Organic light-emitting diode

FIELD: physics.

SUBSTANCE: organic light-emitting diode contains the bearing bottom executed in the form of glass or plastic layer with the anode transparent layer disposed on it. The layer of organic substance with hole conductivity (the hole-transport layer) is located on the anode, then the organic radiating (emission) layer, organic layer with n-type conduction (an electro-transport layer) follow. The emission layer can simultaneously carry out function of an electro-transport stratum. Over organic layers the cathode stratum is located. The cathode is executed from the composite material containing ytterbium, doped by thulium or europium in amount of not less than 10%. The device is characterised by high technical characteristics: the insert voltage makes 4 V, a running voltage at luminosity 150 cd/m2, that there corresponds to quantity of the working monitor, 4 V, efficiency of a luminescence - 2 lm/W. At the mentioned running voltage luminosity slope on 10% makes not less than 4000 hours.

EFFECT: expansion of a circle of substances for emission layer, capable to generate all basic and intermediate colours.

4 cl, 1 tbl, 1 dwg

 

The invention relates to the field of semiconductor optoelectronics, namely the solid-state light sources based on organic light-emitting diodes - acid or OLED - Organic Light Emitting Diodes, which are used to create flat color information screens and color of indicator devices with high consumer properties, as well as cost-effective and efficient light sources.

Organic electroluminescent display of acid is a monolithic thin-film semiconductor device that emits light when it applied voltage. Acid consists of a series of organic thin films, which are enclosed between two thin-film conductors.

Typical acid devices are single-layer or multilayer structure of the sandwich type with thickness of ~100 nm (see USP t, No. 12, s-1215, 2005).

In the above source shows a diagram of the organic light-emitting diode constituting the thin-film device containing a carrier substrate in the form of a glass substrate on which is placed a transparent conductive layer of indium oxide doped with tin, performs the function of the anode. It is a layer of organic matter with hole conductivity, followed by radiant (emissive) layer, for example, on OS is ove aluminum (Alqs), layer with electron conductivity and a metal cathode in the form of a film of aluminum.

As the cathode material should be used metals with a low electron work function of the metal. Low work function are alkaline metals Li(2.95 eV), Na(2.75 eV), K(2.3 eV), Cs(2,14 eV) and alkaline earth metals BA(2.7 eV), CA(3.0 eV), Mg(3.7 eV), whose work output is slightly higher. Mentioned alkali metals are highly active, rapidly oxidized in the air can react with the material of the emitting layer and, for this reason, cannot be used as a cathode of acid.

Traditionally, as a cathode material using aluminum, the output of which is 4.3 eV. Light-emitting diode in which the cathode material is aluminum or another metal with high work function, limits the range of materials for the emissive layer, i.e., not all connections will be lit, which means there will be restrictions, for example, the color will not be provided with high brightness devices, reduced retention of brightness.

Known use as a cathode material magnesium, or calcium, and/or their alloys with aluminum or silver (see for example M. Matsumura, A, lto, Y.Miyamare, Appl. Phys. Lett., 75, 1042-1044, 1999). During operation of the device, the cathode is made of the above materials, quickly oxidizes and breaks down what in General, makes the device unusable.

From the literature it is known to use as cathode material of rare earth elements, covered with a protective layer of aluminum or silver (see, for example, K.C.Lau, W.F Xie, and et. Appl. Phys. Lett, 88, 083507, 2006). Many rare earth metals are characterized by a low work function, for example, Sm(3.2 eV), Yb(at 2.59 eV), Tm(of 3.12 eV), while some of them are quite stable in air. However, the number of works devoted to the use of rare earth metals as the cathode material, is limited. It can be expected that devices with cathodes made of rare-earth metals, will have a sufficiently long service life and to have high performance. It is known that the magnitude of the work function is very sensitive to the surface condition of the metal. Picking the proper floor surface, it is possible to reduce the work function, or, on the contrary, increase. The coating layer of the rare earth metal layer of aluminum or silver, which is characterized by high values of the work function, adversely affects the ability of the cathode to the injection of electrons, which leads, in turn, reduce the performance of acid and, thus, the device inherent disadvantages described above.

Known organic light-emitting diode containing a carrier substrate in the form of glass is of the second substrate on the transparent layer of the anode of indium oxide, doped with tin, which is a layer of organic matter with hole conductivity - hole-transport layer made of N,N'-bis(3-were)-N,N'-diphenylbenzidine, then is radiating (emissive) layer from aluminum (Alq3) with a thickness of 20 nm, and on top of the organic layers is a layer of a cathode made of a rare earth metal samarium or dysprosium, or thulium, or ytterbium and, for comparison, from aluminum. The thickness of the cathode layer is 150 nm (see Proceedings of the 27thInternational Display Research Conference pp.396-399 "EURODISPLAY-2007), taken as a prototype. In the above source shows that the best of rare earth metals as cathode material has a thulium, despite the fact that the work output of thulium higher than that of ytterbium - of 3.12 eV and at 2.59 eV, respectively. Shows voltage-luminance and current-voltage characteristics confirm a significant increase in the efficiency of the device using a cathode of thulium in comparison with traditionally used cathode, made of aluminum, and increase efficiency in comparison with the cathode of ytterbium. Thulium is an expensive material, so its use as a cathode material will lead to high cost of the device.

The challenge which seeks the invention, the two which is the development of organic light-emitting diode with high performance through the use of a new cathode material.

This problem is solved due to the fact that in organic light-emitting diode containing a carrier substrate in the form of a substrate placed on the transparent layer of the anode, which is at least an organic emitting (emissive) layer, on top of which is a metal cathode according to the present invention, the cathode is made of a composite material containing ytterbium, thulium-doped, or europium, in an amount not less than 10%, preferably 10-20%.

Preferably, the presence in the device layer of an organic substance with hole conductivity (hole-transport layer located on the anode, whose role is to ensure the transfer of holes from the anode to the emission layer. As a material for the hole-transport layer are compounds with p-type conductivity, for example N,N'-bis(3-were)-N,N'-diphenylbenzidine.

Preferably, the device layer with electronic conductivity (electron transport layer)located below the cathode layer, which facilitates the injection box electrons in the emissive layer and often combines the function of the emission layer. As a material of the electron-transport layer are used in connection with electronic conductivity (for example, oksikhinolinata derived al the MINIA).

As the supporting framework can be used glass or plastic substrate. Glass substrate placed on them by a layer of anode material which is traditionally indium oxide doped with tin, issued by the industry. In the inventive device uses the above-mentioned substrate. At the same time as the anode material can be used other compounds with high injection holes (for example, transparent oxides of gallium and zinc, titanium nitride and gallium and other) Electroluminescent (emissive) layer is the environment in which directly connects to the injection into it of electron-hole pairs and education quanta of light. The thickness of the emission layer is 30-50 nm. Emission layers may be made of organic compounds, selected according to their ability to generate all the basic and intermediate colors. As the material of the emission layer can be used both organic and metal complexes (for example, Polyphenylene, oksikhinolinata complexes of the metals aluminum, zinc carboxylates of metals and other compounds).

The essence of the invention lies in the fact that, as a cathode material using a composite material consisting of ytterbium, thulium-doped, or europium, is not less than 10%, preferably 10-20%.

It was found experimentally that the use of a cathode made of a composite material consisting of ytterbium, thulium-doped, or europium, in an amount not less than 10%, improves the performance of the device.

The applicant was manufactured organic light-emitting diode in which the cathode is made of ytterbium, thulium, ytterbium doped with thulium, ytterbium doped with europium and aluminum, and defines their characteristics. The data are summarized in table.

Table
The cathodeTmYbYb/TmYb/EuAl
The turn-on voltage, The4.84.84.34.66.5
Working voltage brightness 150 CD/m2In5.45.84.55.510.2
The luminescence efficiency, LM/W 2.91.423.412.210.11

The table shows that when using a cathode made of ytterbium, thulium-doped in an amount of not less than 10%, the value of the voltage on and operating voltage, this voltage with the brightness of 150 CD/m2corresponding to the brightness of the running monitor, reduced in comparison with a cathode made of ytterbium, from 4.8 to 4.3 and 5.8 to 4.5, respectively, and the luminescence efficiency increases from 1.42 to 3.41 lumens/watt. The table also shows that the improved performance of the device occurs when using a cathode made of ytterbium, thulium-doped, in comparison with the cathode of thulium. When using a cathode made of ytterbium-doped europium, the performance of the device is also improved in comparison with a cathode made of ytterbium (see table). In addition, the inventive device in which the cathode is made of ytterbium, thulium-doped or europium in an amount not less than 10%, showed increased stability during operation. When the above working voltage drop the brightness by 10% is not less than 4,000 hours, while mentioned, when using the cathode, traditionally made of al is MINIA, does not exceed 3000 hours.

Experiments have shown that the content of thulium or europium in the composite material is less than 10%, does not improve the performance of the device, and more than 10% enter impractical, since the thulium and europium are precious metals, in addition, a metal europium unstable in air. The improved performance when using the cathode material containing ytterbium-doped europium in the above number, can be explained, apparently, by the fact that the EU has the lowest work function, which greatly facilitates the injection of electrons. The improved performance when using the cathode material containing ytterbium, thulium-doped in the above number, can be explained, apparently, by the fact that the thulium and ytterbium in the condensed state have different formal oxidation States (+2 and +3), which affects the energy level of the electrons injected from the cathode into the electron transport and emissive layer. Theoretical approaches do not allow to predict the observed effect, i.e. the result is not obvious to solve the task and is not obvious from the prior art.

The drawing shows an organic light-emitting diode containing carrier basis, the imp is United in the shape of a glass substrate 1 is placed on the transparent layer of the anode 2 - source holes, made of indium oxide doped with tin. At the anode is a layer of organic matter with hole conductivity 3 - conductor layer holes, made of N,N'(3-were-N,N'-diphenylbenzidine thickness of 20 nm. Then follow the emitting layer (emitter layer) 4 made on the basis of aluminum (Alq3), which is the environment where the connection is injected in him electron-hole pairs and the formation of light quanta. The said layer at the same time performs the function of electron transport layer 5. On top of the organic layers is a layer of the cathode 6 is an electron source made of a material containing ytterbium, thulium-doped in the amount of 20%. The thickness of the emission and cathode layers 50 and 200 nm, respectively.

The device operates as follows. When the supply voltage minus to the cathode 6, and a plus to the anode 2 of them injections, respectively, electrons and holes, i.e. negative and positive charges. In sluchayem layer 4 recombination of these charges, which causes the effect of electroluminescence (light emission). As of the support base 1 of the device used a commercially available glass substrate placed on the transparent layer of indium oxide doped with tin, vypolnjajushej the function of the anode. To obtain the organic film material layers making up the structure of the claimed acid layer and the cathode, used the method of thermal evaporation in vacuum.

The inventive device is characterized by high technical characteristics: switching voltage is 4.3-4.6, working voltage brightness 150 CD/m2that corresponds to the brightness of the running monitor, 4.5-5.5 V, and the efficiency of luminescence is 2.21-3.41 lumens/watt. With said operating voltage drop the brightness by 10% is not less than 4000 hours. The performance of cathode from new material creates the potential for a wider range of substances emission layer that is able to generate all the basic and intermediate colors.

1. Organic light-emitting diode containing a carrier substrate in the form of a substrate placed on the transparent layer of the anode, which is at least radiant (emissive) layer, which is made on the basis of organic compounds that contains at least one material selected according to the ability to generate any primary or intermediate color, and on top of the emitting layer is a metal cathode, wherein the cathode is made of a composite material containing ytterbium, thulium-doped, or europium, in an amount not less than 10%.

2. Organic with etoileui diode according to claim 1, characterized in that it contains a layer of organic matter with hole conductivity (hole-transport layer)made of N,N'-bis(3-were)-N,N'-diphenylbenzidine located on the anode layer.

3. Organic light-emitting diode according to claim 1, characterized in that it contains a layer of organic matter with electronic conductivity (electron transport layer), made of oksikhinolinom derived aluminum, located under the cathode layer.

4. Organic light-emitting diode according to claim 1, characterized in that the layer of the anode is made of indium oxide doped with tin.



 

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