WO2000057499A1 - Organisches elektrolumineszierendes bauteil - Google Patents
Organisches elektrolumineszierendes bauteil Download PDFInfo
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- WO2000057499A1 WO2000057499A1 PCT/DE2000/000783 DE0000783W WO0057499A1 WO 2000057499 A1 WO2000057499 A1 WO 2000057499A1 DE 0000783 W DE0000783 W DE 0000783W WO 0057499 A1 WO0057499 A1 WO 0057499A1
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- Prior art keywords
- layer
- component according
- metal
- top electrode
- mel
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- 239000010410 layer Substances 0.000 claims abstract description 93
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- -1 metal complex salt Chemical class 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 21
- 239000002346 layers by function Substances 0.000 claims abstract description 20
- 239000002800 charge carrier Substances 0.000 claims abstract description 17
- 238000002347 injection Methods 0.000 claims abstract description 14
- 239000007924 injection Substances 0.000 claims abstract description 14
- 229910052709 silver Inorganic materials 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 10
- 150000002739 metals Chemical class 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 239000011777 magnesium Substances 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 239000011575 calcium Substances 0.000 claims description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 3
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- YACSIMLPPDISOJ-UHFFFAOYSA-N 4-(4-anilinophenyl)-3-(3-methylphenyl)-n-phenylaniline Chemical compound CC1=CC=CC(C=2C(=CC=C(NC=3C=CC=CC=3)C=2)C=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 YACSIMLPPDISOJ-UHFFFAOYSA-N 0.000 claims 1
- 239000007983 Tris buffer Substances 0.000 claims 1
- 238000002207 thermal evaporation Methods 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 14
- 239000012044 organic layer Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 239000010953 base metal Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000032258 transport Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 238000010549 co-Evaporation Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 150000002222 fluorine compounds Chemical class 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000010944 silver (metal) Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- 229910015312 LiMgF Inorganic materials 0.000 description 2
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical class N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OGGKVJMNFFSDEV-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(3-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 OGGKVJMNFFSDEV-UHFFFAOYSA-N 0.000 description 1
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- MWTQIXYUBFEPSY-UHFFFAOYSA-M [Ag]F.[Li] Chemical compound [Ag]F.[Li] MWTQIXYUBFEPSY-UHFFFAOYSA-M 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000001017 electron-beam sputter deposition Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- NXEFKYQFCUFLNF-UHFFFAOYSA-K lithium;barium(2+);trifluoride Chemical compound [Li+].[F-].[F-].[F-].[Ba+2] NXEFKYQFCUFLNF-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000012800 visualization 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
- H10K50/805—Electrodes
- H10K50/82—Cathodes
-
- 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
-
- 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
- H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/805—Electrodes
- H10K59/8052—Cathodes
Definitions
- the invention relates to an organic electroluminescent component, in particular an organic light-emitting diode.
- LC displays are not self-emitting and can therefore only be read or recognized easily in particularly favorable ambient lighting conditions. In most cases, this requires a backlighting device, which multiplies the thickness of the flat screen. In addition, the majority of the electrical power consumption is then required for the lighting, and a higher voltage is required for the operation of the lamps or fluorescent tubes, which is usually generated from batteries or accumulators with the aid of “voltage-up converters”. Further disadvantages are the greatly restricted viewing angle of the LC displays and the long switching times of individual pixels, which are typically a few milliseconds and are also strongly temperature-dependent. The delayed image build-up is extremely disruptive when used in transport or video applications, for example.
- OLEDs organic light-emitting diodes
- the switching times are around one microsecond and are only slightly temperature-dependent, which enables use for video applications.
- the reading angle is almost 180 °, and polarization foils, as are required in LC displays, are omitted, so that a greater brightness of the display elements can be achieved. Further advantages are the usability of flexible and non-planar substrates as well as simple and inexpensive production.
- Organic light-emitting diodes are typically constructed as follows.
- a transparent substrate for example glass
- a transparent electrode bottom electrode, anode
- ITO indium tin oxide
- the transparent electrode is then structured using a photolithographic process.
- One or more organic layers consisting of polymers, oligomers, low molecular weight compounds or mixtures are placed on the substrate with the structured electrode of this, applied.
- polymers are polyaniline, poly (p-phenylene-vinylene) and poly (2-methoxy-5- (2'-ethyl) - hexyloxy-p-phenylene-vinylene).
- low molecular weight, preferably positive charge-transporting compounds are N, N'-bis (3-methylphenyl) -N, N '-bis- (phenyl) -benzidine (-TPD), 4,4', 4 "- Tris- (N-3-methylphenyl-N-phenylamino) -triphenylamine (-MTDATA) and 4, 4 ', 4 "-Tris- (carbazol-9-yl) -triphenylamine (TCTA).
- Hydroxyquinoline aluminum III salt (Alq 3 ) is used as an emitter, which may be doped with suitable chromophores (quinacridone derivatives, aromatic hydrocarbons, etc.).
- polymers are usually applied from the liquid phase by knife coating or spin coating, and low-molecular and oligomeric compounds are mostly deposited from the gas phase by vapor deposition or “physical vapor deposition * (PVD).
- PVD physical vapor deposition *
- the total layer thickness can be between 10 nm and 10 ⁇ m, typically it is in the range between 50 and 200 nm.
- a counterelectrode (top electrode, cathode) is applied to the organic layer (s), which usually consists of a metal, a metal alloy or a thin insulator layer and a thick metal layer.
- the cathode layer is usually produced by vapor deposition by thermal evaporation, electron beam evaporation or sputtering.
- metals are used as the cathode material, they must have a low work function (typically ⁇ 3.7 eV) so that electrons can be injected efficiently into the organic semiconductor.
- a low work function typically ⁇ 3.7 eV
- alkali metals, alkaline earth metals or rare earth metals are used for this; the layer thickness is between 0.2 nm and a few hundred nanometers, but generally a few 10 nanometers.
- a nobler, inert metal such as aluminum (Al), copper (Cu), silver (Ag) or gold (Au) to the cathode layer, which protects the base metal layer from moisture and Protects atmospheric oxygen.
- an alloy of an efficiently electron-emitting but corrosion-prone base metal (work function ⁇ 3.7 eV) and a corrosion-resistant noble metal, such as Al, Cu, Ag and Au used.
- the proportion of the base metal in the alloy can be between a few parts per thousand and about 90%.
- the alloys are mostly produced by simultaneous deposition of the metals from the gas phase, for example by co-evaporation, simultaneous sputtering with multiple sources and sputtering using alloy targets.
- a layer of a noble metal, such as Al, Cu, Ag or Au is usually also applied to such cathodes as corrosion protection.
- Cathodes made of noble metals i.e. Metals with a work of> 3.7 eV are very inefficient when used in direct contact with the organic semiconductor
- Electron injectors if a thin insulating intermediate layer (layer thickness generally between 0.2 and 5 nm) is arranged between the uppermost electron-conducting organic layer and the metal electrode, the efficiency of the light-emitting diodes increases considerably. Oxides, such as aluminum oxide, alkali and alkaline earth oxides and other oxides, as well as alkali and alkaline earth fluorides come as an insulating material for such an intermediate layer (see: Appl. Phys. Lett., Vol. 71 (1997), pages 2560 to 2562 ; U.S. Patent 5,677,572; EP-OS 0 822 603).
- a metal electrode is then applied to the thin insulating intermediate layer, which is made of a pure metal or a metal alloy consists.
- the insulating material can also be applied together with the electrode material by co-evaporation (Appl. Phys. Lett., Vol. 73 (1998), pages 1185 to 1187).
- the object of the invention is to design an organic electrolytic component, in particular an organic light-emitting diode, in such a way that on the one hand a hermetic sealing of the top electrode can be dispensed with and on the other hand the selection of materials that can be used on the cathode side is increased .
- a component which is characterized by - a transparent bottom electrode located on a substrate,
- top electrode made of a metal inert to oxygen and moisture
- At least one organic functional layer and arranged between the bottom electrode and the top electrode
- (Mel) (Me2) F m + n containing charge carrier injection layer, where the following applies: m and n are each an integer corresponding to the value of the metals Mel and Me2 (the metal Mel has the value m, the metal Me2 the value) n),
- Me2 Mg, AI, Ca, Zn, Ag, Sb, Ba, Sm or Yb, with the proviso: Mel ⁇ Me2.
- the essential feature of the organic electroluminescent component according to the invention is therefore m a specific structure on the cathode side, namely m the combination of a top electrode which is indifferent to environmental influences with a charge carrier interaction layer made of a special metal complex salt of the composition (Mel) (Me2) F m + n , ie a double fluo ⁇ d. Because of this The top electrode may not be hermetically sealed or sealed.
- the special material for the charge carrier injection layer not only widens the range of materials that can be used on the cathode side, but also improves the emission properties through this material, which results in a significantly higher luminous efficacy, a reduced operating voltage and a longer service life Expression comes.
- the charge carrier injection layer (made of a special metal complex salt) is preferably arranged as a thin insulating layer between the top electrode and the organic functional layer, in the presence of several functional layers between the top functional layer and the top electrode. If, in the component according to the invention, there is also an electron transport layer on the (top) functional layer, the charge carrier injection layer is arranged between this layer and the top electrode. In all of these cases, the thickness of the charge carrier injection layer is preferably approximately 0.1 to 20 nm.
- the charge carrier injection layer can also be integrated in the top electrode, in the (top) organic functional layer or in an electron transport layer that may be present, i.e. the metal complex salt is then part of one of the layers mentioned.
- Such layers can advantageously be produced by co-evaporation of the corresponding materials, for example by co-evaporation of the top electrode material and the metal complex salt.
- the metal complex salt has the composition (Mel) (Me2) F m + n , where m and n correspond to the valency of the respective metal.
- the metal Mel is preferably lithium (Li), the metal Me2 preferably magnesium (Mg), aluminum (Al), calcium (Ca), silver (Ag) or barium (Ba).
- One of the double fluorides LiAgF 2 , LiBaF 3 and L1AIF 4 is advantageously used as the metal complex salt.
- Other such double fluorides are, for example, NaAgF 2 , KAgF 2 , LiMgF 3 , LiCaF 3 , CaAgF 3 and MgBaF 4 .
- Complex salts of this type and processes for their preparation are known per se (see the exemplary embodiments and, for example, “Gelins Handbuch der -Anorganischen Chemie *, 8th edition (1926), system number 5 (fluorine), pages 58 to 72).
- the top electrode which generally has a thickness> 100 nm, preferably consists of one of the following
- Metals aluminum (AI), silver (Ag), platinum (Pt) and gold (Au).
- the electrode material can also be an alloy of two of these metals.
- Other metals for the top electrode are magnesium (Mg), calcium (Ca), zinc (Zn), antimony (Sb) and barium (Ba).
- the bottom electrode is generally made of indium tin oxide (ITO). Other possible materials for the bottom electrode are tin oxide and bismuth oxide. Glass is usually used as the substrate for the bottom electrode.
- ITO indium tin oxide
- Other possible materials for the bottom electrode are tin oxide and bismuth oxide. Glass is usually used as the substrate for the bottom electrode.
- the component according to the invention preferably has two organic functional layers, namely a perforated layer arranged on the bottom electrode, which transports positive charge carriers, and one located thereon
- Emission layer which is also referred to as a luminescent layer.
- a luminescent layer instead of a perforated layer, two or more perforated layers can advantageously also be used.
- the materials for the layers mentioned are known per se.
- the hole-conducting layer (s) in the present case preferably N, N'-bis (3-methylphenyl) -N, N r -bis- (phenyl) - benzidine (m-TPD), 4, 4 ', "-Tris- (N-1-naphthyl-N-phenylamino) triphenylamine (Naphdata) or N, N'-bis-phenyl-N, N'-bis- ⁇ -naphthyl-benzidine (-NPD).
- the material for the emission layer is preferably hydroxyquinoline aluminum III salt (Alq 3 ). This compound can also serve for electron transport at the same time.
- quinacridone can also be used for the emission layer an optionally present electron transport layer of one of the oxadiazole derivatives known for this purpose.
- the invention offers the following further advantages:
- the operating voltage is significantly reduced and the luminous efficacy and efficiency are significantly increased.
- compounds such as LiAlF 4 have the advantage that they are less hygroscopic, which makes handling and storage easier.
- the double fluorides are also easier to evaporate and are less basic (than LiF), which increases the compatibility with the organic functional layers.
- FIG. 1 shows a conventional OLED display
- FIG. 2 shows an OLED display according to the invention
- FIG. 3 luminance / voltage characteristic curves
- FIG. 4 efficiency / luminance characteristic curves
- Figure 5 is a comparison of the luminance of different
- Lithium aluminum hydride LiAlH 4 is carefully hydrolyzed with distilled water, then reacted with an excess of hydrofluoric acid (HF).
- HF hydrofluoric acid
- the precipitated metal complex salt LiAlF-j is suctioned off, washed several times with water and ethanol and then dried.
- Metal complex salt LiAgF 2 from. After the addition of the same volume of ethanol, the complex salt is suctioned off, washed with ethanol and dried.
- the metal complex salt LiCaF 3 is prepared in a corresponding manner, the reaction solution being concentrated if necessary.
- the metal complex salt LiMgF 3 can be produced in the same way, using lithium methylate and magnesium methylate as starting materials.
- ITO layer (12) with a thickness of approximately 100 nm is applied to a glass substrate (11). This layer is then structured photolithographically in such a way that a stripe-shaped structure is produced.
- a layer of m-TPD (13) with a layer is first applied to the coated substrate pretreated in this way - by thermal evaporation
- a layer (15) made of a magnesium-silver alloy (Mg: Ag mixing ratio 10: 1) with a thickness of approximately 150 nm is applied to the organic layer (14) by thermal evaporation using two evaporator sources operated simultaneously and then, also by thermal evaporation, a layer (16) of pure silver with a thickness of approx. 150 nm.
- the metal layers are evaporated through a mask with strip-shaped openings, so that cathode strips are formed which are perpendicular to the ITO strips. In this way, organic light-emitting diodes with an active area of 2 x 2 mm 2 are created at the intersections of the ITO tracks with the metal tracks - together with the organic layers in between. In operation, the ITO layer is contacted positively, the metal tracks are contacted negatively.
- Mg Ag mixing ratio 10: 1
- ITO layer (22) with a thickness of approximately 100 nm is applied to a glass substrate (21). This layer is then structured photolithographically in such a way that a stripe-shaped structure is produced.
- a layer of m-TPD (23) with a thickness of approx. 100 nm is first applied to the coated substrate treated in this way - by thermal evaporation and then a layer (24) made of Alq 3 with a thickness of approx. 65 nm.
- a layer (25) made of LiAlF 4 with a thickness of approximately 1 nm is applied to the organic layer (24) by thermal evaporation and then, also by thermal evaporation, a layer (26) made of aluminum, which serves as a top electrode with a thickness of about 150 nm.
- the two layers are evaporated according to Example 4 through a mask with strip-shaped openings, so that organic light-emitting diodes are formed. In operation, the ITO layer is contacted positively, the top electrode is negative.
- Table 1 summarizes the results of measurements on the OLEDs in accordance with Examples 4 and 5.
- the characteristic parameters here are the threshold voltage (electroluminescence), the voltage and the efficiency, in each case at a luminance of 1500 cd / m 2 , the maximum luminance and the luminance at a current density of 50 mA / cm 2 .
- Table 1 summarizes the results of measurements on the OLEDs in accordance with Examples 4 and 5.
- the characteristic parameters here are the threshold voltage (electroluminescence), the voltage and the efficiency, in each case at a luminance of 1500 cd / m 2 , the maximum luminance and the luminance at a current density of 50 mA / cm 2 .
- the threshold and operating voltage of the display according to the invention are below the corresponding values for the conventional display (example 4), although the thickness of the LiAlF-j layer has not been optimized.
- the values for the efficiency and the luminance achieved in the display according to the invention are above the corresponding values in the conventional display.
- FIG. 3 shows the luminance / voltage characteristics of the displays according to Examples 4 and 5. From this illustration, the increased luminance of the display according to the invention can be clearly seen.
- an aluminum cathode is used, with which efficiencies are normally achieved which are approximately 40 to 50% below the corresponding values for Mg / Ag cathodes (example 4).
- aluminum is more stable than magnesium against environmental influences such as atmospheric oxygen and moisture.
- the efficiency of OLEDs with an Al cathode can be increased, even beyond the corresponding values of OLEDs with a Mg / Ag cathode . In this way highly efficient OLEDs with a stable cathode.
- ITO layer with a thickness of approx. 100 nm is applied to a glass substrate. This layer is then structured by photolithography in such a way that a stripe-shaped structure is produced. A layer of naphdata with a thickness of approx. 55 nm is first applied to the coated substrate pretreated in this way - by thermal evaporation, then a layer of ⁇ -NPD with a thickness of approx. 5 nm and finally a layer of Alq 3 a thickness of approx. 65 nm.
- a layer of a magnesium-silver alloy (Mg: Ag mixing ratio 10: 1) with a thickness of approx. 150 nm is applied to the uppermost organic layer (made of Alq 3 ) by thermal evaporation using two evaporator sources operated at the same time. also by thermal evaporation, a layer of pure silver with a thickness of approx. 150 nm.
- the metal layers are evaporated through a mask with strip-shaped openings, so that cathode strips are formed which are perpendicular to the ITO strips. In this way, organic light-emitting diodes with an active area of - together with the organic layers in between - are created at the points of intersection of the ITO lines
- a display with three organic functional layers is constructed.
- a layer of aluminum with a thickness of 150 nm is then applied to the uppermost organic layer (made of Alq 3 ) by thermal evaporation - in a corresponding manner.
- a display with three organic functional layers is constructed.
- a layer of LiF with a thickness of approx. 0.5 nm is then applied to the uppermost organic layer (made of Alq 3 ) by thermal evaporation and then, also by thermal evaporation, a layer of aluminum with a thickness of approx. 150 nm.
- the two layers are evaporated according to Example 6 through a mask with strip-shaped openings, so that organic light-emitting diodes are formed.
- the ITO layer is contacted positively, the AI cathode negatively.
- a display with three organic functional layers is constructed.
- a layer of L1AIF 4 with a thickness of approx. 0.5 nm is then applied to the uppermost organic layer (made of Alq 3 ) by thermal evaporation and then, also by thermal evaporation, a layer made of aluminum, which serves as a top electrode With a thickness of approx. 150 nm.
- the structuring and the contacting take place in accordance with Example 8.
- a display with three organic functional layers is constructed.
- a layer of LiAgF 2 with a thickness of about 0.5 nm is then applied to the uppermost organic layer (made of Alq 3 ) by thermal evaporation, and a layer of aluminum, which serves as the top electrode, is also applied thereon, also by thermal evaporation with a thickness of approx. 150 nm.
- the structuring and the contacting take place according to example 8.
- a display with three organic functional layers is constructed.
- a layer of LiBaF 3 with a thickness of approximately 0.5 nm is then applied to the uppermost organic layer (made of Alq 3 ) by thermal evaporation and then, also by thermal evaporation, a layer made of aluminum, which serves as a top electrode with a thickness of approx. 150 nm.
- the structuring and the contacting take place according to example 8.
- Table 2 summarizes the results of measurements on the OLEDs in accordance with Examples 6 to 11.
- the characteristic parameters here are the threshold voltage (of the electroluminescence), the voltage and the efficiency, in each case at a luminance of 1500 cd / m 2 , as well as the luminance at a current density of 50 mA / cm 2 .
- the threshold and the operating voltages of the displays according to the invention are comparable to the values which are used for displays with a Mg / Ag -Cathode or with an Al cathode and a LiF intermediate layer (Examples 6 and 8) are obtained and are significantly below the corresponding values for a display with pure Al cathode (Example 7).
- the displays according to the invention are also comparable in terms of efficiency and luminance to the Mg / Ag and Al-LiF displays, a display with a LiBaF 3 charge carrier injection layer (example 11) in particular showing high values.
- FIG. 4 shows the efficiency / luminance characteristics of the displays according to Examples 6 to 11. From this representation in particular the outstanding position of an Al-LiBaF 3 display according to the invention is clearly evident.
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020017012135A KR20010109321A (ko) | 1999-03-24 | 2000-03-13 | 유기 전광 소자 |
JP2000607288A JP2002540566A (ja) | 1999-03-24 | 2000-03-13 | 有機エレクトロルミネセンス構成部材 |
US09/937,290 US6734622B1 (en) | 1999-03-24 | 2000-03-13 | Organic electroluminescent component for an organic light-emitting diode |
EP00920388A EP1171921A1 (de) | 1999-03-24 | 2000-03-13 | Organisches elektrolumineszierendes bauteil |
CA002367303A CA2367303A1 (en) | 1999-03-24 | 2000-03-13 | Organic electroluminescent component |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19913350 | 1999-03-24 | ||
DE19913350.6 | 1999-03-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000057499A1 true WO2000057499A1 (de) | 2000-09-28 |
Family
ID=7902243
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/DE2000/000783 WO2000057499A1 (de) | 1999-03-24 | 2000-03-13 | Organisches elektrolumineszierendes bauteil |
Country Status (8)
Country | Link |
---|---|
US (1) | US6734622B1 (de) |
EP (1) | EP1171921A1 (de) |
JP (1) | JP2002540566A (de) |
KR (1) | KR20010109321A (de) |
CN (1) | CN1201414C (de) |
CA (1) | CA2367303A1 (de) |
TW (1) | TW488185B (de) |
WO (1) | WO2000057499A1 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2002228802A (ja) * | 2001-02-07 | 2002-08-14 | Nec Tokin Corp | フッ化物結晶からなる真空紫外領域用光学部材および光学部材用コーティング材 |
US6998776B2 (en) | 2003-04-16 | 2006-02-14 | Corning Incorporated | Glass package that is hermetically sealed with a frit and method of fabrication |
EP2733765A1 (de) * | 2012-11-20 | 2014-05-21 | InnoLux Corporation | Organische lichtemittierende Diodenanzeigevorrichtung |
US8823163B2 (en) | 2012-08-30 | 2014-09-02 | Corning Incorporated | Antimony-free glass, antimony-free frit and a glass package that is hermetically sealed with the frit |
Families Citing this family (15)
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US6888172B2 (en) * | 2003-04-11 | 2005-05-03 | Eastman Kodak Company | Apparatus and method for encapsulating an OLED formed on a flexible substrate |
CN100463243C (zh) * | 2004-06-14 | 2009-02-18 | 北京大学 | 一种顶出光电极及其制备方法 |
US7812522B2 (en) * | 2004-07-22 | 2010-10-12 | Ifire Ip Corporation | Aluminum oxide and aluminum oxynitride layers for use with phosphors for electroluminescent displays |
CN100399865C (zh) * | 2004-08-23 | 2008-07-02 | 北京大学 | 一种顶出光电极及其制备方法 |
CN100456516C (zh) * | 2005-06-15 | 2009-01-28 | 北京大学 | 顶出光电极及其制备方法 |
TWI268736B (en) | 2005-08-10 | 2006-12-11 | Au Optronics Corp | Organic electroluminescent device (OELD) and display including the same |
JP2007182401A (ja) * | 2006-01-06 | 2007-07-19 | Bando Chem Ind Ltd | 新規な芳香族第3級アミン類とその利用 |
GB2475247B (en) * | 2009-11-10 | 2012-06-13 | Cambridge Display Tech Ltd | Organic optoelectronic device and method |
KR101127767B1 (ko) | 2009-12-09 | 2012-03-16 | 삼성모바일디스플레이주식회사 | 유기 발광 장치 |
KR101182447B1 (ko) | 2010-06-16 | 2012-09-12 | 삼성디스플레이 주식회사 | 유기 발광 소자 및 그 제조 방법 |
KR20120004193A (ko) | 2010-07-06 | 2012-01-12 | 삼성모바일디스플레이주식회사 | 유기 발광 장치 |
CN103180257B (zh) * | 2010-11-17 | 2016-02-17 | 3M创新有限公司 | 减少银的电迁移的方法及由其制备的制品 |
EP2586767A1 (de) | 2011-10-25 | 2013-05-01 | Bayer MaterialScience AG | Verfahren zur Herstellung von Diarylcarbonaten und Polycarbonaten |
KR101918712B1 (ko) | 2012-08-02 | 2018-11-15 | 삼성디스플레이 주식회사 | 유기 발광 장치 |
CN115010151B (zh) * | 2022-06-24 | 2023-08-18 | 山东海容电源材料有限公司 | 锂离子电解液配制用锂盐和锂离子电解液 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0869701A2 (de) * | 1997-04-04 | 1998-10-07 | Mitsubishi Chemical Corporation | Organisches elektrolumineszentes Bauteil |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3529543B2 (ja) * | 1995-04-27 | 2004-05-24 | パイオニア株式会社 | 有機エレクトロルミネッセンス素子 |
EP0835597B1 (de) * | 1996-04-25 | 2003-02-19 | Koninklijke Philips Electronics N.V. | Organische elektrolumineszente vorrichtung |
US5776622A (en) * | 1996-07-29 | 1998-07-07 | Eastman Kodak Company | Bilayer eletron-injeting electrode for use in an electroluminescent device |
US5677572A (en) | 1996-07-29 | 1997-10-14 | Eastman Kodak Company | Bilayer electrode on a n-type semiconductor |
JP3684826B2 (ja) * | 1997-04-04 | 2005-08-17 | 三菱化学株式会社 | 有機電界発光素子 |
JPH10289784A (ja) * | 1997-04-14 | 1998-10-27 | Mitsubishi Chem Corp | 有機電界発光素子 |
JPH11251067A (ja) * | 1998-03-02 | 1999-09-17 | Junji Kido | 有機エレクトロルミネッセント素子 |
-
2000
- 2000-03-13 KR KR1020017012135A patent/KR20010109321A/ko not_active Application Discontinuation
- 2000-03-13 EP EP00920388A patent/EP1171921A1/de not_active Withdrawn
- 2000-03-13 CN CNB00805374XA patent/CN1201414C/zh not_active Expired - Lifetime
- 2000-03-13 CA CA002367303A patent/CA2367303A1/en not_active Abandoned
- 2000-03-13 US US09/937,290 patent/US6734622B1/en not_active Expired - Lifetime
- 2000-03-13 WO PCT/DE2000/000783 patent/WO2000057499A1/de not_active Application Discontinuation
- 2000-03-13 JP JP2000607288A patent/JP2002540566A/ja active Pending
- 2000-03-20 TW TW089105059A patent/TW488185B/zh not_active IP Right Cessation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0869701A2 (de) * | 1997-04-04 | 1998-10-07 | Mitsubishi Chemical Corporation | Organisches elektrolumineszentes Bauteil |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002228802A (ja) * | 2001-02-07 | 2002-08-14 | Nec Tokin Corp | フッ化物結晶からなる真空紫外領域用光学部材および光学部材用コーティング材 |
US6998776B2 (en) | 2003-04-16 | 2006-02-14 | Corning Incorporated | Glass package that is hermetically sealed with a frit and method of fabrication |
US7407423B2 (en) | 2003-04-16 | 2008-08-05 | Corning Incorporated | Glass package that is hermetically sealed with a frit and method of fabrication |
US7602121B2 (en) | 2003-04-16 | 2009-10-13 | Corning Incorporated | Glass package that is hermetically sealed with a frit and method of fabrication |
US8823163B2 (en) | 2012-08-30 | 2014-09-02 | Corning Incorporated | Antimony-free glass, antimony-free frit and a glass package that is hermetically sealed with the frit |
EP2733765A1 (de) * | 2012-11-20 | 2014-05-21 | InnoLux Corporation | Organische lichtemittierende Diodenanzeigevorrichtung |
US9123910B2 (en) | 2012-11-20 | 2015-09-01 | Innolux Corporation | Organic light emitting diode display device and display panel thereof |
US9391291B2 (en) | 2012-11-20 | 2016-07-12 | Innolux Corporation | Organic light emitting diode display device and display panel thereof |
Also Published As
Publication number | Publication date |
---|---|
KR20010109321A (ko) | 2001-12-08 |
CA2367303A1 (en) | 2000-09-28 |
CN1344428A (zh) | 2002-04-10 |
TW488185B (en) | 2002-05-21 |
EP1171921A1 (de) | 2002-01-16 |
JP2002540566A (ja) | 2002-11-26 |
US6734622B1 (en) | 2004-05-11 |
CN1201414C (zh) | 2005-05-11 |
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