WO1991006894A1 - Phototraitements ameliores par l'effet de resonance du plasmon - Google Patents

Phototraitements ameliores par l'effet de resonance du plasmon Download PDF

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Publication number
WO1991006894A1
WO1991006894A1 PCT/US1990/006013 US9006013W WO9106894A1 WO 1991006894 A1 WO1991006894 A1 WO 1991006894A1 US 9006013 W US9006013 W US 9006013W WO 9106894 A1 WO9106894 A1 WO 9106894A1
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Prior art keywords
nanoparticles
solution
particles
plasmon resonance
metal
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PCT/US1990/006013
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English (en)
Inventor
Steven C. Hill
Ramesh C. Patel
Delmar L. Barker
Kim A. Baker
Joseph G. Stumpf
Jeffery E. Jacob
John E. Creange
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Research Corporation Technologies, Inc.
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Publication of WO1991006894A1 publication Critical patent/WO1991006894A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/025—Explicitly spheroidal or spherical shape
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/58—Processes for obtaining metallic images by vapour deposition or physical development
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/413—Nanosized, i.e. having sizes below 100 nm
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/61—Surface treated
    • A61K2800/62—Coated
    • A61K2800/63—More than one coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

Definitions

  • This invention generally relates to the use of the plasmon resonance effect to enhance photoprocesses.
  • the plasmon resonance effect is shown by certain small particles when dispersed in selected media, and this can result in increased intensity of electromagnetic fields
  • the extent to which a particle exhibits the plasmon resonance effect depends on a number of factors, including the size and shape of the particle, the material or materials from which the particle is made, and, in a particle made of a plurality of materials, - j e the order, number, shape and dimensions of the materials from which the particle is made.
  • the plasmon resonance effect may be enhanced in particles comprised of shells and cores of metals and dielectrics and that have sizes on the order of magnitude of nanometers.
  • composite nanoparticles are of special interest because they can be made to exhibit an enhanced plasmon resonance effect at a selected electromagnetic frequency.
  • 20 a is the radius of the core of the particle
  • b is the radius of the particle
  • e 1 is the dielectric constant of the core
  • e 2 is the dielectric constant of the shell, and e 3 is the dielectric constant of the surrounding medium.
  • An object of the present invention is to use the plasmon resonance effect to enhance photo processes.
  • Another object of the present invention is to provide various devices in which features of the plasmon resonance effect associated with nanoparticles are used either to make the device function or to function better.
  • Another object of this invention is to provide various methods and devices with nanoparticles that exhibit the plasmon resonance effect to enhance photo processes that occur in those methods and devices.
  • a further object of the present invention is to provide a substrate material with nanoparticles that exhibit the plasmon resonance effect to facilitate forming an integrated circuit in that substrate.
  • Another object of this invention is to provide a metal catalyst in the form of metal coated nanoparticles where those particles exhibit the plasmon resonance effect to increase the catalytic activity of the metal.
  • Another object of the present invention is to provide a photochemical reaction, of the type where molecules absorb light to reach an excited state, with metal coated nanoparticles that exhibit the plasmon resonance effect to increase the rate at which the molecules absorb light.
  • Another object of the present invention is to use nanoparticles, designed to take advantage of the plasmon resonance effect, to enhance the electromagnetic fields in and around the nanoparticles in such a way that the rates of photochemical reactions, such as those used for solar energy conversion or photochemical decomposition of pollutants, are increased in the media surrounding the particles and/or in media that has moved into the particles.
  • Another object of the present invention is to enhance the effectiveness of photoactivated pharmaceutical agents, such as those used in photodynamic therapy, by binding such agents to nanoparticles that were designed to take advantage of the plasmon resonance effect and to enhance the sensitivity of the pharmaceuticals to light.
  • Another object of the present invention is to enhance the effectiveness of photoactivated pharmaceutical agents by binding such agents as well as antibodies (e.g., tumor specific antibodies) to nanoparticles that were designed to take advantage of the plasmon resonance effect -, r- and to enhance the sensitivity of the pharmaceuticals to light.
  • agents as well as antibodies (e.g., tumor specific antibodies) to nanoparticles that were designed to take advantage of the plasmon resonance effect -, r- and to enhance the sensitivity of the pharmaceuticals to light.
  • Another object of the present invention is to use nanoparticles, designed to take advantage of the plasmon resonance effect, to enhance the absorption of 2 Q electromagnetic energy and hence to enhance the photoactivation of the materials comprising the particles, and to use such photocatalytic particles to catalyze such reactions as the decomposition of pollutants, or the deposition of metals in integrated circuits, c
  • Another object of this invention is to decompose pollutants by a photocatalytic process in which nanoparticles that exhibit the plasmon resonance effect are used to accelerate the decomposition of the pollutants.
  • a further object of the present invention is to
  • Another object of the present invention is to use nanoparticles, designed to take advantage of the plasmon resonance effect, to enhance the absorption of electromagnetic energy in a solar heating device.
  • t - Another object of this invention is to provide a solar heater device with a liquid including nanoparticles that exhibit the plasmon resonance effect to enhance the absorption of solar energy by liquid.
  • a further object of the present invention is to apply nanoparticles that exhibit the plasmon resonance effect, to a terminal of a photochemical battery to enhance the conversion of solar energy to electrical energy.
  • Another object of the present invention is to use coated nanoparticles designed to take advantage of the TC plasmon resonance effect, to enhance the absorption of electromagnetic energy, and hence to block certain wavelengths of optical energy, and to use such particles in sun screens.
  • a further object of this invention is to improve 2o the sensitivity of a test of a solution for a bio-agent by dispersing in the solution nanoparticles that, or that can, exhibit the plasmon resonance effect.
  • Another object of the present invention is to use coated nanoparticles exhibiting the plasmon resonance effect 25 to enhance the fluorescence emission or Raman scattering from molecules near or on the particle, and to use such particles in the detection of chemical or biochemical species.
  • Another object of the present invention is to coat a photo activated pharmaceutical onto nanoparticles that exhibit the plasmon resonance effect to increase the sensitivity of the pharmaceutical to light.
  • Another object of this invention is to use nanometer sized silica particles as nucleation centers for the particles used in solid propellants to control more accurately the size distribution of those particles.
  • Another object of the present invention is to use nanoparticles that exhibit the plasmon resonance effect to improve the sensitivity of a method for developing fingerprints on surfaces.
  • Another object of the present invention is to use coated nanoparticles exhibiting the plasmon resonance effect to enhance the fluorescence emission from molecules near or on the particle, and to use such particles to make fingerprints more visible.
  • Another object of the present invention is to use nanoparticles to enhance, via a plasmon resonance, the electromagnetic fields in and around the nanoparticles in such a way that plasma formation is initiated with substantially lower incident optical densities than is required when no particles are present.
  • a first embodiment of this invention is a method of forming an integrated circuit comprising the step of forming a film by forming a first layer of silver coated nanoparticles, forming a second layer containing TiO- partides over the first layer, and forming a third, protective polymer layer over the second layer. This method further comprises the steps of illuminating the film through a mask to produce Ag centers in the film, and developing the film to change these Ag centers to metallic lines.
  • Another embodiment of this invention is an improved method in which a metal catalyst is used to accelerate a reaction between first and second chemicals.
  • the metal catalyst is provided in the form of metal coated nanoparticles, and those particles are illuminated so that they exhibit the plasmon resonance effect and thereby
  • a further embodiment of the invention is an improved photochemical reaction of the type wherein light absorption causes molecules to reach excited singlet states and then decay to triplet states; and more specifically, the improvement is to
  • a further embodiment of this invention is a method for the photoredox of first and second reactants to produce a fuel, comprising the steps of providing a solution containing those reactants, Q locating metal coated nanoparticles in the solution, and exposing the solution to light to react the first and second reactants together to produce the fuel, wherein the metal
  • coated nanoparticles exhibit the plasmon resonance effect to accelerate the reaction of the two reactants.
  • Another embodiment of this invention is a solar heater device comprising a liquid including nanoparticles 5 that exhibit the plasmon resonance effect, thereby increasing absorption and heating, and means for holding the liquid while it is exposed to solar energy, wherein the nanoparticles enhance the effect of the solar energy on the liquid.
  • a further embodiment of the present invention is a
  • O photochemical battery comprising first and second electrodes, at least one of which is solar responsive such that the electric potential of that electrode changes when it is exposed to light.
  • This battery also comprises a multitude of nanoparticles applied onto that solar responsive electrode, 5 and these particles exhibit the plasmon resonance effect and thus enhance the effect of light on that electrode.
  • a sunscreen base is provided with nanoparticles that exhibit the plasmon resonance effect to inhibit the passage of ultraviolet light
  • a further embodiment of the present invention is a method for testing a solution for a given bio-agent.
  • the method includes the steps of dispersing in the solution a fluorescent agent that is capable of attaching to the given
  • the method further includes the step of testing the solution for fluorescence to determine whether the bio-agent is present in
  • the sensitivity of a photoactivated pharmaceutical is increased by coating the pharmaceutical onto a nanoparticle that exhibits the plasmon resonance effect.
  • a still additional embodiment of this invention use coated nanoparticles in solid propellants. More specifically, particles including a nanometer sized core of a first material, and at least one layer of a second material formed on that core, are used to form the solid particulates of a solid propellant.
  • the present invention also uses the plasmon resonance effect in methods for developing fingerprints on a surface.
  • a first such method comprises the steps of applying to the surface a fluorescent dye to attach that dye to the profile of the fingerprint; and also applying to the surface, nanoparticles that exhibit the plasmon resonance effect to attach those particles to the surface outside the profile of the fingerprints.
  • This method further comprises the steps of illuminating the surface to activate the fluorescent dye to generate fluorescent light, wherein the nanoparticles attenuate activity of any fluorescent dye that has become attached to the surface outside the profile of the fingerprints, and sensing the fluorescent light emitted from the surface to detect the profile of the fingerprint.
  • a second method comprises the steps of applying a fluorophore to the surfaces of nanoparticles that exhibit the plasmon resonance effect, and attaching those particles to the profile of the fingerprint.
  • This second method also comprises the steps of illuminating the surface to activate the fluorophore to generate fluorescent light, wherein the nanoparticles enhance the fluorescent light generated by the fluorophore, and sensing the fluorescent light emitted from the surface to detect the profile of the fingerprint.
  • Figure 1 shows a base or substrate from which an integrated circuit can be made, and which includes TiO-. nanoparticles.
  • Figure 2 generally illustrates how a nanoparticle can be used to improve detection of a specific bio-agent.
  • Figure 3 shows an alternate combination of materials also employing nanoparticles to improve detection of a bio-agent.
  • Figure 4 illustrates a nanoparticle structure that may be used in a process for detecting bio-agents.
  • Figure 5 depicts the nanoparticle structure of Figure 4, as bio-agents are about to be attached to the structure.
  • FIGS 6-13 which are not drawn to scale, show various particles that may be used in or in conjunction with the present invention.
  • Figures 14-22 outline several process that may be used to make the particles shown in Figures 6-13.
  • Figure 23 is a transmission electron micrograph of silver-coated silver bromide nanoparticles.
  • Figure 24 is a transmission electron micrograph of silver coated silver bromide nanoparticle treated with ammonia.
  • Figure 25 shows various optical extinction spectra of silver coated silver bromide nanoparticles.
  • (a) to (d) are spectra of various illuminated solutions of Ag, Br and EDTA. In going from (a) to (d) , the illumination time increases.
  • Figure 26 shows computed extinction efficiencies for silver-coated silver bromide particles in water.
  • the diameter of the core particle is 20 nm and the thicknesses of the silver coats are indicated in nm.
  • the spectrum marked solid is that of a homogeneous 20 nm diameter silver sphere.
  • Figure 27 is an optical extinction spectra of a measured silver coated silver bromide nanoparticle and two computed extinction spectra. The measured spectrum lies between the two computed spectra. In the upper curve all the silver in the coat is assumed to come from the solution. In the lower curve all of the silver is assumed to come from the reduction of AgBr at the particle surface.
  • Particles exhibiting the plasmon resonance effect can be incorporated into, and employed in, such photolithographic methods in various ways.
  • a very thin film 10 ( 1 micron) of such particles 12 on a suitable substrate 14 can be formed by using a suspension of the particles in a mixture containing a monomer 5 and an initiator, and spin coating the substrate.
  • a number of suitable polymer systems can be chosen to produce a thin polymer film containing the particles.
  • another film 16 containing Ti0 2 particles of small diameter can be formed in a similar manner, or by allowing a o titanium (IV) organometallic polymer film to hydrolyze directly to yield the Ti0 2 particle film.
  • a third protective polymer film 20, which may contain a reducing agent (aldeyde, benzoqunone) is finally laid. The total film thickness is kept low to achieve high resolution. Illumination of this 5 film by UV light through a suitable mask 22 produces Ag centers which can be developed to produce metallic lines of copper and/or nickel using an appropriate developer.
  • a variation of the photochemical method, discussed in detail below, which is used to produce metal o (e.g., silver or aluminum) coated particles can be used.
  • a thin polymer film containing dielectric particles with absorbed metal (e.g., silver or aluminum) ions, and photoactivated reducing agents e.g., a combination of organic compounds containing keto- and isopropyl groups
  • photoactivated reducing agents e.g., a combination of organic compounds containing keto- and isopropyl groups
  • an excimer laser e.g., 248 nm 0 emission
  • latent images with much higher resolution can be produced, and developed using conventional methods.
  • metal-coated nanoparticles are used to enhance the rates and/or make more efficient a variety of photochemical reactions.
  • the development is based on the fact that optical fields are resonantly enhanced near the surface of a metal-coated particle having appropriate thickness of cores and coats, and on the fact that the metal-coated particles can be particularly good absorbers of light.
  • light either acts to catalyze a reaction or provides the energy to drive a reaction.
  • concentrated sunlight can increase the speed of reactions in which toxic pollutants are decomposed.
  • toxins such as pesticides or PCB's are decomposed into CO- , water and simple acids. The reactions go faster when the light is more intense.
  • the energy from sunlight can be used to generate electricity in a storage battery, a photovoltaic cell or a photoelectrochemical cell.
  • the energy from sunlight can be used to drive reactions such as photoredox reactions that produce fuels such as formaldehyde or methanol from water and carbon dioxide or ammonia from nitrogen and water.
  • the preferred embodiment is a metal-coated dielectric particle that is coated with Ti0 2 -
  • the particles are dispersed in the liquid that contains the pollutants.
  • the particles are bonded to a surface and only part of the particles is in direct contact with the liquid.
  • the particles are trapped in an agarose or sepharose gel having pores small enough that the particles remain in the gel.
  • the particles are chemically bonded to gel.
  • the preferred embodiment is a metal-coated dielectric particle that is coated with Ti0 2 .
  • the thickness of the core, the metal coat, and the Ti0 2 coat are chosen so as to maximize the intensity of optical fields in and outside the i0 2 layer.
  • the particles may be made by processes described below.
  • the particles are dispersed in the liquid that contains the reactants.
  • the particles are bonded to a surface and only part of the particles is in direct contact with the liquid. 5 In another embodiment, the particles are trapped in an agarose or sepharose gel having pores small enough that the particles remain in the gel.
  • the particles are chemically bonded to gel.
  • the plasmon resonance effect can be used with solar power technology.
  • highly absorbing beads could be placed in water or other liquid to heat up the fluid in solar heater 5 devices.
  • photochemical batteries such as the AgCl photo voltaic battery could be enhanced by the use of small beads on the AgCl electrode. Work already exists that shows by roughening the electrode, the photo current increases 0 markedly as well as SERS effects at the surface of the electrode.
  • Beads can be used as a UV-blocking sun screen.
  • a sphere is designed to improve fluorescence detection of a specific bio-agent.
  • a fluorescent agent F
  • an antibody or antigen 56 with a plasmon resonating sphere 60 in the neighborhood such that the fluorescence of agent F is increased or decreased, depending on whether the sphere goes off or on resonance.
  • agent F should be enhanced and, therefore, make the above process more easily detectable.
  • flat surfaces such as surface 62 shown in Figure 3.
  • Any photo activated pharmaceutical could be coated onto an active sphere which would then become more sensitive to any light shined on it. That would mean shorter treatment time or less intense light to activate the light sensitive drug.
  • any material having a negative real part of the dielectric constant can also be used in sunscreens, in florescence detection, and in photo activated pharmaceuticals.
  • the NRDC materials includes super conductors, conducting polymers and materials with an anomalous dispersion of carrier electrons and heavily doped semiconductors where free carrier motion dominates the dielectric function, and the like.
  • nanometer-sized dielectric particles are used as nucleation centers for the particles used in solid propellants.
  • the particle sizes can be more accurately controlled, and smaller sizes can be obtained. • Consequently, o the properties of the propellant can be more accurately controlled.
  • the size distributions of the particles in solid propellants is important in determining the burn rate and other properties.
  • Well-controlled, uniformly-sized particles can be generated by using very-small dielectric particles as nucleation centers for some salts. These methods can also be applied to other salts such as ammonium nitrate, ammonium perchlorate or other solid phase components of solid propellants. Similar methods can also be used to generate o accurately-sized metallic particles such as aluminum or magnesium which are used in some solid propellants.
  • the major advantages of using accurately sized particles grown on dielectric are that the size distributions can be very well controlled and the particles generated can be much smaller than those presently used.
  • the size distributions now obtained using conventional crystal-growth processes have relatively large standard deviations.
  • the size distributions now obtained using liquid-liquid mixing processes are determined primarily by the shear forces
  • 35 particles of various sizes can be inexpensive and can be purchased in large volumes.
  • a further embodiment of the present invention relates to using metal coated nanoparticles to help develop fingerprints from paper and similar surfaces.
  • This is currently a very active area, and a current method used is to fluorescent label the fingerprint profile by means of a suitable dye, and scan the fluorescence emission to achieve a spatial resolution by means of a gated diode array detector.
  • One problem with this method is the relatively high background fluorescence which originates from the substrate. To circumvent this, the time resolved, longer lived (but generally very weak) triplet emission is detected by the diode array spectrometer operated in the gated mode.
  • the properties of the metals, (e.g. silver or gold) coated nanoparticles can be exploited in two ways:
  • the particles can be prepared with a suitable crosslinking agent (amino acids or proteins) attached to the surface, enabling them to be covalently bonded to the fingerprint profile.
  • a suitable crosslinking agent amino acids or proteins
  • a spatial resolution of the reflectance spectrum can be achieved by directly digitizing the optical signal. This aspect of signal processing is very similar to the reading of bar codes in super markets, and should make it relatively simple to mass produce. At the same time, the method would be extremely sensitive, free from interference, and inexpensive.
  • a suitable fluorophore can be attached to the surface of the particles, which would mark the fingerprint profile as in (1). It is likely that the triplet emission will be enhanced due to the heavy atom effect, and the fluorescence emission increased due to the presence of silver coated particles. The net result will be much higher sensitivity, and reduction from background fluorescence.
  • Laser induced plasmas are formed when the optical intensities in materials are sufficiently large [L.J. Radziemski and D.A. Gremers, eds., Laser Induced Plasmas, (Marcel Decker: New York), 1989]. Once the plasma is initiated it more readily absorbs the incident radiation and grows. The plasma may then protect the underlying surface from the laser beam. The plasma may also be used as a broadband light source, or may be useful for materials processing or other applications. Also pursuant to this invention, a material is provided that provides for plasmas to be generated with lower laser intensities than are now required. In one embodiment of this invention, metal coated nanospheres, designed to enhance the fields at the wavelength of an incident laser beam, are used to decrease the intensity of the incident beam that is required for plasma formation.
  • the nanospheres provide a means of generating plasmas with lower intensity lasers than have been used previously.
  • One very small (20 to 50 nm) nanosphere can enhance the intensity in a small region near the sphere by a factor that is in the hundreds. Since only a very small region of high intensity is required for the plasma formation, a low concentration of very small spheres can be used.
  • each of these particles includes a core surrounded by a shell, and at least one of the core and shell consists essentially of a metal.
  • the metals include the transition metals, the lanthanides and the Group IIIA metals, and the like.
  • the especially preferred metals include the Group VIII and IB metals, especially copper, silver, gold, iron, nickel, palladium, platinum, cobalt, rhodium, iridium, ruthenium, aluminum and the like.
  • Especially preferred metals include copper, silver, gold, nickel, palladium, platinum and aluminum.
  • the other of the core and shell may consist essentially of a dielectric material.
  • dielectric material or core refers to a material which is a non-conductor or a semi conductor.
  • the conductivity of the material may range from 0, but preferable as low as 10 ⁇ to 10 mhos. In a preferred embodiment the conducti .vi.ty ranges from 10-40 to 105 mhos. In a most preferred embodiment, the conductivity ranges from 10 -30 to
  • dielectric material examples include glass, silica, cadmium sulfide, gallium arsenide, polydiacetylene, lead sulfide, titanium dioxide, polymethylacrylate (PMMA), silver bromide, carbon fibers, copper sulfide, silver sulfide and the like.
  • Figures 6-9 show four types of particles, referenced at 70, 72, 74, and 76, respectively, that may be employed in the methods and apparatuses of this invention.
  • Particle 70 consists of core 70a and shell 70b, the core consists essentially of a dielectric material such as silica, and the shell consists essentially of a metal, such as silver, and is disposed immediately over and substantially completely covers core 70a.
  • Particle 72 consists of core 72a, first shell 72b and second shell 72c.
  • Core 72a consists essentially of a dielectric material such as silica
  • shell 72b consists essentially of a first metal and is disposed immediately over and substantially completely covers core 72a
  • shell 72c consists essentially of a second metal and is disposed immediately over and substantially completely covers shell 72b.
  • particle 74 consists of dielectric core 74a, a layer of a first metal 74b disposed immediately over and substantially completely covering layer 74a, a layer of dielectric material 74c such as a polymer, disposed immediately over and substantially completely covering layer 74b, and a layer of a second metal 74d disposed immediately over and substantially completely covering layer 74c.
  • Figure 9 shows a fourth particle 76 that may be used in the practice of this invention and which comprises core 76a comprised of a metal and shell 76b comprised of a dielectric material.
  • particle 76 may be provided with additional layers over shell 76b.
  • FIGS 10-13 show four additional particles, referenced at 80, 82, 84 and 86, respectively, that may be used in, or in conjunction with, the present invention.
  • Each of these particles includes at least a core surrounded by a shell; and in each of these particles, one of the core and shell includes silver halide, and the other of the core and shell includes a dielectric material.
  • particle 80 consists of core 80a and shell 80b, the core consists essentially of a dielectric material such as silica, and the shell consists essentially of silver halide. Further, with this particle, shell 80b is disposed immediately over and substantially completely covers core 80a.
  • This particle does not itself include any metal and thus does not exhibit the plasmon resonance effect.
  • the silver halide in the particle may be changed to metal silver, either to form a layer of metal silver on the particle or to help form a layer of another metal thereon, and to thereby form a particle that does exhibit the plasmon resonance effect.
  • particle 82 a metal coating such as silver, copper, aluminum, gold or palladium is disposed between the dielectric core and the silver halide shell to increase the sensitivity of the silver halide to light. This increased sensitivity is caused by the plasmon resonance effect produced by the metal coating. More specifically, particle 82 consists of dielectric core 82a, metal coating 82b disposed immediately over and covering that core, and a layer of silver halide 82c disposed immediately over and covering layer 82b.
  • particle 84 consists of dielectric core 84a, a layer of silver 84b disposed immediately over and covering core 84a, a layer of dielectric material 84c such as a polymer, disposed immediately over and substantially covering the silver layer, and shell 84d formed of silver halide disposed immediately over and substantially completely covering layer 84c.
  • a silver halide nanoparticle used in or in conjunction with the present invention and that includes both r- silver halide and a dielectric material it is not necessary that the dielectric material and the silver halide form the core and shell of the particle, respectively; and
  • Figure 13 shows silver halide particle 86 that may be used in or with the present invention and which comprises core 86a comprised 0 of silver halide and shell 86b comprised of a dielectric material.
  • the particle 86 shown in Figure 13 it may be desirable to provide the particle with a layer of metal (not shown) to enhance the sensitivity of the silver halide to light; and if this is done, to further provide the particle with a still further coating of a dielectric material (also not shown) between that metal layer and the silver halide core of the particle to prevent the metal and the silver halide from chemically reacting with each other.
  • Figures 6-13 are only representative of 0 nanoparticles that may be used in the present invention, and in particular, only illustrate the general relationship between the cores and the shells of the shown particles.
  • the particle and the core thereof may have any suitable shapes, and specifically, the particles and the cores may have shapes other than spherical.
  • the particles and the cores may be cylindrical or ellipsoidal, have a thread-like shape, or be crystalline shaped.
  • the actual crystal form of the core may be any suitable form; and, for example, these cores may be: Q Tetragonal crystal forms,
  • any suitable dielectric material may be used, and in particular, the dielectric material may be linear or non-linear.
  • metal includes any material having a negative dielectric constant, and so can include superconductors, conducting polymers, materials with an anomalous dispersion of carrier electrons, and heavily doped semiconductors where free carrier electron motion dominates the dielectric function.
  • a metal-halide coated nanoparticle can be prepared by providing a source of metal ions and a source of halide ions in a liquid carrier having dispersed therein charged colloidal dielectirc particles and reacting the halide ions with the metal ions in the presence of the dielectric particles to form coatings of metal halide over individual dielectric particles.
  • silver halide coated dielectric particles such as particle 70 of Figure 6, may be made by a process generally comprising the steps of providing an aqueous solution including negatively charged colloidal dielectric particles, positively charged silver ions, and a halide, and reacting the halide with the silver ions to bond, or grow, coatings of silver halide completely covering individual dielectric particles.
  • concentrations of dielectric particles, silver ions and halide in the solution, and the length of time over which the coatings are allowed to grow on the dielectric particles are selected so that coatings of a uniform preselected thickness are grown on those particles.
  • the specific order in which the dielectric particles, the silver ions and the halide are added to the aqueous solution is not critical; and, for example, the dielectric particles may be dispersed in the solution, then the silver ions may be added, and then the halide may be added.
  • the pH of that solution is adjusted to and thereafter maintained at a level slightly above 2, and even more preferably, between about 3 and 5.
  • the dielectric particles do not have to be negatively charged when they are added to the solution, and, instead, the acidity of the aqueous solution causes the dielectric particles to become negatively charged once the particles are in the solution.
  • the initial concentration of the silver ions in the solution is relatively low, less than 10 ⁇ M; the initial concentration of the halide in the solution is slightly greater than, such as about 10% greater than, the concentration of the silver ions in the solution; and also, the solution is constantly stirred while the halide is being added to it.
  • the silver ions may be added to the solution in any suitable form, and for instance, these ions may be added in the form of a silver salt soluble in water, e.g., silver nitrate.
  • the halide that is added to the solution may be any suitable halide, such as alkali halide, e.g., sodium bromide, potassium bromide, sodium chloride, or potassium chloride, and the like.
  • any suitable dielectric may be used in the above-discussed process, and the dielectric may be linear or non-linear and may have any suitable shape and size.
  • the dielectric particles may be spherically shaped silica particles.
  • the dielectric particles are these silica particles
  • the silver ions are added to the solution in the form of silver nitrate
  • the halide is sodium bromide
  • the silver from the silver nitrate reacts with the r- bromide from the sodium bromide to form silver bromide, which bonds to and forms layers over the silica particles.
  • Figure 15 generally outlines a process for making a metal coating on a dielectric particle, such as coating 72b of particle 72, or coating 74b of particle 74.
  • This process 0 generally comprises the steps of providing an aqueous solution including negatively charged colloidal dielectric particles, metal ions, a secondary alcohol, preferably a lower secondary alcohol containing 3-6 carbon atoms (e.g., isopropanol) and a ketone, preferably containing 3-6 carbon atoms, such as acetone; removing oxygen from the solution; and exposing the solution to ultraviolet light to cause the metal ions to attach to the dielectric particles and form metal coatings completely covering individual dielectric particles.
  • aqueous solution including negatively charged colloidal dielectric particles, metal ions, a secondary alcohol, preferably a lower secondary alcohol containing 3-6 carbon atoms (e.g., isopropanol) and a ketone, preferably containing 3-6 carbon atoms, such as acetone
  • the concentrations of the dielectric particles, the metal ions, the isopropanol and the acetone, and the length of time the solution is exposed to the ultraviolet light are selected so that coatings of a uniform, preselected thickness are formed on the dielectric particles.
  • lower alkyl when used alone or in combination, contains 1-7 carbon atoms.
  • alkyl groups may be straight chained or branched and include such groups as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl, amyl, hexyl, heptyl and the like.
  • a secondary alkanol refers to a lower alkyl alcohol in which the hydroxy group is attached to a secondary carbon.
  • groups include isopropanol, sec-butanol and the like.
  • the preferred ketone is acetone.
  • the acetone absorbs energy from the ultraviolet light and then reacts with isopropanol to form isopropyl radicals.
  • These radicals are powerful reducing agents and cause metal ions that have become attached to the dielectric particles to form metal molecules.
  • the particular order in which the dielectric particles, the metal ions, the isopropanol and the acetone are added to the aqueous solution is not critical; and, for instance, the isopropanol and acetone may be added to the solution, the dielectric particles may then be dispersed in the solution, and then the metal ions may be added.
  • the pH of the solution is adjusted to and thereafter maintained at a level slightly above 2, and even more preferably, between about 3 and 5.
  • the dielectric particles do not have to be negatively charged when they are added to the solution and the acidity of the aqueous solution causes the dielectric particles to become negatively charged.
  • the initial concentration of the metal ions in the solution is relatively low, such as 2 x 10 -4M; and the initial concentration of the acetone and isopropanol in th solution are about equal to each other and much greater than, such as about 400 times greater than, the initial concentration of the metal ion in the solution.
  • the solution is stirred while exposed to the ultraviolet light.
  • metal coatings may be made using a procedure as described above, and for example, the process may be used to form silver coated dielectric particles, gold coated particles or palladium coated particles.
  • the metal ions may be provided in the solution in any suitable manner; and, for example, these ions may be provided by adding a water soluble metal salt such as silver nitrate, to the solution.
  • any suitable dielectric may be used in the above-discussed process, and the dielectric may be linear or non-linear and may have any suitable shape and size.
  • the dielectric particles may be spherically shaped silica particles. When such dielectric particles are used, and the metal ions are added to the solution in form of silver nitrate, then the ultraviolet light, in combination with the acetone and the isopropanol, causes the silver ions to bond to and form metal coatings over the silica particles.
  • the following example illustrates this process for forming metal coated dielectric particles.
  • An aqueous solution is prepared by mixing the following solutions in a 50 ml beaker:
  • the sample is irradiated by a 450 Watt Hg-Xe lamp for one hour, with gentle stirring continued by means of a magnetic stirrer.
  • the solution color, and consequently the thickness of the coat can be 5 controlled by adjusting the period of illumination by UV light. This forms the basis for the preparation of the silver coated silica particles in the present example.
  • Silver coated dielectric particles may also be made by a process employing photoreduction of silver halide, and one such process is outlined in Figure 16.
  • silver halide coated dielectric particles are made, for example, by the process discussed above in connection with Figure 14, and then the coated particles are exposed to light to change the silver halide coatings over the individual particles to metal silver coatings.
  • a more integrated process is used to form silver coated dielectric particles.
  • dielectric particles are dispersed in a solution including silver ions, a halide and an electron hole scavanger, and the metal ions react with the halide to form silver halide coatings completely covering the dielectric particles.
  • the solution is then exposed to ultraviolet light, and this light changes the silver halide coatings to silver coatings.
  • the concentrations of the dielectric particles, the silver ions, the halide and the electron hole scavenger in the solution, and the length of time the solution is exposed to the ultraviolet light are selected so that coatings of a uniform, preselected thickness are formed on the dielectric particles.
  • the initial concentration of silver ions in the solution is greater than the initial concentration of the halide in the solution; and for instance, the former concentration may be about 5 times the latter concentration.
  • the silver ions may be in the solution in any suitable form.
  • the silver ion may be added to the solution in the form of silver nitrate.
  • the halide that is added to the solution may be any suitable halide such as alkali halide, e.g., sodium bromide, potassium bromide, sodium chloride, potassium chloride and the like.
  • any suitable dielectric may be used in this process, and the dielectric be linear or non-linear and have any suitable shape and size.
  • the dielectric particles may be spherically shaped silica particles.
  • the dielectric particles are the silica particles
  • the silver ions are added to the solution in the form of silver nitrate, and
  • the halide is sodium bromide
  • the silver from the silver nitrate reacts with the bromide from the sodium bromide to form silver bromide
  • the ultraviolet light in the presence of EDTA, then reduces the silver bromide coatings to metallic silver.
  • the light source used contain ultraviolet light. It is preferred that the light source contain wavelengths of 150 - 550 nm. The preferred wavelengths range from 200-400 nm.
  • the intensity of light used ranges from 50 watts to 1.5 kilowatts, with the preferred intensity ranging from 250-1000 watts. Especially preferred intensity ranges from 350-550 watts, with an intensity of about 450 watts being the most preferred.
  • the following example illustrates this process for forming silver coated dielectric particles.
  • EXAMPLE 2 Metallic silver on Si0 2 particles can be obtained by photoreduction of silver halides, which are typically prepared in the presence of excess Ag ions. A hole (h ) scavenger, EDTA, is added to the solution. One ml of a 0.002 M NaBr solution is added to 19 ml of a solution which was prepared in a 50 ml beaker mixing the following:
  • the duration of illumination which is in the order of minutes, determines the color of the silver coated silica particles. This color is a result of the thickness of the silver layer, and can range from yellow to a purplish gray.
  • the silver coated silica spheres are prepared, they are purified by dialysis and then placed in a sodium dodecyl sulfate micellar solution, or a micro emulsion.
  • a variation of the process described above may be employed to form metal coatings other than silver on nanoparticles, and this variation utilizes the fact that metallic silver on the dielectric particles will act as a catalyst to help grow metal coatings on those particles from other metal ions in the solution.
  • a solution is provided including dielectric particles, silver halide is formed on those particles, the solution is exposed to light to change at least a portion of the silver halide to metallic silver, and ions of a metal are added to the solution to form coatings of that metal completely covering individual dielectric particles, with the metallic silver on those particles acting as a catalyst to accelerate the formation of the metal coatings.
  • These metal ions may be added to the solution in any suitable manner, and for instance, conventional photographic developing solutions may be added to the solution to add the metal ions.
  • the resulting product comprises a dielectric core, a first coating of silver that substantially completely covers the dielectric core, and a second coating of a metal that completely covers the layer of silver halide.
  • the following example illustrates the coating of silver on an dielectric core of silver bromide.
  • the silver bromide nanoparticles exposed briefly the intense UV light in the presence of EDTA have optical extinction spectra similar to those computed for distribution of silver coated silver bromide nanoparticles.
  • intense it is meant that the intensity of the light ranges from 50 watts to 1.5 kilowatts, with the preferred range being 250-550 watts, and the most preferred having a range of 350-550 watts.
  • the plasmon resonance maximum is shifted to lower wavelengths, a result consistent with theory so long as the coat thickness increases with exposure to light.
  • the resonance maximum of the distributions of coated particles can be controllably shifted to 600 to 700 nm.
  • EXAMPLE 3 Silver bromide colloids were prepared by rapidly mixing equal volumes of AgN0 3 and NaBr solutions. A growth stabilizer (SDS) and an electron donor (EDTA) were added immediately after precipitation. Typically the final concentrations were 1 x 10 -4 M Br-, 4 x 10-4 M Ag+, 5 x 10-4
  • the particle size distributions were characterized with transmission electron microscopy (JEOL 1200EX) .
  • a typical micrograph is shown in Fig 23.
  • a size distribution consistent with the limited micrograph data is the log normal distribution.
  • N(r) N 0 exp(-((ln(r) - ln(r m ) )/ln(s) ) 2 ) , with rm equal to 1 nm or less and s in the renge of 4 to 4.5 nm.
  • the size distributions as determined by TEM did not appear to change markedly with exposure to light.
  • Example optical extenction spectra measured shortly after exposure are shown in Figs. 25a) to d) .
  • the exposure time and/or EDTA concentration, and hence the reduction of Ag + increases in going from a) to d) .
  • the peak extinction shifts to shorter wavelengths as the illumination time is increased. This result is consistent with theory so long as the coat thickness increases with exposure.
  • a spectrum of the ammonia treated solution, shown in Fig 25e) is typical of homogeneous silver nanoparticles.
  • the general shapes of the above spectra are readily reproducible. At comparable illumination times, in the absence of Br , the appearance of color in a given sample is negligible.
  • Theoretical optical extinction spectra of individual silver coated spheres are shown in Fig. 26.
  • the peak of the theoretical extinction shifts from red to blue as the ratio of coat thickness to core radius increases. This data is consistent with the measured spectra where the absorption maxima shift toward the blue as the time of exposure increases, since the coat thickness should increase with exposure time.
  • the computed spectra are very sensitive to the coat thickness. The measured spectra are much more broad than the spectra shown in Fig. 26 because of the distributions of core diameters and coat thicknesses.
  • the magnitudes of the extinction spectra are also characteristic of silver coated particles. For example, at a wavelength of 700 nm the extinction cross section per unit volume of silver is 100's of times larger in a silver coated nanoparticle having the appropriate ratio to core radius to coat thickness that it is in a solid silver sphere. The fact that the theoretical extinction is so large can be used to help verify that the particles are coated with silver. However, since there is a broad distribution of sizes, care must be taken in making the comparision.
  • the reduced silver is in the form of a smooth coat on the surface of a spherical AgBr particle.
  • the extinction efficiencies were computed using the separation of variables solution for concentric spheres based on algorithms.
  • the size distribution of the core particles is described by the log-normal distribution of the above equation.
  • the values of N were determined by setting the total volume of all the particles prior to illumination in the distribution equal to the volume of AgBr.
  • the initial total volume of AgBr was determined by solving the ionic equilibria equations including the Ag -EDTA complex.
  • the size distribution of the coat thickness is a Gaussian, typically with a standard deviation of 2 to 8 nm.
  • the silver coat may be formed either from the reduction of the silver halide of the initial particle, or from the reduction of Ag from solution. Computations have been done for each of the two limiting cases.
  • the total extinction is computed by numerically integrating over distributions of core radii and coat thicknesses.
  • b e ( ⁇ ) jN n (r c )N g (t)Q(r c ,t,m c ,m t ,- ⁇ )TTr 2 dr c dt (2)
  • Nn is the size distribution of the cores
  • N is the size disbribution of the coats
  • Q is y the extinction efficiency
  • m is the refractive index of the core
  • m. is the refractive index of the coat.
  • the refractive index of the silver was computed from the data of Hagemann et al. in J. Ojg. Soc. Am., 65, 742-744 (1975) and Kerker, in J. Op. Soc. Am. B., 1327-1329 (1985) either by itself, or combined with a Drude model in which the increased electron scattering at the surfaces of the very thin coat was taken into account.
  • the refractive index data of Johnson and Christy in Phy_. Rev. B, S , 4370-4379 (1972) was also used for some computations not shown. Linear interpolation was used to obtain the values of refractive index at points not in the data.
  • the refractive index os AgBr was obtained by combining the data from White, J. Opt. Soc. Am, 62, 212 (1972) and James, "Theory of the Photographic Process,” McMillan (1977) p 216.
  • Fig. 27 shows a measured spectrum and two computed spectra.
  • the Ag in the coat is assumed to come only from the solution, i.e., the AgBr cores are not reduced in size as the coat grows.
  • the Ag in the coat is assumed to come only from the reduction of AgBr at the surface of the particle and so the core shrinks as the coat grows. Since the measured curve lies between the two computed spectra, the magnitudes of the plasmon enhanced extinction is in the range of values computed.
  • the main parameters that can be adjusted in fitting the distributions to the spectra are: 1) the thickness and standard deviation of the coats and the limits of the numerical integration for the coats. 2) the size distribution and the limits of integration for the cores.
  • the computed spectra are very sensitive to the distributions of cores and coats chosen and to the limits of integration, which also define the size distributions.
  • the computed spectra depend on the refractive index of silver used. However, by varying the size distributions, similar spectra can be obtained with the different models for silver. The effect of the different assumptions about the source of the Ag for the coat can be seen in Fig. 27. In a preliminary experiment without excess silver a spectrum similar to that shown in Fig. 25d) was generated.
  • the silver coat is formed by the coalescing of many small silver particles.
  • the coat may also contain some AgBr or voids, but it is homogeneous enough to have a refractive index similar to that of bulk islver.
  • the bonds between the particles may be relatively weak because the coat breaks into many small particles when the solution is treated with ammonia.
  • Silver coated dielectric particles may also be formed by a process utilizing chemical reduction of silver ions by hydroquinone at elevated temperatures.
  • Solution I consists of particles which are smaller and better defined, appear darker, and were in the size range of 10 to 30 nm.
  • the particle size range was found to be between 40 to 100 nm, the particles were similarly dark, but contained elongated as well as spherical shapes.
  • the final size distribution may be due in part to the non uniform size of the silica core particles, found to be between 7 to 11 nm by electron microscopy.
  • the coated particles may be removed from the solution in which they were prepared by dialysis, and then placed in a sodium dodecyl sulfate micellar solution or a micro emulsion. Additional coatings of either silver halide, a metal or a polymer, may then be added until the desired final configuration is reached. Polymer coating of any of these particles may be readily achieved in a solution by the well known emulsion polymerization method, in which a suitable amount of monomer and initiator have been added.
  • reaction can be terminated by addition of 25 ml of a 1 % solution of hydroquinone, and cooling the reaction mixture to room temperature. The particles are filtered, washed several times with double distilled water, resuspended in water, and further purified by dialysis.
  • FIG. 21 generally outlines a procedure to make particle 72 of Figure 7.
  • metal coating 72b is formed over dielectric core 72a, for example using the method of illustrated in Figure 17; and then silver halide coating 72c is made over metal layer 72b, for instance by generally following the method shown in Figure 14.
  • Figure 22 generally illustrates a procedure to make particle 74 of Figure 8.
  • metal coating 74b is formed over dielectric core 74a, for example by the process described above in connection with Figure 15, then polymer coating 74c is applied over coating 74b, and then silver halide layer 74d is formed over coating 74c, for example by generally following the procedure discussed above in connection with Figure 14.
  • halides may be replaced with organic anions to form other metal complexes.
  • organic anions include such anions as acetate, formate, citrate, EDTA, malonate, and polypeptides prepared from the natural amino acids, such as poly GLU, poly ASP, and the like. While it is apparent that the invention herein disclosed is well calculated to fulfill the objects

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Abstract

Procédé et appareil utilisant des nanoparticules sélectionnées ayant un effet de résonance du plasmon pour améliorer les phototraitements. Dans un premier mode de réalisation, de telles manoparticules sont utilisées dans un procédé de formation d'un circuit intégré. Dans d'autres modes de réalisation, les nanoparticules sont utilisées pour augmenter l'effet catalytique d'un catalyseur métallique, pour augmenter la vitesse à laquelle les molecules absorbent de la lumière, pour accélérer la réduction de dioxyde de carbone sur l'acide formique, pour accélérer la décomposition d'agents polluants, et pour accélérer la réaction de deux réactants pour produire un combustible. Des modes supplémentaires de réalisation utilisent l'effet de résonance du plasmon pour augmenter l'effet de l'énergie solaire sur une électrode solaire d'une batterie photochimique, et pour inhiber le passage de lumière ultraviolette au travers d'un écran solaire. De même, selon la présente invention, des nanoparticules qui présentent l'effet de résonance du plasmon sont utilisées pour améliorer un test pour une solution d'un bioagent et pour développer des empreintes digitales sur une surface.
PCT/US1990/006013 1989-10-18 1990-10-18 Phototraitements ameliores par l'effet de resonance du plasmon WO1991006894A1 (fr)

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US5869346A (en) * 1993-11-19 1999-02-09 Kyoto-Dai-Ichi Kagaku Co., Ltd. Method of and apparatus for analyzing immunity by raman spectrometry
WO1998009153A1 (fr) * 1996-08-30 1998-03-05 Medifor, Ltd. Resonances collectives dans des ensembles bidimensionnels pour couches minces metalliques colloidales
US9441156B2 (en) 1997-11-13 2016-09-13 Massachusetts Institute Of Technology Highly luminescent color-selective nanocrystalline materials
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WO2011004133A3 (fr) * 2009-07-10 2011-07-21 L'oreal Materiau composite comprenant des filtres uv et des particules plasmoniques et utilisation en protection solaire.
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CN104229923B (zh) * 2013-06-21 2020-07-17 台北医学大学 制备小分子团水的设备和方法以及由其制得的小分子团水
CN112142156A (zh) * 2013-06-21 2020-12-29 台北医学大学 制备小分子团水的设备和方法以及由其制得的小分子团水
TWI552962B (zh) * 2013-06-21 2016-10-11 臺北醫學大學 製備小分子團水之設備和方法以及由其製得之小分子團水
EP2826751A1 (fr) * 2013-06-21 2015-01-21 Taipei Medical University Appareil et procédé de préparation d'un petit amas d'eau et un petit amas d'eau préparé à partir de ces derniers
CN104229923A (zh) * 2013-06-21 2014-12-24 台北医学大学 制备小分子团水的设备和方法以及由其制得的小分子团水
CN111604068A (zh) * 2020-06-21 2020-09-01 安徽理工大学 一种Ag-AgBr/TiO2纳米棒复合阵列薄膜的制备方法
CN111604068B (zh) * 2020-06-21 2022-10-28 安徽理工大学 一种Ag-AgBr/TiO2纳米棒复合阵列薄膜的制备方法
CN115301259A (zh) * 2022-08-08 2022-11-08 陕西师范大学 一种基于等离激元诱导卤化银将大气中二氧化碳转变为碳材料的方法
CN115301259B (zh) * 2022-08-08 2024-04-12 陕西师范大学 一种基于等离激元诱导卤化银将大气中二氧化碳转变为碳材料的方法

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