WO2011113208A1 - 一种玻璃基材发光元件、其制造及其发光方法 - Google Patents

一种玻璃基材发光元件、其制造及其发光方法 Download PDF

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WO2011113208A1
WO2011113208A1 PCT/CN2010/071154 CN2010071154W WO2011113208A1 WO 2011113208 A1 WO2011113208 A1 WO 2011113208A1 CN 2010071154 W CN2010071154 W CN 2010071154W WO 2011113208 A1 WO2011113208 A1 WO 2011113208A1
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Prior art keywords
light
metal layer
emitting element
glass
emitting
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PCT/CN2010/071154
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English (en)
French (fr)
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周明杰
马文波
刘玉刚
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海洋王照明科技股份有限公司
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Priority to JP2012555279A priority Critical patent/JP5548279B2/ja
Priority to EP10847677.1A priority patent/EP2549519B1/en
Priority to CN201080061234.7A priority patent/CN102714120B/zh
Priority to PCT/CN2010/071154 priority patent/WO2011113208A1/zh
Priority to US13/582,781 priority patent/US20120326056A1/en
Publication of WO2011113208A1 publication Critical patent/WO2011113208A1/zh

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
    • G02B5/0215—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures the surface having a regular structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/77742—Silicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/77922—Silicates
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/008—Surface plasmon devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
    • H01J29/02—Electrodes; Screens; Mounting, supporting, spacing or insulating thereof
    • H01J29/10—Screens on or from which an image or pattern is formed, picked up, converted or stored
    • H01J29/18—Luminescent screens
    • H01J29/20—Luminescent screens characterised by the luminescent material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J63/00—Cathode-ray or electron-stream lamps
    • H01J63/02—Details, e.g. electrode, gas filling, shape of vessel
    • H01J63/04—Vessels provided with luminescent coatings; Selection of materials for the coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J63/00—Cathode-ray or electron-stream lamps
    • H01J63/06—Lamps with luminescent screen excited by the ray or stream
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/25—Metals
    • C03C2217/251—Al, Cu, Mg or noble metals
    • C03C2217/252—Al
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/25—Metals
    • C03C2217/251—Al, Cu, Mg or noble metals
    • C03C2217/254—Noble metals
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/25—Metals
    • C03C2217/251—Al, Cu, Mg or noble metals
    • C03C2217/254—Noble metals
    • C03C2217/256—Ag
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/25—Metals
    • C03C2217/262—Light metals other than Al
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B2207/00—Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
    • G02B2207/101—Nanooptics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24273—Structurally defined web or sheet [e.g., overall dimension, etc.] including aperture
    • Y10T428/24322—Composite web or sheet
    • Y10T428/24331—Composite web or sheet including nonapertured component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
    • Y10T428/24521—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness with component conforming to contour of nonplanar surface
    • Y10T428/24545—Containing metal or metal compound
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
    • Y10T428/24612—Composite web or sheet

Definitions

  • the invention belongs to the technical field of luminescent materials, and in particular relates to a luminescent element having a glass substrate as a luminescent material, a manufacturing method thereof and a illuminating method thereof.
  • Conventional materials for illuminating substrates include phosphors, nanocrystals, and glass. Compared to crystals and phosphors, glass has transparency, hardness, and good chemical stability and optical properties. Moreover, glass is more easily processed into various sizes. Shaped products, such as display devices or illumination sources of various shapes or sizes.
  • field emission devices generally use luminescent glass as an illuminant, which has broad application prospects in the field of illumination and display, and has attracted widespread attention from research institutions at home and abroad.
  • the field emission device works on the principle that the anode is opposite to the field emission cathode array in a vacuum environment. Emissive The arrays, FEAs) apply a forward voltage to form an accelerating electric field, and the electrons emitted by the cathode accelerate to illuminate the luminescent material on the anode plate.
  • the field emission device has a wide operating temperature range (-40°C ⁇ 80°C), short response time ( ⁇ 1ms), simple structure, and power saving, which meets the requirements of green environmental protection.
  • materials such as phosphors, luminescent glasses, and luminescent films can be used as luminescent materials in field emission devices, but they all have the essential problem of low luminous efficiency, which greatly limits the application of field emission devices, especially in illumination. Application of the field.
  • the surface plasmon excited by the metal structure increases the density of photon states in the vicinity.
  • the spontaneous radiance will increase, thereby making the internal quantum efficiency of the illuminating matrix.
  • the metal micro/nano structure destroys the waveguide mode of the illuminating matrix, and can radiate photons larger than the total internal reflection angle, thereby improving the light extraction efficiency of the illuminating substrate.
  • the configuration of the non-periodic metal structure is random, the controllability and consistency are poor, and the coupling efficiency between the photons generated by the illuminating center radiation and the surface plasmon is low, and the improvement of the light extraction efficiency is also very limited.
  • a light-emitting element having high light-emitting uniformity, high luminous efficiency, good stability, and simple structure is provided.
  • a light-emitting device light-emitting method which is simple in operation, convenient and reliable, and greatly enhances luminous efficiency of a light-emitting material is also provided.
  • a light-emitting element comprising a light-emitting glass, a metal layer further formed on a surface of the light-emitting glass, the metal layer having a periodic micro-nano structure, and the chemical composition of the light-emitting glass is a rare earth ion doped silicic acid salt.
  • a method of manufacturing a light-emitting element comprising the steps of:
  • a metal layer having a periodic micro/nano structure is formed on the surface of the luminescent glass to obtain the light-emitting element.
  • a cathode ray is emitted to the metal layer, and a surface plasma is formed between the metal layer and the luminescent glass under the excitation of the cathode ray to illuminate the luminescent glass.
  • the metal layer can form a surface plasmon at the interface between the cathode and the luminescent glass under the excitation of the cathode ray, and pass the surface plasmon.
  • the effect makes the internal quantum efficiency of the luminescent glass greatly improved, that is, the spontaneous radiation of the luminescent glass is enhanced, thereby greatly enhancing the luminous efficiency of the luminescent glass, thereby solving the problem that the luminescent material has low luminous efficiency; meanwhile, the periodicity of the metal layer is micro
  • the nanostructure destroys the waveguide mode of the luminescent glass, so that the photon larger than the total internal reflection angle is radiated, that is, the light extraction efficiency of the luminescent glass is increased, thereby greatly improving the overall luminous efficiency of the luminescent glass.
  • the light-emitting element includes a light-emitting glass and a metal layer, the double-layer structure is simple, and at the same time, there is a uniform interface between the light-emitting glass and the metal layer, thereby exhibiting high light-emitting uniformity and stability.
  • the light-emitting element can be obtained only by forming a metal layer on the light-emitting glass. The preparation method has the advantages of simple process, low cost and broad application prospects.
  • FIG. 1 is a schematic structural view of a light-emitting element according to an embodiment of the present invention.
  • FIG. 2 is a schematic structural view of a light-emitting element in which a metal layer is a dot matrix according to an embodiment of the present invention
  • FIG. 3 is a schematic structural view of a light-emitting element having a triangular metal layer according to an embodiment of the present invention
  • FIG. 4 is a schematic structural view of a light-emitting element having a rectangular metal layer according to an embodiment of the present invention
  • FIG. 5 is a luminescence spectrum of a luminescent element prepared in Example 1 shown in FIG. 3 and a luminescent glass without an added metal layer, the luminescence spectrum being detected by a Shimadzu RF-5301 PC spectrometer under a cathode ray excitation of an acceleration voltage of 5 kV. Analysis by the device;
  • FIG. 6 is a schematic structural view of a light-emitting element having a rectangular metal layer according to an embodiment of the present invention.
  • FIG. 7 is a schematic structural view of a light-emitting element having a rectangular metal layer according to an embodiment of the present invention.
  • FIG. 8 is a flow chart of a method for fabricating a light-emitting element according to an embodiment of the present invention.
  • Fig. 9 is a flow chart showing a method of emitting light of a light-emitting element according to an embodiment of the present invention.
  • a light-emitting element 10 includes a light-emitting glass 13 and a metal layer 14 disposed on a surface of the light-emitting glass 13.
  • the luminescent glass 13 is a rare earth ion doped silicate glass
  • the metal layer 14 has a periodically arranged micro/nano structure.
  • the micro-nano structure in which the metal layer 14 is periodically arranged may have the following implementation modes:
  • the periodic micro-nano structure of the metal layer 14 has periodically arranged protrusions.
  • the period of the periodic arrangement is the spacing of two adjacent minimum repeating units. In this embodiment, the period is the spacing between two adjacent protrusions, and the spacing between the two protrusions is the period of the embodiment.
  • the protrusion width or/and the spacing between the two protrusions is preferably 0.05P to 0.95P, most preferably 0.2P to 0.8P;
  • the height of the protrusion Preferably, it is from 0.5 nm to 200 nm, more preferably from 1 nm to 100 nm;
  • the thickness of the metal layer 14 at the bottom between the two protrusions (that is, the portion of the metal layer connecting the adjacent two protrusions) is preferably from 0 nm to 100 nm, more preferably 0 nm to 50 nm;
  • the protrusion cross-sectional shape is preferably at least one of a triangle, a square, a rectangle, a diamond, a circle, an ellipse, a hemisphere, a ring, and an irregular shape.
  • the bottom of each protrusion preferably passes through a thickness greater than 0 nm and less than 100.
  • the metal layers 14 of nm are connected, preferably the metal layers 14 of more than 0 nm and less than 50 nm are connected.
  • the protrusions are periodically arranged on the surface of the light-emitting glass 13 in isolation, as shown in FIG. 2, FIG. 3 and FIG. 4, in FIG.
  • the metal layer 14 at the bottom between the two protrusions has a thickness of 0 nm, and the protrusions are in a lattice shape, and the protrusions are periodically arranged on the surface of the luminescent metal 13; in FIG. 3, the thickness of the metal layer 14 at the bottom between the two protrusions is 0 nm, the protrusions are triangular, and the protrusions are periodically arranged on the surface of the luminescent metal 13; in FIG. 4, the metal layer 14 at the bottom between the two protrusions has a thickness of 0 nm, and the protrusions are circular, rectangular or square, and the protrusions are periodically arranged. It is laid on the surface of the luminescent metal 13.
  • the periodic micro-nano structure described above is a periodically arranged metal grating.
  • the period of the periodic arrangement is the spacing of two adjacent minimum repeating units, and the interval P of the minimum repeating unit is preferably 50 nm to 3000 nm, more preferably 200 nm to 1200 nm; the film thickness of the metal layer 14 It is preferably more than 0 nm, less than 100 nm, more preferably more than 0 nm and less than 50 nm.
  • the periodic micro/nano structure is a thin film of a metal layer 14 periodically arranged with holes.
  • the period of the periodic arrangement is the spacing between two adjacent minimum repeating units.
  • the period is the spacing between two adjacent holes, and the interval between the two holes, that is, the period P is preferably 50 nm to 3000 nm.
  • the thickness of the metal layer 14 is more than 0 nm, less than 100 nm, more preferably more than 0 nm, less than 50 nm; the pore diameter is preferably 0.05P to 0.95P, more preferably 0.2P to 0.8P.
  • the shape of the hole is preferably at least one of a triangle, a square, a rectangle, a diamond, a circle, an ellipse, a hemisphere, a ring, and an irregular shape, and the depth of the hole may be the same as or smaller than the thickness of the metal layer 14.
  • the surface of the luminescent glass 13 has a periodically arranged concave portion and a convex portion, and the concave portion and/or the convex portion surface are covered with a metal film layer.
  • the metal film layer is periodically arranged as the concave portion and the convex portion are periodically arranged.
  • the period of the periodic arrangement is a pitch in which the adjacent convex portion and the concave portion are one repeating unit, and the pitch P of the repeating unit composed of the convex portion and the concave portion, that is, the period P is preferably 50 nm to 3000 nm, and more preferably 200 nm.
  • the thickness of the metal layer 14 on the convex or concave surface is preferably 0 nm to 100 nm, and most preferably 0 nm to 50 nm; and the width of the convex portion or/and the concave portion of the surface of the light-emitting glass 13 is preferably 0.05P to 0.95P. Most preferably, it is 0.2P to 0.8P; the convex portion or/and the concave portion have a cross-sectional shape of at least one of a triangle, a square, a rectangle, a diamond, a circle, an ellipse, a hemisphere, a ring, and an irregular shape.
  • the metal layer 14 on the convex surface When the thickness of the metal layer 14 on the convex surface is 0 nm, the metal layer 14 is substantially distributed on the surface of the light-emitting glass 13 having a periodically arranged concave surface. Therefore, the metal layer 14 having the periodic arrangement is formed.
  • the periodic micro/nano structure is as shown in FIG. 6; when the thickness of the metal layer 14 having the periodic arrangement concave portion and the convex portion surface on the surface of the light-emitting glass 13 is greater than 0 nm, the structure is as shown in FIG. 7.
  • a metal layer 14 is formed on both the concave portion and the convex surface, and the metal layer 14 formed on the concave portion and the convex portion surface fluctuates up and down with the concave portion and the convex portion surface to constitute the periodic micro-nano structure.
  • the thickness of the metal layer 14 having the periodically arranged concave surface on the surface of the light-emitting glass 13 is 0 nm
  • the metal layer 14 is substantially distributed on the surface of the light-emitting glass 13 and has a periodic arrangement convex surface.
  • the upper layer 7 has a thickness of the metal layer 14 having a periodically arranged concave portion and a convex surface formed on the surface of the light-emitting glass 13 and cannot be simultaneously zero.
  • the metal layer 14 may be a metal having good chemical stability, such as a metal which is not easily oxidized and corroded, or a commonly used metal, preferably gold, silver, aluminum, copper, titanium, iron, nickel, cobalt, chromium, More preferably, at least one metal selected from the group consisting of platinum, palladium, magnesium, and zinc is formed of at least one of gold, silver, and aluminum.
  • the metal species in the metal layer 14 may be their single metal or composite metal.
  • the composite metal may be an alloy of two or more of the above metals.
  • the metal layer 14 may be a silver aluminum alloy layer or a gold aluminum alloy layer, wherein the weight fraction of silver or gold is preferably 70% or more.
  • the above-described light-emitting element 10 is used as a light-emitting element, and can be widely applied to a high-luminance and high-speed operation light-emitting device, such as a field emission display, a field emission light source, or a large advertising display card.
  • a field emission display as an example, an anode is applied with a forward voltage to form an accelerating electric field with respect to the field emission cathode array, and electrons emitted from the cathode, that is, a cathode ray 16 is emitted to the metal layer 14, and a metal layer 14 having a periodic micro/nano structure and the luminescent glass 13 are used.
  • the surface plasmon is formed, and the internal quantum efficiency of the luminescent glass 13 is greatly improved by the surface plasmon effect, that is, the spontaneous radiation of the luminescent glass 13 is enhanced; at the same time, the metal layer 14 of the periodic structure destroys the waveguide mode of the luminescent glass 13, When the photon larger than the total internal reflection angle is radiated, that is, the light extraction efficiency of the luminescent glass 13 is increased, the overall luminescence efficiency of the luminescent glass 13 is greatly improved, thereby solving the problem that the luminescent material has low luminous efficiency.
  • the metal layer 14 of the periodic micro-nano structure has good controllability and consistency, and can control the surface plasma by constructing the surface configuration and modulation size parameters of the metal structure, for example, designing a suitable metal.
  • the surface configuration allows the resonant frequency of the surface plasmon to match the wavelength of the radiant substrate to greatly increase the internal quantum efficiency of the luminescent substrate. Therefore, the use of the periodic micro-nano structure metal layer 14 can more effectively help the current solid-state light-emitting devices out of the dilemma of low luminous efficiency, and generate a new type of ultra-high brightness and high-speed operation of the light-emitting device.
  • FIGS. 1 and 8 a flow chart of a method for fabricating a light-emitting device according to an embodiment of the present invention is illustrated. The method includes the following steps:
  • the luminescent glass 13 has a chemical composition of a rare earth ion doped silicate.
  • a metal layer 14 is formed on the surface of the luminescent glass 13, to obtain a light-emitting element 10 having a periodic micro-nano structure.
  • the method for preparing the illuminating glass 13 is prepared by a common method in the art, and the surface of the illuminating glass 13 is provided with a periodically arranged convex portion and a concave portion which can be prepared by an existing micromachining method.
  • the obtained glass can be further cut and polished into a certain size to meet the application requirements.
  • the metal layer 14 is formed on the surface of the luminescent glass 13 by physical or chemical vapor deposition, for example, but not limited to, by an existing micromachining method, sputtering or evaporation method.
  • the metal layer 14 may be a metal with good chemical stability, such as a metal that is not easily oxidized and corroded, or a commonly used metal, preferably gold, silver, aluminum, copper, titanium, iron, nickel, cobalt, chromium, More preferably, at least one metal selected from the group consisting of platinum, palladium, magnesium, and zinc is formed of at least one of gold, silver, and aluminum.
  • the metal species in the metal layer 14 may be their single metal or composite metal.
  • the composite metal may be an alloy of two or more of the above metals.
  • the metal layer 14 may be a silver aluminum alloy layer or a gold aluminum alloy layer, wherein the weight fraction of silver or gold is preferably 70% or more.
  • the metal layer 14 having a periodic micro/nano structure is formed on the surface of the luminescent glass 13 by a conventional micromachining method.
  • the period P of the metal layer 14 is preferably 50 nm to 3000 nm, more preferably 200 nm to 1200 nm; the thickness of the metal layer 14 varies depending on the shape and distribution of the metal layer 14 of the periodic micro/nano structure, and the specific difference is as described above.
  • Four implementations of the micro-nano structure are possible to be a silver aluminum alloy layer or a gold aluminum alloy layer, wherein the weight fraction of silver or gold is preferably 70% or more.
  • the metal layer 14 having a periodic micro/nano structure is formed on the surface of the luminescent glass 13 by a conventional micromachining method.
  • the light-emitting element includes the light-emitting glass 13 and the metal layer 14, this double-layer structure is simple, and has a uniform interface between the light-emitting glass 13 and the metal layer 14, thereby exhibiting high light-emitting uniformity and stability.
  • the illuminating glass 13 is prepared, it is only necessary to perform appropriate micro-machining treatment on the surface of the illuminating glass 13 according to actual needs, and then a metal layer 14 is added on the surface of the luminescent glass 13 to obtain a finished product, so that the preparation method is simple.
  • the required processing equipment is small, so that the light-emitting element has low preparation cost and is suitable for enterprise scale production.
  • the method of emitting light includes the following steps:
  • the light-emitting element 10 has the features described above in terms of various structures and components.
  • the implementation step S12 may employ a field emission display or an illumination source.
  • the anode applies a forward voltage to the field emission cathode array to form an acceleration electric field, and the cathode emits a cathode ray 16 under excitation of the cathode ray 16.
  • the electron beam first penetrates the metal layer 14 to excite the luminescent glass 13 to emit light. In this process, a surface plasmon effect is generated at the interface between the metal layer 14 and the luminescent glass 13, and the internal quantum efficiency of the luminescent glass 13 is greatly improved by this effect.
  • the spontaneous radiation enhancement of the luminescent material is enhanced; at the same time, the waveguide mode of the luminescent glass 13 is destroyed by the periodic micro/nano structure on the metal layer 14, so that the light extraction efficiency is improved, thereby greatly enhancing the luminous efficiency of the luminescent material.
  • SPPs Surface plasmon Plasmon
  • the present embodiment utilizes the excitation performance of the SPPs to increase the optical density of the luminescent glass 13 and enhance its spontaneous emission rate; moreover, the coupling effect of the surface plasmon can be utilized to generate light when the luminescent glass 13 emits light.
  • the resonance effect is coupled to greatly increase the internal quantum efficiency of the luminescent glass 13; at the same time, the periodic metal structure on the surface of the luminescent glass 13 destroys the waveguide mode of the luminescent glass 13, and the photons larger than the total internal reflection angle are radiated, that is, the luminescent glass 13
  • the light extraction efficiency is increased, and thus the overall luminous efficiency of the luminescent glass 13 is greatly improved.
  • the angular frequency of the light-emitting wavelength of the light-emitting glass 13 be ⁇
  • the dielectric constant of the metal layer 14 be ⁇ m
  • the dielectric constant of the dielectric B around the metal layer 14 be ⁇ b
  • the refractive index of the illuminating glass 13 is n g
  • the magnitude of the inverted structure of the periodic structure is ⁇
  • m is an integer
  • the incident angle of the light emitted from the luminescent glass 13 incident on the interface of the metal layer 14 and the luminescent glass 13 is incident.
  • the refractive index of the dielectric B is n b and n is an integer
  • compositions of the light-emitting elements and their preparation methods, as well as their properties and the like, are exemplified below by means of a plurality of embodiments.
  • the basic structure of the glass light-emitting element having the metal thin film of this embodiment is as shown in FIG.
  • a green illuminating glass 13 having a size of 1 ⁇ 1 cm 2 and a surface of 30 Na 2 O• 6Y 2 O 3 • 60 SiO 2 • 4 Tb 2 O 3 (the number is expressed as a molar ratio of each oxide) is used to form a layer on the surface thereof by using the existing micromachining technique.
  • the metal layer 14 of the ordered periodic structure formed by combining three triangular pyramidal silver particles is shown in FIG. 3.
  • the specific structural parameters are also indicated in FIG. 3, and the height of the silver nanoparticles is 30 nm.
  • the light-emitting element of this embodiment was obtained from the light-emitting glass 13 and the metal layer 14.
  • the cathode ray generated by the electron gun bombards the light-emitting element prepared in the present embodiment, and the electron beam first penetrates the metal layer 14 to excite the light-emitting glass 13 to emit light, resulting in an emission spectrum as shown in FIG.
  • the curve 51 in the figure is the luminescence spectrum of the luminescent glass 13 when the metal silver layer is not added;
  • the curve 52 is the luminescence spectrum of the luminescent glass 13 to which the metal structure is added prepared in the present embodiment, as can be seen from the figure, due to the metal layer 14 and A surface plasmon effect is generated between the illuminating glass 13 and the illuminating glass 13 of the metal structure having the metal structure of the present embodiment has an illuminating integrated intensity from 300 nm to 700 nm which is the unmetallized layer 14 with respect to the illuminating glass 13 when the metal layer 14 is not applied.
  • the illuminating glass 13 emits 5.5 times of the integrated intensity, the luminescent performance is greatly improved.
  • the luminescence spectra of the following respective embodiments are similar to those of Embodiment 1, and each of the illuminating elements also has a similar luminescence intensity effect, which will not be described below.
  • the basic structure of the glass light-emitting element having a metal thin film of this embodiment is as shown in FIG.
  • Use surface 30Na2O• 6Y2O3• 60SiO2• 4Tb2O3 (the number before the oxides is expressed as a molar ratio) of the polished green luminescent glass 13 forms a cylindrical silver nanoparticle array arranged in a square lattice as shown in FIG. 4 on the surface thereof by using an existing micromachining technique.
  • the luminescent glass 13 and the silver nanoparticle array constitute the light-emitting element of this embodiment.
  • the periodic metal micro/nano structure is capable of manipulating the surface plasmon by constructing the surface configuration and modulation size parameters of the metal structure, which has wavelength selectivity for enhancement of luminescence.
  • the peak radiation wavelength of the luminescent glass 13 is ⁇
  • the dielectric constant of the metal layer 14 is ⁇ m
  • the period P of ( ⁇ m ⁇ b /( ⁇ m + ⁇ b )) 1/2 can maximize the luminescence.
  • the surface plasmon resonance wavelength ⁇ of the periodic metal micro/nano structure is determined.
  • the value of the period P should be 527 nm.
  • the diameter of the cylindrical metal particles was taken to be 200 nm, and the height was taken as 30 nm.
  • the surface plasmon resonance frequency of the periodic metal structure and the radiation wavelength of the luminescent glass 13 coincide, and the maximum optical density of states can be obtained in the surface layer of the luminescent glass 13, so that the photons emitted from the luminescent glass 13 are better between the surface plasmons and the surface plasmons. Coupling is generated to improve the internal quantum efficiency, thereby improving the luminous efficiency of the light-emitting element.
  • the basic structure of the glass light-emitting element having a metal thin film of this embodiment is as shown in FIG. 30 prepared by the above preparation method of surface polishing Na2O• 6Y2O3• 60SiO2• 4Eu2O3 (the number in front of each oxide is expressed as a molar ratio) polished red luminescent glass 13, using an existing micromachining technique to form a layer of aluminum having a surface period micro-nano structure as shown in FIG.
  • the size of the metal particles is 200 nm
  • the height of the metal layer 14 is 50 nm
  • the depth of the recess of the metal layer 14 from the surface is 10 nm. That is, the light-emitting element of this embodiment.
  • the basic structure of the glass light-emitting element having a metal thin film of this embodiment is as shown in FIG.
  • the recess has a size of 50 nm and a depth of 40 nm, and has a platinum film having a thickness of 20 nm in the concave portion of the micro-nano structure of the glass surface, that is, the light-emitting element of the present embodiment.
  • the basic structure of the glass light-emitting element having a metal thin film of this embodiment is as shown in FIG.
  • 30 Na2O• 6Y2O3• 60SiO2• 2Tm2O3• 1Eu2O3• 1Tb2O3 (the number in front of each oxide is expressed as a molar ratio) polished white luminescent glass 13, which forms a periodic micro/nano structure on its surface by using existing micromachining technology, the period of the micro/nano structure is 600 nm, and the size of the periodic structure convex portion
  • the thickness of the recess is 100 nm
  • the surface of the glass micro/nano structure has a magnesium thin film having a thickness of 10 nm, which is the light-emitting element of the present embodiment.

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Description

一种玻璃基材发光元件、其制造及其发光方法 技术领域
本发明属于发光材料技术领域，具体涉及一种具有玻璃基材作为发光材料的发光元件、其制造方法及其发光方法。
背景技术
传统的作为发光基体的材料包括荧光粉、纳米晶体及玻璃等，相对于晶体和荧光粉而言，玻璃具有透明、坚硬及良好化学稳定性和光学性质；而且玻璃更容易被加工成各种大小形状的产品，如各种形状或尺寸的显示器件或照明光源。
例如，在真空微电子学领域中，场发射器件通常利用发光玻璃作为发光体，其在照明及显示领域显示出了广阔的应用前景，引起国内外研究机构的广泛关注。场发射器件工作原理是：在真空环境下，阳极相对场发射阴极阵列（Field emissive arrays，FEAs）施加正向电压形成加速电场，阴极发射的电子加速轰向阳极板上的发光材料而发光。场发射器件的工作温度范围宽（-40°C~80°C）、响应时间短（<1ms）、结构简单、省电，符合绿色环保要求。另外，荧光粉体、发光玻璃、发光薄膜等材料都可以在场发射器件中作为发光材料使用，但它们都存在发光效率低这一本质问题，极大限制了场发射器件的应用，特别是在照明领域的应用。
金属结构激发的表面等离子体会增大其附近的光子态密度，当发光基体的发光中心位于表面等离子体场的作用范围内时，其自发辐射速率将会增大，从而使发光基体的内量子效率得到提高；同时，金属微纳结构会破坏发光基体的波导模式，可以使大于全内反射角的光子辐射出去，从而提高发光基体的光萃取效率。但是非周期金属结构的构型随机，可控性与一致性较差、发光中心辐射产生的光子与表面等离子体之间的耦合效率低等问题，其对光萃取效率的改善也非常有限。
 技术问题
有鉴于此，提供一种具有发光均匀性高、发光效率高、稳定性好、结构简单的发光元件。
以及一种制备工艺简单、成本低的发光元件制造方法。
还提供一种操作简便、方便可靠、大大增强发光材料发光效率的发光元件发光方法。
 技术解决方案
一种发光元件，其包括发光玻璃，在所述的发光玻璃表面还形成有金属层，所述的金属层具有周期性微纳结构，所述的发光玻璃化学成分为稀土离子掺杂的硅酸盐。
一种发光元件制造方法，其包括如下步骤：
制备表面平整或表面开设有周期性排布的凸部和凹部的发光玻璃；
在所述发光玻璃的表面形成一具有周期性微纳结构的金属层，得到所述发光元件。
以及，一种发光元件的发光方法，其包括如下步骤：
按照上述制造方法获得发光元件；及
对金属层发射阴极射线，在阴极射线激发下金属层与发光玻璃之间形成表面等离子体，使发光玻璃发光。
 有益效果
在上述发光元件中，通过采用在发光玻璃上形成一层具有周期性微纳结构的金属层，该金属层能在阴极射线激发下与发光玻璃之间的界面形成表面等离子体，通过表面等离子体效应，使发光玻璃的内量子效率大大提高，即发光玻璃的自发辐射增强，进而大大增强了发光玻璃的发光效率，从而解决了发光材料发光效率低这一问题；同时，金属层的周期性微纳结构会破坏发光玻璃的波导模式，使大于全内反射角的光子辐射出去，即发光玻璃的光萃取效率增大，从而极大提高了发光玻璃的整体发光效率。因而，在发光元件的发光方法中，只需对金属层发射阴极射线，金属层与发光玻璃之间形成表面等离子体，即能大大增强发光玻璃发光效率，提高其发光可靠性。由于发光元件包括发光玻璃和金属层，这种双层结构简单，同时，在发光玻璃和金属层间有均匀界面，从而表现出很高的发光均匀性和稳定性。在上述的发光元件制备方法中，只需要在发光玻璃上形成一层金属层，即可获得所述发光元件，该制备方法工艺简单、成本低，具有广阔的生产应用前景。
附图说明
下面将结合附图及实施例对本发明作进一步说明，附图中：
图1为本发明实施例的发光元件的结构示意图；
图2为本发明实施例的金属层为点阵形的发光元件结构示意图；
图3为本发明实施例的金属层为三角形的发光元件结构示意图；
图4为本发明实施例的金属层为矩形的发光元件结构示意图；
图5为图3所示的实施例1制备的发光元件与未加金属层的发光玻璃对比的发光光谱，该发光光谱是在5KV加速电压的阴极射线激发下以岛津RF-5301PC光谱仪为检测器分析得出；
图6为本发明实施例的金属层为矩形的发光元件结构示意图；
图7为本发明实施例的金属层为矩形的发光元件结构示意图；
图8为本发明实施例的发光元件制备方法流程图；
图9为本发明实施例的发光元件的发光方法流程图。
 本发明的实施方式
为了使本发明要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
请参阅图1，示出本发明实施例的发光元件10，其包括发光玻璃13以及设于发光玻璃13表面的金属层14。该发光玻璃13是稀土离子掺杂的硅酸盐玻璃，金属层14具有周期性排布的微纳结构。
作为示例，上述的金属层14周期性排布的微纳结构可以有以下几种实现方式：
第一种实现方式，上述金属层14的周期性微纳结构具有周期性排布的突起。该周期性排布的周期是相邻的两个最小重复单元的间距，本实施方式中周期即为相邻的两个突起之间的间距，两个突起之间的间距即本实施例的周期P优选为50nm~3000nm，更优选为200nm~1200nm；所述突起宽度或/和两两突起之间的间距优选为0.05P~0.95P，最优选为0.2P~0.8P；所述突起的高度优选为0.5nm~200nm，更优选为1nm~100nm；两两突起之间底部的金属层14（即连接相邻的两个突起之间的金属层部分）厚度优选为0nm~100nm，更优选为0nm~50nm；所述突起截面形状优选为三角形、正方形、矩形、菱形、圆形、椭圆形、半球形、圆环、不规则形状中的至少一种。
当该两两突起之间底部的金属层14厚度大于0nm时，各突起底部优选通过厚度大于0nm、小于100 nm的金属层14连接，优选为大于0nm、小于50nm的金属层14连接。当该两两突起之间底部的金属层14厚度为0nm时，各突起是彼此孤立的呈周期性排布在发光玻璃13表面，如图2、图3和图4所示，在图2中，两两突起之间底部的金属层14厚度为0nm，突起呈点阵形，突起周期性排布在发光金属13的表面；在图3中，两两突起之间底部的金属层14厚度为0nm，突起呈三角形，突起周期性排布在发光金属13的表面；在图4中，两两突起之间底部的金属层14厚度为0nm，突起呈圆形、矩形或正方形，突起周期性排布在发光金属13的表面。
第二种实现方式，上述的周期性微纳结构是周期性排布的金属光栅。该周期性排布的周期是相邻的两个最小重复单元的间距，最小重复单元的间距基本实施例的周期P优选为50nm~3000nm，更优选为200nm~1200nm；所述金属层14薄膜厚度优选大于0nm、小于100nm，更优选大于0nm、小于50nm。
第三种实现方式，上述的周期性微纳结构是周期性排布有孔的金属层14薄膜。该周期性排布的周期是相邻的两个最小重复单元的间距，本实施方式中周期即为相邻的两孔之间的间距，两孔之间的间距即周期P优选为50nm~3000nm，更优选为200nm~1200nm；所述金属层14薄膜厚度优选大于0nm、小于100nm，更优选大于0nm、小于50nm；所述孔直径优选为0.05P~0.95P，更优选为0.2P~0.8P；该孔形状优选为三角形、正方形、矩形、菱形、圆形、椭圆形、半球形、圆环、不规则形状中的至少一种，孔的深度可以和金属层14的厚度相同，也可以小于金属层14的厚度。
第四种实现方式，发光玻璃13表面具有周期性排布的凹部和凸部，在所述的凹部和/或凸部面上覆有金属膜层。该金属膜层随着凹部和凸部周期性排布而周期性排布。本实施方式中周期性排布的周期是相邻的凸部和凹部为一个重复单元的间距，凸部和凹部组成的一个重复单元的间距即周期P优选为50nm~3000nm，更优选为200nm~1200nm；所述凸部或凹部面上的金属层14厚度优选为0nm~100nm，最优选为0nm~50nm；所述发光玻璃13表面开设的凸部或/和凹部宽度优选为0.05P~0.95P，最优选为0.2P~0.8P；该凸部或/和凹部截面形状优选为三角形、正方形、矩形、菱形、圆形、椭圆形、半球形、圆环、不规则形状中的至少一种。
当上述凸部面上的金属层14厚度为0nm时，金属层14基本上分布在发光玻璃13表面开设的具有周期性排布凹部面上，因此，该具有周期性排布的金属层14构成了所述的周期性微纳结构，如图6所示；当上述发光玻璃13表面开设的具有周期性排布凹部和凸部面上的金属层14厚度均大于0nm时，其结构如图7所示，在凹部和凸部面上均形成有金属层14，该形成于凹部和凸部面上的金属层14随着凹部和凸部面的上下波动从而构成了所述的周期性微纳结构。当上述发光玻璃13表面开设的具有周期性排布凹部面上的金属层14厚度也可为0nm时，此时金属层14基本上分布在发光玻璃13表面开设的具有周期性排布凸部面上7，但是该发光玻璃13表面开设的具有周期性排布凹部和凸部面上的金属层14厚度不能同时为零。
上述的金属层14可以是由化学稳定性良好的金属，例如不易氧化腐蚀的金属，另外也可以是常用的金属，优选为金、银、铝、铜、钛、铁、镍、钴、铬、铂、钯、镁、锌中的至少一种金属形成的，更优选为由金、银、铝中的至少一种金属形成的。金属层14中的金属物种可以是它们的单金属或者复合金属。复合金属可以是上述金属两种或两种以上的合金，例如，金属层14可以是银铝合金层或金铝合金层，其中银或金的重量分数优选为70%以上。
在图1至4和图6至7中，上述发光元件10作为发光元件，可广泛应用于超高亮度和高速运作的发光器件上，例如场发射显示器、场发射光源或大型广告显示牌等产品中。以场发射显示器为例，阳极相对场发射阴极阵列施加正向电压形成加速电场，阴极发射的电子，即对金属层14发射阴极射线16，具有周期微纳结构的金属层14与发光玻璃13之间形成表面等离子体，通过表面等离子体效应，使发光玻璃13的内量子效率大大提高，即发光玻璃13的自发辐射增强；同时，周期性结构的金属层14会破坏发光玻璃13的波导模式，使大于全内反射角的光子辐射出去，即发光玻璃13的光萃取效率增大，因而，发光玻璃13的整体发光效率得到极大提高，从而解决发光材料发光效率低这一问题。同时，周期性微纳结构的金属层14则具有很好的可控性与一致性，其能够通过构造金属结构的表面构型和调制尺寸参数对表面等离子体进行操控，例如，设计合适的金属表面构型使表面等离子体的谐振频率与发光基体的辐射波长相匹配，就能够极大地提高发光基体的内量子效率。因此，采用周期性微纳结构金属层14能够更有效地帮助目前各种固态发光装置走出发光效率低的困境，催生出新型的超高亮度和高速运作的发光器件。
请参阅图1和8，说明本发明实施例的发光元件制造方法的流程，该制造方法包括如下步骤：
S01：制备表面平整或表面开设有周期性排布的凸部和凹部的发光玻璃13，所述的发光玻璃13化学成分为稀土离子掺杂的硅酸盐。
S02：在发光玻璃13的表面形成一金属层14，得到发光元件10，所述的金属层14具有周期性微纳结构。
在步骤S01中，该发光玻璃13制备方法采用本技术领域的常用方法制备而成，该发光玻璃13表面开设有周期性排布的凸部和凹部可采用现有微加工方法制备而成。另外，还可将制得的玻璃进一步切割、抛光加工成一定的尺寸，以符合应用需求。
在步骤S02中，该金属层14是通过将上述至少一种金属通过物理或化学气相沉积法形成于发光玻璃13表面，例如但不限于用现有微加工方法、溅射或蒸镀方法形成于发光玻璃13的表面。其中，金属层14可以是由化学稳定性良好的金属，例如不易氧化腐蚀的金属，另外也可以是常用的金属，优选为金、银、铝、铜、钛、铁、镍、钴、铬、铂、钯、镁、锌中的至少一种金属形成的，更优选为由金、银、铝中的至少一种金属形成的。金属层14中的金属物种可以是它们的单金属或者复合金属。复合金属可以是上述金属两种或两种以上的合金，例如，金属层14可以是银铝合金层或金铝合金层，其中银或金的重量分数优选为70%以上。该具有周期性微纳结构的金属层14是通过现有的微加工方法形成于发光玻璃13表面。金属层14的周期P优选为50nm~3000nm，更优选为200nm~1200nm；其金属层14的厚度根据上述周期性微纳结构的金属层14的形状及分布不同而不同，具体的不同如上述周期性微纳结构的四种实施方式。
由于发光元件包括发光玻璃13和金属层14，这种双层结构简单，在发光玻璃13和金属层14间有均匀界面，从而表现出很高的发光均匀性和稳定性。同时，将发光玻璃13制备后，只需对该发光玻璃13表面根据实际需求做适当的微加工处理，再在该发光玻璃13表面加上一层金属层14即可得成品，因而制备方法简单，所要求的加工设备少，以致该发光元件制备成本低，适合企业化规模生产。
请参阅图1和9，说明本发明实施例的发光元件发光方法的流程，该发光方法包括如下步骤：
S11：按照前述制造方法获得发光元件10；
S12：对金属层14发射阴极射线16，部分阴极射线能够穿透金属层14激发发光玻璃13发光，同时在金属层14与发光玻璃13之间形成表面等离子体，使发光玻璃13的发光得到增强。
发光元件10具有前面描述各种结构及组份等特征。在实际应用中，实现步骤S12可以采用场发射显示器或照明光源，在真空环境下，阳极相对场发射阴极阵列施加正向电压形成加速电场，阴极发射阴极射线16，在阴极射线16的激发下，电子束首先穿透金属层14进而激发发光玻璃13发光，在这个过程中，金属层14与发光玻璃13的界面上产生了表面等离子体效应，通过该效应使发光玻璃13的内量子效率大大提高，即发光材料的自发辐射增强；同时，通过金属层14上的周期微纳结构破坏发光玻璃13的波导模式，使光萃取效率得到提高，进而大大增强了发光材料的发光效率。
表面等离子体（Surface Plasmon，SP）是一种沿金属和介质界面传播的波，其振幅随离开界面的距离而指数衰减。当改变金属表面结构时，表面等离子体激元（Surface plasmon polaritons, SPPs) 的性质、色散关系、激发模式、耦合效应等都将产生重大的变化。SPPs引发的电磁场，不仅仅能够限制光波在亚波长尺寸结构中传播，而且能够产生和操控从光频到微波波段的电磁辐射，实现对光传播的主动操控。因此，本实施例利用该SPPs的激发性能，增大发光玻璃13的光学态密度和增强其自发辐射速率；而且，可利用表面等离子体的耦合效应，当发光玻璃13发出光时，能与其发生耦合共振效应，从而大大提高发光玻璃13的内量子效率；同时，发光玻璃13表面的周期性金属结构会破坏发光玻璃13的波导模式，使大于全内反射角的光子辐射出去，即发光玻璃13的光萃取效率增大，因而，发光玻璃13的整体发光效率得到极大提高。
设发光玻璃13的发光波长的角频率为ω，金属层14的介电常数为εm，金属层14周围的电介质B的介电常数为εb，激发的表面等离子体激元的波数kSP，可用kSP=ω/(c(εmεb/(εm+εb))1/2)近似得出。而当设发光玻璃13的折射率为ng，周期性结构的倒格矢大小为Κ，m为整数，从发光玻璃13发出的光入射在金属层14和发光玻璃13的界面上的入射角为θi，则满足ng(ω/c)sinθi+mK=kSP的光可以激发表面等离子体激元。而当电介质B的折射率为nb，n为整数时，则激发的表面等离子体激元以满足nb(ω/c)sinθj=kSP+nK的角度θj从上下两个表面发射光。
以下通过多个实施例来举例说明发光元件的不同组成及其制备方法，以及其性能等方面。
实施例1
本实施例具有金属薄膜的玻璃发光元件的基本结构如图1所示。选择大小为1×1cm2、表面用30 Na2O• 6Y2O3• 60SiO2• 4Tb2O3（各氧化物前数字表示为摩尔比）抛光的绿色发光玻璃13，利用现有的微加工技术在其表面形成一层由六个三棱锥状的银粒子组合而成的有序周期结构的金属层14，其结构示意图如图3，具体的结构参数也在图3中标出，银纳米粒子的高度为30nm。由发光玻璃13及金属层14即得到本实施例的发光元件。
用电子枪产生的阴极射线轰击本实施例的所制备的发光元件，电子束首先穿透金属层14进而激发发光玻璃13发光，产生如图5所示的发光光谱。图中曲线51为未加金属银层时发光玻璃13的发光光谱；曲线52为本实施例制备的附加了金属结构的发光玻璃13的发光光谱，从图中可以看到，由于金属层14与发光玻璃13之间产生了表面等离子体效应，相对于未加金属层14时发光玻璃13，本实施例的附加了金属结构的发光玻璃13从300nm到700nm的发光积分强度是未加金属层14时发光玻璃13发光积分强度的5.5倍，使发光性能得到极大提高。
以下各个实施例的发光光谱都与实施例1相类似，各发光元件也具有类似的发光强度效果，在下面不再赘述。
实施例2
本实施例的具有金属薄膜的玻璃发光元件的基本结构如图1所示。采用表面用30Na2O• 6Y2O3• 60SiO2• 4Tb2O3（各氧化物前数字表示为摩尔比）抛光的绿色发光玻璃13，利用现有微加工技术在其表面形成如图4所示的按正方形晶格排布的圆柱状银纳米粒子阵列。发光玻璃13和银纳米粒子阵列即构成本实施例的发光元件。
周期金属微纳结构能够通过构造金属结构的表面构型和调制尺寸参数对表面等离子体进行操控，其对发光的增强具有波长选择性。以本实施例的金属纳米点阵为例，设发光玻璃13的峰值辐射波长为λ，金属层14的介电常数为εm，电介质B的介电常数为εb，则满足λ=P×(εmεb/(εm+εb))1/2的周期P能够使发光得到最大的增强。确定周期金属微纳结构的表面等离子体谐振波长λ。本实施例发光玻璃13的峰值辐射波长约为549nm（银n=0.06+3.586i），电介质B为真空，根据上述公式可计算得到周期P的值应取527nm。另外，圆柱金属粒子的直径取为200nm，高度取为30nm。此时，周期金属结构的表面等离子体谐振频率和发光玻璃13的辐射波长重合，能够在发光玻璃13表层得到最大的光学态密度，使发光玻璃13发出的光子更好地与表面等离子体之间产生耦合，使内量子效率得到提高，从而使发光元件的发光效率得到提高。
实施例3
本实施例的具有金属薄膜的玻璃发光元件的基本结构如图1所示。采用表面抛光的上述制备方法制得的用30 Na2O• 6Y2O3• 60SiO2• 4Eu2O3（各氧化物前数字表示为摩尔比）抛光的红色发光玻璃13，利用现有微加工技术在其表面形成如图1所示的一层具有表面周期微纳结构的铝层，结构的周期为700nm，金属粒子的尺寸为200nm，金属层14的高度为50nm，金属层14凹部距离表面的深度为10nm。即为本实施例的发光元件。
实施例4
本实施例的具有金属薄膜的玻璃发光元件的基本结构如图6所示。采用表面用30Na2O• 6Y2O3• 60SiO2• 4Tm2O3（各氧化物前数字表示为摩尔比）抛光的蓝色发光玻璃13，利用现有微加工技术在其表面形成一层具有周期性微纳结构，结构的周期P为450nm，周期微纳结构凹部的尺寸为50nm，深度为40nm，在玻璃表面微纳结构的凹部内具有一层厚度为20nm的铂薄膜，即为本实施例的发光元件。
实施例5
本实施例的具有金属薄膜的玻璃发光元件的基本结构如图8所示。采用表面抛光的上述制备方法制得用30 Na2O• 6Y2O3• 60SiO2• 2Tm2O3• 1Eu2O3• 1Tb2O3（各氧化物前数字表示为摩尔比）抛光的白色发光玻璃13，利用现有微加工技术在其表面形成周期性的微纳结构，微纳结构的周期为600nm，周期结构凸部的尺寸为300nm，凹部的深度为100nm，在玻璃微纳结构的表面具有一层厚度为10nm的镁薄膜，即为本实施例的发光元件。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (11)

  1. 一种发光元件，其包括发光玻璃，其特征在于：所述的发光玻璃表面还形成有金属层，所述的金属层具有周期性微纳结构，所述的发光玻璃化学成分为稀土离子掺杂的硅酸盐。
  2. 根据权利要求1所述的发光元件，其特征在于：所述的周期性微纳结构是具有周期性排布的突起。
  3. 根据权利要求2所述的发光元件，其特征在于：所述周期性排布的周期P为50nm~3000nm，所述突起宽度或/和两两突起间的间距为0.05P~0.95P，所述突起的高度为0.5nm~200nm，两两突起之间底部的金属层厚度为0nm~100nm。
  4. 根据权利要求1所述的发光元件，其特征在于：所述的周期性微纳结构是周期性排布的金属光栅或周期性排布有孔的金属层薄膜。
  5. 根据权利要求4所述的发光元件，其特征在于：所述的周期性排布的周期为50nm~3000nm；所述金属层薄膜厚度大于零，小于100nm；所述孔的直径为0.05P~0.95P。
  6. 根据权利要求1所述的发光元件，其特征在于：所述的发光玻璃表面具有周期性排布的凹部和凸部，在所述的凹部和/或凸部面上覆有金属膜层。
  7. 根据权利要求6所述的发光元件，其特征在于：所述周期性排布的周期P为50nm~3000nm，所述凸部和/或凹部面上的金属膜层厚度为0nm~100nm，所述发光玻璃表面上的凸部或/和凹部宽度为0.05P~0.95P。
  8. 根据权利要求1所述的发光元件，其特征在于：所述的金属层的金属为金、银、铝、铜、钛、铁、镍、钴、铬、铂、钯、镁、锌中的至少一种。
  9. 一种发光元件制造方法，其包括如下步骤：
    制备表面平整或表面开设有周期性排布的凸部和凹部的发光玻璃；
    在所述发光玻璃的表面形成一具有周期性微纳结构的金属层，得到所述发光元件。
  10. 根据利要求9所述的发光元件制造方法，其特征在于，所述金属层采用溅射或蒸镀方法形成于所述发光玻璃的表面。
  11. 一种发光元件的发光方法，其包括如下步骤：
    按照权利要求9或10所述的发光元件制造方法获得发光元件；及
    对金属层发射阴极射线，在阴极射线激发下金属层与发光玻璃之间形成表面等离子体，使发光玻璃发光。
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CN102714120A (zh) 2012-10-03
CN102714120B (zh) 2014-08-06
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US20120326056A1 (en) 2012-12-27

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