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WO2019078100A1 - Procédé de production d'un composite comprenant un métal revêtu de microparticules solides - Google Patents

Procédé de production d'un composite comprenant un métal revêtu de microparticules solides Download PDF

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Publication number
WO2019078100A1
WO2019078100A1 PCT/JP2018/038040 JP2018038040W WO2019078100A1 WO 2019078100 A1 WO2019078100 A1 WO 2019078100A1 JP 2018038040 W JP2018038040 W JP 2018038040W WO 2019078100 A1 WO2019078100 A1 WO 2019078100A1
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Prior art keywords
metal
particles
solution
solid
fine particles
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Japanese (ja)
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西山　宏昭
寛 梅津
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Yamagata University NUC
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Yamagata University NUC
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/16—Both compacting and sintering in successive or repeated steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis

Definitions

  • the present invention makes use of the nonlinear optical absorption of metal ions, colloids and complexes (hereinafter referred to as “metal ions etc.”) derived from the ultrashort pulse property, making use of the extremely short time width of the ultrashort pulse laser light.
  • metal ions colloids and complexes
  • There are various methods such as depositing metal in the ultrashort pulse laser beam focusing position and coating the deposited metal by instantaneously giving very large energy to the deposited metal before the thermal effect appears.
  • the present invention relates to a method for producing a composite formed by accumulating solid fine particles having a function.
  • a highly transparent coating film-forming material having no photosensitivity a solid electrolyte fuel cell electrolyte material, a light emitting diode, a light responsive semiconductor material, a resistor film-forming material, a metal magnetic powder material, a superconducting material
  • the present invention relates to a manufacturing method of forming a pattern by moving an ultrashort pulse laser beam focusing position even in solid fine particles of functional materials such as piezoelectric ceramic thick film materials, dielectric film materials, and fine particle bonding materials.
  • the film density of the film formed by this method is considered to be about 55 to 80% of the theoretical density, and crystal growth by heat is necessary to obtain electric conduction of bulk material level.
  • an aerosol deposition (AD) method is also attracting attention (Patent Document 1). According to this method, it is said that it is possible to form a dense and high hardness film containing ceramic materials including metals at normal temperature.
  • a fine pattern can be obtained without etching, it is difficult to handle fine powder in a working environment or the like. All of these methods require large-scale equipment.
  • an ultrashort pulse laser mainly uses its very short time width, and has the property of instantaneously giving a very large energy to a substance before a thermal effect appears.
  • Conceivable For example, Non-Patent Document 1 reports an example of processing with an ultrashort pulse laser, and according to this, when irradiating a 10 ps (picosecond) pulse laser with a copper target, the surface electron temperature is several While reaching 1000 ° C., the thermal diffusion length is estimated to be less than ⁇ m.
  • Non-Patent Document 2 reports that silver dots were obtained by reduction of silver ions by high-intensity laser beam irradiation with a wavelength of 800 nm, a pulse width of 80 fs, a frequency of 82 MHz, and an output of 14.97 mW.
  • Non-Patent Document 3 utilizes a reduction reaction of silver nitrate by utilizing a relatively weak continuous wave pulse laser using a near infrared light source of wavelength 1064 nm and a visible light source of wavelength 532 nm or 633 nm. It is reported that the patterning of the silver nanoparticle assembly was formed on a glass substrate.
  • the material to be processed has an appropriate light absorption property to the laser beam.
  • a metal (Ag) pattern is formed by irradiating a laser beam to an Ag ink or the like, it is largely assumed that the ink appropriately absorbs the laser beam.
  • Non-Patent Document 4 reports an example of transparent material processing using a femtosecond laser, and emits pulsed light with a wavelength of 800 nm and a pulse width of 120 fs to silica glass to induce lattice defects at a focusing point inside the glass. It is reported that it has produced high density.
  • this method it is difficult to condense the solid particles dispersed in the solution, and even if it is realized, the physical properties of the solid particles are also degraded because the material properties of the irradiated part are modified. Is inevitable.
  • the inventors of the present invention have reached the present invention as a result of examining a method of integrating materials which originally do not have absorption using ultra-short pulse laser and utilizing nonlinear optical absorption derived from ultra-short pulse property. is there.
  • the present invention provides a technique for easily carrying out accumulation of solid fine particles and for facilitating pattern formation, which was difficult to achieve in the prior art.
  • the present inventors have used this metal particle as a micro heat source based on the finding that, according to the ultrashort pulse laser, the metal particle can be deposited using nonlinear optical absorption derived from the ultrashort pulse property.
  • the present invention has been achieved as a result of earnestly examining a method of accumulating materials which originally do not have absorption to laser light, by contemplating the use of.
  • the present inventors disperse
  • the ultrashort pulse laser can momentarily emit high-intensity light pulses derived from its short pulse width, and the non-linear optical absorption produced by the high-intensity pulses can directly process only the vicinity of the focusing point.
  • metal was deposited only in the vicinity of the ultrashort pulse laser focusing point in the solution, and local heat was applied to the deposited metal, whereby the solid fine particles in the periphery were accumulated on the metal surface. This method made it possible to pattern non-photosensitive materials.
  • a highly transparent coating film-forming material having no photosensitivity a solid electrolyte fuel cell electrolyte material, a light emitting diode or a photoresponsive semiconductor material, a resistor film-forming material, a metal magnetic powder material, a superconducting material, a piezoelectric
  • solid fine particles of functional materials such as ceramic thick film materials, dielectric film materials, and fine particle bonding materials
  • metal oxide particles or non-particles dispersed in the solution are deposited by irradiating the solution containing the metal ions, colloids, and / or complexes with the ultrashort pulse laser beam. It is a manufacturing method of the complex containing metal covered with solid particulates including the process of covering solid particulates which consist of metal oxide particles or ceramic particles on the deposited metal.
  • the metal is not particularly limited as long as the deposited metal does not chemically react with the solvent.
  • metals which do not react with water and high temperature steam are selected from the group consisting of silver, copper, nickel, lead, tin, platinum and gold.
  • the melting point of the solid fine particles is preferably 500 ° C to 3500 ° C. Further, the solid fine particles preferably have a diameter of 0.005 ⁇ m to 1 ⁇ m. Furthermore, the concentration of the solid fine particles in the solution is preferably 0.01% by mass to 3.0% by mass.
  • the wavelength of the ultrashort pulse laser beam is preferably 200 nm to 2000 nm. Further, the fluence (energy input to a unit area) of the ultrashort pulse laser beam is preferably 0.01 mJ / cm 2 to 10 mJ / cm 2 . Furthermore, the repetition frequency of the ultrashort pulse laser light is preferably 1 Hz to 500 MHz. The average output of the ultrashort pulse laser beam is preferably 10 mW or more. Moreover, it is preferable that the condensing diameter of the said ultra-short pulse laser beam is 20 micrometers or less.
  • the present invention may further include the steps of immersing the substrate in the solution, and moving the beam spot of the ultrashort pulsed laser light along the surface of the substrate.
  • the present invention further includes the steps of: immersing the substrate in the solution; and moving the beam spot of the ultrashort pulsed laser beam from the surface of the substrate to a predetermined position in the solution away from the substrate. It can be included.
  • the present invention is further directed to a complex comprising a metal coated with solid particles, wherein the metal is present in solution as metal ions, colloids, and / or complexes, to which ultrashort pulsed laser light is applied.
  • the solid fine particles are metal oxide particles, non-metal oxide particles, or ceramic particles, the metal forms a core, and the core has a cavity inside thereof , The complex.
  • the metal is preferably selected from the group consisting of silver, copper, nickel, lead, tin, platinum and gold.
  • the melting point of the solid fine particles is preferably 500 ° C to 3500 ° C. Furthermore, it is preferable that the solid fine particles have a diameter of 0.005 ⁇ m to 1 ⁇ m.
  • the metal is dissolved in a liquid in which solid fine particles (silica, alumina, titanium oxide particles, etc.) are dispersed in a solvent in the state of metal ions, metal complexes, etc.
  • solid fine particles dispersed in a solution can be easily coated on the metal surface, and a composite containing the metal coated with the solid fine particles can be produced, in which case an ultrashort pulse is produced.
  • the present invention can be applied to various occasions such as manufacturing of devices by freely patterning solid particles having various functions such as metal oxides, non-metal oxides or ceramics by controlling irradiation of laser light, etc. It can be expected to apply.
  • the present invention is a low-temperature optical process of irradiating ultrashort pulse laser light in a solution, patterning can be performed without damaging the plastic substrate and elements on the substrate.
  • the present invention deposits metal in a solution containing metal ions, colloids, and / or complexes by irradiating an ultrashort pulse laser beam, and is dispersed in the solution, metal oxide particles, nonmetal oxide particles It is a manufacturing method of the complex containing metal covered with solid particulates including the process of covering solid particulates which consist of object particles or ceramic particles on the deposited metal.
  • a solution holder contains a solution in which silver nitrate is dissolved and solid fine particles are dispersed, A substrate transmitting laser light is placed such that one surface of the substrate is in contact with the solution.
  • the solution is irradiated with ultrashort pulse laser light from the other side of the substrate to precipitate silver in the solution, and at the same time, the deposited fine particles are coated with the solid fine particles dispersed in the solution to form a solid A composite is prepared comprising silver coated with microparticles.
  • the substrate surface (solution side) can be obtained by irradiating a silver nitrate solution with an ultrashort pulse laser beam.
  • Metal silver
  • This metal forms a core
  • the metal surface is locally heated, and after rapid expansion due to evaporation of the solvent on the metal surface, rapid contraction due to reduced pressure occurs.
  • the solid particles dispersed in the solution around the core are subjected to the force of rapid contraction and collide with the metal surface at a high speed, whereby a dense aggregate is accumulated on the metal surface, and the metal coated with the solid particles It is believed that a complex containing is generated.
  • the metal used in the present invention is one that exists as a metal ion, colloid, and / or complex in a solution irradiated with ultrashort pulsed laser light.
  • the type of metal is not particularly limited as long as the deposited metal does not chemically react with the solvent.
  • the metal used in the present invention is, in particular, a metal which does not react with water and high temperature water vapor, selected from the group consisting of silver, copper, nickel, lead, tin, platinum and gold when water is selected as the solvent. Is preferred.
  • metals that react with water or high-temperature water vapor for example, metals having a high ionization tendency such as potassium, magnesium, aluminum, zinc, iron
  • preferable metals can be selected by appropriately selecting a solvent. It is possible.
  • the metal ion is, for example, Ag + , Cu + , Cu 2+ , Ni 2+ , Sn 2+ , Sn 3+ , Sn 4+ , Pb 2+ , Pt 2+ , It may be Au + , Au 3 + or the like.
  • the counter ion of the metal salt is selected from the group consisting of nitrate ion, sulfate ion, carboxylate ion, cyanide ion, sulfonate ion, borate ion, halogen ion, carbonate ion, phosphate ion and perchlorate ion Is preferred.
  • Examples of metals present as colloids in solution include silver colloids, copper colloids, nickel colloids and the like.
  • Examples of the case where the metal is present as a complex in a solution include a case where the metal is easily dispersed or dissolved in a solvent by coordinating a ligand to a metal atom.
  • Examples of silver complexes include silver docosanoate, chloro [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] silver, silver (II) pyridine-2-carboxylate, silver sulfadiazine, etc. Can.
  • copper complexes such as copper (I) acetate, bis (1,3-propanediamine) copper (II) dichloride, cupric acetylacetonate, bis (8-quinolinolato) copper (II) and the like can be mentioned. it can.
  • complexes of gold include tetrachloroaurate (III) tetrahydrate, (dimethyl sulfide) gold (I) chloride, chloro [1,3-bis (2,6-diisopropylphenyl) imidazole-2-ylidene ] Gold (I) etc. can be raised.
  • complexes of lead include lead tetraacetate and lead (II) acetate.
  • it may be a product containing metal complexes such as silver nanoinks and copper nanoinks.
  • the concentration of the metal used in the present invention in the solution is not particularly limited. There is no limitation as long as it can be uniformly dissolved or dispersed at 0.1% by mass or more. In a thin solution of less than 0.1% by mass, the accumulation of solid fine particles degrades the light efficiency.
  • the metal concentration in the solution is increased, the size of the metal core formed by the irradiation with the ultrashort pulse laser light is increased.
  • the concentration of the metal in the solution is preferably 3.0% by mass or less.
  • the solid fine particles used in the present invention are metal oxide particles, non-metal oxide particles, or ceramic particles dispersed in a solution irradiated with ultrashort pulse laser light. Dispersion here does not necessarily have to be uniformly distributed in solid solution throughout the solution, and as long as solid particles are present in the vicinity of the focusing point, part of them may be precipitated.
  • solid fine particles used in the present invention for example, inorganic compounds such as carbides, nitrides, borides and the like can be used.
  • solid particles a plurality of different types of particles may be simultaneously dispersed in a solvent, or solid particles in which solid particles are joined to each other, or solid particles consisting of a plurality of components may be used.
  • solid fine particles such as gold-supported titanium oxide (Au / TiO 2 ) can be used together with the solid fine particles.
  • the melting point of the solid fine particles is preferably 500 ° C to 3500 ° C.
  • the melting point of the solid fine particles is preferably 500 ° C to 3500 ° C.
  • a cross section as shown in FIG. 4 is observed. While the interface between titanium oxide and silver is in wide contact, a void is present inside silver.
  • the ratio of the cross section of the cavity to that of silver is measured to be about 5 to 1,
  • the linear expansion coefficient of titanium oxide (average from room temperature to 1000 ° C.) is 8 ⁇ 10 -6 (1 / K) Because the linear expansion coefficient of silver is 25 ⁇ 10 -6 (1 / K), the maximum temperature reached on the silver surface by irradiation with ultra-short pulse laser light is about 5000 K (4700 ° C. or higher). It is estimated to be. Therefore, if it is solid fine particles having a melting point of 3500 ° C. or less, it is considered that they can be melted and easily accumulated on the metal surface.
  • solid fine particles useful as a coating material for example, silica (1650 ° C.), tin oxide (1080 ° C.), iron oxide (1565 ° C.), chromium oxide (2435 ° C.), beryllium oxide (2570) as solid fine particles of oxide ° C), hafnium oxide (2758 ° C), (reacted with water), dimanganese trioxide (1080 ° C), trimanganese tetraoxide (1567 ° C), manganese oxide (1650 ° C), barium oxide (1920 ° C), strontium oxide (2531 ° C), triiron tetraoxide (1538 ° C), cobalt oxide (1933 ° C), nickel oxide (1984 ° C), lead zirconate titanate (1400 ° C), lithium titanate (1520 ° C), aluminum titanate (aluminum titanate) 1860 ° C), strontium titanate (2080 ° C), lead titanate, lead zirconate, mixed crystal of lead titanate and lead zir
  • chromium carbide (1890 ° C), boron carbide (2763 ° C), vanadium carbide (2840 ° C), tungsten carbide (2870 ° C), molybdenum carbide (2687 ° C), titanium carbide (3170 ° C), carbonization Zirconium (3500 ° C.), niobium carbide (3500 ° C.), tantalum carbide (3880 ° C.), silicon carbide (2730 ° C.), bismuth titanate (1203 ° C.) and the like can be mentioned.
  • niobium nitride 2573 ° C
  • titanium nitride 2930 ° C
  • tantalum nitride (3090 ° C)
  • gallium nitride (2500 ° C)
  • gallium nitride 1100 ° C 2500 ° C.
  • boron nitride 2967 ° C.
  • aluminum nitride 2200 ° C.
  • Boron compounds include boron (2076 ° C), aluminum boride (1655 ° C), chromium boride (2373 ° C), titanium boride (2400 ° C), molybdenum boride (2543 ° C), tungsten boride (2643 ° C) Vanadium boride (2673 ° C.), zirconium boride (3100 ° C.), magnesium boride (800 ° C.), niobium boride (3000 ° C.), tantalum boride (3037 ° C.) and the like.
  • cerium fluoride (1800 ° C.) and the like as a halogen compound
  • hydroxyapatite (1650 ° C.) and the like as a phosphoric acid compound
  • Li 2 S—P 2 S 5 LiCoO 2 , xLi 2 O and the like as a lithium compound -BPO 4 and (0.5 ⁇ x ⁇ 1.5)
  • the compound semiconductor such as a semiconductor with a group II element and group VI element, and the like, respectively.
  • solid particles useful as highly transparent coating film-forming materials include nickel oxide, tricobalt tetraoxide, indium tin oxide, magnesium oxide, zirconium oxide, aluminum nitride, magnesium boride, silicon nitride, silicon carbide, and fluorine. There may be mentioned cerium oxide and the like.
  • solid particles useful as solid electrolyte fuel cell electrolyte materials include scandium oxide, neodymium oxide, gadolinium oxide, samarium oxide (2300 ° C.), yttrium oxide, neodymium oxide, scandium oxide, LiCoO 2 , lithium sulfide compounds, and the like. be able to.
  • lithium sulfide-based compound Li 2 S-P 2 S 5, Li 2 S-P 2 S 5 -LiI, Li 2 S-P 2 S 5 -LiCl, Li 2 S-P 2 S 5 -LiBr , Li 2 S-P 2 S 5 -Li 2 O, Li 2 S-P 2 S 5 -Li 2 O-LiI, Li 2 S-SiS 2, Li 2 S-SiS 2 -LiI, Li 2 S-SiS 2 -LiBr, Li 2 S-SiS 2 -LiCl, Li 2 S-SiS 2 -B 2 S 3 -LiI, Li 2 S-SiS 2 -P 2 S 5 -LiI, Li 2 S-B 2 S 3, Li 2 S-P 2 S 5 -ZmSn (although, m, n is the number of positive .Z is, Ge, Zn, one of Ga.), Li 2 S- GeS 2, Li 2 S-S 5 -Z
  • solid particles useful as light emitting diodes and light responsive semiconductor materials include indium nitride, gallium nitride, aluminum nitride, and semiconductors using group II elements and group VI elements.
  • semiconductors using group II elements and group VI elements include CuInSe 2 , CuInS 2 (CIS), CuIn 1-x Ga x Se 2 (CIGS), Cu 2 ZnSnS 4 (CZTS), CdTe-based semiconductors, etc. It can be mentioned.
  • solid fine particles useful as a resistor film forming material include triiron tetraoxide, cobalt oxide, nickel oxide, rhenium oxide, iridium oxide, ruthenium oxide, ferrite, oxide ceramics and the like.
  • oxide ceramics SrVO 3 , CaVO 3 , LaTiO 3 , SrMoO 3 , CaMoO 3 , SrCrO 3 , SrCrO 3 , CaCrO 3 , CaCrO 3 , LaVO 3 , GdVO 3 , SrMnO 3 , CaMnO 3 , NiCrO 3 , BiCrO 3 , LaCrO 3 , LnCrO 3 , SrRuO 3 , CaRuO 3 , SrFeO 3 , BaRuO 3 , LaRuO 3 , LaMnO 3 , LnMnO 3 , LaFeO 3 , LnFeO 3 , LaCoO 3
  • solid fine particles useful as a superconducting material include YBa-based oxides, BiSrCa-based oxides, and TlBaCa-based oxides.
  • solid fine particles useful as a piezoelectric ceramic thick film material include magnesium oxide, dimanganese trioxide, trimanganese tetraoxide, manganese oxide, barium oxide, strontium oxide, barium titanate, hydroxyapatite and the like.
  • titanium oxide, silica, aluminum nitride, magnesium oxide, barium titanate, lead zirconate titanate, oxide ceramics and the like can be mentioned.
  • oxide ceramics PZT represented by the general formula of PbTiO 3 , PbZrO 3 , Pb (Zr 1-x Ti x ) O 3 (0 ⁇ x ⁇ 1), (Pb 1 -y La y ) (Zr PLZT represented by the general formula of 1-x Ti x ) O 3 (0 ⁇ x, y ⁇ 1), Pb (Mg 1/3 Nb 2/3 ) O 3 , Pb (Ni 1/3 Nb 2/3 ) O 3, Pb (Zn 1/3 Nb 2/3) O 3, BaTiO 3, BaTi 4 O 9, Ba 2 Ti 9 O 20, Ba (Zn 1/3 Ta 2/3) O 3, Ba (Zn 1 / 3 Nb 2/3) O 3, Ba (Mg 1/3 Ta 2/3) O 3, Ba (Mg 1/3 Ta 2/3) O 3, Ba (Mg 1/3 Ta
  • solid fine particles useful as the fine particle bonding material include cordierite, anorthite, gohalenite, calcium aluminate, lithium aluminate, strontium aluminate, mullite, yttrium aluminate, spinel, aluminum nitride and the like.
  • the present invention there are two major methods for irradiating ultra-short pulse laser light.
  • One is a method of irradiating through a transparent substrate which precipitates a metal
  • the other is a method of irradiating a substrate surface through a solution.
  • the former case since it does not pass through the solution, it is not easily affected by solid particles dispersed in the solution.
  • the latter case if the light absorption in solution by the solid particles is small, light loss and scattering can be suppressed, more solid particles can be dispersed in the solvent, and it is effective for the deposited metal.
  • the laser light can be absorbed and does not cause a problem, but conversely, if the light absorption is large, light loss and scattering are likely to occur.
  • the particle diameter of the solid fine particles is changed or By reducing the concentration in the medium, it is possible to control the irradiation of the deposited metal with laser light efficiently.
  • the solvent for the solution used in the present invention is not particularly limited as long as it is suitable for the dispersion of solid particles.
  • a solvent can be selected according to use, such as re-dispersing solid fine particles dispersed in an organic solvent such as toluene in a mixed solvent of alcohol and water.
  • the viscosity of the solution used in the present invention is not particularly limited. If it is desired to thicken the coating of the solid particles covering the core metal, it is conceivable to increase the concentration of the solid particles, and in such a case, the viscosity of the solution becomes high.
  • the solution may contain a dissolving agent such as a dispersing agent used for dispersing the solid fine particles, or any other agent as long as it does not prevent the irradiation of the laser beam.
  • a dissolving agent such as a dispersing agent used for dispersing the solid fine particles, or any other agent as long as it does not prevent the irradiation of the laser beam.
  • the “ultrashort pulse laser” is several femtoseconds (1 femtosecond is 1 ⁇ 10 ⁇ 15 seconds, also described as fs) to several hundreds picoseconds (1 picosecond is 1 ⁇ 10 ⁇ 12). It is a pulse laser having a pulse width of second and ps.
  • the average output of the ultrashort pulse laser beam used in the present invention is preferably 10 mW or more. Moreover, it is preferable that the condensing diameter of ultra-short pulse laser light is 20 ⁇ m or less. By controlling the irradiation amount and the intensity of the ultrashort pulse laser light, it is possible to control the size of the metal core generated.
  • the repetition frequency of the ultrashort pulse laser beam is preferably 1 Hz to 500 MHz.
  • the wavelength of the ultrashort pulse laser beam used in the present invention is not particularly limited as long as it is a wavelength absorbed by the metal ion or the like used in the present invention and has a high molar absorption coefficient. If it is a wavelength with little absorption by solid fine particles, the formation efficiency of the composite according to the present invention is further improved, which is preferable.
  • the wavelength of the ultrashort pulse laser beam used in the present invention is adjusted to the absorption wavelength of the photosensitive metal compound dissolved in the solution, and for example, the molar absorption coefficient of the metal used in the present invention is 5 l / mol. It is preferable to select so as to be at least cm, but it is not particularly limited thereto.
  • the wavelength of the ultrashort pulse laser beam is preferably 200 nm to 2000 nm. Furthermore, the fluence (energy input to a unit area) of ultrashort pulse laser light is preferably 0.01 mJ / cm 2 to 10 mJ / cm 2 .
  • the present invention may further include the steps of immersing the substrate in a solution, and moving the beam spot of ultrashort pulsed laser light along the surface of the substrate.
  • FIG. 3 which is a conceptual cross-sectional view showing another embodiment of the present invention
  • the substrate is immersed in the solution on one surface, and by moving the substrate in the scanning direction in this state,
  • the beam spot of ultrashort pulsed laser light can be moved along the surface.
  • Metal deposition in solution by ultra-short pulse laser irradiation occurs only near the laser focusing point via nonlinear optical absorption.
  • a three-dimensional metal structure coated on solid particles is obtained by arranging the laser focus at an arbitrary position in the solution away from the substrate as well as on the surface of the substrate and scanning three-dimensionally. It is possible to manufacture. That is, the present invention can further include the steps of immersing the substrate in the solution, and moving the beam spot of the ultrashort pulse laser beam to a predetermined position in the solution away from the substrate from the surface of the substrate. . Moreover, it is also possible to take out the three-dimensional structure which consists of solid fine particles by removing a metal core from the manufactured composite by an etching process etc.
  • Example 1 In a brown bottle, 6 ml of pure water and 10 ml of ethanol were placed, and 4 ml of a silver nitrate solution (1 mol / l, Junsei Chemical Co., Ltd.) was placed and stirred. Thereafter, 0.7 ml of a silica nanoparticle dispersed aqueous solution (Sigma-aldrich, LUDOX, TM-50, nanoparticle particle size 22 nm, concentration 50% by mass) was added, and stirred again for 1 hour. The concentration of silica at this time was 2.5% by mass.
  • a silica nanoparticle dispersed aqueous solution Sigma-aldrich, LUDOX, TM-50, nanoparticle particle size 22 nm, concentration 50% by mass
  • the solution was transferred from the brown bottle to a Teflon (registered trademark) solution holder, and a cover glass as a substrate was placed on the holder so that one surface of the substrate was in direct contact with the solution in the holder.
  • a femtosecond laser C-Fiber 780, MenloSystems Ltd.
  • the focal point is adjusted to be the contact surface between the substrate and the solution, central wavelength 780 nm, repetition frequency 100 MHz, pulse width 127 fs, average laser output It irradiated on 20 mW, condensing diameter (theoretical value) 2 micrometers, and the conditions of fluence 6.4 mJ / cm ⁇ 2 >.
  • Example 2 In Example 1, 1.9 ml of titanium oxide nanoparticle dispersed aqueous solution (NTB-1, Showa Denko KK, nanoparticle particle diameter 10 to 20 nm (catalog value), concentration 15 mass%) was used instead of the silica nanoparticle dispersed aqueous solution Solution dispersion and laser light irradiation were performed under the same conditions as Example 1 except for the above.
  • the titanium oxide concentration at this time was 1.5% by mass.
  • Microscopic observation of the cross-sectional shape of the formed composite revealed a silver core of about 5 ⁇ m in diameter with a semicircle and a coating of about 5 ⁇ m thick titanium oxide nanoparticles covering it (FIG. 5).
  • Example 1 (Examples 3 to 7)
  • the dispersion of the solution and the laser light irradiation were performed under the same conditions as in Example 1 using various types of solid fine particles shown in Table 1 in place of the silica nanoparticles.
  • the formation of a complex was confirmed.
  • Example 8 Dispersion of the solution under the same conditions as in Example 2 except that the scanning speed of the holder was 30 ⁇ m / s, the titanium oxide concentration was 1.5 mass%, and the average laser power was changed to 15 mW, 25 mW and 30 mW. Laser light irradiation was performed. The cross section of the obtained composite was observed with a microscope, and the relationship between the cross-sectional area of the coating of titanium oxide and the average laser output was organized in FIG. It can be seen from FIG. 6 that as the laser power increases, a composite with a larger cross-sectional area is obtained.
  • Example 6 In Example 6, the average laser power is fixed at 25 mW, and the titanium oxide concentration, which was 1.5% by mass, is 0.8% by mass (Example 9), 0.3% by mass (Example 10), 0. The solution was dispersed and irradiated with laser light in the same manner as in Example 6 with a decrease of 2% by mass (Example 11) and 0.01% by mass (Example 12). The cross section of the obtained complex was observed microscopically. The relationship between the cross-sectional area of the coating by titanium oxide and the concentration of titanium oxide is shown in FIG. From FIG. 7, it can be seen that although the cross-sectional area changes when the concentration of titanium oxide is changed, when the concentration is 0.1% by mass or more, a favorable composite is obtained even at a low concentration of titanium oxide. .
  • Example 13 to 15 The dispersion of the solution and the laser light irradiation were performed under the same conditions as in Example 2 except that the concentration of titanium oxide was made to be 1.5% by mass and the particle diameter of the nanoparticles was made larger in Example 2. Microscopic observation of the cross section of the composite obtained when the particle size of the nanoparticles is 0.1 ⁇ m (Example 13), 0.5 ⁇ m (Example 14) and 1.0 ⁇ m (Example 15), Also in the case, it was confirmed that a good composite in which the covering layer was formed was obtained.
  • Example 16 Copper sulfate (Example 16), tetrachloroaurate (III) tetrahydrate (Example 17), nickel sulfate (Example 18), lead nitrate (lead nitrate) (4 ml) of the silver nitrate solution (1 mol / l) of Example 1 II) (Example 19)
  • the solution was replaced with 4 ml of each aqueous solution (1 mol / l) and stirred with 6 ml of pure water and 10 ml of ethanol in a brown bottle.
  • silica nanoparticle-dispersed aqueous solution Sigma-aldrich, LUDOX, TM-50, nanoparticle particle size 22 nm, concentration 50% by mass
  • concentration of silica at this time was 2.5% by mass. Accumulation of the silica fine particles was confirmed in any of Examples 16 to 19, and it was also confirmed by microscopic observation of the cross section that a good composite on which the coating layer was formed was obtained.

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Abstract

L'invention concerne une caractéristique avec laquelle il est facile d'accumuler des microparticules solides et également de former un motif, qui était difficile à obtenir dans l'état de la technique. L'invention concerne un procédé de production d'un composite comprenant un métal revêtu de microparticules solides, le procédé comprenant une étape dans laquelle : un métal est déposé, par rayonnement d'une lumière laser à impulsions ultracourtes, dans une solution qui comprend des ions métalliques, un colloïde, et/ou un complexe ; et des microparticules solides dispersées dans la solution recouvrant le métal déposé, les microparticules solides comprenant des particules d'oxyde métallique, des particules d'oxyde non métallique, ou des particules de céramique.
PCT/JP2018/038040 2017-10-16 2018-10-12 Procédé de production d'un composite comprenant un métal revêtu de microparticules solides Ceased WO2019078100A1 (fr)

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WO2022172972A1 (fr) * 2021-02-09 2022-08-18 国立大学法人山形大学 Procédé de production de composite par irradiation laser, et composite
CN115097656A (zh) * 2022-04-22 2022-09-23 东北大学 一种硼化钛纳米粒子在制作光调制器中的应用
JP7596581B1 (ja) 2024-03-28 2024-12-09 大阪瓦斯株式会社 酸化物複合体
CN119461893A (zh) * 2024-11-25 2025-02-18 哈尔滨工业大学（威海） 一种激光表面改性技术用于连接陶瓷/玻璃与金属的方法

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CN113122747B (zh) * 2021-04-22 2021-11-16 合肥工业大学 一种具有优异力学性能的Cu-(WC-Y2O3)复合材料制备方法

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CN119461893A (zh) * 2024-11-25 2025-02-18 哈尔滨工业大学（威海） 一种激光表面改性技术用于连接陶瓷/玻璃与金属的方法

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