WO2000036661A1 - Organic light-emitting devices - Google Patents
Organic light-emitting devices Download PDFInfo
- Publication number
- WO2000036661A1 WO2000036661A1 PCT/GB1999/004144 GB9904144W WO0036661A1 WO 2000036661 A1 WO2000036661 A1 WO 2000036661A1 GB 9904144 W GB9904144 W GB 9904144W WO 0036661 A1 WO0036661 A1 WO 0036661A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- emitting device
- organic light
- light
- dielectric material
- Prior art date
Links
- 239000011368 organic material Substances 0.000 claims abstract description 31
- 239000003989 dielectric material Substances 0.000 claims abstract description 28
- 239000002800 charge carrier Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 29
- 230000004888 barrier function Effects 0.000 claims description 17
- 239000011575 calcium Substances 0.000 claims description 17
- 229910052791 calcium Inorganic materials 0.000 claims description 15
- 238000005247 gettering Methods 0.000 claims description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000004544 sputter deposition Methods 0.000 claims description 11
- 238000007738 vacuum evaporation Methods 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 229910010199 LiAl Inorganic materials 0.000 claims description 2
- 229910005091 Si3N Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims 4
- ATUUNJCZCOMUKD-OKILXGFUSA-N MLI-2 Chemical compound C1[C@@H](C)O[C@@H](C)CN1C1=CC(C=2C3=CC(OC4(C)CC4)=CC=C3NN=2)=NC=N1 ATUUNJCZCOMUKD-OKILXGFUSA-N 0.000 claims 1
- 229910001092 metal group alloy Inorganic materials 0.000 claims 1
- 239000010410 layer Substances 0.000 description 93
- 229910017083 AlN Inorganic materials 0.000 description 9
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 9
- 239000010409 thin film Substances 0.000 description 9
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 5
- 239000000758 substrate Substances 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- -1 poly(phenylenevinylene) Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000001552 radio frequency sputter deposition Methods 0.000 description 2
- 239000005964 Acibenzolar-S-methyl Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000001669 calcium Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002650 laminated plastic Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
Classifications
-
- 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
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/846—Passivation; Containers; Encapsulations comprising getter material or desiccants
-
- 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
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
Definitions
- This invention relates to organic light-emitting devices (OLEDs).
- an OLED is fabricated by coating a glass or plastic substrate with a transparent first electrode (anode) such as indium tin oxide (ITO). At least one layer of a thin film of an electroluminescent organic material is then deposited prior to a final layer which is a film of a second electrode (cathode) which is typically a metal or alloy.
- a transparent first electrode such as indium tin oxide (ITO).
- ITO indium tin oxide
- a layer of a metal having a low work function such as calcium or an alloy containing a metal having a low work function are the preferred materials for the cathode.
- a metal having a low work function such as calcium or an alloy containing a metal having a low work function are the preferred materials for the cathode.
- it is an intrinsic property of such low work function elements that they are very prone to reactions with reactive ambient species such as oxygen or moisture. Such reactions detrimentally affect the electron-injecting properties of the cathode causing the formation of non-emitting black spots with a consequent degradation in device performance.
- an organic light-emitting device comprising at least one layer of a light-emissive organic material interposed between a first electrode and a second electrode, at least one of the first and second electrodes comprising one or more electrode layers on the light-emissive material; wherein the organic light-emitting device further has a stack comprising an inert barrier layer and at least one gettering layer interposed between the outermost electrode layer and the inert barrier layer for absorbing moisture and oxygen.
- the advantages of this aspect of the present invention are particularly pronounced when the electrode upon which the stack is formed comprises at least one layer deposited by vacuum evaporation.
- the inert barrier layer serves to minimize the entry of reactive species into the device, and the gettering layer serves to absorb any traces of reactive species which manage to somehow permeate through the inert barrier layer.
- the inert barrier layer is preferably a layer of an inorganic dielectric material preferably selected from the group consisting of A1N, Al 2 O 3 , SiO 2 and Si 3 N 4 , and preferably has a thickness in the range of 0.01 to 10 microns, further preferably in the range of 1 to 10 microns.
- the inert barrier layer is preferably deposited by a sputtering technique to provide a pinhole-free layer.
- the gettering layer is preferably a layer of a material which displays high reactivity towards moisture and oxygen such as Li, Ca, Ba or Cs, or an alloy of the same such as LiAl, or a hygroscopic oxide such as BaO. It preferably has a thickness in the range of 0.01 to 5 microns. Calcium is a particularly preferred material for the gettering layer.
- the gettering layer may be deposited by a sputtering technique to provide a pinhole-free layer. Alternatively, it may be deposited by a vacuum evaporation technique.
- an organic light-emitting device comprising a layer of light-emissive organic material interposed between a first electrode and a second electrode, at least one of the first and second electrodes comprising one or more electrode layers on the layer of light-emissive organic material for injecting charge carriers into the light-emissive organic material, wherein the organic light-emitting device further comprises a layer of dielectric material on the surface of the outermost electrode layer remote from the layer of light-emissive organic material.
- the advantages of this aspect of the present invention are also particularly pronounced when the electrode upon which the dielectric layer or layers is formed comprises at least one layer deposited by vacuum evaporation.
- the organic light-emitting device further comprises a second layer of dielectric material on the first layer of dielectric material, the thickness of the dielectric layers being selected so as to reduce mechanical stress on the electrode .
- Suitable dielectric materials for each of the first and second layers include inorganic dielectric materials, preferably SiO, A1N, SiO 2 , Si 3 N and Al 2 O 3 .
- the thickness of each of the dielectric layers is preferably in the range of 0.01 to 10 microns, preferably in the range of 1 to 10 microns.
- Each of the dielectric layers may be deposited by a sputtering technique or by a vacuum evaporation technique.
- a method of providing a protective cap on a first electrode of an organic light-emitting device comprising at least one layer of a light-emissive organic material between first and second electrodes for injecting charge carriers into the light-emissive organic material, said method comprising the step of forming a first layer of a dielectric material on the surface of the first electrode opposite the layer of light-emissive organic material by a vacuum evaporation technique.
- the first electrode typically comprises one or more metal layers with the dielectric layer being formed directly on the surface of the outermost metal layer remote from the organic light-emissive material.
- barrier layers and/or gettering layers of the kind discussed above can be provided on the first dielectric layer.
- the advantages of the third aspect of the present invention are pronounced when the subject electrode has been deposited by a vacuum evaporation technique.
- Figure 1 is a schematic cross-sectional view of an organic light-emitting device according to a first embodiment of the present invention.
- Figure 2 is a schematic cross-sectional view of an organic light-emitting device according to a second embodiment of the present invention.
- Figure 3 is a schematic cross-sectional view of an organic light-emitting device according to a third embodiment of the present invention.
- Figure 4 is a schematic cross-sectional view of an organic light-emitting device according to a fourth embodiment of the present invention.
- Figure 5 is a schematic cross-sectional view of an organic light-emitting device according to a fifth embodiment of the present invention.
- Figure 6 is a schematic cross-sectional view of an organic light-emitting device according to a sixth embodiment of the present invention.
- Figure 7 is a schematic cross-sectional view of an organic light-emitting device according to a seventh embodiment of the present invention.
- the device comprises a first electrode layer 4, in this case an anode layer comprised of indium tin oxide (ITO) formed on a substrate 2.
- the substrate may, for example, be one made of glass or a flexible plastic substrate or may be a glass-plastic laminate.
- a first thin film 6 of a light-emissive organic material (in this case, poly(phenylenevinylene) (PPN)) is formed on the ITO layer 4.
- PPN poly(phenylenevinylene)
- This organic PPN layer can be formed by spin-coating a precursor to PPN in a suitable solvent onto the ITO layer and then heating the spin-coated layer to convert the precursor to the polymer PPN.
- a second thin film 8 of an organic material is formed on the first thin film of light-emissive organic material 6.
- This second thin film 8 can, for example, be formed in the same general manner as the first thin film 6 of light-emissive organic material.
- the second thin film of organic material may serve as a light-emissive layer or a charge transport layer or have some other purpose. Further light-emissive organic layers can be provided.
- layer 6 could be a charge-transport layer such as polyethylenedioxythiophene doped with polystyrene sulphonic acid (PEDT:PSS), or polyaniline and the second thin film 8 may be the light-emissive layer such as a blend of 5% poly(2,7-(9,9-di-n-octylfluorene)-3,6-(benzothiadiazole) with 95% poly(2,7-(9,9-di-n-octylfluorene) (5F8BT), poly (2,7-(9,9-di-n-octylfluorene) (F8), poly(2,7-(9,9-di-n-octylfluorene)-(l,4-phenylene-((4-methylphenyl)imino)-l,4-phenylene-((4-methylphenyl)imino)-l,4-phenylene))/polylene
- a thin layer 10 of calcium having a thickness of 200nm is formed on the second thin film of organic material 8.
- This calcium layer functions as a cathode and can be formed, for example, by rf sputtering or dc magnetron sputtering (preferably using neon as a discharge gas) or by vacuum evaporation. Vacuum evaporation is the preferred technique because it causes less damage to the underlying organic material than a sputtering technique.
- a thick layer of aluminium nitride 12 having a thickness of about 10 microns is formed on the thin layer of calcium 10.
- This aluminium nitride layer is preferably deposited by sputtering to provide a pinhole-free layer.
- a conventional sputtering technique such as rf sputtering or dc magnetron sputtering may be employed using a sputter target/cathode made of aluminium and a discharge gas containing nitrogen.
- This thick aluminium nitride layer 12 is very impermeable with respect to ambient species such as oxygen and moisture and therefore serves to effectively protect the underlying calcium cathode layer from these reactive species.
- An organic light-emitting device is shown in Figure 2. It is identical to the device shown in Figure 1 except that an additional layer 14 of aluminium having a thickness of 5 microns is provided between the thin calcium layer 10 and the thick layer of aluminium nitride 12 as a second cathode layer.
- this intermediate layer of aluminium is formed by vacuum evaporation, but it could alternatively be formed by a sputtering technique for example.
- FIG. 3 An organic light-emitting device according to a third embodiment of the present invention is shown in Figure 3. It is similar to the device shown in Figure 2 except that a thick layer 16 of aluminium oxide having a thickness of about 10 microns is provided on the thick layer of aluminium nitride 12. This top layer of aluminium oxide is preferably formed by a sputtering technique in order to provide a pinhole- free layer.
- FIG. 4 An organic light-emitting device according to a fourth embodiment of the present invention is shown in Figure 4.
- This device is identical to that shown in Figure 2 except that a second layer of calcium 18 having a thickness of about 5 microns is provided between the aluminium layer 14 and the aluminium nitride layer 12.
- This second calcium layer is provided to getter any reactive species which may somehow manage to permeate through the overlying aluminium nitride and thus provide protection for the underlying cathode.
- This second layer of calcium 18 is preferably deposited by a sputtering technique in order to provide a pinhole-free layer.
- An organic light-emitting device according to a fifth embodiment of the present invention is shown in Figure 5.
- This device is similar to that shown in Figure 4 except that a sputtered layer of aluminium 20 having a thickness of about 10 microns is provided between the evaporated aluminium layer 14 and the second layer of calcium 18 as an additional barrier layer.
- a further sputtered layer of aluminium is provided between the second calcium layer 18 and the aluminium nitride layer 12.
- An organic light-emissive device according to a seventh embodiment of the present invention is shown in Figure 7.
- the Ca/Al two-layer cathode is capped with a 1000 Angstrom layer 24 of SiO deposited by thermal evaporation from a high temperature ceramic boat and a 10 micron layer 26 of aluminium nitride deposited by sputtering.
- the protective SiO/AIN two-layer cap employed in this embodiment provides excellent cathode protection. It is thought that this is due to the fact that the SiO layer not only acts as a physical barrier but also acts as a gettering layer by reacting with moisture.
- the devices described above all demonstrate the application of the present invention to the protection of a cathode, the present invention can equally be applied to the protection of the anode, or both the anode and the cathode.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2001-7007618A KR100440898B1 (en) | 1998-12-17 | 1999-12-14 | Organic light-emitting devices |
US09/868,262 US6960877B1 (en) | 1998-12-17 | 1999-12-14 | Organic light-emitting devices including specific barrier layers |
EP99959554A EP1145336A1 (en) | 1998-12-17 | 1999-12-14 | Organic light-emitting devices |
AU16694/00A AU1669400A (en) | 1998-12-17 | 1999-12-14 | Organic light-emitting devices |
JP2000588817A JP2002532847A (en) | 1998-12-17 | 1999-12-14 | Organic light emitting devices |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB9827827.8A GB9827827D0 (en) | 1998-12-17 | 1998-12-17 | Organic light-emitting devices |
GB9827827.8 | 1998-12-17 | ||
GBGB9922723.3A GB9922723D0 (en) | 1998-12-17 | 1999-09-24 | Organic light-emitting devices |
GB9922723.3 | 1999-09-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000036661A1 true WO2000036661A1 (en) | 2000-06-22 |
Family
ID=26314857
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1999/004144 WO2000036661A1 (en) | 1998-12-17 | 1999-12-14 | Organic light-emitting devices |
Country Status (6)
Country | Link |
---|---|
US (1) | US6960877B1 (en) |
EP (1) | EP1145336A1 (en) |
JP (1) | JP2002532847A (en) |
CN (1) | CN1150639C (en) |
AU (1) | AU1669400A (en) |
WO (1) | WO2000036661A1 (en) |
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Also Published As
Publication number | Publication date |
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CN1150639C (en) | 2004-05-19 |
EP1145336A1 (en) | 2001-10-17 |
JP2002532847A (en) | 2002-10-02 |
CN1333927A (en) | 2002-01-30 |
AU1669400A (en) | 2000-07-03 |
US6960877B1 (en) | 2005-11-01 |
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