WO1999049989A1 - Voltage controlled color variable light-emitting devices featuring multilayers of discrete polymer layers and molecular/oligomer layers - Google Patents
Voltage controlled color variable light-emitting devices featuring multilayers of discrete polymer layers and molecular/oligomer layers Download PDFInfo
- Publication number
- WO1999049989A1 WO1999049989A1 PCT/US1999/006292 US9906292W WO9949989A1 WO 1999049989 A1 WO1999049989 A1 WO 1999049989A1 US 9906292 W US9906292 W US 9906292W WO 9949989 A1 WO9949989 A1 WO 9949989A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- current
- light
- electroluminescent device
- color
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- 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]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
Definitions
- This invention relates to multilayer light-emitting devices driven by electric field which are commonly referred to as electroluminescent devices. Background:
- PLEDs polymer-based light-emitting devices
- OLEDs organic light-emitting devices
- polymers comprised of only polymers or of only organic molecules.
- polymer-based devices are blends of polythiophene derivatives wherein different components of the blend emit
- LEDs that allow for simple and inexpensive construction, and which provide for most efficient control of operation and color change.
- the invention includes color variable light-emitting devices which are capable of
- the devices of the present invention comprise at least one layer of an electroluminescent polymer and at least one second layer comprising an oligomeric or molecular electroluminescent emitter; the two layers
- transporting layers may be added to improve device operation and control of color.
- variability of the devices of the present invention may range in degree, varying from small spectral changes to obvious visible changes in color.
- the present invention is therefore broad, and will naturally vary with the degree of spectral change
- devices of the present invention may be any type of material that are required or desired for each embodiment.
- devices of the present invention may be any type of material that are required or desired for each embodiment.
- devices of the present invention may be any type of material
- devices of the present invention may also be used in a non-color- variable fashion by applying an
- the present invention also includes a method of producing a color- variable light from an electroluminescent device, the method comprising the steps: (1) obtaining a color variable electroluminescent device of the present invention as described herein, and (2) causing sufficient current to flow into said device so as to cause the device to emit light, and varying the voltage of said current to a sufficient degree so as to cause a variation in the color of the light.
- FIG. 1 shows general schematic representations of optional variations in the structure of
- Figure 1(a) shows a general schematic of a bilayer device which comprises two layers, with one layer being a polymeric layer as described
- oligomeric or molecular layer as described herein (in Figure 1 , the oligomeric or molecular layer is referred to simply as the oligomeric layer, but is to be understood as
- the layers may be in either orientation from top to bottom:
- oligomeric layer referred to simply as the oligomeric layer, but is to be understood as referring to either layer
- Such layers may be in any order such as, from top to bottom, polymeric/oligomeric(or
- the constituent polymers, oligomers and molecules may be the same or different across respective layers.
- the devices of the present invention may be fabricated by spin casting polymer layers on one electrode and then vacuum depositing the oligomer or molecular layer followed by vacuum deposition or sputtering of the second electrode.
- spin casting techniques are conventional and well known to the art, there are a wide variety of other well known methods that
- the Polymers may be used to make a layered structure including Langmuir-Blodgett techniques, dip coating, doctor blading, etc.
- the Polymers may be used to make a layered structure including Langmuir-Blodgett techniques, dip coating, doctor blading, etc.
- electroluminescent polymer(s) used in the polymeric layer(s) of the present invention is the electroluminescent polymer(s) used in the polymeric layer(s) of the present invention.
- inventions may be any material adapted to perform the described function.
- the polymeric layer may comprise a single polymer or a blend of polymers, the polymers selected from the group consisting of conjugated polymers, copolymers, and mixtures thereof.
- the polymers and their derivatives include those selected from several groups including, but are not limited to, conjugated and non-conjugated polymers and copolymers,
- PVK poly(pyridyl vinylene phenylene vinylene)
- PPyVPV poly(pyridyl vinylene phenylene vinylene)
- PVK polyvinylcarbazole
- polypyridine other polypyridines, polypyridylvinylenes, polythiophenes, polyphenylenes, polyphenylenevinylenes, rigid-rod polymers such as polyphenylenebenzobisthiozoles, poly-
- fluorenes other polyvinylcarbazoles, polythienylenevinylenes, emissive polyacetylenes and
- the emissive polymer layer may be a mixture of a polypyridylvinylene (i.e., having relatively greater electron transporting properties) and a polythiophene (i.e., having relatively greater hole transporting properties).
- a polypyridylvinylene i.e., having relatively greater electron transporting properties
- a polythiophene i.e., having relatively greater hole transporting properties
- Another example may be copolymers of emissive and non- emissive polymers such as polyethylenes.
- present invention may include any light-emitting, current conducting material adapted to perform
- oligomer or "oligomeric” are to be understood as
- molecules having from 2 to no more than about 10 repeating units, preferably no more than ten repeating units. Such materials provide for ease of manufacture and also more
- the molecular electroluminescent emitters used in the respectively described layers of the present invention may include any light-emitting, current conducting material adapted to perform
- Figure 2 displays the repeat units of materials that may be used in the example embodiments of the present invention. These repeat units include those for parasexiphenyl (6P),
- poly(pyridyl vinylene phenylene vinylene) PPyVPV
- polyvinylcarbazole PVK
- the electrodes used in the present invention may be selected from any electrode material
- these will include a hole-injecting and electron
- the hole injecting electrode typically may be fabricated from a number of relatively high
- ITO indium tin oxide
- gold doped conjugated polymers
- the electron injecting electrode typically is a relatively low work functioning metal such as
- the hole injecting or electron injecting electrode may be placed upon a substrate which
- the devices of the present invention may be operated by any appropriate source of
- first electrode 1 and the second electrode 2 are electrically connected to a potential difference supplied by source of electrical energy 12. That is, the first
- electrode 1 can be connected to a positive potential (anode) while the second electrode 2 is connected to a negative potential (cathode) or the connections can be reversed, with the first
- the device may reside on a substrate, such as substrate 5.
- the polymer/oligomer layers 6 and 8 of Figure 1(b) are in electrical contact, respectively,
- Electrodes 9 and 10 are electrically connected to a potential
- the electrodes 1 and 2, and 9 and 10, are connected to a voltage source 12 by means of
- connector or contact can be the electrodes themselves. That is, the potential difference from current source 12 may be applied directly to the electrodes in which case electrodes may become
- the devices of the present invention may feature a relatively low turn-on and operating
- the voltage of the current from current source 12 may be varied sufficiently to vary the
- the voltage of the current from current source may be varied using any appropriate voltage regulator device used in electrical arts. The amount of variation in voltage may be seen in the examples supplied herein.
- Figure 1 shows schematically the structure of the a device in accordance with one
- Figure 2 shows repeating units of materials that may be used in accordance with example
- Figure 3 shows the EL spectra of a bilayer device ITO/6P/PPy/Al device in accordance
- Figure 4 shows the current-voltage and luminance-voltage characteristics of a bilayer
- FIG. 5(a) shows EL spectra of a three layer device, ITO/PVK/6P/PPy/Al, in accordance with one embodiment of the present invention.
- Figure 5(b) is a CIE diagram of a three layer device, ITO/PVK/6P/PPy/Al, in accordance with one embodiment of the present invention.
- Figure 6 shows the current-voltage and luminance-voltage characteristics of a three layer
- ITO/PVK/6P/PPy/Al in accordance with one embodiment of the present invention.
- Figure 7 shows the EL spectra of a bilayer device, ITO/PPyVPV/6P/Al, in accordance with one embodiment of the present invention, operated under different applied voltages.
- Figure 8 shows the current-voltage characteristics of a bilayer device
- ITO/PPyVPV/6P/Al in accordance with one embodiment of the present invention.
- Figure 9 shows EL spectra of a three layer device, ITO/PVK/PPyVPV/6P/Al, in
- Figure 10 shows the typical current-voltage (I-V) characteristics of a three layer device
- ITO/PVK/PPyVPV/6P/Al in accordance with one embodiment of the present invention.
- Figure 11 shows the EL spectra of a three layer device, ITO/PPyVPV/6P/PPy/Al, in
- Figure 12 shows the current- voltage characteristics of a three layer device, ITO/PPyVPV/6P/PPy/Al, in accordance with one embodiment of the present invention.
- Figure 13 shows the EL spectra of a bilayer device, ITO/6P/PPyVPV/Al, in accordance
- Figure 14 shows the current- voltage characteristics of a bilayer device, ITO/6P/PPyVPV/Al, in accordance with one embodiment of the present invention.
- Figure 15 shows EL spectra of a three layer device, ITO/PVK/6P/PPyVPV/Al, in accordance with one embodiment of the present invention.
- Figure 16 shows the typical current- voltage (I-V) and luminance-voltage characteristics of a three layer device, ITO/PVK/6P/PPyVPV/Al, in accordance with one embodiment of the present invention.
- Figure 17 shows the EL spectra of a bilayer device, ITO/PVK 6P/A1, in accordance with
- Figure 18 shows the current- voltage and luminance-voltage characteristics of a bilayer
- ITO/PVK/6P/A1 in accordance with one embodiment of the present invention.
- the polymer layers were formed using spin coating
- the solvents used for the polymers are xylenes for PPyVPV;
- tetrahydrofuran (THF) for PVK formic acid for PPy.
- concentration is typically 5-10 mg/ml.
- the fabrication procedure is as follows.
- the PVK layer was first spin coated at ⁇ 3000 m from THF solution
- the thickness of the 6P layer is 400-800 angstroms.
- the PPyVPV layer was subsequently spin coated over the 6P from xylenes solution -2500 ⁇ m. All the spin coating
- the top metal electrode (Al) was deposited by vacuum evaporation at a pressure below 10 "6 torr. To prevent damage to the
- the substrate was mounted on a cold-water cooled surface during evaporation.
- Photoluminescence (PL) and electroluminescence (EL) were measured using a PTI fluorometer (model QM-1).
- the current- voltage (I-V) characteristics were measured simultaneously with EL
- Figure 3 shows the EL spectra of a bilayer device ITO/6P/PPy/Al operated under different
- the EL spectra show two peaks at 425 nm and 450 nm, in
- bilayer EL spectrum can be roughly represented
- the EL appears light blue to the eye. As the voltage increases, a peak at 565 nm appears and eventually becomes dominant.
- Figure 5(a) shows EL spectra of a three layer device ITO/PVK/6P/PPy/Al. At low applied
- the EL spectrum is very similar to that of the bilayer device, which is light blue in color.
- the CIE chromaticity x,y coordinates of the EL spectra at 17 V is calculated to be (0.237,0.224).
- the peak at 450 nm grows.
- a new peak at ⁇ 605 nm appears and grows, which driving the location of the EL spectra in the CIE diagram towards
- the CIE chromaticity x,y coordinates of the spectra at 27 V is calculated to be (0.322,0.315). Below 27 V, the voltage dependent EL spectra are more or less reversible. Above 27 V, the device went through an irreversible change. The features at the blue region disappears
- Figure 6 shows the typical current-voltage (I-V) and luminance-voltage
- the devices have a typical turn on voltage of -15-17 V.
- Figure 7 shows the EL spectra of a bilayer device ITO/PPyVPV/6P/Al operated under different applied voltages. Under low voltages ( ⁇ 10 V), the EL spectra show a main peak at -620 nm, in addition to three weak peaks from 6P. As the voltage increases, the features from 6P increase and becomes dominant above 14 V. The current- voltage characteristics of such devices
- Figure 9 shows EL spectra of a three layer device ITO/PVK/PPyVPV/6P/Al. Similar
- I-V current- voltage
- Figure 11 shows the EL spectra of a three layer device ITO/PPy VPV/6P/PPy/Al operated
- the EL spectra show three main features: three peaks from 6P
- Figure 13 and Figure 14 shows the EL spectra and current-voltage characteristics, respectively, of a bilayer device ITO/6P/PPyVPV/Al operated under different applied voltages.
- Figure 15 shows EL spectra of a three layer device ITO/PVK/6P/PPyVPV/Al. The EL
- spectra show three main features: three peaks from 6P below 450 nm and two peaks at 540 nm
- Figure 16 shows the typical current- voltage (I-V) and luminance- voltage
- the devices have a typical turn on voltage of -15 V.
- Figure 17 and Figure 18 show the EL spectra and current- voltage characteristics, and luminance-voltage respectively, of a bilayer device ITO/PVK/6P/A1.
- the EL spectra of the bilayer device are very similar to those of the single layer ITO/6P/A1 device, and show modest,
- the brightness and quantum efficiency of the bilayer device increase at least two orders of magnitude than those of the single
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002326156A CA2326156A1 (en) | 1998-03-27 | 1999-03-25 | Voltage controlled color variable light-emitting devices featuring multilayers of discrete polymer layers and molecular/oligomer layers |
AU33608/99A AU3360899A (en) | 1998-03-27 | 1999-03-25 | Voltage controlled color variable light-emitting devices featuring multilayers of discrete polymer layers and molecular/oligomer layers |
EP99914985A EP1068030A1 (en) | 1998-03-27 | 1999-03-25 | Voltage controlled color variable light-emitting devices featuring multilayers of discrete polymer layers and molecular/oligomer layers |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US7963898P | 1998-03-27 | 1998-03-27 | |
US60/079,638 | 1998-03-27 | ||
US25659299A | 1999-02-23 | 1999-02-23 | |
US09/256,592 | 1999-02-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999049989A1 true WO1999049989A1 (en) | 1999-10-07 |
Family
ID=26762239
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/006292 WO1999049989A1 (en) | 1998-03-27 | 1999-03-25 | Voltage controlled color variable light-emitting devices featuring multilayers of discrete polymer layers and molecular/oligomer layers |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1068030A1 (en) |
AU (1) | AU3360899A (en) |
CA (1) | CA2326156A1 (en) |
WO (1) | WO1999049989A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1107220A2 (en) * | 1999-11-30 | 2001-06-13 | Sel Semiconductor Energy Laboratory Co., Ltd. | Gradation control for an active matrix EL display |
US6809482B2 (en) | 2001-06-01 | 2004-10-26 | Semiconductor Energy Laboratory Co., Ltd. | Light emitting device and method of driving the same |
GB2410126A (en) * | 2004-01-09 | 2005-07-20 | Dainippon Printing Co Ltd | Light emitting element and process for producing the same |
US7173586B2 (en) | 2003-03-26 | 2007-02-06 | Semiconductor Energy Laboratory Co., Ltd. | Element substrate and a light emitting device |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3854070A (en) * | 1972-12-27 | 1974-12-10 | N Vlasenko | Electroluminescent device with variable emission |
US5093210A (en) * | 1989-06-30 | 1992-03-03 | Ricoh Company, Ltd. | Electroluminescent device |
US5663573A (en) * | 1995-03-17 | 1997-09-02 | The Ohio State University | Bipolar electroluminescent device |
-
1999
- 1999-03-25 WO PCT/US1999/006292 patent/WO1999049989A1/en not_active Application Discontinuation
- 1999-03-25 EP EP99914985A patent/EP1068030A1/en not_active Withdrawn
- 1999-03-25 CA CA002326156A patent/CA2326156A1/en not_active Abandoned
- 1999-03-25 AU AU33608/99A patent/AU3360899A/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3854070A (en) * | 1972-12-27 | 1974-12-10 | N Vlasenko | Electroluminescent device with variable emission |
US5093210A (en) * | 1989-06-30 | 1992-03-03 | Ricoh Company, Ltd. | Electroluminescent device |
US5663573A (en) * | 1995-03-17 | 1997-09-02 | The Ohio State University | Bipolar electroluminescent device |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1107220A2 (en) * | 1999-11-30 | 2001-06-13 | Sel Semiconductor Energy Laboratory Co., Ltd. | Gradation control for an active matrix EL display |
EP1107220A3 (en) * | 1999-11-30 | 2002-08-28 | Sel Semiconductor Energy Laboratory Co., Ltd. | Gradation control for an active matrix EL display |
US6730966B2 (en) | 1999-11-30 | 2004-05-04 | Semiconductor Energy Laboratory Co., Ltd. | EL display using a semiconductor thin film transistor |
US6982462B2 (en) | 1999-11-30 | 2006-01-03 | Semiconductor Energy Laboratory Co., Ltd. | Light emitting display device using multi-gate thin film transistor |
US7525119B2 (en) | 1999-11-30 | 2009-04-28 | Semiconductor Energy Laboratory Co., Ltd. | Light emitting display device using thin film transistors and electro-luminescence element |
US8017948B2 (en) | 1999-11-30 | 2011-09-13 | Semiconductor Energy Laboratory Co., Ltd. | Electric device |
US8890149B2 (en) | 1999-11-30 | 2014-11-18 | Semiconductor Energy Laboratory Co., Ltd. | Electro-luminescence display device |
US6809482B2 (en) | 2001-06-01 | 2004-10-26 | Semiconductor Energy Laboratory Co., Ltd. | Light emitting device and method of driving the same |
US7173586B2 (en) | 2003-03-26 | 2007-02-06 | Semiconductor Energy Laboratory Co., Ltd. | Element substrate and a light emitting device |
US7714818B2 (en) | 2003-03-26 | 2010-05-11 | Semiconductor Energy Laboratory Co., Ltd. | Element substrate and a light emitting device |
GB2410126A (en) * | 2004-01-09 | 2005-07-20 | Dainippon Printing Co Ltd | Light emitting element and process for producing the same |
Also Published As
Publication number | Publication date |
---|---|
AU3360899A (en) | 1999-10-18 |
CA2326156A1 (en) | 1999-10-07 |
EP1068030A1 (en) | 2001-01-17 |
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