WO2022172972A1

WO2022172972A1 - Method for producing composite by laser irradiation, and composite

Info

Publication number: WO2022172972A1
Application number: PCT/JP2022/005217
Authority: WO
Inventors: 宏昭西山; 春加松本
Original assignee: 国立大学法人山形大学
Priority date: 2021-02-09
Filing date: 2022-02-09
Publication date: 2022-08-18
Also published as: DE112022001009T5; JPWO2022172972A1

Abstract

Provided is a composite production method that stably produces a composite in which a boundary distinctly divides a coating layer from a core containing a metal, ceramic, or combination thereof, and in which there are no gaps between the core and the coating layer. The composite production method comprises: preparing a linear material that contains a metal, ceramic, or combination thereof; immersing the linear material in a first dispersion in which a first solid nanomaterial is dispersed; and, while irradiating a first laser light onto the linear material that has been immersed in the first dispersion, moving a condensed region of the first laser light along the linear material to form, in at least a portion of the surface of the linear material, a first coating layer constituted of the first solid nanomaterial, thereby forming a core/first coating layer composite wherein the core is constituted of the linear material. The first solid nanomaterial is constituted of at least one selected from the group consisting of metal oxides, nonmetal oxides, ceramics, metals, and resins.

Description

Composite manufacturing method and composite by laser irradiation

The present invention relates to a composite manufacturing method and a composite by laser irradiation.

In contrast to lithography, which requires complex processes, material patterning by laser irradiation enables arbitrary pattern formation simply by scanning the light-collecting part, so it is expected to be applied to integrated devices with higher functionality and printable electronics. (Non-Patent Document 1).

However, since material patterning by laser irradiation is an optical process, the material to be processed must have photosensitivity, which has been a significant limitation in material selection.

With conventional wiring technology using lasers, it was difficult to wire materials that do not absorb light, and the materials to be processed were limited to materials with photosensitivity. In addition, the material to be processed must have appropriate photosensitivity. If the absorption is too strong for the wavelength of the laser, the light penetration depth will be shallow and the surface will be easily damaged. I couldn't process it because it was worn out.

On the other hand, in recent years, by irradiating femtosecond laser to dilute _AgNO3 solution in which solid fine particles are dispersed, surrounding fine particles are accumulated and solidified while forming a hierarchical structure. It has been proposed to do so (Patent Document 1, Non-Patent Document 2).

For example, accumulation of _TiO2 fine particles in _AgNO3 solution with dissolved Ag ions as metal ions is possible.

When a glass substrate is immersed in an _AgNO3 solution in which _TiO2 fine particles are dispersed and a laser is focused in the solution near the surface of the glass substrate, a reduction reaction occurs with the energy of the laser, and Ag cores are formed on the glass substrate. is formed, and a coating layer (accumulated layer) of _TiO2 particles is formed on the Ag core.

Japanese Patent No. 6964898

However, in the prior art such as Patent Document 1, it is necessary to disperse both the metal ions that are the material of the metal core and the solid fine particles that are the material of the coating layer in the same solution. When the solid fine particles dissolve in the solution or react with the solution to attach another substance, it is difficult to accumulate, and there are restrictions on the combination of the solid fine particles and the solution, and it is difficult to obtain a coating layer having desired properties. is difficult.

In addition, in the prior art such as Patent Document 1, the component of the coating layer may enter the core, or a gap may be formed between the core and the coating layer, and it is difficult to stably obtain the desired composite. was difficult.

Furthermore, when irradiating the laser, it was necessary to achieve both the conditions for forming the core and the conditions for collecting the fine particles around the core to form a coating layer, and there were restrictions on the irradiation conditions. In order to form the core, it is necessary to increase the laser output, but if the laser output is too high, the generated bubbles are too large, making it difficult to collect the fine particles densely.

Therefore, there is a demand for a method of manufacturing a composite that can stably produce a composite in which the boundary between the core and the coating layer is clearly separated and there is no gap between the core and the coating layer.

The gist of the present invention is as follows.
(1) providing a linear material comprising metals, ceramics, or combinations thereof;
immersing the linear material in a first dispersion in which a first solid nanomaterial is dispersed; and irradiating the linear material immersed in the first dispersion with a first laser beam. while moving the condensing portion of the first laser beam along the linear material to cover the surface of the linear material with the first covering layer composed of the first solid nanomaterial. forming at least in part to form a core composed of said linear material/ said first coating layer composite;
The first solid nanomaterial is composed of at least one selected from the group consisting of metal oxides, non-metal oxides, ceramics, metals, and resins.
A method for manufacturing a composite.
(2) The method for producing a composite according to (1) above, wherein there is no gap between the core and the first coating layer of the composite.
(3) The method for producing a composite according to (1) or (2) above, wherein the core of the composite does not contain the first solid nanomaterial.
(4) The above (1) to (3), wherein the first coating layer composed of the first solid nanomaterial is formed on the surface of the linear material concentrically with the linear material. A method for producing a composite according to any one of the above.
(5) The composite according to any one of (1) to (4) above, wherein the concentration of the first solid nanomaterial in the first dispersion is 0.01 to 3.0% by mass. manufacturing method.
(6) The method for producing a composite according to any one of (1) to (5) above, wherein the first solid nanomaterial has a diameter of 1 to 3000 nm.
(7) The method for producing a composite according to any one of (1) to (6) above, wherein the first laser light is near-infrared light.
(8) immersing the composite in a second dispersion in which a second solid nanomaterial is dispersed; and irradiating the composite immersed in the second dispersion with a second laser beam. and moving the condensing portion of the second laser beam along the composite to cover at least one surface of the first coating layer with the second coating layer composed of the second solid nanomaterial. forming into sections to form a composite having the core/first coating layer/second coating layer;
The second solid nanomaterial is composed of at least one selected from the group consisting of metal oxides, non-metal oxides, ceramics, metals, and resins.
A method for producing a composite according to any one of (1) to (7) above.
(9) preparing a substrate;
forming the linear material along the major surface of the substrate; and forming a first solid nanomaterial so as to cover the surface of the linear material between the substrate and the first The method for producing the composite according to any one of (1) to (8) above, comprising forming a coating layer of
(10) forming the linear material along the main surface of the substrate;
immersing at least one main surface of the substrate in a solution or dispersion containing at least one selected from the group consisting of metal ions, metal colloids, and metal complexes; and the substrate immersed in the solution or dispersion While irradiating the main surface of the laser light, moving the laser light condensing part along the surface of the substrate to form a linear metal on the substrate. A method of making the described composite.
(11) a linear material core comprising metal, ceramics, or a combination thereof, and a first coating layer composed of a first solid nanomaterial covering at least a portion of the surface of the linear material core; including
The first solid nanomaterial is composed of at least one selected from the group consisting of metal oxides, non-metal oxides, ceramics, metals, and resins,
there is no gap between the linear material core and the first coating layer;
Complex.
(12) The composite according to (11) above, which does not contain the first solid nanomaterial inside the linear material core.
(13) The composite according to (11) or (12) above, wherein the first solid nanomaterial has a diameter of 1 to 3000 nm.
(14) a substrate;
The linear material core arranged along the main surface of the substrate, and a first solid nanomaterial arranged so as to cover the surface of the linear material core between the substrate and the substrate. The composite according to any one of (11) to (13) above, further comprising a first coating layer.
(15) The composite according to any one of (11) to (14) above, comprising one or more coating layers composed of other solid nanomaterials on the surface of the first coating layer.
(16) providing a convex material comprising metals, ceramics, or combinations thereof;
immersing the convex material in a first dispersion in which a first solid nanomaterial is dispersed; and irradiating the convex material immersed in the first dispersion with a first laser beam. while moving the condensing portion of the first laser light along the convex material to form a localized portion composed of the first solid nanomaterial on at least a part of the surface of the convex material. forming a protective coating;
The first solid nanomaterial is composed of at least one selected from the group consisting of metal oxides, non-metal oxides, ceramics, metals, and resins.
A method for producing a topical coating.
(17) a topical coating composed of a first solid nanomaterial covering at least a portion of the surface of a convex material core comprising metal, ceramic, or a combination thereof;
The first solid nanomaterial is composed of at least one selected from the group consisting of metal oxides, non-metal oxides, ceramics, metals, and resins,
there is no gap between the convex material core and the first coating layer;
topical coating.

According to the present invention, a composite can be stably produced in which the boundary between the core containing metal, ceramics, or a combination thereof and the coating layer is clearly separated and there is no gap between the core and the coating layer. becomes possible.

FIG. 1 is a schematic diagram during formation of a first coating layer 12 around a linear material 10 . FIG. 2 is a cross-sectional view schematically showing this method when irradiation of the first laser beam 30 to the linear material 10 arranged along the main surface of the substrate 40 is started. FIG. 3 is a schematic cross-sectional view of the first coating layer 12 covering the surface of the linear material 10 between itself and the substrate 40 in the first dispersion liquid 20 . FIG. 4 is a schematic cross-sectional view showing a mode of laser irradiation from the substrate side toward a linear material. FIG. 5 is a schematic cross-sectional view showing a mode in which the ends of the linear material are held by the substrate and the laser is irradiated from the ends in parallel with the axial direction of the linear material. FIG. 6 is a schematic cross-sectional view showing a mode in which the linear material 10 is irradiated with the first laser beam 30 and bubbles 24 are generated around the linear material 10 . FIG. 7 shows that the surface tension gradient generated from the temperature distribution (temperature gradient) on the surface of the air bubbles 24 causes the convection indicated by the arrows in the first dispersion liquid 20 to generate air bubbles 24 around the linear material 10 . FIG. 2 is a schematic cross-sectional view showing a mode in which a first solid nanomaterial 22 is collected at a gas-liquid interface with a first dispersion liquid 20. FIG. FIG. 8 is a schematic cross-sectional view of the first covering layer 12 formed to cover the linear material 10 between the substrate 40 and the substrate 40 . FIG. 9 is a schematic cross-sectional view perpendicular to the longitudinal direction of an example of a composite formed by this method. FIG. 10 is a schematic cross-sectional view perpendicular to the longitudinal direction of another example of a composite formed by this method. FIG. 11 is a schematic cross-sectional view perpendicular to the longitudinal direction of another example of a composite formed by this method. FIG. 12 is a schematic cross-sectional view perpendicular to the longitudinal direction of another example of the composite formed by this method. FIG. 13 is a schematic cross-sectional view of a composite having a cavity 14 at the interface between a core 10 made of a linear material and a substrate 40. As shown in FIG. FIG. 14 is a schematic diagram showing a mode in which the inside of a cylindrical substrate such as a transparent tube made of glass is irradiated with a laser. FIG. 15 is a schematic diagram of a composite wiring formed on a curved substrate. FIG. 16 is a schematic cross-sectional view showing a mode in which the laser source 32 is split by a beam splitter 34 and a plurality of first laser beams 30 are irradiated in parallel. FIG. 17 is a schematic diagram of the configuration of a femtosecond laser. FIG. 18 is a scanning electron microscope (SEM) image of the appearance of the composite wiring of Ag core/SiO ₂ coating layer. FIG. 19 is a Y-direction cross-sectional SEM image of the composite wiring shown in FIG. FIG. 20 is a transmission electron microscope (TEM) image of the coating layer of FIG. FIG. 21 is an external SEM image of the formed Ag wiring. FIG. 22 is an appearance SEM image of a composite wiring of a composite coating layer of Ag core/SiO ₂ particles and ZnO nanowires. FIG. 23 is a cross-sectional TEM image of a composite wiring with a composite coating layer of Ag core/SiO ₂ particles and ZnO nanowires. FIG. 24 is a TEM image of the coating layer of FIG. FIG. 25 is a cross-sectional SEM image of the coating layer. FIG. 26 is a mapping photograph of Zn in the area of FIG. 25 by energy dispersive X-ray spectroscopy (EDX). FIG. 27 is an external SEM image of the formed Ag wiring 10 and composite wiring. FIG. 28 is a mapping photograph of Ti by EDX for the area of FIG. FIG. 29 is an external SEM image of composite wiring of Ag core/polystyrene coating layer. FIG. 30 is an external SEM image of wiring formed in a comparative example. FIG. 31 is a cross-sectional TEM image of wiring formed in a comparative example. FIG. 32 is an enlarged TEM image of the portion surrounded by a square in FIG. FIG. 33 is a cross-sectional SEM image of wiring formed on a substrate. FIG. 34 is a mapping photograph of Ag by EDX for the area of FIG. FIG. 35 is a mapping photograph of Ti by EDX for the area of FIG. FIG. 36 is an optical microscope image (FIG. 36(a)) and a fluorescence microscope observation image (FIG. 36(b)) of the composite wiring formed in Example. FIG. 37 is an SEM photograph of the composite wiring formed in Example and mapping images of Si, Ti, and Ag. FIG. 38 is an SEM photograph of the composite wiring formed in Example and mapping images of Ag and Ti. FIG. 39 is a schematic cross-sectional view of two adjacent linear materials each formed with a first coating layer of the same material. FIG. 40 is a schematic cross-sectional view of two adjacent linear materials each having a first coating layer made of a different material. FIG. 41 is a schematic cross-sectional view of two adjacent linear materials each formed with a first coating layer of a different material. FIG. 42 is a schematic external view showing a mode in which air bubbles are generated around the linear material on which the laser beam is focused, and the air bubbles 24 move in accordance with the movement of the light collecting portion along the linear material ( is a perspective view).

The present disclosure provides a linear material comprising metals, ceramics, or combinations thereof, immersing the linear material in a first dispersion in which a first solid nanomaterial is dispersed, and While irradiating the linear material immersed in the first dispersion liquid with the first laser beam, the condensing part of the first laser beam is moved along the linear material to obtain the first laser beam. A first coating layer composed of one solid nanomaterial is formed on at least a part of the surface of the linear material, and a composite of the core composed of the linear material and the first coating layer Manufacture of a composite, comprising forming a body, wherein the first solid nanomaterial is composed of at least one selected from the group consisting of metal oxides, non-metal oxides, ceramics, metals, and resins method.

As a result of intensive research, the present inventors have found that in the formation of a metal core/coating layer composite by laser irradiation in Patent Document 1, the metal core is formed by photochemical reaction of metal ions in the solution, The coating layer is formed by collecting solid nanomaterials by bubbles in the dispersion liquid generated by the thermal energy of the laser beam. and are formed in separate steps. The inventors also found that the core does not have to be composed only of metal, and that laser irradiation can form a coating layer around the core if the core is composed of materials including metals, ceramics, or combinations thereof. Found.

In this method, as schematically shown in FIGS. 1 to 3, a first solid nanomaterial 22 is dispersed in a first dispersion 20 containing a linear material containing metals, ceramics, or a combination thereof. (hereinafter also referred to as a linear material) 10 is immersed, and while irradiating the linear material 10 with the first laser beam 30, the condensing part of the first laser beam 30 is moved along the linear material 10. The core 10/second core 10 is moved to form a first coating layer 12 on at least a portion of the surface of the linear material 10, and the linear material 10 includes metal, ceramics, or a combination thereof. A composite of one covering layer 12 is formed. The composite can be of any shape and is preferably a linear composite wiring.

FIG. 1 is a schematic diagram during formation of a first coating layer 12 around a linear material 10 including metal, ceramics, or a combination thereof. As shown in FIG. 1, when the first laser beam 30 is irradiated and the condensing portion of the first laser beam 30 is moved along the linear material 10, The air bubbles collect the first solid nanomaterial 22 as indicated by the arrows to form the first coating layer 12 around the linear material 10 . The linear material 10 may be short as long as it has a length that allows it to move through the condensing portion of the laser beam 30 , for example, it may be dot-shaped and has a length that allows it to move through the condensing portion of the laser beam 30 . The length of the linear material 10 is preferably 1 μm or longer, more preferably 2 μm or longer, and even more preferably 3 μm or longer. FIG. 2 is a cross-sectional view schematically showing this method when irradiation of the first laser beam 30 to the linear material 10 arranged along the main surface of the substrate 40 is started. FIG. 3 is a schematic cross-sectional view of the first coating layer 12 covering the surface of the linear material 10 between itself and the substrate 40 in the first dispersion liquid 20 . The first coating layer 12 consists essentially of the first solid nanomaterial 22, although it may contain traces of a dispersing agent.

In this method, a linear material containing metal, ceramics, or a combination thereof is immersed in the first dispersion in which the first solid nanomaterial is dispersed, and then irradiated with laser light. . The irradiation direction of the first laser beam when forming the first coating layer is such that the linear material is heated by the first laser beam and bubbles are generated around the linear material serving as the core. It can be in any direction as long as it can cause convection.

As shown in FIGS. 1 to 3, a linear material arranged on the upper main surface of the substrate that transmits the first laser light may be irradiated from the substrate side, that is, from the bottom side. Alternatively, in FIGS. 1 to 3, laser irradiation may be performed from the side opposite to the substrate, that is, from the upper side. Alternatively, in FIGS. 1 to 3, the linear material may be irradiated with laser from a direction parallel or oblique to the main surface of the substrate. Alternatively, as schematically shown in FIG. 4, laser irradiation may be performed from the substrate side, that is, from the upper side toward a linear material arranged on the lower main surface of the substrate that transmits the first laser beam. good. Alternatively, as shown in FIG. 5, only the ends of the linear material 10 may be held on the substrate 40 and the linear material 10 placed in the first dispersion may be irradiated with the laser. Without using a substrate, the linear material may be fixed in the first dispersion liquid by applying optical tweezers or a magnetic field, and laser irradiation may be performed.

When irradiating the linear material from the side of the substrate through which the first laser beam is transmitted, the first laser beam does not pass through the first dispersion liquid and therefore is dispersed in the first dispersion liquid. It is less susceptible to the first solid nanomaterial that is in contact. When laser irradiation is directed toward the linear material from the opposite side of the substrate, light loss and scattering may occur due to the first solid nanomaterial dispersed in the first dispersion, but the first solid nanomaterial having a small diameter By using one solid nanomaterial, reducing the concentration of the first solid nanomaterial in the first dispersion, or the like, the linear material can be efficiently irradiated with the first laser beam. .

As illustrated in FIG. 6 , when the linear material 10 is irradiated with the first laser beam 30 , the linear material 10 is heated and air bubbles are formed around the linear material 10 in the first dispersion liquid 20 . 24 occurs. Air bubbles 24 are generated around the linear material 10 on which the laser beam 30 is focused, and the air bubbles 24 move as the condensing portion moves along the linear material 10 . FIG. 42 shows a mode in which air bubbles 24 are generated around the linear material 10 on which the laser beam 30 is focused, and the air bubbles 24 move in accordance with the movement of the condensing portion along the linear material 10. FIG. 2 shows an external schematic diagram (perspective view). The first solid nanomaterial is collected behind the bubble 24 as the bubble 24 moves. Although not bound by theory, in this method, a surface tension gradient is generated from the temperature distribution (temperature gradient) on the surfaces of the bubbles 24, and as indicated by the arrows in FIG. A convection occurs in the linear material 10 and the first solid nanomaterial 22 is collected at the gas-liquid interface between the air bubbles 24 around the linear material 10 and the first dispersion liquid 20 .

Since the first laser beam 30 is moving along the linear material 10, bubbles are generated around the linear material 10 irradiated with the first laser beam 30, but the movement causes the laser irradiation. When it stops, the bubble disappears. Since the first laser beam 30 is moving in this way, the first solid nanomaterial 22 is accumulated at the contact portion between the end of the bubble 24 and the linear material 10, and as shown in FIG. A first covering layer 12 is formed to cover the linear material 10 between the substrate 40 and the substrate 40 . No gap is formed at the interface between the linear material (core including metal, ceramics, or a combination thereof) 10 and the first coating layer 12 in the resulting composite. When the condensing portion of the first laser beam 30 is moved along the linear material 10, the interface between the linear material 10 and the first coating layer 12 is formed of the linear material 10 in close contact. A core/first coating layer composite is obtained. The moving speed of the condensing portion of the first laser beam 30 is preferably 10 to 2000 μm/sec, more preferably 20 to 1000 μm/sec, still more preferably 30 to 300 μm/sec. In this method, since the coating layer can be formed by such a mechanism, it is possible to achieve both integration of solid nanomaterials, stable formation of the coating layer, and fine patterning. It is possible to obtain composites with structures that are difficult to obtain with laser lithography.

The linear material is irradiated with the first laser beam, and the condensed portion of the first laser beam heats the linear material by irradiating the first laser beam so that the periphery of the linear material is heated. It may be in the linear material or in the vicinity of the linear material as long as air bubbles can be generated in the first dispersion and convection can be caused in the first dispersion.

In this method, since the first solid nanomaterial can be collected by the thermal energy of the first laser beam to form the first covering layer, the first coating layer can be formed even though the laser beam is used. The material for the covering layer is not limited to a photosensitive material, and the range of material selection for the first covering layer is extremely wide. According to this method, various materials can be integrated around the core as coating layers without being limited by material properties, and the material of the first coating layer can be conductive, insulating, semiconducting, magnetic, It can be a material having biocompatibility, antibacterial properties, and the like. According to this method, for example, even if a material such as SiO ₂ that easily transmits a laser is used as the first solid nanomaterial, it is possible to form the first coating layer with a low-power laser. Therefore, according to this method, it is possible to fabricate sensors and devices with various configurations, for example, a micro-sized LED array in which a layer of quantum dots is arranged between p-type and n-type semiconductor layers. can do.

In this method, the dispersion medium of the first dispersion liquid is a liquid, but the dispersion medium can disperse the first solid nanomaterial and does not cause the first solid nanomaterial to dissolve, react, deform, or change properties. There is no particular limitation if any. The dispersion medium of the first dispersion is, for example, water, a mixed liquid of water and ethanol, or a liquid obtained by redispersing a solid nanomaterial dispersed in an organic solvent such as toluene in a mixed liquid of alcohol and water. can be done. Therefore, according to the present method, the dispersion medium of the first dispersion must be a solution in which metal ions, metal colloids, metal complexes, etc. are dispersed, such as those used in the method of Patent Document 1, such as a silver nitrate solution. There is no Thus, according to the present method, the first solid nanomaterial is a material, such as zinc oxide, which could not be conventionally used for dissolving in a solution, such as a silver nitrate solution, used to disperse metal ions and the like. and other solid nanomaterials. The first dispersion may contain other components as long as they do not interfere with the irradiation of the laser beam, such as a dispersant used for dispersing the solid nanomaterial, which is soluble in the dispersion medium. .

The concentration of the first solid nanomaterial in the first dispersion is preferably 0.01-3.0% by mass. When the concentration of the first solid nanomaterial in the first dispersion is within the preferred range, the first coating layer can be formed more efficiently.

The viscosity of the first dispersion is preferably 1.0 mPa·s to 1.2 mPa·s. By setting the viscosity of the first dispersion to be within the preferred range, the concentration of the first solid nanomaterial is ensured, convection in the first dispersion is facilitated, and the first solid nanomaterial is dispersed. It can be made easier to collect.

The first solid nanomaterial is dispersible in the first dispersion, and the temperature at which the first dispersion is heated through the heating of the linear material by laser light irradiation, for example, 70 to 100 ° C. It can be a solid nanomaterial that can be collected by convection by air bubbles at a certain temperature without substantial deformation or alteration. Regarding the dispersibility in the first dispersion liquid, it is not necessary that the solid nanomaterials are uniformly distributed throughout the dispersion liquid, and it is sufficient that the solid nanomaterials are present in the vicinity of the light-collecting part of the laser. A portion of the solid nanomaterial may be precipitated. Moreover, the solid nanomaterial does not necessarily have to exist in the form of primary particles.

Examples of solid nanomaterials include nano-sized fine particles (nanoparticles), nanoclusters, nanocrystals, nanotubes, nanofibers, nanowires, nanorods, nanofilms, nanosheets, and combinations thereof.

The first solid nanomaterial preferably has a diameter of 1-3000 nm, more preferably 5-1000 nm, even more preferably 10-300 nm, still more preferably 15-100 nm. The diameter here means the average value of the maximum lengths in the major axis direction of ten randomly selected first solid nanomaterials when the first solid nanomaterials are observed with an electron microscope.

By having the preferred diameter of the first solid nanomaterial as primary particles or as aggregated particles, the first coating layer can be formed in a shorter time or thicker. The smaller the particle size of the first solid nanomaterial, the easier it is to collect with air bubbles, so the formation time of the first coating layer can be shortened or a thicker first coating layer can be obtained.

The first solid nanomaterial preferably has a density of 0.95-21.45 g/cm ³ , more preferably 1.1-6.0 g/cm ³ . The lower the density of the first solid nanomaterial, the easier it is to collect with air bubbles. For example, since resin particles such as polystyrene beads have a relatively low density, they are easily collected by air bubbles even if they have a large particle size.

The first solid nanomaterial is composed of at least one selected from the group consisting of metal oxides, non-metal oxides, ceramics, metals, and resins.

Examples of metal oxides include zinc oxide, titania, alumina, cobalt oxide, zirconia, ceria, molybdenum oxide, magnesium oxide, tungsten oxide, tin oxide, iron oxide, manganese oxide, cobalt oxide, nickel oxide, zirconate titanate. Lead, strontium titanate, lead titanate, lead zirconate, lead zirconate titanate, indium tin oxide and the like are included.

Examples of non-metal oxides include silica.

　Ceramics are non-metallic inorganic materials, and examples of ceramics include, for example, nitrides, carbides, borides, halides, diamonds, carbon, and quantum dots. Quantum dots are generally colloidal, nanoscale semiconductor crystals with unique optical, electrical, and magnetic properties that obey quantum mechanics. Examples of quantum dots also include PbS, CdS, and the like. Examples of carbon also include graphite, graphene, and the like.

Examples of nitrides include niobium nitride, titanium nitride, tantalum nitride, indium nitride, gallium nitride, indium nitride, gallium nitride, boron nitride, and aluminum nitride.

Examples of carbides include chromium carbide, boron carbide, vanadium carbide, tungsten carbide, molybdenum carbide, titanium carbide, zirconium carbide, niobium carbide, tantalum carbide, silicon carbide, and the like.

Examples of borides include boron, aluminum boride, chromium boride, titanium boride, molybdenum boride, tungsten boride, vanadium boride, zirconium boride, magnesium boride, niobium boride, tantalum boride, and the like. included.

Examples of halides include cerium fluoride and the like. Other first solid nanomaterials include phosphate compounds such as hydroxyapatite, Li ₂ SP ₂ S ₅ , LiCoO ₂ , xLi ₂ O-BPO ₄ (0.5≦x≦1.5), and the like. Examples of lithium-based compounds include compound semiconductors using group II elements and group VI elements.

Examples of metals include Ag, Cu, Au, Pt, Pd, Ni, Pb, Sn, alloys, and the like.

Examples of resins include polystyrene-based resins, polyolefin-based resins, polyacrylic-based resins, polycarbonate-based resins, polyester-based resins, polyvinyl chloride-based resins, polyamide-based resins, and the like.

The first solid nanomaterials include highly transparent coating film-forming materials, solid electrolyte fuel cell electrolyte materials, light-emitting diodes and photoresponsive semiconductor materials, resistor film-forming materials, metal magnetic powder materials, superconducting materials, and piezoelectric ceramics. Solid nanomaterials such as thick film materials, dielectric film materials, fine particle binding materials, and other functional materials may also be used.

The first solid nanomaterial includes particles in which solid particles of different materials are mixed, composite particles in which particles with different shapes such as nanoparticles and nanowires are mixed, composites of solid nanomaterials, solid nanomaterials composed of multiple components, Particles in which solid fine particles such as gold-supported titanium oxide (Au/TiO ₂ ) are supported by solid fine particles, and particles having a composite structure such as a core-shell structure may be used.

According to this method, a fine composite can be formed. The width of the composite can be adjusted by the laser irradiation conditions, and is preferably 1 to 20 μm, more preferably 2 to 10 μm. The width of the composite is the maximum length of the cross-section perpendicular to the longitudinal direction of the composite. The line width of the composite arranged along the main surface of the substrate is the length in the direction perpendicular to the longitudinal direction of the composite and parallel to the main surface of the substrate. The composite formed by the method may be a composite wire.

The thickness of the composite formed by this method can be adjusted by the laser irradiation conditions, and is preferably 100 nm to 10 μm. The thickness and width of the linear material (core comprising metals, ceramics, or combinations thereof) is preferably 1-10 μm. The thickness of the first coating layer is preferably between 100 nm and 10 μm. The first coating layer can cover part or all of the surface of the linear material in the width direction, and preferably covers the entire surface of the linear material in the width direction. The linear material becomes the core as it is, but the larger the thickness and width of the linear material, the easier it is to collect the solid nanomaterials, and the time for forming the first coating layer can be shortened, or the thicker first coating layer can be formed. can be obtained. When the thickness and width of the linear material are large enough to be surrounded by air bubbles, the air bubbles adhere to the linear material and stabilize it, so that the first coating layer can be formed more stably. If the thickness and width of the linear material are too large, the air bubbles cannot envelop the linear material, and particles tend to gather only at the edges of the linear material. If the thickness and width of the linear material are too small, air bubbles move easily, making it difficult to stably form the first coating layer. Therefore, the diameter of the bubble is preferably about 1.1 to 4.0 times, more preferably about 2.0 to 3.5 times, the thickness and width of the linear material. The width of the composite and core is the length of the chord forming the maximum length in a cross section perpendicular to the longitudinal direction of the composite and core, and the thickness of the composite and core is perpendicular to said chord. Maximum length in a direction. The width of the composite and the core arranged along the main surface of the substrate is the maximum length in the direction perpendicular to the longitudinal direction of the composite and the core and parallel to the main surface of the substrate, The thickness of the composite and the core arranged in the same direction is the maximum length of the composite in the direction perpendicular to the longitudinal direction of the composite and the major surface of the substrate. The thickness of the first coating layer is the average value of the thickness in the cross section perpendicular to the longitudinal direction of the composite.

9 and 10 show schematic cross-sectional views perpendicular to the longitudinal direction of an example of the composite formed by this method. As shown in FIG. 5, when a laser beam is emitted from the end of the linear material in a direction parallel to the axial direction of the linear material and the condensing part is moved along the linear material, the linear material Since the laser is irradiated on the outer periphery of the linear material, the first solid nanomaterial can gather around the entire periphery of the linear material to form the first coating layer. A composite having a cross-sectional shape of the shape can be obtained. A first coating layer with a circular cross section is formed around the linear material with a circular cross section. A first covering layer with a rectangular cross section is formed around the linear material with a rectangular cross section. In FIG. 5, if a laser beam is irradiated perpendicularly or obliquely to the axial direction of the linear material, a difference in energy due to the laser irradiation occurs at the periphery of the linear material. They are not formed in a concentric shape, but are formed with a deviation.

11 and 12 show schematic cross-sectional views of another example of the composite formed by this method in the direction perpendicular to the longitudinal direction. As shown in FIGS. 1 to 3, while irradiating a laser from the transparent substrate side toward a linear material placed on the main surface of the substrate, moving the condensing part along the linear material, As schematically shown in FIGS. 6 to 8, the first solid nanomaterials can gather on the surface of the linear material to form the first coating layer, so that as schematically shown in FIGS. 11 and 12, A composite having a substantially concentric cross-sectional shape can be obtained. A first coating layer having a semicircular cross section is formed around the linear material having a semicircular cross section. A first covering layer with a rectangular cross section is formed around the linear material with a rectangular cross section.

The linear material used according to the present method preferably has a substantially circular, substantially elliptical, substantially rectangular, substantially semi-elliptical, or substantially semi-circular cross-section, more preferably substantially circular or substantially semi-circular. It has a circular cross section. Since the core made of the linear material has a substantially circular or semicircular cross-sectional shape, when the linear material is irradiated with a laser beam to generate bubbles, It becomes easier to collect solid nanomaterials in

In the composite formed by this method, the first coating layer preferably has a substantially circular, substantially elliptical, substantially rectangular, substantially semi-elliptical, or substantially semi-circular cross-section, more preferably It has a substantially circular or semicircular cross section. The first coating layer preferably has a cross-section that is substantially similar to the linear material.

The composite formed by this method includes two or more linear materials and may include a first coating layer composed of one or more materials. A first coating layer can be formed for each adjacent linear material. FIG. 39 shows a schematic cross-sectional view of two adjacent linear materials 10 each having the first covering layer 12 of the same material formed thereon. The interval between adjacent linear materials is not particularly limited, and when the first coating layers formed on two or more linear materials are brought into contact with each other, the interval between adjacent linear materials may be narrowed. In the case where the first coating layers formed on the above linear materials are not in contact with each other, the distance between adjacent linear materials should be widened.

A first covering layer of a different material can be formed for each adjacent linear material. FIG. 40 and FIG. 41 show schematic cross-sectional views of two adjacent

linear materials

101 and 102 formed with first coating layers 121 and 122 of different materials, respectively. FIG. 40 shows an example in which the first coating layer 121 is formed on the linear material 101 and then the first coating layer 122 is formed on the linear material 102 . FIG. 41 shows an example in which the first covering layer 122 is formed on the linear material 102 and then the first covering layer 121 is formed on the linear material 101 .

In this method, since the temperature of the linear material increases due to the laser irradiation, a part of the surface of the substrate in contact with the linear material may be melted. A cavity 14 may be formed in at least a part of the interface between.

The substrate used in this method is not particularly limited as long as it can form a linear material and does not dissolve or react with the dispersion medium for dispersing the first solid nanomaterial. calcium chloride and the like. The substrate may be coated with another material, for example a transparent conductive film such as indium tin oxide (ITO).

When a linear material is arranged along the main surface of the substrate, the temperature of the linear material increases due to the laser irradiation. And the substrate and bonding strength are improved. Further, since the substrate is in contact with the linear material heated by laser irradiation, the substrate preferably has a melting point higher than the temperature of the linear material to be heated in order to avoid damaging the substrate. For example, _SiO2 glass has a high softening point, so when used as a substrate, the surface in contact with a linear material is difficult to melt. The surface in contact with is easy to melt.

The shape of the substrate used in this method is not particularly limited as long as it has a structure that allows a linear material immersed in a dispersion liquid to be irradiated with a laser beam. For example, the composite wiring 100 can be formed inside a tubular substrate 40 such as a transparent tube made of glass as shown in FIG. 14 or on a substrate 40 having a curved main surface as shown in FIG.

According to this method, it is possible to obtain a composite having no gaps at the interface between the core containing metal, ceramics, or a combination thereof and the first coating layer. Since there is no gap at the interface between the core and the first coating layer, it is possible to obtain a composite in which the interface between the core and the first coating layer is in intimate contact. The presence or absence of interfacial gaps is a scanning electron microscope image (SEM image) or a transmission electron microscope image of the FIB processed surface of the cross section perpendicular to the longitudinal direction of the composite in a viewing range that includes the entire cross section of the composite. It is determined by observing with (TEM image).

If the laser beam continues to irradiate the same part of the linear material without moving the laser beam, air bubbles are generated around the linear material and the solid nanomaterials are collected, but the air bubbles continue to be generated in the same position. Therefore, gaps due to air bubbles are formed at the interface between the linear material and the first coating layer.

In this method, while the linear material is irradiated with the first laser beam, the focusing portion of the first laser beam is moved along the linear material. When the solid nanomaterials are gathering, no additional air bubbles are generated around the linear material on which the first solid nanomaterial is gathering, so a composite with no gaps at the interface can be formed.

The first solid nanomaterials forming the first coating layer are strongly agglomerated with each other. The first coating layer and the core are also strongly bonded. The first coating layer can be maintained around the core even if the substrate forming the composite is fractured. Without wishing to be bound by theory, it is believed that the first solid nanomaterials are aggregated together by van der Waals forces and liquid bridge forces.

The first solid nanomaterial is collected from the first dispersion by the action of the surface of the bubbles, but since the surface temperature of the bubbles rises only to a temperature similar to the boiling point of the first dispersion, the first solid nanomaterial is The temperature of solid nanomaterials rises only up to about 70-100°C. Therefore, the first solid nanomaterial constituting the first coating layer is not substantially sintered or melted, and the shape and properties of the first solid nanomaterial before forming the first coating layer are similar to those of the first solid nanomaterial. substantially maintained. Therefore, for example, when quantum dots having a core-shell structure are used as the first solid nanomaterial, the first coating layer can be formed while maintaining the properties of the quantum dots before coating. Since this method does not involve a sintering process, it is also possible to form the first coating layer composed of a high-melting-point material such as tantalum carbide, which is difficult to sinter.

According to the method, composites can be obtained that do not contain the first solid nanomaterial inside a core that contains metals, ceramics, or combinations thereof. In the method of Patent Document 1, in which the formation of the metal core and the formation of the coating layer are performed simultaneously, the solid nanomaterial constituting the coating layer may enter the interior of the core, which may affect the properties of the core. For example, if you want to obtain a metal core with low resistivity, even if you try to form a metal core composed _only of Ag, which has excellent conductivity, solid nanomaterials such as insulator SiO enter the inside of the metal core. , the conductivity of the metal core decreases. According to this method, a composite composed of the core and the first coating layer can be formed without affecting the properties of the core. A composite can be formed consisting of one coating layer. The resistivity of the metal core in the composite formed by this method is preferably between 1×10 ⁻⁸ Ω·m and 10×10 ⁻⁸ Ω·m. According to this method, it is also possible to form a core composed only of ceramics or a composite core of metal and ceramics, and to form a coating layer on the surface of the composite core.

The wavelength of the first laser light is not particularly limited as long as it is a wavelength at which the linear material used in this method is absorbed and heated. The wavelength of the first laser light can be selected according to the absorption wavelength of the linear material. The wavelength of the first laser light is preferably a wavelength at which the linear material has an absorption coefficient of 4000/cm or more.

The wavelength of the first laser light is preferably 200 nm to 2000 nm. The first laser light is more preferably near-infrared light with a wavelength of 780 nm to 2500 nm. When the linear material is a metal, the first laser beam is preferable because the wavelength of 200 nm to 1000 nm is easily absorbed. When the linear material is ceramics, the first laser light is preferable because the wavelength of 200 nm to 700 nm is easily absorbed. The size of the bubbles to be generated can be controlled by controlling the irradiation amount and intensity of the first laser light.

The first laser light can be continuous wave (CW) laser light or pulsed laser light. In the case of pulsed laser light, the repetition frequency (number of pulses/second) is preferably 1 MHz or higher, more preferably 10 MHz or higher, and still more preferably 100 MHz or higher, in order to efficiently heat a linear material and form bubbles. is.

Examples of continuous wave (CW) lasers include general semiconductor lasers (various wavelengths from visible to infrared), Yb fiber lasers (wavelength around 1030 nm), YAG lasers (around 1064 nm), and the like. The average power of the CW laser is preferably between 10 and 1000 mW. The condensed diameter of the CW laser beam is preferably 0.1 to 20 μm.

The pulsed laser light may be ultrashort pulsed laser light. Ultrashort pulse laser light is a few femtoseconds (1 femtosecond is 1×10 ⁻¹⁵ seconds, also denoted as fs) to several hundred picoseconds (1 picosecond is 1×10 ⁻¹² seconds, also denoted as ps ) is a pulsed laser with a pulse width of The average output of the ultrashort pulse laser light is preferably 10 mW or more. The focused diameter of the ultrashort pulse laser beam is preferably 20 μm or less. The repetition frequency of the ultrashort pulse laser light is preferably 1 Hz to 500 MHz. The fluence (energy applied to a unit area) of the wavelength of the pulse laser light as the first laser is preferably 0.01 mJ/cm ² to 10 mJ/cm ² .

In this method, as shown in FIG. 16, a plurality of composites can be simultaneously formed by splitting the laser source 32 with a beam splitter 34 and irradiating a plurality of first laser beams 30 in parallel.

The method for producing the present composite preferably comprises: immersing the composite in a second dispersion in which a second solid nanomaterial is dispersed; While irradiating the laser light of 2, the condensing part of the second laser light is moved along the composite, so that the second coating layer composed of the second solid nanomaterial is covered with the first laser light. forming on at least a portion of a surface of a coating layer of to form a composite having said core/ said first coating layer/ said second coating layer, said second solid nanomaterial comprising: It is composed of at least one selected from the group consisting of metal oxides, non-metal oxides, ceramics, metals and resins.

The second solid nanomaterial may be the same as or different from the first solid nanomaterial, and may be selected according to the function of the second coating layer. The material, thickness, etc. of the second coating layer may be the same as or different from the material, thickness, etc. of the first coating layer, and may be selected according to the function of the second coating layer. The medium of the second dispersion may be the same as or different from the medium of the first dispersion, and may be a medium in which the second solid nanomaterial is easily dispersed. The second laser beam may be the same as or different from the first laser beam, and may be selected according to the material of the second coating layer and the like.

Even when forming the second coating layer on the first coating layer, a multilayer coating layer in which the coating layers are in close contact with each other without forming a gap at the interface between the first coating layer and the second coating layer can be obtained. The same applies to the case of obtaining three or more coating layers.

The method preferably comprises preparing a substrate, forming a linear material along a major surface of the substrate, and forming a first Forming a first coating layer composed of solid nanomaterials. As schematically illustrated in FIGS. 3, 8, and 11 to 13, in a cross section perpendicular to the axial direction of the linear material, preferably the surface of the core is the substrate and the first coating layer. covered.

In this method, the metal, ceramics, or combination thereof contained in the linear material is not particularly limited as long as it is a material that is heated by absorbing the first laser light, and commercially available metals, ceramics, or , or metals, ceramics, or combinations thereof made by any desired method. Materials including metals, ceramics, or combinations thereof include, for example, silver (Ag), indium tin oxide (ITO), glass containing dispersed metal particles, or combinations thereof. For materials including metals, ceramics, or combinations thereof, a first laser light having a wavelength that can be absorbed and heated may be used, and the wavelength of the first laser light is matched to the wavelength of the first laser light that is absorbed and heated. Materials including metals, ceramics, or combinations thereof may be used. The linear material preferably includes metal, ceramics containing metallic elements, or combinations thereof. The linear shape is not particularly limited. , and may be a three-dimensional shape.

The metal contained in the linear material is not particularly limited as long as it can be heated by absorbing the first laser beam and does not react with the first dispersion liquid, and has the properties required for the core of the composite. selected accordingly. The metals contained in the linear material can be metals, alloys, or intermetallics. The metal contained in the linear material is preferably composed of at least one selected from the group consisting of Ag, Cu, Au, Pt, Pd, Ni, Pb, and Sn, or an alloy containing them.

The ceramics contained in the linear material is not particularly limited as long as it can be heated by absorbing the first laser beam and does not react with the first dispersion liquid, and has the properties required for the core of the composite. selected accordingly. The ceramics contained in the linear material can be ceramics containing metallic elements, ceramics containing non-metallic elements, or a combination thereof, preferably ceramics containing metallic elements. The ceramics contained in the linear material are preferably indium tin oxide (ITO), fluorinated tin oxide ₍ FTO), _Si3N4 , SiC, _Al2O3 _, Si, _ZrO2 , _Ag2O , Cu ₂ O, and at least one selected from the group consisting of carbon or a combination thereof, more preferably indium tin oxide (ITO), fluorine-added tin oxide (FTO), Al ₂ O ₃ , ZrO ₂ , Ag ₂ O and Cu ₂ O or at least one selected from the group consisting of Cu 2 O or a combination thereof.

When the composite core is made of metal, the metal core preferably has a resistivity of 1×10 ⁻⁸ Ω·m to 10×10 ⁻⁸ Ω·m. When the coating layer of the composite is made of an insulator, the coating layer preferably has a resistivity of 1 MΩ·m or more.

The method of forming the linear material is not particularly limited, and may be formed by laser irradiation, screen printing, lithography, plating, or the like. For example, Ag nano-ink may be applied onto a polyimide film substrate by spin coating and irradiated with a laser to form a linear material composed of Ag.

A linear material may be formed by laser irradiation. An example of formation by laser irradiation is to move the light collecting part while irradiating a laser so as to focus light in a mixed solution of water, ethanol, etc. containing metal ions. It can be reduced to deposit linear metal. In the case of Ag, when a laser beam is irradiated so as to focus light in a mixed solution of water, ethanol, etc. containing silver nitrate, and the light-collecting portion is moved, the Ag ions in the solution are reduced by the light energy of the laser and turned into Ag. Structured linear metal can be deposited. Similarly for Cu and Au, Cu ions and/or Au ions can be reduced by laser light energy to form Cu or Au wiring on the substrate. Composite linear materials can also be obtained by mixing ceramics such as SiO ₂ in addition to water and ethanol containing metal ions to the mixed solution.

When forming a linear material by laser irradiation, the laser for forming the linear material and the first laser for forming the first coating layer may be the same or different. Preferably, the laser for forming the linear material is a laser capable of obtaining a photoreduction action, and the first laser for forming the first coating layer is suitable for heating the linear material. Also, longer wavelength lasers are used. For example, a linear material may be formed using an inexpensive laser such as an ultraviolet laser, and the first coating layer may be formed using a near-infrared laser.

In this method, preferably, forming the linear material along the major surface of the substrate includes at least one major surface of the substrate being at least one selected from the group consisting of metal ions, metal colloids, and metal complexes. The substrate is immersed in a solution or dispersion containing one species, and while irradiating the main surface of the substrate immersed in the solution or dispersion with a laser beam, the laser beam condensing part is moved along the surface of the substrate. forming said line of material thereon.

A solution or dispersion containing at least one selected from the group consisting of metal ions, metal colloids, and metal complexes is a solution or dispersion for forming a metal-containing material by irradiating with a laser to deposit a metal. be. The laser beam is preferably an ultraviolet laser beam that provides a photoreduction effect.

Metals contained in metal ions, metal colloids, and metal complexes are preferably metals that do not react with water and high-temperature steam when water is selected as the solvent, such as silver, copper, nickel, lead, tin, platinum and metals. Selected from the group consisting of gold. Even in the case of metals that react with water or high-temperature steam (for example, metals with a high ionization tendency such as potassium, magnesium, aluminum, zinc, and iron), it is possible to select a preferable metal by appropriately selecting a solvent. It is possible.

When the metal is present as ions in the solution or dispersion, the metal ions are for example Ag ⁺ , Cu ⁺ , Cu ²⁺ , Ni ²⁺ , Sn ²⁺ , Sn ³⁺ , Sn ⁴⁺ , Pb ²⁺ , Pt ²⁺ , Au ⁺ , Au3 ⁺ , and the like. The counterion of the metal salt is selected from the group consisting of nitrate, sulfate, carboxylate, cyanide, sulfonate, borate, halide, carbonate, phosphate and perchlorate. is preferred.

Examples of metals that exist as colloids in solutions or dispersions include silver colloids, copper colloids, and nickel colloids. Examples of the case where the metal exists as a complex in a solution or dispersion include a case in which a metal atom is coordinated with a ligand to facilitate dispersion and dissolution in a solvent.

Examples of silver complexes include silver docosanoate, silver chloro[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]silver, silver (II) pyridine-2-carboxylate, and silver sulfadiazine. can be mentioned. Examples of copper complexes include copper(I) acetate, bis(1,3-propanediamine)copper(II) dichloride, cupric acetylacetonate, bis(8-quinolinolato)copper(II), and the like. can be done. Examples of gold complexes include tetrachloroaurate(III) acid tetrahydrate, (dimethylsulfide)gold(I) chloride, chloro[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene ] Gold (I) and the like can be mentioned. Examples of lead complexes include lead tetraacetate and lead (II) acetate. Furthermore, it may be a product containing a metal complex such as silver nanoink or copper nanoink.

The concentration of the metal in the solution or dispersion is not particularly limited, but is preferably 0.1% by mass or more. When the concentration of the metal is 0.1% by mass or more, the thickness of the linear material formed by laser light irradiation can be increased. Although the upper limit of the metal concentration in the solution or dispersion is not particularly limited, it may be 3.0% by mass or less.

The present disclosure also provides a linear material core comprising metals, ceramics, or combinations thereof, and a first nanomaterial comprising a first solid nanomaterial covering at least a portion of the surface of the linear material core. The first solid nanomaterial is composed of at least one selected from the group consisting of metal oxides, non-metal oxides, ceramics, metals, and resins, and comprises the linear material core and the The target is a composite having no gap between it and the first coating layer.

The composite of the present disclosure preferably does not contain the first solid nanomaterial inside the linear material core.

In the composite of the present disclosure, the first solid nanomaterial constituting the first coating layer preferably has a diameter of 1-3000 nm.

The composite of the present disclosure preferably includes a substrate, the linear material cores arranged along the main surface of the substrate, and the surfaces of the linear material cores arranged so as to cover the surface between the substrate and the substrate. and a first coating layer composed of a first solid nanomaterial. As schematically illustrated in FIGS. 3, 8, and 11 to 13, in a cross section perpendicular to the axial direction of the linear material, preferably, the surface of the material core is the substrate and the first coating layer. covered with

Preferably, the linear material core of the composite of the present disclosure has a substantially semi-circular cross-section. The closer the cross section is to a semicircular shape, the easier it is to collect the solid nanomaterials, and the shorter the time to form the coating layer.

Preferably, the linear material core and coating layer of the composite of the present disclosure have cross sections of similar shapes to each other.

The composite of the present disclosure preferably includes one or more coating layers composed of other solid nanomaterials on the surface of the first coating layer. The composite of the present disclosure can comprise a second coating layer composed of a second solid nanomaterial overlying the surface of the first coating layer. The composite of the present disclosure can further comprise a third coating layer composed of a third solid nanomaterial overlying the surface of the second coating layer; A plurality of coating layers can be provided such as a coating layer of . The solid nanomaterials constituting each coating layer may be different from each other or the same, but preferably different from each other. Due to the multi-layered structure of such a coating layer, the composite of the present disclosure can comprise a coating layer such as, for example, an insulating layer, a semiconductor layer, or a layer in which different semiconductors are joined to form a pn junction. .

For other configurations related to the composite of the present disclosure, the configuration related to the composite described in the method for manufacturing the composite described above is applied.

The present disclosure also provides a convex material comprising metals, ceramics, or combinations thereof, immersing the convex material in a first dispersion in which a first solid nanomaterial is dispersed; and while irradiating the convex material immersed in the first dispersion liquid with the first laser light, moving the condensing part of the first laser light along the convex material, forming a localized coating of said first solid nanomaterial on at least a portion of a surface of a convex material, said first solid nanomaterial being a metal oxide, a non-metal oxide; The present invention is directed to a method for producing a topical coating composed of at least one selected from the group consisting of materials, ceramics, metals, and resins.

The shape of the convex material (hereinafter also referred to as convex material) containing metal, ceramics, or a combination thereof (hereinafter also referred to as convex material) may be any shape having convex portions, and may be linear, dotted, or irregular. As in the case of irradiating the linear material with the first laser beam described above, when the convex material is irradiated with the first laser beam and the condensing part is moved, the bubbles move and move the first laser beam. of solid nanomaterials can be collected behind the bubbles to form a first coating layer.

The thickness of the localized coating formed by this method is preferably 100 nm to 10 μm. The thickness and diameter of the protrusions are preferably 1 to 10 μm. The diameter is equivalent circle diameter. The convex material in the method of making the topical coating can be the same as the linear material described above.

For other configurations related to the method for producing the topical coating, the configurations described in the method for producing the composite described above are applied.

The present disclosure also provides a topical coating composed of a first solid nanomaterial covering at least a portion of a surface of a convex material core comprising metals, ceramics, or combinations thereof, wherein said first The solid nanomaterial is composed of at least one selected from the group consisting of metal oxides, non-metal oxides, ceramics, metals, and resins, and is between the convex material core and the first coating layer It is intended for topical coatings without gaps in the

The thickness of this topical coating is preferably between 100 nm and 10 μm. The thickness and diameter of the convex material core is preferably between 1 and 10 μm. The diameter is equivalent circle diameter. The material of the convex material core can be the same as the linear material described above. The shape of the convex material core (hereinafter also referred to as convex material core) containing metal, ceramics, or a combination thereof (hereinafter also referred to as convex material core) may be any shape having a convex portion, and may be linear, dotted, or irregular. .

For other configurations regarding this topical coating, the configurations described in the composite above apply.

(Example 1)
(Formation of linear material)
In a brown bottle, 6 mL of pure water and 10 mL of ethanol were put, and 4 mL of a silver nitrate solution (1 mol/L, Junsei Chemical Co., Ltd.) was added and stirred. The solution was transferred from the brown bottle to a Teflon (registered trademark) holder, and a cover glass having a thickness of 0.15 mm as the substrate was placed on the holder so that one main surface of the substrate was in direct contact with the solution in the holder. .

Next, using a femtosecond laser (C-Fiber 780, Menlo Systems Ltd.) having the configuration shown in FIG. Irradiation was performed under the conditions of a repetition frequency of 100 MHz, a pulse width of 127 fs, an average laser output of 40 mW, and a focused diameter (theoretical value) of 2 μm.

By moving the holder horizontally at a scanning speed of 30 μm/sec, a linear metal made of Ag was continuously formed on the substrate surface in the scanning direction. The line width of the formed metal wire was 3.5 to 4.0 μm, and the thickness was 2 μm.

(Formation of first coating layer)
A solution of 300 μL of water and 183 μL of ethanol was mixed with 17 μL of SiO ₂ nanoparticle dispersion (Sigma-aldrich, LUDOX, TM-50, particle size (diameter) 22 nm, concentration 50% by mass), and the SiO concentration was ₂ . A 0.5% by weight _SiO2 particle dispersion was prepared.

The prepared _SiO2 particle dispersion is transferred to a Teflon holder, and as schematically shown in FIG. 4, the linear metal formed on the substrate is in direct contact with the _SiO2 particle dispersion in the holder. I put it on the holder so that I could do it. A femtosecond laser (C-Fiber780, MenloSystems Ltd.) having the configuration shown in FIG. While irradiating at 40 mW and a condensed diameter (theoretical value) of 2 μm, the laser condensing part was moved at 300 μm / sec along the linear metal, and SiO A first coating layer of _two particles was formed to form a composite wiring of Ag core/SiO ₂ coating layer.

FIG. 18 shows an appearance SEM image of a composite wiring 100 having a first coating layer composed of SiO ₂ particles around an Ag core, that is, a composite wiring of Ag core/SiO ₂ coating layer. The line width of the composite wiring increased by the amount corresponding to the formation of the first coating layer, and the line width of the formed composite wiring was 10 μm and the thickness was 3.6 μm.

A carbon protective film was attached to the formed composite wiring, and a cross section processed with a focused ion beam (FIB) was observed under a microscope. FIG. 19 shows a Y-direction cross-sectional SEM image (SEM image of the FIB-processed surface) of the composite wiring shown in FIG. A SiO ₂ coating layer 12 having a thickness of about 1.5 μm, which is a first coating layer composed of SiO ₂ particles, was densely formed around an approximately semicircular Ag core 10 having a diameter of 4 μm. No gap was found at the interface between the Ag core and the _SiO2 coating layer. The interface between the Ag core and the _SiO2 coating layer was clearly formed, and no _SiO2 particles were found inside the Ag core. A cavity 14 was found at the interface between the Ag core 10 and the substrate 40 .

FIG. 20 shows a TEM image of the coating layer of FIG. Although the SiO ₂ particles constituting the SiO ₂ coating layer were densely packed, they were not melted and maintained the diameter of the SiO ₂ particles before the accumulation.

The resistivity of the fabricated composite wiring with Ag core/SiO ₂ coating layer with a length of 5 mm was measured. The resistivity of the composite wiring measured by removing the coating layer only at both ends to expose the Ag core was 6.7×10 ⁻⁸ Ω·m. When the resistivity between both ends of the Ag/SiO ₂ composite wiring of the same length covered with the SiO ₂ coating layer up to both ends was measured, it was 50 MΩ or more with a length of 5 mm, and insulation was confirmed.

(Example 2)
As in Example 1, a linear material to be Ag cores was formed on a cover glass. FIG. 21 shows an appearance SEM image of the formed Ag wiring.

In a solution of 168 μL of water and 300 μL of ethanol, 17 μL of SiO ₂ nanoparticle dispersion (Sigma-Aldrich, LUDOX, TM-50, particle size (diameter) 22 nm, concentration 50% by weight) and 84 mg of ZnO nanowire powder (Sigma-Aldrich). , 773980, length 300 nm, diameter 50 nm, powder) were mixed to prepare a dispersion of _SiO2 nanoparticles and ZnO nanowires with a _SiO2 concentration of 4.65 wt% and a ZnO concentration of 16.4 wt%. .

A substrate on which an Ag wiring serving as a core was formed was prepared in the same manner as in Example 1, except that the average laser output was 30 mW and the laser focusing portion was moved along the linear material at 50 μm/sec. It was immersed in a ZnO particle dispersion and irradiated with a laser to form a composite wiring of a composite coating layer of Ag core/SiO ₂ particles and ZnO nanowires.

FIG. 22 shows an appearance SEM image of a composite wiring of a composite coating layer of Ag core/SiO ₂ particles and ZnO nanowires. The composite wiring thus formed had a line width of 4.5 to 9.1 μm and a thickness of 2.9 μm.

As in Example 1, the cross-sectional shape of the formed composite wiring was observed under a microscope. FIG. 23 shows a cross-sectional TEM image of the composite wiring. A first covering layer 12 of a composite of SiO ₂ nanoparticles and ZnO nanowires with a thickness of about 1.2 μm was densely formed around an approximately semicircular Ag core 10 with a diameter of 4.62 μm. No gap was observed at the interface between the Ag core and the composite coating layer. The interface between the Ag core and the composite coating layer was clearly formed, and SiO ₂ and ZnO were not found inside the Ag core.

FIG. 24 shows a TEM image of the first coating layer 12 of FIG. _SiO2 particles and ZnO nanowires were densely accumulated in the coating layer. FIG. 25 shows a cross-sectional SEM image of the coating layer, and FIG. 26 shows a mapping photograph of Zn in the area of FIG. 25 by energy dispersive X-ray analysis (EDX). ZnO nanowires are shown in white areas surrounded by squares in FIG. 25, and it was found from the mapping photograph of Zn that the ZnO nanowires are dispersed in the coating layer.

(Example 3)
As in Example 1, a linear material to be Ag cores was formed on a cover glass.

A solution of 204 μL of water and 279 μL of ethanol was mixed with 17 μL of TiO ₂ nanoparticle dispersion (Sigma _- Aldrich, 700347, particle size (diameter) <150 nm, concentration 33-37 wt%) to give a TiO concentration of 1.7. A mass % TiO ₂ particle dispersion was prepared.

In the same manner as in Example 1, the substrate on which the Ag wiring serving as the core was formed was immersed in the prepared TiO ₂ particle dispersion and irradiated with a laser to form an Ag core/TiO ₂ coating layer with a line width of 4.6 μm. Composite wiring was formed.

As in Example 1, the cross-sectional shape of the formed composite wiring was observed under a microscope. A TiO ₂ coating layer 12, which is a first coating layer composed of TiO ₂ particles, was densely formed around the Ag core 10 having a substantially semicircular shape. No gap was found at the interface between the Ag core and the _TiO2 coating layer. The interface between the Ag core and the _TiO2 coating layer was clearly formed, and no _TiO2 particles were found inside the Ag core.

FIG. 27 shows an appearance SEM image of the formed Ag wiring 10 and composite wiring 100 . FIG. 28 shows a mapping photograph of Ti measured by EDX in the area of FIG. It was found that Ti was present throughout the composite wiring.

(Example 4)
As in Example 1, a linear material to be Ag cores was formed on a cover glass.

A solution of 68 μL of water and 172 μL of ethanol was mixed with 160 μL of a polystyrene bead dispersion (Funakoshi co.jp, FCDG003, particle size 0.2 μm, 10 mg / ml) to obtain polystyrene beads having a polystyrene bead concentration of 0.44% by mass. A particle dispersion was prepared.

In the same manner as in Example 1, the substrate on which the Ag wiring serving as the core was formed was immersed in the prepared polystyrene bead dispersion and irradiated with a laser to form a composite wiring of Ag core/polystyrene coating layer with a line width of 2.3 μm. formed.

As in Example 1, the cross-sectional shape of the formed composite wiring was observed under a microscope. A polystyrene coating layer 12, which is a first coating layer made of polystyrene beads, was densely formed around the Ag core 10 having a substantially semicircular shape. No gap was observed at the interface between the Ag core and the polystyrene coating layer. The interface between the Ag core and the polystyrene coating layer was clearly formed, and no polystyrene beads were found inside the Ag core.

FIG. 29 shows an external SEM image of the composite wiring 100 formed. Although polystyrene beads were accumulated in the coating layer, they were not melted and the diameter of the polystyrene beads before accumulation was maintained.

(Comparative example 1)
In a brown bottle, 170 μL of pure water and 220 μL of ethanol were added, and 90 μL of silver nitrate solution (1 mol/L, Junsei Chemical Co., Ltd.) was added and stirred. After that, 16 μL of ZnO nanoparticle-dispersed aqueous solution (Sigma-Aldrich, 721077, average particle diameter <40 nm, concentration 20 wt %) was added and stirred again for 1 hour to prepare a dispersion in which Ag ions and ZnO particles were dispersed. The concentration of ZnO in the prepared dispersion was 1.1% by weight.

The prepared dispersion was transferred from the brown bottle to a Teflon (registered trademark) holder, and a 1 mm thick slide glass serving as a substrate was placed on the holder so that one surface of the substrate was in direct contact with the dispersion in the holder. .

Next, using a femtosecond laser (C-Fiber 780, Menlo Systems Ltd.), the focal point was adjusted to the contact surface between the substrate and the dispersion liquid. Wiring was formed on the substrate surface by horizontally moving the holder at a scanning speed of 50 μm/sec while irradiating under the conditions of an output of 30 mW and a focused beam diameter (theoretical value) of 2 μm.

FIG. 30 shows an external SEM image of the formed wiring. FIG. 31 shows a cross-sectional TEM image of the formed wiring. FIG. 32 shows an enlarged TEM image of the portion surrounded by a square in FIG. Since the ZnO particles were dissolved in the AgNO ₃ solution, the ZnO particles were only accumulated on the right edge of the Ag core and no coating layer was formed. The line width of the formed wiring was as thin as 6 μm. The layer around the Ag core is carbon used for fixing the substrate and the composite wiring when cutting out the cross section.

(Comparative example 2)
Except that 1.9 mL of TiO ₂ nanoparticle-dispersed aqueous solution (NTB-1, Showa Denko K.K., nanoparticle diameter 10 to 20 nm (catalog value), concentration 15% by mass) was used instead of the ZnO nanoparticle-dispersed aqueous solution. A dispersion was prepared under the same conditions as in Comparative Example 1, and wiring was formed on the substrate by laser irradiation. The concentration of _TiO2 in the prepared dispersion was 1.5% by weight.

FIG. 33 shows a cross-sectional SEM image of wiring formed on a substrate. A semicircular Ag core with a diameter of about 5 μm and a coating layer of titanium oxide particles with a thickness of about 5 μm covering the core were confirmed. Ag was contained inside the TiO2 coating layer, _TiO2 particles were embedded inside the Ag core, and a gap was formed between the Ag core and the coating layer. FIG. 34 shows a mapping photograph of Ag measured by EDX in the area of FIG. 33, and FIG. 35 shows a mapping photograph of Ti measured by EDX in the area of FIG. Ag was detected inside the _TiO2 coating layer and Ti was detected inside the Ag core.

(Example 5)
In a brown bottle, put 311 μL of pure water and 489 μL of ethanol, add 200 μL of a silver nitrate solution (1 mol / L, Junsei Chemical Co., Ltd.) and stir. A shaped material was formed.

In a solution of 210 μL of water and 491 μL of ethanol, 297 μL of CdSe/ZnS core-shell quantum dot dispersion (Sigma-Aldrich, 900227-1 ML, particle size: core diameter 4.2 nm, shell thickness 2 nm, overall diameter 8.2 nm, fluorescence wavelength 665 nm, 1 mg in 1 mL water) was mixed to prepare a quantum dot dispersion with a CdSe/ZnS quantum dot concentration of 0.05% by mass.

In the same manner as in Example 1, the substrate on which the Ag wiring serving as the core is formed is immersed in the prepared quantum dot dispersion and irradiated with a laser to form a composite Ag core/quantum dot coating layer with a line width of 4.5 μm. Wiring was formed.

The formed composite wiring was observed with an epi-illumination fluorescence microscope (G excitation). FIG. 36 shows an optical microscope image (FIG. 36(a)) and a fluorescence microscope observation photograph (FIG. 36(b)) of the formed composite wiring. Red fluorescence based on a fluorescence wavelength of 665 nm was confirmed from the formed composite wiring.

(Example 6)
In a brown bottle, put 11.3 mL of pure water and 4 mL of ethanol, 4 mL of silver nitrate solution (1 mol / L, Junsei Chemical Co., Ltd.) and 0.68 mL of SiO colloid solution (Sigma _- Aldrich, LUDOX TM-50, 50 wt% , 420778, particle size of 22 nm or less) were added and stirred. The solution was transferred from the brown bottle to a Teflon holder, and a _CaF2 substrate (Sigma Koki, OPCF-20C01-P) with a thickness of 1 mm was placed so that one major surface of the substrate was in direct contact with the solution in the holder. I put it on the holder so that I could do it.

Next, the focused part of the femtosecond laser was adjusted to be the contact surface between the substrate and the solution. Irradiation was performed under the condition of 0.9 μm. The femtosecond laser used was obtained by converting light from FLINT1.0 (manufactured by Light conversion) into a double wave by a harmonic unit HIRO 2H (manufactured by Light conversion).

By horizontally moving the holder at a scanning speed of 500 μm/sec, a linear material composed of Ag and SiO ₂ was continuously formed on the surface of the CaF ₂ substrate in the scanning direction. The linear material formed had a line width of 2.3 to 2.8 μm and a thickness of 1.3 μm.

A solution of 2.7 mL water and 4.5 mL ethanol was mixed with 0.26 mL TiO ₂ nanoparticle dispersion (Sigma-Aldrich, 700347, particle size (diameter) <150 nm, concentration 33-37 wt%) to obtain TiO A TiO ₂ particle dispersion with a ₂ concentration of 1.8% by weight was prepared.

The prepared _TiO2 particle dispersion was transferred to a Teflon holder, and as schematically shown in Fig. 4, the linear material formed on the substrate was in direct contact with the _TiO2 particle dispersion in the holder. I put it on the holder so that I could do it. Adjust the focal part of the femtosecond laser so that it becomes a linear material, and irradiate under the conditions of a center wavelength of 517 nm, a repetition frequency of 75 MHz, a pulse width of 88 fs, an average laser output of 20 mW, and a focal diameter (theoretical value) of 0.9 μm. while moving the focusing part of the laser along the linear material at 300 μm/sec to form a _first coating layer of TiO particles around the linear material to be the core, and the line width A composite wiring was formed with a core of Ag and SiO ₂ with a thickness of 4.4 μm and a coating layer of TiO ₂ . The movement of the laser condensing part was stopped halfway so that the part where the first coating layer was formed and the part where the first coating layer was not formed could be compared. As a femtosecond laser, light from FLINT1.0 (manufactured by Light conversion) was converted into a double wave by a harmonic unit HIRO 2H (manufactured by Light conversion).

The formed composite wiring was subjected to SEM observation and elemental mapping analysis. FIG. 37 shows an SEM photograph of the formed composite wiring and mapping images of Si, Ti, and Ag. Ti, Ag, and Si were detected from the _TiO2 -coated portion, and Ag and Si were detected from the uncoated portion.

(Example 7)
(Forming two linear materials)
12 mL of pure water and 4 mL of ethanol were placed in a brown bottle, and 4 mL of silver nitrate solution (1 mol/L, Junsei Chemical Co., Ltd.) was added and stirred. The solution was transferred from the brown bottle to a Teflon (registered trademark) holder, and a cover glass having a thickness of 1 mm was placed on the holder so that one main surface of the substrate was in direct contact with the solution in the holder.

Next, the focal point of the femtosecond laser was adjusted to be the contact surface between the substrate and the solution, with a central wavelength of 517 nm, a repetition frequency of 75 MHz, a pulse width of 88 fs, an average laser output of 16 mW, and a focal diameter (theoretical value) of 0. Irradiation was performed under the condition of 0.9 μm. The femtosecond laser used was obtained by converting light from FLINT1.0 (manufactured by Light conversion) into a double wave by a harmonic unit HIRO 2H (manufactured by Light conversion).

By horizontally moving the holder at a scanning speed of 500 μm/sec, a first linear material made of Ag was continuously formed on the substrate surface in the scanning direction.

Next, the second linear material was formed by moving the holder while irradiating the femtosecond laser so that the line-to-line gap was 2 μm with respect to the first linear material. The first linear material and the second linear material thus formed had a line width of 2 μm and a thickness of 1 μm.

The prepared TiO ₂ particle dispersion is transferred to a Teflon holder, and as schematically shown in Fig. 4, two linear materials formed on the substrate are aligned with the TiO ₂ particle dispersion in the holder. It was put on the holder so that it was in direct contact with the The focal part of the femtosecond laser was adjusted to be a linear material, and the first linear material had a central wavelength of 517 nm, a repetition frequency of 75 MHz, a pulse width of 88 fs, an average laser output of 23 mW, and a lens numerical aperture of 0.5. 7. While irradiating with a condensed diameter (theoretical value) of 0.9 μm, move the laser condensing part at 300 μm/sec along the linear material to form the first linear material that will be the core. A first coating layer of _TiO2 particles was formed around the . Then, the second linear material is similarly irradiated with a laser to form a first coating layer of _TiO2 particles around the second linear material that serves as the core, and two Ag wirings are formed as the core. A composite wiring was formed with TiO ₂ as a coating layer. The movement of the laser condensing part to the first linear material and the second linear material was stopped halfway so that the part where the first coating layer was formed and the part where the first coating layer was not formed could be compared. As a femtosecond laser, light from FLINT1.0 (manufactured by Light conversion) was converted into a double wave by a harmonic unit HIRO 2H (manufactured by Light conversion). The formed composite wiring had a 1 μm thick TiO ₂ coating layer over Ag cores with a 2 μm line-to-line gap and a line width of 2 μm each. No gap was found at the interface between the Ag core and the _TiO2 coating layer.

The formed composite wiring was subjected to SEM observation and elemental mapping analysis. FIG. 38 shows an SEM photograph of the formed composite wiring and mapping images of Ag and Ti. Ti and AgSi were detected from the _TiO2 -coated portion, and Ag was detected from the uncoated portion.

100 composite wiring 10 linear materials (cores containing metals, ceramics, or combinations thereof)
101 linear materials (cores containing metals, ceramics, or combinations thereof)
102 linear materials (cores containing metals, ceramics, or combinations thereof)
12 First covering layer 121 First covering layer 122 First covering layer 20 First dispersion 22 First solid nanomaterial 24 Bubble 30 First laser light 32 Laser source 34 Beam splitter 40 Substrate

Claims

preparing a linear material comprising metals, ceramics, or combinations thereof;
immersing the linear material in a first dispersion in which a first solid nanomaterial is dispersed; and irradiating the linear material immersed in the first dispersion with a first laser beam. while moving the condensing portion of the first laser beam along the linear material to cover the surface of the linear material with the first covering layer composed of the first solid nanomaterial. forming at least in part to form a core composed of said linear material/ said first coating layer composite;
The first solid nanomaterial is composed of at least one selected from the group consisting of metal oxides, non-metal oxides, ceramics, metals, and resins.
A method for manufacturing a composite.
The manufacturing method of the composite according to claim 1, wherein there is no gap between the core and the first coating layer of the composite.
The method for producing a composite according to claim 1 or 2, wherein the interior of the core of the composite does not contain the first solid nanomaterial.
4. The first coating layer composed of the first solid nanomaterial is formed on the surface of the linear material concentrically with the linear material. A method for producing a composite of
The method for producing a composite according to any one of claims 1 to 4, wherein the concentration of said first solid nanomaterial in said first dispersion is 0.01 to 3.0% by mass.
The method for producing a composite according to any one of claims 1 to 5, wherein the first solid nanomaterial has a diameter of 1 to 3000 nm.
The method for producing a composite according to any one of claims 1 to 6, wherein the first laser light is near-infrared light.
soaking the composite in a second dispersion in which a second solid nanomaterial is dispersed; and irradiating the composite soaked in the second dispersion with a second laser beam, A second coating layer composed of the second solid nanomaterial is formed on at least part of the surface of the first coating layer by moving the focusing portion of the second laser beam along the body. to form a composite having the core/first coating layer/second coating layer;
The second solid nanomaterial is composed of at least one selected from the group consisting of metal oxides, non-metal oxides, ceramics, metals, and resins.
A method for producing the composite according to any one of claims 1 to 7.
preparing the substrate,
forming the linear material along the main surface of the substrate; A method for producing the composite according to any one of claims 1 to 8, comprising forming a coating layer of
forming the linear material along the main surface of the substrate;
immersing at least one main surface of the substrate in a solution or dispersion containing at least one selected from the group consisting of metal ions, metal colloids, and metal complexes; and the substrate immersed in the solution or dispersion 10. The method according to claim 9, wherein a linear metal is formed on the substrate by moving the focusing part of the laser beam along the surface of the substrate while irradiating the main surface of the A method for producing a composite of
a linear material core comprising a metal, ceramic, or a combination thereof; and a first coating layer composed of a first solid nanomaterial covering at least a portion of a surface of the linear material core,
The first solid nanomaterial is composed of at least one selected from the group consisting of metal oxides, non-metal oxides, ceramics, metals, and resins,
there is no gap between the linear material core and the first coating layer;
Complex.
The composite according to claim 11, wherein the interior of the linear material core does not contain the first solid nanomaterial.
The composite according to claim 11 or 12, wherein said first solid nanomaterial has a diameter of 1-3000 nm.
substrate,
The linear material core arranged along the main surface of the substrate, and a first solid nanomaterial arranged so as to cover the surface of the linear material core between the substrate and the substrate. A composite according to any one of claims 11 to 13, comprising a second coating layer.
The composite according to any one of claims 11 to 14, comprising one or more coating layers composed of other solid nanomaterials on the surface of the first coating layer.
providing a convex material comprising metals, ceramics, or combinations thereof;
immersing the convex material in a first dispersion in which a first solid nanomaterial is dispersed; and irradiating the convex material immersed in the first dispersion with a first laser beam. while moving the condensing portion of the first laser light along the convex material to form a localized portion composed of the first solid nanomaterial on at least a part of the surface of the convex material. forming a protective coating;
The first solid nanomaterial is composed of at least one selected from the group consisting of metal oxides, non-metal oxides, ceramics, metals, and resins.
A method for producing a topical coating.
A topical coating composed of a first solid nanomaterial covering at least a portion of the surface of a convex material core comprising metal, ceramic, or a combination thereof, comprising:
The first solid nanomaterial is composed of at least one selected from the group consisting of metal oxides, non-metal oxides, ceramics, metals, and resins,
there is no gap between the convex material core and the first coating layer;
topical coating.