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US-12622166-B2 - Organic electronic device comprising an anode layer, a cathode layer, at least one emission layer (EML) and at least one hole injection layer (HIL)

US12622166B2US 12622166 B2US12622166 B2US 12622166B2US-12622166-B2

Abstract

The present invention relates to an organic electronic device comprising an anode layer, a cathode layer, at least one emission layer (EML) and at least one hole injection layer (HIL), wherein the hole injection layer is arranged between the anode layer and the at least one emission layer.

Inventors

  • Thomas Rosenow
  • Vygintas Jankus
  • Markus Hummert
  • Moo Jin Park
  • Vladimir Uvarov
  • Annette Steudel

Assignees

  • NOVALED GMBH

Dates

Publication Date
20260505
Application Date
20210127
Priority Date
20200128

Claims (20)

  1. 1 . An organic electronic device comprising an anode layer, a cathode layer, at least one emission layer (EML) and at least one hole injection layer (HIL), wherein the hole injection layer is arranged between the anode layer and the at least one emission layer; wherein the hole injection layer comprises an organic matrix compound (OMC) and a metal complex, wherein the metal complex has the formula (II): M n⊕ (L ⊖ ) n (II), wherein M is a metal ion, n is the valency of M, wherein n is an integer from 1 to 4 L is a ligand; and the at least one emission layer comprises at least one emitter matrix compound (EMC), wherein the HOMO level of the emitter matrix compound (EMC) and the HOMO level of the organic matrix compound (OMC) fulfills the following equation: −0.24 eV<[HOMO level (EMC)−HOMO level (OMC)]≤0.8 eV; wherein the organic matrix compound (OMC) of the hole injection layer and/or the emitter matrix compound (EMC) has a molecular weight Mw of ≥400 and ≤2000 g/mol.
  2. 2 . The organic electronic device of claim 1 , wherein the organic matrix compound (OMC) and the emitter matrix compound (EMC) have the formula (I): (Ar 1 ) k -(Ar 2 ) m -Ar 3 -(Ar 4 ) p -(Ar 5 ) q -(Ar 6 ) r (I), wherein k, m, q, r are independently from each other 0, 1 or 2, p is 1, 2 or 3, wherein 2≤k+m+q+r+p≤11, Ar 1 to Ar 6 are independently selected from a substituted or unsubstituted unsaturated 5- to 7-member ring of a heterocycle, a substituted or unsubstituted C 6 to C 30 aryl or a substituted or unsubstituted C 3 to C 30 heteroaryl, a substituted or unsubstituted fluorene, or a fused ring system comprising 2 to 6 substituted or unsubstituted 5- to 7-member rings and the rings are selected from the group comprising (i) unsaturated 5- to 7-member ring of a heterocycle, (ii) 5- to 6-member of an aromatic heterocycle, (iii) unsaturated 5- to 7-member ring of a non-heterocycle, (iv) 6-member ring of an aromatic non-heterocycle; wherein the substituents are selected from the group H, D, C 1 to C 12 alkyl, unsubstituted C 6 to C 18 aryl, unsubstituted C 3 to C 18 heteroaryl, a fused ring system comprising 2 to 6 unsubstituted 5- to 7-member rings and the rings are selected from the group comprising unsaturated 5- to 7-member ring of a heterocycle, 5- to 6-member of an aromatic heterocycle, unsaturated 5- to 7-member ring of a non-heterocycle, and 6-member ring of an aromatic non-heterocycle; and wherein the organic matrix compound (OMC) and the emitter matrix compound (EMC) are selected the same or selected different.
  3. 3 . The organic electronic device according to claim 1 , wherein the hole injection layer is non-emissive.
  4. 4 . The organic electronic device according to claim 1 , wherein the hole injection layer is arranged adjacent to the anode layer, alternatively in direct contact with the anode layer.
  5. 5 . The organic electronic device according to claim 1 , wherein the HOMO level of the organic matrix compound (OMC) is further away from vacuum level than the HOMO level of N4,N4′″-di(naphthalen-1-yl)-N4,N4′″-diphenyl-[1,1′:4′,1″: 4″,1′″-quaterphenyl]-4,4′″-diamine when determined under the same conditions.
  6. 6 . The organic electronic device according to claim 1 , wherein the organic matrix compound (OMC) fulfills the following equation: −7 eV<HOMO level (OMC)<−4.85 eV; wherein the HOMO level is calculated with the program package TURBOMOLE V6.5.
  7. 7 . The organic electronic device according to claim 1 , wherein the organic matrix compound (OMC) and the emitter matrix compound (EMC) have the formula (I): (Ar 1 ) k -(Ar 2 ) m -Ar 3 -(Ar 4 ) p -(Ar 5 ) q -(Ar 6 ) r (I), wherein k, m, q, r are independently from each other 0, 1 or 2, p is 1, 2 or 3, wherein 2≤k+m+q+r+p≤11, Ar 1 to Ar 6 are independently selected from substituted or unsubstituted biphenylene, substituted or unsubstituted fluorene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted pyrene, substituted or unsubstituted perylene, substituted or unsubstituted triphenylene, substituted or unsubstituted tetracene, substituted or unsubstituted tetraphene, substituted or unsubstituted dibenzofurane, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthene, substituted or unsubstituted carbazole, substituted or unsubstituted azepine, substituted or unsubstituted dibenzo[b,f]azepine, 9,9′-spirobi[fluorene], substituted or unsubstituted spiro[fluorene-9,9′-xanthene], substituted or unsubstituted 9,14-dihydrodibenzo[2,3:6,7]azepino[4,5-b]indole, or a substituted or unsubstituted aromatic fused ring system comprising at least three substituted or unsubstituted aromatic rings selected from the group comprising substituted or unsubstituted non-hetero, substituted or unsubstituted hetero 5-member rings, substituted or unsubstituted 6-member rings or substituted or unsubstituted 7-member rings, substituted or unsubstituted fluorene, or a fused ring system comprising 2 to 6 substituted or unsubstituted 5- to 7-member rings and the rings are selected from the group comprising (i) unsaturated 5- to 7-member ring of a heterocycle, (ii) 5- to 6-member of an aromatic heterocycle, (iii) unsaturated 5- to 7-member ring of a non-heterocycle, (iv) 6-member ring of an aromatic non-heterocycle, wherein the substituents are selected from the group H, D, C 1 to C 12 alkyl, unsubstituted C 6 to C 18 aryl, unsubstituted C 3 to C 18 heteroaryl, a fused ring system comprising 2 to 6 unsubstituted 5- to 7-member rings and the rings are selected from the group comprising unsaturated 5- to 7-member ring of a heterocycle, 5- to 6-member of an aromatic heterocycle, unsaturated 5- to 7-member ring of a non-heterocycle, and 6-member ring of an aromatic non-heterocycle; and wherein the organic matrix compound (OMC) and the emitter matrix compound (EMC) are selected the same or selected different.
  8. 8 . The organic electronic device according to claim 1 , wherein M is selected from the group comprising a metal ion wherein the corresponding metal has an electronegativity value according to Allen of less than 2.4, an alkali, alkaline earth, rare earth or transition metal, a metal with an atomic mass≥24 Da, or a metal with an atomic mass≥24 Da and M has an oxidation number≥2.
  9. 9 . The organic electronic device according to claim 1 , wherein the metal complex has a molecular weight Mw of ≥287 and ≤2000 g/mol.
  10. 10 . The organic electronic device according to claim 1 , wherein L is selected from a group comprising at least three carbon atoms, alternatively at least four carbon atoms, or at least two oxygen atoms or one oxygen and one nitrogen atom, two to four oxygen atoms, two to four oxygen atoms and zero to two nitrogen atoms, or at least one or more groups selected from halogen, F, CN, substituted or unsubstituted C 1 to C 6 alkyl, substituted or unsubstituted C 1 to C 6 alkoxy, alternatively two or more groups selected from halogen, F, CN, substituted or unsubstituted C 1 to C 6 alkyl, substituted or unsubstituted C 1 to C 6 alkoxy, at least one or more groups selected from halogen, F, CN, substituted C 1 to C 6 alkyl, substituted C 1 to C 6 alkoxy, alternatively two or more groups selected from halogen, F, CN, perfluorinated C 1 to C 6 alkyl, perfluorinated C 1 to C 6 alkoxy, one or more groups selected from substituted or unsubstituted C 1 to C 6 alkyl, substituted or unsubstituted C 6 to C 12 aryl, or substituted or unsubstituted C 3 to C 12 heteroaryl, wherein the substituents are selected from D, C 6 aryl, C 3 to C 9 heteroaryl, C 1 to C 6 alkyl, C 1 to C 6 alkoxy, C 3 to C 6 branched alkyl, C 3 to C 6 cyclic alkyl, C 3 to C 6 branched alkoxy, C 3 to C 6 cyclic alkoxy, partially or perfluorinated C 1 to C 16 alkyl, partially or perfluorinated C 1 to C 16 alkoxy, partially or perdeuterated C 1 to C 6 alkyl, partially or perdeuterated C 1 to C 6 alkoxy, COR 6 , COOR 6 , halogen, F or CN; wherein R 6 is selected from C 6 aryl, C 3 to C 9 heteroaryl, C 1 to C 6 alkyl, C 1 to C 6 alkoxy, C 3 to C 6 branched alkyl, C 3 to C 6 cyclic alkyl, C 3 to C 6 branched alkoxy, C 3 to C 6 cyclic alkoxy, partially or perfluorinated C 1 to C 16 alkyl, partially or perfluorinated C 1 to C 16 alkoxy, partially or perdeuterated C 1 to C 6 alkyl, partially or perdeuterated C 1 to C 6 alkoxy.
  11. 11 . The organic electronic device according to claim 1 , wherein the metal complex according to formula (II) is non-emissive.
  12. 12 . The organic electronic device according to claim 1 , wherein the organic matrix compound (OMC) and the emitter matrix compound (EMC) have the formula (I): (Ar 1 ) k -(Ar 2 ) m -Ar 3 -(Ar 4 ) p -(Ar 5 ) q -(Ar 6 ) r (1), wherein k, m, q, r are independently from each other 0, 1 or 2, p is 1, 2 or 3, wherein 2≤k+m+q+r+p≤11, Ar 1 to Ar 6 are independently selected from substituted or unsubstituted unsaturated 5- to 7-member ring of a heterocycle, substituted or unsubstituted C 6 to C 30 aryl, substituted or unsubstituted C 3 to C 30 heteroaryl, a substituted or unsubstituted fluorene, or a fused ring system comprising 2 to 6 substituted or unsubstituted 5- to 7-member rings and the rings are selected from the group comprising (i) unsaturated 5- to 7-member ring of a heterocycle, (ii) 5- to 6-member of an aromatic heterocycle, (iii) unsaturated 5- to 7-member ring of a non-heterocycle, (iv) 6-member ring of an aromatic non-heterocycle; Ar 2 if k=1, Ar 3 , Ar 4 if q=1, Ar 5 if r=1: are independently selected from substituted or unsubstituted unsaturated 5- to 7-member ring of a heterocycle, substituted or unsubstituted C 6 to C 30 arylene, substituted or unsubstituted C 3 to C 30 heteroarylene, substituted or unsubstituted biphenylene, substituted or unsubstituted fluorene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted pyrene, substituted or unsubstituted perylene, substituted or unsubstituted triphenylene, substituted or unsubstituted tetracene, substituted or unsubstituted tetraphene, substituted or unsubstituted dibenzofurane, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthene, substituted or unsubstituted carbazole, substituted or unsubstituted azepine, substituted or unsubstituted dibenzo[b,f]azepine, 9,9′-spirobi[fluorene], substituted or unsubstituted spiro[fluorene-9,9′-xanthene], substituted or unsubstituted 9,14-dihydrodibenzo[2,3:6,7]azepino[4,5-b]indole, or a substituted or unsubstituted aromatic fused ring system comprising at least three substituted or unsubstituted aromatic rings selected from the group comprising substituted or unsubstituted non-hetero, substituted or unsubstituted hetero 5-member rings, substituted or unsubstituted 6-member rings or substituted or unsubstituted 7-member rings; Ar 2 if k=0, Ar 3 if m=0 and k=0, Ar 4 if q and r=0, Ar 5 if r=0: are independently selected from substituted or unsubstituted unsaturated 5- to 7-member ring of a heterocycle, substituted or unsubstituted C 6 to C 30 aryl, substituted or unsubstituted C 3 to C 30 heteroaryl, substituted or unsubstituted biphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted naphthalenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted perylenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted tetracenyl, substituted or unsubstituted tetraphenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted xanthenyl, substituted or unsubstituted carbazole, substituted or unsubstituted azepine, substituted or unsubstituted dibenzo[b,f]azepine, 9,9′-spirobi[fluorenyl], substituted or unsubstituted spiro[fluorenyl-9,9′-xanthene], substituted or unsubstituted 9,14-dihydrodibenzo[2,3:6,7]azepino[4,5-b]indole, or a substituted or unsubstituted aromatic fused ring system comprising at least three substituted or unsubstituted aromatic rings selected from the group comprising substituted or unsubstituted non-hetero, substituted or unsubstituted hetero 5-member rings, substituted or unsubstituted 6-member rings or substituted or unsubstituted 7-member rings; wherein the substituents are selected from the group H, D, C 1 to C 12 alkyl, unsubstituted C 6 to C 18 aryl, unsubstituted C 3 to C 18 heteroaryl, a fused ring system comprising 2 to 6 unsubstituted 5- to 7-member rings and the rings are selected from the group comprising unsaturated 5- to 7-member ring of a heterocycle, 5- to 6-member of an aromatic heterocycle, unsaturated 5- to 7-member ring of a non-heterocycle, and 6-member ring of an aromatic non-heterocycle; and wherein the organic matrix compound (OMC) and the emitter matrix compound (EMC) are selected the same or selected different, and wherein the metal complex has the formula (II).
  13. 13 . The organic electronic device according to claim 1 , wherein the organic matrix compound (OMC) and the emitter matrix compound (EMC) are selected from the group of compounds comprising at least ≥1 to ≤6 substituted or unsubstituted aromatic fused ring systems comprising heteroaromatic rings, at least ≥1 to ≤3 substituted or unsubstituted unsaturated 5- to 7-member ring of a heterocycle, at least ≥2 to ≤5 substituted or unsubstituted aromatic fused ring systems comprising heteroaromatic rings, at least ≥1 to ≤3 substituted or unsubstituted unsaturated 5- to 7-member ring of a heterocycle, at least 3 or 4 substituted or unsubstituted aromatic fused ring systems comprising heteroaromatic rings, at least ≥1 to ≤3 substituted or unsubstituted unsaturated 5- to 7-member ring of a heterocycle, at least an aromatic fused ring systems comprising heteroaromatic rings are unsubstituted, or at least ≥1 to ≤3 unsubstituted unsaturated 5- to 7-member ring of a heterocycle.
  14. 14 . The organic electronic device according to claim 1 , wherein the organic matrix compound (OMC) and the emitter matrix compound (EMC) are selected from the group of compounds comprising a substituted or unsubstituted aromatic fused ring systems with at least ≥2 to ≤6-fused aromatic rings selected from the group comprising substituted or unsubstituted non-hetero aromatic rings, substituted or unsubstituted hetero 5-member rings, substituted or unsubstituted 6-member rings, substituted or unsubstituted unsaturated 5- to 7-member ring of a heterocycle, an unsubstituted aromatic fused ring systems with at least ≥2 to ≤6 fused aromatic rings selected from the group comprising unsubstituted non-hetero aromatic rings, unsubstituted hetero 5-member rings, unsubstituted 6-member rings, or unsubstituted unsaturated 5- to 7-member ring of a heterocycle.
  15. 15 . The organic electronic device according to claim 1 , wherein the organic matrix compound (OMC) and the emitter matrix compound (EMC) are selected from the group of compounds comprising at least ≥1 to ≤6 substituted or unsubstituted aromatic fused ring systems with at least one unsaturated 5-member ring, at least ≥1 to ≤6 substituted or unsubstituted aromatic fused ring systems with at least one unsaturated 6-member ring, at least ≥1 to ≤6 substituted or unsubstituted aromatic fused ring systems with at least one unsaturated 7-member ring, at least ≥1 to ≤6 substituted or unsubstituted aromatic fused ring systems with at least one unsaturated 5-member ring comprises at least 1 to 3 hetero-atoms or at least ≥1 to ≤6 substituted or unsubstituted aromatic fused ring systems with at least one unsaturated 7-member ring comprises at least 1 to 3 hetero-atoms.
  16. 16 . The organic electronic device according to claim 1 , wherein for the organic matrix compound (OMC) and the emitter matrix compound (EMC) comprise the hetero-atom is selected from the group comprising O, S, N, B, P or Si.
  17. 17 . The organic electronic device according to claim 1 , wherein the organic matrix compound (OMC) and the emitter matrix compound (EMC) is free of hetero-atoms which are not part of an aromatic ring or part of an unsaturated 7-member-ring.
  18. 18 . The organic electronic device according to claim 1 , wherein the organic matrix compound (OMC) and the emitter matrix compound (EMC) are selected from compounds comprising at least ≥6 to ≤12 aromatic rings; at least ≥4 to ≤11 non-hetero aromatic rings; at least ≥1 to ≤4 hetero aromatic 5-member-rings; at least 1 or 2 unsaturated 5- to 7-member-ring of a heterocycle, at least ≥6 to ≤12 aromatic rings, wherein therefrom at least ≥4 to ≤11 are non-hetero aromatic rings and at least ≥1 to ≤4 aromatic rings are hetero aromatic rings, wherein the total number of non-hetero aromatic rings and hetero aromatic rings in total does not exceed 12 aromatic rings, at least ≥6 to ≤12 aromatic rings, wherein therefrom at least ≥4 to ≤11 are non-hetero aromatic rings, and at least ≥1 to ≤4 aromatic rings are hetero aromatic rings, wherein the total number of non-hetero aromatic rings and hetero aromatic rings in total does not exceed 12 aromatic rings; and the hole transport compound or the hole transport compound according to formula I is selected from the group of compounds comprising at least ≥1 to ≤4 hetero aromatic 5-member-rings, or at least 1 or 2 unsaturated 5- to 7-member-ring of a heterocycle.
  19. 19 . The organic electronic device according to claim 1 , wherein for formula (I): Ar 3 is selected from D1 to D17: Ar 1 is selected from D7 to D15 and D17, if m>0 and k>0, or is selected from D7 to D15 and D17, if k>0 and m=0, or is selected from D1 to D6, if k>1; Ar 2 is selected from D1 to D6, if m>0 and k>0; or is selected from D7 to D15 and D17, if m>0 and k=0; Ar 4 is selected from D1 to D6, if q>0, or is selected from D1 to D6, if q=0 and r>0; or is selected from D7 to D15 and D17, if q and r=0; Ar 5 is selected from D1 to D6, if q>0 and r>0, or is selected from D7 to D15 and D17, if q>0 and r=0; Ar 6 is selected from D7 to D15 and D17, if r>0, q>0, or is selected from D7 to D15 and D17, if r>0, q=0, or is selected from D1 to D6, if r>1.
  20. 20 . The organic electronic device according to claim 1 , wherein the organic matrix compound (OMC) or the emitter matrix compound (EMC) according to formula (I) is selected from F1 to F13:

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application is a U.S. national phase application of PCT/EP2021/051885, filed Jan. 27, 2021, which claims priority to European Patent Application No. 20154092.9, filed Jan. 28, 2020. The content of these applications is incorporated herein by reference. TECHNICAL FIELD The present invention relates to an organic electronic device containing an anode layer, a cathode layer, at least one emission layer (EML) and at least one hole injection layer (HIL), wherein the hole injection layer comprises an organic matrix compound. BACKGROUND ART Organic electronic devices, such as organic light-emitting diodes OLEDs, which are self-emitting devices, have a wide viewing angle, excellent contrast, quick response, high brightness, excellent operating voltage characteristics, and color reproduction. A typical OLED comprises an anode layer, a hole injection layer HIL, a hole transport layer HTL, an emission layer EML, an electron transport layer ETL, and a cathode layer, which are sequentially stacked on a substrate. In this regard, the HIL, the HTL, the EML, and the ETL are thin films formed from organic compounds. When a voltage is applied to the anode and the cathode, holes injected from the anode move to the EML, via the HIL and HTL, and electrons injected from the cathode move to the EML, via the ETL. The holes and electrons recombine in the EML to generate excitons. When the excitons drop from an excited state to a ground state, light is emitted. The injection and flow of holes and electrons should be balanced, so that an OLED having the above-described structure has low operating voltage, excellent efficiency and/or a long lifetime. Performance of an organic light emitting diode may be affected by characteristics of the hole injection layer, and among them, may be affected by characteristics of the organic matrix compound and the metal complexes which are contained in the hole injection layer. WO2017029370 relates to metal amides of general Formula Ia and for their use as hole injection layer (HIL) for an Organic light-emitting diode (OLED), and a method of manufacturing Organic light-emitting diode (OLED) comprising an hole injection layer containing a metal amide of general Formula Ia. In WO2017029370 is disclosed hole transport layer which may comprises in addition a triarylamine compound having the Formula VIIa: The emission layer (EML) may be formed of a combination of a host and a dopant. WO2017029366 relates to a hole injection layer for an OLED comprising a triarylamine compound doped with a charge neutral metal amide compound, characterized in that the hole injection layer has a thickness of at least about ≥20 nm to about ≤1000 nm and the charge neutral metal amide compound has the Formula Ia. In WO2017029366 is disclosed a hole injection layer (HIL) comprises a triarylamine compound having the Formula VIIa: The emission layer (EML) may be formed of a combination of a host and a dopant. WO2017102861 relates to an organic electronic component (10) comprising at least one organic layer (3), which has a fluorinated sulphonamide metal salt of the following formula 1: (1) wherein M is either a bivalent or higher-order metal having an atomic mass of greater than 26 g/mol or a monovalent metal having an atomic mass of greater than or equal to 39 g/mol, wherein 1≤n≤7, and wherein R1, R2 are selected independently of each other and from a group comprising a fluoride-substituted aryl radical, a fluoride-substituted alkyl radical, and a fluoride-substituted aryl-alkyl radical. The matrix material is a hole-transport material. The organic electronic component comprises a light-emitting layer. US2016336519A1 provides a novel light-emitting element, a light-emitting element with a long lifetime, or a light-emitting element with high emission efficiency. The light-emitting element includes an EL layer between a pair of electrodes. The EL layer includes at least a light-emitting layer containing a fluorescent substance and a host material, a first electron-transport layer containing a first electron-transport material, and a second electron-transport layer containing a second electron-transport material, which are in contact with each other and in this order. The LUMO level of each of the host material and the second electron-transport material is higher than the LUMO level of the first electron-transport material. US2019198789A1 discloses an organic light emitting diode and an organic light emitting display including the same, where the organic light emitting diode includes: a first electrode; a light emitting stack disposed on the first electrode; and a second electrode disposed on the light emitting stack, where the light emitting stack includes a hole transport layer and a blue light emitting layer such that the hole transport layer and the blue light emitting layer are sequentially stacked on the first electrode, where the blue light emitting layer includes a blue host mater