Patent Application
20050037235
This application claims priority under 35USC 119 from Japanese Patent Application No. 2003-207082, the disclosure of which is incorporated by reference herein.
1. Field of the Invention
The present invention relates to an organic electroluminescent device and specifically to an organic electroluminescent device that can be designed to have a simple device structure.
2. Description of the Related Art
In recent years, investigations have been made regarding a light-emitting device using a liquid crystal compound. Among such light-emitting devices, a device that can achieve high-speed response or high luminance at a low driving voltage is particularly desired. For example, Japanese Patent Application Laid-Open (JP-A) No. 2002-170685 discloses a technique of utilizing orientation characteristics of a liquid crystal compound, in which the state of the liquid crystal orientation is controlled by temperature and voltage so that the luminance of emitted light can be controlled. In such a technique, however, the liquid crystal layer needs to contain plural components including a carrier-transporting material and a luminescent material; therefore the device structure can be complicated.
Appl. Phys. Lett., Vol. 73, No. 11, 14 September, 1998, pp. 1595-1597 discloses a liquid crystal cell including a layer (monolayer) in which a host liquid crystal compound is doped with a fluorescent dye, wherein the host liquid crystal compound is used as a charge-transporting material. However, such a device has a complicated structure, because the fluorescent dye has no liquid-crystallinity and the host liquid crystal compound is used as the charge-transporting material. Appl. Phys. Lett., Vol. 77, No. 11, 11 September, 2000, pp. 1587-1589 discloses an organic light-emitting device which uses a mixture of a liquid crystal compound with a fluorescent dye in order to emit light. However, this device also has a complicated structure. Further, Appl. Phys. Lett., Vol. 72, No. 21, 25 May, 1998, pp. 2639-2641 discloses an example of a light-emitting device having a three-layer structure. However, since the device has the three-layer structure, the structure of this device is also complicated.
The present invention has been made in view of the above-described circumstances and provides an organic electroluminescent device that can be designed to have a simple structure and can offer high luminance at low driving voltage.
An aspect of the invention is to provide an organic electroluminescent device including: a pair of electrodes; and a layer that is disposed between the pair of electrodes and contains a compound represented by the following formula (1):
In formula (1), A1 and A2 each independently represent an aromatic ring and may be substituents any of positions 2, 3, 4 and 5 of the thiophene ring; B represents a substituent having a positive Hammett substituent constant σp; C represents a substituent having a negative Hammett substituent constant up; n1 and n2 each independently represent an integer of 0, 1 or 2, wherein n1 and n2 are not 0 at the same time; and the thiophene ring may have a substituent selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkoxy group and a halogen atom.
A detailed description is provided below of the present inventive organic electroluminescent device (also referred to as the inventive device or the inventive light-emitting device).
An aspect of the invention is to provide an organic electroluminescent device including a pair of electrodes and a layer that is disposed between the pair of electrodes and contains the compound represented by the following formula (1):
In formula (1), A1 and A2 each independently represent an aromatic ring and may be substituents at any of positions 2, 3, 4 and 5 of the thiophene ring; B represents a substituent having a positive Hammett substituent constant σp; C represents a substituent having a negative Hammett substituent constant up; n 1 and n2 each independently represent an integer of 0, 1 or 2, wherein n1 and n2 are not 0 at the same time; and the thiophene ring may have a substituent selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkoxy group and a halogen atom.
The compound represented by formula (1) may be a compound represented by the following formula (2):
In formula (2), A1 and A2 each independently represent an aromatic ring; B represents a substituent having a positive Hammett substituent constant σp; R1 and R2 each independently represent an alkyl group; n1 and n2 each independently represent an integer of 0, 1 or 2, wherein n1 and n2 are not 0 at the same time; and the thiophene ring may have a substituent selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkoxy group and a halogen atom.
A1 and A2 each independently represent an aromatic ring, and either one of A1 and A2 is preferably an aromatic ring having 5 to 10 carbon atoms. Preferred examples of such an aromatic ring include 1,4-phenylene, thiophene-2,5-diyl, 2,6-naphthalene, thiazole-2,5-diyl, pyridine-2,3-diyl, benzofuran-2,5-diyl, benzofuran-2,6-diyl, benzothiophene-2,5-diyl, benzothiophene-2,6-diyl, pyrimidine-2,5-diyl, pyrazine-2,5-diyl and pyridazine-3,6-diyl. More preferred are 1,4-phenylene, 2,6-naphthalene and thiophene-2,5-diyl. Either one of A1 and A2 is more preferably 2,6-naphthalene. In a particularly preferred manner, A1 is 1,4-phenylene and A2 is 2,6-naphthalene; or A1 is 2,6-naphthalene and A2 is 1,4-phenylene. A1 and A2 may have a substituent. Preferred examples of such a substituent include an alkyl group having 1 to 8 carbon atoms, an alkoxy group and a halogen atom. More preferred is an alkyl group having 1 to 4 carbon atoms (such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl).
A1 and A2 may be substituents at any of positions 2, 3, 4 and 5 of the thiophene ring. In formula (1), A1 is preferably a substituent at position 2 or 5 of the thiophene ring, and A2 is preferably a substituent at position 5 or 2 of the thiophene ring. More preferably, the compound represented by formula (1) is represented by formula (2).
In Formula (1), C represents a substituent having a negative Hammett substituent constant σp. Specifically, C represents an electron-donating group such as a substituted amino group and an alkoxy group. A straight-chain alkyl-substituted amino group is particularly preferred as such a group.
In formulae (1) and (2), B represents a substituent having a positive Hammett substituent constant σp. Specifically, B preferably represents an ester group (—COOR3), a sulfonyl group (—SO2R3), a sulfoxy group (—SO3R3), or any of the substituents shown below, and more preferably represents the ester group, wherein R3 represents an alkyl group having 1 to 16 carbon atoms, and preferably a straight-chain alkyl group having 1 to 12 carbon atoms.
A description is provided below of the Hammett substituent constant up. Hammett's rule is an empirical rule that was proposed by L. P. Hammett in 1935 for the purpose of quantitatively discussing the effect of substituents on the reaction or equilibrium of benzene derivatives. The substituent constants obtained according to Hammett's rule include σp and am values. These values are shown in many general textbooks. For example, the text “Lange's Handbook of Chemistry,” the 12th edition, edited by J. A. Dean, 1979 (McGraw-Hill) or “Kagaku no Ryoiki” (Journal of Japanese Chemistry), an extra issue, 122, 96-103, 1979 (Nankodo), the disclosures of which are incorporated herein by reference, may be used in the invention.
In formula (2), R1 and R2 each independently represent an alkyl group, preferably a straight-chain alkyl group, and more preferably a straight-chain alkyl group having 1 to 6 carbon atoms (such as methyl, ethyl and propyl).
In the invention, the thiophene ring group in formulae (1) and (2) may also have a substituent, which may preferably be an alkyl group having 1 to 8 carbon atoms, an alkoxy group or a halogen atom, particularly preferably an alkyl group having 1 to 4 carbon atoms (such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl).
Preferred examples of the liquid crystal compound represented by formula (1) or (2) are shown as follows:
The compound according to the invention may be synthesized by any known method including, but not limited to, the synthesis method disclosed in European Patent Application Publication No. 1 394 158 A1, the disclosure of which is incorporated by reference.
The inventive light-emitting device includes a pair of electrodes (positive and negative electrodes) (preferably a pair of electrodes, at least one of which is a transparent electrode) and a layer that is disposed between the pair of electrodes and contains the compound represented by formula (1) or (2). The device having a light-emitting layer may also have any other layer such as a hole-injecting layer, a hole-transporting layer, an electron-injecting layer, an electron-transporting layer, and a protective layer. Each of such layers may also have any other function. Each layer may be produced with any of various materials. In a preferred mode, the compound according to the invention is contained as a main component of the layer and has the function of emitting light by itself (the function of forming a light-emitting layer).
The layer that contains at least one compound represented by formula (1) or (2) according to the invention may also contain any additive or the like for appropriately optimizing light emission. The layer may contain the compound according to the invention at any concentration and preferably contains it as a main component. A mixture with the compound according to the invention may be used in the inventive device. In such a case, the compound or the liquid crystal compound is preferably used in combination with a polymer medium, a spacer such as a particulate material/a sealing agent, an orientation-controlling agent, or any other liquid-crystalline compound (such as 4-cyano-4′-pentylbiphenyl).
In terms of optimizing the emission performance and/or simplifying the device structure, the compound according to the invention preferably exhibits liquid crystallinity, more preferably exhibits a smectic or nematic phase, and particularly preferably exhibits a smectic phase. The liquid crystal compound that exhibits the smectic phase can emit light of higher luminance as compared with the nematic phase or any other liquid crystal phase, and thus is useful for a liquid crystal light-emitting device.
The layer that contains the compound represented by formula (1) or (2) may also contain any other material such as a binder of a polymer medium and a spacer of a particulate material or a sealing agent, as needed. Examples of the polymer medium include acrylic polymers such as PMMA, imide polymers such as fluorinated polyimide, and polycarbonate. Examples of the particulate material include glass beads, plastic beads and alumina beads, and cross-linked cured transparent resins that are insoluble in a solvent or the like for use in preparation of a coating liquid for the light-emitting layer. The sealing agent may include an epoxy resin, a curing agent, a thickener, and the like, and can cause a reaction and curing when the curing agent dispersed in the sealing agent is dissolved.
The material for the hole-injecting layer or the hole-transporting layer should only have any one of the function of injecting holes from the positive electrode, the function of transporting holes and the function of blocking electrons injected from the negative electrode. Examples of such a material include carbazole, imidazole, triazole, oxazole, oxadiazole, polyarylalkane, pyrazoline, pyrazolone, phenylenediamine, arylamine, amino-substituted chalcone, styrylanthracene, fluorenone, hydrazone, stilbene, silazane, aromatic tertiary amine compounds, styrylamine, aromatic dimethylidine compounds, porphyrin compounds, polysilane compounds, poly(N-vinylcarbazole), aniline copolymers, thiophene oligomers or polymers, electrically conductive macromolecular oligomers or polymers such as polythiophene, carbon films, and derivatives of any of the above. The thickness of the hole-injecting or transporting layer is not limited by the material and is preferably from 1 nm to 5 μm, more preferably from 5 nm to 1 μm, and still more preferably from 10 nm to 500 nm. The hole-injecting or transporting layer may have a monolayer structure including one or more of the above materials or a multilayer structure including plural layers which are the same or different in composition. The hole-injecting or transporting layer may be formed by vacuum deposition, LB method, ink jetting, printing, transfer method, or coating (such as spin coating, casting or dip coating) with a solution or dispersion of a hole-injecting or transporting material in a solvent. In the coating method, the material may be dissolved or dispersed together with a resin component. Examples of such a resin component include polyvinyl chloride, polycarbonate, polystyrene, poly(methyl methacrylate), polyester, polysulfone, polyphenylene oxide, polybutadiene, poly(N-vinylcarbazole), hydrocarbon resins, ketone resins, phenoxy resins, polyamide, ethyl cellulose, polyvinyl acetate, ABS resins, polyurethane, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, and silicone resins.
The material for the electron-injecting or transporting layer should only have any one of the function of injecting electrons from the negative electrode, the function of transporting electrons and the function of blocking holes which would otherwise be injected from the positive electrode. Examples of such a material include a variety of metal complexes such as metal complexes of triazole, triazine, oxazole, oxadiazole, fluorenone, anthraquinodimethane, anthrone, diphenylquinone, thiopyran dioxide, carbodiimide, fluorenylidenemethane, distyrylpyrazine, an aromatic ring (such as naphthalene or perylene) tetracarboxylic anhydride, phthalocyanine, or an 8-quinolinol derivative; and metal complexes having methallophthalocyanine, benzoxazole or benzothiazole as a ligand. The electron-injecting or transporting layer may have any thickness but generally preferably has a thickness of 1 nm to 5 μm, more preferably of 5 nm to 1 μm, and still more preferably of 10 nm to 500 nm. The electron-injecting or transporting layer may have a monolayer structure including one or more of the above materials or a multilayer structure including plural layers which are the same or different in composition. The electron-injecting or transporting layer may be formed by vacuum deposition, LB method, ink jetting, printing, transfer method, or coating (such as spin coating, casting or dip coating) with a solution or dispersion of an electron-injecting or transporting material in a solvent. In the coating method, the material may be dissolved or dispersed together with a resin component. Examples of such a resin component include the same materials exemplified for the hole-injecting or transporting layer in the above.
The negative electrode supplies electrons to the electron-injecting layer, the electron-transporting layer, the light-emitting layer, or the like. The negative electrode should be selected in view of adhesion to the adjacent layer such as the electron-injecting layer, the electron-transporting layer and the light-emitting layer, ionization potential, stability, or the like. The material for the negative electrode may be a metal, an alloy, a metal oxide, an electrically conductive compound, or any mixture thereof. Specific examples of such a material include alkali metals (such as Li, Na, K, and Cs) or fluorides or oxides thereof; alkaline earth metals (such as Mg and Ca) or fluorides or oxides thereof; gold, silver, lead, aluminum; a sodium-potassium alloy or mixture; a lithium-aluminum alloy or mixture; a magnesium-silver alloy or mixture; indium; and rare earth metals such as ytterbium. Preferred are materials having a work function of 4 eV or less. More preferred are aluminum, a lithium-aluminum alloy or mixture and a magnesium-silver alloy or mixture. The thickness of the negative electrode may appropriately be selected depending on the material, and is generally preferably from 10 nm to 5 μm, more preferably from 50 nm to 1 μm, and still more preferably from 100 nm to 1 μm. The negative electrode may be formed by electron beam deposition, sputtering, resistance heating vacuum deposition, coating, or the like. A single metal may be vapor-deposited, or two or more components may be vapor-deposited at the same time. Different metals may be vapor-deposited at the same time to form an alloy electrode. Alternatively, a previously prepared alloy may be vapor-deposited. The sheet resistance of the positive or negative electrode is preferably as low as possible, for example, preferably at most several hundreds ohms per square.
The positive electrode supplies holes to the hole-injecting layer, the hole-transporting layer, the light-emitting layer, or the like. The positive electrode may be made of a metal, an alloy, a metal oxide, an electrically conductive compound, or any mixture thereof, and preferably made of a material having a work function of 4 eV or more. Examples of such a material include electrically conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO); metals such as gold, silver, chromium, and nickel; any mixture or laminate of the metal(s) and the conductive metal oxide(s); inorganic conductive substances such as copper iodide and copper sulfide; organic conductive materials such as polyaniline, polythiophene and polypyrrole; and a laminate of any of the above materials and ITO. The electrically conductive metal oxide is preferred, and ITO is particularly preferred in terms of productivity, high conductivity, transparency, and the like. The thickness of the positive electrode may appropriately be selected depending on the material and is generally preferably from 10 nm to 5 μm, more particularly from 50 nm to 1 μm, and still more preferably from 100 nm to 500 nm.
The positive electrode is usually a layer formed on a soda-lime glass substrate, an alkali-free glass substrate, a transparent resin substrate, or the like. Of the glass materials, the alkali-free glass is preferably used in terms of less ion elution from the glass. The soda-lime glass is preferably used when it has a barrier coating such as a silica coating. The substrate may have any thickness that is enough to keep the mechanical strength. For example, the thickness of the glass substrate is preferably 0.2 mm or more, and more preferably 0.7 mm or more.
The positive electrode may be formed by any of various methods depending on the material. For example, an ITO film electrode may be formed by electron beam deposition, sputtering, resistance heating vacuum deposition, chemical reaction (such as a sol-gel process), or coating with a dispersion of indium tin oxide.
The positive electrode may be subjected to cleaning or any other treatment so that the driving voltage for the device can be reduced or that luminous efficiency can be increased. For example, an UV-ozone treatment or a plasma treatment is effective for the ITO electrode.
The organic electroluminescent device may also have a heater that heats the device up to a temperature at which a liquid crystal compound of the device exhibits a liquid crystal phase. Examples of the heater include those utilizing Joule heat by electric current, those utilizing laser beam heating, and those utilizing Peltier effect. Specific examples of the heater include electric heaters, Peltier device, heat exchangers and the like.
Examples of the device using the compound-containing light-emitting layer according to the invention are described below with reference to the drawings.
In each of the above devices, for example, the compound represented by formula (1) having liquid crystallinity is used in the light-emitting layer. In the case of such a device, an external electric field is preferably applied in a temperature range in which the compound exhibits a liquid crystal phase. As another method, the compound is preferably heated under an external electric field up to a temperature at which the compound exhibits an isotropic phase and then cooled to a temperature in which the compound exhibits a liquid crystal phase. Particularly preferably, the external electric field is applied in a temperature range in which the compound exhibits a liquid crystal phase. There is no need to add a fluorescent dye or the like to the light-emitting layer. The device can have such a simple structure, and can provide high luminance at low driving voltage.
The present invention is more specifically described by means of the examples recited below. However, the examples should not be construed to limit the scope of the invention.
A device having a structure shown in
Compound 1 exhibits monotropic liquid crystallinity. C represents a solid state, SX1 and SX2 represent a smectic phase, and I represents an isotropic phase.
A device having a structure shown in
Compound 2 exhibits enantiotropic liquid crystallinity. C represents a solid state, SC represents a smectic C phase, SA represents a smectic A phase, and I represents an isotropic phase.
A device having a structure shown in
Example 4 was performed in the same manner as in Example 2 except that temperature of the light-emitting layer was altered. The device did not emit light in a solid state (60° C.) and an isotropic phase (90° C.), while the device emitted light in a liquid crystal state, selectively.
A device having a structure shown in
A device having a structure shown in
As described above, the device according to the invention does not need to have plural specifically-structured organic compound layers and can emit light using a simple structure. There is no need to add a fluorescent dye or the like to the light-emitting layer in such a simple device, and thus the light-emitting layer does not need to be sealed from air contact. Because of this feature, the device structure can also be made simple. If both electrodes are a transparent electrode such as an ITO electrode, the electrodes may not be distinguished from each other for operation and thus can be highly convenient. In such a case, emitted light can also be taken from both front and rear sides.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2003-207082 | Aug 2003 | JP | national |
