US20130141916A1 - Display device - Google Patents

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Publication number
US20130141916A1
US20130141916A1 US13/583,919 US201113583919A US2013141916A1 US 20130141916 A1 US20130141916 A1 US 20130141916A1 US 201113583919 A US201113583919 A US 201113583919A US 2013141916 A1 US2013141916 A1 US 2013141916A1
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United States
Prior art keywords
light
display device
emitting material
voltage
hexafluoroacetylacetonate
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US13/583,919
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English (en)
Inventor
Norihisa Kobayashi
Kazuki Nakamura
Yuichi Watanabe
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Chiba University NUC
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Chiba University NUC
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Assigned to NATIONAL UNIVERSITY CORPORATION CHIBA UNIVERSITY reassignment NATIONAL UNIVERSITY CORPORATION CHIBA UNIVERSITY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WATANABE, YUICHI, KOBAYASHI, NORIHISA, NAKAMURA, KAZUKI
Publication of US20130141916A1 publication Critical patent/US20130141916A1/en
Abandoned legal-status Critical Current

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V9/00—Elements for modifying spectral properties, polarisation or intensity of the light emitted, e.g. filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1503—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G02F1/157—Structural association of cells with optical devices, e.g. reflectors or illuminating devices
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/163—Operation of electrochromic cells, e.g. electrodeposition cells; Circuit arrangements therefor
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G09F9/302—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements characterised by the form or geometrical disposition of the individual elements
    • G09F9/3023—Segmented electronic displays
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G09F9/37—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements being movable elements
    • G09F9/372—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements being movable elements the positions of the elements being controlled by the application of an electric field
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/04—Materials and properties dye
    • G02F2202/046—Materials and properties dye fluorescent

Definitions

  • the present invention relates to a display device, and more specifically to a display device comprising both reflective type and light emission type.
  • a device for displaying information i.e., display device
  • television or monitor for PC is an indispensable in the information society in recent years.
  • Display type of the display device can be largely categorized into three types of reflective type, transmission type, and light emission type. Generally, in manufacturing the display device, a person who manufactures the display device selects preferable display type depending on the environment for the display device.
  • solubility of an electric field light-emitting material with respect to a liquid crystal material is low, so that sufficient light-emitting property is not liable to be obtained.
  • liquid crystal phase transition temperature is decreased by mixing the electric field light-emitting material, and liquid crystal phase becomes isotropic phase by applying a high voltage during spontaneous light emission, so that liquid crystal structure is liable to disappear.
  • a display device comprises a pair of substrates which are disposed facing each other, and on each of which electrodes are formed and a material layer which is sandwiched between the pair of substrates.
  • the material layer contains a coloring material which changes color upon the application of a voltage, and a light-emitting material which emits light upon photoexcitation.
  • a high quality display device can be provided by preventing complicated element structure without damaging portability in undesirable manner.
  • FIG. 1 shows a schematic cross-sectional view of a display device according to an embodiment 1 of the present invention.
  • FIG. 2 is a view for describing display in a reflective type display method of a display device according to an embodiment 1 of the present invention.
  • FIG. 3 is a schematic view illustrating another example of a material layer of a display device.
  • FIG. 4 is a schematic view illustrating a third example of a material layer of a display device.
  • FIG. 5 is a view for describing display in a light emission type display method of a display device according to an embodiment 1 of the present invention.
  • FIG. 6 is a view for describing principle of display of a display device according to an embodiment 1 of the present invention.
  • FIG. 7 is a view for describing principle of display of a display device according to an embodiment 1 of the present invention.
  • FIG. 8 is a view illustrating appearances (display state) of a display device according to example 1.
  • FIG. 9 is a view illustrating a measurement result of a display device according to example 1.
  • FIG. 10 is a view illustrating electrode shapes (segments) of a display device fabricated in example 2.
  • FIG. 11 a view illustrating appearances (display state) of a display device fabricated in example 2.
  • FIG. 12 is a view illustrating appearances (display state) of a display device fabricated in example 3.
  • FIG. 13 is a view for describing display in a light emission type display method of a display device according to an embodiment 2 of the present invention.
  • FIG. 14 shows a schematic cross-sectional view of a display device according to another embodiment of embodiment 2.
  • FIG. 15 shows a schematic cross-sectional view of a display device according to a third embodiment of embodiment 2.
  • FIG. 16 shows a schematic cross-sectional view of a display device according to a fourth embodiment of embodiment 2.
  • FIG. 17 is a view illustrating changes of electric current value and light absorption when DC voltages are applied to a display device in example 4.
  • FIG. 18 is a view illustrating light absorption spectrums when DC voltages are applied to a display device in example 4.
  • FIG. 19 is a photographic view illustrating change in coloring when a DC voltage is applied to a display device in example 4.
  • FIG. 20 is a view illustrating light intensity when an AC voltage is applied to a display device in example 4.
  • FIG. 21 is a photographic view illustrating change in light emission when an AC voltage is applied to a display device in example 4.
  • FIG. 22 is a view illustrating light absorption spectrum and light intensity spectrum when a coloring mode (reflective type) and a light emission mode (light emission type) are respectively drived in example 4.
  • FIG. 23 is a photographic view illustrating a mode driving for a display device in example 4.
  • FIG. 24 is a view illustrating changes of electric current value and light absorption when DC voltages are applied to a display device in example 5.
  • FIG. 25 is a photographic view illustrating change in coloring when a DC voltage is applied to a display device in example 5.
  • FIG. 26 is a view illustrating light intensity when an AC voltage is applied to a display device in example 5.
  • FIG. 27 is a photographic view illustrating change in light emission when an AC voltage is applied to a display device in example 5.
  • FIG. 28 is a view illustrating light intensities when AC voltages are respectively set to 4 V and 6 V in example 5.
  • FIG. 1 is a schematic cross-sectional view of a display device 1 (hereinafter referred to as “present display device”) according to an embodiment of the present invention.
  • the present display device 1 comprises a pair of substrates disposed facing each other, on each of which electrodes 21 , 31 are formed, and a material layer 4 sandwiched between the pair of substrates 2 , 3 .
  • a light source 5 (described below in FIG. 2 ) is provided in order to light being irradiated into the pair of substrates 2 , 3 and the material layer 4 (hereinafter referred to as “panel portion”). If necessary, light can be irradiated into the panel portion.
  • the light source 5 preferably has a light source for photoexcitation which allows a light-emitting material to emit light. This effect is apparent from the description below, in this manner, light (excited light) having the wavelength range in which the light-emitting material emits light can be supplied, and thereby displaying the light emission type display by allowing the light-emitting material to emit light.
  • the term “light source for photoexcitation” means a light source where light emission is within the wavelength range of absorbed light in order to allow the light emission material to emit light, and more specifically means a light source where peak wavelength of light emission is within the wavelength range of light absorption of the light-emitting material.
  • the pair of substrates 2 , 3 are used for sandwiching the material layer 4 , and maintaining it.
  • At least one of the substrates 2 , 3 may be transparent.
  • one of the substrates 2 , 3 is transparent and the other one comprises a part having reflecting function, in this manner, the substrate having reflective function may be used as reflecting plate, thereby providing a reflective type display device which has more convenient configuration.
  • both substrates 2 , 3 are transparent, they may be used for transmission type, and moreover used for reflective type by forming a reflective plate on one side of the substrates 2 , 3 .
  • the material for the substrates 2 , 3 are not specifically limited as long as they has hardness to an extent, chemical stability, and can be stably maintain the material layer 4 . Examples thereof include glass, plastic, metal, semiconductor, or the like. In case of using the transparent substrate, glass or plastic may be used, and in case of having reflective function, metal, semiconductor, or the like may be used.
  • electrodes 21 , 31 are formed on each side (inner side) of the substrates 2 , 3 facing each other.
  • the electrodes 2 , 3 are used for applying a voltage to the material layer 4 sandwiched therebetween, materials for electrodes 2 , 3 are not specifically limited as long as they have favorable electric conductivity. Examples thereof preferably include transparent electrodes such as ITO, IZO, or the like when the substrates 2 , 3 are transparent, and metal electrodes such as Cu, Al, or the like when the substrates 2 , 3 are not transparent.
  • the transparent electrode may be employed, moreover a metal substrate may be used as an electrode by utilizing electric conductivity of the metal substrate itself. (In this case, the electrode is also formed on the substrate.)
  • insulator, and the like are preferably provided between the substrate and the electrode.
  • the electrodes according to the present embodiment may be formed as a shape which is adjusted to pattern such as a character to be displayed, and may also be formed by electrode pattern divided into multiple identical regions being aligned on plural substrates.
  • each of regions is to be a pixel, and display is controlled in each pixel. Therefore, it has an advantage in displaying complicated shapes.
  • the electrodes according to the present embodiment are connected to a power source via wirings having respective electric conductivities, and applying a voltage or applying no voltage to the material layer 4 can be controlled by turning on the power source or turning off the power source.
  • the strength of the voltage can be appropriately modulated depending on space between the pair of substrates or space between the pair of electrodes.
  • the strength of the electric field is preferably 1.0 ⁇ 10 4 V/m or more and 1.0 ⁇ 10 6 V/m or less, and more preferably 1.0 ⁇ 10 5 V/m or less.
  • the material layer 4 according to the present embodiment includes a coloring material or a light-emitting material by different stimuli, and specifically a coloring material 41 and a light-emitting material 42 .
  • the material layer 4 according to the present embodiment preferably contains a solvent for maintaining these materials, and a supporting electrolyte in addition to the coloring material 41 and the light-emitting material 42 .
  • the supporting electrolyte is not specifically limited as long as it expedites oxidation-reduction of the coloring material 41 .
  • Examples thereof preferably include lithium salt, potassium salt, sodium salt, and the like.
  • lithium salt include LiCl, LiBr, LiI, LiBF 4 , LiClO 4 , and the like
  • examples of potassium salt include KCl, KI, KBr, and the like
  • examples of sodium salt include NaCl, NaBr, BaI, and the like.
  • the concentration of the supporting electrolyte, not specifically limited, is preferably 10 mM or more and 1 M or less.
  • the solvent is not specifically limited as long as the coloring material 41 and the light-emitting material 42 are stably maintained.
  • the solvent may be a polar solvent such as water, and the like, and may be also organic solvent having no polarity, ionic liquid, ionic electric conducting polymer. Examples thereof include carbonic acid propylene, dimethyl sulfoxide, N,N-dimethyl formamide, tetrahydrofuran, acetonitrile, polyvinyl sulfuric acid, polystyrene sulfonic acid, poly acrylic acid, and the like.
  • the coloring material 41 is a material which changes its color upon applying a voltage thereto. Display can be obtained by the color change.
  • the coloring material 41 preferably contains at least any of an organic electrochromic material and an inorganic electrochromic material.
  • examples of the organic electrochromic material include viologen derivative, polypyrrole derivative, polyaniline derivative, polythiophene derivative, phenylester derivative, anthraquinone derivative, phenylamine derivative, and the like.
  • examples thereof included 1,4-diacetyl benzene, N,N′-dimethyl viologen, poly(3,4-ethylenedioxythiophene), polyaniline, 1,4-diheptyl viologen, 4,4′-biphenyl dicarboxylic acid diethyl ester, and dimethyl terephthalate.
  • examples of the inorganic electrochromic material include transition metal oxide such as iridium hydroxide titanium oxide, and metal hydroxide such as iridium hydroxide. Examples of the organic electrochromic material are shown below in chemical formula 1. Preferably, at least any thereof may be used as examples.
  • the coloring material 41 can change its color upon applying a voltage between electrodes. It is possible to distinguish the colored region from the other region, therefore the coloring material 41 can be used for a reflective type display.
  • image is shown in FIG. 2 (herein, a coloring portion is a portion upon applying a voltage, non-coloring portion is a portion upon applying no voltage.).
  • the concentration of the coloring material 41 for example, is preferably 0.5 mM or more and 300 mM or less, and more preferably 100 mM or less.
  • the present display device a plurality of displays can be performed based on the combination of the coloring material 41 and the light-emitting material 42 .
  • the concentration of the light-emitting material 42 is set to be 1, the concentration of the coloring material 41 is preferably 0.1 or more and 5 or less, more preferably 0.5 or more and 2 or less.
  • the light-emitting material 42 is a material which is excited to emit light upon irradiation of light.
  • a rare earth metal complex is preferably used in view of energy migration with respect to the coloring material 41 .
  • the rare earth metal complex is a rare earth metal and a compound in which ligand is liganded to the rare earth element.
  • examples of the rare earth metal used for the rare earth metal complex include Eu, Tb, Yb, and the like.
  • the light-emitting material 42 include at least any of tris(hexafluoroacetylacetonate) europium(III), tris(hexafluoroacetylacetonate) terbium(III), and tris(hexafluoroacetylacetonate) ytterbium(III).
  • the peak wavelength of light absorption for exciting light emission may be in the wavelength range of visible light, and moreover may be preferably in the outside wavelength range of visible light (e.g., in the wavelength range of less than 360 nm and larger than 830 nm).
  • the concentration of the light-emitting material 42 is not specifically limited as long as the light-emitting material 42 has the above-mentioned function.
  • the concentration thereof is preferably 0.5 mM or more and 300 mM or less, and more preferably 100 mM or less.
  • the coloring material 41 is preferably adjacent to the light-emitting material 42 .
  • means for the coloring material 41 being adjacent to the light-emitting material 42 comprises: as shown in FIG. 1 , dispersed arrangement of the coloring material 41 and the light-emitting material 42 with relative high concentration; as shown in FIG. 3 , alternate laminated formation of the coloring material 41 and the light-emitting material 42 ; and as shown in FIG. 4 , chemical combination of the coloring material 41 and the light-emitting material 42 such as covalent bond, and the like.
  • examples of the chemical combination thereof include tris(hexafluoroacetylacetonate) europium (triphenylphosphin oxide)/polyaniline, tris(hexafluoroacetylacetonate) terbium (triphenylphosphin oxide)/polyaniline, tris(hexafluoroacetylacetonate) ytterbium (triphenylphosphin oxide)/polyaniline, tris(hexafluoroacetylacetonate) europium (1,4-diacetyl benzene), tris(hexafluoroacetylacetonate) terbium (1,4-diacetyl benzene), and tris(hexafluoroacetylacetonate) ytterbium (1,4-diacetyl benzene).
  • the coloring material 41 and the light-emitting material 42 are alternately laminated with respective thicknesses of 10 nm or less. Maintaining such range of thicknesses easily leads to energy migration between the coloring material 41 and the light-emitting material 42 . Thus, a plurality of display states can be performed.
  • the present display device e.g. in the bright place, can display information by employing the reflective type display method (see the above FIG. 2 ). Specifically, in a portion of pixels, a voltage is applied between a pair of electrodes thereof. A color in the area where the voltage is applied different from a color in the area where the voltage is not applied, which leads to display screen. Moreover, when the voltage is not applied, no image is displayed. In this case, it is preferably that the light source does not emit light.
  • FIGS. 6 and 7 describe the principle thereof, and are views illustrating energy migration of the coloring material 41 (electrochromic material) and the light-emitting material 42 (rare earth complex).
  • FIG. 6 shows the light-emitting display stage
  • FIG. 7 shows the reflective type display state (coloring state), respectively.
  • Eu(hfa) 3 (H 2 O) 2 is used as the light-emitting material 42
  • N,N′-diheptyl viologen is used as the coloring material 41 .
  • Left sides of the respective figures are views illustrating energy level of the coloring material 41 (electrochromic material)
  • right sides of the respective figures are views illustrating energy level of the light-emitting material 42 .
  • the voltage between electrodes is removed in the area (pixels) to be displayed, so that excited light from the light source is emitted. Then, in this area, light is excited by the light-emitting material 42 obtaining energy from the light source, so that light is emitted. However, in the area (pixels) where the voltage is applied between electrodes, the energy migrates into the coloring material 41 which is adjacent thereto, so that the energy becomes useless. As a result, the light-emitting area can also be distinguished from non-light-emitting area.
  • energy difference between ground state and excited state of the coloring material 41 is less than or equal to that of the light-emitting material 42 (preferably the difference of more than or equal to 1800 cm ⁇ 1 ). In this manner, it is possible to migrate energy from the light-emitting material 42 to the coloring material 41 (Förster type energy migration), and display for light emission or non-light emission can be controlled by suppressing the light emission.
  • the display device according to the present embodiment has excellent effect such that the electrodes are not only used for coloring and non-coloring, but also used for masks of light emission and non-light emission.
  • an area where the voltage is applied becomes non-light emission area, and an area where the voltage is not applied becomes light emission area.
  • the following configuration can be also used: an area where the voltage is not applied becomes non-light emission area, and an area where the voltage is applied becomes light emission area.
  • the effect on the above display device was confirmed using the material layer 4 including the coloring material 41 and the light-emitting material 42 .
  • the material layer contained propylene carbonate as a solvent, 50 mM of TBAP as a supporting electrolyte, 10 mM of N,N′-diheptyl as a coloring material, and 10 mM of tris(hexafluoroacetylacetonate) europium complex (Eu(hfa) 3 (H 2 O) 2 ) as a light-emitting material described in the chemical formula 3 below.
  • the material layer was placed in 70 ⁇ m spacers between a pair of substrates on which ITO electrodes have been formed, and the absorption characteristics and light-emitting intensity were measured upon applying a voltage (DC 2.2 V) or applying no voltage during photo-irradiation.
  • FIG. 8 shows appearances of the display device according to the present example.
  • FIG. 9 shows the result of the measurement. In this example, the wavelength of excited light from the light source was 337 nm.
  • a display device can be used as a reflective type display device without irradiating excited light, and just by applying or removing the voltage
  • a display device can be enabled by irradiating excited light, removing the voltage on the part where light must be emitted, and applying the voltage on the part where light must not be emitted, in order to create light and shade.
  • FIG. 10 shows schematic electrode structures
  • FIG. 11 shows the result of the actual display.
  • the distance between electrodes and applied voltage of 2.2 V were also the same as in the example 1.
  • the material layer contained propylene carbonate as a solvent, 200 mM of TBAP as a supporting electrolyte, 50 mM of DMT as a coloring material, and 50 mM of tris(hexafluoroacetylacetonate) europium(III) bis(triphenylphosphin oxide) as a light-emitting material described in the chemical formula 4 below.
  • the material layer was placed in 70 ⁇ m spacers between a pair of substrates on which ITO electrodes have been formed, and the absorption characteristics and light-emitting intensity were measured upon applying the voltage (DC 4 V) or applying no voltage during photo-irradiation.
  • FIG. 12 shows appearances of the display device according to the present example. In this example, the wavelength of excited light was 365 nm.
  • the present example 3 which is the same as in the above examples 1 and 2, for instance, under a bright environment, it can be used as a reflective type display device without irradiating excited light, and just by applying or removing voltage, whereas, under a dark environment, a display device can be enabled by irradiating excited light, removing the voltage on the part where light must be emitted, and applying the voltage on the part where light must not be emitted, in order to create light and shade.
  • the light-emitting material emits light upon photoexcitation.
  • an electrochemical light-emitting material 42 which can emit light upon excitation based on an AC voltage, can replace or be added to the light-emitting material in embodiment 1.
  • the examples of the electrochemical light-emitting material 42 preferably include Ru(bpy) 3 (PF 6 ) 2 , RuPF 6 , RuCl 6 , PVB (polyvinyl butyral), DPA (9,10-Diphenyl anthracene), TBAP (tetrabutylammonium perchlorate), and the like.
  • the concentration of the electrochemical light-emitting material 42 is not specifically limited as long as it can emit light by excitation based on the AC voltage, and it can be appropriately adjusted depending on the types of materials.
  • the concentration thereof is preferably 5 M or less, more preferably 1 mM or more and 1 M or less, and even more preferably 5 mM or more and 100 mM or less.
  • the structure as the display device is the same as in the above embodiment 1.
  • FIG. 13 shows a schematic view of a constitution of the element according the present embodiment 2.
  • the display device for example when the DC voltage was applied, information can be displayed by employing the reflective type display method. Specifically, for a portion of pixels, the voltage is applied between the pair of electrodes. Then, the difference between the area with applied voltage and the area without applied voltage becomes a display screen. Of course, when the voltage is not applied, it can stay without displaying any screen.
  • the display device may include a pair of substrates, and a reflecting plate, placed on one side of the substrates, irradiating light from another light source (i.e., emitting light different from excited light in the above embodiment 1) into the pair of substrates.
  • the strength of the voltage when applying the DC voltage can be appropriately modified by the distance between the pair of substrates, and the distance between the pair of electrodes.
  • example of the electric field is preferably 1.0 ⁇ 10 4 V/m or more and 1.0 ⁇ 10 6 V/m or less, and more preferably 1.0 ⁇ 10 5 V/m or less.
  • information can be displayed by employing a light emission type display method upon applying an AC voltage.
  • the display device when applying a direct current (in case of displaying coloring), the electrochromic material 41 is colored by oxidation-reduction reaction, whereas the electrochemical light-emitting material 42 does not emit light because it produces either an oxidant body or a reducing body.
  • the electrochemical light-emitting material 42 when applying an alternating current (in case of light-emitting display), the electrochemical light-emitting material 42 can emit light because it produces both the oxidant body and the reducing body, but the electrochromic material 41 is not actually colored because it repeats coloring and disappearance of coloring at a high speed.
  • the display device can have both a coloring mode and a light-emitting mode. As a result, unnecessary installation of mask, and the like that conceal the location with unclear display state is reduced, thereby facilitating the desired display screen.
  • the strength of the AC voltage can be appropriately modified by distance between the pair of substrates, and distance between the pair of electrodes.
  • examples of the electric field preferably is 1.0 ⁇ 10 4 V/m or more and 1.0 ⁇ 10 6 V/m or less, and more preferably 1.0 ⁇ 10 5 V/m or less.
  • the frequency of the AC voltage coloring and disappearance of coloring in the electrochromic material 41 are not felt on human eyes to an extent.
  • the frequency of the AC voltage may be to an extent that the electrochemical light-emitting becomes possible, and, although it is not limited, for example, 10 Hz or more and 1000 Hz or less is preferable, 30 Hz or more and 500 Hz or less is more preferable, and 50 Hz or more and 200 Hz or less is even more preferable.
  • a high quality display can be provided without damaging the portability by preventing complication of the element structure.
  • the display device comprises a pair of substrates 2 , 3 , a pair of electrodes 21 , 31 that are formed on the surface of the respective substrates 2 , 3 facing each other, and the material layer 4 including the electrochemical light-emitting material 42 sandwiched between the pair of electrodes, wherein one of the pair of electrodes is modified by the electrochromic material 41 .
  • one of the pair of electrodes is modified by the electrochromic material.
  • modification refers to the state of being maintained on electrode with a certain level of viscosity or with a solid state.
  • polymer membrane such as an ionic exchange membrane that maintains the electrochromic material 41 , is formed on the electrode.
  • FIG. 15 shows a schematic cross-sectional view of the display device according to the present embodiment.
  • the display device according to the embodiment comprises a pair of substrates 2 , 3 , a pair of electrodes 21 , 31 that are formed on the surface of the respective substrates 2 , 3 facing each other, and the material layer 4 including the electrochromic material 41 sandwiched between the pair of electrodes, wherein one of the pair of electrodes is modified by the electrochemical light-emitting material 42 .
  • one of the pair of electrodes is modified by the electrochemical light-emitting material 42 .
  • modification refers to the state of being maintained on electrode with a certain level of viscosity or with a solid state.
  • polymer membrane such as an ionic exchange membrane that maintains the electrochemical light-emitting material 42
  • modifying one electrode with the electrochemical light-emitting material 42 raises the concentration of the electrochemical light-emitting material 42 around the electrode, and it has the advantage of achieving functions of light emission type and reflective type more clearly.
  • the display device comprises a pair of substrates 2 , 3 , a pair of electrodes 21 , 31 that are formed on the surface of the respective substrates 2 , 3 facing each other, and the material layer 4 sandwiched between the pair of electrodes, wherein one electrode is modified by the electrochemical light-emitting material 42 and the other electrode is modified by the electrochromic material 41 .
  • FIG. 16 shows the schematic cross-sectional view of the display device according to the present embodiment.
  • one electrode is modified by the electrochemical light-emitting material 42
  • the other electrode is modified by the electrochromic material 41 .
  • modification refers to the state of being maintained on electrode with a certain level of viscosity or with a solid state.
  • polymer membrane such as an ionic exchange membrane that maintains the electrochemical light-emitting material 42 , is formed on the electrode.
  • a high quality display can be provided without damaging the portability by preventing complication of the element structure.
  • modifying one electrode with the electrochemical light-emitting material 42 and modifying the other electrode with the electrochromic material 41 raises the concentrations of the electrochemical light-emitting material 42 and the electrochromic material 41 around the respective electrodes, and it has the advantage of achieving functions of light emission type and reflective type more clearly.
  • glass substrates were used for a pair of substrates, ITO for an electrode material, DMT for an electrochromic material, Ru complex (Ru(bpy) 3 (PF 6 ) 2 ) for an electrochemical light-emitting material, DMSO for a solvent, and TBAP for a supporting electrolyte.
  • concentration of DMT was 50 mM, that of Ru complex 10 mM, and that of the supporting electrolyte 100 mM.
  • the above electrolyte layer was sandwiched between the pair of substrates with spacers in order to the space between the pair of electrodes being maintained with 70 ⁇ m.
  • FIG. 17 is a view illustrating changes of current value and light absorption at 530 nm when changing DC voltages from ⁇ 4 V to 0 V.
  • FIG. 18 shows light absorption spectrum when changing the DC voltages to ⁇ 2.5 V, ⁇ 3.0 V, ⁇ 3.5 V, and ⁇ 4.0 V.
  • FIG. 19 shows is a photographic view illustrating change of coloring based on change of the voltage.
  • FIG. 20 is a view illustrating light-emitting intensity when applying AC voltage of ⁇ 4 V and 50 Hz.
  • FIG. 21 is a photographic view illustrating the change of light emission in this case.
  • FIG. 22 shows spectrums of light absorption and light intensity when operating a coloring (reflective type) mode and a light-emitting mode (light emission type), and
  • FIG. 23 is a photographic view thereof.
  • any display device of light emission type and reflective type could be realized by selecting the AC voltage or the DC voltage.
  • the effectiveness of the display device according to the present invention was confirmed by this embodiment.
  • PET Polyethylene terephthalate
  • VYLON 200, Toyobo Polyethylene terephthalate
  • Ru complex Ru(bpy) 3 (PF 6 ) 2
  • DMSO for a solvent
  • TBAP for a supporting electrolyte.
  • Ru complex was applied with 9% by weight of Flemion (ethanol solution) using spin-coating method (1000 rpm, 10 s, 1500 rpm, 10 s), and then immersed in 5 mM of Ru complex aqueous solution to absorb Ru complex into ionic exchange membrane, thereby modifying the other electrode. Also, the distance of 300 ⁇ m between electrodes was maintained by spacers, and the electrolytic layer containing 50 mM of TBAP and 20% by weight of DMSO was sandwiched between the pair of substrates.
  • FIG. 24 is a view illustrating changes of the current value and light absorption at 530 nm when changing DC voltages from ⁇ 4 V to 0 V.
  • FIG. 25 is a photographic view illustrating change of coloring based on change of the voltage.
  • FIG. 26 is a view illustrating the light-emitting intensity when applying AC voltage of ⁇ 4 V and 50 Hz.
  • FIG. 27 is a photographic view illustrating change of the light emission in this case.
  • FIG. 28 shows light-emitting intensities when applying the DC voltages of 4 V and 6 V, respectively.
  • any display device of light emission type and reflective type could be realized by selecting the AC voltage or the DC voltage.
  • the effectiveness of the display device according to the present invention was confirmed by this embodiment.
  • the present invention is industrially applicable as a display device.

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  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
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