WO2003003482A1 - Dispositifs oled a composes d'injection et de transport de trou thermostables - Google Patents

Dispositifs oled a composes d'injection et de transport de trou thermostables Download PDF

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Publication number
WO2003003482A1
WO2003003482A1 PCT/US2001/020583 US0120583W WO03003482A1 WO 2003003482 A1 WO2003003482 A1 WO 2003003482A1 US 0120583 W US0120583 W US 0120583W WO 03003482 A1 WO03003482 A1 WO 03003482A1
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hole
group
coumarin
injection
electron
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PCT/US2001/020583
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English (en)
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Xiaobo Shi
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Emagin Corporation
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Priority to EP01950594A priority Critical patent/EP1451881A1/fr
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Publication of WO2003003482A1 publication Critical patent/WO2003003482A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C07C211/56—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/58—Naphthylamines; N-substituted derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/59—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole

Definitions

  • Organic electroluminescent devices also known as organic light emitting diode (“OLED”) devices comprise an anode, a cathode and an electroluminescent medium made up of extremely thin layers (typically less than 1.0 micrometer in combined thickness) separating the anode and the cathode.
  • OLED organic light emitting diode
  • a basic two-layer light emitting diode comprises one organic layer that is specifically chosen to inject and transport holes and a second organic layer that is specifically chosen to inject and transport electrons. The interface between the two layers provides an efficient site for the recombination of the injected hole-electron pair, which results in electroluminescence.
  • the electroluminescent medium can comprise additional layers, including, but not limited to, an emitter layer between the hole injection and transport and the electron injection and transport layers in which recombination of holes and electrons occurs. Since light emission is directly related to current density through the organic electroluminescent medium, the thin layers coupled with increased charge injection and transport efficiencies have allowed acceptable light emission levels (e.g., brightness levels capable of being visually detected in ambient light) to be achieved with low applied voltages in ranges compatible with integrated circuit drivers, such as field effect transistors.
  • acceptable light emission levels e.g., brightness levels capable of being visually detected in ambient light
  • integrated circuit drivers such as field effect transistors.
  • a large variety of organic compounds having the appropriate characteristics can be used in the layers of the electroluminescent medium. For example, variations in the chemical structures of compounds in the various layers can result in changes in ionization potential, mobility of holes or electrons, or the wavelength of emitted light. Nevertheless, the performance of OLEDs may be limited by the organic materials, rendering them undesirable for many applications.
  • Hole-injection and hole-transport organic compounds have tended to be an unstable part of the electroluminescent medium of OLEDs. These materials are thought to undergo a morphological change when exposed to increased temperatures or when stored for long periods of time. Since efficient operation of the hole- injection and hole-transport layers depends on their amorphous nature, morphological changes may lead to degradation of the OLED.
  • the temperature at which morphological changes occur and an amorphous material becomes crystalline is the glass transition temperature of the material.
  • the glass transition temperature of hole- injection and hole-transport compounds has generally been below 100°C.
  • Triarylamine derivatives such as NN-diphenyl-N,N-bis(3-methylphenyl)- 1 , 1 '-biphenyl-4,4'-diamine (TPD) and NN'-bis(l -naphthyl)-NN'-diphenyl- 1,1'- biphenyl-4,4'-diamine ( ⁇ PD) are the most widely used derivatives in the hole injection and hole transport layers of OLEDs (Tang et al (1987) Appl Phys. Let. 51:913-15; Mitschke et al. (2000) J Mater. Chem. 10:1471-1507). However, these triarylamines tend to crystallize on aging or if left at ambient temperatures.
  • hole-injection and hole-transport materials Improvements to the stability of hole-injection and hole-transport materials have been made, including inserting a triarylamine derivative into a polymer matrix or covalently attaching triarylamines to a polymer backbone (Mitschke et al. (2000)).
  • hole-transport and hole-injection materials such as the "starburst amines,” have been designed that have higher glass transition temperatures (Kurwabara et al. (1994) Adv. Mater.
  • the present invention relates to an organic light emitting diode device comprising: (a) a cathode; (b) an anode; and (c) at least two organic layers between the anode and the cathode, wherein the at least two organic layers comprise a first organic layer formed from at least one electron-injection/electron- transport material and a second organic layer formed from at least one hole- injection/hole-transport material, wherein the electron-injection/electron-transport material is adjacent to the cathode and the hole-injection/hole-transport material is adjacent to the anode, the at least one hole-injection/hole-transport material comprising a compound of formula 1 :
  • R ⁇ is selected from the group consisting of biphenyl, naphthyl, phenyl
  • Q is selected from the group consisting of a bond, C ⁇ -C 4 alkyl,
  • R 2 and R 3 are each independently selected from the group consisting of aryl, F, CI, -CF 3 , saturated alkyl of up to 10 carbon atoms, SO 2 R6, Si(R6) 3 , and ORe, or R 2 and R 3 taken together form a heterocyclic ring of up to 8 atoms, wherein one of the 8 atoms is nitrogen and another of the 8 atoms is either nitrogen or oxygen, or R 2 and 3 taken together with the phenyl group to which they are attached form a fused polycyclic aromatic system, wherein the fused polycyclic aromatic system comprises up to 16 carbon atoms;
  • R and R5 are each independently selected from the group consisting of:
  • R 6 is C1-C4 straight or branched saturated alkyl
  • R 7 and R 8 are each independently selected from the group consisting of
  • R 9 is selected from the group consisting of Ci-C ⁇ alkyl and aryl; and wherein one of the bottom electrode and the top electrode is a cathode and the other is an anode.
  • the present invention relates to an organic light emitting diode device comprising: (a) a cathode; (b) an anode; (c) a layer formed from at least one electron-injection/electron-transport material that is adjacent to the cathode; (d) a hole-injection layer that is adjacent to the anode; and (e) at least one hole-transport layer that is adjacent to the hole-injection layer, wherein at least one of the hole-injection and hole-transport layers comprises a compound of formula 1, wherein one of the bottom electrode and the top electrode is a cathode and the other is an anode.
  • the present invention relates to an organic light- emitting diode device that emits green light, comprising: (a) a bottom electrode that is an anode comprising indium tin oxide; (b) a hole-injection layer adjacent to the anode comprising bis(N,N'-l-na ⁇ hthyl-phenyl-amino-biphenyl)-biphenyl amine (BPA-DNPB); (c) a hole-transport layer adjacent to the hole-injection layer comprising bis(carbazol-N-biphenyl)-biphenyl amine (BPA-BCA); (d) an emitter layer adjacent to the hole-transport layer comprising tris(hydroxyquinoline) aluminum (ALQ) and a compound selected from the group consisting of Coumarin 6, Coumarin 485, Coumarin, 487, Coumarin 490, Coumarin 498, Coumarin 500, Coumarin 503, Coumarin 504, Coumarin 504T, Coumarin 510, Coumarin 515,
  • the present invention relates to an organic light- emitting diode device that emits white or blue light, comprising: (a) a bottom electrode that is an anode comprising indium tin oxide; (b) a hole-injection layer adjacent to the anode comprising BPA-DNPB; (c) a hole-transport layer adjacent to the hole-injection layer comprising BPA-BCA; (d) an emitter layer adjacent to the hole-transport layer comprising DCJTB, IDE- 120 and IDE- 102; (e) an electron- transport layer adjacent to the emitter layer comprising ALQ; and (f) a top electrode that is a cathode comprising lithium fluoride and aluminum.
  • the present invention relates to a microdisplay device, comprising: (a) at least one bottom electrode that is an anode; (b) at least one top electrode that is a cathode; and (c) at least two organic layers between the at least one bottom electrode and the at least one top electrode, wherein the at least two organic layers comprise a first organic layer formed from at least one electron- injection/electron-transport material that is adjacent to the at least one cathode and a second organic layer formed from at least one hole-injection/hole-transport material that is adjacent to the at least one anode, the at least one hole-injection/hole-transport material comprising a compound of formula 1.
  • the present invention relates to an organic light emitting diode device comprising: (a) a cathode; (b) an anode; and (c) at least two organic layers between the anode and the cathode, wherein the at least two organic layers comprise a first organic layer formed from at least one electron- injection/electron-transport material and a second organic layer formed from at least one hole-injection/hole-transport material, wherein the electron-injection/electron- transport material is adjacent to the cathode and the hole-injection/hole-transport material is adjacent to the anode, the at least one hole-injection/hole-transport material comprising a compound of formula 1, wherein R ⁇ is selected from the group consisting of biphenyl, naphthyl, and phenyl, and wherein one of the bottom electrode and the top electrode is a cathode and the other is an anode.
  • the present invention relates to an organic light emitting diode device comprising: (a) a cathode; (b) an anode; and (c) at least two organic layers between the anode and the cathode, wherein the at least two organic layers comprise a first organic layer formed from at least one electron- injection/electron-transport material and a second organic layer formed from at least one hole-injection/hole-transport material, wherein the electron- injection/electron-transport material is adjacent to the cathode and the hole- injection/hole-transport material is adjacent to the anode, the at least one hole- injection/hole-transport material comprising a compound of formula 1, wherein Ri is selected from the group consisting of biphenyl, naphthyl, phenyl and
  • Q is a bond
  • one of the bottom electrode and the top electrode is a cathode and the other is an anode
  • the present invention relates to an organic light emitting diode device comprising: (a) a cathode; (b) an anode; and (c) at least two organic layers between the anode and the cathode, wherein the at least two organic layers comprise a first organic layer formed from at least one electron- injection/electron-transport material and a second organic layer formed from at least one hole-injection/hole-transport material, wherein the electron-injection/electron- transport material is adjacent to the cathode and the hole-injection/hole-transport material is adjacent to the anode, the at least one hole-injecti on/hole-transport material comprising a compound of formula 1, wherein R 2 and R 3 are each aryl, and wherein one of the bottom electrode and the top electrode is a cathode and the other is an anode.
  • the present invention relates to an organic light emitting diode device comprising: (a) a cathode; (b) an anode; and (c) at least two organic layers between the anode and the cathode, wherein the at least two organic layers comprise a first organic layer formed from at least one elecrron- injection/electron-transport material and a second organic layer formed from at least one hole-injectionhole-transport material, wherein the electron-injection/electron- transport material is adjacent to the cathode and the hole-injection/hole-transport material is adjacent to the anode, the at least one hole-injection/hole-transport material comprising a compound of formula 1, wherein Rj is
  • R 2 and R 3 are each C C 4 straight or branched chain alkyl, and wherein one of the bottom electrode and the top electrode is a cathode and the other is an anode.
  • the present invention relates to an organic light emitting diode device comprising: (a) a cathode; (b) an anode; and (c) at least two organic layers between the anode and the cathode, wherein the at least two organic layers comprise a first organic layer formed from at least one electron- injection/electron-transport material and a second organic layer formed from at least one hole-injection/hole-transport material, wherein the electron-injection/electron- transport material is adjacent to the cathode and the hole-injection/hole-transport material is adjacent to the anode, the at least one hole-injection/hole-transport material comprising a compound of formula 1, wherein R4 and R 5 are taken together with the nitrogen to which they are attached are selected from the group consisting of:
  • the present invention relates to an organic light emitting diode device comprising: (a) a cathode; (b) an anode; and (c) at least two organic layers between the anode and the cathode, wherein the at least two organic layers comprise a first organic layer formed from at least one electron- injection/electron-transport material and a second organic layer formed from at least one hole-injection/hole-transport material, wherein the electron-injection/electron- transport material is adjacent to the cathode and the hole-injection/hole-transport material is adjacent to the anode, the at least one hole-injection/hole-transport material comprising a compound of formula 1, wherein R 4 and R 5 are taken together with the nitrogen to which they are attached so as to form a heterocycle selected from the group consisting of:
  • one of the bottom electrode and the top electrode is a cathode and the other is an anode.
  • the present invention relates to an organic light emitting diode device comprising: (a) a cathode; (b) an anode; and (c) at least two organic layers between the anode and the cathode, wherein the at least two organic layers comprise a first organic layer formed from at least one electron- injection/electron-transport material and a second organic layer formed from at least one hole-injection hole-transport material, wherein the electron-injection/electron- transport material is adjacent to the cathode and the hole-injection/hole-transport material is adjacent to the anode, the at least one hole-injection/hole-transport material comprising a compound of formula 1, wherein P ⁇ and R 5 are each independently selected from the group consisting of phenyl, naphthyl, biphenyl, anthracenyl and fiuorenyl, and wherein one of the bottom electrode and the top electrode is a cathode and the other is an anode.
  • Figure 1 shows an OLED stack.
  • Figure 2 shows an OLED stack comprising a bottom anode and a top cathode on a substrate.
  • Figure 3 shows an OLED stack comprising a bottom cathode and a top anode on a substrate.
  • FIG. 4 shows a preferred OLED stack of the present invention.
  • DETAILED DESCRIPTION OF THE INVENTION FABRICATION OF OLED DEVICES OLEDs can be fabricated by any method known to those skilled in the art. In one embodiment, OLEDs are formed by vapor deposition of each layer. In a preferred embodiment, OLEDs are formed by thermal vacuum vapor deposition. "Bottom electrode,” as used herein, means an electrode that is deposited directly onto the substrate.
  • Top electrode means an electrode that is deposited at the end of the OLED that is distal to the substrate.
  • Hole-injection layer is a layer into which holes are injected from an anode when a voltage is applied across an OLED.
  • Hole-transport layer is a layer having high hole mobility and high affinity for holes that is between the anode and the emitter layer. It will be evident to those of skill in the art that the hole-injection layer and the hole-transport layer can be a single layer, or they can be distinct layers comprising different chemical compounds. A compound of formula I is useful both in both hole-injection and hole-transport layers.
  • Electrode-injection layer is a layer into which electrons are injected from a cathode when a voltage is applied across an OLED.
  • Electrode-transport layer is a layer having high electron mobility and high affinity for electrons that is between the cathode and the emitter layer. It will be evident to those of skill in the art that the electron-injection layer and the electron-transport layer can be a single layer, or they can be distinct layers comprising different chemical compounds.
  • an OLED comprises a bottom electrode 102, which is either an anode or a cathode, a top electrode 101, which is a cathode if the bottom electrode is an anode and which is an anode if the bottom electrode is a cathode, and an electroluminescent medium having at least two layers 103, 104, one comprising at least one hole-injection/hole-transport material that is adjacent to the anode and the other comprising at least one electron-injection/electron- transport layer that is adjacent to the cathode.
  • the top electrode is the cathode 201 and the bottom electrode, which is deposited directly onto the substrate 205, is the anode 202. Between the cathode and the anode are an electron-injection/electron- transport layer 203 adjacent to the cathode 201 and a hole-injection/hole-transport layer 204 adjacent to the anode 202.
  • the top electrode is the anode 202 and the bottom electrode, which is deposited directly onto the substrate 205, is the cathode 201.
  • the cathode and the anode are a hole-injection/hole-transport layer 204 adjacent to the anode 202 and an electron-injection/electron-transport layer 203 adjacent to the cathode 201.
  • the top electrode is the cathode 201 and the bottom electrode, which is deposited directly onto the substrate 205, is the anode 202.
  • the OLED further comprises an electron-transport layer 403 adjacent to the cathode 201, a hole-injection/hole-transport layer comprising a hole-injection layer 404 adjacent to the anode 202 and at least one hole-transport layer 407 adjacent to the hole-injection layer 404. Between the electron-transport layer 403 and the hole- transport layer 407, the OLED further comprises an emitter layer 406 wherein holes and electrons recombine to produce light.
  • the OLED comprises a hole-injection layer adjacent to the anode and at least two hole-transport layers, a first hole-transport layer adjacent to the hole-injection layer and a second hole-transport layer adjacent to the first hole-transport layer.
  • the hole-injection layer and the at least two hole-transport layers are deposited separately. In another embodiment, at least two of the layers are inter-deposited.
  • the OLED comprises an electron-injection layer and at least one electron-transport layer.
  • the electroluminescent medium comprises a hole- injection/hole-transport layer adjacent to the anode, an electron-injection/electron- transport layer adjacent to the cathode, and an emitter layer between the hole- injection/hole-transport layer and the electron-injection/electron-transport layer.
  • the OLED can further comprise an additional layer adjacent to the top electrode.
  • the layer comprises indium tin oxide.
  • a typical OLED is formed by starting with a semi- transparent bottom electrode deposited on a glass substrate.
  • the electrode is an anode.
  • the electrode is a cathode.
  • the top electrode is semi-transparent.
  • An anode is typically about 800 A thick and can have one layer comprising a metal having a high work function, a metal oxide and mixtures thereof.
  • the anode comprises a material selected from the group consisting of a conducting or semiconducting metal oxide or mixed metal oxide such as indium zinc tin oxide, indium zinc oxide, ruthenium dioxide, molybdenum oxide, nickel oxide or indium tin oxide, a metal having a high work function, such as gold or platinum, and a mixture of a metal oxide and a metal having a high work function.
  • the anode further comprises a thin layer (approximately 5-15 A thick) of dielectric material between the anode and the first hole-injection/hole-transport layer.
  • the anode comprises a thin layer of an organic conducting material adjacent to the hole- injection/hole-transport layer.
  • organic conducting materials include, but are not limited to, polyaniline, PEDOT-PSS, and a conducting or semi-conducting organic salt thereof.
  • a semi-transparent cathode is typically between 70 and 150 A thick.
  • the cathode comprises a single layer of one or more metals, at least one of which has a low work function.
  • metals include, but are not limited to, lithium, aluminum, magnesium, calcium, samarium, cesium and mixtures thereof.
  • the low work function metal is mixed with a binder metal, such as silver or indium.
  • the cathode further comprises a layer of dielectric material adjacent to the electron-injection/electron-transport layer, the dielectric material including, but not limited to, lithium fluoride, cesium fluoride, lithium chloride and cesium chloride.
  • the dielectric material is lithium fluoride or cesium fluoride.
  • the cathode comprises either aluminum and lithium fluoride, a mixture of magnesium and silver, or a mixture of lithium and aluminum.
  • the cathode comprises magnesium, silver and lithium fluoride.
  • the hole-injection/hole-transport layer is about 750 A thick.
  • the hole-injection/hole-transport material comprises a compound of formula 1.
  • the hole-injection/hole-transport layer comprises a hole-injection layer comprising BPA- DNPB and a hole-transport layer comprising BPA-BCA.
  • an OLED comprises an emitter layer between the electron-injection/electron-transport layer and the hole-injection/hole-transport layer in which electrons from the electron-injection/electron-transport layer and holes from the hole-injecting/hole-transport layer recombine.
  • OLEDs emit visible light of different colors.
  • Emitter layers typically comprise at least one host compound, either alone or together with at least one dopant compound. Examples of host compounds include, but are not limited to, ALQ, LDE-120 and IDE-140 (Idemitsu Kosan Co., Ltd., Tokyo, Japan).
  • Examples of dopant compounds include, but are not limited to, Coumarin 6, Coumarin 485, Coumarin, 487, Coumarin 490, Coumarin 498, Coumarin 500, Coumarin 503, Coumarin 504, Coumarin 504T, Coumarin 510, Coumarin 515, Coumarin 519, Coumarin 521, Coumarin 521T, Coumarin 522B, Coumarin 523, Coumarin 525, Coumarin 535, Coumarin 540A, Coumarin 545, quinacridone derivatives such as diethyl pentyl quinacridone and dimethyl quinacridone, distyrylamine derivatives, such as IDE-102, IDE-105 (Idemitsu Kosan Co., Ltd., Tokyo, Japan), rubrene, DCJTB, pyrromethane 546, and mixtures thereof.
  • the structure of DCJTB is shown below:
  • An emitter layer may be between 200-400 A thick.
  • the electron-injection/electron-transport layer is typically about 350 A thick and comprises a compound such as ALQ, or a suitable oxadiazole derivative.
  • the elecfron-injection/electron-transport layer is ALQ.
  • an OLED of the present invention comprises a 750 A thick hole-injection/hole-transport layer of bis(N,N'-l-naphthyl-phenyl-amino- biphenyl)-l -naphthyl amine (NA-DNPB), a 750 A thick emitter/electron transport layer of ALQ, and either Mg:Ag or LiF/Al cathode.
  • an OLED of the present invention comprises a 550
  • an OLED of the present invention is a down- emitter that emits green light and comprises an anode comprising indium tin oxide, a hole-injection layer adjacent to the anode comprising BPA-DNPB, a hole-transport layer adjacent to the hole-injection layer comprising BPA-BCA, an emitter layer adjacent to the hole-transport layer comprising ALQ and a compound selected from the group consisting of Coumarin 6, Coumarin 485, Coumarin, 487, Coumarin 490, Coumarin 498, Coumarin 500, Coumarin 503, Coumarin 504, Coumarin 504T, Coumarin 510, Coumarin 515, Coumarin 519, Coumarin 521, Coumarin 52 IT, Coumarin 522B, Coumarin 523, Coumarin 525, Coumarin 535, Coumarin 540A, Coumarin 545, and mixtures thereof, an electron-transport layer adjacent to the emitter layer comprising ALQ, and a cathode comprising either lithium fluoride and aluminum or magnesium and silver.
  • an OLED of the present invention is an up- emitter that emits green light and comprises an anode comprising molybdenum oxide, a hole-injection layer adjacent to the anode comprising BPA-DNPB, a hole-transport layer adjacent to the hole-injection layer comprising BPA-BCA, an emitter layer adjacent to the hole-transport layer comprising ALQ and a compound selected from the group consisting of Coumarin 6, Coumarin 485, Coumarin, 487, Coumarin 490,
  • an OLED of the present invention emits white or blue light and comprises an anode comprising indium tin oxide, a hole- injection layer adjacent to the anode comprising BPA-DNPB, a hole-transport layer adjacent to the hole-injection layer comprising BPA-BCA, an emitter layer adjacent to the hole-transport layer comprising DCJTB, IDE-102 and IDE-120, an electron- transport layer adjacent to the emitter layer comprising ALQ, and a cathode comprising lithium fluoride and aluminum.
  • the OLED display device is a microdisplay.
  • a microdisplay is a display device that is not viewable by the unaided eye, and therefore requires the use of an optic.
  • the sub-pixel size of a microdisplay device is less than about 15 microns, more preferably less than about 5 microns, and most preferably between about 2 microns and about 3 microns.
  • the multi-layered OLED devices of the invention allow for a "staircase" change in the energy difference of electrons and holes as they travel from the electrodes through each layer toward the emitter layer, where they recombine to emit light.
  • the anode and cathode of an OLED have an energy difference of about 1.6-1.8 eV.
  • a typical band gap of electrons and holes in the emitter layer is about 2.7 eV-2.9 eV, so that radiation emission resulting from recombination is in the visible light region (1.75 to 3 eV).
  • the increase in energy difference of holes and electrons from the anode and cathode to the emitter layer is accomplished incrementally as the electrons and holes travel through the layers between the electrodes and the emitter layer.
  • the present invention relates to OLEDs having incorporated in the electroluminescent medium organic compounds with variable ionization potentials (IP) and electron affinities (EA) and high glass transition temperatures. Specifically, the present invention relates to OLEDs having hole-injection and hole-transport layers with variable IP and high glass transition temperatures. In particular, the present invention relates to OLEDs having hole-injection and hole-transport layers comprising a compound of formula 1 :
  • Ri is selected from the group consisting of biphenyl, naphthyl, phenyl
  • R 2 and R 3 are each independently selected from the group consisting of aryl, F, CI, -CF 3 , saturated alkyl of up to 10 carbon atoms, preferably of between 1 and 4 carbon atoms, SO 2 R 6 , Si(R 6 ) 3 , and OR ⁇ , or R 2 and R 3 taken together form a heterocyclic ring of up to 8 atoms, wherein one of the 8 atoms is nitrogen and another of the 8 atoms is either nitrogen or oxygen, or R 2 and R 3 taken together with the phenyl group to which they are attached form a fused polycyclic aromatic system, wherein the fused polycyclic aromatic system comprises up to 16 carbon atoms;
  • Rj and R 5 are each independently selected from the group consisting of:
  • R and R 5 taken together with the nitrogen to which they are attached are selected from the group consisting of:
  • R ⁇ is C 1 -C 4 straight or branched saturated alkyl
  • R and R 8 are each independently selected from the group consisting of - R 9 , C1-C4 alkyl, aryl, -SCH 3 , -CF 3 , -CI, -Br, -NO 2 , and -COOR 9 ; and R is selected from the group consisting of -C 6 alkyl and aryl. Additional compounds for this embodiment include compounds of formula 1, wherein R 4 and R 5 are each independently selected from the group consisting of:
  • Such OLEDs incorporating organic compounds with variable IP and high glass transition temperatures in the hole-injection and hole-transport layers are longer- lived and can withstand higher temperatures than OLEDs that incorporate traditional triarylamines in those layers.
  • the variable IP of these materials also permits staircase tuning of the hole energies to increase the quantum efficiency of the OLEDs.
  • Hole- injection and hole-transport layers comprising a compound of formula 1 typically have glass transition temperatures in the range of 130-180°C. Therefore, the OLEDs of the present invention can be operated at higher current densities, which results in increased brightness, without changing the morphology of the hole-injection and hole- transport layers and degrading the device.
  • DPPF diphenylphosphino ferrocene
  • Pd 2 (dba) 3 tris(dibenzylideneacetone) dipalladium
  • the reaction mixture is then heated to about 95°C for about 20 hours.
  • reaction yield ranges from 70% to 95%, depending upon the selection Mass spectroscopic analysis may be used to confirm the formation of the compound of formula 3.
  • the thermal properties and glass transition temperatures of compounds of formula 1 are determined using differential scanning calorimetry (DSC) and thermo gravimetric analysis (TGA).
  • Silica gel having average particle size of 230-400 mesh from Whatman was used in a 20 cm column for purification. Compounds were eluted using 5% CH 2 C1 2 in hexane as the mobile phase. Sublimation was performed using a train sublimation apparatus designed in the laboratory at a pressure of 1.0 x 10 "6 torr and at temperature of 350 °C.
  • Mass spectroscopy was performed on a SFNNIGAN 4500 instrument from Sfhnigan Corporation using direct ionization with methane as the gas at a pressure of 0.4 millitorr.
  • TGA was performed on a TGA-50 instrument from Shimadzu.
  • DSC was performed using a DSC-50 instrument from Shimadzu.
  • DPPF diphenylphosphino ferrrocene
  • Pd 2 (dba) 3 tris(dibenzylideneacetone) dipalladium
  • BPA-BPBBr biphenylamino-bis-biphenyl bromide
  • BPA-BCA was further purified by sublimation (see Materials, above). Mass spectroscopic (see Materials, above) analysis confirmed the formation of BPA-BCA.
  • the glass transition temperature (T g ) was determined by DSC (see Materials, above) to be about 162°C.
  • EXAMPLE 2 SYNTHESIS OF NA-DNPB
  • catalytic amounts of DPPF (285 mg) and Pd 2 (dba) 3 (312 mg) were added to a solution of 0.74 g (1 eq) of 1-aminonaphthalene, 4.70 g (3 eq) of 4,4'-dibromobiphenyl and 1.05 g (2.2 eq) of sodium tert-butoxide in anhydrous toluene.
  • the reaction mixture was heated at 95°C for 30 hours.
  • NA-BPBBr 1 -naphthyl-amino-bis-biphenyl bromide
  • NA-DNPB (8) was isolated by silica gel chromatography (see Materials, Example 1, above). 1.5 g of crude product was obtained (85% yield). NA-DNPB (8) was further purified by sublimation (see Materials, Example 1, above). Mass spectroscopic analysis (see Materials, Example 1, above) confirmed the formation of NA-DNPB (8).
  • the glass transition temperature (T g ) was determined by DSC (see Materials, Example 1, above) to be about 147°C.
  • EXAMPLE 3 SYNTHESIS OF BIS(CARBAZOL-N-BIPHENYL)-l -NAPHTHYL
  • AMINE (NA-BCA) NA-BPBBr was synthesized as described above in Example 2.
  • 0.35 mmol (320 mg) of Pd 2 (dba) 3 and 0.5 mmol (280 mg) of DPPF were added to a solution of 2 mmol (1.216 g) of NA-BPBBr (7) and 5.5 mmol (0.55 g) of sodium tert-butoxide dissolved in 25 mL of anhydrous toluene.
  • 5.0 mmol (0.85 g) of carbazole dissolved in 20 mL of toluene were added to this solution.
  • the reaction mixture was heated at 95°C for 30 hours.
  • NA-BCA (9) was isolated by silica gel chromatography (see Materials, Example 1, above). 1.20 g of crude product was obtained (85% yield). NA-BCA (9) was further purified by sublimation (see Materials, Example 1, above). Mass spectroscopic analysis (see Materials, Example 1, above) confirmed the formation of NA-BCA (9).
  • EXAMPLE 4 FORMATION OF AN OLED USING BPA-BCA AS HOLE- INJECTION AND HOLE-TRANSPORT LAYERS
  • a 750 A thick hole-injection/hole-transport layer of BPA-BCA was thermally evaporated on pre-cleaned indium tin oxide (ITO) substrate in high vacuum (10 "6 -10 "7 torr) at room temperature. This was followed by evaporation of a 750 A thick emitter/electron transport layer of ALQ.
  • a cathode comprising a 7.5 A layer of LiF followed by a 500 A layer of Al was then deposited. The resulting OLED demonstrated diode behavior and emitted green light when direct voltage was applied.
  • the OLED demonstrated quantum efficiency of 5.2 cd/A and 1.6% ph/e, a low driving voltage (6.8 Volts) at a current density of 20 mA/cm 2 , and a brightness level of 590 cd/m 2 for green emission.
  • EXAMPLE 5 FORMATION OF AN OLED USING NA-DNPB AS HOLE- INJECTION AND HOLE-TRANSPORT LAYERS
  • a 750 A thick hole-injection/hole-transport layer of NA-DNPB was thermally evaporated on pre-cleaned indium tin oxide (ITO) substrate that has been ashed in oxygen plasma (400 W power, 300 millitorr pressure, oxygen flow 50 cc/min) for one minute (see Example 4, above). This was followed by evaporation of a 750 A thick emitter/electron transport layer of ALQ and a either a Mg:Ag or LiF/Al cathode (see Example 4, above).
  • ITO indium tin oxide
  • the resulting OLED demonstrated diode behavior and emitted green light when direct voltage was applied.
  • the OLED demonstrated quantum efficiency of 2.95 cd/A and 0.91% ph/e, a low driving voltage (7.4 Volts) at a current density of 20 mA/cm , and a brightness level of 1053 cd/m for green emission.
  • EXAMPLE 6 FORMATION OF AN OLED USING BPA-DNPB AS HOLE- INJECTION LAYER AND BPA-BCA AS HOLE-TRANSPORT LAYER A 550 A thick hole-injection layer of BPA-DNPB was thermally evaporated on pre-cleaned indium tin oxide (ITO) substrate in high vacuum (see Example 5, above). This was followed by evaporation of a 200 A thick hole-transport layer of BPA-BCA, evaporation of a 350 A thick emitter layer of ALQ doped with 2.5% of coumarin 6 (see Example 4, above), and evaporation of a 300 A thick electron transport layer of ALQ, and a LiF/Al cathode (see Example 4, above).
  • ITO indium tin oxide
  • the resulting OLED demonstrated diode behavior and emitted green light when direct voltage was applied.
  • the OLED demonstrated quantum efficiency of 14.3 cd/A and 4.0% ph/e, a low driving voltage (7.0 Volts) at a current density of 20 mA/cm 2 , and a brightness level of 2,900 cd/m 2 for green emission.

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Abstract

L'invention concerne des dispositifs OLED multicouche, à couches d'injection et/ou de transport de trou constituées de composés aryl amine qui présentent des valeurs de Tg relativement élevées (on se réfère donc à des composés aryl amine thermostables). Ce type de dispositif permet d'introduire une modification, par échelons, de la différence d'énergie propre aux trous et aux électrons à mesure qu'ils se déplacent depuis les électrodes vers la couche émissive, réduisant la tension d'exploitation et donnant un rendement quantique élevé de luminescence pour une densité de courant spécifique. L'invention concerne également des appareils à microaffichage comprenant le type de dispositif considéré, à couches d'injection et/ou de transport de trou constituées de composés aryl amine.
PCT/US2001/020583 2001-06-28 2001-06-28 Dispositifs oled a composes d'injection et de transport de trou thermostables WO2003003482A1 (fr)

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EP01950594A EP1451881A1 (fr) 2001-06-28 2001-06-28 Dispositifs oled a composes d'injection et de transport de trou thermostables
PCT/US2001/020583 WO2003003482A1 (fr) 2001-06-28 2001-06-28 Dispositifs oled a composes d'injection et de transport de trou thermostables

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018188441A (ja) * 2009-03-31 2018-11-29 株式会社半導体エネルギー研究所 カルバゾール誘導体、発光素子、発光装置、電子機器、照明装置

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0848579A2 (fr) * 1996-12-16 1998-06-17 Toyo Ink Manufacturing Co., Ltd. Matériau pour dispositif organique électroluminescent et dispositif électroluminescent l'utilisant
WO1999020596A1 (fr) * 1997-10-20 1999-04-29 Chisso Corporation Derives amines et dispositif electroluminescent organique realise a partir desdits derives
EP0969532A2 (fr) * 1998-07-04 2000-01-05 Bayer Aktiengesellschaft Dispositifs électroluminescents comprenant des complexes métalliques d'azométhine
EP0973210A2 (fr) * 1998-07-16 2000-01-19 Sumitomo Electric Industries, Ltd. Dérivés de triphenylamine et dispositif organique électroluminescent les contenant

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0848579A2 (fr) * 1996-12-16 1998-06-17 Toyo Ink Manufacturing Co., Ltd. Matériau pour dispositif organique électroluminescent et dispositif électroluminescent l'utilisant
WO1999020596A1 (fr) * 1997-10-20 1999-04-29 Chisso Corporation Derives amines et dispositif electroluminescent organique realise a partir desdits derives
EP0969532A2 (fr) * 1998-07-04 2000-01-05 Bayer Aktiengesellschaft Dispositifs électroluminescents comprenant des complexes métalliques d'azométhine
EP0973210A2 (fr) * 1998-07-16 2000-01-19 Sumitomo Electric Industries, Ltd. Dérivés de triphenylamine et dispositif organique électroluminescent les contenant

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018188441A (ja) * 2009-03-31 2018-11-29 株式会社半導体エネルギー研究所 カルバゾール誘導体、発光素子、発光装置、電子機器、照明装置

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