WO2016035855A1 - 金属系粒子集合体の製造方法 - Google Patents

金属系粒子集合体の製造方法 Download PDF

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WO2016035855A1
WO2016035855A1 PCT/JP2015/075079 JP2015075079W WO2016035855A1 WO 2016035855 A1 WO2016035855 A1 WO 2016035855A1 JP 2015075079 W JP2015075079 W JP 2015075079W WO 2016035855 A1 WO2016035855 A1 WO 2016035855A1
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metal
substrate
particle aggregate
based particle
particles
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PCT/JP2015/075079
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English (en)
French (fr)
Japanese (ja)
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知浩 福浦
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住友化学株式会社
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Priority to KR1020177007984A priority Critical patent/KR20170048431A/ko
Priority to JP2016546693A priority patent/JP6591989B2/ja
Publication of WO2016035855A1 publication Critical patent/WO2016035855A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/008—Surface plasmon devices
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to a method for producing a metal particle aggregate in which a plurality of metal particles are two-dimensionally arranged apart from each other.
  • Plasmon is a free-electron rough wave generated by collective oscillation of free electrons in a metal nanostructure.
  • Patent Document 1 JP-A-2007-139540 (Patent Document 1) and Non-Patent Documents 1 and 2 can be mentioned.
  • Patent Document 1 discloses that a particle aggregate composed of a large number of plate-like metal particles independent from each other is used as a fluorescence enhancement element by utilizing a localized plasmon resonance phenomenon. This particle aggregate is formed by performing DC sputtering on a substrate heated to 200 to 300 ° C. at a low growth rate (film deposition rate of 1 to 2 nm / min).
  • Non-Patent Document 1 is a document relating to localized plasmon resonance by silver nanoparticles, and a substrate heated to 250 to 350 ° C. as a method for forming a particle assembly consisting of a large number of independent silver nanoparticles on a substrate. Disclosed are a method of performing DC sputtering on a substrate, and a method of performing heat treatment (annealing) at 250 to 600 ° C. after spin coating a silver particle dispersion on a substrate.
  • Non-Patent Document 1 since both methods disclosed in Patent Document 1 and Non-Patent Document 1 include a high-temperature heat treatment step, it is necessary to use a substrate having high heat resistance, and there is a problem that the application range is greatly limited. It was.
  • the DC sputtering method it is necessary to keep the growth rate of metal particles low and substrate heating may be required.
  • roll-to-roll formation of particle aggregates while transporting a long substrate fed from a roll
  • It is difficult to produce a continuous or large-scale industrial particle assembly such as a method in which a substrate is processed and the substrate after processing is sequentially wound into a roll.
  • the method of performing heat treatment after spin coating since it involves two steps and requires substrate heating, it is difficult to produce a continuous or large-scale industrial particle aggregate such as roll-to-roll.
  • Non-Patent Document 2 proposes a method of forming a film made of silver grains on a substrate using a so-called silver mirror reaction.
  • the present inventors have conducted research so far that the localized plasmon resonance of metal-based particle aggregates effectively acts to effectively obtain the light emission enhancement effect of the light emitting device and the conversion efficiency improvement effect of the photoelectric conversion device.
  • Non-Patent Document 2 Surface D is considered to be the most difficult for silver particles to form a continuous film (see Non-Patent Document 2, p. 6858, "Experimental Methods”). Also in this case, conductivity was confirmed in the silver particle film.
  • an object of the present invention is to produce a metal-based particle aggregate having a shape (the shape of the metal-based particle itself and the arrangement of the metal-based particles) advantageous for enhancing the light emission of the light-emitting element and improving the conversion efficiency of the photoelectric conversion element. It is to provide a method for manufacturing.
  • the present invention provides the following method for producing a metal particle aggregate.
  • Method for producing a metal particle aggregate in which 30 or more metal particles are two-dimensionally arranged apart from each other, and an average distance between adjacent metal particles is in the range of 1 to 150 nm Because Forming a metal-based particle aggregate on the substrate by reducing the cations in a state where the substrate is in contact with a liquid containing a metal cation constituting the metal-based particles; When the time from when the substrate is brought into contact with the liquid to when the metal layer formed on the substrate is conductive is T, the time when the substrate is brought into contact with the liquid is 0.35 T or more and less than T A manufacturing method.
  • the average particle diameter of the metal-based particles is in the range of 200 to 1600 nm, the average height is in the range of 55 to 500 nm, and the aspect ratio defined by the ratio of the average particle diameter to the average height is 1 to 8.
  • a predetermined shape (the shape of the metal-based particles themselves and the arrangement of the metal-based particles) that can generate localized plasmon resonance advantageous for light emission enhancement of the light-emitting elements and conversion efficiency improvement of the photoelectric conversion elements.
  • the metal-based particle aggregate having the aspect) can be produced with high productivity.
  • a high-temperature heat treatment step such as substrate heating can be eliminated, and a metal-based particle aggregate can be formed in a short time and in a single step.
  • the present invention can also be applied to continuous or large-scale industrial production methods.
  • the light emission efficiency of a light emitting element [organic EL (electroluminescence) element, inorganic EL element, inorganic LED (light emitting diode) element, quantum dot light emitting element, etc.] or photoelectric conversion element [solar cell] It is possible to provide an enhancement element (metal particle aggregate and metal particle aggregate laminated substrate) of an optical element that can significantly improve the conversion efficiency of the element or the like] as compared with a conventional plasmon material.
  • 2 is an AFM image of a metal-based particle assembly obtained in Comparative Example 1. It is a SEM image (50000 times scale) when the metallic particle assembly obtained in Comparative Example 1 is viewed from directly above.
  • 2 is an AFM image of the metal-based particle aggregate obtained in Example 1. It is a SEM image (100,000 times scale) when the metallic particle assembly obtained in Example 1 is viewed from directly above.
  • 3 is an AFM image of a metal-based particle assembly obtained in Example 2. It is a SEM image (50000 times scale) when the metal type particle aggregate obtained in Example 2 is seen from right above.
  • 3 is an AFM image of a metal-based particle aggregate obtained in Comparative Example 2.
  • Example 4 is an AFM image of the metal-based particle aggregate obtained in Example 3. It is a SEM image (100,000 times scale) when the metallic particle assembly obtained in Example 3 is viewed from directly above.
  • 6 is an AFM image of the metal-based particle assembly obtained in Example 4. It is a SEM image (100,000 times scale) when the metallic particle assembly obtained in Example 4 is viewed from directly above.
  • 6 is an AFM image of a metal-based particle aggregate obtained in Comparative Example 3.
  • 6 is an absorption spectrum of the metal-based particle aggregate obtained in Example 4. It is a figure explaining the absorption-spectrum measuring method using the objective lens (100 times) of a microscope.
  • 6 is an AFM image of a metal-based particle aggregate obtained in Comparative Example 4.
  • FIG. 17A is a schematic diagram showing a measurement system of an emission spectrum of a photoexcited light emitting device
  • FIG. 17B is a schematic cross-sectional view showing a photoexcited light emitting device having a metal particle aggregate and an insulating layer. It is the emission spectrum detected about the light excitation light emitting element of Example 5, and the light excitation light emitting element of a comparison object.
  • Metal-based particle aggregate is an aggregate of a plurality of metal-based particles (particles made of a metal-based material), and these metal-based particles are two-dimensionally arranged apart from each other.
  • metal-based particle aggregates having a predetermined shape advantageous for enhancing light emission of the light-emitting element and improving the conversion efficiency of the photoelectric conversion element, that is, 30 or more metal-based particles are separated from each other.
  • the metal particles have an average interparticle distance (1 to 150 nm) within a predetermined range, and more preferably the metal particles have a predetermined shape (average particle size 200 to 1600 nm, average A metal particle aggregate having a height of 55 to 500 nm and an aspect ratio of 1 to 8) can be produced with good control and high productivity.
  • the definitions of “average interparticle distance”, “average particle diameter”, “average height”, and “aspect ratio” of metal-based particles will be described later.
  • the production method of the present invention reduces a metal cation in a state where the substrate is in contact with a liquid containing a metal cation (hereinafter, also referred to as “metal cation”) constituting the metal-based particles, and thereby a metal composed of the above metal.
  • metal cation a metal cation constituting the metal-based particles
  • the substrate 100 can be brought into contact with the liquid 20 containing metal cations by immersing the substrate 100 in the liquid 20 contained in the tank 10.
  • the generated metal zero valence
  • the substrate 100 is brought into contact with the liquid 20 containing metal cations by immersing the substrate 100 in the liquid 20 contained in the tank 10.
  • the generated metal zero valence
  • the solvent includes water, but may further include a water-miscible organic solvent (for example, alcohols).
  • the concentration of the metal cation in the liquid 20 is relatively low in order to form the metal-based particle aggregate 200 having the above-mentioned predetermined or preferable shape (the predetermined average interparticle distance and preferable metal-based particle shape) with good control. More specifically, it is preferably 0.02 mol / L or less, and more preferably 0.01 mol / L or less. When the concentration of the metal cation exceeds 0.02 mol / L, the deposition rate of the zero-valent metal becomes too fast, and it becomes difficult to control the shape of the metal-based particle aggregate 200, particularly the average interparticle distance. However, it does not become an individual particle aggregate but tends to be a flat continuous metal film.
  • the liquid 20 preferably contains a metal cation and a reducing agent capable of reducing the metal cation to a zero-valent metal.
  • a reducing agent capable of reducing the metal cation to a zero-valent metal.
  • this reducing agent is preferably contained in the liquid 20 immediately before the substrate 100 is brought into contact (immersion) with the liquid 20.
  • the reducing agent one having a small reducing power is preferably used, and its standard oxidation-reduction potential is preferably ⁇ 0.5 V or more, preferably ⁇ 0.45 V or more.
  • the standard oxidation-reduction potential here is a value when PH7 is 25 ° C. and the standard hydrogen electrode is the cathode. If the reducing agent used has a reducing power that is too high, the deposition rate of the zero-valent metal becomes too high, and it becomes difficult to control the shape of the metal-based particle aggregate, particularly the average interparticle distance. It does not become an individual particle aggregate but tends to be a flat continuous metal film.
  • Specific examples of the reducing agent having a standard oxidation-reduction potential of ⁇ 0.5 V or more include glucose and ascorbic acid.
  • the concentration of the reducing agent in the liquid 20 is relatively high. Is preferred.
  • the concentration of the reducing agent is, for example, 30% or more of the saturation concentration, and preferably 40% or more.
  • the saturation concentration referred to here is the saturation concentration when the reducing agent is dissolved in the solvent (containing no metal cation) contained in the liquid 20 at a temperature at which the substrate 100 is brought into contact with the liquid 20. Even when the concentration of the reducing agent is excessively low, it is difficult to control the shape of the metal-based particle aggregate 200, and the metal-based particles do not become individual particle aggregates, but become a flat continuous metal film. It is easy to end up.
  • the liquid 20 may contain one or more additives such as a complexing agent that binds to a metal cation to form a complex ion and stabilizes the metal cation.
  • additives such as a complexing agent that binds to a metal cation to form a complex ion and stabilizes the metal cation.
  • the process of immersing the substrate 100 in the liquid 20 containing a metal cation and a reducing agent to form the metal-based particle aggregate 200 on the substrate 100 is basically an electroless plating (chemical plating) using a plating bath. The same can be done.
  • a resin substrate resin film
  • the use of the resin substrate enables continuous and large-scale industrial metal-based particle aggregates 200 to be manufactured by roll-to-roll.
  • the temperature at which the substrate 100 is brought into contact (immersion) with the liquid 20 is not particularly limited, and is, for example, 10 to 100 ° C., preferably 15 to 60 ° C., more preferably 20 to 40 ° C.
  • the contact (immersion) time is appropriately controlled so that a plurality of metal-based particles are arranged apart from each other in the resulting metal-based particle assembly 200. .
  • the metal layer formed on the substrate 100 exhibits conductivity (beyond a state where a plurality of metal-based particles grow excessively and are separated from each other).
  • the contact (immersion) time is 0.35 T or more and less than T, and may be 0.4 or more. Preferably, it is more preferably 0.5 or more. Within this range, the closer the contact (immersion) time is to T, the larger the average particle diameter and average height of the metal-based particles and the smaller the average interparticle distance.
  • the metal layer formed on the substrate 100 exhibits conductivity means that a multimeter [tester (“E2378A” manufactured by Hewlett-Packard Co., Ltd.)] is used as a metal layer on the substrate 100 with 10 to 10 When the contact is 15 mm away, it means that “overload” is not displayed when the range setting is “30 M ⁇ ”, that is, a resistance value of less than 30 M ⁇ is measured.
  • the time T is preferably obtained in advance by a preliminary experiment before actually performing the process of bringing the substrate 100 into contact (immersion) with the liquid 20.
  • the metal constituting the metal-based particles is used as an anode, and the substrate 100 is used as a cathode, as in electroplating (electroplating).
  • the metal particle aggregate 200 may be formed on the substrate 100 by electrodeposition in which a current is applied between both electrodes.
  • the substrate 100 does not have conductivity, as will be described later.
  • the metal constituting the metal-based particle When the metal constituting the metal-based particle is a nanoparticle or an aggregate thereof, it shows a plasmon resonance peak (hereinafter also referred to as “plasmon peak”) that appears in the ultraviolet to visible region in an absorption spectrum measurement by an absorptiometry. It is a material, and metal particles can be deposited on the substrate 100 by a process of reducing the metal cations while the substrate 100 is in contact with the liquid 20 containing the metal cations. Examples of such a metal include noble metals such as gold, silver, copper, platinum, and palladium; other metals such as aluminum; alloys containing the noble metal or other metals.
  • the type of the metal is the use of the metal-based particle aggregate (for example, the type of the optical element when the metal-based particle aggregate is applied as an enhancement element of the optical element using the plasmon resonance effect), and It is preferable to select appropriately according to the absorption spectrum peak wavelength, emission spectrum peak wavelength, reflection spectrum peak wavelength, etc. of the active layer of the optical element to be enhanced.
  • the material constituting the substrate 100 can be selected from a wide range, but is particularly non-conductive when the metal-based particle assembly laminated substrate is applied as an enhancement element of an optical element by utilizing its plasmon resonance effect. It is preferable to use a substrate made of a material. This is because the plasmon resonance effect is reduced when electrons can be transferred between some or all of the metal-based particles via the substrate.
  • non-conductive materials include glass, various inorganic insulating materials (SiO 2 , ZrO 2 , mica, etc.), various resin materials, and the like.
  • the surface of the substrate 100 on which the metal-based particle aggregate 200 is formed is preferably as smooth as possible.
  • the metal-based particle assembly laminated substrate is applied as, for example, an enhancement element of a light-emitting element
  • light can be extracted from the substrate surface (surface opposite to the metal-based particle assembly 200). It is preferable to use a light-transmitting substrate, and it is more preferable to use an optically transparent substrate.
  • the manufacturing method of this invention may further include the process of forming an insulating layer in the surface of the metal type particle aggregate 200 so that it may explain in full detail later.
  • a metal particle aggregate having a predetermined or preferable shape (a predetermined average interparticle distance and a preferable shape of the metal particle itself) is manufactured with good controllability and productivity. be able to. Therefore, the present invention is useful as a method for producing a metal-based particle aggregate having specific characteristics such as showing extremely strong plasmon resonance that is first manifested by precise shape control.
  • This metal-based particle aggregate which is a plasmon material, can be suitably applied as an enhancement element for optical elements including light-emitting elements and photoelectric conversion elements, and can improve the luminous efficiency of the applied light-emitting elements and the conversion efficiency of the photoelectric conversion elements. This can be significantly improved as compared with the prior art.
  • the range of action of localized plasmon resonance is within a very narrow range of 10 nm or less from the surface of the metal nanoparticles.
  • the range of action of localized plasmon resonance is within a very narrow range of 10 nm or less from the surface of the metal nanoparticles.
  • the distance between the metal nanoparticle and the molecule to be excited increases, the localized plasmon resonance no longer effectively affects the light emission enhancement effect, and the energy transfer of the Forster mechanism appears. This is because if the range (1 nm to 10 nm) is exceeded, almost no light emission enhancement effect can be obtained.
  • the distance between the metal nanoparticles effective for obtaining an effective light emission enhancement effect and the molecule to be excited is 10 nm or less.
  • the enhancement effect of the optical element using the localized plasmon resonance phenomenon of the conventional metal nanoparticles or aggregates thereof is not always satisfactory due to the limitation of the range of action of localized plasmon resonance.
  • the optical element has an active layer having a thickness of several tens of nanometers or more (for example, a light emitting layer of a light emitting element, a light absorbing layer of a photoelectric conversion element)
  • the metal nanoparticles are close to the active layer, Or even if it can be placed inside, the direct enhancement effect by localized plasmon resonance can be obtained only in a part of the active layer, so the luminous efficiency and conversion efficiency improvement effect is partial.
  • the metal-based particle aggregate that can be obtained by the production method of the present invention is a relatively large particle size in which the metal-based particles constituting the metal particle aggregate are generally considered to have a small light emission enhancement effect.
  • extremely strong plasmon resonance due to having a specific average interparticle distance and preferably having a specific shape of the metal-based particles
  • the range of action of the plasmon resonance that is significantly extended the range in which the enhancement effect by plasmons extends).
  • the usefulness of the metal-based particle aggregate having a predetermined shape that can be obtained by the production method of the present invention is, for example, as follows.
  • the intensity of the plasmon resonance exhibited by the metal-based particle aggregate is not a mere sum of the localized plasmon resonances exhibited by individual metal-based particles at a specific wavelength, but is more than that. That is, preferably, 30 or more metal particles having a specific shape are densely arranged at a predetermined average inter-particle distance, so that individual metal particles interact with each other, and extremely strong plasmon resonance is expressed. . This is considered to be expressed by the interaction between the localized plasmons of the metal-based particles.
  • a plasmon peak is observed as a peak in the ultraviolet to visible region. From the magnitude of the absorbance value at the maximum wavelength of the plasmon peak, the plasmon resonance intensity of the plasmon material
  • the metal-based particle assembly according to the present invention formed on the glass substrate can be evaluated in a simplified manner, and the maximum of the plasmon peak on the longest wavelength side in the visible light region is measured when the absorption spectrum is measured.
  • the absorbance at the wavelength can be 0.4 or more, further 0.7 or more, and even 0.9 or more.
  • the absorption spectrum of the metal particle aggregate can be measured by absorptiometry using a sample formed on a glass substrate as a measurement sample.
  • the absorption spectrum is the back side of the glass substrate on which the metal particle aggregates are laminated (the side opposite to the metal particle aggregates), and the ultraviolet to visible light region from the direction perpendicular to the substrate surface.
  • an absorption spectrum measurement may be performed using an objective lens and a spectrophotometer to narrow the measurement field.
  • the action range of plasmon resonance (the range in which the plasmon enhances the effect) can be significantly extended.
  • Such an elongation action is also preferably caused by an interaction between localized plasmons of metal-based particles, which is caused by densely arranging 30 or more metal-based particles having a specific shape at a predetermined average interparticle distance. It is thought that it was expressed.
  • the plasmon resonance operating range which has heretofore been generally limited to the range of the Forster distance (about 10 nm or less), can be extended to, for example, about several hundred nm. .
  • the extension of the plasmon resonance operating range is extremely advantageous for enhancing optical elements such as light emitting elements and photoelectric conversion elements. That is, due to the substantial extension of the working range, even if the active layer has a thickness of several tens of nanometers or more, the entire active layer can be enhanced, thereby enhancing the optical element. (Emission efficiency, conversion efficiency, etc.) can be significantly improved.
  • the plasmon material has to be arranged so that the distance from the active layer is within the range of the Förster distance.
  • the active The enhancement effect by plasmon resonance can be obtained by disposing the layer at a position separated by, for example, 10 nm, further several tens of nm (for example, 20 nm), and even several hundred nm.
  • the metal-based particle aggregate can be disposed in the vicinity of the light extraction surface that is considerably away from the light-emitting layer. It is possible to suppress the light emitted from the light from being totally reflected at the interfaces of the various light emitting element constituent layers that pass before reaching the light extraction surface, so that the light extraction efficiency can be improved.
  • the metal-based particle assembly according to the present invention uses such metal-based particles that are difficult to cause dipole-type localized plasmons in the visible light region.
  • a very large number of surface free electrons contained in the metal-based particles can be effectively excited as plasmons, and extremely strong plasmon resonance and plasmon resonance This makes it possible to achieve a significant extension of the working range.
  • the metal-based particle aggregate according to the present invention can have the following advantageous effects.
  • the average particle diameter of the metal-based particles is kept constant and the average interparticle distance is decreased (when the metal-based particles are arranged more densely), in the visible light region.
  • the maximum wavelength of the plasmon peak on the longest wavelength side is shifted to the short wavelength side.
  • This peculiar phenomenon is the Mie scattering theory generally accepted for plasmon materials [in accordance with this theory, the maximum wavelength of the plasmon peak shifts to the longer wavelength side (red shift) as the particle size increases. ] Is against this.
  • the unique blue shift as described above also has a structure in which the metal-based particle aggregate according to the present invention has a structure in which metal-based particles are closely arranged at a predetermined average inter-particle distance, and preferably the metal-based particles are This is considered to be due to the interaction between the localized plasmons of the metal-based particles accompanying the specific shape.
  • the metal-based particle aggregate (stacked on the glass substrate) has the longest wavelength in the absorption spectrum in the visible light region measured by the absorptiometry according to the shape of the metal-based particles and the average interparticle distance.
  • a certain plasmon peak may exhibit a maximum wavelength in a wavelength region of, for example, 350 to 550 nm.
  • the metal-based particle aggregate is typically about 30 to 500 nm (for example, 30 to 250 nm) as compared with the case where the metal-based particles are arranged with a sufficiently long inter-particle distance (for example, 1 ⁇ m). Blue shift can occur.
  • Such a metal-based particle aggregate in which the maximum wavelength of the plasmon peak is blue-shifted compared to the conventional one is extremely advantageous, for example, in the following points.
  • a blue (or near-wavelength region, hereinafter the same) luminescent material especially a blue phosphorescent material
  • development of a material that can withstand practical use is difficult at present.
  • the light emission efficiency can be increased to a sufficient extent.
  • a photoelectric conversion element for example, by blue shifting the resonance wavelength, a wavelength region that could not be used in the active layer itself can be used effectively, and conversion efficiency can be improved.
  • the average particle diameter of the metal-based particles is preferably in the range of 200 to 1600 nm. In order to effectively obtain the effects (1) to (3) above, more preferably 200 to 1200 nm, still more preferably 250 to It is 500 nm, particularly preferably in the range of 300 to 500 nm.
  • the average particle diameter of the metal-based particles is preferably selected appropriately according to the type of optical element to which the metal-based particle aggregate is applied as an enhancement element and the type of metal constituting the metal-based particles.
  • the average particle size of the metal-based particles means that 10 particles are randomly selected in the SEM observation image from directly above the metal-based particle assembly in which the metal-based particles are two-dimensionally arranged, and each particle image includes Randomly draw 5 tangential diameters (however, any straight line with a tangential diameter can only pass through the interior of the particle image, one of which is only the interior of the particle and is the longest drawable line)
  • the average value of 10 selected particle diameters when the average value (hereinafter, this average value is also referred to as tangential diameter average value) is used as the particle diameter of each particle.
  • the tangent diameter is defined as a perpendicular line connecting the interval (projection image) of a particle between two parallel lines in contact with it (Nikkan Kogyo Shimbun, “Particle Measurement Technology”, 1994, page 5). .
  • the measurement method of the average particle diameter will be described more specifically.
  • the SEM observation image is measured using a scanning electron microscope “JSM-5500” manufactured by JEOL Ltd.
  • the obtained observation image is read at 1280 pixels by 960 pixels by using free image processing software “ImageJ” manufactured by the National Institutes of Health.
  • the average height of the metal-based particles is preferably in the range of 55 to 500 nm. In order to effectively obtain the effects (1) to (3) above, more preferably 55 to 300 nm, still more preferably 70 to Within the range of 150 nm.
  • the average height of the metal-based particles refers to 10 measured values when 10 particles are randomly selected in the AFM observation image of the metal-based particle aggregate and the heights of these 10 particles are measured. Average value.
  • the aspect ratio of the metal-based particles is preferably in the range of 1 to 8, and it is preferable that the metal-based particle aggregate is appropriately selected within this range in accordance with the type of optical element to which the metal-based particle aggregate is applied as an enhancement element.
  • the metal-based particles when used as an enhancement element of a light emitting element, the metal-based particles tend to have a flat shape, and in this case, in order to obtain a higher enhancement effect, the aspect ratio is more preferably 2 to 8. Preferably, it is 2.5-8.
  • the metal particles when used as an enhancement element of a photoelectric conversion element, in order to obtain a higher enhancement effect, the metal particles tend to be more preferable as they are closer to a true sphere.
  • the aspect ratio of the metal-based particles is defined by the ratio of the average particle diameter to the average height (average particle diameter / average height).
  • the surface of the metal-based particles is preferably a smooth curved surface, but the surface may contain some minute irregularities (roughness).
  • the metal particles may be indefinite.
  • the variation in size between the metal-based particles is as small as possible.
  • the distance between the large particles is increased, and it is preferable that the interaction between the large particles is facilitated by filling the space between the small particles.
  • the metal-based particles are arranged so that the average distance (average interparticle distance) between the adjacent metal-based particles is in the range of 1 to 150 nm.
  • the average interparticle distance is preferably in the range of 1 to 100 nm, more preferably 1 to 50 nm, and even more preferably 1 to 20 nm in order to effectively obtain the effects (1) to (3).
  • the average interparticle distance is less than 1 nm, electron transfer based on the Dexter mechanism occurs between particles, which is disadvantageous in terms of deactivation of localized plasmons.
  • the metal-based particle aggregate according to the present invention in which the metal-based particles are arranged apart from each other does not exhibit conductivity when measured according to the above-described method (that is, the resistance value is 30 M ⁇ under the above measurement conditions). As a result, “Overload” is displayed.)
  • the average interparticle distance means that 30 particles are randomly selected in an SEM observation image from directly above a metal particle aggregate in which metal particles are two-dimensionally arranged, and each selected particle is adjacent to each other. It is the average value of the interparticle distances of these 30 particles when the interparticle distance with the matching particles is obtained.
  • the inter-particle distance between adjacent particles is a value obtained by measuring the distances between all adjacent particles (the distance between the surfaces) and averaging them.
  • the SEM observation image is measured using a scanning electron microscope “JSM-5500” manufactured by JEOL Ltd.
  • the obtained observation image is read at 1280 pixels by 960 pixels by using free image processing software “ImageJ” manufactured by the National Institutes of Health.
  • a random number generation function “RANDBETWEEN” of spreadsheet software “excel” manufactured by Microsoft Corporation is used, and 1 to 1280 to 30 random numbers (x 1 to x 30 ), 1 to 960 to 30 random numbers (y 1 to y 30 ) are obtained respectively.
  • (X 30 , y 30 ) is obtained from 30 random number combinations (x 1 , y 1 ) from the obtained 30 random numbers.
  • 30 sets of coordinate points (x 1 , y 1 ) to (x 30 , y 30 ) are set with the x-coordinate of the random number generated from 1 to 1280 and the y-coordinate of the random number generated from 1 to 960. obtain. Then, for each of a total of 30 particle images including the coordinate point, an interparticle distance between the particle and an adjacent particle is obtained, and then an average particle is obtained as an average value of the interparticle distance between the 30 adjacent particles. Get the distance between. If at least one of the 30 coordinate points that are 30 random number combinations is not included in the particle image, or if two or more coordinate points are included in the same particle, the random number combination is discarded. Then, random number generation is repeated until all 30 coordinate points are included in different particle images.
  • the number of metal particles contained in the metal particle aggregate is 30 or more, preferably 50 or more.
  • the number of metal particles contained in the metal particle aggregate is, for example, 300 or more, and further in light of the general element area of the optical element. It can be 17500 or more.
  • the number density of the metal particles in the metal particle aggregate is preferably 7 particles / ⁇ m 2 or more, and more preferably 15 particles / ⁇ m 2 or more.
  • the manufacturing method of the present invention includes an insulating layer forming step after the step of forming the metal-based particle aggregate, and the insulating layer covering the surface of each metal-based particle is formed on the thin film of the metal-based particle aggregate. It may be formed.
  • Such an insulating layer is preferable not only for ensuring the non-conductivity of the metal-based particle aggregate, but also when the metal-based particle aggregate is applied to an optical element. That is, in an optical element such as an electric energy-driven light-emitting element or photoelectric conversion element, a current flows in each layer constituting the element, but if the current flows in the metal-based particle aggregate, the enhancement effect by plasmon resonance is sufficient. May not be obtained.
  • the material constituting the insulating layer is not particularly limited as long as it has good insulating properties.
  • SiO 2 or Si 3 N 4 Etc. can be used.
  • the thickness of the insulating layer is not particularly limited as long as desired insulating properties are ensured, but an active layer when applied to an optical element as described later (for example, a light emitting layer of a light emitting element or a light absorbing layer of a photoelectric conversion element). Since the distance between the metal particle aggregate and the metal-based particle aggregate is preferably as short as possible, it is preferable that the distance is as small as possible within a range in which desired insulation is ensured.
  • the metal-based particle assembly according to the present invention can be incorporated into various optical elements in a state of being integrated with a substrate used in manufacturing the same.
  • the metal-based particle assembly according to the present invention exhibits extremely strong plasmon resonance, and further, since the action range of plasmon resonance is significantly extended, for example, 10 nm or more, further 20 nm or more, and still more Can enhance the entire active layer having a thickness greater than that.
  • the active layer disposed at a position separated by, for example, 10 nm, further several tens of nm (for example, 20 nm), and even several hundred nm or more can be enhanced extremely effectively.
  • the distance between the active layer and the metal-based particle aggregate is preferably 100 nm or less, more preferably 20 nm or less, and further preferably 10 nm or less.
  • the maximum wavelength of the emission wavelength (for example, in the case of a light-emitting element) or the absorption wavelength (for example in the case of a photoelectric conversion element) exhibited by the active layer matches or is close to the maximum wavelength of the plasmon peak of the metal-based particle aggregate.
  • the maximum wavelength of the plasmon peak of the metal particle aggregate can be controlled by adjusting the metal species, average particle diameter, average height, aspect ratio and / or average particle distance of the metal particles constituting the metal particle aggregate.
  • the light emitting layer is, for example, 1) composed of a monomolecular film in which dye molecules are arranged in a plane, 2) composed of a matrix doped with dye molecules, 3) composed of a light emitting low molecule, 4) It can be made of a light-emitting polymer.
  • the light emitting layer of 1) can be obtained by a method of removing the solvent after spin-coating the dye molecule-containing liquid.
  • the dye molecules include rhodamine 101, rhodamine 110, rhodamine 560, rhodamine 6G, rhodamine B, rhodamine 640, rhodamine 700 and other rhodamine dyes sold by Exciton, coumarin 503 sold by Exciton, etc. Of coumarin pigments.
  • the light emitting layer of 2) can be obtained by a method of removing a solvent after spin-coating a liquid containing a dye molecule and a matrix material.
  • a transparent polymer such as polyvinyl alcohol or polymethyl methacrylate can be used.
  • Specific examples of the dye molecule can be the same as those in the light emitting layer of 1).
  • the light emitting layer 3) can be obtained by a dry or wet film forming method including a spin coating method and a vapor deposition method.
  • Specific examples of the light-emitting small molecule include tris (8-quinolinolato) aluminum complex [tris (8-hydroxyquinoline) aluminum complex; Alq 3 ], bis (benzoquinolinolato) beryllium complex [BeBq].
  • the light emitting layer of 4) can be obtained by a wet film forming method using a light emitting polymer-containing liquid such as a spin coat method.
  • a light emitting polymer-containing liquid such as a spin coat method.
  • Specific examples of the light emitting polymer include ⁇ -conjugated polymers such as F8BT [poly (9,9-dioctylfluorene-alt-benzothiadiazole)], poly (p-phenylene vinylene), and polyalkylthiophene.
  • the metal-based particle assembly and the metal-based particle assembly laminated substrate according to the present invention can be used for analysis applications and color material applications.
  • the analytical application includes application to surface enhanced Raman spectroscopy using surface enhanced Raman scattering.
  • Examples of the color material use include use as a color imparting material for various articles (automobiles, ceramics, etc.).
  • color rendering that is difficult to achieve with pigments and pigments can be achieved.
  • Examples of the color filter include a filter that transmits only light having a specific wavelength or blocks light having a specific wavelength.
  • a reducing solution B was obtained by mixing 40 mL of a 1.9 mol / L glucose aqueous solution and 20 mL of methanol.
  • the silver ion solution A1 and the reducing solution B are mixed to obtain a mixed solution, which is immediately poured into a water tank containing four non-alkali glass substrates, and the substrate (non-alkali glass substrate) is immersed in the mixed solution. After that, it was allowed to stand in a dipped state until the following predetermined time.
  • Preparation of the liquid mixture and immersion in the liquid mixture were performed in an environment of 25 ° C., and the temperature of the liquid mixture during the immersion treatment (metal-based particle assembly formation treatment) was also about 25 ° C.
  • the four substrates were arranged so that one of their main surfaces (the surface opposite to the surface on which the metal-based particle aggregates were formed) was in contact with the bottom surface of the water tank so as not to overlap each other.
  • Example 2 45 minutes after the start of immersion, one substrate was pulled out of the water tank, and the substrate was washed with a 50% by volume acetone aqueous solution to obtain a metal-based particle assembly of Example 2.
  • FIGS. 2, 4, 6, and 8 show the metal-based particle aggregates obtained in Comparative Example 1, Example 1, Example 2, and Comparative Example 2, respectively.
  • An AFM image is shown. “VN-8010” manufactured by Keyence Corporation was used for AFM image shooting (the same applies hereinafter). The image size of these AFM images is 5 ⁇ m ⁇ 5 ⁇ m (the same applies to the following AFM images). From the AFM image, the “average height” of the silver particles constituting the metal-based particle aggregate was determined.
  • 3 and 7 show SEM images when the metal-based particle aggregates obtained in Comparative Example 1, Example 1, and Example 2 are viewed from directly above, respectively.
  • 3 and 7 are enlarged images on a scale of 50000 times
  • FIG. 5 is an enlarged image on a scale of 100000 times. From the SEM image, the “average particle diameter” and the “average interparticle distance” of the silver particles were determined according to the above measurement method, and the “aspect ratio” (average particle diameter / The average height was calculated.
  • the presence or absence of conductivity of the metal-based particle aggregate was confirmed by the above-described method using a tester [Multimeter (“E2378A” manufactured by Hewlett-Packard Company)].
  • a tester Multimeter (“E2378A” manufactured by Hewlett-Packard Company)
  • the concentration of the reducing agent and silver ions is the concentration in the mixed solution obtained by mixing the silver ion solution A1 and the reducing solution B.
  • the standard redox potential of glucose at pH 7, 25 ° C. and the standard hydrogen electrode as the cathode is ⁇ 0.428V.
  • the average particle size, the average height, the aspect ratio, and the average interparticle distance could not ask.
  • each of the metal-based particle aggregates or continuous films (in a state of being laminated on the substrate) of Comparative Example 1, Example 1, Example 2, and Comparative Example 2 was measured using a microscope objective lens (100 times).
  • the absorption spectrum was measured by the method. Specifically, referring to FIG. 15, a visible light region from the direction perpendicular to the substrate surface on the substrate 100 side of metal-based particle assembly laminated substrate 500 (the side opposite to metal-based particle assembly 200). Of incident light. Then, the transmitted light that has been transmitted to the metallic particle aggregate 200 side and has reached 100 times the objective lens 600 is collected by the objective lens 600, and this condensed light is detected by the spectrophotometer 700 to obtain an absorption spectrum. Obtained.
  • the spectrophotometer 700 used was an ultraviolet-visible spectrophotometer “MCPD-3000” manufactured by Otsuka Electronics Co., Ltd., and the objective lens 600 used was “BD Plan 100 / 0.80 ELWD” manufactured by Nikon. Table 1 also shows the maximum wavelength of the absorption peak at the longest wavelength side in the visible light region obtained by this absorption spectrum measurement and the absorbance at the maximum wavelength.
  • a reducing solution B was obtained by mixing 40 mL of a 1.9 mol / L glucose aqueous solution and 20 mL of methanol.
  • the silver ion solution A2 and the reducing solution B are mixed to obtain a mixed solution, which is immediately poured into a water tank containing three non-alkali glass substrates, and the substrate (non-alkali glass substrate) is immersed in the mixed solution. After that, it was allowed to stand in a dipped state until the following predetermined time.
  • Preparation of the liquid mixture and immersion in the liquid mixture were performed in an environment of 25 ° C., and the temperature of the liquid mixture during the immersion treatment (metal-based particle assembly formation treatment) was also about 25 ° C.
  • the three substrates were arranged so that one of their principal surfaces (the surface opposite to the surface on which the metal-based particle aggregate is formed) is in contact with the bottom surface of the water tank so as not to overlap each other.
  • Example 4 40 minutes after the start of immersion, one substrate was pulled out of the water tank, and the substrate was washed with a 50% by volume acetone aqueous solution to obtain a metal-based particle assembly of Example 4.
  • FIGS. 9, 11, and 13 show AFM images of the metal-based particle aggregates obtained in Example 3, Example 4, and Comparative Example 3, respectively. From the AFM image, the “average height” of the silver particles constituting the metal-based particle aggregate was determined.
  • Example 10 and 12 show SEM images when the metal-based particle aggregates obtained in Example 3 and Example 4 are viewed from directly above, respectively. Both are magnified images on a scale of 100,000 times. From the SEM image, the “average particle diameter” and the “average interparticle distance” of the silver particles were determined according to the above measurement method, and the “aspect ratio” (average particle diameter / The average height was calculated.
  • the absorption spectrum was measured by a measurement method using an objective lens (100 times) of a microscope.
  • Table 2 also shows the maximum wavelength of the absorption peak at the longest wavelength side in the visible light region obtained by this absorption spectrum measurement and the absorbance at the maximum wavelength.
  • the absorption spectrum obtained for Example 4 is shown in FIG.
  • a reducing solution B was obtained by mixing 40 mL of a 1.9 mol / L glucose aqueous solution and 20 mL of methanol. Next, the silver ion solution A3 and the reducing solution B are mixed to obtain a mixed solution, which is immediately poured into a water tank containing one non-alkali glass substrate, and the substrate (non-alkali glass substrate) is immersed in the mixed solution. After that, it was allowed to stand in a dipped state until the following predetermined time. Preparation of the liquid mixture and immersion in the liquid mixture were performed in an environment of 25 ° C., and the temperature of the liquid mixture during the immersion treatment (metal-based particle assembly formation treatment) was also about 25 ° C. The substrate was disposed so that one of its main surfaces (the surface opposite to the surface on which the metal-based particle aggregate is formed) is in contact with the bottom surface of the water tank.
  • FIG. 16 shows an AFM image of the metal-based particle assembly obtained in Comparative Example 4. Moreover, the presence or absence of conductivity of the metal-based particle assembly was confirmed by the above-described method using a tester [Multimeter (“E2378A” manufactured by Hewlett-Packard Company)]. The measurement results are shown in Table 2 together with the substrate immersion conditions. When SEM image and AFM image were confirmed, it was not an aggregate of metal particles separated from each other but a continuous film, so it was not possible to determine the average particle size, average height, aspect ratio and average interparticle distance. It was.
  • Example 5 Production of photoexcited light emitting device and evaluation of light emission enhancement>
  • the metal-based particle aggregate of Example 4 was formed on a 0.7 mm thick soda glass substrate.
  • an SOG (spin-on-glass) solution was spin-coated on the metal-based particle aggregate, and an insulating layer having an average thickness of 30 nm was laminated.
  • an organic SOG material “OCD T-7 5500T” manufactured by Tokyo Ohka Kogyo Co., Ltd. diluted with ethanol was used.
  • Average thickness means the same conditions as when forming on a metal-based particle aggregate (same coating solution with the same composition and the same coating amount), and when directly spin-coating on a soda glass substrate. It is an average value of thicknesses at arbitrary five points.
  • an Alq 3 light emitting layer having an average thickness of 80 nm was formed on the insulating layer by vacuum vapor deposition to obtain a photoexcited light emitting device.
  • a photoexcited light emitting device was produced in the same manner as described above except that the metal particle aggregate was not formed.
  • the degree of light emission enhancement was evaluated as follows. Referring to FIG. 17A showing a measurement system of the emission spectrum of the photo-excited light-emitting element and FIG. 17B which is a schematic sectional view of the photo-excited light-emitting element, the light-emitting layer 2 is formed on the light-emitting layer 2 side of the photo-excited light-emitting element 1.
  • the photoexcited light-emitting element 1 was caused to emit light by irradiating the excitation light 3 from a direction perpendicular to the surface of the substrate.
  • a UV-LED South Walker, UV-LED 375-nano, excitation light wavelength 375 nm
  • the light emitted from the excitation light source 4 was condensed by the lens 5 to be the excitation light 3, which was irradiated.
  • a wavelength cut filter 8 (sigma optical machine) that collects the light emission 6 from the optical excitation light emitting element 1 emitted in the direction of 40 ° with respect to the optical axis of the excitation light 3 by the lens 7 and cuts the light having the wavelength of the excitation light.
  • FIG. 17B is a schematic cross-sectional view showing the photoexcited light emitting device 1 including the metal particle aggregate 200, the insulating layer 300, and the light emitting layer 2 in this order on the substrate 100 made of soda glass.
  • FIG. 18 shows emission spectra detected for the photoexcited light-emitting device of Example 5 and the photoexcited light-emitting device to be compared.
  • An integrated value in the emission wavelength region was determined for the detected emission spectrum.
  • a value (emission enhancement magnification) obtained by dividing the integrated value obtained from the emission spectrum measured for the photoexcited light emitting device of Example 5 by the integrated value obtained from the emission spectrum measured for the photoexcited light emitting device to be compared was found to be 8 .6 times, and a remarkable light emission enhancement effect was recognized despite the large thickness of the light emitting layer.
  • 1 light excitation light emitting element 1 light excitation light emitting element, 2 light emitting layer, 3 excitation light, 4 excitation light source, 5, 7 lens, 6 light emission from light excitation light emitting element, 8 wavelength cut filter, 9 spectrometer, 10 bath, 20 liquid containing metal cation, 100 substrate, 200 metal particle aggregate, 300 insulating layer, 500 metal particle aggregate laminated substrate, 600 objective lens, 700 spectrophotometer.

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JP2018025431A (ja) * 2016-08-09 2018-02-15 浜松ホトニクス株式会社 被検体分析方法

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JPS6115986A (ja) * 1984-06-29 1986-01-24 Nobuyuki Koura 安定な銀の無電解めつき液
JP2000026977A (ja) * 1998-07-13 2000-01-25 Daiwa Kasei Kenkyusho:Kk 貴金属を化学的還元析出によって得るための水溶液
JP2013010884A (ja) * 2011-06-30 2013-01-17 Nippon Steel & Sumikin Chemical Co Ltd 金属微粒子複合体及びその製造方法
JP2013110395A (ja) * 2011-10-26 2013-06-06 Sumitomo Chemical Co Ltd 光電変換素子

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Publication number Priority date Publication date Assignee Title
JPS6115986A (ja) * 1984-06-29 1986-01-24 Nobuyuki Koura 安定な銀の無電解めつき液
JP2000026977A (ja) * 1998-07-13 2000-01-25 Daiwa Kasei Kenkyusho:Kk 貴金属を化学的還元析出によって得るための水溶液
JP2013010884A (ja) * 2011-06-30 2013-01-17 Nippon Steel & Sumikin Chemical Co Ltd 金属微粒子複合体及びその製造方法
JP2013110395A (ja) * 2011-10-26 2013-06-06 Sumitomo Chemical Co Ltd 光電変換素子

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018025431A (ja) * 2016-08-09 2018-02-15 浜松ホトニクス株式会社 被検体分析方法

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