Stock material or miscellaneous articles – Composite – Of inorganic material
Reexamination Certificate
2001-11-08
2004-07-06
Kelly, Cynthia (Department: 1774)
Stock material or miscellaneous articles
Composite
Of inorganic material
C428S917000, C313S504000, C313S506000, C427S066000
Reexamination Certificate
active
06759146
ABSTRACT:
BACKGROUND
This invention relates to optoelectronic devices and, more particularly, to organic light emitting devices (organic EL devices). More specifically, the present invention relates to substantially stable organic EL devices and devices possessing extended operational life time, such as at least about 1,000 hours in embodiments, which is prior to their luminance decreasing to some percent of its initial luminance value, such as about 50 percent of the initial luminance, and which devices do not in embodiments, for example, usually degrade in the form of experiencing a decrease in their luminance at high temperatures, such as about 100° C., and moreover, which devices are not substantially adversely affected by high temperatures, such as having a life time of at least about 100 hours at these temperatures.
The organic light emitting devices of the present invention can be utilized in various devices, such as displays that typically are operated over a broad range of temperature conditions. The operational stability at high temperature conditions provided by the organic light emitting devices of this invention enables in embodiments the use of these devices at high temperatures for extended periods of time.
REFERENCES
An organic electroluminescent (EL) device can be comprised of a layer of an organic luminescent material interposed between an anode, typically comprised of a transparent conductor, such as indium tin oxide, and a cathode, typically a low work function metal such as magnesium, calcium, aluminum, or the alloys thereof with other metals. The EL device functions on the primary principle that under an electric field, positive charges (holes) and negative charges (electrons) are respectively injected from the anode and cathode into the luminescent layer and undergo recombination to form excitonic states which subsequently emit light. A number of organic EL devices have been prepared from a laminate of an organic luminescent material and electrodes of opposite polarity, which devices include a single crystal material, such as single crystal anthracene as the luminescent substance as described, for example, in U.S. Pat. No. 3,530,325, the disclosure of which is totally incorporated herein by reference. These types of devices are believed to require excitation voltages on the order of 100 volts or greater.
An organic EL device with a multilayer structure can be formed as a dual layer structure comprising one organic layer adjacent to the anode supporting hole transport, and another organic layer adjacent to the cathode supporting electron transport and acting as the organic luminescent zone of the device. Examples of these devices are disclosed in U.S. Pat. Nos. 4,356,429; 4,539,507; 4,720,432, and 4,769,292, the disclosures of which are totally incorporated herein by reference, wherein U.S. Pat. No. 4,769,292, the disclosure of which is totally incorporated herein by reference, discloses, for example, an organic EL device comprising three separate layers, a hole transport layer, a luminescent layer, and an electron transport layer, which layers are laminated in sequence and are sandwiched between an anode and a cathode, and wherein a fluorescent dopant material is added to the emission zone or layer whereby the recombination of charges results in the excitation of the fluorescent material. In some of these multilayer structures, such as, for example, organic light emitting devices described in U.S. Pat. No. 4,720,432, the disclosure of which is totally incorporated herein by reference, the organic light emitting device further comprises a buffer layer interposed between the hole transport layer and the anode. The combination of the hole transport layer and the buffer layer forms a dual-layer hole transport region, reference S. A. Van Slyke et al., “Organic Electroluminescent Devices with Improved Stability,”
Appl. Phys. Lett.
69, pp. 2160-2162, 1996, the disclosure of which is totally incorporated herein by reference.
There have also been attempts to obtain electroluminescence from organic light emitting devices containing mixed layers, for example, layers in which both the hole transport material and the emitting electron transport material are mixed together in one single layer, see, for example, Kido et al., “Organic Electroluminescent Devices Based On Molecularly Doped Polymers,”
Appl. Phys. Lett.
61, pp. 761-763, 1992; S. Naka et al., “Organic Electroluminescent Devices Using a Mixed Single Layer,”
Jpn. J. Appl. Phys.
33, pp. L1772-L1774, 1994; W. Wen et al.,
Appl. Phys. Lett.
71, 1302 (1997); and C. Wu et al., “Efficient Organic Electroluminescent Devices Using Single-Layer Doped Polymer Thin Films with Bipolar Carrier Transport Abilities”,
IEEE Transactions on Electron Devices
44, pp. 1269-1281, 1997. In a number of these devices, the electron transport material and the emitting material can be the same or the mixed layer can further comprise an emitting material as a dopant. Other examples of organic light emitting devices which are formed of a single organic layer comprising a hole transport material and an electron transport material can be found, for example, in U.S. Pat. Nos. 5,853,905; 5,925,980; 6,114,055 and 6,130,001, the disclosures of which are totally incorporated herein by reference. As indicated in the article by S. Naka et al., these single mixed layer organic light emitting devices are generally less efficient than multilayer organic light emitting devices. These devices, which include only a single mixed layer of a hole transport material, such as NBP (N,N′-di(naphthalene-1-yl)-N,N′-diphenyl-benzidine), and an emitting electron transport material, such as Alq
3
(tris (8-hydroxyquinoline) aluminum), are believed to be unstable and to have poor efficiency. The instability of these devices is believed to be caused by the direct contact between the electron transport material in the mixed layer and the hole injecting contact comprised of indium tin oxide (ITO), which results in the formation of an unstable cationic electronic transport material, and the instability of the mixed layer/cathode interface, see H. Aziz et al.,
Science
283, 1900 (1999), the disclosure of which is totally incorporated herein by reference. In addition, the single mixed layer may result in high leakage currents and hence poor efficiency, see Z. D. Popovic et al.,
Proceedings of the SPIE, Vol.
3176, “Organic Light-Emitting Materials and Devices II”, San Diego, Calif., Jul. 21-23, 1998, pp. 68 to 73, the disclosure of which is totally incorporated herein by reference.
While recent progress in organic EL research has elevated the potential of organic EL devices for widespread applications, the operational stability of current available devices may in some instances be below expectations. A number of known organic light emitting devices have relatively short operational lifetimes before their luminance drops to some percentage of its initial value. Providing interface layers as described, for example, in S. A. Van Slyke et al., “Organic Electroluminescent Devices with Improved Stability,”
Appl. Phys. Lett.
69, pp. 2160-2162, 1996, and doping as described, for example, in Y. Hamada et al., “Influence of the Emission Site on the Running Durability of Organic Electroluminescent Devices”,
Jpn. J. Appl. Phys.
34, pp. L824-L826, 1995, may perhaps increase the operational lifetime of organic light emitting devices for room temperature operation, however, the effectiveness of these organic light emitting devices deteriorates for high temperature device operation. In general, the device lifetime can be reduced by a factor of about two for each 10° C. increment in the operational temperature. Moreover, at high temperatures, the susceptibility of the organic light emitting devices to degrade is increased as described, for example, in Zhou et al., “Real-Time Observation of Temperature Rise and Thermal Breakdown Processes in Organic Leds Using an IR Imaging And Analysis System”,
Advanced Materials
12, pp 265-269, 2000, which further reduces the stability
Aziz Hany
Hor Ah-Mee
Hu Nan-Xing
Popovic Zoran D.
Garrett Dawn
Kelly Cynthia
Palazzo E. O.
Xerox Corporation
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