WO2007142287A1 - Dispositif de conversion de lumière en lumière - Google Patents

Dispositif de conversion de lumière en lumière Download PDF

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Publication number
WO2007142287A1
WO2007142287A1 PCT/JP2007/061524 JP2007061524W WO2007142287A1 WO 2007142287 A1 WO2007142287 A1 WO 2007142287A1 JP 2007061524 W JP2007061524 W JP 2007061524W WO 2007142287 A1 WO2007142287 A1 WO 2007142287A1
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Prior art keywords
light
optical
conversion device
electrode
layer
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PCT/JP2007/061524
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English (en)
Japanese (ja)
Inventor
Shin-Ya Tanaka
Shinichi Morishima
Masaaki Yokoyama
Kenichi Nakayama
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Sumitomo Chemical Company, Limited
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Publication of WO2007142287A1 publication Critical patent/WO2007142287A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/12—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof structurally associated with, e.g. formed in or on a common substrate with, one or more electric light sources, e.g. electroluminescent light sources, and electrically or optically coupled thereto
    • H01L31/14—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof structurally associated with, e.g. formed in or on a common substrate with, one or more electric light sources, e.g. electroluminescent light sources, and electrically or optically coupled thereto the light source or sources being controlled by the semiconductor device sensitive to radiation, e.g. image converters, image amplifiers or image storage devices
    • H01L31/141—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof structurally associated with, e.g. formed in or on a common substrate with, one or more electric light sources, e.g. electroluminescent light sources, and electrically or optically coupled thereto the light source or sources being controlled by the semiconductor device sensitive to radiation, e.g. image converters, image amplifiers or image storage devices the semiconductor device sensitive to radiation being without a potential-jump barrier or surface barrier
    • H01L31/143—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof structurally associated with, e.g. formed in or on a common substrate with, one or more electric light sources, e.g. electroluminescent light sources, and electrically or optically coupled thereto the light source or sources being controlled by the semiconductor device sensitive to radiation, e.g. image converters, image amplifiers or image storage devices the semiconductor device sensitive to radiation being without a potential-jump barrier or surface barrier the light source being a semiconductor device with at least one potential-jump barrier or surface barrier, e.g. light emitting diode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/12—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof structurally associated with, e.g. formed in or on a common substrate with, one or more electric light sources, e.g. electroluminescent light sources, and electrically or optically coupled thereto
    • H01L31/14—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof structurally associated with, e.g. formed in or on a common substrate with, one or more electric light sources, e.g. electroluminescent light sources, and electrically or optically coupled thereto the light source or sources being controlled by the semiconductor device sensitive to radiation, e.g. image converters, image amplifiers or image storage devices
    • H01L31/145—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof structurally associated with, e.g. formed in or on a common substrate with, one or more electric light sources, e.g. electroluminescent light sources, and electrically or optically coupled thereto the light source or sources being controlled by the semiconductor device sensitive to radiation, e.g. image converters, image amplifiers or image storage devices the semiconductor device sensitive to radiation being characterised by at least one potential-jump barrier or surface barrier
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K19/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic element specially adapted for rectifying, amplifying, oscillating or switching, covered by group H10K10/00
    • H10K19/901—Assemblies of multiple devices comprising at least one organic element specially adapted for rectifying, amplifying, oscillating or switching
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/30—Devices specially adapted for multicolour light emission
    • H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to a light-to-light conversion device, and particularly to a light-to-light conversion device having an intermediate electrode between a light receiving part and a light emitting part.
  • Non-patent Document 1 Patent Document 1
  • This is a phenomenon in which holes are accumulated in the organic semiconductor near the interface with the metal layer by light irradiation, and a large amount of electrons are tunneled from the metal layer into the organic semiconductor by the high electric field formed by the holes.
  • a combination of an organic semiconductor and a metal layer using such a phenomenon is referred to as a “photoelectric current multiplication element”.
  • Non-Patent Document 2 shows an example of the configuration.
  • reference numeral 12 denotes a photocurrent multiplication layer
  • 13 denotes a first electrode arranged on the light incident side
  • 14 denotes a light emitting layer
  • 15 denotes a hole transport layer
  • 18 denotes incident light applied to the photocurrent multiplication layer.
  • 19 is the emitted light.
  • Reference numeral 16 denotes a glass substrate on which the other electrode is provided.
  • the electrode force of 1 is also injected into the photocurrent multiplication layer 12 and reaches the light emitting layer 14.
  • the hole transport layer 15 supplies holes that combine with electrons when the light emitting layer 14 emits light.
  • an effect of amplifying light and an effect of converting wavelength can be obtained.
  • the former photoamplification effect is that more electrons than the number of incident photons are injected into the organic EL layer by the photocurrent multiplication effect, and the number of photons emitted by the light emission in the organic EL layer is injected into the photocurrent multiplication layer. This is because the number of incident photons becomes larger.
  • the latter wavelength conversion effect is due to the fact that the wavelength of light emitted from the organic EL layer depends on the material of the organic EL layer regardless of the wavelength of the incident light.
  • Non-patent Document 3 an element in which a photomultiplier element and an organic EL element are juxtaposed on the same substrate or an element in which they are stacked are known. Furthermore, when these layers are laminated, it is also known to insert an intermediate electrode at the junction between the light-to-light conversion part and the light emitting part in order to improve the purpose and characteristics of shielding incident light (Patent Document 4). ).
  • Patent Document 1 JP 2002-341395 A
  • Patent Document 2 JP 2002-76430 A
  • Patent Document 3 Japanese Patent Laid-Open No. 2002-100797
  • Patent Document 4 Japanese Patent Laid-Open No. 2000-91623
  • Non-Patent Document 2 "Applied Physics” Vol. 64 (1995), 1036
  • Non-Patent Document 3 The 49th JSAP Joint Lecture Meeting 28p— M— 10 Disclosure of Invention
  • An object of the present invention is to provide an optical one-optical conversion device having high spatial resolution in a stacked optical one-optical conversion device having an intermediate electrode inserted between a photomultiplier portion and a light emitting portion. .
  • the present invention has a light receiving portion having a layer containing a photoconductive organic semiconductor that causes a photocurrent multiplication phenomenon by light irradiation and a layer containing an organic electroluminescent material that emits light by current injection on the same substrate.
  • An optical-optical conversion device having an electrically separated intermediate electrode between light emitting portions is provided.
  • the present invention provides, as a light-to-light conversion device, a first electrode on which light from the outside is incident, and converts the light incident on the first electrode into electricity.
  • a light receiving portion, a light emitting portion that emits light by electricity converted in the light receiving portion, and a second electrode provided on the light emitting portion on the opposite side to the light receiving portion side are laminated, and the light receiving portion
  • An intermediate electrode is provided between the light emitting portion and the light emitting portion, and the intermediate electrode is partitioned into a plurality of electrically separated cells.
  • the area force of the largest cell among the plurality of cells of the intermediate electrode can be less than the electrode area of the smaller one of the first and second electrodes.
  • the intermediate electrode is electrically separated, light emission of the organic EL element power can be obtained only in the portion of the individual intermediate electrodes that has received the incident light. Spatial resolution can be achieved in the light emission of the EL element corresponding to the pattern of the intermediate electrode. Furthermore, since the light-to-light conversion device according to the present invention inserts the intermediate electrode, light emitted by the light-emitting portion is not reflected by the intermediate electrode and reabsorbed toward the light-receiving portion. Has light conversion efficiency. The light-to-light conversion device of the present invention only suppresses incident light leaking from between cells by laminating a layer having a function of scattering light between a plurality of cells of the intermediate electrode.
  • the optical-to-optical conversion device of the present invention has a wavelength resolving function by bringing a layer having a function of selecting the wavelength of incident light and EL light emission close to or in contact with the light receiving part and the light emitting part. It is possible to realize a device having both functions, so that a display in which optical-optical conversion devices are arranged in a matrix (for example, the optical-optical conversion devices of the present invention are arranged in a matrix.
  • Image intensifiers, optical amplification elements, optical switches, optical sensors, flexible sheet display devices for example, using the optical-optical conversion device of the present invention on a flexible substrate
  • it can be preferably used.
  • FIG. 1 is a cross-sectional view showing an example of a basic configuration of a light-to-light conversion device according to a third embodiment of the present invention having an intermediate electrode and patterning the intermediate electrode.
  • FIG. 2 is a plan view showing an example of a patterning of an intermediate electrode in the optical-optical conversion device of the present invention.
  • FIG. 3 is a cross-sectional view showing a basic configuration of a light-to-light conversion device with a wavelength selection layer inserted according to a second embodiment of the present invention.
  • FIG. 4 is a perspective view for explaining an example of the manufacturing process of the optical one-optical conversion device according to the present invention.
  • FIG. 5 is a cross-sectional view showing a configuration example of a conventional optical-optical conversion device.
  • FIG. 6 is a cross-sectional view showing an example of the basic configuration of a light-to-light conversion device having an intermediate electrode and patterning the intermediate electrode according to the first embodiment of the present invention.
  • FIG. 7 Cross-sectional view showing an example of a light-to-light conversion device ((a), (b)) in which layers having the function of scattering light are laminated between cells constituting the intermediate electrode (reference numerals 1, 2, (Omitted 6, 7 and 10)
  • hole is also referred to as “hole”.
  • FIG. 6 is a cross-sectional view showing an example of the basic configuration of the optical one-optical conversion device according to the first embodiment of the present invention.
  • the light-to-light conversion device according to this embodiment includes a first electrode 2 provided on the surface of a base substrate 1 made of a material such as glass, and a hole transport layer 6 formed on the first electrode 2.
  • the light emitting layer 5 formed on the opposite side of the hole transport layer 6 from the first electrode 2, the intermediate electrode 4 provided on the opposite side of the hole transport layer 6 from the light emitting layer 5, and the intermediate electrode 4 on the opposite side of the light-emitting layer 5 to convert light incident on the device into electricity, and the second on the opposite side of the intermediate electrode 4 with respect to the light-receiving unit 3
  • the first electrode 2 and the second electrode 7 are usually made of at least one of a metal oxide, a metal sulfate, a metal, or a combination force thereof. Quality is used.
  • the light receiving section 3 usually causes a photocurrent multiplication phenomenon by light irradiation.
  • the light emitting layer 5 and the hole transport layer 6 form a light emitting portion 10.
  • the intermediate electrode 4 provided between the light receiving portion 3 and the light emitting layer 5 is partitioned into a plurality of electrically separated cells.
  • the intermediate electrode is usually composed of a metal layer.
  • FIG. 2 is a plan view showing an example in which the intermediate electrode 4 is partitioned into a plurality of cells.
  • the intermediate electrode 4 is configured by providing a plurality of rectangular cells 22 in a matrix.
  • the size of each of the plurality of cells of the intermediate electrode may be different, but from the viewpoint of improving spatial resolution and optical-optical conversion efficiency, the largest cell
  • the area force of the first electrode and the second electrode is preferably less than the smaller electrode area of the first and second electrodes.
  • the lower limit is 0.000025%.
  • the size of the cell is not particularly limited, but from the viewpoint of improving spatial resolution, the cell diameter force is preferably 5 mm or less, preferably 1 mm or less, and the lower limit is usually 1 m, preferably 10 / zm.
  • the distance between adjacent cells is not particularly limited, but the distance between the cells is preferably 1 mm or less, preferably 100 ⁇ m or less, from the viewpoint of contrast with the emitted light due to the transmission of incident light.
  • the lower limit that is more preferred is usually 1 ⁇ m, preferably 5 ⁇ m.
  • the intermediate electrode 4 in the optical-optical conversion device may be patterned in an arbitrary shape.
  • the pattern shape include a circular shape, an elliptical shape, a rectangular shape (that is, a square shape, a rectangular shape), a rhombus shape, and a honeycomb shape, and the viewpoint power for improving the spatial resolution of the optical-optical conversion device of the present invention is also included. More preferably, a rectangular shape, a honeycomb shape, or a honeycomb shape, which can increase the pixel density of the intermediate electrode, is preferred. These shapes Includes those that are slightly distorted and those that have irregularities.
  • the cells 22 constituting the intermediate electrode 4 in the light-to-light conversion device may be arranged in a dot matrix.
  • the light emitting unit 10 immediately above the dot region 10 Only the part of ⁇ ⁇ emits light. Therefore, the dots of the intermediate electrode 4 corresponding to the pattern shape of the incident light emit light, and the pattern shape of the incident light can be reproduced. Further, by reducing the dot size of the intermediate electrode 4 and increasing the density, the spatial resolution (resolution) increases, and the reproducibility of the pattern shape of incident light can be further improved.
  • a layer 9 having a function of scattering light is provided so as to cover between the cells 22 of the cell 22 constituting the intermediate electrode 4 (in some cases, the outer edge of each cell and between the cells). They may be stacked (see Figure 7).
  • the viewpoint of the device manufacturing process and the adhesion at the interface between the light receiving part, the light emitting part, and the intermediate electrode are improved. It is also preferable from the viewpoint of device yield.
  • FIG. 3 is a cross-sectional view showing a basic configuration of an optical-to-optical conversion device according to the second embodiment of the present invention.
  • the optical one-optical conversion device according to this embodiment has basically the same configuration as the optical one-optical conversion device according to the first embodiment.
  • the difference from the first embodiment is that a wavelength selection layer 8 having a function of selecting wavelengths (colors) of incident light and outgoing light is provided. This wavelength selection layer 8 improves the wavelength resolution.
  • wavelength selection for incident light can be achieved.
  • the output light power S can be obtained only when green light is incident.
  • wavelength selection for the emitted light can be achieved. For example, only green When a wavelength selective layer that selectively transmits light is used, the emitted light can be obtained only when the light emitted from the light emitting unit 10 is green.
  • the layer having the function of selecting the wavelength of the incident light may be disposed in proximity to or in contact with both the light receiving unit 3 and the light emitting unit 10.
  • the wavelength selection layer 8 can also be patterned in the same manner as the intermediate electrode 4.
  • the pattern coordinates of the wavelength selection layer 8 on the light receiving unit 3 side and the light emitting unit 10 side may be aligned and laminated on both sides or at least one side of the patterned intermediate electrode 4.
  • the wavelength (color) selected by the light receiving unit 3 and the light emitting unit 10 at the same coordinate position may be the same, and pixels corresponding to RGB colors may be regularly arranged.
  • the input light is a full-color image
  • a full-color image similar to the input light according to the resolution of the intermediate electrode 4 can be output, so that the light-light having both spatial resolution and wavelength resolution can be output.
  • a conversion device can be made.
  • the color filter has three colors of red, blue and green arranged uniformly, and the position of the pixel of each color and the position of the cell of the intermediate electrode 4 in the plane of the color filter are In this case, when mixed light of red, blue, and green is applied to the color filter as incident light, the light transmitted through the color filter is wavelength-decomposed only to the pixel color of the transmitted color filter and input. The light is received by the light receiving unit 3 at an intensity corresponding to the light intensity of each color of the incident light. Since the optical amplification function of the optical one-optical conversion device of the present invention depends on the intensity of light incident on the light receiving unit 3, the intensity of light emitted from the light emitting unit 10 also changes in synchronization.
  • the wavelength selection layer 8 includes a color filter, an interference filter, an inorganic phosphor, an organic phosphor, a microresonator, a prism, a diffraction grating, and the like.
  • the wavelength selected by the wavelength selection layer 8 is not particularly limited, but infrared, visible light, near-ultraviolet region, etc. are preferable.
  • the light receiving unit 3 when the light receiving unit 3 is formed close to or in contact with the intermediate electrode 4, materials having different absorption wavelengths may be patterned as the light receiving unit 3. In this case, the light receiving unit 3 also has a function as a wavelength selection layer. In addition, as the light emitting unit 10, materials having different emission colors may be patterned and laminated on the opposite side of the intermediate electrode 4 from the light receiving unit 3. In this case, the light emitting unit 10 also has a function as a wavelength selection layer.
  • FIG. 1 is a cross-sectional view showing a basic configuration of an optical-optical conversion device according to a third embodiment of the present invention.
  • the optical one-optical conversion device according to this embodiment has basically the same configuration as the optical one-optical conversion device according to the first embodiment.
  • the difference from the first embodiment is that the light receiving unit 3 and the light emitting unit 10 are reversed. At this time, the polarity of the voltage applied from the outside to the first electrode and the second electrode also needs to be reversed.
  • two or more of the light-to-light conversion devices are installed on the same substrate, and the light emission color of at least some of the devices is different from the light emission color of the light emission units of other devices.
  • Such a configuration is also included.
  • This embodiment is preferable from the viewpoint of a device manufacturing process in which a large-sized device can be constructed only by juxtaposing a large number of optical one-optical conversion devices.
  • Examples of the base substrate 1 in the optical-to-optical conversion device of the present invention include glass, plastic, polymer film, silicon substrate, and the like as long as they do not change when these electrodes and layers are formed. It is done. When this substrate is opaque, it is preferable that the electrode force located on the side opposite to the base substrate 1 with respect to the light emitting portion 10 is transparent or translucent.
  • the first electrode 2 that is close to or in contact with the base substrate 1 and the second electrode 7 that sandwiches the light receiving part 3 and the light emitting part 10 between the first electrode 2 in the optical one-optical conversion device of the present invention are transparent.
  • metal oxides, metal sulfides, and metal thin films that are translucent, have high transmittance, and high electrical conductivity can be suitably used, and are appropriately selected depending on the organic layer to be used.
  • indium oxide, zinc oxide, tin oxide, and their composites such as indium 'tin' oxide (ITO), indium 'zinc' oxide, etc.
  • a film made of a material such as NESA, gold, platinum, silver, or copper is used, and ITO, indium “zinc” oxide, and tin oxide are preferable.
  • the production method include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.
  • the film thicknesses of the first electrode 2 and the second electrode 7 are forces that can be appropriately selected in consideration of light transmittance and electrical conductivity, for example, 10 nm to 10 ⁇ m, preferably It is 20 nm to l ⁇ m, more preferably 50 nm to 500 nm.
  • the organic EL layer functioning as the light emitting part 10 in the photoelectric conversion device of the present invention includes charge transport materials and light emitting materials used for low molecular weight organic EL elements, and polymer light emitting materials used for polymer organic EL elements. Materials are illustrated. Examples of light emission colors include light emission of intermediate colors and white in addition to light emission of the three primary colors of red, blue, and green.
  • Organic EL display as a material for low-molecular-weight organic EL devices (Co-authored by Shizuo Tokito, Chiba Adachi, Hideyuki Murata, Ohm Co., Ltd., 2004, first edition, first edition) 17-48 Fluorescent and phosphorescent light emitting materials, hole transport materials, electron block materials, hole block materials, and electron transport materials described on pages 83, 99 to 99, 101 to 120 are used to produce vacuum deposition methods, etc. Can be produced by a method. More specifically, as the hole transporting material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209988 are disclosed. No. 2-311591, No. 3-37 992, No. 3-152184, No. 11-35687, No. 11-217392, and No. 2000-80167. The thing etc. are illustrated.
  • Examples of phosphorescent light emitting materials further include triplet light emitting complexes. Specifically, for example, Ir (ppy), Btp Ir (acac) having iridium as a central metal, and platinum as a central metal. PtOEP
  • TTA And Eu
  • each layer is generally a force of 5 to 200 nm that is appropriately selected so that the light emission efficiency and the drive voltage have desired values.
  • the hole transport layer include 10-: LOOnm, and preferably 20-80 nm.
  • As a light emitting layer 10-100 nm is illustrated, and 20-80 nm is preferable.
  • the hole blocking layer 5 to 50 nm is exemplified, and 10 to 30 nm is preferable.
  • the electron injection layer include 10 to 100 nm, and 20 to 80 nm force S is preferable.
  • Examples of materials for polymer-type organic EL devices include “polymer EL materials” (Toshihiro Ohnishi, Tamami Koyama, Kyoritsu Publishing Co., Ltd., published in 2004, first edition), pages 33-58.
  • an organic electoluminescence device can be constructed by laminating a charge injection layer and a charge transport layer.
  • the hole transport material, the electron transport material, and the light emitting material of the polymer compound include W099Z13692 publication specification, WO99 / 48160 publication specification, GB2340304A, WOOOZ53656 publication specification, WOOl / 19834 ⁇ Open specification, WOOOZ55927 open specification, GB2348316, WO00Z46321 open specification, WO00Z06665 open specification, W099Z54943 open specification, W099Z5438 5 open specification, US5777070, WO98Z06773 open specification, WO97Z05184 open specification, WOOOZ35987 open specification, WOOOZ53 Published specification, WO01 / 34 722 published specification, W099Z24526 published specification, WO00Z22027 published specification, W O00Z22026 published specification, W098Z27136 published specification, US573636, W098 / 21262 published specification, US5741921, WO97Z09394 published specification, W096
  • Examples thereof include derivatives and copolymers thereof, and (co) polymers of aromatic amines and derivatives thereof.
  • the light-emitting material and the charge transport material may be mixed with the above-described light-emitting material or charge transport material for a low molecular weight organic EL device.
  • Examples of the thickness of the polymer light emitting layer include 5 to 300 nm, preferably 30 to 200 nm force S, and more preferably 40 to 150 nm.
  • the charge injection layer include a layer containing a conductive polymer, an anode material and a hole transport material included in the hole transport layer provided between the anode and the hole transport layer.
  • the charge injection layer is a layer containing a conductive polymer
  • the layer is provided adjacent to the electrode between at least one electrode and the light emitting layer.
  • Electrical conductivity of the conducting polymer 1 0-7 to small Ku the leakage current between the preferred instrument emitting pixels that SZcm least 10 at 3 SZcm less, 10- 5 S / cm or more 10 2 S / cm or less, more preferably tool 10- 5 S / cm or more 10 ZCM less is more preferable.
  • SZcm Normally in order to electrical conductivity of the conductive polymer 10- 7 SZcm least 10 3 SZcm below, doped with an appropriate amount of ions to the conductive polymer.
  • the kind of ions to be doped is an anion for a hole injection layer and a cation for an electron injection layer.
  • cation include polystyrene sulphonate ion, anoleno benzene sulfonate ion, camphor sulfonate ion and the like, and examples of cation include lithium ion, sodium ion, potassium ion, tetraptylammonium. -Um ion and so on.
  • the film thickness of the charge injection layer is, for example, 1 to 150 nm, and 2 to: LOOnm is preferable.
  • the material used for the charge injection layer may be appropriately selected in relation to the material of the electrode and the adjacent layer, polyarine and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylenediamine.
  • -Lene and its derivatives Polyethylene-lenylene and its derivatives, Polyquinoline and its derivatives, Polyquinoxaline and its derivatives, Conductive polymers such as polymers containing aromatic amine structures in the main chain or side chain; Metal phthalocyanines (Copper phthalocyanine etc.); Carbon etc. are illustrated.
  • the cathode and Z or the anode may be provided in contact with the cathode and Z or the anode.
  • a metal fluoride, a metal oxide, or an organic insulating material is used as the material of the insulating layer.
  • the material include metal fluorides and metal oxides such as alkali metals and alkaline earth metals.
  • the layers having the materials described so far (light-emitting layer and charge transport layer), the polymer is not included! /
  • the film formation method of the light-emitting layer, the charge transport layer and the charge injection layer is as follows.
  • the film is formed by a coating method or a printing method, and it is only necessary to remove the solvent by applying this solution and then drying it. However, the same method can be applied, which is very advantageous in manufacturing.
  • Film formation methods from solution include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen printing.
  • Application methods such as a printing method, a flexographic printing method, an offset printing method, a capillary coating method, a nozzle coating method, and an inkjet printing method can be used.
  • a charge injection material that is in the form of emulsion and dispersed in water or alcohol can be formed into a film by the same method as the solution.
  • the solvent is not particularly limited, but a solvent capable of uniformly dispersing the polymer material is preferable.
  • the solvent is a chlorine solvent such as chloroform, methylene chloride, dichloroethane, an ether solvent such as tetrahydrofuran, toluene, xylene, tetralin, -Sole, aromatic hydrocarbon solvents such as n-hexylbenzene and cyclohexylbenzene, aliphatic hydrocarbon solvents such as decalin and bicyclohexyl, ketones such as acetone, methylethyl ketone, and 2-heptanone Solvent, ethyl acetate, butyl acetate, ethyl cellulose Examples are ester solvents such as buacetate and propylene glycol monomethyl ether acetate.
  • an electron transport layer for facilitating electron transport to the light-emitting portion 10 is also provided for the intermediate electrode 4 force
  • the electron transport material a high molecular material that injects and transports electrons from the electrode
  • a ⁇ and ⁇ conjugated polymer or a polymer material containing an electron transporting group in the polymer can be used as appropriate. More specifically, the materials described in the literature describing the above hole transporting polymers can be used. It also includes the use in combination with low molecular weight electron transport materials.
  • the film thickness of the electron transport layer varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. ⁇ 1 ⁇ m, preferably 2 to 500 nm, more preferably 5 nm to 200 nm.
  • the hole-transporting material and the electron-transporting material used in the present invention have a light-emitting mechanism in addition to charge transport. It is also possible to use it.
  • This insolubilization process involves using a soluble precursor or a polymer having a soluble group to convert the precursor to a conjugated polymer by heat treatment or reducing the solubility by decomposing the soluble group.
  • a method using a hole transporting polymer having a crosslinking group in the molecule, or a method of mixing a monomer or macromer that causes a crosslinking reaction by heat, light, electron beam, or the like Illustrated.
  • Examples of the crosslinking group include a polymer having a bur group, a (meth) acrylate group, an oxetane group, a cyclobutadiene group, a gen group and the like in the side chain.
  • the introduction rate of these groups is not particularly limited as long as it is insolubilized in the solvent used for film formation of the electron transporting polymer. Examples are 0.1 wt% to 30 wt%, 0.5 wt% to 20 wt% is preferable, and lwt% to 10 wt% is more preferable.
  • the monomer or macromer that causes a crosslinking reaction is a compound having a weight average molecular weight of 2000 or less in terms of polystyrene, and has two or more vinyl groups, (meth) acrylate groups, oxetane groups, cyclobutadiene groups, and gen groups.
  • acid anhydride groups and Also exemplified are compounds capable of cross-linking reaction between molecules such as cinnamic acid.
  • those described in “Current Status and Prospects of UV'EB Curing Technology” supervised by Kunihiro Kashimura, published by CMC Publishing Co., Ltd. 20 2002, 1st edition, 1st edition, 2nd chapter
  • the purity affects the performance of the element such as charge transport characteristics and light-emitting characteristics.
  • Polymerization is preferably performed after purification by column chromatography, such as distillation, sublimation purification, or recrystallization.
  • the material for the photocurrent multiplication layer examples include 3, 4, 9, 10 perylene tetra force norevoxic 3, 4, 9, 10 bis (methinoreimide) (abbreviation Me-PTC), 3, 4, 9, 10 perylene tetra Carboxylic 3, 4, 9, 10 Bis (phenylethylimide), 3, 4, 9, 10 Perylenetetracarboxylic dianhydride, Imidazole'perylene, Copper phthalocyanine, Titanium phthalocyanine, Vanadyl phthalocyanine, Magnesium phthalocyan -, Metal-free phthalocyanine, naphthalocyanine, naphthalene, 2,9 dimethylquinacridone, unsubstituted quinacridone, pentacene, 6,13 pentacenequinone, 5,7,12,14 pentacent
  • a resin-dispersed material in which the above material is dispersed in a resin such as polycarbonate or polybulutyl can also be used.
  • the method for producing a photocurrent multiplication layer made of these materials include vacuum processes such as vacuum deposition, cluster deposition, and molecular beam deposition. Among these materials, those that can form soluble emulsions are dispersed in resin.
  • the mold material include a method of forming a film by the above-described coating method or printing method.
  • the film thickness of the photocurrent multiplication layer is generally 50 to: LOOOnm, preferably 100 to 800, more preferably 200 to 500.
  • the intermediate electrode 4 in the optical-optical conversion device of the present invention may be a further layer. However, it is preferable to combine two or more materials, especially three or more materials, because the performance of the light receiving unit 3 and the light emitting unit 10 can be further enhanced.
  • the material in contact with the light receiving portion 3 is formed from an aggregate of fine particles during film formation so that the interface between the light receiving portion 3 and the intermediate electrode 4 has a very fine concavo-convex structure force.
  • gold, silver, and the like can be used, but gold is preferable from the viewpoint of improving the efficiency of converting the light of the light receiving unit 3 into electricity.
  • dissimilar metals such as aluminum (A1) may be laminated on the intermediate electrode 4.
  • the thickness of the intermediate electrode is preferably 1 to lOOnm, more preferably 3 to 80nm, and still more preferably 5 to 50nm.
  • the material in contact with the light emitting section 10 is preferably a material having a small work function.
  • metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, norium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium And alloys of two or more of them, or one or more of them and one or more of gold, silver, platinum, copper, manganese, titanium, conoretol, nickel, tungsten, tin, graph Eight or graphite intercalation compounds are used.
  • alloys include magnesium silver alloy, magnesium indium alloy, magnesium aluminum alloy, indium silver alloy, lithium aluminum alloy, lithium-magnesium alloy, lithium indium alloy, calcium-aluminum alloy, etc. From the viewpoint of improving the luminous efficiency of the part, calcium, barium, and magnesium-silver alloy are preferable. Also, a laminated structure of two or more layers may be used. When combining two or more kinds of materials for the intermediate electrode, the materials are in the order from the side in contact with the light receiving unit 3 to the side in contact with the light emitting unit 10 (1) magnesium silver alloy Z lithium Z calcium Z barium ( 2) Silver Z Aluminum Z Nickel (3) Gold Z Silver is preferable. By doing so, the performance of each of the light receiving unit 3 and the light emitting unit 10 can be particularly efficiently extracted.
  • the film thickness can be appropriately selected in consideration of electrical conductivity and durability.
  • 1S For example, 10 nm to 10 ⁇ m, preferably 20 nm to l ⁇ m, more preferably 30 nm to 500 nm. .
  • the material of the layer 9 having the function of scattering light is laminated.
  • the material a material in which two or more compounds having different refractive indexes are mixed can be used.
  • high refractive index compounds such as metal oxides such as titanium oxide and aluminum oxide, metal composite oxides, and low refractive index compounds such as rosin, acrylic esters, methacrylic esters, and the like.
  • Spherical hollow fine particles obtained by polymerizing monomers such as acid esters and styrene, porous fine particles, multi-layered fine particles such as core-shell structures, low refractive index compounds such as fluororesin fine particles and hollow glass fine particles
  • a combination with a compound having a high refractive index such as an organic titanium compound is preferred.
  • a printing method such as a gravure coating method, a spray coating method, a screen printing method, a flexographic printing method, and an offset printing method can be used.
  • the material of the layer having the function of scattering light has photosensitivity like a photoresist, it can be patterned with light.
  • the light-to-light conversion device of the present invention may have layers other than the first electrode, the light receiving unit, the light emitting unit, the second electrode, and the intermediate electrode.
  • FIG. 4 is a perspective view schematically illustrating an example of the manufacturing process of the light-to-light conversion device of the present invention.
  • an ITO transparent electrode patterned as the first electrode 2 is formed on the base substrate 1. Then, copper phthalocyanine was deposited on the first electrode 2 as a hole transporting layer 6 by vacuum deposition of 10 nm, 4,4, 1 bis [N- (1-naphthyl) N ferroamino] biphenyl (NPD) by 50 nm. .
  • Alq was vacuum deposited to form a film.
  • the layers were sequentially formed by a single vacuum.
  • the intermediate electrode 4 was formed by lOnm vacuum deposition without using a metal.
  • a photoelectric element made of an organic semiconductor material and functioning as the light receiving unit 3 is formed on the intermediate electrode 4.
  • 3, 4, 9, 10-perylenetetracarboxylic dianhydride (NTCDA) was formed in a thickness of 80 ° C., and then 30 times of gold was formed as the second electrode 7 by vacuum deposition.
  • a light-to-light conversion device 120 was produced.
  • Example 2 a manufacturing process of the optical-light conversion device 100 according to Embodiment 3 of the present invention shown in FIG. 1 will be described.
  • the positions of the light receiving unit 3 and the light emitting unit 10 shown in the light-to-light conversion device 120 of Example 1 are different.
  • the ITO transparent electrode patterned as the first electrode 2 on the base substrate 1 as a photocurrent multiplication layer functioning as the light receiving portion 3 made of an organic semiconductor material, 3, 4, 9, 10 —Perylenetetracarboxylic dianhydride (NTCDA) was deposited to 800 nm.
  • NTCDA Perylenetetracarboxylic dianhydride
  • a light-light conversion device was produced in the same manner as in Example 2 except that the intermediate electrode 4 was not provided.
  • Example 2 and Comparative Example 1 the characteristics of the produced optical-to-optical conversion device are as follows: an external voltage (20V) in a state where a laser beam having a wavelength of 400 nm and a light intensity of 56 W / cm 2 is irradiated from the light receiving unit 3 side. The luminance of the light emitted from the light emitting unit 10 at that time is measured with a luminance meter (trade name: BM-8, manufactured by Topcon), and finally the ratio of the number of emitted photons to the number of incident photons is determined. The light-to-light conversion efficiency was calculated by conversion.
  • BM-8 luminance meter
  • Example 1 As shown in Table 1, it was confirmed that the light-to-light conversion devices of Example 1 and Example 2 exhibited higher light-light conversion efficiency than Comparative Example 1.
  • the light-to-light conversion device of Example 1 shows that the light emitted from the light-emitting portion is observed through the ITO transparent electrode, and exhibits higher light-to-light conversion efficiency than the light-to-light conversion device of Example 2. It was also recognized. Furthermore, it was confirmed that both the light-to-light conversion devices of Example 1 and Example 2 were observed to emit light only from the portion where the cells constituting the intermediate electrode were present, and had high spatial resolution.
  • the light-to-light conversion device provides high spatial resolution and light by providing the intermediate electrode, which is cut into a plurality of electrically separated cells, between the light receiving unit and the light emitting unit. -Has light conversion efficiency.
  • the light-light conversion device of the present invention can achieve higher light-light conversion efficiency by laminating a layer having a function of scattering light between the plurality of cells of the intermediate electrode.
  • Such a light-light conversion device of the present invention is a display device in which light-light conversion devices are arranged in a matrix, an image intensifier, a light amplification element, a light switch, a light sensor, or a flexible sheet display device. It can be preferably used.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Photo Coupler, Interrupter, Optical-To-Optical Conversion Devices (AREA)

Abstract

Le problème à résoudre dans le cadre de la présente invention consiste à mettre à disposition un dispositif de conversion de lumière en lumière à couches comportant une électrode intermédiaire insérée entre une unité de réception de lumière et une unité d'émission de lumière et possédant une résolution spatiale élevée. La solution proposée consiste en une électrode intermédiaire qui est disposée entre une unité de réception de lumière formée par un élément d'amplification de photocourant et une unité d'émission de lumière formée par une couche EL organique. L'électrode intermédiaire est isolée électriquement. Il est ainsi possible d'obtenir un dispositif de conversion de lumière en lumière possédant une forte efficacité de conversion de lumière en lumière et une excellente résolution spatiale.
PCT/JP2007/061524 2006-06-09 2007-06-07 Dispositif de conversion de lumière en lumière WO2007142287A1 (fr)

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CA2665047A1 (fr) * 2006-09-29 2008-04-10 University Of Florida Research Foundation, Inc. Procede et appareil de detection et de presentation d'ir.
MX2012013643A (es) 2010-05-24 2013-05-01 Univ Florida Metodo y aparato para proporcionar una capa de bloqueo de carga en un dispositivo de conversion ascendente de infrarrojo.
CN105742395B (zh) * 2011-02-28 2019-02-15 佛罗里达大学研究基金会有限公司 带有增益(ec)的上转换器件和光检测器
EP2727154B1 (fr) 2011-06-30 2019-09-18 University of Florida Research Foundation, Inc. Procédé et appareil permettant de détecter un rayonnement infrarouge avec gain
WO2017039774A2 (fr) 2015-06-11 2017-03-09 University Of Florida Research Foundation, Incorporated Nanoparticules à absorption d'ir monodispersées et procédés et dispositifs associés
KR102229319B1 (ko) * 2019-02-27 2021-03-19 한국과학기술연구원 색상 제어가 가능한 박막 태양전지 및 이의 제조방법
JPWO2022144678A1 (fr) * 2020-12-29 2022-07-07

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JPS5893293A (ja) * 1981-11-30 1983-06-02 Hitachi Ltd 光増幅器
JPS6388872A (ja) * 1986-10-01 1988-04-19 Komatsu Ltd 光メモリ
JPH0637353A (ja) * 1992-06-30 1994-02-10 Nichia Chem Ind Ltd 固体映像変換素子
JP2000091623A (ja) * 1998-09-10 2000-03-31 Futaba Corp 光変調素子

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
JPS5893293A (ja) * 1981-11-30 1983-06-02 Hitachi Ltd 光増幅器
JPS6388872A (ja) * 1986-10-01 1988-04-19 Komatsu Ltd 光メモリ
JPH0637353A (ja) * 1992-06-30 1994-02-10 Nichia Chem Ind Ltd 固体映像変換素子
JP2000091623A (ja) * 1998-09-10 2000-03-31 Futaba Corp 光変調素子

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