WO2001067823A1 - Element electroluminescent organique et polymere photosensible - Google Patents

Element electroluminescent organique et polymere photosensible Download PDF

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Publication number
WO2001067823A1
WO2001067823A1 PCT/JP2001/001734 JP0101734W WO0167823A1 WO 2001067823 A1 WO2001067823 A1 WO 2001067823A1 JP 0101734 W JP0101734 W JP 0101734W WO 0167823 A1 WO0167823 A1 WO 0167823A1
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group
organic electroluminescent
electroluminescent device
photosensitive
layer
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PCT/JP2001/001734
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English (en)
Japanese (ja)
Inventor
Shouko Ichinosawa
Yoshiharu Sato
Tomoyuki Ogata
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Mitsubishi Chemical Corporation
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Priority to AU36107/01A priority Critical patent/AU3610701A/en
Publication of WO2001067823A1 publication Critical patent/WO2001067823A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • 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
    • H10K59/80—Constructional details
    • H10K59/875—Arrangements for extracting light from the devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H10K50/155—Hole transporting layers comprising dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine

Definitions

  • the present invention relates to an organic electroluminescent device and a novel photosensitive polymer. More specifically, the present invention relates to a thin film device that emits light by applying an electric field to a light emitting layer made of an organic compound. Background art
  • thin-film electroluminescence (EL) devices include inorganic materials such as ZnS, CaS, and SrS, which are II-V group compound semiconductors, as well as Mn and rare earth elements, which are emission centers. (Eu, Ce, Tb, Sm, etc.) is commonly used.
  • EL devices made from the above inorganic materials are:
  • Figure 1 shows the principle of the optical interference effect.
  • the light that has exited the light-emitting layer and the light that has been reflected at the ITO / glass interface after exiting the light-emitting layer interfere with each other.
  • the interference condition is given by the following equation, where L is the difference in optical distance between the direct light and the reflected light:
  • organic layer means the entire “layer composed of an organic compound existing between the anode and the cathode”, and includes, for example, a light-emitting layer and a hole injection layer described later.
  • FIG. 2 shows the results of the optical interference characteristics calculated at an emission wavelength corresponding to each of the three primary colors of blue (460 nm), green (520 nm), and red (625 nm), with the ITO film thickness being 100 nm.
  • the optimum film thickness of the element differs depending on the emission color: for example, in the hole transport layer film thickness where the blue emission intensity has the maximum value, the red emission intensity has the minimum value c
  • the first hole transport layer thickness at which the emission intensity reaches a maximum value is 50 feet or less, and considering the possibility of element short-circuiting. It is not a practical film thickness.
  • the thickness of the hole transport layer at which the light emission intensity reaches a maximum value is about 150 nm, and there is a possibility that the drive voltage may increase with the current conductivity of the hole transport material. 3.
  • pixels are formed by a deposition process using a shadow mask. Therefore, when applied to a multi-color or full-color display, the deposition thickness must be changed for each sub-pixel. It takes time.
  • the main cause of degradation is the degradation of the thin film shape of the organic layer.
  • the deterioration of the thin film shape is caused by crystallization (or aggregation) of the organic amorphous thin film, which is caused by a temperature rise due to heat generation or the like during element driving.
  • this low heat resistance is mainly due to the low glass transition temperature (hereinafter abbreviated as Tg) of the material.
  • Tg glass transition temperature
  • N, N'_diphenyl-N, N '-(3-methylphenyl) -1 ,,-biphenyl-4,4'-diamine (usually called TPD) has a Tg of 60 ° C and a star.
  • the Tg of the burst-type aromatic triamine is 75 ° C (J. Phys. in., Vol. 97, p. 6240, 1993).
  • the Tg of 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl having a naphthyl group is 96 ° C. (IEICE Technical Report, 0ME95-54, 1995), all of which have highly symmetric structures.
  • the organic amorphous thin film formed from these aromatic amine compounds crystallizes due to a rise in temperature, and causes an interdiffusion phenomenon in a two-layer device structure of a hole transport layer and a light emitting layer. .
  • deterioration phenomena such as light emission characteristics of the device, particularly, a decrease in luminance and an increase in drive voltage appear, and eventually lead to a reduction in drive life.
  • Polyvinylcarbazole has a high Tg of 200 ° C, but has low durability due to problems such as trapping holes.
  • the driving life of polysilane is as short as several seconds due to light deterioration and the like.
  • Polyphosphazene has a high ionization potential and does not exhibit properties superior to conventional aromatic diamines.
  • C a hole in which an aromatic diamine compound is dispersed in polycarbonate ⁇ PMMA by 30 to 80% by weight.
  • a transport layer has been studied (Jpn. J. Appl. Phys., Vol. 31, p. L960, 1992)
  • a low-molecular compound acts as a plasticizer to lower Tg, and the device characteristics are also aromatic diamine. It is lower than when the compound is used alone.
  • a polyether containing aromatic diamine which is a hole-transporting polymer, having a Tg exceeding 200 ° C is disclosed.
  • the properties and stability are not sufficient (see JP-A-9-188756).
  • JP-A-9-188756 there is a report of a hole transport film in which a hole transport material is dispersed in an organic binder having a crosslinked structure. In this case, if the amount of the hole transporting material dispersed in the film is small, the hole transporting property is insufficient.
  • the ratio becomes large, it acts like a plasticizer and acts as a plasticizer to improve the durability and the heat
  • the properties are reduced, and the hole transport material may agglomerate or crystallize.
  • it is also necessary to ensure the compatibility between the binder and the hole transport material, which increases the restrictions on the material, which makes it practically difficult.
  • the method of dispersing the hole transport material in the organic binder has not yet achieved sufficient characteristics.
  • the contact between the anode and the hole transport layer is important.
  • the hole injection layer between the anode and the hole transport layer in order to improve the contact between the two layers.
  • the conditions required for the material used for the hole injection layer are that a uniform thin film can be formed with good contact with the anode and that it is thermally stable, that is, the melting point and the glass transition temperature are high. It is mentioned. Furthermore, the ionization potential is low, holes can be easily injected from the anode, and the hole mobility is high.
  • Starburst-type aromatic triamines have the advantage of low ionization potential and good transparency, but are inferior in heat resistance due to their low glass transition point and melting point, and have low stability to local heating during continuous operation. Bad, ⁇ temperature drop and voltage rise are problems.
  • Conjugated polymers such as poly (vinylenevinylene), poly (p-phenylenevinylene), and poly (vinylene) have problems in the production process due to insufficient solubility.
  • a hole injection layer composed of a low-molecular-weight hole transport material and an electron-accepting compound is formed by a vacuum evaporation method.
  • a vacuum evaporation method Japanese Patent Application Laid-Open No. 11-251067.
  • the organic electroluminescent device has a serious problem in improving the color purity and the stability of the device for practical use.
  • the high voltage at the time of driving the organic electroluminescent device, and the unstable stability and emission characteristics including heat resistance are major problems for light sources such as facsimile machines, copiers, and backlights for liquid crystal displays.
  • Color purity This is an undesirable characteristic for a display device such as a full-color display. This is particularly serious when considering applications to in-vehicle displays.
  • the present inventor has conducted intensive studies in view of the above situation, and as a result, by using a conductive resin layer and adjusting the thickness of the layer, each color can be increased without increasing the drive voltage of the element. In each case, it was found that an element having the maximum light interference effect could be formed.
  • the gist of the present invention is that the substrate has at least two or more minimum light emitting units showing different light emission colors,
  • Each minimum light emitting unit has a laminated structure having a light emitting layer and an optional layer as necessary between at least an anode and a cathode,
  • the light emitting layer or any layer is a resin layer formed using a photosensitive composition
  • the organic electroluminescent device according to the present invention is characterized in that the resin layer has a different thickness between the minimum light-emitting units that emit different colors.
  • the gist of the present invention is an organic electroluminescent device having at least an anode, a cathode, and a resin layer on a substrate,
  • the resin layer is patterned using a photosensitive composition, and the photosensitive composition has a photosensitive group on a side chain and a charge transporting group on a main chain or a side chain.
  • An organic electroluminescent device characterized by containing a polymer.
  • FIG. 1 is a diagram illustrating an optical interference effect in the organic electroluminescent device of the present invention.
  • Figure 2 Diagram showing light interference characteristics at emission wavelengths corresponding to blue, green, and red.
  • Figure 3 Diagram showing the difference in the emission spectrum shape of the organic electroluminescent device depending on the presence or absence of the light interference effect.
  • Figure 4 Energy level diagram showing the relationship between ionization potential and electron affinity.
  • FIG. 5 is a schematic cross-sectional view showing one example of the organic electroluminescent device of the present invention.
  • FIG. 6 is a schematic sectional view showing another example of the organic electroluminescent device of the present invention.
  • FIG. 7 is a schematic sectional view showing another example of the organic electroluminescent device of the present invention.
  • FIG. 8 1 H—NMR spectrum of the polymer of the present invention obtained in Example 1.
  • FIG. 9 1 H—NMR spectrum of the polymer of the present invention obtained in Example 2.
  • Figure 10 Diagram showing the voltage characteristics of the sample obtained in Test Example 4.
  • the thickness of the resin layer provided in the element is adjusted. Effectively improve the color purity of each minimum emission unit.
  • the organic electroluminescent device which has a light-emitting layer formed of an aluminum complex of 8-hydroxyquinoline, which is typically used in organic electroluminescent devices and has the structure shown in Fig. 1, has a light interference effect.
  • Figure 3 shows the results of the introduction.
  • the thickness of the ITO is 10Onm, and when the interference effect on the wavelength of 52Onm is maximized, the thickness of the hole transport layer becomes 180nm. Normally, in a device in which the light interference effect is not considered, the thickness of the hole transport layer is about 70 nm.
  • FIG. 3 shows the emission spectra of the devices having the hole transport layers having different thicknesses.
  • the light emitting portion on the long wavelength side is reduced compared to the device not optimized, and the half width of the spectrum is narrowed.
  • the values of the CIE chromaticity coordinates are as follows: the element with a hole transport layer with a thickness of 70 nm is (0.3347, 0.536), while the hole transport layer with a thickness of 180 nm is The device has (0.310, 0.562), which is improved from yellow-green to green.
  • this method using the light interference effect can be applied to red light emission and blue light emission, and can be said to be an effective method for realizing a full-color display.
  • the minimum emission units of three colors of RGB are provided is described as an example.However, if the organic electroluminescent element has the minimum emission units of two or more colors on the same substrate, the effect of the present invention can be utilized. It is. Of course, the color may be other than RGB.
  • the resistivity of general organic compounds is about 10 to 10 ⁇ ⁇ cm.
  • the resin layer of the present invention is formed using such a material, if the layer is thick, the driving voltage of the element may increase as described above. Therefore, the resistivity of the resin layer is preferably about 10 to 10 ⁇ ⁇ cm.
  • Such an organic electroluminescent device uses a photosensitive composition containing a photosensitive polymer having a photosensitive group in a side chain and a charge transporting group in a main chain or a side chain. , Can be easily manufactured.
  • a resin layer is sequentially formed in the minimum emission unit of each color.
  • the application step 1) by selecting the optimum film thickness for each color of the minimum emission unit, a resin layer having a different film thickness for each color can be formed. Specifically, for example, the concentration (viscosity) of the coating solution and the number of rotations of the spin coater may be adjusted for each color.
  • the resin layer formed by patterning for each color is sandwiched directly between the anode and the cathode or via an optional layer provided as necessary (the resin layer is a light emitting layer). Or as an optional layer provided between the anode and the cathode as required.In particular, the layer is used as a light-emitting layer or between the anode and the light-emitting layer.
  • a structure provided as a hole injecting / transporting layer is preferred A structure provided as a hole injecting / transporting layer is most preferred.
  • the photosensitive composition used in the present invention may be a photo-curable type or a photo-solubilizable type, but is preferably a photo-curable type.
  • the photo-curable type will be described.
  • the layer formed using the photocurable photosensitive composition is cured and insolubilized by photocrosslinking, etc., to improve the durability of the layer and to remove the non-insolubilized portion with a solvent or the like. Thereby, layer patterning becomes possible, and the device fabrication process is simplified.
  • the photosensitive polymer of the present invention has a charge-transporting group in the same molecule, and the charge-transporting group may be electron-donating or electron-accepting. It is electron donating.
  • the charge-transporting group may be electron-donating or electron-accepting. It is electron donating.
  • a case having an electron donating group will be described.
  • the photosensitive polymer of the present invention itself has a hole transporting property because it contains an electron donating group in the same molecule, an electron donating compound is added to a composition containing a usual photosensitive resin.
  • a composition ratio (the ratio of the photosensitive group to the electron donating group in the composition) depends on the film forming property. ) Is not limited, so that the hole transport property can be kept high.
  • the conductivity of the layer can be increased and the voltage of the device can be reduced.
  • a photosensitive polymer having a photocrosslinkable group (photosensitive group) and a hole transporting group (electron donating group) in the same molecule is used as the resin layer forming composition of the present invention. Therefore, one material can fulfill the two roles of the formation of the minimum emission unit by pattern formation and the hole transport, and the properties can be sufficiently exerted.
  • the layer of the present invention which is formed by using the photosensitive composition and patterned by light irradiation, is unnecessary for a solvent. Therefore, it is possible to form a layer on the layer by a coating method using a solvent. Since a layer containing a low-molecular compound as a main component is soluble in a solvent, it was not possible to stack one or more layers on an electrode and a layer containing a high-molecular compound as a main component. .
  • a polymer layer can be further formed on the resin layer formed using the photosensitive composition. It is also possible to use a light-emitting layer. Therefore, it is preferable because the range of selection of the material of the organic electroluminescent element is widened and the degree of freedom in element design is increased.
  • the photosensitive group in the photosensitive polymer of the present invention may be any group that exerts a function of curing or solubilizing the polymer having the photosensitive group by exposure. This includes, but is not limited to, photo registration Examples thereof include photosensitive groups used for photopolymerization, photodimerization, and photolysis. Above all, since there is no gas generation or volume shrinkage, a photopolymerization type, a photodimerization type and the like are preferable. In particular, a group containing an ethylenically unsaturated double bond such as a cinnamoyl group, a cinnamilidene group, a vinyl group, and an acryloyl group is preferable.
  • the electron donating group refers to a group in which electrons are given to a partner by a resonance effect or an induction effect to generate a hole, and the substituent constant in the Hammett rule tends to be zero. Things.
  • an electron-accepting group is a group that attracts electrons from a partner, and refers to a group that tends to be ⁇ 7> 0.
  • the electron donating group in the photosensitive polymer of the present invention is not limited to this. Examples thereof include groups having an alkyl group, an alkoxy group, and primary, secondary, and tertiary amino groups.
  • the electron donating group may be contained in the main chain of the photosensitive polymer or may be contained as a side chain, but is preferably provided as a side chain via a divalent aromatic group. In this case, it is bonded to the main chain. Particularly preferred is a case where a group having a primary, secondary or tertiary amino group is bonded to the main chain via a divalent aromatic group.
  • a vinyl polymer is preferred, and among them, a copolymer having the following polymerized structural units (II) and (III) is particularly preferred.
  • Ar 1 represents a divalent aromatic group which may have a substituent
  • Ar 2 and Ar 3 each independently represent an aromatic group which may have a substituent R to R each independently represent a hydrogen atom, an optionally substituted alkyl group or an aromatic group
  • Y and Z each represent a direct bond or a divalent linking group.
  • the resin layer in the organic electroluminescent device of the present invention when used as a light emitting layer, it may be a layer containing a fluorescent dye as necessary.
  • the conditions required for a hole-injecting / transporting layer forming material include high hole injection efficiency from the anode and efficient transport of the injected holes. Material.
  • the ionization potential is small, the transparency to visible light is high, the hole mobility is large, the stability is high, and impurities that can become traps are produced. It is required that it hardly occurs at the time and use.
  • Ar is a divalent benzene ring, a naphthalene ring, An anthracene ring or a biphenyl group, wherein the substituent is a halogen atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group; an alkenyl group such as a vinyl group; a methoxycarbonyl group; A C 2-7 alkoxycarbonyl group such as a ethoxycarbonyl group; a C 1-6 alkoxy group such as a methoxy group and an ethoxy group; an aryloxy group such as a phenoxy group, a benzyloxy group; a getylamino group; And a dialkylamino group such as a propylamino group.
  • an alkyl group having 1 to 3 carbon atoms such as a methyl group or an ethyl group
  • an alkenyl group such as a vinyl group
  • Ar and Ar are preferably each independently substituted with a substituent such as phenyl, naphthyl, anthryl, pyridyl, and tria.
  • a substituent such as phenyl, naphthyl, anthryl, pyridyl, and tria.
  • a C27 alkoxy radical such as a methoxycarbonyl group or an ethoxycarbonyl group; a C27 alkoxy group such as a methoxy group or an ethoxy group; an aryl group such as a phenoxy group or a benzyloxy group.
  • R to R each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic group which may have a substituent.
  • substituent of the alkyl group include a methoxy group and a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom.
  • substituent of the aromatic group a methyl group, a methoxy group, or Examples include halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom.
  • RR is preferably an alkyl group having 16 carbon atoms such as a hydrogen atom, a methyl group or an ethyl group; an aromatic ring group such as a phenyl group, a naphthyl group, an anthryl group or a tolyl group, particularly preferably Represents an aryl group.
  • Y and Z represent a direct bond or a divalent linking group.
  • Is a linking group, to one CR 2 CR 3 R 4 group, one CO- group or a CRCR - groups attached at 'group (RR' is arbitrary), a conjugated system between the two groups Preferred to form.
  • Specific examples of the linking group include the following groups. k represents an integer of 1 or more, and is preferably 14.
  • the ratio of (II) structure to (III) structure in one molecule depends mainly on the photosensitivity caused by the (II) structure and the level of hole transportability mainly caused by the (III) structure However, it is usually 1: 9 to 9: 1.
  • the photosensitive polymer having a polymerized structural unit represented by the general formulas ( ⁇ ) and (III) of the present invention does not impair the performance of the present invention. It may have a repeating unit derived from another radically polymerizable monomer and may contain a plurality of types of polymerized structural units corresponding to general formulas (11) and (III). If the amount of the repeating unit other than the II) structure or (I II) structure is too large, the photocurable property of the photosensitive polymer and the hole transport property will be reduced. Preferably, it is at most 20 mol%, more preferably 0 mol%.
  • the weight-average molecular weight of the photosensitive polymer is not particularly limited, but is usually about 1,000 to 1,000,000.
  • the element is required to have a heat resistance of 90 ° C or more.
  • the photosensitive polymer of the present invention has a Tg of 90 ° C. or higher.
  • the photosensitive polymer of the present invention can be obtained, for example, by combining an electron-donating group-substituted vinyl monomer and a photosensitive group-substituted vinyl monomer with 2,2,1-azobisisobutyronitrile (AIBN), 2,2,1-azobis It is synthesized by radical copolymerization in an organic solvent such as toluene using a known photopolymerization initiator such as (2-methylbutyronitrile).
  • polymerized structural units represented by the general formulas (II) and (III) are shown in Tables 2 and 3, but are not limited thereto.
  • a resin layer having an effective Tg of 90 ° C. or more can be formed.
  • the photosensitive composition By using a resin layer made of an amorphous thin film that has improved heat resistance and is not easily crystallized as a hole injecting / transporting layer, it is particularly possible to provide a structure in which the layer is in contact with the light emitting layer.
  • the photosensitive composition also sufficiently is c the present invention can be suppressed at a high temperature of the molecular interdiffusion the above 90 ° C at the interface between the light emitting layer further electron-accepting compound May be contained.
  • a mixture of a photosensitive polymer having a high Tg and an electron-accepting compound it becomes possible to improve not only the heat resistance but also the emission characteristics of the device. That is, by mixing an electron-accepting compound with an electron-donating group-containing polymer, charge transfer occurs, and as a result, holes, which are free carriers, are generated, and the electric conductivity of the layer is reduced. It will be higher. Since a layer having such a composition can improve the electrical junction between the organic layer and the anode, when this layer is used as a layer in contact with the anode, a so-called hole injection layer, the driving voltage decreases and This is particularly preferable because the stability during continuous driving is also improved.
  • the content of the electron-accepting compound, the photosensitive polymer arbitrary preferable in the range of 0.1 to 50 by weight 0/0. More preferably, a concentration range of 1 to 30% by weight is desirable for practical characteristics.
  • the electron-accepting compound may be any as long as it causes charge transfer with the above-mentioned photosensitive polymer, but as a result of investigations by the present inventors, the ionization potential of the photosensitive polymer: P (polymer ) And the electron affinity of the electron-accepting compound (Acceptor): EA (Acceptor)
  • the ionization potential and electron affinity are determined based on the vacuum level. It is.
  • the ionization potential is defined as the energy required to emit an electron at the HOMO (highest occupied molecular orbital) level of a substance to the vacuum level, and the electron affinity is determined by the electron at the vacuum level being the LUMO (minimum vacancy) of the substance.
  • LUMO minimum vacancy
  • Molecular orbital It is defined as the energy that falls to a level and stabilizes.
  • the difference between the ionization potential at the HOMO level of the photosensitive polymer shown in FIG. 4 and the electron affinity at the LUMO level of the electron-accepting compound is preferably 0.7 eV or less.
  • the electron affinity can be obtained by subtracting the optical band gap from the above-mentioned ionization potential, or from the above-mentioned formula from the electrochemical reduction potential. Can be obtained in the same way.
  • the relational expression between the ionization potential and the electron affinity is obtained by using an oxidation potential and a reduction potential.
  • the electron-accepting compound in the present invention is not particularly limited as long as it satisfies the above relational formula.
  • X represents a halogen atom
  • rings A, B and C each independently represent a phenyl group which may have a substituent.
  • electron-accepting compound represented by the general formula (I) include the following compounds.
  • the photosensitive composition of the present invention may be a binder resin other than the above-described photosensitive polymer or various other resins other than the electron-accepting compound as long as the performance of the resin layer or the photosensitive composition is not performed. It may contain other components such as additives.
  • the organic electroluminescent device of the present invention will be described with reference to the drawings. However, the organic electroluminescent device of the present invention is not limited to the structure (layer structure) described in the specification.
  • FIG. 5 is a cross-sectional view schematically showing an example of the structure of the organic electroluminescent device of the present invention.
  • the organic electroluminescent device of the present invention is not limited to this structure.
  • 1 represents a substrate
  • 2 represents an anode
  • 3 represents a hole injection layer
  • 5 represents a light emitting layer
  • 7 represents a cathode.
  • FIG. 1 an example of an element having a “resin layer” as a hole injection layer 3 which is a feature of the present invention.
  • the substrate 1 serves as a support for the organic electroluminescent device, and a quartz-glass plate, a metal plate or a metal foil, a plastic film-sheet, or the like is used.
  • a glass plate or a plate made of a transparent synthetic resin such as polyester, polymethacrylate, polycarbonate, or polysulfone is preferable.
  • a synthetic resin substrate it is necessary to pay attention to gas barrier properties. If the gas barrier property of the substrate is too low, the organic electroluminescent element may be deteriorated by outside air passing through the substrate, which is not preferable. Therefore, one of the preferred methods is to provide a dense silicon oxide film on one or both sides of the synthetic resin substrate to ensure gas barrier properties.
  • An anode 2 is provided on the substrate 1, and the anode 2 plays a role of injecting holes into the hole injection layer 3.
  • This anode is typically made of a metal such as aluminum, gold, silver, nickel, palladium, platinum, a metal oxide such as an oxide of indium and / or tin, a metal halide such as copper iodide, or a carbon. It is composed of black or conductive polymers such as poly (3-methylthiophene), polypyrrole, and polyaniline.
  • the anode 2 is usually formed by a sputtering method, a vacuum evaporation method, or the like in many cases.
  • the anode 2 can be formed.
  • a conductive polymer a thin film can be formed directly on the substrate 1 by electrolytic polymerization, or the anode 2 can be formed by applying a conductive polymer on the substrate 1 (Appl. Phys. Lett., Vol. 60, p. 2711, 1992).
  • the anode 2 may have a multilayer structure formed by laminating different substances. The thickness of the anode 2 depends on the required transparency.
  • the visible light transmittance is usually desired to be 60% or more, preferably 80% or more. In this case, the thickness is usually 5 to 1000 nm, preferably. Or about 10 to 500 nm. If opaque, the anode 2 may be as thick as the substrate 1.
  • a hole injection layer 3 formed using the photosensitive polymer of the present invention and, if necessary, a photosensitive composition containing an electron-accepting compound is provided.
  • the hole injection layer is formed by a coating method
  • the photosensitive polymer, an electron-accepting compound, if necessary, a binder that does not trap holes, a resin, a coating improver, etc. are mixed in a suitable solvent to prepare a photosensitive composition.
  • This is applied onto the anode 2 by a known coating method such as spin coating or dip coating, and dried.
  • the dried photosensitive composition layer is irradiated with light through a photomask using an exposure light source such as a halogen lamp. Patterning is performed by removing the non-insolubilized portion (uncured portion) with a solvent, etc., to obtain the desired drawing pattern (pattern formation).
  • the patterning simplifies the device fabrication process, and the photocrosslinking cures the layer, which also helps to improve the durability of the layer.
  • the thickness of the hole injection layer 3 is usually 5 to 1000 nm, preferably 10 to 500 nm.
  • the thickness of the resin layer of the present invention is slightly different in each minimum light emitting unit.
  • variation in film thickness due to uneven coating is usually It is 10% or less of the set film thickness, and the difference in the film thickness in the resin layer of the present invention is even larger. That is, in the present invention, the difference in the film thickness between the minimum emission units of different colors is provided more than the difference in the film thickness between the minimum emission units of the same color. 5 is provided.
  • the light emitting layer 5 is formed of a compound capable of efficiently transporting electrons from the cathode toward the hole injection layer 3 between the electrodes to which an electric field is applied. You. For this purpose, it is required that the compound has a high electron affinity, a high electron mobility, a high stability, and a small amount of impurities that become traps during production or use.
  • Materials satisfying such conditions include metal complexes such as aluminum complex of 8-hydroxyquinoline (JP-A-59-194393) and metal complexes of 10-hydroxybenzo [h] quinoline (particularly, Kaihei 6 — 322362)-bisstyrylbenzene derivatives (JP-A-11-245087 and JP-A-2-222484), bisstyrylarylene derivatives (JP-A-2-247278), (2-hydroxyphenyl) Metal complexes of benzothiazole (JP-A-8-315983), silole derivatives and the like.
  • metal complexes such as aluminum complex of 8-hydroxyquinoline (JP-A-59-194393) and metal complexes of 10-hydroxybenzo [h] quinoline (particularly, Kaihei 6 — 322362)-bisstyrylbenzene derivatives (JP-A-11-245087 and JP-A-2-222484), bisstyrylarylene derivatives (JP-A-2-247278), (2-hydroxyphen
  • an aluminum complex of 8-hydroxyquinoline is used as a host material, and a fluorescent dye for laser, such as coumarin, is used.
  • a fluorescent dye for laser such as coumarin
  • the emission wavelength can be varied by selecting the fluorescent dye.
  • Fluorescent dyes with poor film properties can be used,
  • this is also effective for the purpose of improving the driving life of the device c
  • a metal complex such as an aluminum complex of 8-hydroxyquinoline as a host material, a naphthacene derivative represented by rubrene (JP-A-4-335087) and a quinacridone derivative (JP-A-5_ 70773), and condensed polycyclic aromatic rings such as perylene (Japanese Patent Laid-Open No. 5-198377) by doping the host material with 0.1 to 10 weight by weight.
  • the light emission characteristics of the device particularly the driving stability, can be greatly improved.
  • the thickness of the light emitting layer 5 is usually 10 to 200 nm, preferably 30 to 100 thighs.
  • the light emitting layer 5 can also be formed by a coating method in the same manner as the hole injection layer 3, but when the above low-molecular compound is used, a vacuum evaporation method is usually used.
  • a method of doping the light emitting layer material (host material) with the above-mentioned fluorescent dyes such as the naphthacene derivative, quinacridone derivative, and perylene a method of co-evaporation and an evaporation source are mixed at a predetermined concentration in advance. Method Strengthen.
  • dopants are usually uniformly doped in the thickness direction of the light emitting layer, but may have a concentration distribution in the thickness direction. For example, doping may be performed only near the interface with the hole injection layer, or conversely, doping may be performed near the negative electrode interface.
  • the photosensitive polymer of the present invention When the photosensitive polymer of the present invention exhibits fluorescence, it may be used for the light emitting layer.
  • the photosensitive composition containing the photosensitive polymer and, if necessary, other binder resins, various additives, and fluorescent dyes. After a photosensitive composition film is formed by a known coating method, this is preferably exposed and developed to form a layer.
  • the “resin layer”, which is a feature of the present invention is used as the light-emitting layer, the preferred film thickness is different for each color, but is usually 5 to L 000 nm, preferably 10 to 500 nm.
  • the hole injection layer 3 may be formed using the photosensitive composition of the present invention, or a known hole injection / transport material may be used. It may be formed by using.
  • a cathode 7 is provided on the light emitting layer 5.
  • the cathode 7 plays a role of injecting electrons into the light emitting layer 5.
  • the material used as the cathode 7 includes the material used for the anode 2
  • a metal having a low work function is preferable, and tin, magnesium, indium, Appropriate metals such as calcium, aluminum and silver or alloys thereof are used.
  • Specific examples include a low work function alloy electrode such as a magnesium silver alloy, a magnesium-indium alloy, and an aluminum-lithium alloy.
  • the thickness of the cathode 7 is usually the same as that of the anode 2.
  • a metal layer having a high work function and stable against the air is further laminated thereon in order to increase the stability of the device.
  • Metals such as aluminum, silver, nickel, chromium, gold and platinum are used for this purpose.
  • the hole injection layer has a function of receiving holes from the anode (hole injection) and a function of transporting the received holes to the light emitting layer (hole transport). In addition to the light-emitting function, it also has the function of receiving electrons from the cathode (electron injection) and the function of transporting the received electrons to the point where they are combined with holes in the light-emitting layer (electron transport).
  • a hole transport layer 4 is provided between the hole injection layer 3 and the light emitting layer 5, and furthermore, as shown in FIG.
  • it is also possible to provide a structure in which the layers are divided according to functions for example, by providing an electron transport layer 6 between the phosphor layer 5 and the cathode 7, that is, a function-separated element.
  • a layer containing the photosensitive polymer of the present invention is formed as a hole injection layer 3 in the same manner as in the device having the configuration of FIG.
  • a hole transport layer 4 may be separately provided between the hole injection layer 3 and the light emitting layer 5, or a layer including the photosensitive polymer of the present invention may be separately provided as the hole transport layer 4. It may be provided between the hole injection layer 3 and the light emitting layer 5.
  • the material of the hole transport layer 4 needs to be a material that can efficiently transport the injected holes. It is more preferable that the hole injection efficiency from the hole injection layer 3 is high. For this purpose, it is required that the hole mobility is high and the stability is excellent, and that impurities serving as traps are hardly generated during production or use. Further, a smaller ionization potential is more preferable.
  • the layer is in direct contact with the light-emitting layer, it is preferable that a substance that quenches light emission be not included.
  • Examples of such a hole transport material include, for example, two or more tertiary amines including two or more tertiary amines represented by 4,4′-bis [N- (1-naphthyl) phenylamino] biphenyl.
  • Aromatic diamines in which a condensed aromatic ring is substituted with a nitrogen atom JP-A-5-234681), 4,4 ', 4 "-tris (1-naphthylphenylamino) triphenylamine and the like.
  • Aromatic amine compounds having a starburst structure J. Lumin., Vol. 72-74, pp. 985, 1997), and aromatic amide compounds composed of trimeric triunylamine ( Chem.
  • a material for the hole transport layer 4 a polyvinyl ether containing polyvinyl carbazole, polyvinyl triphenylamine (JP-A-7-53953), and tetraphenylbenzidine is used.
  • Polymer materials such as sulfone (Polym. Adv. Tech., Vol. 7, p. 33, 1996).
  • the hole transport layer 4 is formed by laminating the above material on the hole injection layer 3 by a coating method or a vacuum evaporation method.
  • the coating method it can be formed in the same manner as the hole injection layer 3 described above.
  • the binder resin include polycarbonate, polyarylate, polyester and the like. If the amount of the binder resin is large, the hole mobility is lowered, so that a small amount is desirable, and usually 50% by weight or less is preferable.
  • the hole transport material is put into a loop placed in a vacuum vessel, the inside of the vacuum vessel is evacuated to about 10 Pa by a suitable vacuum pump, and then the root is heated. The hole transport material is evaporated to form a hole transport layer 4 on the substrate 1 on which the hole injection layer 3 is formed, which is placed facing the rutupo.
  • the thickness of the hole transport layer 4 is usually 10 to 300 nm, preferably 30 to 100 nm. In order to uniformly form such a thin film, a vacuum evaporation method is generally used.
  • the luminous efficiency of the organic electroluminescent device can be further improved.
  • the compound used for the electron transport layer 6 is required to be capable of easily injecting electrons from the cathode and having a higher electron transport ability.
  • electron transporting materials include aluminum complexes of 8-hydroxyquinoline and oxaziazole derivatives already mentioned as materials for the light-emitting layer (Appl. Phys. Lett., 55, 1489, 1989, etc.). And a system in which they are dispersed in a resin such as polymethyl methacrylate ( ⁇ ) (Appl. Phys. Lett., Vol. 61, pp.
  • the thickness of the electron transport layer 6 is usually 5 to 200 nm, preferably 10 to 100 nrnX ".
  • an ultra-thin film (0.1 to 5 nm) of LiF, Li 20, etc. is placed at the interface between the cathode and the organic layer (the light-emitting layer 5 in the structure of FIGS.
  • the efficiency of the device can be further improved by introducing the following method (Appl. Phys. Lett., Vol. 70, p. 152, 1997; IEEE Trans. Electron. Devices, 44). Vol., P. 1245, 1997).
  • the structure opposite to that of FIG. 5, that is, the cathode 7, the light emitting layer 5, the hole injection layer 3, and the anode 2 can be laminated on the substrate in this order, and as described above, at least one
  • the layers can be stacked in the reverse order of the layers shown in FIGS. 6 and 7.
  • reaction solution is released into 150 ml of methanol, the precipitated light gray crude product is dissolved in tetrahydrofuran, released into a large amount of methanol, reprecipitated, purified, and purified in 1.8 g A gray powder was obtained. The yield was 43%.
  • the structure is shown below.
  • Example 2 The glass substrate obtained in Example 1 was placed on a glass substrate which had been subjected to ultrasonic cleaning with acetone, water with pure water, ultrasonic cleaning with isopropyl alcohol, drying with dry nitrogen, and UV / ozone cleaning.
  • the molecules were spin-coated under the following conditions:
  • Example 2 the polymer obtained in Example 1 and TBPAH (tris (4-bromophenyl) aluminum-hexaclont antimonate), which is an electron-accepting compound, were added.
  • the reduction potential of the above electron accepting compound TBPAH is reported to be 1.06 eV (vs SCE), so that the electron affinity is 5.36 eV. Therefore, the difference from the ionization potential of the polymer containing an aromatic amino group is 10 lleV.
  • a coating solution (photosensitive composition) containing the polymer obtained in Example 1 and coumarin 510 as a fluorescent dye was prepared and spin-coated on a glass substrate under the following conditions:
  • the Kumari down 510 including 8.2 wt 0/0, a uniform thin film having a thickness 2 OOnm was formed.
  • the thin film sample was irradiated with light of 366 nm wavelength at 3 J / cm through a photomask using a xenon lamp as a light source using an ultraviolet exposure apparatus (UX-1000 SM manufactured by Shio Electric Co., Ltd.). Thereafter, development was carried out for 1 minute with a 2-propanol solution containing 20% by weight of 0 : 0 form . The pattern was formed using 2-propanol as the stop solution.
  • the reaction solution was discharged into 150 ml of methanol, the precipitated light gray crude product was dissolved in tetrahydrofuran, released into a large amount of methanol, reprecipitated, purified, and purified 0.3 g Was obtained as a pale yellow powder. Yield was 22%.
  • the structure is shown below.
  • Example 2 After ultrasonic cleaning with acetone, water cleaning with pure water, ultrasonic cleaning with isopropyl alcohol, drying with dry nitrogen, and UVZ ozone cleaning, the polymer obtained in Example 2 was placed on a glass substrate. Sbincourt was performed under the following conditions:
  • a uniform thin film having a thickness of 60 nm was formed by the above spin coating.
  • This thin film sample was irradiated with light of 366 nm wavelength at 4 J / cm through a photomask using a xenon lamp as a light source using an ultraviolet exposure apparatus (UX-1000 SM manufactured by Shio Electric Co., Ltd.).
  • UX-1000 SM manufactured by Shio Electric Co., Ltd.
  • the pattern was formed using 2-propanol as a stop solution.
  • the voltage characteristics of the obtained sample were measured. The results are shown in FIG.
  • the conductivity of the resin layer formed using the photosensitive composition is 8.5 X 10 ⁇
  • An organic electroluminescent device having the structure shown in FIG. 5 was manufactured by the following method.
  • ITO indium tin oxide
  • a glass substrate 1 manufactured by Geomatech Co., Ltd .; electron beam film-forming product; sheet resistance: 15 ⁇
  • the anode 2 was formed by patterning into a stripe having a width of 2 mm by using.
  • the patterned ITO substrate was cleaned in the order of ultrasonic cleaning with acetone, water cleaning with pure water, ultrasonic cleaning with isopropyl alcohol, dried with nitrogen blow, and finally cleaned with ultraviolet rays.
  • the polymer of the present invention obtained in Example 1 was spin-coated on the IT0 substrate under the following conditions, and naturally dried at room temperature for 90 minutes to form a uniform thin film having a thickness of 60 nm. Been formed.
  • the obtained thin film was exposed at 2 J / cm using a UV exposure apparatus (same as in Test Example 2) under a nitrogen atmosphere, and was photocrosslinked to form a hole injection layer 3.
  • the substrate on which the hole injection layer 3 was formed was placed in a vacuum evaporation apparatus. After rough exhaust of the above equipment was performed by an oil rotary pump, the degree of vacuum in the equipment was reduced. The gas was evacuated using an oil diffusion pump equipped with a liquid nitrogen trap until the pressure became 2xl (T 6 Torr (approximately 2.7xlO— 4 Pa)) or less, and put it in a ceramic crucible placed in the above equipment.
  • '8-hydroxyquinoline complex of aluminum represented by the following structural formula, Al (C 9 H 6 N 0) 3 (E-1)
  • the crucible temperature of the aluminum 8-hydroxyquinoline complex was controlled in the range of 304 to 324 ° C, the degree of vacuum during deposition was 2.3 ⁇ 10—Torr (about 3.1 ⁇ 10 Pa), and the deposition rate was The thickness of the deposited light emitting layer was 75 nm in 0.1 to 0.7 ⁇ sec.
  • the substrate temperature during the vacuum deposition of the light emitting layer 5 was kept at room temperature.
  • the element on which the light-emitting layer 5 was vapor-deposited was once taken out of the vacuum vapor deposition apparatus into the atmosphere, and a 2 mm-wide striped shadow mask was used as a cathode vapor deposition mask, and the anode 2 was used as a mask. It is closely attached to the element so that it is perpendicular to the ITO stripe, and it is installed in another vacuum vapor deposition device and the degree of vacuum in the device is 2x10 Torr (about 2.7xl (T Pa)) in the same way as the organic layer.
  • a magnesium-silver alloy electrode was vapor-deposited to a film thickness of 44 nm by a dual simultaneous vapor deposition method as a cathode 7.
  • the vapor deposition was performed using a molybdenum boat.
  • the vacuum was 1x10 Torr (approximately 1.3xl (T Pa))
  • the evaporation time was 3 minutes and 20 seconds
  • the atomic ratio of magnesium to silver was 10: 1.5.
  • aluminum is formed using magnesium
  • the cathode 7 was completed by laminating it on a silver alloy film.
  • the degree of vacuum during aluminum deposition was 1.5 x 1 0 "5 Torr (about 2. 0x10- 3 Pa)
  • substrate temperature during deposition of the two-layered cathode deposition time was 1 minute 2 00 seconds. More mug Neshiumu. Silver alloy and aluminum maintained at room temperature did.
  • a device was manufactured in the same manner as in Example 3, except that no photocrosslinking due to exposure was performed when the hole injection layer 3 was formed.
  • Table 14 shows the emission characteristics of these devices.
  • the luminous luminance is the value at a current density of 250 mA / cm
  • the luminous efficiency is the value at 100 cd / m
  • the luminous current is the slope of the luminance-current density characteristic
  • the voltage is the value at lOOcdZm.
  • Example 14 A device was fabricated in the same manner as in Example 3, except that the polymer of the present invention obtained in Example 2 was used for the hole injection layer 3. Table 14 shows the emission characteristics of this device.
  • a device was produced in the same manner as in Reference Example 1 except that the polymer of the present invention obtained in Example 2 was used for the hole injection layer 3.
  • Table 14 shows the emission characteristics of this device.
  • Example 3 and Reference Example 1 and Example 4 and Reference Example 2 (each having the same material and layer configuration and differing only in whether or not the photosensitive composition layer is photocrosslinked) in Table 1-4. Comparing the values of luminance, luminous efficiency, and luminance / current, the device characteristics were improved by the photocrosslinking of the hole injection layer 3 formed of the photosensitive composition containing the photosensitive polymer of the present invention. You can see that it has not dropped.
  • An organic electroluminescent device having the structure shown in FIG. 6 was manufactured by the following method.
  • I0 indium tin oxide
  • a glass substrate 1 with a thickness of 120 nm manufactured by Geomatech Co., Ltd .; electron beam filmed product; sheet resistance 15 ⁇
  • the anode 2 was formed by patterning into a stripe having a width of 2 mm using the above and etching with hydrochloric acid.
  • the mixed solution of the polymer of the present invention and TBPAH obtained in Example 1 was spin-coated on the above ITO substrate under the following conditions, and 120. By drying at C for 60 minutes, a uniform thin film having a thickness of 60 nm was formed.
  • the substrate on which the hole injection layer 3 was formed was placed in a vacuum evaporation apparatus.
  • the device was evacuated using an oil diffusion pump equipped with a liquid nitrogen trap until the degree of vacuum in the device became 2 ⁇ 10 Torr (about 2.7 ⁇ 10 Pa) or less.
  • the degree of vacuum during deposition is 2.8X10 Torr (about 3.7
  • a film having a thickness of 20 nm was laminated on the hole injection layer 3 with XlO 4 Pa) to complete the hole transport layer 4.
  • the light emitting layer 5 and subsequent layers were manufactured in the same manner as in Example 3.
  • the organic electroluminescent device of the present invention can easily control the optical path length (effectively use the light interference effect) in the device by controlling the thickness of the resin layer, as compared with the case of using a low molecular weight vapor-deposited film. It is.
  • the layer formed using the photosensitive composition of the present invention can easily control the film thickness independently for the minimum emission unit of each color, interference of the emission wavelength for each color effectively occurs. It can be easily designed to make it work.
  • the resin layer formed using the photosensitive composition containing the polymer has Even if patterning is performed by the photolithography process, the characteristics of the organic electroluminescent device are not degraded, and both the productivity and the various characteristics of the device can be achieved.
  • the organic electroluminescent device can be used as a light source (for example, a light source of a copier, a liquid crystal display, or the like) utilizing the characteristics of a flat panel display (for example, a 0A computer or a wall-mounted television) or a surface light emitter. It can be applied to backlight sources for instruments, display boards, and sign lamps, and its technical value is particularly high for in-vehicle display elements that require high heat resistance.

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  • Chemical & Material Sciences (AREA)
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Abstract

Cette invention concerne un élément électroluminescent organique dont la couche de résine comprend une couche luminescente ou quelconque qui renferme un polymère photosensible. En jouant sur l'épaisseur de la couche de résine, on obtient une grande pureté de couleur par suite d'un effet d'interférence lumineuse. Le polymère photosensible présente les unités structurelles (II) et (III).
PCT/JP2001/001734 2000-03-06 2001-03-06 Element electroluminescent organique et polymere photosensible WO2001067823A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006101018A1 (fr) 2005-03-23 2006-09-28 Semiconductor Energy Laboratory Co., Ltd. Materiau composite, materiau pour element emetteur de lumiere, element emetteur de lumiere, dispositif emetteur de lumiere et dispositif electronique
EP1844504A1 (fr) * 2005-01-31 2007-10-17 Semiconductor Energy Laboratory Co., Ltd. Materiau d'injection a trou, materiau pour un element luminescent, element luminescent, compose organique, monomere, et melange de monomeres
WO2011040531A1 (fr) * 2009-10-01 2011-04-07 日立化成工業株式会社 Matériau pour électronique organique, élément électronique organique, élément électroluminescent organique, élément d'affichage utilisant un élément électroluminescent organique, dispositif d'éclairage et dispositif d'affichage
US8974922B2 (en) 2004-04-02 2015-03-10 Samsung Display Co., Ltd. Phenylcarbazole-based compounds and fluorene-based compounds and organic light emitting device and flat panel display device comprising the same

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06275381A (ja) * 1993-03-18 1994-09-30 Hitachi Ltd 多色発光素子とその基板
JPH0753953A (ja) * 1993-08-19 1995-02-28 Mitsubishi Chem Corp 有機電界発光素子
JPH07240277A (ja) * 1994-02-25 1995-09-12 Idemitsu Kosan Co Ltd 有機エレクトロルミネッセンス素子
JPH10195131A (ja) * 1996-12-24 1998-07-28 Thomson Csf 光重合性正孔注入ポリマー及び表示におけるその使用
JPH10310606A (ja) * 1997-05-09 1998-11-24 Minolta Co Ltd 新規スチリル系高分子化合物、その製造方法および用途
JP2000012882A (ja) * 1998-06-25 2000-01-14 Fuji Photo Film Co Ltd 反応性芳香族アミンをホール輸送層に含む光起電力素子およびその製造方法
JP2000036390A (ja) * 1998-05-13 2000-02-02 Mitsubishi Chemicals Corp 有機電界発光素子
JP2000286479A (ja) * 1999-03-29 2000-10-13 Toshiba Corp 機能素子および多成分多相系高分子成形体

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06275381A (ja) * 1993-03-18 1994-09-30 Hitachi Ltd 多色発光素子とその基板
JPH0753953A (ja) * 1993-08-19 1995-02-28 Mitsubishi Chem Corp 有機電界発光素子
JPH07240277A (ja) * 1994-02-25 1995-09-12 Idemitsu Kosan Co Ltd 有機エレクトロルミネッセンス素子
JPH10195131A (ja) * 1996-12-24 1998-07-28 Thomson Csf 光重合性正孔注入ポリマー及び表示におけるその使用
JPH10310606A (ja) * 1997-05-09 1998-11-24 Minolta Co Ltd 新規スチリル系高分子化合物、その製造方法および用途
JP2000036390A (ja) * 1998-05-13 2000-02-02 Mitsubishi Chemicals Corp 有機電界発光素子
JP2000012882A (ja) * 1998-06-25 2000-01-14 Fuji Photo Film Co Ltd 反応性芳香族アミンをホール輸送層に含む光起電力素子およびその製造方法
JP2000286479A (ja) * 1999-03-29 2000-10-13 Toshiba Corp 機能素子および多成分多相系高分子成形体

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9917258B2 (en) 2004-04-02 2018-03-13 Samsung Display Co., Ltd. Phenylcarbazole-based compounds and fluorene-based compounds and organic light emitting device and flat panel display device comprising the same
US10211406B2 (en) 2004-04-02 2019-02-19 Samsung Display Co., Ltd. Phenylcarbazole-based compounds and fluorene-based compounds and organic light emitting device and flat panel display device comprising the same
US8974922B2 (en) 2004-04-02 2015-03-10 Samsung Display Co., Ltd. Phenylcarbazole-based compounds and fluorene-based compounds and organic light emitting device and flat panel display device comprising the same
US11950501B2 (en) 2004-04-02 2024-04-02 Samsung Display Co., Ltd. Phenylcarbazole-based compounds and fluorene-based compounds and organic light emitting device and flat panel display device comprising the same
US11482678B2 (en) 2004-04-02 2022-10-25 Samsung Display Co., Ltd. Phenylcarbazole-based compounds and fluorene-based compounds and organic light emitting device and flat panel display device comprising the same
US10573821B2 (en) 2004-04-02 2020-02-25 Samsung Display Co., Ltd. Phenylcarbazole-based compounds and fluorene-based compounds and organic light emitting device and flat panel display device comprising the same
US9478754B2 (en) 2004-04-02 2016-10-25 Samsung Display Co., Ltd. Phenylcarbazole-based compounds and fluorene-based compounds and organic light emitting device and flat panel display device comprising the same
EP1844504A1 (fr) * 2005-01-31 2007-10-17 Semiconductor Energy Laboratory Co., Ltd. Materiau d'injection a trou, materiau pour un element luminescent, element luminescent, compose organique, monomere, et melange de monomeres
EP1844504A4 (fr) * 2005-01-31 2010-08-04 Semiconductor Energy Lab Materiau d'injection a trou, materiau pour un element luminescent, element luminescent, compose organique, monomere, et melange de monomeres
EP2528127A1 (fr) * 2005-03-23 2012-11-28 Semiconductor Energy Laboratory Co., Ltd. Dispositif électroluminescent et dispositif électronique
KR101290099B1 (ko) * 2005-03-23 2013-07-26 가부시키가이샤 한도오따이 에네루기 켄큐쇼 복합재료, 발광소자용 재료, 발광소자, 발광장치 및전자기기
WO2006101018A1 (fr) 2005-03-23 2006-09-28 Semiconductor Energy Laboratory Co., Ltd. Materiau composite, materiau pour element emetteur de lumiere, element emetteur de lumiere, dispositif emetteur de lumiere et dispositif electronique
US7977865B2 (en) 2005-03-23 2011-07-12 Semiconductor Energy Laboratory Co., Ltd. Composite material, material for light-emitting element, light-emitting element, light-emitting device and electronic device
US8986854B2 (en) 2005-03-23 2015-03-24 Semiconductor Energy Laboratory Co., Ltd. Composite material, material for light-emitting element, light-emitting element, light-emitting device and electronic device
US9583714B2 (en) 2009-10-01 2017-02-28 Hitachi Chemical Company, Ltd. Material for organic electronics, organic electronic element, organic electroluminescent element, display element using organic electroluminescent element, illuminating device, and display device
JPWO2011040531A1 (ja) * 2009-10-01 2013-02-28 日立化成株式会社 有機エレクトロニクス用材料、有機エレクトロニクス素子、有機エレクトロルミネセンス素子、及びそれを用いた表示素子、照明装置、表示装置
WO2011040531A1 (fr) * 2009-10-01 2011-04-07 日立化成工業株式会社 Matériau pour électronique organique, élément électronique organique, élément électroluminescent organique, élément d'affichage utilisant un élément électroluminescent organique, dispositif d'éclairage et dispositif d'affichage

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