Abstract:
To provide an organic electroluminescence element which is highly efficient and has a long operation life, a metallic compound is used as an electron transport layer and a metal complex which is capable of triplet emission is used as a light-emitting element. An organic material which is mainly responsible for electron hole transport is provided so as to surround the electron transport layer and the light-emitting element.

Description:
BACKGROUND  
       [0001]     Exemplary aspects of the present invention relate to an organic electroluminescence device manufactured by using a liquid-phase process, a manufacturing method thereof and electronic equipment.  
         [0002]     An organic electroluminescence (EL) element, which is a constituent member of the organic electroluminescence device, generally has an organic light-emitting layer made of an organic light-emitting material between an anode and a cathode. Electrons and electron holes, which are injected through the anode and the cathode, are recombined in the light-emitting layer and an excited energy is emitted as light. Such organic EL device usually has an electron hole injection layer (also called “electron hole transport layer”) that becomes an anode buffer and an electron injection layer (also called “electron transport layer”) that becomes a cathode buffer because a charge injection barrier among the electrodes and the light-emitting layer is high. They are provided in layers in the organic EL device.  
         [0003]     An electron injection material (also called “electron transport material”) has a high reactivity with oxygen and the like in principal. Specifically, it has a high probability of undergoing chemical change under normal conditions. Therefore, it is difficult to maintain reliability of the electron injection material for a prolonged period. For this reason, a part including the cathode which injects and transfers electrons becomes a deterioration factor. Demands for organic electroluminescence have been increasing every day and reliability is becoming a major issue. A related art electron injection transfer layer made of previously-existing organic materials is not sufficient and a radical enhancement is needed.  
       SUMMARY  
       [0004]     Exemplary aspects of the present invention have been developed in consideration of the above-mentioned and/or other problems, provide an organic electroluminescence element which is reliable and/or has a long operation life.  
         [0005]     Exemplary aspects of the present invention also provide electronic equipment having an organic electroluminescence device according to an exemplary aspect of the present invention.  
         [0006]     An organic electroluminescence device of an exemplary aspect of the present invention has a functional organic material layer provided between an electrode formed on a base body and an electrode that opposes the electrode. The functional organic material layer contains at least a metal oxide particle, a metal complex and an organic material.  
         [0007]     An organic electroluminescence device according to an exemplary aspect of the present invention conducts an electron injection and propagation, which is a key factor for deterioration, through not only the organic material but also together with an inorganic material.  
         [0008]     In an organic electroluminescence device according to an exemplary aspect of the present invention, in addition to the light-emitting functional part, a hole injection layer, a hole transport layer and an electron injection layer may exist in a form of at least a layer or layers.  
         [0009]     In a manufacturing method according to an exemplary aspect of the present invention, a liquid-phase process is used. When the liquid-phase process is used, the light-emitting functional part can be more easily formed compared with a case where it is formed by a vapor process. Such liquid-phase process includes a spin-coat method, a dip method and a droplet discharging method.  
         [0010]     Electronic equipment according to an exemplary aspect of the present invention includes the above-described organic electroluminescence device of an exemplary aspect of the present invention. 
     
    
     BRIEF DESCRIPTION OF THE DRAWINGS  
       [0011]      FIG. 1  is a schematic showing a structure of an organic electroluminescence device according to an exemplary aspect of the present invention;  
         [0012]      FIG. 2  is a schematic along the plane A-A shown in  FIG. 1 ;  
         [0013]      FIGS. 3A through 3C  are schematics for explaining manufacturing processes of the organic electroluminescence device in sequence;  
         [0014]      FIGS. 4A and 4B  are schematics for explaining the following manufacturing process after the process shown in  FIG. 3C ;  
         [0015]      FIG. 5  is a schematic of an exemplary embodiment of the present invention; and  
         [0016]      FIG. 6  is a schematic of an electronic equipment of an exemplary aspect of the present invention. 
     
    
     DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS  
       [0017]     Exemplary embodiments of the present invention will now be described in detail with reference to the accompanying drawings.  
         [0018]     An example of an organic electroluminescence device according to the present exemplary embodiment is described with reference to  FIG. 1  and  FIG. 2 .  FIG. 1  is a schematic showing an organic electroluminescence device  1 .  FIG. 2  is a schematic of the organic electroluminescence device along the plane A-A shown in  FIG. 1 .  
         [0019]     The organic electroluminescence device  1  has a dot that emits a green (G) light in a real display region  4  as shown in  FIG. 1  and this enables the organic electroluminescence device to display in one color.  
         [0020]     As shown in  FIG. 2 , the organic electroluminescence device  1  of this exemplary embodiment is a bottom-emission type. This means that the light is taken out from a substrate  20  side. Therefore, a transparent or translucent substrate made of, for example, glass, quartz and resin (plastic or a plastic film) is used as the substrate  20 .  
         [0021]     When the organic electroluminescence device is a so-called top-emission type, the light is taken out from a sealing substrate (not shown in the figures) side which is opposed to the substrate  20 . Therefore, either the transparent substrate or an opaque substrate can be used as the substrate  20 . As the opaque substrate, for example, ceramics, such as alumina, a metal sheet treated with insulating, such as a stainless steel treated with surface oxidation, heat-hardening resin and thermoplastic resin can be used.  
         [0022]     In this exemplary embodiment, an electroluminescence element is provided on a base body  100 . The base body  100  includes the substrate  20  and a circuit member  11  formed on the substrate  20 .  
         [0023]     The circuit member  11  includes a protection layer  12  formed on the substrate  20  and made of, for example, an oxide silicon layer, a driving thin film transistor (TFT)  123  formed on the protection layer, a first interlayer insulation layer  15  and a second interlayer insulation layer  18 . The driving TFT  123  includes a semiconductor layer  13  made of silicon, a gate insulating layer  14  formed on the semiconductor layer  13 , a gate electrode  19  formed on the gate insulating layer  14 , a source electrode  16  and a drain electrode  17 .  
         [0024]     The organic electroluminescence element is provided on the circuit member  11 . The organic electroluminescence element includes a picture electrode  23  which serves as an anode, a hole injection layer  70  which injects or transports electron holes from the picture electrode  23  and is formed on the picture electrode  23 , an organic light-emitting layer  60  having a light-emitting function and formed on the hole injection layer  70 , and a cathode  50  formed on the organic light-emitting layer  60 . Although not shown in the figure, an electron-injection layer that injects or transports electrons from the cathode  50  may be provided between the organic light-emitting layer  60  and the cathode  50  according to need.  
         [0025]     When an electron hole injected from the hole injection layer  70  and an electron from the cathode  50  are bound to each other in the organic light-emitting layer  60 , the above-described organic electroluminescence element  1  emits light.  
         [0026]     The picture electrode  23  which serves as the anode is made of a transparent conductive material because the bottom-emission type is adopted in this exemplary embodiment. As the transparent conductive material, besides Indium Tin Oxide (ITO), for example, Indium Zinc Oxide (IZO) (registered trademark) (Idemitsu Kosan Co., Ltd. make) and the like can also be used.  
         [0027]     A thickness of the picture electrode  23  is not particularly limited. For example, it may be 50-200 nm. A surface of the picture electrode  23  is made to be lyophilic by being treated in an oxygen plasma. At the same time, the surface of the electrode is cleaned and a work function is adjusted. The oxygen plasma treatment may be performed in, for example, the following conditions: 100-800 kW of plasma power, 50-100 ml/min of oxygen gas flow rate, 0.5-10 mm/sec of substrate carrying speed and 70-90° C. of substrate temperature.  
         [0028]     As an electron hole transport material of the hole injection layer  70 , for example, 4-polyethelenedioxithiophene (PEDOT) and polystyrenesulphonic acid (PSS) (see Formula 1) manufactured by Bayer AG can be used. For example, a material in which a mixture of polythiophene derivative, such as PEDOT and PSS and the like dissolved in solvent, can be used. As a polar solvent, for example, isopropyl alcohol (IPA), n-butanol, γ-butyrolactone, N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI) and its derivatives and glycol ether series, such as carbitol acetate and butyl carbitol acetate can be used. The exemplary embodiment is not limited to this, for example, this layer may be omitted.  
                         
 
         [0029]     As a light-emitting material for a light emitting functional part  60 , organic material as polyvinyl carbazole (see Formula 2) and triallylamine-base polymer (for example, ADS254BE, see Formula 3), such metal complex as iridium metal complex having 2,2′-bipyridine-4,4′-dicarboxylic acid (see Formula 4) as its ligand and metallic compound particles as zirconium oxide, titanium oxide and silicon carbide can be used.  
                         
 
         [0030]     The cathode  50  is formed so as to cover the light emitting functional part  60  and an organic bank layer  221 .  
         [0031]     As a material to form the cathode  50 , a material with a small work function in a light emitting functional part  60  side (the bottom side) of the cathode  50  may be used. For example, calcium, magnesium and the like can be used. In the upper side (the sealing side) of the cathode  50 , a material with higher work function than that of the light emitting functional part  60  side, which is, for example, aluminum can be used. When aluminum is used in the cathode  50 , this aluminum can serve as a reflecting layer that reflects a light emitted from the light emitting functional part  60 . A thickness of the cathode  50  is not particularly limited. For example, it may be 100-1000 nm, and preferably, 200-500 nm. In this exemplary embodiment, the cathode  50  does not have to be transparent because the organic electroluminescence device of this exemplary embodiment is the bottom-emission type.  
         [0032]     The surface of the second interlayer insulation layer  18  on which the picture electrode  23  is formed is covered with the picture electrode  23 , a lyophilic control layer  25  and the organic bank layer  221 . The lyophilic control layer  25  is mainly made of the lyophilic material, such as silicon oxide and the organic bank layer  221  is made of acrylic resin, polyimide and the like. The picture electrode  23  has an opening  25   a  formed in the lyophilic control layer  25  and an opening  221   a  formed in the organic bank layer  221 . The hole injection layer  70  and the light emitting functional part  60  are piled up in this order from the picture electrode  23  side in the opening  25   a  and the opening  221   a.  In this exemplary embodiment, the lyophilic material of the lyophilic control layer  25  is at least more lyophilic than the acrylic resin or the polyimide of the organic bank layer  221 .  
         [0000]     Exemplary Embodiment of Manufacturing Method  
         [0033]     Next, one example of a method of manufacturing the organic electroluminescence device  1  according to the present exemplary embodiment will be described with reference to  FIGS. 3A through 3C  and  FIGS. 4A and 4B . Each sectional view shown in  FIGS. 3A-3C  and  FIGS. 4A and 4B  correspond to a sectional view along the plane A-A in  FIG. 1 .  
         [0034]     (1) First, components as far as the circuit member  11  shown in  FIG. 2  are formed on the substrate  20  by a commonly used method and the base body  100  is obtained as shown in  FIG. 3A . Subsequently, a transparent conductive layer which becomes the picture electrode  23  is formed so as to cover the whole area of the top layer (the second interlayer insulation layer  18 ) of the base body  100 . Then, this transparent conductive layer is patterned so as to form the picture electrode  23  has an opening  23   a.    
         [0035]     (2) Next, the lyophilic control layer  25  made of the insulating layer is formed on the picture electrode  23  and the second interlayer insulation layer  18 , as shown in  FIG. 3B . Subsequently, a black matrix layer (not shown in the figures) is formed in a concave portion formed between two different picture electrodes  23  in the lyophilic control layer  25 . Specifically, the black matrix layer is formed by sputtering, for example, chromium metal in the concave portion of the lyophilic control layer  25 .  
         [0036]     (3) Next, the organic bank layer  221  is formed on a predetermined position of the lyophilic control layer  25 , more particularly, so as to cover the black matrix layer as shown in  FIG. 3C . The organic bank layer is formed by forming an organic layer. The organic layer may be formed by, for example, applying a solution in which resist, such as acrylic resin and polyimide resin, is dissolved. The solution can be applied by a spin-coat method, a dip-coat method and the like. Any material can be adopted to form the organic layer as long as it will not dissolve in a solvent of the later-described liquid material and it is easily patterned by etching and the like. Then, the organic layer is patterned by a photolithography technique or an etching technique and the opening  221   a  is formed in the organic layer. In this way, the organic bank layer  221  is formed.  
         [0037]     Next, a lyophilic area and a lyophobic area are formed by a plasma treatment. Specifically, the plasma treatment includes a preheating process, a lyophilic process, a lyophobic process and a cooling process. In the lyophilic process, an upper face of the organic bank layer  221 , a wall surface of the opening  221   a,  an electrode face  23   c  of the picture electrode  23  and an upper face of the lyophilic control layer  25  are made to be lyophilic. In the lyophobic process, the upper face of the organic bank layer  221  and the wall surface of the opening  221   a  are made to be lyophobic.  
         [0038]     Specifically, a treated body (a layered body composed of the picture electrode  23  and the organic bank layer  221  and the like provided on the base body  100 ) is heated to a predetermined temperature, for example, about 70-80° C. Subsequently, the treated body is treated in atmosphere with the plasma treatment (the oxygen plasma treatment) by using oxygen as a reactive gas. This is the lyophilic process. Then, as the lyophobic process, another plasma treatment (CF 4  plasma treatment) using tetrafluoromethane as the reactive gas is performed. Then, the treated body that was heated in the plasma treatment is cooled down to room temperature. In this way, the lyophilic area and the lyophobic area are respectively formed in predetermined positions.  
         [0039]     In the CF 4  plasma treatment, the electrode face  23   c  of the picture electrode  23  and the lyophilic control layer  25  will be also affected to some extent. However, ITO that is used to form the picture electrode  23 , silicon oxide, titanium oxide and the like, used to form the lyophilic control layer  25 , have a weak affinity for fluorine. Therefore, hydroxyl given in the lyophilic process will not be replaced by fluorine group and the lyophilic area is maintained.  
         [0040]     (4) Next, the hole injection layer  70  is formed as shown in  FIG. 3C . To form the hole injection layer  70 , a thin film having a thickness of from a few nanometers to a few hundreds nanometers is formed by a liquid-phase process. The liquid-phase process is a method of forming a thin film by dissolving or dispersing a desired film material in a liquid and applying the liquid with the spin-coat method, the dip-method or a droplet discharging method (an ink-jet method) and the like. The spin-coat method and the dip-method are ideal for applying the whole surface. Meanwhile, the thin film can be patterned in a desired position with the droplet discharging method. Such liquid-phase process is also adopted in the later-descirbed film forming processes to form the light emitting functional part, the electron injection layer, the cathode and the like.  
         [0041]     In the hole injection layer forming process, the hole injection layer  70  can be formed in a predetermined position without patterning by etching and the like because an electron hole transport layer forming material is applied on the electrode face  23   c  by the droplet discharging method.  
         [0042]     In a case where the hole injection layer forming material is selectively applied by the droplet discharging method (the ink-jet method), first, the hole injection layer forming material is filled in a droplet discharge head (not shown in the figures). Second, a discharge nozzle of the droplet discharge head is opposed to the electrode face  23   c  placed in the opening  25   a  that is formed in the lyophilic control layer  25 . Third, a droplet whose volume is controlled is discharged to the electrode face  23   c  from the discharge nozzle while the droplet discharge head and the substrate are relatively moved.  
         [0043]     The droplet discharged from the discharge nozzle spreads on the electrode face  23   c  which is treated with the lyophilic treatment and the droplet is then filled in the opening  25   a  of the lyophilic control layer  25 . The droplet is shed and will not adhere to the upper face of the organic bank layer  221  which is treated with the lyophobic (ink) treatment. Therefore, even if the droplet is discharged from the predetermined position and to the upper surface of the organic bank layer  221 , the upper surface will not be wet with the droplet and the shed droplet will fall into the opening  25   a  of the lyophilic control layer  25 . In this way, the droplet is easily and precisely provided on the predetermined position.  
         [0044]     To form the hole injection layer  70 , as described above, for example, PEDOT and PSS can be used as the electron hole transfer material. Furthermore, the hole injection layer  70  is not indispensable. In the above-described way, a layered body  400  including at least the anode (picture electrode)  23 , the hole injection layer  70  and the organic bank layer  221  formed on the base body  100  is obtained.  
         [0045]     (5) Next, the light emitting functional part  60  is formed on the hole injection layer  70  as shown in  FIG. 4A . The manufacturing process of the light emitting functional part  60  is the same as that of the hole injection layer  70 . For example, the material is discharged to a predetermined position of the hole injection layer  70  by the droplet discharging method. Then, a drying process is performed. In this way, the light emitting functional part  60  can be formed in the opening  221   a  that is formed in the organic bank layer  221 .  
         [0046]     As the material to form the light emitting functional part  60 , in addition to the above-mentioned materials, such organic substances  65  as polyvinyl carbazole, polyfluorene-based polymer derivatives, (poly)paraphenyleneVinylene derivatives, polyphenylene derivatives, polythiophene derivatives and triallylamine derivatives, such metal complex  80  as a three-coordinate iridium metal complex having 2,2′- bipyridine-4,4′-dicarboxylic acid as its ligand and such metallic compound particles  90  as zirconium oxide, titanium oxide and silicon carbide can be used.  
         [0047]     An exemplary embodiment of the light emitting functional part will now be described. First, synthesis of a complex is conducted. The above-mentioned 2,2′- bipyridine-4,4′-dicarboxylic acid (manufactured by TOKYO KASEI KOGYO CO., LTD.) is dissolved in a polar solvent, such as water, alcohol (ethanol, isopropyl alcohol and the like) and dimethylformamide. At the same time, iridium chloride is separately dissolved in the same kinds of solvent. A concentration of the solution is adjusted such that a ratio of the ligand to the metal becomes 3:1. After the dissolution, they are mixed and agitated. After the sufficient reaction for 2-3 hours, sediment is taken out by using a filter. Then, it is cleaned with ethanol and dried. In the above-described way, an iridium complex is completed. Next, after the complex is dissolved in a halogen-based solvent (here, chloroform is adopted), this solution is accordingly added in another solution which includes the same kind of solvent and the zirconium oxide which is dispersed in the solvent in order to coordinate the complex with the zirconium oxide. After the adding, the solution is agitated for a day in order to make a sufficient reaction. In this way, a zirconium oxide particle covered with the iridium complex is completed. Next, the polyvinyl carbazole and ADS254BE are dissolved in a nonpolar solvent, such as xylene, toluene, cyclo hexyl benzene and dihydrobenzofuran. Then, the above-described zirconium oxide is added to the solution of the polyvinyl carbazole and ADS254BE. After the zirconium oxide is sufficiently dispersed, this solution is applied to the hole injection layer  70  or an anode  23  made of, for example, ITO by the liquid-phase process. Here, as described above, the liquid-phase process means the method of forming a thin film by applying the liquid with the spin-coat method, the dip-method or a droplet discharging method (an ink-jet method) and the like.  
         [0048]     Alternatively, the above-described process may be performed in such way that the zirconium oxide is applied and fixed on the anode  23  made of, for example, ITO in an appropriate manner, and this is soaked in the above-described complex solution. In this case, the light-emitting functional part is completed by applying a polyvinyl carbazole dissolved in the above-mentioned nonpolar solvent after the soaking. A frame format of the light-emitting functional part is shown in  FIG. 5 .  
         [0049]     In the above-described way, a layered body  500  including at least the anode (picture electrode)  23 , the hole injection layer  70  and the light emitting functional part  60  formed on the base body  100  is obtained.  
         [0050]     (6) Next, the electron injection layer, which is not shown in the figures, is formed according to need. To form the electron injection layer, an electron injection layer forming material is applied to the light emitting functional part  60  by the droplet discharging method.  
         [0051]     (7) Next, the cathode  50  is formed on the light emitting functional part  60 R,  60 B,  60 G as shown in  FIG. 4B . In the forming process of the cathode  50 , a film of a cathode material, such as aluminum is formed by, for example, deposition, sputtering and the like.  
         [0052]     Then, a sealing substrate  30  is formed in a sealing process. In this sealing process, a film  45  having a drying capability is adhered to the inside of the sealing substrate  30 . Furthermore, the sealing substrate  30  and the substrate  20  are sealed with a sealant resin (not shown in the figures) in order to reduce the likelihood or prevent water and oxygen from entering into the inside of the completed organic electroluminescence element. As the sealant resin, a heat-hardening resin and an ultraviolet curing resin are used. Moreover, this sealing process may be performed in an inactive gas atmosphere, such as nitrogen, argon and helium.  
         [0053]     The organic electroluminescence device  1  obtained through the above-described processes finely emits light from the picture electrode  23  side when a voltage of, for example, smaller than 10 V, is applied between the both electrodes.  
         [0054]     Though the cathode  50  is formed by a vapor process, such as deposition, sputtering and the like in the above-described exemplary embodiment, the cathode may be formed by the liquid-phase process of using a solution or dispersion liquid containing a conductive material.  
         [0055]     For example, the cathode  50  may be composed of a main cathode that is adjacent to the light emitting functional part  60  and a supplementary cathode that is put on the top of the main cathode. The main cathode and the supplementary cathode may be both formed of the conductive material. The main cathode and the supplementary cathode are both formed by the liquid-phase process, such as the droplet discharging method.  
         [0056]     As the conductive material to form the main cathode, a conductive polymer material that includes a polymer compound including, for example, ethylene dioxythiophene, is used. Particularly, as the conductive polymer material, a dispersion liquid of 3,4-ethylene dioxythiophene/polystyrene sulfonate can be used. Furthermore, as the conductive material to form the main cathode  50 , the metal particle may be used instead of the conductive polymer material, or the metal particle may be used together with the conductive polymer material. Especially, when the main cathode is made of the mixture material of the conductive polymer material and the metal particle, the main cathode can be calcined in relatively low temperature while the conductivity of the main cathode  50  is maintained. As the metal particle, gold, silver, aluminum and the like can be used. In addition to the metal particle, such as gold and silver, carbon paste may also be used.  
         [0057]     The supplementary cathode  223  is provided on the main cathode in order to enhance the conductivity of the whole cathode  50 . The supplementary cathode  223  also protects the main cathode from oxygen and moisture by covering it and it can be made of the conductive metal particles. The metal particles are not especially limited as long as they are chemically stable conductive material, for example, metal and alloyed metal can be used to form them. To be more specific, aluminum, gold, silver and the like may be used.  
         [0058]     As described above, when the cathode  50  is formed by the liquid-phase process, a vacuum environment is not necessary unlike the vapor process. Furthermore, the cathode  50  can be consecutively formed subsequently to the formation of the light emitting functional part  60 . Therefore, the manufacturing process can be simplified and the productivity is raised. Furthermore, when the picture electrode (anode) is also formed by the liquid-phase process, the whole organic electroluminescence element including the anode, a functional layer (the hole injection layer, the light-emitting layer) and the cathode can be formed by the liquid-phase process. Therefore, the manufacturing process can be simplified and the productivity is raised.  
         [0059]     Though the bottom-emission type is explained in the above-described exemplary embodiment, the present invention is not limited to this and can also be applied to the top-emission type and a type in which light is emitted from both top and bottom.  
         [0060]     According to the manufacturing method of this exemplary embodiment, the functional organic layer, for example, all the hole injection layer, the organic light-emitting layer and the electron injection layer are formed by the liquid-phase process. Therefore, each layer can be more easily formed compared with a case where the each layer is formed by the vapor process.  
         [0061]     5. Electronic Equipment  
         [0062]     Next, an exemplary embodiment of the electronic equipment according to the present invention will be described. The electronic equipment of an exemplary aspect of the present invention has the above-described organic electroluminescence device  1  as a display part. To be more specific, a cellular phone shown in  FIG. 6  can be taken as an example.  
         [0063]     In  FIG. 6 , reference numeral  1000  designates a body of the cellular phone and reference numeral  1001  designates the display part which is the organic electroluminescence device  1  of the present exemplary embodiment. Because the cellular phone shown in  FIG. 6  has the display part  1001  made of the organic electroluminescence device of the present exemplary embodiment, the cellular phone has a fine display properties.  
         [0064]     In addition to the cellular phone, the electronic equipment of the present exemplary embodiment includes a mobile information processor, such as a word processor and a personal computer, a wristwatch type electronic equipment, a flat panel display (for example, television) and the like.  
         [0000]     Industrial Applicability  
         [0065]     The present invention is not limited to the above-described exemplary embodiments but may also be applied to a small-molecular type organic electroluminescence element.  
         [0066]     Furthermore, though the display device having the organic electroluminescence element is described in the exemplary embodiment above, the present invention is not limited to this. The present invention may also be applied to a head of an ink-jet printer and the like.