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WO2023249069A1 - Élément de conversion de longueur d'onde et dispositif électroluminescent l'utilisant - Google Patents

Élément de conversion de longueur d'onde et dispositif électroluminescent l'utilisant Download PDF

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Publication number
WO2023249069A1
WO2023249069A1 PCT/JP2023/023052 JP2023023052W WO2023249069A1 WO 2023249069 A1 WO2023249069 A1 WO 2023249069A1 JP 2023023052 W JP2023023052 W JP 2023023052W WO 2023249069 A1 WO2023249069 A1 WO 2023249069A1
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WIPO (PCT)
Prior art keywords
wavelength
light
phosphor
conversion element
reflective layer
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PCT/JP2023/023052
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English (en)
Japanese (ja)
Inventor
忠昭 長尾
クマール バルン バルマン
ピニヤ ダビーッド エルナンデス
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National Institute for Materials Science
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National Institute for Materials Science
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Priority to JP2024529062A priority Critical patent/JP7744065B2/ja
Publication of WO2023249069A1 publication Critical patent/WO2023249069A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • 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
    • 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
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • 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
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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
    • C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/851—Wavelength conversion means
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Definitions

  • the present invention relates to a wavelength conversion element and a light emitting device using the same. Specifically, the present invention relates to a wavelength conversion element that emits white light and a light emitting device using the same.
  • Patent Document 1 discloses a composition in which a carbon nanoparticle phosphor is dispersed in a water-soluble solvent, and the carbon nanoparticle phosphor contains a carbon atom, an oxygen atom, a nitrogen atom, and optionally a hydrogen atom,
  • the intensity of the peak (285.98 eV) derived from the C--N bond and/or C--O bond is higher than that derived from the C--C bond and/or C--H bond (284.95 eV).
  • the Raman spectrum has peaks based on the G and D bands, and the composition is reported to be a blue-emitting phosphor upon excitation with ultraviolet light.
  • Patent Document 1 discloses that a white light emitting device is provided by combining such a carbon nanoparticle phosphor with a red phosphor or a green phosphor and using it together with an excitation source that emits ultraviolet light.
  • a white light emitting device is combined with a phosphor, it is difficult to adjust the chromaticity.
  • highly accurate adjustment of the combination of phosphors is required. Therefore, it would be advantageous if the chromaticity and color temperature could be adjusted more easily.
  • An object of the present invention is to provide a wavelength conversion element and a light emitting device whose chromaticity can be adjusted using only one type of phosphor.
  • a further object of the present invention is to provide a wavelength conversion element and a light emitting device that emit white light along a blackbody locus using only one type of phosphor.
  • the wavelength conversion element includes a first reflective layer, a second reflective layer, and a phosphor layer located between the first reflective layer and the second reflective layer,
  • the layer has an excitation wavelength dependence of the emission wavelength and converts the irradiated excitation light into light having a wavelength longer than the excitation light
  • the first reflective layer has a dependence of the excitation wavelength on the excitation light.
  • the second reflective layer reflects light in a first wavelength range located on the long wavelength side, and the second reflective layer reflects light in a second wavelength range that overlaps at least a part of the first wavelength range, and Between the first reflective layer and the second reflective layer, the first wavelength region and the second wavelength region of the light obtained by wavelength-converting the excitation light in the phosphor layer overlap.
  • the phosphor layer converts the resonant light into light with a wavelength longer than the longest wavelength in the second wavelength region
  • the second reflective layer converts the resonant light into light with a wavelength longer than the longest wavelength in the second wavelength region.
  • the light whose excitation light is wavelength-converted in the phosphor layer the light is outside the second wavelength region, and the longest wavelength of the resonant light in the second wavelength region is the wavelength-converted light in the phosphor layer.
  • the light is outside the second wavelength region, and the longest wavelength in the second wavelength region where the resonant light is wavelength-converted by the phosphor layer.
  • Light with longer wavelengths may be mixed to produce white light emission.
  • the first wavelength range may be in a range of 480 nm or more and 590 nm or less
  • the second wavelength range may be in a range of 450 nm or more and 520 nm or less.
  • the emission spectrum of the emitted light has peaks in a wavelength range of 450 nm or more and 500 nm or less, and a wavelength range of 580 nm or more and 650 nm or less, and the intensity of each of the peaks is dependent on the output of the excitation light. It may have.
  • the first wavelength range may be in the range of 480 nm or more and 590 nm or less
  • the second wavelength range may be in the range of 395 nm or more and 425 nm or less, and 500 nm or more and 560 nm or less.
  • the emission spectrum of the emitted light has a peak in a wavelength range of 450 nm or more and 500 nm or less and a wavelength range of 580 nm or more and 650 nm or less, and the peak intensity in the wavelength range of 450 nm or more and 500 nm or less is the excitation light.
  • the peak intensity in the wavelength range of 580 nm or more and 650 nm or less may have a dependence on the output of the excitation light.
  • the phosphor layer may be excited by light having a wavelength of 330 nm or more and 420 nm or less to emit blue light having a peak in a wavelength range of 450 nm or more and 500 nm or less.
  • the phosphor layer may contain a phosphor selected from the group consisting of a carbon nanoparticle phosphor, an organic nanoparticle phosphor, an organometallic complex phosphor, an inorganic phosphor, and a semiconductor quantum dot phosphor. .
  • the phosphor layer may contain carbon nanoparticle phosphor and emit blue light when irradiated with ultraviolet light.
  • the carbon nanoparticle phosphor contains a carbon element, an oxygen element, a nitrogen element, and a hydrogen element, and the carbon element exists as amorphous carbon and graphitic carbon, and the amorphous carbon and the graphite
  • the ratio of the amorphous carbon to the total amount is 60% by volume or more and less than 99% by volume
  • the graphitic carbon is 1% by volume or more and less than 40% by volume
  • the nitrogen element is at least pyridine type carbon.
  • Nitrogen exists as nitrogen, amide type nitrogen, pyrrole type nitrogen, and graphite type nitrogen, and the content of the pyridine type nitrogen may be greater than that of the graphite type nitrogen.
  • the content p (atomic %) of the carbon element, the content q (atomic %) of the nitrogen element, and the content r (atomic %) of the oxygen element are, respectively, 0.58 ⁇ p/(p+q+r) ⁇ 0.65 0.15 ⁇ q/(p+q+r) ⁇ 0.30 0.12 ⁇ r/(p+q+r) ⁇ 0.25 may be satisfied.
  • the phosphor layer may be a resin molded body in which the carbon nanoparticle phosphor is dispersed.
  • the excitation light may have a wavelength in a range of 330 nm or more and 420 nm or less.
  • the first reflective layer may have a superlattice structure of an aluminum nitride layer and a silicon dioxide layer.
  • the second reflective layer may have a superlattice structure of a tantalum oxide layer and a silicon dioxide layer.
  • a light emitting device includes an excitation source and a wavelength conversion element, and the wavelength conversion element is the wavelength conversion element described above, thereby solving the above problem.
  • the excitation source may emit excitation light having a wavelength in a range of 330 nm or more and 420 nm or less.
  • the excitation source may be selected from the group consisting of light emitting diodes (LEDs), laser diodes (LDs), semiconductor lasers, and organic EL emitters (OLEDs).
  • the excitation source may have variable output.
  • the light emitting device may be a white light emitting diode, a lighting fixture including a plurality of white light emitting diodes, or a backlight for a liquid crystal panel.
  • the wavelength conversion element of the present invention includes a first reflective layer, a second reflective layer, and a phosphor layer located between these layers and having an emission wavelength dependent on an excitation wavelength.
  • the first reflective layer reflects light in a first wavelength range
  • the second reflective layer reflects light in a second wavelength range that overlaps at least a portion of the first wavelength range.
  • the phosphor layer has the dependence of the emission wavelength on the excitation wavelength, in addition to converting the wavelength of the excitation light radiated thereto, the phosphor layer can convert the wavelength of the light that is confined and resonated within the wavelength conversion element.
  • the wavelength conversion element of the present invention enables light emission with adjusted chromaticity, which is a combination of light obtained by wavelength-converting excitation light and light obtained by wavelength-converting resonant light. Furthermore, by appropriately setting the first wavelength range and the second wavelength range, white light emission along the blackbody locus is made possible. If such a wavelength conversion element is used together with an excitation source, a light emitting device such as a white lighting device or a backlight for a display can be provided.
  • FIG. 1 is a schematic diagram showing a wavelength conversion element of the present invention.
  • FIG. 1 is a schematic diagram showing a light emitting device of the present invention. It is a figure showing the synthesis process of carbon nanoparticle phosphor (CD1).
  • FIG. 2 is a diagram showing an XRD pattern of carbon nanoparticle phosphor (CD1) powder.
  • FIG. 2 is a diagram showing TEM images of a carbon nanoparticle phosphor (CD1) solution at various magnifications.
  • FIG. 2 is a diagram showing an XPS spectrum of a carbon nanoparticle phosphor (CD1) solution.
  • FIG. 3 shows a deconvoluted HRXPS spectrum of a carbon nanoparticle phosphor (CD1) solution.
  • FIG. 1 is a schematic diagram showing a wavelength conversion element of the present invention.
  • FIG. 1 is a schematic diagram showing a light emitting device of the present invention. It is a figure showing the synthesis process of carbon nanoparticle phosphor (CD1).
  • FIG. 2
  • FIG. 2 is a diagram showing the emission spectrum of a carbon nanoparticle phosphor (CD1) solution.
  • FIG. 2 is a diagram showing two-dimensional luminescence mapping of a carbon nanoparticle phosphor (CD1) solution. It is a figure which shows the state of light emission of the carbon nanoparticle fluorescent substance (CD1) containing resin molding.
  • FIG. 2 is a diagram showing the emission spectrum of a carbon nanoparticle phosphor (CD2) solution.
  • 3 is a diagram showing a transmission spectrum of a reflective layer M1 in the wavelength conversion element of Example 1.
  • FIG. 3 is a diagram showing a transmission spectrum of a reflective layer M1 in the wavelength conversion element of Example 1.
  • FIG. 2 is a diagram showing an emission spectrum of a light emitting device using the wavelength conversion element of Example 1, and an emission spectrum of a phosphor layer used in the wavelength conversion element.
  • 3 is a diagram showing chromaticity calculated from the emission spectrum of a light emitting device using the wavelength conversion element of Example 1.
  • FIG. 3 is a diagram showing the transmission spectrum of the reflective layer M1 in the wavelength conversion element of Example 2.
  • FIG. 3 is a diagram showing a transmission spectrum of a reflective layer M2 in the wavelength conversion element of Example 2.
  • FIG. FIG. 6 is a diagram showing an emission spectrum of a light emitting device using the wavelength conversion element of Example 2, and an emission spectrum of a phosphor layer used in the wavelength conversion element.
  • FIG. 7 is a diagram showing chromaticity calculated from the emission spectrum of a light emitting device using the wavelength conversion element of Example 2.
  • FIG. 7 is a diagram showing the transmission spectrum of the reflective layer M1 in the wavelength conversion element of Example 3.
  • FIG. 7 is a diagram showing a transmission spectrum of a reflective layer M3 in the wavelength conversion element of Example 3.
  • FIG. 7 is a diagram showing an emission spectrum of a light emitting device using the wavelength conversion element of Example 3, and an emission spectrum of a phosphor layer used in the wavelength conversion element.
  • FIG. 7 is a diagram showing chromaticity calculated from the emission spectrum of a light emitting device using the wavelength conversion element of Example 3.
  • FIG. 7 is a diagram showing the transmission spectrum of the reflective layer M1 in the wavelength conversion element of Example 3.
  • FIG. 7 is a diagram showing a transmission spectrum of a reflective layer M3 in the wavelength conversion element of Example 3.
  • FIG. 7 is a diagram showing an emission spectrum of a light emitting device using the wavelength conversion element of Example 3, and an
  • FIG. 7 is a diagram showing an emission spectrum of a light emitting device using the wavelength conversion element of Example 4 and an emission spectrum of a phosphor layer used in the wavelength conversion element.
  • FIG. 7 is a diagram showing chromaticity calculated from the emission spectrum of a light emitting device using the wavelength conversion element of Example 4.
  • FIG. 7 is a diagram showing emission spectra of a light emitting device using the wavelength conversion element of Example 2 when irradiated with excitation light of different outputs.
  • FIG. 16A is a diagram showing chromaticity calculated from the emission spectrum of FIG. 16A.
  • FIG. 7 is a diagram showing emission spectra of a light emitting device using the wavelength conversion element of Example 3 when irradiated with excitation light of different outputs.
  • FIG. 17A is a diagram showing chromaticity calculated from the emission spectrum of FIG. 17A.
  • FIG. 3 shows an XRD pattern of a yellow powder obtained in the synthesis procedure of graphitic carbon nitride phosphor (g-C 3 N 4 ).
  • FIG. 2 is a diagram showing a 13 C-CP-MAS-NMR spectrum of a yellow powder obtained in the synthesis procedure of graphitic carbon nitride phosphor (g-C 3 N 4 ).
  • FIG. 3 is a diagram showing the emission spectrum of a graphitic carbon nitride phosphor (g-C 3 N 4 ) dispersion.
  • FIG. 3 shows an XRD pattern of a yellow powder obtained in the synthesis procedure of graphitic carbon nitride phosphor (g-C 3 N 4 ).
  • FIG. 2 is a diagram showing a 13 C-CP-MAS-NMR spectrum of a yellow powder obtained in the synthesis procedure of graphitic carbon nitride phosphor
  • FIG. 7 is a diagram showing an emission spectrum of a light emitting device using the wavelength conversion element of Example 5 and an emission spectrum of a phosphor layer used in the wavelength conversion element.
  • FIG. 7 is a diagram showing chromaticity calculated from the emission spectrum of a light emitting device using the wavelength conversion element of Example 5.
  • FIG. 1 is a schematic diagram showing a wavelength conversion element of the present invention.
  • the wavelength conversion element 100 of the present invention includes a first reflective layer 110, a second reflective layer 120, and a phosphor layer 130 located between them.
  • the phosphor layer 130 is not particularly limited as long as it converts the irradiated excitation light into light having a longer wavelength than the excitation light and has the excitation wavelength dependence of the emission wavelength.
  • the dependence of the emission wavelength on the excitation wavelength means that if the wavelength of the excitation light is shifted to the long wavelength side, the emission wavelength will also be shifted to the long wavelength side, and if the wavelength of the excitation light is shifted to the short wavelength side, the emission wavelength will also be shortened. It has the property of shifting toward the wavelength side.
  • the first reflective layer 110 reflects light in a first wavelength region (also referred to as a first stop band) located on the longer wavelength side than the wavelength of the excitation light, and transmits light in other wavelengths.
  • the second reflective layer 120 reflects light in a second wavelength range (also referred to as a second stop band) that overlaps at least a portion of the first wavelength range, and transmits light in other wavelengths. Note that the second wavelength range may include the entire first wavelength range.
  • a laminate 140 consisting of a first reflective layer 110, a second reflective layer 120, and a phosphor layer 130 located between them is a wavelength conversion element 100 disposed on a substrate 150.
  • the substrate 150 is not essential, it is preferable to use it because it facilitates handling of the wavelength conversion element 100.
  • the substrate 150 may be made of a material that has a transmittance of 50% or more at least to the wavelength of the excitation light.
  • the substrate 150 is made of a material that has a transmittance of 70% or more for light having a wavelength in the range of not less than the wavelength of the excitation light and not more than 1 ⁇ m. In this case, the light converted by the wavelength conversion element 100 can be extracted via the substrate 150.
  • the substrate 150 is illustratively made of glass such as quartz glass, borosilicate glass, or soda lime glass, fluoride single crystal such as calcium fluoride or barium fluoride, cycloolefin polymer, cycloolefin copolymer, polyimide resin, or polycarbonate resin. , polyethylene terephthalate, acrylic resin, epoxy resin, and the like. These are preferable because their transmittance exceeds 80% in the wavelength range from about 350 nm ultraviolet rays to 1 ⁇ m.
  • the wavelength conversion element of the present invention emits light that is a combination of the wavelength-converted excitation light from the excitation source and the wavelength-converted light having a specific wavelength that has resonated and amplified. Using only seed phosphors allows for chromaticity-tuned light emission. Explain in detail.
  • excitation light 160 from an excitation source (not shown) is incident through the substrate 150. Note that it is assumed that the peak position of the wavelength of the excitation light 160 that enters the wavelength conversion element 100 is on the shorter wavelength side than the lower limit of the first wavelength range that the first reflective layer 110 has.
  • the excitation light 160 passes through the first reflective layer 110 and reaches the phosphor layer 130.
  • the phosphor layer 130 is excited by the excitation light 160 and emits light 170 having a longer wavelength than the excitation light 160 (converts the wavelength).
  • the wavelength-converted light 170 enters the second reflective layer 120.
  • the second reflective layer 120 reflects the light 180 having the second wavelength range out of the light 170 and transmits the other light 170'.
  • light with a wavelength in a region where the first wavelength region and the second wavelength region overlap is repeatedly reflected within the stacked body 140 and resonates.
  • the phosphor layer 130 has an excitation wavelength dependence of the emission wavelength, it is excited by the light 180 reflected and resonated within the laminate 140, and emits light 190 having a longer wavelength than the wavelength of the light 180 (after wavelength conversion). ).
  • light 190' having a wavelength longer than the longest wavelength in the second wavelength region of the second reflective layer 120 passes through the second reflective layer 120 and is emitted from the wavelength conversion element 100. be done.
  • the wavelength conversion element 100 transmits at least the light 170' that has passed through the second reflective layer 120 out of the wavelength-converted light 170, and the light 170' that has passed through the second reflective layer 120 out of the wavelength-converted light 190. It can emit light 190' and exhibit a mixed luminescent color. For example, the light 170' and the light 190' may be mixed to emit white light.
  • the wavelength-converted light 170 when the wavelength-converted light 170 is completely included in the second wavelength region (second stop band), most of the wavelength-converted light 170 is Very little light 170' is reflected by the second reflective layer 120 and transmitted through the second reflective layer 120.
  • the present invention also includes such cases.
  • the wavelength and intensity of the light 170' and the wavelength and intensity of the light 190' can be controlled by adjusting the transmittance in wavelength ranges other than the above, so the chromaticity and color temperature of the emitted color from the wavelength conversion element 100 can be controlled. Can be adjusted.
  • a phosphor whose emission wavelength was dependent on the excitation wavelength was used, which emitted blue light having an emission peak wavelength in the range of 450 nm to 500 nm when excited with ultraviolet rays having a wavelength of 330 nm to 420 nm.
  • the chromaticity and color temperature adjustment of the emitted light color of the wavelength conversion element 100 in this case will be explained.
  • the first reflective layer 110 reflects light in a first wavelength range of 480 nm or more and 590 nm or less, and transmits light of other wavelengths. Further, the second reflective layer 120 reflects light in a second wavelength range of 450 nm or more and 520 nm or less, and transmits light of other wavelengths. In this case, when irradiated with ultraviolet light, it emits yellow to red light.
  • the excitation light 160 which is ultraviolet light
  • a wavelength located in the second stop band is reflected by the second reflective layer 120 to become light 180, and this light 180 resonates within the stacked body 140.
  • the light 180 that resonates and is intensified within the laminate 140 excites the phosphor in the phosphor layer 130 and is converted into yellow to red light 190 having a wavelength of, for example, 580 nm or more and 650 nm or less.
  • Ru Of the light 190, those having wavelengths longer than the longest wavelength of the second stop band are transmitted through the second reflective layer 120 and are emitted as light 190'. In this way, when a single phosphor that emits blue light when excited by ultraviolet light is used, a wavelength conversion element that emits yellow to red light can be provided.
  • the chromaticity can be adjusted by selecting the transmittance (or reflectance) of the first reflective layer 110 or the second reflective layer 120. For example, if the transmittance of the second stop band in the second reflective layer 120 is 50%, part of the blue light 170 passes through the second reflective layer 120 and is emitted as light 170'. , enables emission of a mixture of slight blue and yellow to red.
  • the transmittance of the first stop band is substantially 0%, and the transmittance of the parts other than the first stop band is 60% or more, and for the second reflective layer 120, the transmittance of the first stop band is substantially 0%.
  • the transmittance of the second stop band is 3% or more and 5% or less, and the transmittance of the parts other than the second stop band is 60% or more. This makes it possible to provide a wavelength conversion element that emits yellow to orange light.
  • the wavelength conversion element 100 has peaks in the emission spectrum of the emitted light in the wavelength range of 450 nm to 500 nm and in the wavelength range of 580 nm to 650 nm, and the intensity of these peaks is determined by the irradiated ultraviolet light ( (excitation light) output dependence. That is, the larger the excitation light output, the higher the emission intensity. In this case, the chromaticity does not change even when the output of the excitation light changes, so a stable wavelength conversion element can be provided.
  • excitation light irradiated ultraviolet light
  • the first reflective layer 110 reflects light in a first wavelength range of 480 nm or more and 590 nm or less, and transmits light of other wavelengths. Further, the second reflective layer 120 reflects light in a second wavelength region of 395 nm or more and 425 nm or less and 500 nm or more and 560 nm or less, and transmits light of other wavelengths. In this case, white light is emitted by irradiation with ultraviolet rays.
  • the excitation light 160 which is ultraviolet light, passes through the first reflective layer 110 and is wavelength-converted into blue light 170 in the phosphor layer 130.
  • light 170' having a wavelength of more than 425 nm and less than 500 nm passes through the second reflective layer 120 and is emitted.
  • light having a wavelength of 500 nm or more resonates within the stacked body 140 .
  • the light 180 that resonates and is intensified within the stacked body 140 excites the phosphor layer 130 and is wavelength-converted into yellow to red light 190 having a wavelength of, for example, 580 nm or more and 650 nm or less.
  • the light 190 passes through the second reflective layer 120 and is emitted as light 190'.
  • a wavelength conversion element that emits white light, which is a mixture of blue light and yellow to red light, can be provided.
  • the transmittance of light having a wavelength longer than 425 nm and less than 500 nm in the second reflective layer 120 is adjusted.
  • the intensity of yellow to red light 190 produced by wavelength conversion of this light 180 is controlled.
  • white light at various color temperatures, such as light bulb color, warm white, daylight white, and daylight color.
  • the transmittance of the first stop band is substantially 0%, and the transmittance of the parts other than the first stop band is 60% or more, and for the second reflective layer 120, The transmittance of the second stop band is 7% or more and 15% or less, and the transmittance of the other stop bands is 60% or more.
  • the wavelength conversion element 100 has an emission spectrum of emitted light that has peaks in a range of 450 nm to 500 nm and a range of 580 nm to 650 nm, and a peak intensity in a wavelength range of 450 nm to 500 nm.
  • the chromaticity and color temperature can be controlled by changing the output of the excitation light, so when combined with an excitation source, it is possible to provide a light emitting device whose chromaticity can be adjusted by controlling the output of the excitation source.
  • the color temperature changes along the blackbody locus in the chromaticity coordinates, for example, increasing the excitation light output brings the color closer to a light bulb color, and decreasing the excitation light output brings the color closer to blue-white light. Enables white light emission.
  • the wavelength conversion element 100 of the present invention emits white light whose color temperature changes along the blackbody locus in the chromaticity coordinates, and the deviation thereof can be suppressed within the range of ⁇ 0.01.
  • Such a selection can be made by a person skilled in the art who understands the emission characteristics of phosphors based on the content of this specification.
  • the second wavelength range of the second reflective layer 120 overlaps at least a portion of the first wavelength range of the first reflective layer 110, but the second wavelength range overlaps with the first wavelength range of the first reflective layer 110. It may include all wavelengths.
  • the second reflective layer 120 is the same as the first reflective layer 110, delicate chromaticity adjustment is possible.
  • the first wavelength region and the second wavelength region of the reflective layer are both in the range of 480 nm or more and 590 nm or less, and a phosphor that emits blue light when excited by ultraviolet is used.
  • the excitation light 160 which is ultraviolet light, passes through the first reflective layer 110 and is wavelength-converted into blue light 170 in the phosphor layer 130. Most of the light 170 is transmitted through the second reflective layer 120 and becomes light 170'.
  • the light 180 slightly reflected by the second reflective layer 120 resonates within the stacked body 140.
  • the light 180 is used as excitation light, and the yellow to red light 190 generated by wavelength conversion in the phosphor layer 130 is also small.
  • This small amount of light passes through the second reflective layer 120 and becomes light 190'. Therefore, the light emitted from the wavelength conversion element is a mixture of blue light and slight yellow to red light, so we provide a wavelength conversion element that emits blue light with delicately adjusted chromaticity. can.
  • the first reflective layer 110 and the second reflective layer 120 are not particularly limited as long as they can reflect light having a specific wavelength and transmit other wavelengths as described above.
  • a distributed Bragg reflector can be used.
  • Such a DBR has a superlattice structure in which two or more types of dielectric materials having different refractive indices are laminated.
  • dielectric materials include nitrides such as gallium nitride (GaN) and aluminum nitride (AlN), niobium oxide (Nb 2 O 5 ), titanium oxide (TiO 2 ), zirconium oxide (ZrO 2 ), and tantalum oxide (Ta 2 O). 5 ), and oxides such as silicon dioxide (SiO 2 ). Two or more types of dielectric materials having relatively different refractive indexes may be selected from these, and the film thickness and the number of pairs may be changed as appropriate.
  • the first reflective layer 110 can employ a superlattice structure of an aluminum nitride layer and a silicon dioxide layer.
  • the second reflective layer 120 can employ a superlattice structure of a tantalum oxide layer and a silicon dioxide layer.
  • the phosphor layer 130 can convert the irradiated excitation light into light having a longer wavelength by irradiation with the excitation light, and contains a phosphor whose emission wavelength is dependent on the excitation wavelength. There are no restrictions. Whether or not the emission wavelength is dependent on the excitation wavelength can be easily determined by measuring the excitation spectrum and emission spectrum of the phosphor.
  • the phosphor included in the phosphor layer 130 one that is excited by ultraviolet rays with a wavelength of 330 nm or more and 420 nm or less and emits blue light having a peak in a wavelength range of 450 nm or more and 500 nm or less can be used.
  • a wavelength conversion element that emits yellow to red light or even white light using ultraviolet rays as excitation light.
  • a phosphor that is excited by blue light with a wavelength of 420 nm or more and 480 nm or less and emits green light with a wavelength of 490 nm or more and 550 nm or less, or yellow to red light with a wavelength of 550 nm or more and 770 nm or less may be used.
  • a wavelength conversion element that emits white light using blue light as excitation light.
  • the phosphor layer 130 preferably contains at least one type of phosphor selected from the group consisting of carbon nanoparticle phosphor, organic nanoparticle phosphor, organometallic complex phosphor, inorganic phosphor, and semiconductor quantum dot phosphor. Contains the body.
  • the organic nanoparticle phosphor is, for example, 4,4'-(2,7-bis[4- ⁇ 1,2,2-triphenylvinyl ⁇ phenyl]-9H-fluorene-9,9-diyl)bis(N,N , N-trimethylbutan-1-aminum) bromide (TPEFN), ten bis(monoacylglycerol) bisphenol-A, Ttrz-DI nano-dot (TNAP(N,N,6,10-tetra(napht) halen-2-yl)-6 , 10-dihydro-6, 10-diaza-16b-boraanthra [3,2,1-de]tetracen-8-amine), etc.
  • TPEFN 4,4'-(2,7-bis[4- ⁇ 1,2,2-triphenylvinyl ⁇ phenyl]-9H-fluorene-9,9-diyl)bis(N,N , N-trimethylbutan-1-aminum) bromide
  • organic nanoparticle phosphors are well known and can be easily obtained and manufactured.
  • inorganic phosphors examples include (NH 4 )SnCl 6 :Sb 3+ , Cs 2 ScCl 5 .H 2 O perovskite, BaZrO 3 :M (where M is Eu 3+ , Pb 2+ , Mn 2+ , and Y 3+ , At least one selected from lanthanide cations other than Eu 3+ such as Tb 3+ and Yb 3+ ), Y 2 O 3 :Bi, Ba 9 Lu 2 Si 6 O 24 :Bi 3+ , Eu 3+ and the like.
  • These inorganic phosphors are well known and can be easily obtained and manufactured.
  • Semiconductor quantum dot phosphors include, for example, CsPbBr 3 , CdSe/CdS, Zn 0.45 Cd 0.55 , Si nanoparticles, In 2 S 3 :Mn, Cu, MoS 2 , WS 2 , ZnS, rhenium oxide, etc. be. These semiconductor quantum dot phosphors are well known and can be easily obtained and manufactured.
  • a carbon nanoparticle phosphor is a phosphor made of nanoparticles whose main component is carbon such as amorphous carbon or graphitic carbon.
  • the carbon nanoparticle phosphor is preferably one that is excited by irradiation with ultraviolet light having a wavelength of 330 nm or more and 420 nm or less, and emits blue light having a peak in the wavelength range of 450 nm or more and 500 nm or less.
  • ultraviolet light having a wavelength of 330 nm or more and 420 nm or less
  • blue light having a peak in the wavelength range of 450 nm or more and 500 nm or less.
  • the carbon nanoparticle phosphor preferably contains elemental carbon, elemental oxygen, elemental nitrogen, and elemental hydrogen, and the carbon element is present as amorphous carbon and graphitic carbon, and the amorphous carbon and
  • the ratio of the graphitic carbon to the total amount of the amorphous carbon is 60% by volume or more and less than 99% by volume, the graphitic carbon is 1% by volume or more and less than 40% by volume, and the nitrogen element is At least pyridine-type nitrogen, amide-type nitrogen, pyrrole-type nitrogen, and graphite-type nitrogen are present, and the content of the pyridine-type nitrogen is greater than that of the graphite-type nitrogen.
  • the proportion of the amorphous carbon and the graphitic carbon in the total amount of the amorphous carbon is 60% by volume or more and 65% by volume or less with respect to the amorphous carbon, and the graphitic carbon 35% by volume or more and less than 40% by volume. This makes it possible to obtain a phosphor with good color purity.
  • the carbon nanoparticle phosphor preferably has a carbon element content p (atomic %), a nitrogen element content q (atomic %), and an oxygen element content r (atomic %), respectively. 0.58 ⁇ p/(p+q+r) ⁇ 0.65 0.15 ⁇ q/(p+q+r) ⁇ 0.30 0.12 ⁇ r/(p+q+r) ⁇ 0.25 satisfy. Thereby, the deviation from the blackbody locus in the chromaticity coordinates can be suppressed within the range of ⁇ 0.03. More preferably, the p and q satisfy 0.25 ⁇ q/p ⁇ 0.3.
  • Such a carbon nanoparticle phosphor is produced by heating a raw material solution in which a carbon source is dissolved in a nitrogen-containing organic solvent. Further, a nitrogen source may be dissolved in the raw material solution.
  • organic substances that are decomposed into carbon by heating are used.
  • organic substances include at least one selected from the group consisting of citric acid, citric acid monohydrate, ammonium citrate, benzoic acid, ascorbic acid, glucose, fructose, and sucrose.
  • nitrogen-containing organic solvents include formamide and N-methylformamide.
  • the concentration of the carbon source in the organic solvent is preferably 0.05 mol/L or more and 0.2 mol/L or less. Within this range, a phosphor can be obtained in which the volume percentages of amorphous carbon and graphitic carbon relative to the total amount are both in the above-mentioned preferred range. More preferably, the concentration of the carbon source in the organic solvent is 0.1 mol/L or more and 0.15 mol/L or less. As a result, when irradiated with ultraviolet light, the color emitted by the carbon nanoparticle phosphor is 0.2 ⁇ x ⁇ 0.3 and 0.25 ⁇ at the (x, y) value on the CIE1931 chromaticity coordinates. It is possible to satisfy y ⁇ 0.4.
  • nitrogen source examples include ethylenediamine, ammonia, formamide, and arginine.
  • the heating conditions are not particularly limited as long as the carbon source is decomposed and the carbon reacts with nitrogen in the organic solvent or nitrogen in the nitrogen source.
  • the raw material solution is heated at a temperature of 150° C. or more and 230° C. or less for a period of 5 hours or more and 15 hours or less. Under these conditions, the reaction proceeds efficiently and a carbon nanoparticle phosphor can be obtained. Heating is more preferably performed at a temperature of 170° C. or higher and 210° C. or lower for a period of 7 hours or more and 10 hours or less.
  • the carbon nanoparticle phosphor is obtained in a state dispersed in the solvent.
  • the solid content may be recovered from the obtained product by centrifugation or the like, and then dried by heating in a vacuum.
  • the phosphor layer 130 may be a single crystal made of the above-mentioned phosphor, or may be a resin molded body in which powder made of the above-mentioned phosphor is dispersed.
  • the resin used for the resin molding may be any water-soluble polymer that transmits light with wavelengths from the ultraviolet region to the visible region, such as polyvinyl alcohol, sodium polyacrylate, polyacrylamide, polyethyleneimine, polyethylene oxide, and polyvinylpyrrolidone. , carboxyl vinyl polymer, etc.
  • the phosphor layer 130 can be formed into a thin film by spin coating or dropping, or can be formed into a bulk phosphor layer 130 by drying.
  • a fiber-shaped resin molded body can also be provided by electrospinning or the like. Such a resin molded body is easy to handle.
  • the content of the phosphor in the resin molding is preferably in the range of 0.01% by mass or more and 5% by mass or less. Within this range, concentration quenching can be suppressed and high emission intensity and high quantum efficiency can be expected. More preferably, the content of the carbon nanoparticle phosphor is in the range of 0.01% by mass or more and 1% by mass or less. Note that the content can be appropriately designed depending on the selected phosphor.
  • the method for manufacturing the wavelength conversion element 100 of the present invention is not particularly limited as long as the laminate 140 shown in FIG. 1 can be obtained.
  • the first reflective layer 110 is formed on the substrate 150 by physical vapor deposition, chemical vapor deposition, etc., and then the first reflective layer 110 is A phosphor layer 130 is formed by applying a solution containing a phosphor by a drop casting method, a spray coating method, a dipping method, a spin coating method, etc., and then a physical vapor deposition method or a chemical vapor deposition method is applied.
  • a method of forming the second reflective layer 120 on the phosphor layer 130 by a method or the like can be adopted.
  • the phosphor is a single crystal
  • a first layer is formed on one surface of the phosphor layer 130, which is a single crystal, by a physical vapor deposition method, a chemical vapor deposition method, or the like.
  • the second reflective layer 120 may be similarly formed on the other surface of the phosphor layer 130.
  • FIG. 2 is a schematic diagram showing a light emitting device of the present invention.
  • the light emitting device 200 in FIG. 2 shows a board-mounted white light emitting diode lamp.
  • a light emitting device 200 of the present invention includes at least an excitation source 240 and a wavelength conversion element 100, and the wavelength conversion element 100 is the wavelength conversion element described in Embodiment 1. With such a configuration, it is possible to provide a light emitting device that emits light of a desired color.
  • the excitation source 240 one that emits light having a peak in a wavelength range of 200 nm or more and 600 nm or less is used.
  • excitation sources include light emitting diodes (LEDs), laser diodes (LDs), organic EL light emitters (OLEDs), semiconductor lasers, and fluorescent lamps.
  • the wavelength of the excitation light from the excitation source 240 is appropriately set depending on the selected phosphor.
  • a violet light emitting diode having a peak in the range from 330 nm to 420 nm may be used as the excitation source 240.
  • a blue light emitting diode having a peak in the range from 430 nm to 480 nm may be used as the excitation source 240.
  • the excitation source 240 may have a variable output. Thereby, depending on the design of the wavelength conversion element 100, the chromaticity and color temperature can be adjusted by controlling the output of the excitation light.
  • the light emitting device 200 has lead wires 210 and 220, which are fixed to a white alumina substrate 230 with high visible light reflectance.
  • a violet light emitting diode element having an emission peak wavelength of 380 nm is mounted as an excitation source 240 on one end of one lead wire 210, and is electrically connected to the excitation source 240 using a conductive paste or the like.
  • An excitation source 240 is electrically connected to one end of the other lead wire 220 via a thin gold wire 250 .
  • the other ends of the lead wires 210, 220 are exposed to the outside and function as electrodes.
  • the wavelength conversion element 100 is placed above the excitation source 240.
  • the wavelength conversion element 100 here includes, for example, a first reflective layer 110 that reflects light in a first wavelength range of 480 nm or more and 590 nm or less and transmits other wavelengths, a range of 395 nm or more and 425 nm or less, and a second reflective layer 120 that reflects light in a second wavelength range of 500 nm or more and 560 nm or less and transmits other wavelengths; and a second reflective layer 120 that is excited by ultraviolet irradiation and has a peak in the 450 nm or more and 500 nm or less range.
  • a laminate 140 is provided on a quartz substrate, and includes a phosphor layer 130, which is a resin molded body in which carbon nanoparticle phosphors are dispersed, which emit blue light having an emission wavelength dependent on the excitation wavelength.
  • the transmittance in the first wavelength range is substantially 0%, and the average transmittance in the other wavelength ranges is 70%.
  • the transmittance in the second wavelength range is 10%
  • the average transmittance in the wavelength range of more than 425 nm and less than 500 nm is 60%
  • the transmittance is assumed to be 80%.
  • a wall member 280 made of white silicone resin or the like is provided around the periphery of the alumina substrate 230, and an excitation source 240 on which the wavelength conversion element 100 is placed is located in the center of the alumina substrate 230.
  • the excitation source 240 and the wavelength conversion element 100 are sealed with a transparent resin 270 such as epoxy resin, which is filled in a recess surrounded by a wall member 280.
  • the excitation source 240 emits light with a peak wavelength of 380 nm.
  • This light enters the wavelength conversion element 100 of the present invention, passes through the quartz substrate and the first reflective layer 110, and is wavelength-converted into blue light (light 170 in FIG. 1) by the phosphor layer 130.
  • light 170' having a wavelength longer than 425 nm and less than 500 nm passes through the second reflective layer 120 and is emitted from the wavelength conversion element 100.
  • light having a wavelength of 425 nm or less and a wavelength of 500 nm or more is reflected by the second reflective layer 120.
  • light 180 having a wavelength of 500 nm or more is also reflected by the first reflective layer 110, so it is repeatedly reflected between the first reflective layer 110 and the second reflective layer 120, resonate.
  • the resonant light 180 excites the phosphor layer 130 and is wavelength-converted into yellow to red light (light 190 in FIG. 1).
  • light 190' having a wavelength exceeding 560 nm passes through the second reflective layer 120 and is emitted from the wavelength conversion element 100.
  • ultraviolet light is constantly emitted from the excitation source 240, so the wavelength conversion and resonance described above occur repeatedly, and the light 170' and the light 190' continue to be emitted from the wavelength conversion element 100.
  • the light 170' and the light 190' emitted from the wavelength conversion element 100 are reflected by the wall member 280, transmitted through the resin 270, and emitted from the light emitting device 200.
  • the light emitted from the light emitting device 200 is a mixture of blue light 170' and yellow to red light 190', and thus becomes white light. In this way, even when using a single phosphor that emits blue light when excited by ultraviolet light, by adjusting the stop bands of the first reflective layer 110 and the second reflective layer 120, blue light (light 170' ) and yellow to red light (light 190') can be provided.
  • the phosphors employed in the first reflective layer 110, second reflective layer 120, and phosphor layer 130 in the wavelength conversion element 100 are not limited to the above-mentioned configurations, and may be used to obtain a desired emission color. It can be adjusted accordingly.
  • the wavelength conversion element 100 according to the first embodiment it is possible to provide a light-emitting device that emits light of any color even when using one type of phosphor, and can emit light of any color from blue to red, white, and even infrared. It is possible to provide a light emitting device that can be changed up to Such modifications are also within the scope of this invention.
  • the wavelength conversion element according to Embodiment 1 may be employed in a bullet type white light emitting diode lamp. Such modifications can be easily made by those skilled in the art.
  • the light emitting device according to Embodiment 2 may be a lighting fixture, a backlight for a liquid crystal panel, etc. that includes a plurality of white light emitting diodes.
  • FIG. 3 is a diagram showing the synthesis process of carbon nanoparticle phosphor (CD1).
  • a raw material solution was prepared by dissolving 0.12 M citric acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) as a carbon source in 20 mL of formamide (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) as an organic solvent. Next, the raw material solution was heated at 200° C. for 8 hours.
  • the obtained product was centrifuged (rotation speed: 800 rpm), and the separated solid content was first mixed with ethanol and then with ultrapure water (manufactured by Merck & Co., Ltd., Milli-Q (registered trademark)). I washed each one several times. The solid content after washing was dried in vacuum (degree of vacuum: 1 to 1000 Pa) at 60° C. for 4 hours to obtain carbon nanoparticle phosphor (CD1) powder.
  • FIG. 4 is a diagram showing an XRD pattern of carbon nanoparticle phosphor (CD1) powder.
  • Carbon nanoparticle phosphor (CD1) powder was dispersed in dimethyl sulfoxide (DMSO, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and passed through a 20 nm syringe filter. At this time, the concentration of the carbon nanoparticle phosphor (CD1) in DMSO was 0.0025% by mass (0.025mg/mL). When the thus obtained carbon nanoparticle phosphor (CD1) dispersion was irradiated with light with a wavelength of 365 nm emitted from a lamp, blue light emission was confirmed.
  • DMSO dimethyl sulfoxide
  • a carbon nanoparticle phosphor (CD1) dispersion was prepared by a dispersion method and observed using a high-resolution transmission electron microscope (HR-TEM) (JEM 2100F, manufactured by JEOL). The results are shown in Figure 5.
  • HR-TEM high-resolution transmission electron microscope
  • FIG. 5 is a diagram showing TEM images of the carbon nanoparticle phosphor (CD1) dispersion at various magnifications.
  • the average particle size of the carbon nanoparticle phosphor (CD1) was in the range of 1 nm or more and 20 nm or less.
  • the average particle size is measured by measuring the particle size of at least 100 nanoparticles observed in an arbitrary 500 nm square area in a transmission image obtained using a transmission electron microscope (TEM) at a magnification of 1000 times or more. It was calculated as the average value. Note that since the nanoparticles are not perfectly spherical, the longest diameter was taken as the particle size of the nanoparticles. From the above, it was confirmed that carbon nanoparticle phosphors were dispersed in the liquid sample.
  • the ratio of the carbon element content p (atomic %), the nitrogen element content q (atomic %), and the oxygen element content r (atomic %) to their total is, respectively, 0.58 ⁇ p/(p+q+r) ⁇ 0.65 0.15 ⁇ q/(p+q+r) ⁇ 0.30 0.12 ⁇ r/(p+q+r) ⁇ 0.25 It was confirmed that the requirements were met.
  • FIG. 7 is a diagram showing a deconvoluted HRXPS spectrum of a carbon nanoparticle phosphor (CD1) dispersion.
  • FIG. 7 shows the result of deconvolution of the N-1s peak of the XPS spectrum shown in FIG. 6. According to FIG. 7, it was found that the N-1s peak is composed of four main peaks corresponding to binding energies of 398.7 eV, 399.6 eV, 400.3 eV, and 401.3 eV. Each of these peaks was determined to correspond to a type of nitrogen doping center within the carbon framework: pyridine-type nitrogen, amide-type nitrogen, pyrrole-type nitrogen, and graphite-type nitrogen.
  • the absorption spectrum of the carbon nanoparticle phosphor (CD1) dispersion was measured using an ultraviolet-visible-near-infrared spectrophotometer (manufactured by JASCO Corporation, V-570). It was found that it absorbs light well.
  • the emission spectrum of the carbon nanoparticle phosphor (CD1) dispersion was measured using a spectrofluorophotometer (manufactured by JASCO Corporation, FP-8500). The results are shown in FIGS. 8 and 9.
  • FIG. 8 shows the emission spectrum when the carbon nanoparticle phosphor (CD1) dispersion liquid was irradiated with excitation light having a wavelength of 370 nm. According to the emission spectrum, it can be seen that the carbon nanoparticle phosphor (CD1) dispersion emits blue light with a peak at 450 nm when excited by excitation light with a wavelength of 370 nm.
  • FIG. 9 is a diagram showing two-dimensional luminescence mapping of a carbon nanoparticle phosphor (CD1) solution.
  • FIG. 9 shows the state when excitation light of various wavelengths is irradiated.
  • the emission wavelength changes when the wavelength of excitation light changes, and the emission wavelength has excitation wavelength dependence. Specifically, when the wavelength of the excitation light is 400 nm to 450 nm, it emits blue-green light, when the wavelength of the excitation light is 500 nm, it emits green light (near the peak wavelength 525 nm), and when the wavelength of the excitation light is 550 nm to 575 nm, it emits orange light. , red light (peak wavelength 660 nm) was emitted when the wavelength of excitation light was 600 nm.
  • FIG. 10 is a diagram showing the state of light emission of a resin molded body containing carbon nanoparticle phosphor (CD1).
  • the emission wavelength of the obtained resin molded body changed as the excitation light wavelength changed, similar to the liquid sample shown in FIG.
  • FIG. 11 is a diagram showing the emission spectrum of a carbon nanoparticle phosphor (CD2) dispersion.
  • Example 1 to Example 4 Wavelength conversion element
  • wavelength conversion elements shown in Table 2 were manufactured by combining the carbon nanoparticle phosphor CD1 or CD2 that emits blue light upon ultraviolet excitation with the reflective layer shown in Table 1.
  • quartz glass was used as a substrate using an RF (radio frequency) sputtering device (manufactured by Shibaura Mechatronics Co., Ltd., CFS-4EP).
  • RF radio frequency
  • -LL reflective layers M1 to M3 were formed on the quartz glass.
  • the sputtering conditions were: distance between substrates 110 mm, RF output 300 W, and no substrate heating.
  • the reflective layer M3 is made by laminating 5 pairs of Ta 2 O 5 and SiO 2 , and has a total thickness of 170 nm for Ta 2 O 5 as a high refractive index layer and 290 nm for a total thickness of SiO 2 as a low refractive index layer. shall be held.
  • the transmission spectra of each of the reflective layers M1 to M3 were measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by JASCO Corporation, V-570). The results are shown in FIGS. 12A, 12B, 13A, 13B, 14A, and 14B, respectively.
  • the laminate of quartz glass/reflective layer/resin molding was placed in an RF sputtering device, and reflective layers M1 to M3 were formed on the resin molding.
  • the film-forming conditions for each reflective layer were as described above. In this way, wavelength conversion elements of Examples 1 to 4 were obtained.
  • the wavelength conversion elements of Examples 1 to 4 were combined with an ultraviolet light emitting diode element having an emission peak at a wavelength of 355 nm as an excitation source to produce a light emitting device.
  • Ultraviolet light (output 0.03 mW) from the ultraviolet light emitting diode element was incident on the quartz glass side of the wavelength conversion elements of Examples 1 to 4, and the emission spectrum of the light emitted from the wavelength conversion elements was measured.
  • the results are shown in FIG. 12C, FIG. 13C, FIG. 14C and FIG. 15A, respectively.
  • CIE1931 chromaticity (x, y) was calculated from the emission spectrum.
  • the results are shown in FIGS. 12D, 13D, 14D and 15B, and Table 3, respectively.
  • FIG. 12A and 12B are diagrams each showing the transmission spectrum of the reflective layer M1 in the wavelength conversion element of Example 1.
  • FIG. 12C is a diagram showing the emission spectrum of a light emitting device using the wavelength conversion element of Example 1 and the emission spectrum of the phosphor layer used in the wavelength conversion element.
  • FIG. 12D is a diagram showing chromaticity calculated from the emission spectrum of a light emitting device using the wavelength conversion element of Example 1.
  • 13A and 13B are diagrams showing the transmission spectra of the reflective layer M1 and the reflective layer M2 in the wavelength conversion element of Example 2, respectively.
  • FIG. 13C is a diagram showing the emission spectrum of a light emitting device using the wavelength conversion element of Example 2 and the emission spectrum of the phosphor layer used in the wavelength conversion element.
  • FIG. 13D is a diagram showing chromaticity calculated from the emission spectrum of a light emitting device using the wavelength conversion element of Example 2.
  • 14A and 14B are diagrams showing the transmission spectra of the reflective layer M1 and the reflective layer M3 in the wavelength conversion element of Example 3, respectively.
  • FIG. 14C is a diagram showing the emission spectrum of a light emitting device using the wavelength conversion element of Example 3 and the emission spectrum of the phosphor layer used in the wavelength conversion element.
  • FIG. 14D is a diagram showing chromaticity calculated from the emission spectrum of a light emitting device using the wavelength conversion element of Example 3.
  • FIG. 15A is a diagram showing the emission spectrum of a light emitting device using the wavelength conversion element of Example 4 and the emission spectrum of the phosphor layer used in the wavelength conversion element.
  • FIG. 15B is a diagram showing chromaticity calculated from the emission spectrum of a light emitting device using the wavelength conversion element of Example 4.
  • each of the reflective layers was as designed as shown in Table 1.
  • the stop band transmittance of the reflective layer M1 was substantially 0%, and the average transmittance of the other regions was 70%.
  • the stop band transmittance of the reflective layer M2 was 5%, and the average transmittance of the other regions was 75%.
  • the stop band transmittance of the reflective layer M3 was 18% on the short wavelength side and 8% on the long wavelength side, and the average transmittance in the other regions was 80%.
  • the emission spectra shown by dotted lines are all emission spectra when the phosphor layer used in each example was excited with light at a wavelength of 355 nm.
  • the phosphor emits blue light upon excitation with ultraviolet light and has excitation wavelength dependence of the emission wavelength, and both the first reflective layer and the second reflective layer have a reflective layer M1. It has been found that the wavelength conversion element of Example 1 employing the above can be combined with an ultraviolet light emitting diode element as an excitation source to provide a light emitting device with finely adjusted blue chromaticity.
  • the excitation light which is ultraviolet light
  • the reflective layer M1 passes through the reflective layer M1 and is wavelength-converted into blue light in the phosphor layer.
  • Most of the blue light passes through the opposing reflective layer M1 and is emitted, and only a very small amount of the reflected light resonates between the reflective layers.
  • the yellow to red light emitted by wavelength conversion of the resonant light in the phosphor layer also has low intensity. This yellow to red light passes through the opposing reflective layer M1 and is emitted together with the blue light described above.
  • the reflective layer M1 is employed as the first reflective layer, and the reflective layer M1 is employed as the second reflective layer along with a phosphor that emits blue light upon ultraviolet excitation and has an excitation wavelength dependence of the emission wavelength.
  • the excitation light which is ultraviolet light
  • the reflective layer M1 passes through the reflective layer M1 and is wavelength-converted into blue light in the phosphor layer.
  • a part of the blue light is transmitted through the reflective layer M2 and emitted, but another part of the blue light is reflected by the reflective layer M2 and resonates between the reflective layers M1 and M2.
  • the resonant and enhanced blue light excites the phosphor layer and is wavelength converted into yellow to red light. This yellow to red light passes through the reflective layer M2 and is emitted. In this way, when a single phosphor that emits blue light when excited by ultraviolet light is used, it is possible to provide a light emitting device in which blue light emission is suppressed and yellow to red light emission is increased.
  • the reflective layer M1 is employed as the first reflective layer, and the reflective layer M1 is employed as the second reflective layer, along with a phosphor that emits blue light upon ultraviolet excitation and has an excitation wavelength dependence of the emission wavelength. It was found that by combining the wavelength conversion element of Example 3 employing layer M3 with an excitation source, the emission of blue light and yellow to red light was increased, resulting in a light-emitting device that emitted white light.
  • the excitation light which is ultraviolet light
  • the reflective layer M1 passes through the reflective layer M1 and is wavelength-converted into blue light in the phosphor layer.
  • a component having a wavelength of more than 422 nm and less than 507 nm is transmitted through the reflective layer M3 and emitted.
  • components with a wavelength of 422 nm or less and components with a wavelength of 507 nm or more are reflected at the reflective layer M3 and resonated between the reflective layers M1 and M3.
  • the resonant and enhanced blue light component excites the phosphor layer and is wavelength converted into yellow to red light. This yellow to red light passes through the reflective layer M3 and is emitted.
  • a wavelength conversion element that emits white light, which is a mixture of blue light and yellow to red light, can be provided.
  • the reflective layer M1 is employed as the first reflective layer, and the reflective layer M1 is employed as the first reflective layer, together with a phosphor that emits blue light when excited by ultraviolet light and whose emission wavelength does not depend on the excitation wavelength.
  • the wavelength conversion element of Example 4 in which the reflective layer M3 was used as a layer, unlike the case of using the wavelength conversion element of Example 3, white light emission did not occur. This indicates that it is essential for the phosphor to have its emission wavelength dependent on the excitation wavelength.
  • the first reflective layer and the second reflective layer are located between them, have excitation wavelength dependence of the emission wavelength, and emit excitation light with a longer wavelength than the excitation light.
  • the first reflective layer is configured to reflect light in a first wavelength region located on the longer wavelength side than the peak wavelength of the excitation light, and
  • the second reflective layer reflect light having a second wavelength range that overlaps at least a part of the first wavelength range. It has been shown that it can be done. Such light emission occurs between the first reflective layer and the second reflective layer in a region where the first wavelength region and the second wavelength region overlap among the light emitted from the phosphor layer.
  • the resonant light is converted into light with a wavelength longer than the longest wavelength in the second wavelength region in the phosphor layer, and the excitation light is converted into light with a wavelength longer than the longest wavelength in the second wavelength region.
  • Light with a wavelength outside the second wavelength range and light with a wavelength longer than the longest wavelength of the second wavelength range obtained by wavelength conversion of the resonant light in the phosphor layer are transmitted through the second reflective layer. This is due to the fact that these lights are emitted and mixed.
  • FIG. 16A is a diagram showing the emission spectra of the light emitting device using the wavelength conversion element of Example 2 when irradiated with excitation light of different outputs
  • FIG. 16B is a diagram showing the chromaticity calculated from the emission spectrum of FIG. 16A
  • FIG. 17A is a diagram showing the emission spectrum when the light emitting device using the wavelength conversion element of Example 3 is irradiated with excitation light of different outputs
  • FIG. 17B is a diagram showing the chromaticity calculated from the emission spectrum of FIG. 17A.
  • the emission spectrum when the wavelength conversion element of Example 2 is irradiated with ultraviolet rays has peaks in the range of 450 nm or more and 500 nm or less and in the range of 580 nm or more and 650 nm or less, and these peak intensities are , had an output dependence on ultraviolet light, that is, excitation light.
  • the chromaticity does not change even when the output of the excitation light changes, so it was shown that a stable wavelength conversion element can be provided.
  • the emission spectrum when the wavelength conversion element of Example 3 is irradiated with ultraviolet rays has peaks in the range of 450 nm to 500 nm, and in the range of 580 nm to 650 nm, and in the range of 450 nm to 500 nm.
  • the peak intensities in the following range had no output dependence on ultraviolet light, that is, excitation light, and the peak intensities in the range from 580 nm to 650 nm had excitation light output dependence.
  • the chromaticity and color temperature can be controlled by changing the output of the excitation light, resulting in a light-emitting device whose color temperature can be adjusted by the output of the excitation source.
  • the output of the excitation light was increased, the color became closer to a light bulb color, and when the output of the excitation light was decreased, the color became closer to a blue-white light.
  • all such chromaticity and color temperature controls were along the blackbody locus, with deviations within ⁇ 0.01.
  • Graphitic carbon nitride phosphor (g-C 3 N 4 )
  • a graphitic carbon nitride phosphor (g-C 3 N 4 ) was synthesized as a phosphor different from the carbon nanoparticle phosphor using the following procedure.
  • the yellow powder thus obtained was subjected to X-ray diffraction measurement by Cu-K ⁇ ray irradiation using an X-ray diffraction device (Rint Ultima III, manufactured by Rigaku). The results are shown in FIG.
  • FIG. 18 shows an XRD pattern of a yellow powder obtained in the synthesis procedure of graphitic carbon nitride phosphor (g-C 3 N 4 ).
  • FIG. 19 is a diagram showing a 13 C-CP-MAS-NMR spectrum of a yellow powder obtained in the synthesis procedure of graphitic carbon nitride phosphor (g-C 3 N 4 ).
  • the resonance at 164.5 ppm originates from the carbon atom to which an amino group (-NH 2 ) is attached.
  • the resonance at 156.5 ppm comes from the sp2 carbon bonded to three nitrogen atoms in the triazine or heptazine ring.
  • Graphite-like carbon nitride phosphor (g-C 3 N 4 ) powder is dispersed in dimethyl sulfoxide (DMSO, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and passed through a 20 nm syringe filter to form graphite-like carbon nitride phosphor (g-C 3 N 4 ) powder. A C 3 N 4 ) dispersion was obtained. At this time, the concentration of graphitic carbon nitride phosphor (g-C 3 N 4 ) in DMSO was 0.0025% by mass (0.025 mg/mL).
  • the emission spectrum of the graphitic carbon nitride phosphor (g-C 3 N 4 ) dispersion thus obtained was measured using a spectrofluorophotometer (manufactured by JASCO Corporation, FP-8500). The results are shown in FIG.
  • FIG. 20 is a diagram showing the emission spectrum of a graphitic carbon nitride phosphor (g-C 3 N 4 ) dispersion.
  • FIG. 20 shows emission spectra when a graphite-like carbon nitride phosphor (g-C 3 N 4 ) dispersion was irradiated with excitation light of various wavelengths.
  • the graphite-like carbon nitride phosphor (g-C 3 N 4 ) dispersion emits blue light with a peak around 460 nm when excited by excitation light with a wavelength of 300 nm to 400 nm.
  • the graphitic carbon nitride phosphor (g-C 3 N 4 ) dispersion has excitation wavelength dependence of the emission wavelength.
  • Example 5 Wavelength conversion element
  • the wavelength conversion element shown in Table 6 was manufactured by combining the graphite-like carbon nitride phosphor (g-C 3 N 4 ) that emits blue light upon ultraviolet excitation with the reflective layer shown in Table 5. .
  • AlN aluminum nitride
  • silicon oxide SiO 2
  • tantalum oxide Ti 2 O 5
  • quartz glass was used as a substrate using an RF (radio frequency) sputtering device (manufactured by Shibaura Mechatronics Co., Ltd., CFS-4EP). -LL).
  • RF radio frequency
  • nine pairs of Ta 2 O 5 and SiO 2 were laminated on the quartz glass by sputtering to form a reflective layer M4.
  • the thickness of each layer was 200 nm in total for Ta 2 O 5 as a high refractive index layer, and 80 nm in total for SiO 2 as a low refractive index layer.
  • the sputtering conditions were: distance between substrates 110 mm, RF output 300 W, and no substrate heating.
  • the transmission spectrum of the obtained reflective layer M4 was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by JASCO Corporation, V-570), it was found that it had a stop band in the wavelength range of 450 nm to 550 nm. confirmed.
  • a phosphor layer which was a resin molding in which g-C 3 N 4 was dispersed, was formed on the reflective layer M4.
  • Polyvinylpyrrolidone (PVP) powder (2 g) was added to deionized water (60 mL) and held at 90° C. for 3 hours to prepare a PVP aqueous solution (PVP concentration: 3.3% by mass).
  • g-C 3 N 4 was added to a PVP aqueous solution (4 mL) and stirred. This was drop cast onto the reflective layer M4 and dried at 90° C. for 1 hour to obtain a laminate of quartz glass/reflective layer/phosphor layer.
  • the content of the graphitic carbon nitride phosphor in the phosphor layer thus obtained was 0.07% by mass.
  • the laminate of quartz glass/reflective layer/resin molded body was placed in an RF sputtering device, and a reflective layer M4 was formed on the resin molded body.
  • the conditions for forming the reflective layer were as described above. In this way, the wavelength conversion element of Example 5 was obtained.
  • the wavelength conversion element of Example 5 was combined with an ultraviolet light emitting diode element having an emission peak at a wavelength of 355 nm as an excitation source to produce a light emitting device.
  • Ultraviolet light (output 0.03 mW) from the ultraviolet light emitting diode element was incident on the quartz glass side of the wavelength conversion element of Example 5, and the emission spectrum of the light emitted from the wavelength conversion element was measured.
  • the results are shown in Figure 21A.
  • CIE1931 chromaticity (x, y) was calculated from the emission spectrum.
  • the results are shown in FIG. 21B and Table 7, respectively.
  • FIG. 21A is a diagram showing the emission spectrum of a light-emitting device using the wavelength conversion element of Example 5 and the emission spectrum of the phosphor layer used in the wavelength conversion element.
  • FIG. 21B is a diagram showing chromaticity calculated from the emission spectrum of a light emitting device using the wavelength conversion element of Example 5.
  • the emission spectrum shown by the dotted line is the emission spectrum when the phosphor layer used was excited with light at a wavelength of 355 nm.
  • the phosphor emits blue light upon excitation with ultraviolet light and has excitation wavelength dependence of the emission wavelength, and both the first reflective layer and the second reflective layer have a reflective layer M4.
  • the wavelength conversion element of Example 5 with an ultraviolet light emitting diode element as an excitation source, the emission intensity of blue light decreases and the emission intensity of yellow to red light increases, resulting in white light emission. It turned out to be a device.
  • the excitation light which is ultraviolet light
  • a component with a wavelength of less than 450 nm and a component with a wavelength of more than 550 nm are transmitted through the reflective layer M4 and emitted.
  • a part of the component with a wavelength of 450 nm or more and 550 nm or less is transmitted through the reflective layer M4 and emitted, but the other part is reflected by the reflective layer M4, and the other part is reflected by the reflective layer M4 that faces each other. It resonates between M4.
  • the resonant and enhanced blue light component excites the phosphor layer and is wavelength converted into yellow to red light.
  • This yellow to red light passes through the reflective layer M4 and is emitted.
  • a wavelength conversion element that emits white light which is a mixture of blue light and yellow to red light, can be provided.
  • a wavelength conversion element with adjusted chromaticity and color temperature can be provided by simply selecting the width of the stop band of a pair of reflective layers using a phosphor whose emission wavelength is dependent on the excitation wavelength. Therefore, it is advantageous for device design.
  • a wavelength conversion element that emits white light can be provided.
  • Such wavelength conversion elements are used in light emitting devices such as lighting devices and backlights for displays.
  • wavelength conversion element 110 first reflective layer 120 second reflective layer 130 phosphor layer 140 laminate 150 substrate 160 excitation light 170, 170', 180, 190, 190' light 200 light emitting device 210, 220 lead wire 230 alumina Substrate 240 Excitation source 250 Fine gold wire 270 Resin 280 Wall member

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Abstract

Un élément de conversion de longueur d'onde de la présente invention comprend : une première couche réfléchissante ; une seconde couche réfléchissante ; et une couche de luminophore située entre ces couches réfléchissantes. La première couche réfléchissante réfléchit la lumière dans une première région de longueur d'onde. La seconde couche réfléchissante réfléchit la lumière dans une seconde région de longueur d'onde qui chevauche au moins une partie de la première région de longueur d'onde. La couche de luminophore a une dépendance de longueur d'onde d'excitation sur la longueur d'onde d'émission de lumière et convertit la lumière d'excitation projetée en une lumière ayant une longueur d'onde plus longue que la lumière d'excitation. La première couche réfléchissante et la seconde couche réfléchissante résonnent, entre celles-ci, la lumière d'une longueur d'onde dans une région de chevauchement entre la première région de longueur d'onde et la seconde région de longueur d'onde, la lumière étant de la lumière obtenue par conversion de longueur d'onde de la lumière d'excitation par la couche de luminophore. La lumière résonante est convertie par la couche de luminophore en une lumière d'une longueur d'onde plus longue que la longueur d'onde la plus longue dans la seconde région de longueur d'onde. Au niveau de la seconde couche réfléchissante, de la lumière obtenue par la lumière d'excitation convertie en longueur d'onde par la couche de luminophore, la lumière d'une longueur d'onde à l'extérieur de la seconde région de longueur d'onde et la lumière d'une longueur d'onde supérieure à la longueur d'onde la plus longue dans la seconde région de longueur d'onde et obtenues par la lumière résonante convertie en longueur d'onde par la couche de luminophore sont chacune transmises par la seconde couche réfléchissante et sortent de celle-ci.
PCT/JP2023/023052 2022-06-23 2023-06-22 Élément de conversion de longueur d'onde et dispositif électroluminescent l'utilisant Ceased WO2023249069A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080128728A1 (en) * 2004-09-10 2008-06-05 Luminus Devices, Inc. Polarized light-emitting devices and methods
JP2015511775A (ja) * 2012-03-30 2015-04-20 コーニンクレッカ フィリップス エヌ ヴェ 発光デバイス及び波長変換材料を含む光共振器
WO2018163955A1 (fr) * 2017-03-09 2018-09-13 国立研究開発法人物質・材料研究機構 Composition, procédé pour sa production et utilisation associée

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080128728A1 (en) * 2004-09-10 2008-06-05 Luminus Devices, Inc. Polarized light-emitting devices and methods
JP2015511775A (ja) * 2012-03-30 2015-04-20 コーニンクレッカ フィリップス エヌ ヴェ 発光デバイス及び波長変換材料を含む光共振器
WO2018163955A1 (fr) * 2017-03-09 2018-09-13 国立研究開発法人物質・材料研究機構 Composition, procédé pour sa production et utilisation associée

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