shape of the tip is a line, the shape of the tip is a line consisting of two or more planes, for example, a mountain ridgeline. Adjacent planes are connected by one side. When the shape of the tip is a point, the shape of the tip is, for example, a cone or a pyramid. The preferred shape of the tip shape depends on the application used. For example, when the functional device of the present invention is used as an electron-emitting device, it is easier for the needle-shaped metal oxide to emit electrons when the tip is sharp.
  • lightning falls on a lightning rod (sharp tip), but on the other hand, the tip is sharp when a voltage is applied to an object to emit electrons.
  • the present inventors have confirmed that the conical shape makes it much easier to emit electrons.
  • the respective central axes of the needle-shaped metal oxides in the case of crystals, the longitudinal crystal axes
  • the electron-emitting ability is higher when the respective central axes are parallel to each other. This is because the height is not constant unless they are parallel. If the height is not constant, low heights do not emit electrons, only high ones emit electrons from the tip.
  • the needle-shaped metal oxides whose central axes are arranged parallel to each other have a larger number of tips that function for electron emission, and the electron emission ability is inevitably higher.
  • the shape of the needle-shaped metal oxide is prismatic, it is preferable that the opposing surfaces in the prism have parallel portions.
  • the laser oscillation function is higher when the opposing surfaces in the prism are parallel to each other.
  • the material of the substrate used for the functional element examples include a metal oxide single crystal such as aluminum oxide, a semiconductor single crystal, a ceramic, a silicon, Fe, and Ni. Metal, glass, plastic, and the like.
  • the thickness of the substrate is not particularly limited, but is preferably ⁇ ⁇ ⁇ ! ⁇ 10 O mm. Commercially available materials of these materials can be purchased, cut, and subjected to secondary processing as desired, and used as the substrate of the functional element of the present invention.
  • the shape and size of the substrate are not particularly limited as long as the surface has a substantially planar portion suitable for growing a needle-shaped metal oxide, and may be a plate, a rectangular parallelepiped, a prism, or a triangular prism. Various shapes of substrates can be used.
  • the size of the substrate may vary greatly depending on the use of the functional element, and any desired size can be used. (For example, the value related to the size may be on the order of tens of meters, or may be on the order of millimeters
  • the density at which the needle-shaped metal oxide is present on the substrate is as follows: 0.01 to L per unit area having lOiumXlOm on the upper surface of the substrate. It is preferable that the number is 0.10 to 100, and the number is 0.1 to 100, more preferably 1 to 100,0. 0 is preferred. If the density is less than 0.01, the effect of increasing the surface area of the acicular metal oxide is poor and not preferable. In order to increase the surface area of the needle-shaped metal oxide present on the substrate, it is preferable to increase the density, but it is preferable to increase the surface area by 10 ⁇ m X 10 0 ⁇ per unit area. If the number exceeds 0,000, the thickness of each needle-like metal oxide must be reduced as a result, and the strength of the needle-like metal oxide is out of the practical range and is preferred. Not good.
  • the needle-shaped metal oxide in the functional element of the present invention includes hydrogen (Group 1), boron (Group 13), carbon (Group 14), nitrogen (Group 15), phosphorus (Group 15), and arsenic. Except for (Group 15), oxides of at least one element selected from the group consisting of elements of Groups 1 to 15 of the periodic table are preferred.
  • Specific metal types include, for example, L i, N a, K, R b, C s, Be, M g, C a, S r, B a, A l, G a, In, T l, S i, G e, S n, P b, S b, B i, S c, Y, L a, Th, C e, P r, N d, P m, S m, E u, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, M n, T c, R e, F e, R u, O s, C o, R h, I r, N i, P d, P t, C u, A g, A u, Z n, C d, And at least one component such as H g, preferably L i, N a, K, R
  • the functional element of the present invention has a function for an electric, electronic or optical component device. It is preferable because it is suitable for a sexual element.
  • These metals can be used alone or in combination of two or more. For example, M g ⁇ , A 1 2 O 3, I ⁇ 2 ⁇ 3, S i 0 2 , S n ⁇ 2 , T i 0 2 , ⁇ ⁇ ⁇ , barium titanate, S r T i 0 3 , PZT, YBCO, YSZ, YAG, ITO (InzOa / SnOz)
  • the needle-like metal oxide in the functional element of the present invention may be basically crystalline or amorphous, but is more preferably crystalline.
  • the crystalline material may be one or more single crystals, polycrystalline, one or more semi-crystalline materials having both an amorphous part and a crystalline part, or a mixture thereof. Good. Particularly preferred is a single crystal.
  • the metal oxides may be mixed to form a single layer, or metal oxide layers having different compositions may be stacked.
  • the functional element of the present invention basically comprises a substrate and a plurality of needle-like metal oxides extending upward from the upper surface thereof. A planar metal oxide film is formed between them. That is, the structure may be such that a metal oxide film is first formed on the surface of the substrate, and a needle-shaped metal oxide grown thereon is formed.
  • the functional element of the present invention may have such a structure.
  • the functional element of the present invention is manufactured by vaporizing a metal compound as a raw material of a needle-shaped metal oxide and bringing the obtained metal compound gas into contact with a substrate in the presence of an oxide-forming substance. It can be. That is, the functional element of the present invention has volatility or sublimability and reacts with an oxide-forming substance to form a metal oxide. The resulting metal compound gas is vaporized, and the obtained metal compound gas is sprayed onto the surface of the substrate with a nozzle or the like to bring the surface of the substrate into contact with the metal compound gas in the presence of the oxide-forming substance. According to the above, it can be manufactured by growing a plurality of metal oxides on the surface of the substrate.
  • the oxide-forming substance is a substance capable of reacting with a metal compound serving as a raw material of a needle-shaped metal oxide to finally form an oxide.
  • a substance that reacts with For example, when a zinc Asechiruase Tone DOO as a metal compound [Z n (C 5 H 7 O 2) 2], Z n (C 5 H 7 0 2) 2 reacts with water (H 2 ⁇ )
  • an oxide (ZnO) can be formed via a route presumed to be a two-step reaction as shown in the following formula.
  • water is one example of an oxide-forming substance.
  • the substrate In order to grow a plurality of metal oxides from the surface of the substrate, when the metal compound gas is blown onto the substrate surface, the substrate is placed in a reaction zone containing the oxide-forming substance and the temperature of the metal compound gas is increased. It must be heated to a higher temperature. this At this time, the reaction zone preferably contains air at atmospheric pressure, and a metal compound gas is blown onto the surface of the substrate together with a carrier gas made of an inert gas such as nitrogen gas. This is preferred.
  • the contact between the surface of the substrate and the metal compound gas causes a plurality of acicular metal oxides to grow on the surface of the substrate, and extends to the functional element of the present invention, that is, the substrate and the upper surface thereof
  • a plurality of needle-shaped metal oxides, the needle-shaped metal oxides extending upward from the upper surface of the substrate, and their central axes are arranged substantially parallel to each other.
  • the acicular metal oxide has a weighted average circle-converted diameter of 0.01 to 100.0 ⁇ , and a weighted average aspect ratio of 0.1 or more; Objects are present at a density of 0.01 to 100,000 per unit area of 1 ⁇ 1 O jum on the upper surface of the substrate, sufficient to form a functional element. Time is needed.
  • the reaction zone where the substrate is placed contains air, and the vaporized metal compound is contained in the air of the reaction zone. It is highly economical and technically easy to grow needle-like metal oxide from the substrate by reacting with water, ammonia and the like, which is preferable. Further, it is preferable that the reaction zone is at normal pressure, that is, at atmospheric pressure, because a large capital investment is not required.
  • the present inventors refer to this manufacturing method performed in an air atmosphere at atmospheric pressure as “atmospheric pressure open type CVD”.
  • the CVD method chemical vapor A method of forming a metal oxide crystal on a substrate surface by deposition is known.
  • conventional CVD is generally performed under vacuum.
  • the present inventors have developed a technique for forming, on a substrate, needle-shaped metal oxides extending upward from the upper surface of the substrate and having their respective central axes arranged substantially parallel to each other at a high density.
  • the present invention was adjusted by appropriately adjusting the conditions such as the temperature of the metal compound gas, the concentration of the metal compound gas sprayed on the substrate, the speed of the spray, and the temperature of the substrate. It has been found that a functional element can be easily obtained.
  • Japanese Patent Application Laid-Open No. 50-65797 discloses that a zinc alloy or a mixture thereof composed of a metal having a higher boiling point than zinc and zinc is heated in an atmosphere containing oxygen.
  • a method for producing zinc oxide whiskers characterized in that acicular zinc oxide whiskers are formed on a substrate.
  • This product Although the fabrication method is not clearly described, a metal oxide is formed on the substrate (wall surface of the device) under atmospheric pressure.
  • the technology disclosed in this publication merely provides a whisker obtained by cutting the obtained whisker from a substrate (wall surface of the device) and using the whisker as a reinforcing agent for resin or ceramics.
  • a structure made of a needle-shaped metal oxide formed on the surface thereof as a functional element for an electric, electronic or optical device.
  • the metal compound used as a raw material for forming the acicular oxide when producing the functional element of the present invention has a volatile or sublimable property, and the above-described oxide-forming substance
  • the metal compound is a metal compound capable of forming a metal oxide corresponding to the above metal compound by reacting with oxygen, water and the like contained in the atmosphere.
  • the metal compound also includes a simple metal.
  • a substance that does not exist in the normal atmosphere, such as ozone is supplied and present in the reaction zone containing the oxide-forming substance on which the substrate is placed, and a metal that reacts with these and forms an oxide is formed.
  • Compounds may be used.
  • Examples of such a metal compound include alkoxides in which the hydrogen of the hydroxyl group of an alcohol is substituted with a metal, atoms of a metal or a metal-like element, and acetyl acetate to an atom of a metal or a metal-like element.
  • metal complexes can be used. Among these, metal acetyl acetate compounds, metal alkoxide compounds, and the like can be more preferably used.
  • Examples of complexes that can be used as the metal compound in the production method of the present invention include J3-diketons, ketoesters, hydroxycarboxylic acids or salts thereof, and various kinds of salts as metals.
  • One kind of ligands such as bases, ketoalcohols, polyamines, alkanolamines, phenolic active hydrogen compounds, dicarboxylic acids, dalicols, and fluoresceins Or 2 Compounds having more than one kind of bond can be mentioned.
  • the needle-shaped metal oxide of the functional element of the present invention extends upward from the upper surface of the substrate, and its central axes are arranged substantially parallel to each other. is necessary.
  • the parallelism of each central axis of the needle-shaped metal oxide can be measured by the X-ray opening curve method, and the fluctuation in the direction in which the needle-shaped metal oxide extends is measured by this measurement method. It is preferable that the angle of (squashing based on a direction perpendicular to the surface of the substrate) be within 10 degrees, more preferably within 5 degrees. This fluctuation is often determined by the substrate used for the functional element of the present invention.
  • the central axis parallelism fluctuates. But it is small.
  • One factor in selecting a single crystal seed is that the lattice constant of the metal oxide crystal seed when the acicular metal oxide to be formed is a crystal and the lattice constant of the single crystal seed used as the substrate are close. Is preferred.
  • the lattice constant can be measured by a conventionally known method such as a wide-angle X-ray diffraction method.
  • This value is the lattice constant of the surface in contact with the metal oxide crystal species, in which the single crystal seed used as the substrate is in contact with the metal oxide crystal seed.
  • Particularly preferred are, specifically, silicon and oxides.
  • It is a single crystal of a metal oxide such as noremium, magnesium oxide, and SrTiO 3 .
  • the crystals 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. There may be. Most preferably, it is a single crystal.
  • the substrate surface is a specific surface of the single crystal.
  • the (100) plane is selected as a metal oxide forming zinc oxide on a magnesium oxide substrate.
  • the silicon substrate has a (111) plane
  • the aluminum oxide substrate has a (001) plane
  • the SrTiO 3 substrate has a (001) plane. I like it.
  • the fluctuation of the crystal axis can be generally suppressed to 5 degrees or less.
  • the fluctuation of the crystal axis generally tends to be large.
  • the fluctuation of the crystal axis is preferably at most 20 degrees. Also, it is preferable that the angle be 15 degrees or less. Further, it is particularly preferable that the angle is 10 degrees or less. In the case of a substrate made of any of these materials, the fluctuation of the crystal axis can be reduced by subjecting the surface to an orientation treatment.
  • the functional element of the present invention is, for example, an electron-emitting element for an electric or electronic device, a laser-oscillating element for an optical device, or the like
  • needle-like metal oxides are arranged on a substrate at regular intervals. May be preferred to be present.
  • a substrate is prepared by a known fine processing method, for example, a carbon dioxide laser, a YAG laser, an electron beam or an X-ray lithography. This can be achieved by, for example, forming convex portions at regular intervals on the substrate by etching. The reasons are as follows.
  • the functional element of the present invention when the functional element of the present invention is manufactured by “atmospheric pressure open type CVD”, a metal compound is sprayed on the surface of the substrate to grow acicular metal oxide on the surface of the substrate. The growth from the convex part has priority over the part. Therefore, if convex portions arranged at regular intervals are formed on the substrate in advance, needle-like metal oxides arranged at regular intervals can be manufactured.
  • the functional element of the present invention is, for example, an electron-emitting element, a laser-oscillation element, or the like, the functional element may have needle-like metal oxides arranged at regular intervals obtained in this manner. I like it.
  • the dispersion of the distance between one needle-like metal oxide and the needle-like metal oxide around the needle-like metal oxide is within 1 ⁇ of soil. Also, it is preferable that the distance is within ⁇ 0.5 m. More preferably, it is within ⁇ 0.25 m.
  • FIG. 1 is a schematic view of an example of a preferred manufacturing apparatus for manufacturing the functional element of the present invention.
  • N 2 is such as door La-up by the re-cooling and dehydration to using liquid nitrogen, flow rate 1. Flow in the direction of the arrow in the 2 dm 3 / min.
  • the chamber temperature 1 1 5 ° with a metal compound heated chamber set at C, Z n (C 5 H 7 0 2) 2 was vaporized by re heated by the heater, resulting metal compound gas is a metal compound Is flushed with N 2 and sprayed onto the substrate via the nozzle and the slit.
  • the lines after the heating tank are heated by a ribbon heater (not shown).
  • As a substrate previously heated to (0 0 0 1) Mengasu Li Tsu me with A 1 2 O 3 single crystal plate which faces, by Li 5 5 0 ° C to the heater.
  • Z n a (C 5 H 7 O 2) 2 on the substrate on the substrate, the acicular metal oxide is grown on the substrate.
  • a gaseous metal is required to obtain a needle-shaped metal oxide having a specific shape as in the present invention. It is important to control the temperature conditions of the compound and the substrate.
  • the temperature of the gaseous metal compound varies depending on the metal compound used, but it is preferable to heat the metal compound to a temperature at which the metal compound volatilizes or sublimes or higher. It is more preferably from 30 to 600 ° C, particularly preferably from 50 to 300 ° C.
  • the metal compound thus gasified may be directly sprayed on the substrate, or another gas may be used as a medium (carrier gas). It may be used as a spray to form the acicular metal oxide.
  • a method of spraying another gas as a medium to form acicular metal oxides is preferable.
  • the preferred value of the flow rate of the medium gas (carrier gas) is related to the temperature at which the metal compound is vaporized and the atmosphere of the reaction zone where acicular metal oxides are formed. Under a normal pressure atmosphere at room temperature, a space volume value expressed by a value obtained by dividing the flow rate by the volume of the metal compound heating tank for 1 minute is preferably 20 Z minutes or less, more preferably 5 Z minutes. It is as follows.
  • the growth rate of the acicular metal oxide is determined by the concentration of the metal compound gas on the substrate. It is an important factor to make the oxide of the group easier to obtain.
  • the concentration of the metal compound gas on the substrate is basically determined by the degree of supersaturation of the vaporized metal compound on the substrate. The degree of supersaturation is specified by [ ⁇ (actual vapor pressure) 1 (equilibrium vapor pressure) ⁇ equilibrium vapor pressure] X100. It is preferable that the degree of supersaturation when producing the acicular metal oxide in the present invention is 1% or more. Further, it is more preferably at least 10%, and particularly preferably at least 20%.
  • the gas (carrier gas) as a medium preferably used when spraying the vaporized metal compound is not particularly limited as long as it does not react with the metal compound used.
  • Examples thereof include an inert gas such as nitrogen gas, helium, neon, and argon; a carbon dioxide gas; an organic fluorine gas; and an organic substance such as heptane and hexane.
  • inert gas is preferred from the viewpoint of safety and economy.
  • nitrogen gas is the most preferred in terms of economy.
  • the distance between the outlet of the metal compound and the surface of the substrate is the size of the metal oxide to be formed.
  • the distance between the outlet and the surface of the metal oxide is defined as the ratio of the length of the major axis of the opening. I like it. Further, 0.05 to 0.7 is more preferable, and 0.1 to 0.5 is particularly preferable. In general, when the ratio exceeds 1, the efficiency of conversion of the metal compound gas into the acicular metal oxide tends to decrease.
  • the temperature of the substrate itself at the time of spraying the metal compound gas to form the needle-shaped metal oxide is higher than the temperature of the metal compound gas, and the temperature at which the metal oxide can be formed near and on the surface of the substrate.
  • this temperature is preferably from 0 to 800 ° C, more preferably from 20 to 800 ° C, and even more preferably from 100 to 700 ° C.
  • the metal compound When producing the functional element of the present invention, the metal compound is volatilized or volatilized. Oxygen, water, etc., which reacts with the metal compound, are present in the system from the place where the metal compound gas is obtained by sublimation to the nozzle for blowing the obtained metal compound gas into the reaction zone. In this case, metal oxides are formed in the apparatus before being discharged into the reaction zone, and clogging occurs, so that it is not possible to obtain a needle-shaped metal oxide having a desired form. Not good. However, if the reaction rate of the metal compound with oxygen, water, etc. is extremely low, oxygen, water, etc. may be allowed to coexist in the system in advance.
  • the atmosphere in the reaction zone where the vaporized metal compound contacts the substrate may be under reduced pressure, under normal pressure or under pressure.
  • the acicular metal oxide when performed under highly reduced pressure, for example in an ultra-vacuum, the acicular metal oxide must be grown over a long period of, for example, several days. This is not preferable for industrial implementation because the growth rate of the acicular metal oxide is low and the productivity is poor.
  • When performed under pressure there is no problem with the growth rate of the metal oxide, but it is not preferable because equipment for pressurization is required. In general, it is preferable to carry out at 0.01 to 20 atm, and 0.1 to: L 0 atm is more preferable, and it is more preferable to carry out at normal pressure. Especially preferred.
  • the reaction time required to form the acicular metal oxide is not particularly limited, but it is necessary to take a sufficient time to obtain the acicular metal oxide having an aspect ratio specified in the present application. Is preferred.
  • the reaction time varies depending on the reaction conditions and the type of raw materials. For example, when zinc acetyl acetate is used as a metal compound raw material, needle-like metal oxides grow in about 5 minutes under an atmospheric pressure atmosphere, and grow to a length of 100 minutes in 300 minutes. You. However, when zinc acetyl acetate is used as the metal compound raw material, the reaction time is preferably longer than 10 minutes, and more preferably 15 minutes or longer.
  • a metal compound When forming an acicular composite metal oxide containing two or more metals, a metal compound can be mixed and vaporized, or a vaporized gaseous metal compound can be mixed. Les ,. Also, both methods can be used in combination.
  • acicular metal oxides are present at a high density, and there is a gap between each of the acicular metal oxides.
  • the functional element of the present invention including a needle-shaped metal oxide having a special structure is used in an electric, electronic or optical device, deformation may occur during use depending on the form of use. That is, when physical stress is applied to the needle-shaped metal oxide, there is a possibility that many rod-shaped bodies (needle-shaped bodies) are knocked down.
  • thermoplastic resin thermosetting resin
  • organic material such as an instant adhesive such as an elastomer or cyanoacrylate
  • inorganic material such as glass or ceramic
  • a metal may be used to hold the acicular metal oxides together. You can also.
  • thermoplastics used to hold needle-like metal oxides together include low, medium or high density polyethylene, polypropylene, polymethylpentene, polyvinyl chloride. , Polystyrene, acrylonitrile linoleic styrene copolymer (hereinafter abbreviated as "SAN resin”), acrylonitrile-butadiene-styrene copolymer ( Abbreviated as "ABS resin”), polyamide, polyacetal, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyphenylene ether, Polymethyl acrylate, polyetherimide, polysulfone, polyetherimide, polylate, polyphenylenesulfide, styrene One pig Copolymers and their hydrogenated compositions, etc., and polyblends and copolymers combining two or more of these, for example, polycarbonate and acrylonitrile Diene-styrene copolymers
  • thermosetting resins used to hold the needle-shaped metal oxides together include epoxy resins, xylene resins, guanamine resins, diaryl phthalate resins, vinyl ester resins, and phenolic resins. Nol resin, unsaturated polyester resin, furan resin, poly PT 1 7
  • Examples include mid, poly (P-hydroxybenzoic acid), polyurethane, maleic acid resin, melamine resin, and urine resin.
  • elastomers used to hold needle-like metal oxides together include natural rubber, butadiene rubber, silicone rubber, polyisoprene rubber, chloroprene rubber, and ethylene propylene. Rubber, butynole rubber, isobutylene rubber, styrene butadiene rubber, styrene / isoprene / styrene block copolymer rubber, acryl rubber, acrylonitrile butadiene rubber, Synthetic rubbers such as hydrochloride rubber, chlorosolephonated polyethylene rubber, polysulfide rubber, and the like. In addition, polytetrafluoroethylene, petroleum resin, alkyd resin, etc. can be used. Further, cyanoacrylate, which is generally used as an instant adhesive, can also be used.
  • the functional element of the present invention having a needle-shaped metal oxide having a special structure which is obtained by the above-described manufacturing method, has an extremely high surface area of the needle-shaped metal oxide, and has a sharp tip depending on the type of metal used. It can be shaped like a prism, depending on the type of metal used, and has various other characteristics. It can be used for electronic, optical or optical devices.
  • an electric, electronic, or optical device that can use the functional element of the present invention will be described with reference to examples.
  • various metal oxide functions namely, electron emission function, magnetic material function, electromagnetic wave shield function, piezoelectric material function, ferroelectric function, conductor function, resistance or insulation function, It can be used for equipment that utilizes the heat conversion function.
  • an optical device it can be used for a device utilizing a transparent function, a light transmission / absorption / reflection function, a heat transmission / absorption / reflection function, a light oscillation function, an optical waveguide function, a photocatalytic function, and the like.
  • the needle-like metal oxide When zinc oxide is selected as the needle-like metal oxide in the functional element of the present invention, the needle-like metal oxide has a shape with a sharp tip.
  • a lightning rod with a sharp tip causes lightning to fall intensively, but the reverse theory is to use a needle-shaped metal oxide covered with a conductive material.
  • the present invention when a voltage is applied to a functional element containing a conductive element or a functional element made of a conductive needle-shaped metal oxide, electrons are easily emitted from the sharp tip of the needle-shaped metal oxide. They found out.
  • the present inventors have confirmed that the needle-shaped metal oxide has an electron emission capability of 10 times or more at the same voltage as that of a non-needle-shaped metal oxide, that is, a flat metal oxide. ing.
  • the functional element of the present invention is an electron-emitting element, for example, a part or the whole of the functional element having a sharp-pointed ZnO is covered with a conductive material or a needle-shaped metal oxide.
  • a conductive material or a needle-shaped metal oxide By making the object itself conductive (for example, a needle-like metal oxide made of ZnO doped with A 1), it can be used as an electron-emitting device.
  • the conductive material used at this time preferably has a specific resistivity of 10 ⁇ Zm or less, and more preferably ⁇ or less.
  • a conductive material for example, metals and or metal paste, ⁇ ⁇ ⁇ (I ⁇ 2 0 3 / S ⁇ 0 2) conductive metal oxides such as, conductive resins.
  • conductive metal oxides such as, conductive resins.
  • specific examples include copper, nickel, chromium, iron, gold, silver, and nickel. Radium, aluminum, zinc, tin, silicon, titanium and their alloys.
  • the conductive materials include one in the periodic table except for hydrogen (Group 1), boron (Group 13), nitrogen (Group 15), phosphorus (Group 15), and arsenic (Group 15). If the element is a metal, it can be selected from oxides and carbonaceous materials. In particular, carbonaceous materials are preferred. Specific examples of the carbonaceous material include graphite, graphite, diamond, diamond-like carbon (DLC), and carbon nitride.
  • die Diamond and diamond-like carbon are more preferable because of their high electron emission capability.
  • Various methods such as vapor deposition, sputtering, diving, CVD, and PVD (physical calcium or deposition) can be used to form these conductive or easily conductive materials. Available.
  • Examples of the electric / electronic device using the functional element of the present invention as an electron-emitting device include, for example, an electron-emitting device such as a cold-cathode tube of a liquid crystal display, a field-emission display, or a plasma display. And a television electron gun. It can also be used for flat fluorescent lamps, taking advantage of its ability to emit electrons over a large area.
  • the flat fluorescent lamp is a type of fluorescent lamp that emits light on its surface differently from a normal fluorescent lamp having a tubular shape.
  • the liquid crystal display currently used as a backlight can be used as a backlight not only in combination with a cold cathode tube and light guide plate on the side of a display device, but A flat fluorescent lamp can be used as a back light by itself.
  • the electron-emitting device including the functional element of the present invention easily emits electrons even at the same voltage as compared with a flat plate. Therefore, when the functional element of the present invention is used as an electric / electronic device, it is possible to obtain the same luminance as a conventional electric / electronic device at a low voltage. Therefore, by using the functional element of the present invention, it is possible to manufacture an energy-saving electric / electronic device that achieves high luminance at the same voltage as in the past.
  • the functional element of the present invention has a large surface area.
  • Currently used capacitors are generally referred to as multilayer ceramic capacitors.
  • the capacitance is proportional to the surface area and inversely proportional to the thickness of a ferroelectric material such as titanium titanate.
  • a conventional multilayer ceramic capacitor has a high capacitance by forming a thin ferroelectric material into a multilayer of about 100 layers through electrodes.
  • the functional element of the present invention for example, a functional element using a ferroelectric oxide such as titanium titanate as an acicular metal oxide can be used as a high-capacitance capacitor element.
  • An insulating oxide such as zinc oxide is used as a needle-shaped metal oxide, and a thin film of a conductive material is first formed thereon, and then a ferroelectric oxide such as barium titanate is used.
  • a high-capacitance capacitor can also be obtained by forming a thin film layer.
  • the layer thickness of ferroelectrics, such as titanium titanate, in current multilayer ceramic capacitors cannot be reduced to less than 6 ⁇ .
  • the theoretical capacity is 30 times that of the current multilayer ceramic capacitor. In this case, a thin film of conductive material is further formed.
  • ferroelectric metal oxides such as barium titanate, that is, by forming two layers, the capacitance can be further increased. With three or more layers, it is possible to further increase the number of layers.
  • ferroelectric metal oxides that can be used when the functional element of the present invention is used as a capacitor include barium titanate and titanium titanate. And the like. These can be effectively used for "atmospheric pressure open CVD" for producing the acicular metal oxide of the present invention, but the method for forming acicular metal oxide is not particularly limited. Absent.
  • the conductive material for example, metal, ITO (I n 2 ⁇ 3 / S n ⁇ 2) a conductive metal oxide such as can and Ruco use.
  • the type of metal is not particularly limited, but specific examples include copper, nickele, chromium, iron, gold, silver, iron, radium, aluminum, zinc, tin, silicon, titanium, and the like. Alloy.
  • As a method for forming the conductive film various methods such as vapor deposition, sputtering, diving, CVD, and PVD can be used.
  • Electric and electronic devices that use a functional element as a capacitor element have a high capacitance and can be used for small electric and electronic devices such as mobile phones.
  • Ferroelectric memory has the characteristics of being non-volatile, having a short access time, a long life, and low power consumption. For this reason, in recent years, development has been promoted as a non-contact IC card using ferroelectric memory.
  • PZT that is, a metal oxide containing three elements, Pb, Zr, and Ti
  • Pb, Zr, and Ti As a ferroelectric, PZT, that is, a metal oxide containing three elements, Pb, Zr, and Ti, is generally used, but the ferroelectric currently used is formed on a substrate. It is composed of a metal oxide exhibiting strong conductivity formed in a planar shape. For this reason, the memory property is low, and the use is limited.
  • a memory function can be imparted to each of the needle-shaped metal oxides, so that the memory element has a high storage capacity. be able to.
  • the gap between each of the needle-shaped metal oxides is filled with an insulating material, and the insulating material embedded in every one or more of the needle-shaped metal oxides
  • metal oxides exhibiting ferroelectricity include, for example, metal oxides containing three elements of Ba, Na and Nb, Sr and Nb in addition to PZT described above. Examples thereof include metal oxides containing elements as components.
  • the functional device of the present invention can be used, for example, as a disk material such as a DVD (Digital Versatile Disc) or a storage device of a computer, which has become popular in recent years. Is very useful.
  • the surface area of the functional element of the present invention is large. This large surface area can be used for sensor elements.
  • a sensor is a device that converts a physical quantity into a resistance value and detects it.
  • metal oxides such as nickel oxide, cobalt oxide, and barium titanate are used as temperature sensors.
  • tin oxide, iron oxide, zinc oxide, and the like are used as gas sensors.
  • Aluminum oxide, zinc oxide, zinc oxide, etc. are used as humidity sensors.
  • metal oxide thin films can be formed by vapor deposition or sputtering, or binders can be used to paste the metal oxides.
  • a method such as coating on a substrate is used.
  • it is required to increase the sensitivity of the sensor or to improve the response.
  • the functional element of the present invention has a large surface area, it can be used as a sensor with high sensitivity and high response.
  • a sensor is provided by providing electrodes on the tip of the needle-shaped metal oxide and the substrate surface. Electric The pole is not particularly limited as long as it is a conductive material.
  • An electric / electronic device using a sensor composed of such a functional element has high sensitivity and high responsiveness, so it can be reduced in size and can detect subtle environmental changes. Therefore, the functional element of the present invention is very useful.
  • G a N red laser wavelength of 410 nm vs. 6500 nm
  • an optical device that integrates three structures, a laser emission part, a mirror part that reflects a laser, and a current injection electrode, has been considered.
  • the composition of each part is different, and the heat generated by long-term use causes thermal mutual diffusion of atoms, resulting in a problem of reduced performance.
  • the functional element of the present invention for example, a needle-shaped metal oxide composed of Zn
  • a laser having a wavelength (380 nm) lower than that of a GaN laser can be obtained.
  • Can oscillate Therefore, higher-density recording is possible than when GaN is used for reading, and at the same time, high-speed transmission is also possible.
  • the optical device using the functional element of the present invention as a laser oscillation element has a simpler structure than using GaN as a laser oscillation element, and the performance is reduced due to thermal mutual diffusion of atoms.
  • the functional element of the present invention for example, a needle-shaped metal oxide composed of Zn
  • a needle-like metals oxides C o ⁇ besides Z n O, ANATA one peptidase type T i O 2, Norechiru type T i ⁇ 2, M n ⁇ , B a T i 0 3, C d O etc. the wavelength, each of which oscillates when using the metallic oxide, C 0 O in 3 1 0 nm, the anatase type T i ⁇ 2 3 8 8 nm, rutile T i O 2 in 3 5 4 nm, M It is 459 nm for nO, 459 nm for BaTi i3, and 539 nm for CdO, and is used as a low-wavelength laser oscillator. Can be.
  • the functional element and the excitation source are used in combination.
  • the excitation source excites the atoms that constitute the functional element by applying energy such as electromagnetic waves, heat, and current to the substrate.When the atoms de-excit and return to the ground state, they emit an electromagnetic wave with a certain wavelength. Lamps and electric currents are examples of the excitation source.
  • Zn nanocrystals formed on a substrate were described as an ultraviolet laser oscillator. Use has been reported.
  • the ZnO nanocrystals formed on the substrate are The calculated diameter is 100 nm, that is, the aspect ratio (circular conversion diameter of the length Z section) is 0.05, and the needle-shaped metal oxide of the present invention is 0.1 or more. Very small.
  • a functional element containing a needle-shaped metal oxide having an aspect ratio of 0.1 or more is used as a laser oscillation element as in the present invention, laser oscillation becomes high. . The reason is considered as follows.
  • the functional element of the present invention is a high-output laser-oscillator element because a large number of needle-like metal oxides having a certain size exist on the substrate.
  • the optical device using the laser oscillation element comprising the functional element of the present invention can oscillate a laser having a wavelength lower than that of the conventional one. Accordingly, high-density information or high-speed transmission of high-sensitivity information becomes possible, and the functional element of the present invention is very useful.
  • the functional element of the present invention has an optical switch function and is an optical switch element that can be highly integrated.
  • An optical device using the functional element of the present invention as an optical switch element is, for example, an optical device in which each of the high-density needle-like metal oxides has an optical switch function. It measures integration.
  • the optical switch function can be achieved by setting two electrodes on each needle-shaped metal oxide in the functional element of the present invention, applying a voltage between the electrodes, and shifting the phase. Can be.
  • Such a highly integrated optical switch can be easily achieved by taking advantage of the feature of the functional element of the present invention that a large number of needle-like metal oxides are present on a substrate.
  • the kind of the metal oxide used for the functional element of the present invention is not particularly limited.
  • the optical device using the optical switch composed of the functional element of the present invention can be used as a highly integrated optical switch in the optical communication field, so that the information with the advance of the advanced information society in the future It is possible to respond to the sophistication and large capacity of the communication
  • the representative examples of the electric / electronic device and the optical device in which the functional element of the present invention can be used have been described above.
  • Other applications include insulators, conductors, solid electrolytes, fluorescent display tubes, and EL devices.
  • Electric and electronic devices such as elements, actuators, piezoelectric bodies, thermistors, varistors, superconductors, thermoelectric emission elements, electromagnetic shielding materials, etc. or photodielectrics, optical sensors, solar cells And optical devices such as a light wavelength conversion element and a light absorption filter.
  • the functional element of the present invention is characterized in that, for example, a needle-shaped metal oxide having a sharp tip extends upward from the upper surface of the substrate, and its central axes are arranged substantially parallel to each other.
  • the thickness (circular diameter) of the needle-shaped metal oxide is 0.1 ⁇ , preferably 0.0 ⁇ .
  • thermoelectric emission element If a functional element with a temperature of 5 ⁇ or less is used as a thermoelectric emission element, it can be used in a freezer.
  • titanium oxide in combination with a photosensitizer
  • the functionality of the present invention including acicular metal oxide of titanium oxide has been studied. Since the element has a large surface area, the light irradiation area is large, and the efficiency of converting light into electricity can be increased.
  • the functional device was manufactured using the apparatus schematically shown in FIG. Were charged zinc Asechiruase Tone one preparative the metal compound heated tank [Z n (C 5 H 7 0 2) 2]. The metal compound heating tank was heated, and zinc acetyl acetate was vaporized at an internal temperature of 115 ° C. On the other hand, an Al 2 ⁇ 3 single crystal plate (10 nini X 5 mm) serving as a substrate is placed on the heater located directly below the blow-out slit, and the (001) plane is slit. And heated to 550 ° C. 1 the metal compound heating tank.
  • Gold (conductive) is applied to the obtained functional element by sputtering.
  • a 1 2 O 3 and temperature 6 0 0 ° C of the single crystal plate was prepared a functional element in the same manner as in Example 1 except that the flow rate of dry nitrogen gas to 2 dm 3 / min.
  • Gold conductive material was vapor-deposited to a thickness of 0.1 ⁇ on the obtained functional element by sputtering, and then observed by SEM.
  • Figure 3 shows the obtained SEM image.
  • the weighted average value of the circular equivalent diameter of the cross section of the needle-shaped ZnO was 3.6 ⁇ m
  • the weighted average value of the length was 80 ⁇
  • the density was ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇
  • Example 3 Using the same apparatus as in Example 1, a functional element was manufactured. Te Tri source proxy Chita Natick preparative the metal compound heated tank [T i (0 C 3 H 7 - i) 4] were charged. The metal compound heating tank was heated to evaporate tetrasilso proxy titanate at an internal temperature of 130 ° C.
  • a MgO single crystal plate (10 mm X 5 mm) serving as a substrate is placed on the heater located directly below the blowout slit so that the (100) plane faces the slit. And heated to 450 ° C. Dry nitrogen gas is introduced into the metal compound heating tank at a flow rate of 1.5 dm 3 Z, and the vaporized tetrasoproxy titanate in the heating tank is entrained with the nitrogen gas. It was sprayed on the surface of the crystal plate. 3 0 seconds after the spraying starts and remove the functionality elements from the device consisting of a substrate and needle-like metal oxide grown thereon (T i ⁇ 2).
  • Gold (conductive material) was deposited to a thickness of 0.1 ⁇ on the obtained functional element by sputtering, and then observed by SEM.
  • Figure 4 shows the obtained SEM image.
  • the weighted average value of the average circular equivalent diameter of the cross section of the needle-shaped Ti 0 2 was 0.8 ⁇ m
  • the weighted average value of the length was 5 ⁇
  • the density was ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ . It had 2500 pieces per unit area, and the crystal axis fluctuation was 2.1 degrees.
  • Example 4 A functional element was manufactured in the same manner as in Example 3, except that the temperature of the MgO single crystal plate was set at 550 ° C.
  • Gold conductive substance was evaporated to a thickness of 0.1 ⁇ on the obtained functional element by sputtering, and observed by SEM.
  • Example 2 Using the same apparatus as in Example 1, a functional element was manufactured. Were charged zinc Asechiruase Tone preparative the metal compound heated tank [Z n (C 5 ⁇ 7 ⁇ 2) 2]. The metal compound heating tank was heated, and zinc acetyl acetate was vaporized at an internal temperature of 115 ° C. On the other hand, place a silicon plate (10 mm X 5 mm) on the heater above the heater located directly below the blow-out slit so that the (1 1 1) plane faces the slit. And heated to 550 ° C.
  • Dry nitrogen gas is introduced into the metal compound heating tank at a flow rate of 1.2 dm 3 / min, and the vaporized zinc acetyl acetate in the heating tank is entrained with the nitrogen gas, and silicon dioxide is applied under atmospheric pressure atmosphere. Sprayed on the surface of the board. Three hundred minutes after the start of spraying, the functional element composed of the substrate and the needle-shaped metal oxide ( ⁇ ) grown thereon was removed from the apparatus.
  • Gold conductive material was vapor-deposited to a thickness of 0.1 ⁇ on the obtained functional element by sputtering, and then observed by SEM.
  • Example 2 Using the same apparatus as in Example 1, a functional element was manufactured. Were charged zinc Asechiruase Tone preparative the metal compound heated tank [Z n (C 5 ⁇ 7 ⁇ 2) 2]. The metal compound heating tank was heated to evaporate zinc acetyl acetate at an internal temperature of 115 ° C. On the other hand, the substrate on top of the heater located beneath the scan Li Tsu preparative out can blow A 1 2 0 3 single crystal plate (1 0 mm X 5 mm) (0 0 0 1) plane force S scan Li Tsu It was set so as to face the heat and heated to 550 ° C.
  • Dry nitrogen gas was introduced into the metal compound heating tank at a flow rate of 1.2 dm 3 / min to remove the vaporized zinc acetyl acetate in the heating tank with nitrogen. Along with the gas, it was sprayed onto the surface of the A12 ⁇ 3 single crystal plate at atmospheric pressure. After 15 minutes from the start of spraying, the functional element consisting of the substrate and the needle-shaped metal oxide (ZnO) grown on it was removed from the device.
  • ZnO needle-shaped metal oxide
  • Sputtered gold (conductive material) was deposited on the obtained functional element to a thickness of 0.1 nm and then observed by SEM.
  • a functional device was manufactured in the same manner as in Example 6, and a circuit (FIG. 8) using the obtained functional device as an electron-emitting device was created.
  • the electron-emitting device, the silicon plate (6), and the conductive paste (7) are connected so that the nickel layer (3) formed on the functional device and the copper plate (8) are connected via the conductive paste (7).
  • a copper plate (8) An external electrode was attached to the copper plate (8), and this external electrode was connected to a ground.
  • a copper plate (4) covered with an insulating film (5) was prepared except for leaving a square portion of 2 mm square, and an external electrode was attached to this copper plate, and the external electrode was connected to the anode.
  • the copper plate (4) covered with the insulating film (5) and the functional element formed with the nickel layer (3) are combined with the portion of the copper plate (4) not covered with the insulating film (5) and the nickel layer (3). Then, it was fixed via another silicon (S i) plate (6) so that the distance between them was 0.5 mm, and a circuit device whose cross section was as shown in Fig. 8 was created.
  • a circuit device was prepared in the same manner as described above, using a nickel flat plate of 1 O mm X 5 mm X 0.5 mm in place of the functional element having the nickel layer formed thereon.
  • the emission current at 5 kV was 0.4 ⁇ A.
  • the functional element for an electric, electronic or optical device according to the present invention has an excellent feature that the thickness can be reduced despite the extremely large surface area of the metal oxide on the substrate. Having. Functional elements having such characteristics include, for example, energy-saving electron-emitting elements capable of emitting electrons at a low voltage, high-capacitance capacitor elements, high-density memory elements, and high-performance memory elements. It can be advantageously applied to elements for electric or electronic devices such as sensitivity sensor elements, laser oscillation elements, especially laser oscillation elements with low wavelengths such as ultraviolet light, and elements for optical devices such as highly integrated optical switch elements. It can be. Further, according to the method of the present invention, the electric, electronic or optical device of the present invention can be manufactured effectively and efficiently without requiring a large capital investment. In the method of the present invention, for example, the reaction can be carried out in an air atmosphere at atmospheric pressure.

Abstract

L'invention concerne un élément fonctionnel pour un dispositif électrique, électronique ou optique comportant un substrat et plusieurs aiguilles d'oxyde métallique se trouvant sur sa surface supérieure. Ces aiguilles d'oxyde métallique s'étendent depuis cette surface supérieure du substrat vers le haut, leurs axes centraux étant disposés de manière sensiblement parallèle les uns par rapport aux autres; elles ont un diamètre moyen pondéré spécifique dans leur configuration circulaire, et un rapport de forme moyen pondéré spécifique; et elles se trouvent sur la surface supérieure de ce substrat selon une densité spécifique. On produit cet élément suivant un procédé qui consiste à vaporiser un composé métallique pouvant former un oxyde métallique par réaction avec une substance capable de former un oxyde, et à souffler sur la surface du substrat le gaz du composé métallique qui en résulte, ledit substrat étant placé dans une zone de réaction où se trouve une substance formant un oxyde, et chauffé à une température supérieure à celle du gaz du composé métallique.
PCT/JP1999/001477 1998-04-30 1999-03-24 Element fonctionnel pour dispositif electrique, electronique ou optique, et son procede de production WO1999057345A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US09/647,489 US6810575B1 (en) 1998-04-30 1999-03-24 Functional element for electric, electronic or optical device and method for manufacturing the same
DE19983159T DE19983159B4 (de) 1998-04-30 1999-03-24 Verfahren zur Herstellung eines Funktionselementes zur Verwendung in einer elektrischen, elektronischen oder optischen Vorrichtung
GB0023716A GB2352562B (en) 1998-04-30 1999-03-24 Functional element for use in an electric, an electronic or an optical device and method for producing the same

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JP10/134300 1998-04-30
JP13430098 1998-04-30
JP10/285892 1998-09-24
JP28589298 1998-09-24

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JP2001206800A (ja) * 2000-01-26 2001-07-31 Masasuke Takada 酸化亜鉛単結晶およびその製造方法
JP2008098220A (ja) * 2006-10-06 2008-04-24 Asahi Kasei Corp 発光ダイオード
CN109225294A (zh) * 2017-07-11 2019-01-18 中国科学院上海硅酸盐研究所 一种绿色催化合成安息香的方法

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JPH02237070A (ja) * 1989-03-09 1990-09-19 Olympus Optical Co Ltd 電荷移動錯体層の形成方法
JPH05306200A (ja) * 1992-04-30 1993-11-19 Matsushita Electric Ind Co Ltd 微細構造の製造方法

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Publication number Priority date Publication date Assignee Title
JP2001206799A (ja) * 2000-01-26 2001-07-31 Masasuke Takada 酸化亜鉛単結晶およびその製造方法
JP2001206800A (ja) * 2000-01-26 2001-07-31 Masasuke Takada 酸化亜鉛単結晶およびその製造方法
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JP2008098220A (ja) * 2006-10-06 2008-04-24 Asahi Kasei Corp 発光ダイオード
CN109225294A (zh) * 2017-07-11 2019-01-18 中国科学院上海硅酸盐研究所 一种绿色催化合成安息香的方法
CN109225294B (zh) * 2017-07-11 2021-03-16 中国科学院上海硅酸盐研究所 一种绿色催化合成安息香的方法

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GB2352562A (en) 2001-01-31

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