JP3758761B2 - Heterofine particle fusion product and method for producing the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a heterofusion of metal fine particles and compound fine particles and a method for producing the same.
[0002]
[Prior art]
Compound particles such as metal particles and metal oxide particles exhibit characteristics different from normal particles (for example, 1 μm or more) when the particles are made ultrafine so that the particle size is 100 nm or less. This is because the number of atoms existing on the surface increases with respect to the total number of atoms, that is, the specific surface area increases, and therefore the influence of surface energy on the properties of the particles cannot be ignored.
[0003]
Ultrafine particles such as those mentioned above are suitable for discovering new surface phenomena and grasping their outlines, etc. In addition, ultrafine particles have a lower melting point and sintering temperature compared to bulk, and their properties can be applied to various fields. Since there is a possibility of application, research on the physical properties of ultrafine particles themselves, research on how to use ultrafine particles, and the like are underway.
[0004]
Conventional ultrafine particles are produced by, for example, the following physical methods and chemical methods. In other words, physical ultrafine particles are produced by evaporating metals, etc. in an inert gas, cooling and condensing by collision with the gas, and generating ultrafine particles. Sputtering method to be used, metal is heated under vacuum, vaporized metal atoms are co-deposited with organic solvent on a substrate cooled below the freezing point of organic solvent, metal vapor synthesis method to obtain ultrafine particles, metal on oil Examples include a vacuum evaporation method on a fluid oil to be deposited.
[0005]
In addition, chemical ultrafine particles can be produced using a liquid phase using a colloidal method in which a noble metal salt is reduced under reflux conditions in alcohol coexisting with a polymer surfactant, or hydrolysis of a metal alkoxide. An alkoxide method, a coprecipitation method in which a precipitant is added to a mixed solution of metal salts to obtain precipitated particles, and a method for producing chemical ultrafine particles using a gas phase include a thermal decomposition reaction of a metal carbonyl compound or the like. Pyrolysis method of organometallic compounds to obtain ultrafine metal particles, reduction, oxidation or nitridation method of metal chlorides to obtain ultrafine particles by reducing, oxidizing or nitriding metal chlorides in a reactive gas stream, oxides and hydrates Examples include a reduction in hydrogen method in which heating is performed in a hydrogen stream and a solvent evaporation method in which a metal salt solution is sprayed from a nozzle and dried in hot air.
[0006]
[Problems to be solved by the invention]
By the way, research and development on conventional ultrafine particles are mainly related to aggregates of ultrafine particles (ultrafine powder), and research on the properties and applications of ultrafine particles as a single unit, as well as various operations and controls, has been sufficiently conducted. It cannot be said that it is broken. This is due to the above-described conventional method for producing ultrafine particles, and many of the conventional production methods are suitable for producing ultrafine particles as an aggregate, but it is difficult to obtain ultrafine particles as a single particle. Because there was.
[0007]
As described above, research on various operations and controls for single ultrafine particles has not been sufficiently performed, and application from single ultrafine particles based on them has not been specifically promoted. For example, by realizing the fusion of single ultrafine particles under controlled conditions, it is predicted that it will be possible to produce ultrafine products and materials having properties different from bulk, Realization of fusion of metal ultrafine particles and compound ultrafine particles under controlled conditions is expected to enable the development of various ultrafine devices and functional materials. It cannot be obtained in the research and development process, and it has hindered the application development of ultrafine particles.
[0008]
The present invention provides a hetero fine particle fusion product that enables control of the fusion state and the like by realizing fusion between different kinds of fine particles under controlled conditions, such as metal ultra fine particles and compound ultra fine particles, and the production thereof. It aims to provide a method.
[0009]
[Means for Solving the Problems]
The first hetero fine particle fusion product according to the present invention is a fusion product of a metal fine particle and a compound fine particle comprising a compound containing a metal constituting the metal fine particle as described in claim 1, wherein the metal fine particle And the compound fine particles are characterized by being fused so that the interface between the metal fine particles and the compound fine particles is lattice-matched by simultaneous irradiation with a high energy beam in a vacuum atmosphere.
[0010]
As described in claim 5, the second hetero fine particle fusion in the present invention comprises a metal fine particle composed of one kind of metal selected from Al, Mg, Be, Ca, Ce, Ti and Zr, and the metal. It is a fusion product of compound fine particles made of a compound containing, wherein the fusion interface between the metal fine particles and the compound fine particles is lattice-matched.
[0011]
In addition, as described in claim 7, the method for producing a heterofine particle fusion product of the present invention can simultaneously apply metal fine particles and compound fine particles comprising a compound containing a metal constituting the metal fine particles in a vacuum atmosphere. It is characterized in that at least one of the metal fine particles and the compound fine particles is moved by irradiating an energy beam and fused while being lattice-matched at the interface between the metal fine particles and the compound fine particles.
[0012]
The method for producing a hetero fine particle fusion according to the present invention is characterized in that, as described in claim 8, 1 × 10 5 as the high energy beam. ¹⁹ e / cm ² It is characterized by irradiating an electron beam having an intensity of sec or more. Further, as described in claim 9, the electron beam is radiated in a magnetic field parallel to the irradiation direction.
[0013]
That is, in the present invention, adjacent metal fine particles and compound fine particles containing the metal are simultaneously irradiated with a high energy beam to move at least one of the metal fine particles and the compound fine particles without melting them, and This is based on the finding that it is possible to perform fusion while maintaining the state of metal fine particles and compound fine particles and lattice matching at the fusion interface.
[0014]
Here, in the present invention, the metal fine particles and the compound fine particles are fine particles having a particle size of 1 μm or less, and at least one of them has a particle size that can be moved by irradiation with a high energy beam. Examples of the fine particles movable by irradiation with the high energy beam mainly include ultrafine particles having a particle diameter of 200 nm or less, and at least one of the metal fine particles and the compound fine particles is preferably the ultrafine particles as described above. Depending on the type and irradiation conditions of the energy beam and the initial distance between the metal fine particles and the compound fine particles, fine particles having a particle size larger than that can be moved and fused by irradiation with a high energy beam.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, modes for carrying out the present invention will be described.
[0016]
FIG. 1 is a diagram schematically showing one embodiment of a process for producing a hetero ultrafine particle fusion product according to the present invention. First, as shown in FIG. 1A, adjacent metal fine particles 1 and compound fine particles 2 are simultaneously irradiated with a high energy beam 3 in a vacuum atmosphere.
[0017]
Here, examples of the metal fine particles 1 include Al fine particles, Mg fine particles, Be fine particles, Ca fine particles, Ce fine particles, Ti fine particles, and Zr fine particles. These metal fine particles 1 have a small standard free energy of formation of oxides, and it is difficult to obtain fine particles of these single metals, particularly ultrafine particles themselves, by ordinary methods. Furthermore, compound fine particles containing the metal, for example, metal It has never been possible to fuse oxide fine particles while maintaining their metallic state. Among these, the present invention is particularly effective for Al fine particles that are easily oxidized.
[0018]
The metal fine particles 1 used in the present invention are not limited to the above-mentioned metals that easily form oxides. For example, fine particles of various metals such as W fine particles, Mo fine particles, and Cu fine particles can be applied. is there. W, Mo, and Cu are elements that easily form ultrafine metal particles, as will be described in detail later, and are therefore suitable as one starting material for the heterofine particle fusion of the present invention.
[0019]
The metal fine particles 1 described above are preferably metal ultrafine particles having a particle size in the range of 0.5 to 200 nm. Such metal ultrafine particles can be moved relatively easily by irradiation with a high energy beam 3 to be described later, and various properties as ultrafine particles can be obtained. Are preferably used. Furthermore, the preferable particle diameter of the ultrafine metal particles is in the range of 0.5 to 100 nm, which can easily move and can realize the enveloping and fusion described later, and the particularly preferable particle diameter range is 2 to 50 nm.
[0020]
However, when attention is paid only to the fusion phenomenon with the compound fine particles 2 by irradiation with the high energy beam 3, the particle size of the metal fine particles 1 may be in the range of 0.5 to 500 nm, although it depends on the particle size of the compound fine particles 2. . Even with the metal fine particles 1 having such a particle size, the compound fine particles 2 may be changed depending on the type of the high energy beam 3 and the irradiation conditions, the initial distance between the metal fine particles 1 and the compound fine particles 2, the particle size of the compound fine particles 2, and the like. Can be fused. If the particle size of the metal fine particles 1 exceeds 500 nm, there is a high possibility that the fusion phenomenon cannot be induced even when the high energy beam 3 is irradiated.
[0021]
The compound fine particle 2 which is the other starting material of the hetero fine particle fusion of the present invention is composed of a compound containing a metal constituting the metal fine particle 1, such as a metal oxide, metal carbide, metal nitride, metal boride and the like. is there. Among these, for example, metal oxides that can take several states with different crystal systems and valences and the like relatively easily are preferably used, thereby producing metal fine particles (particularly metal ultrafine particles) and compound fine particles described later. The method can be easily applied.
[0022]
The particle size of such compound fine particles 2 is set in the range of 20 nm to 1 μm. The compound fine particles 2 having a particle diameter of less than 20 nm are difficult to produce themselves, whereas if the particle diameter exceeds 1 μm, the characteristics as fine particles cannot be obtained. Thus, the compound fine particles 2 having various particle diameters can be fused with the metal fine particles 1, and if the compound ultrafine particles having a particle diameter of 20 to 200 nm are used, the metal fine particles 1 have a relatively large particle diameter. Even in the case where is used, both of these can be fused well. Furthermore, when the metal fine particles 1 and the compound fine particles 2 are both ultrafine particles, the possibility that new characteristics appear in the obtained hetero ultrafine particle fusion is increased.
[0023]
Although FIG. 1 illustrates the case where the metal fine particles 1 are smaller than the compound fine particles 2, the present invention is not limited to this, and even if the compound fine particles 2 are smaller as described above, they can be fused depending on conditions. However, it is easier to make the metal fine particles 1 that are easily activated, for example, ultrafine particles (that is, the metal fine particles 1 are smaller than the compound fine particles 2) and fuse them with the compound fine particles 2 while moving them.
[0024]
The metal fine particles 1 and the compound fine particles 2 as described above are not particularly limited as long as the metal fine particles 1 and the compound fine particles 2 can be operated and controlled as a single metal fine particle and a single compound fine particle, and those obtained by various production methods can be used. Can be used, but in particular, a method for producing metal fine particles (particularly metal ultrafine particles) and compound fine particles composed of a stable phase by irradiating metastable compound particles described in detail below with a high energy beam Is preferably used. Such a method is suitable for compounds such as W, Mo, Cu, etc., in which oxides are easily decomposed, and Al, etc., in which metastable compound particles (particularly metastable oxide particles) are easily obtained. Here, Al ultrafine particles and Al ₂ O _Three The fine particles will be described as a specific example.
[0025]
That is, θ-Al disposed on a carbon support film having a reducing action. ₂ O _Three 1 × 10 in vacuum atmosphere to metastable compound particles such as fine particles ¹⁹ e / cm ² • Irradiate a high energy beam such as an electron beam with an intensity of sec or more. Such a high energy beam brings about a local heating effect such as metastable oxide fine particles and a displacement effect of oxygen atoms. As a result, α-Al which is a stable phase ₂ O _Three And Al ₂ O _Three Ultrafine particles composed of Al, which is a constituent metal of
[0026]
The Al ultrafine particles obtained in this way are pure metal ultrafine particles having no surface oxide, both of which can be separated as a single substance, and can be used as the metal fine particles 1 as one starting material. In addition, θ-Al used to produce Al ultrafine particles ₂ O _Three Α-Al produced simultaneously with fine particles and Al ultrafine particles ₂ O _Three The fine particles can be used as the compound fine particles 2 which is the other starting material.
[0027]
The high energy beam 3 irradiating the metal fine particles 1 and the compound fine particles 2 is not particularly limited as long as it has energy capable of fusing the metal fine particles 1 and the compound fine particles 2. For example, the strength is 1 × 10 ¹⁹ e / cm ² -An electron beam of sec or more, a particle beam such as an ion beam having the same intensity as this electron beam, a photon such as a laser, an X-ray, a γ-ray, a neutron beam, etc. ¹⁹ e / cm ² -An electron beam of sec or more is preferably used.
[0028]
When an electron beam is used as the high energy beam 3, the irradiation intensity is 1 × 10 ¹⁹ e / cm ² If it is less than sec, there is a possibility that the metal fine particles 1 and the compound fine particles 2, particularly the metal fine particles 1, cannot be activated to the extent that a hetero fine particle fusion can be formed. In other words, 1 × 10 ¹⁹ e / cm ² -The electron beam (3) having an intensity of sec or more particularly brings about an activation effect of metal fine particles, a local heating effect, and the like, and these make it possible to produce hetero fine particle fusions. The same applies to the case where a particle beam, photon, X-ray, γ-ray, neutron beam or the like is used as the high energy beam 3.
[0029]
Moreover, when irradiating an electron beam as the high energy beam 3, it is preferable to irradiate the electron beam in a magnetic field parallel to the irradiation direction, in other words, in a magnetic field having an axis coinciding with the irradiation axis of the electron beam. . As a result, Lorentz force acts on the metal fine particles 1 and the compound fine particles 2, particularly the metal fine particles 1 existing in the electron beam irradiation range, and the metal fine particles 1 can be easily moved.
[0030]
The irradiation atmosphere of the high energy beam 3 is 1 × 10 ^-3 It is preferable to use a vacuum atmosphere of Pa or lower, which can prevent oxidation of the metal fine particles 1 and adsorption of residual gas atoms. The irradiation with the high energy beam 3 is preferably performed on the carbon support film having the reducing action as described above. Irradiation with the high energy beam 3 can be performed, for example, on a room temperature stage of an electron microscope (especially a TEM apparatus or the like).
[0031]
When the adjacent metal fine particles 1 and compound fine particles 2 are simultaneously irradiated with the high energy beam 3 as described above, the metal fine particles 1 and the compound fine particles 2 start to be activated and finally approach, as shown in FIG. In addition, the metal fine particles 1 and the compound fine particles 2 are fused to obtain a hetero fine particle fusion body 4.
[0032]
At this time, although depending on the respective sizes, the metal fine particles 1 usually move so as to approach the compound fine particles 2. The crystal orientation of the metal fine particles 1 and the compound fine particles 2 before irradiation with the high energy beam 3 is random, but when the metal fine particles 1 and the compound fine particles 2 are fused, a specific crystal plane is aligned. In order to reduce the interfacial energy, for example, the atomic arrangement of the metal fine particles 1 is changed, and as shown in FIG. 1B, the hetero fine particle fusion in which the metal fine particles 1 and the compound fine particles 2 are fused in a lattice-matched state. 4 is obtained.
[0033]
That is, the metal fine particles 1 and the compound fine particles 2 are fused so that the interface is lattice-matched while maintaining the respective states. The specific crystal surface 1a of the metal fine particle 1 and the specific crystal surface 2a of the compound fine particle 2 are parallel to each other and have a heteroepitaxial relationship.
[0034]
In this way, the adjacent metal fine particles 1 and compound fine particles 2 are simultaneously irradiated with the high energy beam 3 in a vacuum atmosphere, thereby maintaining the state of the metal fine particles 1 and the compound fine particles 2 respectively, and the fusion interface. Can be obtained. Since the hetero fine particle fusion 4 has a heteroepitaxial relationship as described above, it is stable and excellent in interfacial strength, and is useful for application to various ultrafine products, various devices, various functional materials, and the like. . Further, as described above, the fusion 4 of the metal fine particles 1 and the compound fine particles 2 maintaining the metal state is obtained using Al ultrafine particles or the like, which are difficult to obtain ultrafine particles of a single metal by a normal method. Can do.
[0035]
Further, in the hetero fine particle fusion 4 shown in FIG. 1B, the metal fine particles 1 and the compound fine particles 2 have a specific fusion interface. When 3 is irradiated, as shown in FIG. 1C, the fusion further proceeds and the metal fine particles 1 are taken into the compound fine particles 2. That is, a hetero fine particle fusion 4 ′ in which the metal fine particles 1 are fused so as to be three-dimensionally wrapped in the compound fine particles 2 is obtained. Also in this hetero fine particle fusion 4 ', the lattice matching of the fusion interface, that is, the heteroepitaxial relationship is maintained.
[0036]
The above-described heterofine particle fusion 4 'in the encapsulated state has a heteroepitaxial relationship, and the metal fine particles (particularly, the metal ultrafine particles) 1 are encapsulated in the compound fine particles 2 while maintaining the metal state. The metal fine particles 1 can be stably present, and are useful for application to various ultrafine products, various devices, various functional materials, and the like. In addition, a fusion body in which Al ultrafine particles, which are difficult to obtain ultrafine particles of simple metals themselves, are stably present in the compound fine particles can be obtained.
[0037]
Further, when metastable compound particles are used as the compound fine particles 2, depending on the irradiation condition of the high energy beam 3, the compound particles can be generated from the metastable compound particles simultaneously with the fusion of the metal fine particles 1 and the compound fine particles 2. Can do. According to this, it is possible to obtain a composite fusion product in which the metal fine particles 1 and the stable compound particles are fused and the stable compound particles are further fused with the metastable compound particles.
[0038]
In the above-described heterofine particle fusion in an encapsulated state, the state in which the compound fine particles are three-dimensionally encapsulated in the metal fine particles can be realized by controlling the particle size of the initial metal fine particles 1 and the compound fine particles 2 or the like.
[0039]
In the above embodiment, the hetero fine particle fusion body 4 of the metal fine particles 1 and the compound fine particles 2 that have not passed through the molten state can be formed on the room temperature stage. In general, since it is difficult to irradiate a high energy beam 3 such as an electron beam under controlled heating conditions, it is significant to enable generation of the heterofine particle fusion 4 on a room temperature stage, Since the fusion product can be generated without melting, it is possible to obtain an advantage that lattice defects such as residual strain and misfit dislocation are not formed in the vicinity of the interface.
[0040]
【Example】
Next, specific examples of the present invention will be described.
[0041]
Example 1
First, spherical θ-Al with a particle size of about 100 nm ₂ O _Three Fine particles (purity = 99.8%) were prepared, dispersed in alcohol, and then coated on a carbon support film and dried. Next, the spherical θ-Al ₂ O _Three The carbon support membrane in which the fine particles are arranged was placed on a room temperature stage arranged in a vacuum chamber of a 200 kV TEM apparatus (manufactured by JEOL Ltd., JEM-2010 (trade name)).
[0042]
Next, the above vacuum chamber is 1 × 10 ^-Five After evacuating to a vacuum of Pa, θ-Al having a particle size of about 100 nm disposed on the carbon support film ₂ O _Three 1 × 10 for fine particles ²⁰ e / cm ² -Irradiated with an electron beam of sec (irradiation diameter = 250 nm). And by this electron beam irradiation, θ-Al ₂ O _Three Al ultrafine particles having a diameter of about 2 to 30 nm were produced from the fine particles. At this time, α-Al having a diameter of about 20 to 100 nm ₂ O _Three Ultrafine particles were generated at the same time.
[0043]
The above-mentioned Al ultrafine particles and θ-Al ₂ O _Three Microparticles were used to generate heteroparticulate fusions. Specifically, while maintaining the state (including the degree of vacuum) that the carbon support film having the generated Al ultrafine particles is placed in the vacuum chamber of the TEM device, the carbon support film is selected from among the Al ultrafine particles on the carbon support film. , Θ-Al ₂ O _Three Al ultrafine particles having a diameter of about 10 nm located in the vicinity of the fine particles were selected. And these Al ultrafine particles and θ-Al ₂ O _Three 1 × 10 simultaneously with fine particles ²⁰ e / cm ² • Irradiated with an electron beam of sec.
[0044]
While performing electron beam irradiation, Al ultrafine particles and θ-Al ₂ O _Three The state of fine particles was observed in situ. As a result, Al ultrafine particles are θ-Al. ₂ O _Three Approaching the fine particles was observed. θ-Al ₂ O _Three The microparticles hardly move under these conditions. Furthermore, when the electron beam was continuously irradiated, Al ultrafine particles and θ-Al were added after about 500 seconds from the start of the electron beam irradiation. ₂ O _Three Fine particles were fused. The TEM observation result in this state is schematically shown in FIG.
[0045]
As shown in FIG. 2, Al ultrafine particles 11 and θ-Al ₂ O _Three In the hetero-fused body 13 with the fine particle 12, the fusion interface is lattice-matched, and the {200} plane of the Al ultrafine particle 11 and the θ-Al ₂ O _Three The {113} plane of the fine particles 12 had a heteroepitaxial relationship. Al ultrafine particles 11 and θ-Al used for the production of this fusion 13 ₂ O _Three The microparticles 12 are initially those that did not have a clear crystallographic relationship.
[0046]
Also, using another Al ultrafine particle 11, θ-Al ₂ O _Three 1 × 10 simultaneously with fine particles 12 ²⁰ e / cm ² When irradiated with an electron beam of sec, as shown in the schematic diagram of the TEM observation result in FIG. 3, θ-Al ₂ O _Three Α-Al having a diameter of about 20 to 50 nm around the fine particles 12 ₂ O _Three At the same time as the formation of ultrafine particles 14, this α-Al ₂ O _Three A state in which the ultrafine particles 14 and the Al ultrafine particles 11 were fused was obtained. Thus, the fusion mode can be controlled by appropriately setting the irradiation conditions of the electron beam and the shape and position of the original Al ultrafine particles.
[0047]
Example 2
In Example 1, θ-Al ₂ O _Three Al ultrafine particles with a diameter of about 10 nm and α-Al with a diameter of 100 nm or less, produced by electron beam irradiation on the fine particles ₂ O _Three Using ultrafine particles, hetero-fine particle fusions were produced.
[0048]
Specifically, the produced Al ultrafine particles and α-Al ₂ O _Three While maintaining the state (including the degree of vacuum) that the carbon support film having ultrafine particles is placed in the vacuum chamber of the TEM apparatus, α-Al having a diameter of 100 nm or less is selected from the ultrafine Al particles on the carbon support film. ₂ O _Three Select Al ultrafine particles with a diameter of about 10 nm located in the vicinity of the ultrafine particles. ²⁰ e / cm ² • Irradiated with an electron beam of sec.
[0049]
While performing electron beam irradiation, Al ultrafine particles and α-Al ₂ O _Three The state with ultrafine particles was observed in situ. FIG. 4A is a diagram schematically showing a TEM observation result after irradiating the electron beam for 120 seconds. From this figure, the Al ultrafine particles 11 and α-Al are irradiated by the electron beam irradiation. ₂ O _Three It can be seen that the ultrafine particles 14 are beginning to fuse. FIG. 4B is a diagram schematically showing a TEM observation result after the electron beam is further irradiated for 60 seconds. From this figure, by continuously irradiating the electron beam, the Al ultrafine particles 11 and α-Al ₂ O _Three Fusion with the ultrafine particles 14 proceeds, and the Al ultrafine particles 11 are almost α-Al. ₂ O _Three It can be seen that the heterofusion 15 incorporated into the ultrafine particles 14 is obtained.
[0050]
The heterofusion 15 obtained by this example is composed of Al ultrafine particles 11 and α-Al. ₂ O _Three The fusion interface with the ultrafine particles 14 is lattice-matched, and the {200} face of the Al ultrafine particles 11 and the α-Al ₂ O _Three It was confirmed that the ultrafine particles 14 had a heteroepitaxial relationship with the {110} plane. Al ultrafine particles 11 and α-Al used for the production of this fusion 13 ₂ O _Three The ultrafine particles 14 are initially those that did not have a clear crystallographic relationship.
[0051]
In addition, α-Al mentioned above ₂ O _Three Instead of ultrafine particles, θ-Al ₂ O _Three The flake-like α-Al dispersed on the carbon support film simultaneously with the fine particles ₂ O _Three Even when ultrafine particles were used, similar heterofusions could be obtained.
[0052]
Example 3
In Example 1, θ-Al ₂ O _Three Al ultrafine particles generated by electron beam irradiation of particles and α-Al ₂ O _Three From the fine particles, Al ultrafine particles different from Example 2 and α-Al ₂ O _Three Fine particles were selected to produce heterofine particle fusions.
[0053]
Specifically, the produced Al ultrafine particles and α-Al ₂ O _Three While maintaining the state (including the degree of vacuum) that the carbon support film having fine particles is placed in the vacuum chamber of the TEM apparatus, α-Al having a diameter of about 100 nm is selected from the Al ultra fine particles on the carbon support film. ₂ O _Three Select Al ultrafine particles with a diameter of about 15 nm located in the vicinity of the fine particles. ²⁰ e / cm ² • Irradiated with an electron beam of sec.
[0054]
While performing electron beam irradiation, Al ultrafine particles and α-Al ₂ O _Three The state of fine particles was observed in situ. FIG. 5A is a diagram schematically showing a TEM observation result after irradiating the electron beam for 420 seconds, and FIG. 5B schematically shows a TEM observation result after further irradiating the electron beam for 660 seconds. FIG.
[0055]
As is apparent from FIG. 5, at the stage of irradiation with an electron beam for 420 seconds, the Al ultrafine particles 11 and α-Al ₂ O _Three A hetero-fusion 15 with the fine particles 14 is formed. By irradiating the hetero-fusion 15 with an electron beam for 660 seconds, the fusion proceeds and the Al ultrafine particles 11 become α-Al. ₂ O _Three It can be seen that the heterofusion 15 'encapsulated in the microparticles 14 is formed. Also in this encapsulated heterofusion 15 ', the fusion interface had a heteroepitaxial relationship.
[0056]
【The invention's effect】
As described above, according to the present invention, it is possible to obtain a hetero fine particle fusion in which the fusion state and the like are controlled, for example, on a room temperature stage under easy control conditions. And since the hetero fine particle fusion body of the present invention has controllability and operability of the fusion state, it greatly contributes to various application developments from metal ultrafine particles and compound fine particles.
[Brief description of the drawings]
FIG. 1 is a diagram schematically showing a production process of a hetero fine particle fusion product according to an embodiment of the present invention.
FIG. 2 is a diagram schematically showing a TEM observation result of a hetero fine particle fusion product produced in Example 1 of the present invention.
FIG. 3 is a diagram schematically showing a TEM observation result of another hetero fine particle fusion product produced in Example 1 of the present invention.
FIG. 4 is a diagram schematically showing a TEM observation result of the hetero ultrafine particle fusion product produced in Example 2 of the present invention.
FIG. 5 is a diagram schematically showing a TEM observation result of another hetero fine particle fusion product produced in Example 3 of the present invention.
[Explanation of symbols]
1 …… Ultrafine metal particles
2. Compound fine particles
3. High energy beam
4 …… Heterofine particle fusion

Claims (10)

A fusion product of metal fine particles and compound fine particles comprising a compound containing a metal constituting the metal fine particles,
The hetero fine particle fusion product, wherein the metal fine particles and the compound fine particles are fused so that the interface between the metal fine particles and the compound fine particles is lattice-matched by simultaneous irradiation with a high energy beam in a vacuum atmosphere. . The hetero fine particle fusion according to claim 1, wherein
The hetero fine particle fusion product, wherein the metal fine particles and the compound fine particles are fused by irradiating an electron beam as the high energy beam in a magnetic field parallel to the irradiation direction. The hetero fine particle fusion according to claim 1, wherein
The heterofine particle fusion product, wherein the metal fine particles are fused so as to be encased in the compound fine particles. The hetero fine particle fusion according to claim 1, wherein
The hetero fine particle fusion product, wherein the metal fine particles comprise one kind of metal selected from Al, Mg, Be, Ca, Ce, Ti, Zr, W, Mo and Cu. A fusion of a metal fine particle made of one kind of metal selected from Al, Mg, Be, Ca, Ce, Ti and Zr and a compound fine particle made of a compound containing the metal, wherein the metal fine particle and the compound fine particle A heterofine particle fusion product characterized in that the fusion interface of is lattice-matched. The hetero fine particle fusion according to claim 5,
The heterofine particle fusion product, wherein the metal fine particles are fused so as to be encased in the compound fine particles. At least one of the metal fine particles and the compound fine particles is moved by simultaneously irradiating the metal fine particles and the compound fine particles made of a compound containing a metal constituting the metal fine particles with a high energy beam in a vacuum atmosphere, and moving the metal fine particles and the compound fine particles. A method for producing a hetero fine particle fusion product, comprising fusing the fine particles and compound fine particles while lattice-matching them. The method for producing a hetero fine particle fusion according to claim 7,
A method for producing a hetero fine particle fusion product, comprising irradiating an electron beam having an intensity of 1 × 10 ¹⁹ e / cm ² · sec or more as the high energy beam. The method for producing a hetero fine particle fusion according to claim 8,
A method for producing a hetero fine particle fusion product, wherein the electron beam is irradiated in a magnetic field parallel to the irradiation direction. The method for producing a hetero fine particle fusion according to claim 7,
A method for producing a hetero fine particle fusion product, wherein fine particles of one kind of metal selected from Al, Mg, Be, Ca, Ce, Ti, Zr, W, Mo, and Cu are used as the metal fine particles.

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