US20020011782A1 - Organic electroluminescent device with improved hole injecting structure - Google Patents
Organic electroluminescent device with improved hole injecting structure Download PDFInfo
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- US20020011782A1 US20020011782A1 US09/234,457 US23445799A US2002011782A1 US 20020011782 A1 US20020011782 A1 US 20020011782A1 US 23445799 A US23445799 A US 23445799A US 2002011782 A1 US2002011782 A1 US 2002011782A1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229920000553 poly(phenylenevinylene) Polymers 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
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- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 4
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 claims description 2
- GENZLHCFIPDZNJ-UHFFFAOYSA-N [In+3].[O-2].[Mg+2] Chemical compound [In+3].[O-2].[Mg+2] GENZLHCFIPDZNJ-UHFFFAOYSA-N 0.000 claims description 2
- BEQNOZDXPONEMR-UHFFFAOYSA-N cadmium;oxotin Chemical compound [Cd].[Sn]=O BEQNOZDXPONEMR-UHFFFAOYSA-N 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims 2
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- 229910052681 coesite Inorganic materials 0.000 description 10
- 229910052906 cristobalite Inorganic materials 0.000 description 10
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- 229910052682 stishovite Inorganic materials 0.000 description 10
- 229910052905 tridymite Inorganic materials 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
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- 229910010272 inorganic material Inorganic materials 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
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- 150000003512 tertiary amines Chemical class 0.000 description 2
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 238000011109 contamination Methods 0.000 description 1
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- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
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- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
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- 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]
- H10K50/17—Carrier injection 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]
- H10K50/17—Carrier injection layers
- H10K50/171—Electron injection layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/917—Electroluminescent
Definitions
- the present invention pertains to organic thin-film electroluminescent devices and a method of manufacture of such devices.
- OELDs organic electroluminescent devices
- Representatives of early OELDs are Gurnee et al U.S. Pat. No. 3,172,862, issued Mar. 9, 1965; Gurnee U.S. Pat. No. 3,173,050, issued Mar. 9, 1965; and Dresner U.S. Pat. No. 3,710,167, issued Jan. 9, 1973.
- These devices comprised a single organic emitting layer having thicknesses above 1 mm and two electrodes (cathode and anode). Alkali metals were used as the cathode materials as they had the lowest work function values.
- Tang et al U.S. Pat. No. 4,356,429 disclosed an OELD with two organic layers, in which the organic luminescent medium consisted of two extremely thin layers separating the anode and the cathode. These comprised one layer injecting and transporting holes and the other layer injecting and transporting electrons and also acting as the organic luminescent zone of the device.
- 5,668,438 disclosed an OELD in which the materials making up the electron transporting layer (ETL) and the hole transporting layer (HTL) were selected so that the energy barrier for hole injection from the HTL to the ETL was substantially higher than the energy barrier for electron injection from the ETL to the HTL. In that case, light was emitted from the HTL rather than the ETL.
- ETL electron transporting layer
- HTL hole transporting layer
- Hung et al U.S. Pat. No. 5,776,623 disclosed an OELD containing a transparent electron-injecting electrode.
- the electrode included a thin non-conductive layer contacting the electroluminescent layer and a conductive transparent overcoat layer. The thickness of the nonconductive layer was selected so that the bilayer acted as an electron injecting contact and provided stability against atmospheric corrosion.
- Vanslyke et al U.S. Pat. No. 5,061,569 disclosed an internal junction OELD in which the hole injecting and transporting zone included a tertiary amine containing at least two tertiary amine moieties and including, attached to a tertiary amine nitrogen atom, an aromatic moiety containing at least two fused aromatic rings.
- Tokito et al U.S. Pat. No. 5,783,292 disclosed an OELD in which organic-inorganic composite thin film was used.
- This invention comprises an OELD and method of manufacture in which an inorganic buffer layer is included in the hole injecting region.
- the device comprises in order: an ITO-covered glass substrate which behaves as the hole injector and is transparent and transmissive to optical radiation, a layer of inorganic material as a buffer to the hole injection, an organic single layer or multilayer structure for electroluminescence and carrier confinement, and a layer of low-work-function material as an electron injector which is stable relative to atmospheric corrosion.
- the buffer layer may also be included in the electron injecting region.
- FIGS. 1 and 2 which are schematic diagrams of an embodiment of the OELD of the invention.
- FIG. 3 is a graphical representation of the results of different thickness of buffer layer in terms of brightness.
- FIG. 4 is a graphical representation of the results of FIG. 3 in terms of electroluminescent efficiency.
- An electroluminescent (EL) device 100 of the invention is schematically illustrated in FIG. 1.
- Anode 102 is separated from cathode 104 by an inorganic buffer layer 106 and an organic luminescent medium 108 , which, as shown in this embodiment, consists of two superimposed layers.
- Layer 110 which is located above the buffer layer 106 , forms a hole injecting zone of the organic luminescent medium.
- layer 112 which forms an electron transporting zone of the organic luminescent medium.
- the anode and the cathode are connected to an external AC or DC power source 114 by conductors 116 and 118 , respectively.
- the power source can be pulsed or continuous wave.
- the EL device 100 When the EL device 100 is forward biased, i.e., the potential of the anode is higher than that of the cathode, there occurs injection of holes (positive charge carriers) into the lower organic layer, as schematically shown at 120 , while electrons are injected into the upper organic layer, as schematically shown at 122 , in the luminescent medium.
- the injected holes and electrons each migrate toward the oppositely charged electrode, as shown by the arrows 124 and 126 , respectively. This results in hole-electron recombination.
- a migrating electron drops from its conduction potential to a valence band in filing a hole, energy is released as light.
- the organic luminescent medium forms between the electrodes a luminescent zone receiving mobile charge carriers from each electrode.
- the released light can be emitted from the organic luminescent material through one or more edges 128 of the organic luminescent medium separating the electrodes, through the anode, through the cathode, or through any combination of the foregoing.
- Organic EL device 200 shown in FIG. 2 is illustrative of one preferred embodiment of the invention. Same as in previous OELDs'fabrication, a transparent anode electrode is used in the present invention.
- Layer 202 is a transparent and insulating support onto which is deposited a conductive and light transmissive 204 . Typically, this layer is made from metal or metal oxide such as ITO.
- This layer as an anode electrode, possesses a relatively high work function.
- Adjacent to 204 is the anode-combined buffer layer 206 , which, in this embodiment, is selected from the group consisting of SiO x , Y 2 O 3 , and Ta 2 O 5 , where x is from 1 to 2.
- the organic luminescent medium 208 consisting of hole injecting zone 210 and electron transporting zone 212 in which luminescence occurs.
- the top electrode 214 acts as the electron injector with a relatively low work function. It is usually either a single metal or a multi-metal mixture formed by codeposition in vacuum.
- the preferred embodiments above describe an OELD which positions the buffer layer between the anode and the luminescent medium.
- the buffer layer may also increase efficiency when positioned between the cathode and the luminescent medium, for example, between the cathode and electron transporting layer.
- multiple buffer layers such as a buffer layer adjacent the anode and a further buffer layer adjacent the cathode are possible. There is no requirement for identical buffer layers in such a multi-layer structure with the buffer layers on opposed sides of the luminescent medium able to be of different materials or mixtures as required.
- the buffer layers described have been selected from a particularly group of oxides.
- the buffer layer is chosen from insulating metal oxides, semiconductor oxides, diamond-like carbon and nitrogen doped carbon.
- insulating metal oxides semiconductor oxides
- diamond-like carbon diamond-like carbon
- nitrogen doped carbon a number of different materials may be used in the buffer layer to perform the same function. The list provided is not considered exhaustive.
- the electroluminescent element contained within the device can comprise variety of materials found suitable for such purposes. These include the inclusion of molecules selected from Alq, TPD, NPB and TPBI as well as a variety of polymers.
- the polymers may include such polymers as poly (paraphenylene vinylene) (PPV), PPV copolymers and derivatives. Again, this is not an exhaustive list of possible materials for this element.
- the anode can be made from many suitable materials for the purpose. Typically such anodes are made from transparent conducting oxides. These include indium-tin-oxide, aluminum- or indium-doped zinc oxide, tin oxide, magnesium-indium-oxide and cadmium-tin-oxide.
- the device structure has an inorganic buffer layer and a two organic-layer stack, namely hole transporting layer and fluorescent emitting and electron transporting layer.
- An indium-tin-oxide coated glass substrate was sequentially ultrasonicated in a commercial detergent, rinsed in deionized water, degreased in organic solvent, such as ethanol and acetone, and exposed to ultraviolet light and ozone for a few minutes.
- a fluorescent emitting and electron transporting layer of Alq (600 Angstroms) was then deposited onto the hole transporting layer.
- the OELDs were fabricated according to the procedure of Example 1.
- the buffer layers with different thicknesses of SiO 2 were used.
- Table 1 lists the EL luminance quantum efficiency measured in unit of candela per ampere, and luminance output under a constant current bias of 20 mA/cm 2 .
- the luminance efficiency it can be observed that there may be a reduction in efficiency with a particularly thin layer.
- the efficiency increases towards the thickness of 1 nm. There may then be a tailing off of efficiency as the thickness increases.
- This particular buffer layer is an insulating layer and will inhibit current as the layer thickness increases.
- the thickness as provided in this table shows the performance of SiO 2 . Different thicknesses may provide different results with alternative materials used as the buffer layer.
- FIG. 3 shows the B-I-V curves of four devices with different thicknesses of buffer layer (SiO 2 )
- FIG. 4 shows the electroluminescent efficiency of the four devices with different thicknesses of buffer layer (SiO 2 ).
- the OELDs were fabricated according to the procedure of Example 1. Buffer layers made of different inorganic materials, such as SiO 2 , Y 2 O 3 and Ta 2 O 5 , were used. Table 2 lists the EL luminance quantum efficiency measured in unit of candela per ampere and luminance output under a constant current bias of 20 mA/cm 2 (the thickness of the inorganic materials is about 1.0 nm). TABLE 2 Materials SiO 2 Y 2 O 3 Ta 2 O 5 CIEx 0.339 0.334 0.335 CIEy 0.562 0.562 0.562 Luminance 1,820 1,280 1,360 Luminance Eff. (cd/A) 9.1 6.4 6.8
- the OELDs were fabricated according to the procedure of Example 1.
- the substrate with buffer layer was further treated by radiation, which effectively protects the surface of the buffer layer against harmful contamination. Even higher EL efficiency can be obtained thereby.
- the fabrication procedure provided in the examples again discloses a method of manufacturing an OELD which incorporates a buffer layer between the cathode and anode.
- the examples given deposit the buffer layer onto the intended anode of the device.
- the layer may be deposited prior to deposition of the cathode or onto the cathode be the device is deposited in reverse.
- the order of the layers in the examples are for these preferred embodiments only.
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Abstract
Description
- The present invention pertains to organic thin-film electroluminescent devices and a method of manufacture of such devices.
- Fabrication of organic electroluminescent devices (OELDs) can be traced back to 1960's. Representatives of early OELDs are Gurnee et al U.S. Pat. No. 3,172,862, issued Mar. 9, 1965; Gurnee U.S. Pat. No. 3,173,050, issued Mar. 9, 1965; and Dresner U.S. Pat. No. 3,710,167, issued Jan. 9, 1973. These devices comprised a single organic emitting layer having thicknesses above 1 mm and two electrodes (cathode and anode). Alkali metals were used as the cathode materials as they had the lowest work function values.
- Tang et al U.S. Pat. No. 4,356,429 disclosed an OELD with two organic layers, in which the organic luminescent medium consisted of two extremely thin layers separating the anode and the cathode. These comprised one layer injecting and transporting holes and the other layer injecting and transporting electrons and also acting as the organic luminescent zone of the device.
- Improvements were then achieved by using different cathode materials. Tang et al U.S. Pat. No. 4,885,211 disclosed an OELD with its cathode comprising a layer of a plurality of metals other than single alkali metals, at least one of the metals having a work function of less than 4 eV. Hung et al U.S. Pat. No. 5,608,287 disclosed OELDs having a conductive electron injector. Shi et al U.S. Pat. No. 5,668,438 disclosed an OELD in which the materials making up the electron transporting layer (ETL) and the hole transporting layer (HTL) were selected so that the energy barrier for hole injection from the HTL to the ETL was substantially higher than the energy barrier for electron injection from the ETL to the HTL. In that case, light was emitted from the HTL rather than the ETL.
- More recently, Hung et al U.S. Pat. No. 5,776,623 disclosed an OELD containing a transparent electron-injecting electrode. The electrode included a thin non-conductive layer contacting the electroluminescent layer and a conductive transparent overcoat layer. The thickness of the nonconductive layer was selected so that the bilayer acted as an electron injecting contact and provided stability against atmospheric corrosion.
- However, only very few patents have dealt with the hole injecting structure. Vanslyke et al U.S. Pat. No. 5,061,569 disclosed an internal junction OELD in which the hole injecting and transporting zone included a tertiary amine containing at least two tertiary amine moieties and including, attached to a tertiary amine nitrogen atom, an aromatic moiety containing at least two fused aromatic rings. Tokito et al U.S. Pat. No. 5,783,292 disclosed an OELD in which organic-inorganic composite thin film was used.
- It is an object of the present invention to provide an OELD with an increased electroluminescent efficiency and/or improved stability or which will at least provide the public with a useful choice.
- This invention comprises an OELD and method of manufacture in which an inorganic buffer layer is included in the hole injecting region.
- Preferably, the device comprises in order: an ITO-covered glass substrate which behaves as the hole injector and is transparent and transmissive to optical radiation, a layer of inorganic material as a buffer to the hole injection, an organic single layer or multilayer structure for electroluminescence and carrier confinement, and a layer of low-work-function material as an electron injector which is stable relative to atmospheric corrosion. The buffer layer may also be included in the electron injecting region.
- Preferred embodiments of this invention can be better appreciated by reference to the following description considered in conjunction with the drawings in which:
- FIGS. 1 and 2 which are schematic diagrams of an embodiment of the OELD of the invention;
- FIG. 3 is a graphical representation of the results of different thickness of buffer layer in terms of brightness; and
- FIG. 4 is a graphical representation of the results of FIG. 3 in terms of electroluminescent efficiency.
- An electroluminescent (EL)
device 100 of the invention is schematically illustrated in FIG. 1.Anode 102 is separated fromcathode 104 by aninorganic buffer layer 106 and an organicluminescent medium 108, which, as shown in this embodiment, consists of two superimposed layers.Layer 110, which is located above thebuffer layer 106, forms a hole injecting zone of the organic luminescent medium. Abovelayer 110 islayer 112, which forms an electron transporting zone of the organic luminescent medium. The anode and the cathode are connected to an external AC orDC power source 114 byconductors - When the
EL device 100 is forward biased, i.e., the potential of the anode is higher than that of the cathode, there occurs injection of holes (positive charge carriers) into the lower organic layer, as schematically shown at 120, while electrons are injected into the upper organic layer, as schematically shown at 122, in the luminescent medium. The injected holes and electrons each migrate toward the oppositely charged electrode, as shown by thearrows 124 and 126, respectively. This results in hole-electron recombination. When a migrating electron drops from its conduction potential to a valence band in filing a hole, energy is released as light. Hence the organic luminescent medium forms between the electrodes a luminescent zone receiving mobile charge carriers from each electrode. Depending upon the choice of alternative constructions, the released light can be emitted from the organic luminescent material through one ormore edges 128 of the organic luminescent medium separating the electrodes, through the anode, through the cathode, or through any combination of the foregoing. -
Organic EL device 200 shown in FIG. 2 is illustrative of one preferred embodiment of the invention. Same as in previous OELDs'fabrication, a transparent anode electrode is used in the present invention.Layer 202 is a transparent and insulating support onto which is deposited a conductive and light transmissive 204. Typically, this layer is made from metal or metal oxide such as ITO. This layer, as an anode electrode, possesses a relatively high work function. Adjacent to 204 is the anode-combinedbuffer layer 206, which, in this embodiment, is selected from the group consisting of SiOx, Y2O3, and Ta2O5, where x is from 1 to 2. Above 206 is the organicluminescent medium 208, consisting ofhole injecting zone 210 andelectron transporting zone 212 in which luminescence occurs. The top electrode 214 acts as the electron injector with a relatively low work function. It is usually either a single metal or a multi-metal mixture formed by codeposition in vacuum. - The preferred embodiments above describe an OELD which positions the buffer layer between the anode and the luminescent medium. The buffer layer may also increase efficiency when positioned between the cathode and the luminescent medium, for example, between the cathode and electron transporting layer. Furthermore, multiple buffer layers such as a buffer layer adjacent the anode and a further buffer layer adjacent the cathode are possible. There is no requirement for identical buffer layers in such a multi-layer structure with the buffer layers on opposed sides of the luminescent medium able to be of different materials or mixtures as required.
- The buffer layers described have been selected from a particularly group of oxides. In preferred embodiments, the buffer layer is chosen from insulating metal oxides, semiconductor oxides, diamond-like carbon and nitrogen doped carbon. Of course, a number of different materials may be used in the buffer layer to perform the same function. The list provided is not considered exhaustive.
- The electroluminescent element contained within the device can comprise variety of materials found suitable for such purposes. These include the inclusion of molecules selected from Alq, TPD, NPB and TPBI as well as a variety of polymers. The polymers may include such polymers as poly (paraphenylene vinylene) (PPV), PPV copolymers and derivatives. Again, this is not an exhaustive list of possible materials for this element.
- Similarly, the anode can be made from many suitable materials for the purpose. Typically such anodes are made from transparent conducting oxides. These include indium-tin-oxide, aluminum- or indium-doped zinc oxide, tin oxide, magnesium-indium-oxide and cadmium-tin-oxide.
- The invention and its advantages are further illustrated by the specific examples which follow:
- Fabrication Procedure
- An OELD satisfying the requirements of the invention was constructed in the following manner. The device structure has an inorganic buffer layer and a two organic-layer stack, namely hole transporting layer and fluorescent emitting and electron transporting layer.
- An indium-tin-oxide coated glass substrate was sequentially ultrasonicated in a commercial detergent, rinsed in deionized water, degreased in organic solvent, such as ethanol and acetone, and exposed to ultraviolet light and ozone for a few minutes.
- An inorganic buffer layer (0-200 Angstroms) was then deposited on top of the ITO coated substrate by evaporation.
- Onto the buffer layer was deposited a hole transporting layer of TPD or NPB (500-1,500 Angstroms), evaporated from a tantalum boat.
- A fluorescent emitting and electron transporting layer of Alq (600 Angstroms) was then deposited onto the hole transporting layer.
- On top of the Alq layer was deposited a 1,500-Angstrom thick cathode formed of a 10:1 atomic ratio of Mg and Ag.
- The above sequence completed the deposition of the OELD. The device was then packaged in a dry glove box for protection against ambient environment.
- OELDs with SiO2 Buffer Layer
- The OELDs were fabricated according to the procedure of Example 1. The buffer layers with different thicknesses of SiO2 were used. Table 1 lists the EL luminance quantum efficiency measured in unit of candela per ampere, and luminance output under a constant current bias of 20 mA/cm2.
TABLE 1 SiO2 Thickness (nm) 0 0.5 1.0 1.5 CIEx 0.334 0.338 0.339 0.339 CIEy 0.562 0.563 0.562 0.562 Luminance 1,140 960 1,820 1,680 Luminance Eff. (cd/A) 5.7 4.8 9.1 8.4 - Referring to the luminance efficiency, it can be observed that there may be a reduction in efficiency with a particularly thin layer. However, as shown in this example using SiO2, the efficiency increases towards the thickness of 1 nm. There may then be a tailing off of efficiency as the thickness increases. This particular buffer layer is an insulating layer and will inhibit current as the layer thickness increases. The thickness as provided in this table shows the performance of SiO2. Different thicknesses may provide different results with alternative materials used as the buffer layer.
- Brightness-Current-Voltage (B-I-V) Characteristics
- The OELDs were fabricated according to the procedure of Example 1. FIG. 3 shows the B-I-V curves of four devices with different thicknesses of buffer layer (SiO2)
- Quantum Efficiency of the Devices with Different Thicknesses of SiO2
- The OELDs were fabricated according to the procedure of Example 1. FIG. 4 shows the electroluminescent efficiency of the four devices with different thicknesses of buffer layer (SiO2).
- OELDs with Different Buffer Layers
- The OELDs were fabricated according to the procedure of Example 1. Buffer layers made of different inorganic materials, such as SiO2, Y2O3 and Ta2O5, were used. Table 2 lists the EL luminance quantum efficiency measured in unit of candela per ampere and luminance output under a constant current bias of 20 mA/cm2 (the thickness of the inorganic materials is about 1.0 nm).
TABLE 2 Materials SiO2 Y2O3 Ta2O5 CIEx 0.339 0.334 0.335 CIEy 0.562 0.562 0.562 Luminance 1,820 1,280 1,360 Luminance Eff. (cd/A) 9.1 6.4 6.8 - Further Treatment of the Buffer Layer
- The OELDs were fabricated according to the procedure of Example 1. The substrate with buffer layer was further treated by radiation, which effectively protects the surface of the buffer layer against harmful contamination. Even higher EL efficiency can be obtained thereby.
- The fabrication procedure provided in the examples again discloses a method of manufacturing an OELD which incorporates a buffer layer between the cathode and anode. The examples given deposit the buffer layer onto the intended anode of the device. Again, it should be noted that the layer may be deposited prior to deposition of the cathode or onto the cathode be the device is deposited in reverse. The order of the layers in the examples are for these preferred embodiments only.
- Further aspects of this invention may become apparent to those skill in the art to which the invention relates. It should be noted that integers referred to throughout the specification are deemed to incorporate known equivalents and the disclosure of the preferred embodiments did not be considered limiting to the scope of the invention as defined by the appended claims.
Claims (18)
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Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3172862A (en) | 1960-09-29 | 1965-03-09 | Dow Chemical Co | Organic electroluminescent phosphors |
US3173050A (en) | 1962-09-19 | 1965-03-09 | Dow Chemical Co | Electroluminescent cell |
US3710167A (en) | 1970-07-02 | 1973-01-09 | Rca Corp | Organic electroluminescent cells having a tunnel injection cathode |
US4356429A (en) | 1980-07-17 | 1982-10-26 | Eastman Kodak Company | Organic electroluminescent cell |
US4757235A (en) * | 1985-04-30 | 1988-07-12 | Nec Corporation | Electroluminescent device with monolithic substrate |
US4885211A (en) | 1987-02-11 | 1989-12-05 | Eastman Kodak Company | Electroluminescent device with improved cathode |
DE69110922T2 (en) * | 1990-02-23 | 1995-12-07 | Sumitomo Chemical Co | Organic electroluminescent device. |
US5061569A (en) | 1990-07-26 | 1991-10-29 | Eastman Kodak Company | Electroluminescent device with organic electroluminescent medium |
US5482896A (en) * | 1993-11-18 | 1996-01-09 | Eastman Kodak Company | Light emitting device comprising an organic LED array on an ultra thin substrate and process for forming same |
JPH08102360A (en) | 1994-09-29 | 1996-04-16 | Toyota Central Res & Dev Lab Inc | Orfanic/inorganic complex thin-film electroluminescent element |
US5608287A (en) | 1995-02-23 | 1997-03-04 | Eastman Kodak Company | Conductive electron injector for light-emitting diodes |
US5741626A (en) * | 1996-04-15 | 1998-04-21 | Motorola, Inc. | Method for forming a dielectric tantalum nitride layer as an anti-reflective coating (ARC) |
KR980005265A (en) | 1996-06-06 | 1998-03-30 | 빈센트 비. 인그라시아 | Organic electroluminescent devices emitted from the hole transport layer |
US5734225A (en) * | 1996-07-10 | 1998-03-31 | International Business Machines Corporation | Encapsulation of organic light emitting devices using siloxane or siloxane derivatives |
US5776623A (en) | 1996-07-29 | 1998-07-07 | Eastman Kodak Company | Transparent electron-injecting electrode for use in an electroluminescent device |
US5932964A (en) * | 1996-09-24 | 1999-08-03 | Mccann & Associates, Inc. | Europium-containing group IIA fluoride epitaxial layer on silicon |
JPH10125469A (en) * | 1996-10-24 | 1998-05-15 | Tdk Corp | Organic electroluminescent element |
US6140763A (en) * | 1998-07-28 | 2000-10-31 | Eastman Kodak Company | Interfacial electron-injecting layer formed from a doped cathode for organic light-emitting structure |
US6067222A (en) * | 1998-11-25 | 2000-05-23 | Applied Materials, Inc. | Substrate support apparatus and method for fabricating same |
-
1999
- 1999-01-21 US US09/234,457 patent/US6351067B2/en not_active Expired - Lifetime
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