WILLMANN STEFFEN (DE)
HEGGEMANN ULRICH (DE)
| WO2009050115A1 | 2009-04-23 | |||
| WO2021048044A1 | 2021-03-18 | |||
| WO2009050115A1 | 2009-04-23 | |||
| WO2021048044A1 | 2021-03-18 |
| CN111302926A | 2020-06-19 | |||
| US20110031876A1 | 2011-02-10 | |||
| US4036605A | 1977-07-19 | |||
| JP2018137314A | 2018-08-30 | |||
| US20110031876A1 | 2011-02-10 |
"Photoelectron Spectrophotometer in air", SURFACE ANALYZER, 11 June 2012 (2012-06-11), pages 1 - 6
"CRC Handbook of Chemistry and Physics", 2008, pages: 12 - 114
| CLAIMS 1. An organic electronic device comprising a substrate, an anode layer, a cathode layer, at least one first emission layer, and a hole injection layer, wherein - the hole injection layer comprises a metal complex, wherein - the metal complex comprises a metal ion M selected from Ce(IV), Hf(IV) or Zr(IV); and - the metal complex comprises at least one anionic ligand L, wherein the anionic ligand comprising per ligand L at least 14 covalently bound atoms; - the anode layer comprises a first anode sub-layer and a second anode sub-layer, wherein - the first anode sub-layer comprises a first metal having a work function in the range of ≥ 4 and ≤ 6 eV, and - the second anode sub-layer comprises a transparent conductive oxide; wherein - the hole injection layer is arranged between the first emission layer and the anode layer, - the first anode sub-layer is arranged closer to the substrate, and - the second anode sub-layer is arranged closer to the hole injection layer. 2. An organic electronic device comprising a substrate, an anode layer, a cathode layer, at least one first emission layer, and a hole injection layer, wherein - the hole injection layer comprises a metal complex, wherein the metal complex has the formula I: wherein M is a metal ion selected from Ce, Hf or Zr, preferably Ce(IV), Hf(IV) or Zr(IV); L is an anionic ligand comprising at least 14 covalently bound atoms, wherein at least two atoms are selected from carbon atoms; AL is an ancillary ligand which coordinates to the metal M; n is an integer selected from 0 to 2; - the anode layer comprises a first anode sub-layer and a second anode sub-layer, wherein - the first anode sub-layer comprises a first metal having a work function in the range of ≥ 4 and ≤ 6 eV, - the second anode sub-layer comprises a transparent conductive oxide; wherein - the hole injection layer is arranged between the first emission layer and the anode layer, - the first anode sub-layer is arranged closer to the substrate, and - the second anode sub-layer is arranged closer to the hole injection layer. 3. The organic electronic device according to claim 1 or 2, wherein M is selected from Ce or Hf 4. The organic electronic device according to any of claims 1 to 3, wherein the ligand L and the ligand L of formula I comprising: - at least three carbon atoms, alternatively at least four carbon atoms, and/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, and/or - at least one or more groups selected from halogen, F, CN, substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C1 to C6 alkoxy, alternatively two or more groups selected from halogen, F, CN, substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C1 to C6 alkoxy, at least one or more groups selected from halogen, F, CN, substituted C1 to C6 alkyl, substituted C1 to C6 alkoxy, alternatively two or more groups selected from halogen, F, CN, perfluorinated C1 to C6 alkyl, perfluorinated C1 to C6 alkoxy, one or more groups selected from substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C6 to C12 aryl, and/or substituted or unsubstituted C3 to C12 heteroaryl, wherein the substituents are selected from D, C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C16 alkyl, partially or perfluorinated C1 to C16 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy, COR3, COOR3, halogen, F or CN; wherein R3 may be selected from C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C16 alkyl, partially or perfluorinated C1 to C16 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy. 5. The organic electronic device according to any of claims 1 to 4, wherein the ligand L and the ligand L of formula I are selected from G1 to G76: 6. The organic electronic device according to any of claims 1 to 5, wherein the metal complex and the metal complex of formula I of the hole injection are selected from the following formulas (la) to (Id): wherein A1 and A2 are independently selected from substituted or unsubstituted C1 to C12 alkyl, substituted or unsubstituted C6 to C12 aryl, substituted or unsubstituted C3 to C12 heteroaryl; A3 is selected from H, D, F, CN, substituted or unsubstituted C1 to C12 alkyl, substituted or unsubstituted C6 to C12 aryl, substituted or unsubstituted C3 to C12 heteroaryl; wherein the substituents of A1, A2 and A3 are independently selected from D, C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C16 alkyl, partially or perfluorinated C1 to C16 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy, COR1, COOR1, halogen, F or CN, wherein R1 is selected from C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C16 alkyl , partially or perfluorinated C1 to C16 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy. 7. The organic electronic device according to claim 6, wherein - the substituents on A1 and A2 are independently selected from halogen, preferably F, C1 to C3 perhalogenated, perfluorinated alkyl or perfluorinated alkoxy, preferably perfluorinated C1 to C3 alkyl or perfluorinated C1 to C3 alkoxy, or -(O)l-CmH2m- CnHalon2n+1 with 1= 0 or 1, preferably 0, m = 1 or 2, preferably 1 and n = 1 to 3, preferably n =1 or 2 and Halo = halogen, preferably F; and/or - at least one of A1 and A2 is substituted alkyl and the substituents of the alkyl are fluorine with the number nr (of fluorine substituents) and nn (of hydrogens) follow the equation: nF > nH + 2; and/or - at least one of A1 and A2 is selected from perfluorinated C1 to C6 alkyl, phenyl substituted with F or CF3; and/or - at least one of A1 and A2 is selected from perfluorinated alkyl or aryl. 8. The organic electronic device according to claim 6 or 7 , wherein at least one of A1 and A2 comprises a substituent, wherein at least one of the substituents of A1 and A2 are independently selected from C3 to C9 heteroaryl, C1 to C6 alkoxy, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C16 alkyl, partially or perfluorinated C1 to C16 alkoxy, partially or perdeuterated C1 to C6 alkoxy, COR1, COOR1, halogen, F or CN; preferably at least one of A1 and A2 comprises at least two substituents, wherein the substituents on A1 and A2 are independently selected from C3 to C9 heteroaryl, C1 to C6 alkoxy, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C16 alkyl, partially or perfluorinated C1 to C16 alkoxy, partially or perdeuterated C1 to C6 alkoxy, COR1, COOR1, halogen, F or CN; and further preferred A1 and A2 comprise at least one substituent independently selected from halogen, F, CF3, C2F5, C3F7, C4F9, OCF3, OC2F5, or CN; and in addition preferred A1 and A2 may comprise at least two substituents independently selected from halogen, F, CF3, C2F5, C3F7, C4F9, OCF3, OC2F5 or CN; wherein R1 is selected from C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C16 alkyl, partially or perfluorinated C1 to C16 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy. 9. The organic electronic device according to any of claims 6 to 8, wherein the sum of A1 and A2 comprise ≥ 3 carbon atoms and ≤ 25 carbon atoms. 10. The organic electronic device according to any of claims 6 to 9, wherein A3 is selected from H or D, preferably H. 87 11. The organic electronic device according to any of claims 1 to 10, wherein the metal complex and the metal complex of formula I are free of alkoxy, COR1 and/or COOR1 groups, wherein R1 is selected from C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C16 alkyl, partially or perfluorinated C1 to C16 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy. 12. The organic electronic device according to any of claims 1 to 11, wherein the metal complex and the metal complex of formula I are selected from E1 to E28: wherein M is selected from Ce(IV), Zr(IV) or Hf(IV), preferably M is Ce(IV) or Hf(IV). 13. The organic electronic device according to any of claims 2 to 12, wherein AL is selected from the group comprising H2O, C2 to C40 mono- or multi-dentate ethers and C2 to C40 thioethers, C2 to C40 amines, C2 to C40 phosphine, C2 to C20 alkyl nitrile or C2 to C40 aryl nitrile, or a compound according to Formula (II); R6 and R7 are independently selected from C1 to C20 alkyl, C1 to C20 heteroalkyl, C6 to C20 aryl, heteroaryl with 5 to 20 ring-forming atoms, halogenated or perhalogenated C1 to C20 alkyl, halogenated or perhalogenated C1 to C20 heteroalkyl, halogenated or perhalogenated C6 to C20 aryl, halogenated or perhalogenated heteroaryl with 5 to 20 ring-forming atoms, or at least one R6 and R7 are bridged and form a 5 to 20 member ring, or the two R6 and/or the two R7 are bridged and form a 5 to 40 member ring or form a 5 to 40 member ring comprising an unsubstituted or C1 to C12 substituted phenanthroline. 14. The organic electronic device according to any of claims 2 to 13, wherein “n” is an integer selected from 0, 1 or 2, preferably 2, further preferred 1 and in addition preferred 0. 15. The organic electronic device according to any of claims 1 to 14, wherein the first metal of the first anode sub-layer is selected from the group comprising Ag, Mg, Al, Cr, Pt, Au, Pd, Ni, Nd, Ir. 16. The organic electronic device according to any of preceding claims 1 to 15, wherein the organic electronic device further comprises a hole transport layer, wherein the hole transport layer is arranged between the hole injection layer and the at least one emission layer. 17. The organic electronic device according to claim 1 to 16, wherein the hole transport layer comprises a matrix compound and/or the hole injection layer comprises a matrix compound, wherein the matrix compound in the hole injection layer and hole transport layer are selected the same. 18. The organic electronic device according to any of the preceding claims 1 to 17, wherein the organic electronic device is a light emitting device or a display device. 19. A metal complex of formula (I) represented by formula (la): wherein M is a metal ion selected from Ce, Hf or Zr, preferably Ce or Hf; A1 is selected from substituted C6 to C12 aryl, substituted or unsubstituted C3 to C12 heteroaryl; and A2 is selected from a substituted C3 alkyl; wherein the substituents of A1 and A2 are independently selected from D, C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C16 alkyl, partially or perfluorinated C1 to C16 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy, COR1, COOR1, halogen, F or CN, wherein R1 is selected from C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C16 alkyl, partially or perfluorinated C1 to C16 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy; A3 is selected from H or D; or A1 is selected from formulas D11 to D22: wherein the "*"denotos the binding position; preferably A1 is D12, D18 and/or D20; and A2 is selected from substituted or unsubstituted C1 to C12 alkyl; wherein the substituents of A2 are independently selected from D, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, partially or perfluorinated C1 to C16 alkyl, partially or perdeuterated C1 to C6 alkyl, halogen, F or CN; A3 is selected from H or D. |
According to one embodiment, L of formula (I) is selected from (G1) to (G18), preferably from (G2) to (G10). According to one embodiment, wherein the metal complex and the metal complex of formula I of the hole injection are selected from the following formulas (Ia) to (Id): wherein A 1 and A 2 are independently selected from substituted or unsubstituted C 1 to C 12 alkyl, substituted or unsubstituted C 6 to C 12 aryl, substituted or unsubstituted C 3 to C 12 heteroaryl; A 3 is selected from H, D, F, CN, substituted or unsubstituted C 1 to C 12 alkyl, substituted or unsubstituted C 6 to C 12 aryl, substituted or unsubstituted C 3 to C 12 heteroaryl; wherein the substituents of A 1 , A 2 and A 3 are independently 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 1 , COOR 1 , halogen, F or CN, wherein R 1 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. According to one embodiment, wherein A 1 and A 2 may be selected different. The negative charge in compounds of formulas (I), (Ia) to (Id), may be delocalised partially or fully over the N(SO 2 ) 2 group, NSO 2 group or CO 2 group or CO group and optionally also over the A 1 and A 2 groups. According to one embodiment, wherein - the substituents on A 1 and A 2 are independently selected from halogen, preferably F, C 1 to C 3 perhalogenated, perfluorinated alkyl or perfluorinated alkoxy, preferably perfluorinated C 1 to C 3 alkyl or perfluorinated C 1 to C 3 alkoxy, or –(O) l -C m H2 m -C n Halo n2n+1 with l= 0 or 1, preferably 0, m = 1 or 2, preferably 1 and n = 1 to 3, preferably n =1 or 2 and Halo = halogen, preferably F; and/or - at least one of A 1 and A 2 is substituted alkyl and the substituents of the alkyl are fluorine with the number nF (of fluorine substituents) and nH (of hydrogens) follow the equation: n F > n H + 2; and/or - at least one of A 1 and A 2 is selected from perfluorinated C 1 to C 6 alkyl, phenyl substituted with F or CF 3 ; and/or - at least one of A 1 and A 2 is selected from perfluorinated alkyl or aryl. According to one embodiment of the present invention, the substituents on A 1 and A 2 are independently selected from halogen, with F especially preferred, C 1 to C 3 perhalogenated, especially perfluorinated alkyl or alkoxy, or -(O) l -C m H 2m -C n Hal n2n+1 with l= 0 or 1, especially 0, m = 1 or 2, especially 1 and n = 1 to 3, especially n =1 or 2 and Hal= halogen, especially F. According to one embodiment of the present invention, at least one of A 1 and A 2 is substituted alkyl and the substituents of the alkyl moiety are fluorine with the number nF (of fluorine substituents) and n H (of hydrogens) follow the equation: n F > n H + 2. According to one embodiment of the present invention, at least one of A 1 and A 2 is selected from perfluorinated C 1 to C 6 alkyl and/or phenyl substituted with F or CF 3 . According to one embodiment of the present invention, at least one of A 1 and A 2 is selected from perfluorinated alkyl or aryl. According to one embodiment of the present invention, the sum of A 1 and A 2 comprise ≥ 3 carbon atoms and ≤ 25 carbon atoms, or ≥ 4 carbon atoms and ≤ 24 carbon atoms, or ≥ 5 carbon atoms and ≤ 18 carbon atoms. According to one embodiment of the present invention, at least one of A 1 and A 2 is substituted C 3 to C 6 alkyl. According to one embodiment of the present invention, at least one of A 1 and A 2 is substituted C 3 to C 6 linear or cyclic alkyl. According to one embodiment of the present invention, compound of formula (I) is free of alkoxy, COR 1 and/or COOR 1 groups. According to one embodiment of the present invention, A 2 is aryl or heteroaryl, whereby the substituents of the aryl and/or heteroaryl moiety are selected from hydrogen, halogen, F, CN or trifluoro methyl. According to one embodiment of the present invention A 2 is phenyl or six-membered heteroaryl, which is substituted with 1 to 5 F atoms. According to one embodiment of the present invention, A 1 is substituted or unsubstituted C 1 to C 6 alkyl or substituted phenyl and A 2 is substituted C 3 to C 6 alkyl; alternatively, A 1 is substituted or unsubstituted C 1 to C 4 alkyl or substituted phenyl and A 2 is substituted C 3 to C 4 alkyl or substituted phenyl. According to one embodiment, wherein the metal complex of the hole injection layer may be selected from the following formulas (Ia) to (Id), wherein at least one of A 1 and A 2 may comprises a substituent, wherein at least one of the substituents of A 1 and A 2 may be independently selected from C 3 to C 9 heteroaryl, C 1 to C 6 alkoxy, C 3 to C 6 branched alkoxy, C 3 to C 6 cyclic alkoxy, partially or perfluorinated C 1 to C 1 6 alkyl, partially or perfluorinated C 1 to C 16 alkoxy, partially or perdeuterated C 1 to C 6 alkoxy, COR 1 , COOR 1 , halogen, F or CN; preferably at least one of A 1 and A 2 may comprises at least two substituents, wherein the substituents on A 1 and A 2 may be independently selected from C 3 to C 9 heteroaryl, C 1 to C 6 alkoxy, 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 alkoxy, COR 1 , COOR 1 , halogen, F or CN; and further preferred A 1 and A 2 comprise at least one substituent independently selected from halogen, F, CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , OCF 3 , OC 2 F 5 , or CN; and in addition preferred A 1 and A 2 may comprise at least two substituents independently selected from halogen, F, CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , OCF 3 , OC 2 F 5 or CN; wherein R 1 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. According to one embodiment, wherein the metal complex of the hole injection layer may be selected from the following formulas (Ia), (Ib), (Ic), (Id), wherein M is selected from Ce(IV), Zr(IV) or Hf(IV), preferably M is Ce(IV) or Hf(IV); A 1 , A 2 and A 3 may be independently selected from substituted or unsubstituted C 1 to C 12 alkyl, substituted or unsubstituted C 6 to C 12 aryl, substituted or unsubstituted C 3 to C 12 heteroaryl; wherein at least one of A 1 , A 2 and A 3 may comprises a substituent, wherein at least one of the substituents of A 1 , A 2 and A 3 may be independently selected from C 3 to C 9 heteroaryl, C 1 to C 6 alkoxy, 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 alkoxy, COR 1 , COOR 1 , halogen, F or CN; preferably at least one of A 1 , A 2 and A 3 may comprises at least two substituents, wherein the substituents on A 1 , A 2 and A 3 may be independently selected from C 3 to C 9 heteroaryl, C 1 to C 6 alkoxy, 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 alkoxy, COR 1 , COOR 1 , halogen, F or CN; and further preferred A 1 , A 2 and A 3 comprise at least one substituent independently selected from halogen, F, CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , OCF 3 , OC 2 F 5 , or CN; and in addition preferred A 1 , A 2 and A 3 may comprise at least two substituents independently selected from halogen, F, CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , OCF 3 , OC 2 F 5 or CN. The sum of A 1 ,A 2 and A 3 may comprise ≥ 3 carbon atoms and ≤ 25 carbon atoms. According to one embodiment, wherein the sum of A 1 and A 2 may comprise ≥ 3 carbon atoms and ≤ 25 carbon atoms. According to one embodiment, wherein A 3 is selected from H or D, preferably H. According to one embodiment, wherein the metal complex of the hole injection layer may be selected from the following formulas (Ia) to (Id), wherein A 3 is selected from H or D, preferably H and at least one of A 1 and A 2 may comprises a substituent, wherein at least one of the substituents of A 1 and A 2 may be independently selected from C 3 to C 9 heteroaryl, C 1 to C 6 alkoxy, 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 alkoxy, COR 1 , COOR 1 , halogen, F or CN; preferably at least one of A 1 and A 2 may comprises at least two substituents, wherein the substituents on A 1 and A 2 may be independently selected from C 3 to C 9 heteroaryl, C 1 to C 6 alkoxy, 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 alkoxy, COR 1 , COOR 1 , halogen, F or CN; and further preferred A 1 and A 2 comprise at least one substituent independently selected from halogen, F, CF 3 , C 2 F 5 , C 3 F7, C 4 F 9 , OCF 3 , OC 2 F 5 , or CN; and in addition preferred A 1 and A 2 may comprise at least two substituents independently selected from halogen, F, CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , OCF 3 , OC 2 F 5 or CN; wherein R 1 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. According to one embodiment, wherein the metal complex of the hole injection layer may be selected from the following formulas (Ia), (Ib), (Ic), (Id), wherein M is selected from Ce(IV), Zr(IV) or Hf(IV), preferably M is Ce(IV) or Hf(IV); A 3 is selected from H or D, preferably H and A 1 and A 2 may be independently selected from substituted or unsubstituted C 1 to C 12 alkyl, substituted or unsubstituted C 6 to C 12 aryl, substituted or unsubstituted C 3 to C 12 heteroaryl; wherein at least one of A 1 and A 2 may comprises a substituent, wherein at least one of the substituents of A 1 and A 2 may be independently selected from C 3 to C 9 heteroaryl, C 1 to C 6 alkoxy, 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 alkoxy, COR 1 , COOR 1 , halogen, F or CN; preferably at least one of A 1 and A 2 may comprises at least two substituents, wherein the substituents on A 1 and A 2 may be independently selected from C 3 to C 9 heteroaryl, C 1 to C 6 alkoxy, 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 alkoxy, COR 1 , COOR 1 , halogen, F or CN; and further preferred A 1 and A 2 comprise at least one substituent independently selected from halogen, F, CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , OCF 3 , OC 2 F 5 , or CN; and in addition preferred A 1 and A 2 may comprise at least two substituents independently selected from halogen, F, CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , OCF 3 , OC 2 F 5 or CN. According to one embodiment, wherein the metal complex and the metal complex of formula I are free of alkoxy, COR 1 and/or COOR 1 groups, wherein R 1 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 1 6 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. According to one embodiment, wherein the metal complex of the hole injection layer may be selected from the following formulas (Ia) to (Id), wherein A 1 , A 2 and/or A 3 are selected from the following Formulas D1 to D71:
wherein the “*” denotes the binding position. According to one embodiment, wherein the metal complex of the hole injection layer may be selected from the following formulas (Ia) to (Id), wherein one A 1 , A 2 or A 3 is selected from the above formulae D1 to D34 and/or D38 to D71; preferably D3 to D34 and/or D39 to D71. According to one embodiment, wherein the metal complex of the hole injection layer may be selected from the following formulas (Ia) to (Id), wherein A 1 is selected from formula D1 to D34 and/or D38 to D71, A 2 is selected from substituted or unsubstituted C 1 to C 12 alkyl, and A 3 is selected from H, D, F, CN, C 1 to C 4 alkyl, partially or perfluorinated C 1 to C 4 alkyl. According to one embodiment, wherein the metal complex and the metal complex of formula I are selected from E1 to E28:
wherein M is selected from Ce(IV), Zr(IV) or Hf(IV), preferably M is Ce(IV) or Hf(IV). Preferably, the metal complex and the metal complex of formula I are selected from E2 to E17. According to an embodiment, the metal complex of formula I is selected from formulae H1 to H14:
According to one embodiment, the metal complex of formula I is selected from H1 to H3, H11, H12, H13 and/or H14. According to one embodiment, the metal complex of formula I is selected from H1 to H3, H7, H10, H12, H13 and/or H14. Matrix compound of the hole injection layer According to one embodiment the hole injection layer may further comprises a matrix compound, preferably the matrix compound is a covalent matrix compound. According to one embodiment the hole transport layer may further comprises a matrix compound, preferably the matrix compound is a covalent matrix compound. According to one embodiment the hole transport layer comprises a matrix compound and the hole injection layer comprises a matrix compound. According to one embodiment the hole transport layer comprises a matrix compound and the hole injection layer comprises a matrix compound, wherein the matrix compound in the hole injection layer and hole transport layer are selected the same. According to one embodiment the covalent matrix compound of the hole injection layer and/or hole transport layer may be selected from at least one organic compound. The covalent matrix may consists substantially from covalently bound C, H, O, N, S, which optionally comprise in addition covalently bound B, P, As and/or Se. According to one embodiment of the organic electronic device, the hole injection layer and/or hole transport layer further comprises a matrix compound, wherein the matrix compound of the hole injection layer and/or hole transport layer may be selected from organic compounds consisting substantially from covalently bound C, H, O, N, S, which optionally comprise in addition covalently bound B, P, As and/or Se. Organometallic compounds comprising covalent bonds carbon-metal, metal complexes comprising organic ligands and metal salts of organic acids are further examples of organic compounds that may serve as covalent matrix compounds of the hole injection layer and/or hole transport layer. In one embodiment, the covalent matrix compound lacks metal atoms and majority of its skeletal atoms may be selected from C, O, S, N. Alternatively, the covalent matrix compound lacks metal atoms and majority of its skeletal atoms may be selected from C and N. According to one embodiment, the covalent matrix compound of the hole injection layer and/or hole transport layer may have a molecular weight Mw of ≥ 400 and ≤ 2000 g/mol, preferably a molecular weight Mw of ≥ 450 and ≤ 1500 g/mol, further preferred a molecular weight Mw of ≥ 500 and ≤ 1000 g/mol, in addition preferred a molecular weight Mw of ≥ 550 and ≤ 900 g/mol, also preferred a molecular weight Mw of ≥ 600 and ≤ 800 g/mol. In one embodiment, the HOMO level of the covalent matrix compound may be more negative than the HOMO level of N2,N2,N2',N2',N7,N7,N7',N7'-octakis(4-methoxyphenyl)-9,9'- spirobi[fluorene]-2,2',7,7'-tetraamine (CAS 207739-72-8) when determined under the same conditions. In one embodiment, the HOMO level of the covalent matrix compound , when calculated using TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany) by applying the hybrid functional B3LYP with a 6-31G* basis set in the gas phase, may be more negative than -4.27 eV, preferably more negative than -4.3 eV, alternatively more negative than -4.5 eV, alternatively more negative than -4.6 eV, alternatively more negative than - 4.65 eV. In one embodiment, the HOMO level of the covalent matrix compound may be more negative than the HOMO level of N2,N2,N2',N2',N7,N7,N7',N7'-octakis(4-methoxyphenyl)-9,9'- spirobi[fluorene]-2,2',7,7'-tetraamine (CAS 207739-72-8) and more positive than the HOMO level of N-([1,1'-biphenyl]-4-yl)-N-(2-(9,9-diphenyl-9H-fluoren-4-yl) phenyl)-9,9-dimethyl-9H-fluoren- 2-amine when determined under the same conditions. In one embodiment of the present invention, the covalent matrix compound may be free of alkoxy groups. Preferably, the covalent matrix compound comprises at least one arylamine moiety, alternatively a diarylamine moiety, alternatively a triarylamine moiety. Preferably, the matrix compound of the hole injection layer and/or hole transport layer is free of metals and/or ionic bonds. Compound of formula (IIIa) or a compound of formula (IIIb) According to another aspect of the present invention, the at least one matrix compound, also referred to as “substantially covalent matrix compound”, of the hole injection layer and/or hole transport layer may comprises at least one arylamine compound, diarylamine compound, triarylamine compound, a compound of formula (IIIa) or a compound of formula (IIIb): wherein: T 1 , T 2 , T 3 , T 4 and T 5 are independently selected from a single bond, phenylene, biphenylene, terphenylene or naphthenylene, preferably a single bond or phenylene; T 6 is phenylene, biphenylene, terphenylene or naphthenylene; Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 are independently selected from substituted or unsubstituted C 6 to C 20 aryl, or substituted or unsubstituted C 3 to C 20 heteroarylene, substituted or unsubstituted biphenylene, substituted or unsubstituted fluorene, substituted 9- fluorene, substituted 9,9-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 9-phenylcarbazole, substituted or unsubstituted azepine, substituted or unsubstituted dibenzo[b,f]azepine, substituted or unsubstituted 9,9'-spirobi[fluorene], substituted or unsubstituted spiro[fluorene-9,9'- xanthene], 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 and/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 of Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 are selected the same or different from the group comprising H, D, F, C(-O)R 2 , CN, Si(R 2 ) , P( 2 2 2 2 3 -O)(R )2, OR , S(-O)R, S(-O)2R, substituted or unsubstituted straight-chain alkyl having 1 to 20 carbon atoms, substituted or unsubstituted branched alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cyclic alkyl having 3 to 20 carbon atoms, substituted or unsubstituted alkenyl or alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aromatic ring systems having 6 to 40 aromatic ring atoms, and substituted or unsubstituted heteroaromatic ring systems having 5 to 40 aromatic ring atoms, 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, wherein R 2 may be selected from H, D, straight-chain alkyl having 1 to 6 carbon atoms, branched alkyl having 1 to 6 carbon atoms, cyclic alkyl having 3 to 6 carbon atoms, alkenyl or alkynyl groups having 2 to 6 carbon atoms, C 6 to C 18 aryl or C 3 to C 18 heteroaryl. According to an embodiment of the organic electronic device, wherein the matrix compound of the hole injection layer and/or hole transport layer comprises a compound of formula (IIIa) or formula (IIIb): wherein T 1 , T 2 , T 3 , T 4 and T 5 may be independently selected from a single bond, phenylene, biphenylene, terphenylene or naphthenylene, preferably a single bond or phenylene; T 6 is phenylene, biphenylene, terphenylene or naphthenylene; Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 may be independently selected from substituted or unsubstituted C 6 to C 20 aryl, or substituted or unsubstituted C 3 to C 20 heteroarylene, substituted or unsubstituted biphenylene, substituted or unsubstituted fluorene, substituted 9-fluorene, substituted 9,9-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 9- phenylcarbazole, substituted or unsubstituted azepine, substituted or unsubstituted dibenzo[b,f]azepine, substituted or unsubstituted 9,9'- spirobi[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanthene], 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 and/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 of Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 are selected the same or different from the group comprising H, straight-chain alkyl having 1 to 20 carbon atoms, branched alkyl having 1 to 20 carbon atoms, cyclic alkyl having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, C 6 to C 18 aryl, 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. Preferably, the substituents of Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 are selected the same or different from the group comprising H, straight-chain alkyl having 1 to 6 carbon atoms, branched alkyl having 1 to 6 carbon atoms, cyclic alkyl having 3 to 6 carbon atoms, alkenyl or alkynyl groups having 2 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, C 6 to C 18 aryl, C 3 to C 18 heteroaryl, a fused ring system comprising 2 to 4 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; more preferred the substituents are selected the same or different from the group consisting of H, straight-chain alkyl having 1 to 4 carbon atoms, branched alkyl having 1 to 4 carbon atoms, cyclic alkyl having 3 to 4 carbon atoms and/or phenyl. Thereby, the compound of formula (IIIa) or (IIIb) may have a rate onset temperature suitable for mass production. According to an embodiment of the organic electronic device, wherein the matrix compound of the hole injection layer and/or hole transport layer comprises a compound of formula (IIIa) or formula (IIIb): wherein T 1 , T 2 , T 3 , T 4 and T 5 may be independently selected from a single bond, phenylene, biphenylene, terphenylene or naphthenylene, preferably a single bond or phenylene; T 6 is phenylene, biphenylene, terphenylene or naphthenylene; Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 may be independently selected from unsubstituted C 6 to C 20 aryl, or unsubstituted C 3 to C 20 heteroarylene, unsubstituted biphenylene, unsubstituted fluorene, substituted 9-fluorene, substituted 9,9-fluorene, unsubstituted naphthalene, unsubstituted anthracene, unsubstituted phenanthrene, unsubstituted pyrene, unsubstituted perylene, unsubstituted triphenylene, unsubstituted tetracene, unsubstituted tetraphene, unsubstituted dibenzofurane, unsubstituted dibenzothiophene, unsubstituted xanthene, unsubstituted carbazole, substituted 9-phenylcarbazole, unsubstituted azepine, unsubstituted dibenzo[b,f]azepine, unsubstituted 9,9'- spirobi[fluorene], unsubstituted spiro[fluorene-9,9'-xanthene], or a unsubstituted aromatic fused ring system comprising at least three unsubstituted aromatic rings selected from the group comprising unsubstituted non-hetero, unsubstituted hetero 5-member rings, unsubstituted 6-member rings and/or unsubstituted 7-member rings, unsubstituted fluorene, or a fused ring system comprising 2 to 6 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. According to an embodiment of the organic electronic device, wherein the matrix compound of the hole injection layer and/or hole transport layer comprises a compound of formula (IIIa) or formula (IIIb): wherein T 1 , T 2 , T 3 , T 4 and T 5 may be independently selected from a single bond, phenylene, biphenylene, terphenylene or naphthenylene, preferably a single bond or phenylene; T 6 is phenylene, biphenylene, terphenylene or naphthenylene; Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 may be independently selected from unsubstituted C 6 to C 20 aryl, or unsubstituted C 3 to C 20 heteroarylene, unsubstituted biphenylene, unsubstituted fluorene, substituted 9-fluorene, substituted 9,9-fluorene, unsubstituted naphthalene, unsubstituted anthracene, unsubstituted phenanthrene, unsubstituted pyrene, unsubstituted perylene, unsubstituted triphenylene, unsubstituted tetracene, unsubstituted tetraphene, unsubstituted dibenzofurane, unsubstituted dibenzothiophene, unsubstituted xanthene, unsubstituted carbazole, substituted 9-phenylcarbazole, unsubstituted azepine, unsubstituted dibenzo[b,f]azepine, unsubstituted 9,9'- spirobi[fluorene], unsubstituted spiro[fluorene-9,9'-xanthene]. Thereby, the compound of formula (IIIa) or (IIIb) may have a rate onset temperature suitable for mass production. According to an embodiment wherein T 1 , T 2 , T 3 , T 4 and T 5 may be independently selected from a single bond, phenylene, biphenylene or terphenylene. According to an embodiment wherein T 1 , T 2 , T 3 , T 4 and T 5 may be independently selected from phenylene, biphenylene or terphenylene and one of T 1 , T 2 , T 3 , T 4 and T 5 are a single bond. According to an embodiment wherein T 1 , T 2 , T 3 , T 4 and T 5 may be independently selected from phenylene or biphenylene and one of T 1 , T 2 , T 3 , T 4 and T 5 are a single bond. According to an embodiment wherein T 1 , T 2 , T 3 , T 4 and T 5 may be independently selected from phenylene or biphenylene and two of T 1 , T 2 , T 3 , T 4 and T 5 are a single bond. According to an embodiment wherein T 1 , T 2 and T 3 may be independently selected from phenylene and one of T 1 , T 2 and T 3 are a single bond. According to an embodiment wherein T 1 , T 2 and T 3 may be independently selected from phenylene and two of T 1 , T 2 and T 3 are a single bond. According to an embodiment wherein T 6 may be phenylene, biphenylene, terphenylene. According to an embodiment wherein T 6 may be phenylene. According to an embodiment wherein T 6 may be biphenylene. According to an embodiment wherein T 6 may be terphenylene. According to an embodiment wherein Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 may be independently selected from K1 to K16: wherein the asterix “*” denotes the binding position. According to an embodiment, wherein Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 may be independently selected from K1 to K15; alternatively selected from K1 to K10 and K13 to K15. According to an embodiment, wherein Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 may be independently selected from the group consisting of K1, K2, K5, K7, K9, K10, K13 to K16. The rate onset temperature may be in a range particularly suited to mass production, when Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 are selected in this range. The “matrix compound of formula (IIIa) or formula (IIIb) “ may be also referred to as “hole transport compound”. According to one embodiment the matrix compound of formula (IIIa) or formula (IIIb) may comprises at least ≥ 1 to ≤ 6 substituted or unsubstituted aromatic fused ring systems comprising heteroaromatic rings. According to one embodiment the matrix compound of formula (IIIa) or formula (IIIb) may comprises at least ≥ 1 to ≤ 6 substituted or unsubstituted aromatic fused ring systems comprising heteroaromatic rings and at least ≥ 1 to ≤ 3 substituted or unsubstituted unsaturated 5- to 7-member ring of a heterocycle, preferably ≥ 2 to ≤ 5 substituted or unsubstituted aromatic fused ring systems comprising heteroaromatic rings. According to one embodiment the matrix compound of formula (IIIa) or formula (IIIb) may comprises at least ≥ 1 to ≤ 6 substituted or unsubstituted aromatic fused ring systems comprising heteroaromatic rings and at least ≥ 1 to ≤ 3 substituted or unsubstituted unsaturated 5- to 7-member ring of a heterocycle, preferably ≥ 2 to ≤ 5 substituted or unsubstituted aromatic fused ring systems comprising heteroaromatic rings, and at least ≥ 1 to ≤ 3 substituted or unsubstituted unsaturated 5- to 7-member ring of a heterocycle, further preferred 3 or 4 substituted or unsubstituted aromatic fused ring systems comprising heteroaromatic rings and optional at least ≥ 1 to ≤ 3 substituted or unsubstituted unsaturated 5- to 7-member ring of a heterocycle, and additional preferred wherein the aromatic fused ring systems comprising heteroaromatic rings are unsubstituted and optional at least ≥ 1 to ≤ 3 unsubstituted unsaturated 5- to 7-member ring of a heterocycle. According to one embodiment the matrix compound of formula (IIIa) or formula (IIIb) may comprises at least ≥ 1 to ≤ 6 substituted or unsubstituted aromatic fused ring systems, preferably ≥ 2 to ≤ 5 substituted or unsubstituted aromatic fused ring systems, and further preferred 3 or 4 substituted or unsubstituted aromatic fused ring systems. According to one embodiment the matrix compound of formula (IIIa) or formula (IIIb) may comprises at least ≥ 1 to ≤ 6 substituted or unsubstituted aromatic fused ring systems, preferably ≥ 2 to ≤ 5 substituted or unsubstituted aromatic fused ring systems, and further preferred 3 or 4 substituted or unsubstituted aromatic fused ring systems, which comprises substituted or unsubstituted heteroaromatic rings. According to one embodiment the matrix compound of formula (IIIa) or formula (IIIb) may comprises at least ≥ 1 to ≤ 3 or 2 substituted or unsubstituted unsaturated 5- to 7-member ring of a heterocycle. According to one embodiment the matrix compound of formula (IIIa) or formula (IIIb) may comprises at least ≥ 1 to ≤ 3 or 2 substituted or unsubstituted unsaturated 7-member ring of a heterocycle. According to one embodiment substituted or unsubstituted aromatic fused ring systems of the matrix compound of formula (IIIa) or formula (IIIb) may comprises at least ≥ 1 to ≤ 3 or 2 substituted or unsubstituted unsaturated 5- to 7-member ring of a heterocycle. According to one embodiment the substituted or unsubstituted aromatic fused ring systems of the matrix compound of formula (IIIa) or formula (IIIb) may comprises at least ≥ 1 to ≤ 3 or 2 substituted or unsubstituted unsaturated 7-member ring of a heterocycle. According to one embodiment the matrix compound of formula (IIIa) or formula (IIIb) may comprises at least ≥ 1 to ≤ 6 substituted or unsubstituted aromatic fused ring systems, preferably ≥ 2 to ≤ 5 substituted or unsubstituted aromatic fused ring systems, and further preferred 3 or 4 substituted or unsubstituted aromatic fused ring systems, and wherein the aromatic fused ring system comprises substituted or unsubstituted unsaturated 5- to 7-member ring of a heterocycle. According to one embodiment the matrix compound of formula (IIIa) or formula (IIIb) may comprises at least ≥ 1 to ≤ 6 substituted or unsubstituted aromatic fused ring systems, preferably ≥ 2 to ≤ 5 substituted or unsubstituted aromatic fused ring systems, and further preferred 3 or 4 substituted or unsubstituted aromatic fused ring systems, which comprises substituted or unsubstituted heteroaromatic rings, and wherein the aromatic fused ring system comprises substituted or unsubstituted unsaturated 5- to 7-member ring of a heterocycle. According to one embodiment the matrix compound of formula (IIIa) or formula (IIIb) may comprises at least ≥ 1 to ≤ 6 substituted or unsubstituted aromatic fused ring systems, preferably ≥ 2 to ≤ 5 substituted or unsubstituted aromatic fused ring systems, and further preferred 3 or 4 substituted or unsubstituted aromatic fused ring systems, and wherein the aromatic fused ring system comprises at least ≥ 1 to ≤ 3 or 2 substituted or unsubstituted unsaturated 5- to 7-member ring of a heterocycle. According to one embodiment the matrix compound of formula (IIIa) or formula (IIIb) may comprises at least ≥ 1 to ≤ 6 substituted or unsubstituted aromatic fused ring systems, preferably ≥ 2 to ≤ 5 substituted or unsubstituted aromatic fused ring systems, and further preferred 3 or 4 substituted or unsubstituted aromatic fused ring systems, which comprises substituted or unsubstituted heteroaromatic rings, and wherein the aromatic fused ring system comprises at least ≥ 1 to ≤ 3 or 2 substituted or unsubstituted unsaturated 5- to 7-member ring of a heterocycle. According to one embodiment the matrix compound of formula (IIIa) or formula (IIIb) may comprises: - a substituted or unsubstituted aromatic fused ring systems with at least ≥ 2 to ≤ 6, preferably ≥ 3 to ≤ 5, or 4 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 and/or substituted or unsubstituted unsaturated 5- to 7- member ring of a heterocycle; or - an unsubstituted aromatic fused ring systems with at least ≥ 2 to ≤ 6, preferably ≥ 3 to ≤ 5, or 4 fused aromatic rings selected from the group comprising unsubstituted non-hetero aromatic rings, unsubstituted hetero 5-member rings, unsubstituted 6-member rings and/or unsubstituted unsaturated 5- to 7-member ring of a heterocycle. It should be noted here that the wording “aromatic fused ring system” may include at least one aromatic ring and at least one substituted or unsubstituted unsaturated 5- to 7- member ring. It should be noted here that the substituted or unsubstituted unsaturated 5- to 7- member ring may not be an aromatic ring. According to one embodiment the matrix compound of formula (IIIa) or formula (IIIb) may comprises at least at least ≥ 1 to ≤ 6, preferably ≥ 2 to ≤ 5, or further preferred 3 or 4 of the substituted or unsubstituted aromatic fused ring systems with: - at least one unsaturated 5-member ring, and/or - at least one unsaturated 6-member ring, and/or - at least one unsaturated 7-member ring; wherein preferably at least one unsaturated 5- and/or at least one unsaturated 7-member ring comprises at least 1 to 3, preferably 1 hetero-atom. According to one embodiment the matrix compound of formula (IIIa) or formula (IIIb) may comprises at least at least ≥ 1 to ≤ 6, preferably ≥ 2 to ≤ 5, or further preferred 3 or 4 of the substituted or unsubstituted aromatic fused ring systems with: - at least one aromatic 5-member ring, and/or - at least one aromatic 6-member ring, and/or - at least one aromatic 7-member ring; wherein preferably at least one aromatic 5- and/or at least one aromatic 7-member ring comprises at least 1 to 3, preferably 1 hetero-atom; wherein the substituted or unsubstituted aromatic fused ring system comprises at least ≥ 1 to ≤ 3 or 2 substituted or unsubstituted unsaturated 5- to 7-member ring of a heterocycle. According to one embodiment the matrix compound of formula (IIIa) or formula (IIIb) may comprises : - at least ≥ 6 to ≤ 12, preferably ≥ 7 to ≤ 11, further preferred ≥ 8 to ≤ 10 or 9 aromatic rings; and/or - at least ≥ 4 to ≤ 11, preferably ≥ 5 to ≤ 10, further preferred ≥ 6 to ≤ 9 or in addition preferred 7 or 8 non-hetero aromatic rings, preferably the non-hetero aromatic rings are aromatic C 6 rings; and/or - at least ≥ 1 to ≤ 4, preferably 2 or 3 aromatic 5-member-rings, preferably hetero aromatic 5- member-rings; and/or - at least 1 or 2 unsaturated 5- to 7-member-ring of a heterocycle, preferably at least 1 or 2 unsaturated 7-member-ring of a heterocycle; - at least ≥ 6 to ≤ 12, preferably ≥ 7 to ≤ 11, further preferred ≥ 8 to ≤ 10 or 9 aromatic rings, wherein therefrom at least ≥ 4 to ≤ 11, preferably ≥ 5 to ≤ 10, further preferred ≥ 6 to ≤ 9 or in addition preferred 7 or 8 are non-hetero aromatic rings, and at least ≥ 1 to ≤ 4, preferably 2 or 3 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/or - at least ≥ 6 to ≤ 12, preferably ≥ 7 to ≤ 11, further preferred ≥ 8 to ≤ 10 or 9 aromatic rings, wherein therefrom at least ≥ 4 to ≤ 11, preferably ≥ 5 to ≤ 10, further preferred ≥ 6 to ≤ 9 or in addition preferred 7 or 8 are non-hetero aromatic rings, and at least ≥ 1 to ≤ 4, preferably 2 or 3 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 comprises at least ≥ 1 to ≤ 4, preferably 2 or 3 aromatic 5-member-rings, preferably hetero aromatic 5-member-rings, and/or the hole transport compound or the hole transport compound according to formula (I) comprises at least 1 or 2 unsaturated 5- to 7-member-ring of a heterocycle, preferably at least 1 or 2 unsaturated 7-member-ring of a heterocycle. According to one embodiment the matrix compound of formula (IIIa) or formula (IIIb) may comprises a hetero-atom, which may be selected from the group comprising O, S, N, B or P, preferably the hetero-atom may be selected from the group comprising O, S or N. According to one embodiment the matrix compound of formula (IIIa) or formula (IIIb) may comprises at least at least ≥ 1 to ≤ 6, preferably ≥ 2 to ≤ 5, or further preferred 3 or 4 of the substituted or unsubstituted aromatic fused ring systems with: - at least one aromatic 5-member ring, and/or - at least one aromatic 6-member ring, and/or - at least one aromatic 7-member ring; wherein preferably at least one aromatic 5- and/or at least one aromatic 7-member ring comprises at least 1 to 3, preferably 1 hetero-atom; wherein the substituted or unsubstituted aromatic fused ring system optional comprises at least ≥ 1 to ≤ 3 or 2 substituted or unsubstituted unsaturated 5- to 7-member ring of a heterocycle; and wherein the substituted or unsubstituted aromatic fused ring system comprises a hetero-atom, which may be selected from the group comprising O, S, N, B, P or Si, preferably the hetero-atom may be selected from the group comprising O, S or N. According to one embodiment the matrix compound of formula (IIIa) or formula (IIIb) may be free of hetero-atoms which are not part of an aromatic ring and/or part of an unsaturated 7- member-ring, preferably the hole transport compound or the hole transport compound according to formula (I) may be free on N-atoms except N-atoms which are part of an aromatic ring or are part of an unsaturated 7-member-ring. According to one embodiment, the hole transport compound comprises at least one naphthyl group, carbazole group, dibenzofurane group, dibenzothiophene group and/or substituted fluorenyl group, wherein the substituents are independently selected from methyl, phenyl or fluorenyl. According to an embodiment of the electronic device, wherein the matrix compound of formula (IIIa) or formula (IIIb) are selected from F1 to F18:
The matrix compound of the hole injection layer and/or hole transport layer may be free of HTM014, HTM081, HTM163, HTM222, EL-301, HTM226, HTM355, HTM133, HTM334, HTM604 and EL-22T. The abbreviations denote the manufacturers' names, for example, of Merck or Lumtec.
Hole injection layer
The hole injection layer (HIL) may be formed on the anode layer by vacuum deposition, spin coating, printing, casting, slot-die coating, Langmuir-Blodgett (LB) deposition, or the like. When the HIL is formed using vacuum deposition, the deposition conditions may vary according to the hole transport compound that is used to form the HIL, and the desired structure and thermal properties of the HIL. In general, however, conditions for vacuum deposition may include a deposition temperature of 100° C to 350° C, a pressure of 10 -8 to 10 -3 Torr (1 Torr equals 133.322 Pa), and a deposition rate of 0.1 to 10 nm/sec. When the HIL is formed using spin coating or printing, coating conditions may vary according to the hole transport compound that is used to form the HIL, and the desired structure and thermal properties of the HIL. For example, the coating conditions may include a coating speed of about 2000 rpm to about 5000 rpm, and a thermal treatment temperature of about 80° C to about 200° C Thermal treatment removes a solvent after the coating is performed.
The HIL may be formed of a metal complex or a metal complex of formula (I) or formulae (la) to (Id) and optionally of any compound of formulae (Illa) or (IHb).
The thickness of the HIL may be in the range from about 1 nm to about 15 nm, and for example, from about 2 nm to about 15 nm, alternatively about 2 nm to about 12 nm.
When the thickness of the HIL is within this range, the HIL may have excellent hole injecting characteristics, without a substantial penalty in driving voltage.
According to one embodiment of the present invention, the hole injection layer may comprise:
- at least about ≥ 0.5 wt.-% to about ≤ 30 wt.-%, preferably about ≥ 0.5 wt.-% to about ≤ 20 wt.- %, and more preferred about ≥ 15 wt.-% to about ≤ 1 wt.-% of a metal complex of formula (I) or formulae (la) to (Id), and
- at least about > 70 wt.-% to about < 99.5 wt.-%, preferably about > 80 wt.-% to about < 99.5 wt.-%, and more preferred about > 85 wt.-% to about < 99 wt.-% of a matrix compound and/or compound of formulae (Illa) or (IHb); preferably the wt.-% of the metal complex of formula (I) or formulae (la) to (Id) is lower than the wt.-% of the matrix compound or compound according to formulae (Illa) or (IIIb); wherein the weight-% of the components are based on the total weight of the hole injection layer.
Preferably, the hole injection layer is free of ionic liquids, metal phthalocyanine, CuPc, HAT-CN, Pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile, F 4 TCNQ, metal fluoride and/or metal oxides, wherein the metal in the metal oxide is selected from Re and/or Mo. Thereby, the hole injection layer can be deposited under conditions suitable for mass production.
According to an embodiment of the organic electronic device, wherein the hole injection layer is non-emissive.
It is to be understood that the hole injection layer is not part of the anode layer.
Further layers
In accordance with the invention, the organic electronic device may comprise, besides the layers already mentioned above, further layers. Exemplary embodiments of respective layers are described in the following: Substrate
The substrate may be any substrate that is commonly used in manufacturing of, electronic devices, such as organic light-emitting diodes. If light is to be emitted through the substrate, the substrate shall be a transparent or semitransparent material, for example a glass substrate or a transparent plastic substrate. If light is to be emitted through the top surface, the substrate may be both a transparent as well as a non-transparent material, for example a glass substrate, a plastic substrate, a metal substrate, a silicon substrate or a transistor backplane. Preferably, the substrate is a silicon substrate or transistor backplane.
Hole transport layer
According to one embodiment of the organic electronic device, wherein the organic electronic device further comprises a hole transport layer, wherein the hole transport layer is arranged between the hole injection layer and the at least one emission layer.
The hole transport layer may comprises a matrix compound, preferably a covalent matrix compound. According to one embodiment the covalent matrix compound of the hole transport layer may be selected from at least one organic compound.
According to one embodiment the matrix compound in the hole injection layer and hole transport layer are selected the same.
The covalent matrix may consists substantially from covalently bound C, H, O, N, S, which optionally comprise in addition covalently bound B, P, As and/or Se.
According to one embodiment of the organic electronic device, the hole transport layer comprises a matrix compound, wherein the matrix compound of the hole transport layer may be selected from organic compounds consisting substantially from covalently bound C, H, O, N, S, which optionally comprise in addition covalently bound B, P, As and/or Se.
According to one embodiment, the covalent matrix compound of the hole transport layer may have a molecular weight Mw of ≥ 400 and ≤ 2000 g/mol, preferably a molecular weight Mw of ≥ 450 and ≤ 1500 g/mol, further preferred a molecular weight Mw of > 500 and < 1000 g/mol, in addition preferred a molecular weight Mw of ≥ 550 and ≤ 900 g/mol, also preferred a molecular weight Mw of ≥ 600 and ≤ 800 g/mol.
Preferably, the matrix compound of the hole injection layer and the matrix compound of the hole transport layer are selected the same.
According to one embodiment of the organic electronic device, wherein the hole transport layer of the organic electronic device comprises a matrix compound according to formulae (Illa) or (Illb), preferably the matrix compound in the hole injection layer and hole transport layer are selected the same. The hole transport layer may be free of HTM014, HTM081, HTM163, HTM222, EL-301, HTM226, HTM355, HTM133, HTM334, HTM604 and EL-22T. The abbreviations denote the manufacturers' names, for example, of Merck or Lumtec.
The hole transport layer (HTL) may be formed on the HIL by vacuum deposition, spin coating, slot-die coating, printing, casting, Langmuir-Blodgett (LB) deposition, or the like. When the HTL is formed by vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for the formation of the HIL. However, the conditions for the vacuum or solution deposition may vary, according to the hole transport compound that is used to form the HTL.
The thickness of the HTL may be in the range of about 5 nm to about 250 nm, preferably, about 10 nm to about 200 nm, further about 20 nm to about 190 nm, further about 40 nm to about 180 nm, further about 60 nm to about 170 nm, further about 80 nm to about 200 nm, further about 100 nm to about 180 nm, further about 110 nm to about 140 nm.
When the thickness of the HTL is within this range, the HTL may have excellent hole transporting characteristics, without a substantial penalty in driving voltage.
Electron blocking layer
The function of an electron blocking layer (EBL) is to prevent electrons from being transferred from an emission layer to the hole transport layer and thereby confine electrons to the emission layer. Thereby, efficiency, operating voltage and/or lifetime may be improved. Typically, the electron blocking layer comprises a triarylamine compound.
If the electron blocking layer has a high triplet level, it may also be described as triplet control layer.
The function of the triplet control layer is to reduce quenching of triplets if a phosphorescent green or blue emission layer is used. Thereby, higher efficiency of light emission from a phosphorescent emission layer can be achieved. The triplet control layer may be selected from triaiylamine compounds with a triplet level above the triplet level of the phosphorescent emitter in the adjacent emission layer.
The thickness of the electron blocking layer may be selected between 2 and 20 nm.
Emission layer (EML)
The at least one first emission layer (EML), also referred to as first emission layer may be formed on the HTL or EBL by vacuum deposition, spin coating, slot-die coating, printing, casting, LB deposition, or the like. When the EML is formed using vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for the formation of the HIL. However, the conditions for deposition and coating may vary, according to the compound that is used to form the EML.
According to the present invention it is preferred that the organic electronic device comprises one emission layer that is named “first emission layer”. However the organic electronic device optionally comprises two emission layers, wherein the first layer is named first emission layer and second layer is named second emission layer.
It may be provided that the at least one emission layer also referred to as first emission layer is free of the matrix compound of the hole injection layer.
It may be provided that the at least one emission layer does not comprise the compound of Formulae (Illa) or (Illb).
The at least one emission layer (EML) may be formed of a combination of a host and an emitter dopant. Example of the host are Alq3, 4,4'-N,N'-dicarbazole-biphenyl (HTC-10), poly(n- vinyl carbazole) (PVK), 9,10-di(naphthalene-2-yl)anthracene (ADN), 4,4',4"-tris(carbazol-9-yl)- triphenylamine(TCTA), l,3,5-tris(N-phenylbenzimidazole-2-yl)benzene (TPBI), 3-tert-butyl-9,10- di-2-naphthylanthracenee (TBADN), di styrylarylene (DSA) and bis(2-(2-hydroxyphenyl)benzo- thiazolate)zinc (Zn(BTZ)2).
The emitter dopant may be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters which emit light via a thermally activated delayed fluorescence (TADF) mechanism may be preferred due to their higher efficiency. The emitter may be a small molecule or a polymer.
Examples of red emitter dopants are PtOEP, Ir(piq)3, and Btp21r(acac), but are not limited thereto. These compounds are phosphorescent emitters, however, fluorescent red emitter dopants could also be used.
Examples of phosphorescent green emitter dopants are Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2(acac), Ir(mpyp)3.
Examples of phosphorescent blue emitter dopants are F2Irpic, (F2ppy) 2 lr(tmd) and Ir(dfppz)3 and ter-fluorene. 4.4'-bis(4-diphenyl amiostyryl)biphenyl (DPAVBi), 2,5,8, 11-tetra- tert-butyl perylene (TBPe) are examples of fluorescent blue emitter dopants.
The amount of the emitter dopant may be in the range from about 0.01 to about 50 parts by weight, based on 100 parts by weight of the host. Alternatively, the at least one emission layer may consist of a light-emitting polymer. The EML may have a thickness of about 10 nm to about 100 nm, for example, from about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML may have excellent light emission, without a substantial penalty in driving voltage. Hole blocking layer (HBL)
A hole blocking layer (HBL) may be formed on the EML, by using vacuum deposition, spin coating, slot-die coating, printing, casting, LB deposition, or the like, in order to prevent the diffusion of holes into the ETL. When the EML comprises a phosphorescent emitter dopant, the HBL may have also a triplet exciton blocking function.
The HBL may also be named auxiliary ETL or a-ETL.
When the HBL is formed using vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for the formation of the HIL. However, the conditions for deposition and coating may vary, according to the compound that is used to form the HBL. Any compound that is commonly used to form a HBL may be used. Examples of compounds for forming the HBL include oxadiazole derivatives, triazole derivatives, phenanthroline derivatives and triazine derivatives.
The HBL may have a thickness in the range from about 5 nm to about 100 nm, for example, from about 10 nm to about 30 nm. When the thickness of the HBL is within this range, the HBL may have excellent hole-blocking properties, without a substantial penalty in driving voltage.
Electron transport layer (ETL)
The organic electronic device according to the present invention may further comprise an electron transport layer (ETL).
According to another embodiment of the present invention, the electron transport layer may further comprise an azine compound, preferably a triazine compound.
In one embodiment, the electron transport layer may further comprise a dopant selected from an alkali organic complex, preferably LiQ
The thickness of the ETL may be in the range from about 15 nm to about 50 nm, for example, in the range from about 20 nm to about 40 nm. When the thickness of the EIL is within this range, the ETL may have satisfactory electron-injecting properties, without a substantial penalty in driving voltage.
According to another embodiment of the present invention, the organic electronic device may further comprise a hole blocking layer and an electron transport layer, wherein the hole blocking layer and the electron transport layer comprise an azine compound. Preferably, the azine compound is a triazine compound.
Electron injection layer (EIL) An optional EIL, which may facilitates injection of electrons from the cathode, may be formed on the ETL, preferably directly on the electron transport layer. Examples of materials for forming the EIL include lithium 8-hydroxyquinolinolate (LiQ), LiF, NaCl, CsF, Li2O, BaO, Ca, Ba, Yb, Mg which are known in the art. Deposition and coating conditions for forming the EIL are similar to those for formation of the HIL, although the deposition and coating conditions may vary, according to the material that is used to form the EIL.
The thickness of the EIL may be in the range from about 0.1 nm to about 10 nm, for example, in the range from about 0.5 nm to about 9 nm. When the thickness of the EIL is within this range, the EIL may have satisfactory electron-injecting properties, without a substantial penalty in driving voltage.
Cathode layer
The cathode layer is formed on the ETL or optional EIL. The cathode layer may be formed of a metal, an alloy, an electrically conductive compound, or a mixture thereof. The cathode layer may have a low work function. For example, the cathode layer may be formed of lithium (Li), magnesium (Mg), aluminum (Al), aluminum (Al)-lithium (Li), calcium (Ca), barium (Ba), ytterbium (Yb), magnesium (Mg)-indium (In), magnesium (Mg)-silver (Ag), or the like. Alternatively, the cathode layer may be formed of a transparent conductive oxide, such as ITO or IZO.
The thickness of the cathode layer may be in the range from about 5 nm to about 1000 nm, for example, in the range from about 10 nm to about 100 nm. When the thickness of the cathode layer is in the range from about 5 nm to about 50 nm, the cathode layer may be transparent or semitransparent even if formed from a metal or metal alloy.
It is to be understood that the cathode layer is not part of an electron injection layer or the electron transport layer.
Organic electronic device
According to one embodiment of the organic electronic device, wherein the hole injection layer may comprise a first hole injection sub-layer comprising the metal complex of formula (I) and a second hole injection sub-layer comprising a matrix compound, wherein the first hole injection sub-layer is arranged closer to the anode layer and the second hole injection sub-layer is arranged closer to the at least one emission layer; preferably the matrix compound consists of a covalent matrix compound.
According to one embodiment of the organic electronic device, wherein the hole injection layer may comprise a first hole injection sub-layer comprising the metal complex of formula (I) and a second hole injection sub-layer comprising a matrix compound, wherein the first hole injection sub-layer is arranged closer to the anode layer comprising a first anode sub-layer and a second anode sub-layer and the second hole injection sub-layer is arranged closer to the at least one emission layer; preferably the matrix compound consists of a covalent matrix compound.
According to one embodiment of the organic electronic device, wherein the hole injection layer may comprise a first hole injection sub-layer comprising the metal complex of formula (I) and a second hole injection sub-layer comprising a matrix compound comprising of at least one arylamine compound, diarylamine compound, triarylamine compound and/or compound of formulae (Illa) or (Illb), wherein the first hole injection sub-layer is arranged closer to the anode layer and the second hole injection sub-layer is arranged closer to the at least one emission layer.
According to one embodiment of the organic electronic device, wherein the hole injection layer may comprise a first hole injection sub-layer comprising the metal complex of formula (I) and a second hole injection sub-layer comprising the matrix compound comprising of at least one arylamine compound, diarylamine compound, triarylamine compound and/or compound of formulae (Illa) or (Illb), wherein the first hole injection sub-layer is arranged closer to the anode layer comprising a first anode sub-layer and a second anode sub-layer and the second hole injection sub-layer is arranged closer to the at least one emission layer.
According to one embodiment of the organic electronic device, the hole injection layer may comprise a first hole injection sub-layer consisting essentially of the metal complex of formula (I) or formulae (la) to (Id) and a second hole injection sub-layer comprising a matrix compound, wherein the first hole injection sub-layer is arranged closer to the anode layer comprising at least a first anode sub-layer and a second anode sub-layer and the second hole injection sub-layer is arranged closer to the at least one emission layer; preferably the matrix compound consists of a covalent matrix compound.
According to one embodiment of the organic electronic device, the hole injection layer may comprise a first hole injection sub-layer consisting essentially of the metal complex of formula (I) or formulae (la) to (Id) and a second hole injection sub-layer comprising a matrix compound comprising of at least one arylamine compound, diarylamine compound, triarylamine compound and/or compound of formulae (Illa) or (Illb), wherein the first hole injection sub-layer is arranged closer to the anode layer comprising at least a first anode sub-layer and a second anode sub-layer and the second hole injection sub-layer is arranged closer to the at least one emission layer.
In the context of the present specification the term “consisting essentially of “ especially means and/or includes a concentration of ≥ 90% (vol/vol) more preferred ≥ 95% (vol/vol) and most preferred ≥ 99% (vol/vol). According to one embodiment of the organic electronic device, wherein the hole injection layer may be arranged in direct contact with the anode layer comprising at least a first anode sub- layer and a second anode sub-layer.
According to one embodiment of the present invention, wherein the organic electronic device may comprise the hole injection layer comprising the metal complex of formula (I) or formulae (la) to (Id) and the matrix compound comprising at least one arylamine compound, diarylamine compound, triarylamine compound and/or a compound of formulae (Illa) or (Illb), wherein in formula (I) or formulae (la) to (Id) M is selected from Ce(IV), Zr(IV) or Hf(IV), preferably M is Ce(IV) or Hf(IV).
According to another embodiment, wherein the organic electronic device can be a light emitting device or a display device.
According to one aspect of the present invention, there is provided an organic electronic device comprising: a substrate; an anode layer comprising at least two anode sublayers or more comprises at least a first anode sub-layer and a second anode sub-layer formed on the substrate; a hole injection layer comprising a metal complex of formula (I), a hole transport layer, at least a first emission layer, an electron transport layer and a cathode layer.
According to another aspect of the present invention, there is provided an organic electronic device comprising: a substrate; an anode layer comprising at least two anode sublayers or more comprises a first anode sub-layer and a second anode sub-layer formed on the substrate, a hole injection of the present invention comprising a first and a second hole injection sub-layer, a hole transport layer, at least a first emission layer, an optional hole blocking layer, an electron transport layer, an optional electron injection layer, and a cathode layer, wherein the first hole injection sub-layer is arranged adjacent to the anode layer and the second hole injection sub-layer arranged adjacent to the hole transport layer, and wherein the first hole injection sub-layer comprises or consists of the metal complex of formula (I) or formulae (la) to (Id) and the second sub-layer comprises or consists of a matrix compound or compound of formulae (Illa) or (Illb).
According to another aspect of the present invention, there is provided an organic electronic device comprising: a substrate; an anode layer comprising at least two anode sublayers or more comprises a first anode sub-layer and a second anode sub-layer formed on the substrate; a hole injection layer comprising a matrix compound or a compound of formulae (Illa) or (Illb) and a metal complex of formula (I) or formulae (la) to (Id), a hole transport layer, an electron blocking layer, at least a first emission layer, a hole blocking layer, an electron transport layer and a cathode layer. According to another aspect of the present invention, there is provided an organic electronic device comprising: a substrate; an anode layer comprising at least two anode sublayers or more comprises a first anode sub-layer and a second anode sub-layer formed on the substrate, a hole injection of the present invention comprising a first hole injection and a second hole injection sub-layer, a hole transport layer, an electron-blocking layer, at least a first emission layer , a hole blocking layer, an electron transport layer, an optional electron injection layer, and a cathode layer, wherein the first hole injection sub-layer is arranged adjacent to the anode layer comprising at least a first anode sub-layer and a second anode sub-layer and the second hole injection sub-layer is arranged adjacent to the hole transport layer, and wherein the first hole injection sub-layer comprises or consists of the metal complex of formula (I) or formulae (la) to (Id) and the second sub-layer comprises or consists of a matrix compound or a compound of formulae (Illa) or (Illb).
According to another aspect of the present invention, there is provided an organic electronic device comprising: a substrate; an anode layer comprising at least two anode sublayers or more comprises a first anode sub-layer and a second anode sub-layer formed on the substrate, a hole injection layer comprising a matrix compound or a compound of formulae (Illa) or (Illb) and a metal complex of formula (I) or formulae (la) to (Id), a hole transport layer, an electron blocking layer, at least a first emission layer, a hole blocking layer, an electron transport layer, an optional electron injection layer, and a cathode layer.
According to another aspect of the present invention, there is provided an OLED comprising: a substrate; an anode layer comprising a first anode sub-layer and a second anode sub- layer formed on the substrate, a hole injection of the present invention comprising a first hole injection and a second hole injection sub-layer, a hole transport layer, an electron blocking layer, at least a first emission layer, a hole blocking layer, an electron transport layer, an optional electron injection layer, and a cathode layer, wherein the first hole injection sub-layer is arranged adjacent to the anode layer comprising at least a first anode sub-layer and a second anode sub-layer and the second hole injection sub-layer is arranged adjacent to the hole transport layer, and wherein the first hole injection sub-layer comprises or consists of the metal complex of formula (I) or formulae (la) to (Id) and the second hole injection sub-layer comprises or consists of a matrix compound or a compound of formulae (Illa) or (Illb).
According to various embodiments of the present invention, there may be provided further layers arranged between the above mentioned layers, on the substrate or on the top electrode. For example, the organic electronic device according to Fig. 5 may be formed by a process, wherein on a substrate (110), an anode layer (120) comprising at least a first anode sub- layer (121) and a second anode sub-layer (122), a hole injection layer (130) comprising a matrix compound of formulae (Illa) or (Illb) and metal complex of formula (I) or formulae (la) to (Id), a hole transport layer (140), a first emission layer (150), a hole blocking layer (155), an electron transport layer (160), and a cathode layer (190) are subsequently formed in that order.
Method of manufacturing
According to another aspect of the present invention, there is provided a method of manufacturing an organic electronic device, the method using:
- at least one deposition source, preferably two deposition sources and more preferred at least three deposition sources.
The methods for deposition that can be suitable comprise:
- deposition via vacuum thermal evaporation;
- deposition via solution processing, preferably the processing may be selected from spincoating, printing, casting; and/or
- slot-die coating.
According to various embodiments of the present invention, there is provided a method using:
- a first deposition source to release the matrix compound according to the invention, and
- a second deposition source to release the metal complex of formula (I) or formulae (la) to (Id). The method comprising the steps of forming the hole injection layer; whereby for an organic electronic device:
- the hole injection layer is formed by releasing the matrix compound according to the invention from the first deposition source and the metal complex of formula (I) or formulae (la) to (Id) from the second deposition source.
According to various embodiments of the present invention, the method may further include forming the layers in the following order on the hole injection layer, at least one layer selected from the group consisting of forming a hole transport layer, forming a hole blocking layer, forming a first emission layer , forming a hole blocking layer, forming an electron transporting layer and/or forming an electron injection layer and/ or forming a cathode layer.
According to various embodiments of the present invention, the method may further include the steps for forming an organic electronic device, wherein
- on a substrate an anode layer comprising at least a first anode sub-layer and a second anode sub-layer is formed, - on the anode layer comprising at least a first anode sub-layer and a second anode sub-layer a hole injection layer, which comprises a matrix compound according to invention and a metal complex of formula (I) or formulae (la) to (Id) is formed,
- on the hole injection layer, which comprises a matrix compound and a metal complex of formula (I) or formulae (la) to (Id), a hole transport layer is formed,
- on the hole transport layer at least a first emission layer is formed,
- on the emission layer an electron transport layer is formed, optionally a hole blocking layer and/or an electron transport layer are formed on the emission layer,
- and finally a cathode layer is formed,
- optional an electron blocking layer is formed in that order between the hole transport layer and the emission layer,
- optional an electron injection layer is formed between the electron transport layer and the cathode layer.
According to various embodiments, the organic electronic device may have the following layer structure, wherein the layers having the following order: an anode layer comprising at least a first anode sub-layer and a second anode sub-layer, a hole injection layer comprising a matrix compound according to the invention and a metal complex of formula (I) or formulae (la) to (Id), a hole transport layer, optional an electron blocking layer, at least a first emission layer, optional a hole blocking layer, an electron transport layer, optional an electron injection layer, and a cathode layer.
According to one embodiment, the organic electronic device of the present invention is formed by deposition of the hole injection layer in vacuum.
According to another aspect, it is provided an electronic device comprising at least one organic light emitting device according to any embodiment described throughout this application, preferably, the electronic device comprises the organic light emitting diode in one of embodiments described throughout this application. More preferably, the organic electronic device is a display device.
Metal complex
According to another aspect of the invention, a metal complex of formula I is provided represented by formula (la): wherein M is a metal ion selected from Ce, Hf or Zr, preferably Ce or Hf; A 1 is selected from substituted C 6 to C 12 aryl, substituted or unsubstituted C 3 to C 12 heteroaryl; and A 2 is selected from a substituted C 3 alkyl; wherein the substituents of A 1 and A 2 are independently selected from D, C 6 aryl, C 3 to C 9 heteroaryl, C 1 to C 6 alkyl, 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 1 , COOR 1 , halogen, F or CN, wherein R 1 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; A 3 is selected from H or D; or A 1 is selected from formulas D11 to D22: wherein the “*” denotes the binding position; preferably A 1 is D12, D18 and/or D20; and A 2 is selected from substituted or unsubstituted C 1 to C 12 alkyl; wherein the substituents of A 2 are independently selected from D, C 3 to C 6 branched alkyl, C 3 to
C 6 cyclic alkyl, partially or perfluorinated Ci to C 16 alkyl, partially or perdeuterated Ci to
C 6 alkyl, halogen, F or CN;
A 3 is selected from H or D.
According to one embodiment, wherein for the metal complex of formula (I) according to the present invention represented by formula (Ia) the following formula is excluded:
Thereby, the thermal stability, for example decomposition temperature, and/or rate onset temperature may be obtained in a range suitable for mass production of organic electronic devices.
According to another embodiment, wherein the metal complex has the formula (la): wherein
M is a metal ion selected from Ce, Hf or Zr, preferably Ce or Hf;
A 1 is selected from substituted C 6 to C 12 aryl, substituted or unsubstituted C 3 to C 12 heteroaryl;
A 2 is selected from a substituted C 3 alkyl;
A 3 is selected from H or D; wherein the substituents of A 1 and A 2 are independently 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 1 , COOR 1 , halogen, F or CN, wherein R 1 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 Ce 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.
Preferably, A 2 may be selected from partially or perfluorinated isopropyl, more preferred A 2 is selected from perfluorinated isopropyl.
According to an embodiment, A 1 is selected from substituted C 6 to C 12 aryl, wherein at least one substituent of A 1 is selected from partially or perfluorinated C 1 to C 16 alkyl or CN, preferably at least two substituents are selected from partially or perfluorinated C 1 to C 16 alkyl or CN.
According to an embodiment, A 1 is selected from substituted C 6 to C 12 aryl, wherein at least one substituent of A 1 is selected from CF 3 or CN, preferably at least two substituents are selected from CF 3 or CN.
According to an embodiment, A 1 is selected from formulas D1 to D34 and/or D38 to D71. According to one embodiment, wherein the metal complex has the formula (la): wherein
M is a metal ion selected from Ce, Hf or Zr, preferably Ce or Hf;
A 1 is selected from formulas D11 to D22: wherein the denotes the binding position; preferably A 1 is D12, D18 and/or D20;
A 2 is selected from substituted or unsubstituted C 1 to C 12 alkyl;
A 3 is selected from H or D; wherein the substituents of A 2 are independently selected from D, C 3 to C 6 branched alkyl, C 3 to C 6 cyclic alkyl, partially or perfluorinated C 1 to C 16 alkyl, partially or perdeuterated C 1 to
C 6 alkyl, halogen, F or CN.
Preferably, A 2 may be selected from partially or perfluorinated C 1 to C 4 alkyl.
According to an embodiment, the metal complex of formula (la) is selected from formulae
H4 to H13:
Hereinafter, the embodiments are illustrated in more detail with reference to examples.
However, the present disclosure is not limited to the following examples. Reference will now be made in detail to the exemplary aspects. Description of the Drawings
The aforementioned components, as well as the claimed components and the components to be used in accordance with the invention in the described embodiments, are not subject to any special exceptions with respect to their size, shape, material selection and technical concept such that the selection criteria known in the pertinent field can be applied without limitations.
Additional details, characteristics and advantages of the object are disclosed in the dependent claims and the following description of the respective figures which in an exemplary fashion show preferred embodiments according to the invention. Any embodiment does not necessarily represent the full scope, however, and reference is made therefore to the claims and herein for interpreting the scope. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the present invention as claimed.
Figures 1 to 9
FIG. 1 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention;
FIG. 2 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention;
FIG. 3 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention.
FIG. 4 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention;
FIG. 5 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention;
FIG. 6 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention;
FIG. 7 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention;
FIG. 8 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention;
FIG. 9 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention. Hereinafter, the figures 1 to 9 are illustrated in more detail with reference to examples. However, the present disclosure is not limited to the following figures.
Herein, when a first element is referred to as being formed or disposed "on" or “onto” a second element, the first element can be disposed directly on the second element, or one or more other elements may be disposed there between. When a first element is referred to as being formed or disposed "directly on" or “directly onto” a second element, no other elements are disposed there between.
FIG. 1 is a schematic sectional view of an organic electronic device (100), according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) that comprises a first anode sub-layer (121) and a second anode sub-layer (122) and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). Onto the HIL (130), a first emission layer (EML) (150), and a cathode layer (190) are disposed.
FIG. 2 is a schematic sectional view of an organic electronic device (100), according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) that comprises a first anode sub-layer (121), a second anode sub-layer (122) and a third anode sub-layer (123), and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120) comprising a first anode sub-layer (121), a second anode sub-layer (122) and a third anode sub-layer (123). Onto the HIL (130), a first emission layer (EML) (150), and a cathode layer (190) are disposed.
FIG. 3 is a schematic sectional view of an organic electronic device (100), according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) that comprises a first anode sub-layer (121) and a second anode sub-layer (122), and a hole injection layer (HIL) (130) comprising a first hole injection sub- layer (131) and a second hole injection sub-layer (132). The HIL (130) comprising a first hole injection sub-layer (131) and a second hole injection sub-layer (132) is disposed on the anode layer (120). Onto the HIL (130), a first emission layer (EML) (150), and a cathode layer (190) are disposed.
FIG. 4 is a schematic sectional view of an organic electronic device (100), according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) that comprises a first anode sub-layer (121) a second anode sub-layer (122) and a third anode sub-layer (123), and a hole injection layer (HIL) (130) comprising a first hole injection sub-layer (131) and a second hole injection sub-layer (132). The HIL (130) comprising a first hole injection sub-layer (131) and a second hole injection sub-layer (132) is disposed on the anode layer (120). Onto the HIL (130), a first emission layer (EML) (150), and a cathode layer (190) are disposed.
FIG. 5 is a schematic sectional view of an organic electronic device (100), according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) that comprises a first anode sub-layer (121) and a second anode sub-layer (122), and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). Onto the HIL (130), an hole transport layer (HTL) (140), a first emission layer (EML) (150), a hole blocking layer (BL) (155), an electron transport layer (ETL) (160), and a cathode layer (190) are disposed.
FIG. 6 is a schematic sectional view of an organic electronic device (100), according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) that comprises a first anode sub-layer (121), a second anode sub-layer (122) and a third anode sub-layer (123), and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). Onto the HIL (130), an hole transport layer (HTL) (140), a first emission layer (EML) (150), a hole blocking layer (HBL) (155), an electron transport layer (ETL) (160), and a cathode layer (190) are disposed.
FIG. 7 is a schematic sectional view of an organic electronic device (100), according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) that comprises a first anode sub-layer (121) and a second anode sub-layer (122) and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). Onto the HIL (130), a hole transport layer (HTL) (140), an electron blocking layer (EBL) (145), a first emission layer (EML) (150), a hole blocking layer (HBL) (155), an electron transport layer (ETL) (160), and a cathode layer (190) are disposed.
FIG. 8 is a schematic sectional view of an organic electronic device (100), according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) that comprises a first anode sub-layer (121) and a second anode sub-layer (122) and a hole injection layer (HIL) (130). The HIL (130) comprises a first hole injection sub-layer (131) and a second hole injection sub-layer (132), wherein the first hole injection sub-layer (131) is disposed on the second anode sub-layer (122) and the second hole injection sub-layer (132) is disposed on the first hole injection sub-layer (131). Onto the HIL (130), a hole transport layer (HTL) (140), an electron blocking layer (EBL) (145), a first emission layer (EML) (150), a hole blocking layer (HBL) (155), an electron transport layer (ETL) (160), and a cathode layer (190) are disposed.
FIG. 9 is a schematic sectional view of an organic electronic device (100), according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) that comprises a first anode sub-layer (121), a second anode sub-layer (122) and a third anode sub-layer (123), and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). Onto the HIL (130), a hole transport layer (HTL) (140), an electron blocking layer (EBL) (145), a first emission layer (EML) (150), a hole blocking layer (HBL) (155), an electron transport layer (ETL) (160), an electron injection layer (EIL) (180) and a cathode layer (190) are disposed.
While not shown in Fig. 1 to Fig. 9, a capping and/or a sealing layer may further be formed on the cathode layer 190, in order to seal the organic electronic device 100. In addition, various other modifications may be applied thereto.
Hereinafter, the embodiments are illustrated in more detail with reference to examples. However, the present disclosure is not limited to the following examples.
Detailed description
The invention is furthermore illustrated by the following examples which are illustrative only and non-binding.
The compound of formulae (Illa) and (Illb) and metal complexes of formula (I) or formulae (la) to (Id) may be prepared by methods known in the art.
Decomposition temperature Tdec
The decomposition temperature Tdec is measured by loading a sample of 9 to 11 mg into a Mettler Toledo 100 pL aluminum pan without lid under nitrogen in a Mettler Toledo TGA-DSC Imachine. The following heating program was used: 25°C isothermal for 3 min; 25°C to 600°C with 10 K/min.
The decomposition temperature was determined based on the onset of the decomposition in TGA.
The decomposition temperature indicates the temperature at which the compound decomposes. The higher the decomposition temperature the higher the thermal stability of a compound.
Rate onset temperature
The rate onset temperature (TRO) is determined by loading 100 mg compound into a VTE source. As VTE source a point source for organic materials may be used as supplied by Kurt J. Lesker Company (www.lesker.com) or CreaPhys GmbH (http://www.creaphys.com). The VTE source is heated at a constant rate of 15 K/min at a pressure of less than 10 -5 mbar and the temperature inside the source measured with a thermocouple. Evaporation of the compound is detected with a QCM detector which detects deposition of the compound on the quartz crystal of the detector. The deposition rate on the quartz crystal is measured in Ǻngstrom per second. To determine the rate onset temperature, the deposition rate is plotted against the VTE source temperature. The rate onset is the temperature at which noticeable deposition on the QCM detector occurs. For accurate results, the VTE source is heated and cooled three time and only results from the second and third run are used to determine the rate onset temperature.
To achieve good control over the evaporation rate of an organic compound, the rate onset temperature may be in the range of 100 to 300 °C. If the rate onset temperature is below 100 °C the evaporation may be too rapid and therefore difficult to control. If the rate onset temperature is above 300 °C the evaporation rate may be too low which may result in low tact time and decomposition of the organic compound in VTE source may occur due to prolonged exposure to elevated temperatures.
The rate onset temperature is an indirect measure of the volatility of a compound. The higher the rate onset temperature the lower is the volatility of a compound.
HOMO and LUMP levels of the matrix compound, compound of formula (Illa) or a compound of formula (nib)
The HOMO and LUMO levels of the matrix compound, compound of formula (Illa) or a compound of formula (Illb) are calculated with the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The optimized geometries and the HOMO and LUMO energy levels of the molecular structures are determined by applying the hybrid functional B3LYP with a 6-31G* basis set in the gas phase. If more than one conformation is viable, the conformation with the lowest total energy is selected.
If calculated by this method, the HOMO level of N2,N2,N2',N2',N7,N7,N7',N7'-octakis(4- methoxyphenyl)-9,9'-spirobi[fluorene]-2,2',7,7'-tetraamine is -4.27 eV.
LUMP levels of the metal complex or metal complex of formula (I) and formulae (la) to (Id)
The LUMO levels of the metal complex or metal complex of formula (I) and formulae (la) to (Id) are calculated with the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The optimized energies of the LUMO are obtained from a single point calculation at the B3LYP Def-TZVP D3BJ in the gas phase, from a geometry optimization at the B3LYP Def-SV(P) D3BJ level of theory. If more than one conformation is viable, the conformation with the lowest total energy is selected.
In Table A are shown LUMO levels for metal complexes of formula (I) represented by formula (la) which were calculated by the method described above. Table A: Metal complexes of formula (I) represented by formula (la)
As can be seen in Table A, the LUMO levels of metal complexes of formula (I) represented by formula (la) have LUMO levels further away from vacuum level compared to comparative compound CC-1 and comparative compound CC-2.
Without being bound by theory, a LUMO level further away from vacuum level may enable particularly efficient injection into adjacent layers comprising compounds with a HOMO level further away from vacuum level.
General procedure for fabrication of QLEDs
For Examples 1 to 25 in Table 3, a glass substrate with an anode layer comprising a first anode sub-layer of 120 nm Ag, a second anode sub-layer of 8 nm ITO and a third anode sub-layer of 10 nm ITO was cut to a size of 50 mm x 50 mm x 0.7 mm, ultrasonically washed with water for 60 minutes and then with isopropanol for 20 minutes. The liquid film was removed in a nitrogen stream, followed by plasma treatment to prepare the anode layer. The plasma treatment was performed in an atmosphere comprising 97.6 vol.-% nitrogen and 2.4 vol.-% oxygen at 75 W for 30 seconds.
Then, the matrix compound and the metal complex were co-deposited in vacuum on the anode layer, to form a hole injection layer (HIL) having a thickness of 10 nm. The composition of the hole injection layer can be seen in Table 3.
Then, the matrix compound was vacuum deposited on the HIL, to form a HTL having a thickness of 123 nm. The matrix compound in the HTL is selected the same as the matrix compound in the HIL. The matrix compound can be seen in Table 3. Then N-(4-(dibenzo[b,d]furan-4-yl)phenyl)-N-(4-(9-phenyl-9H-fluor en-9- yl)phenyl)-[1,1'-biphenyl]-4-amine (CAS 1824678-59-2) was vacuum deposited on the HTL, to form an electron blocking layer (EBL) having a thickness of 5 nm.
Then 97 vol.-% H09 as EML host and 3 vol.-% BD200 (Sun Fine Chemicals, Korea) as fluorescent blue emitter dopant were deposited on the EBL, to form a blue-emitting first emission layer (EML) with a thickness of 20 nm.
Then a hole blocking layer was formed with a thickness of 5 nm by depositing 2-(3 '- (9,9-dimethyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-dip henyl-1,3,5-triazine on the emission layer EML.
Then the electron transporting layer having a thickness of 31 nm was formed on the hole blocking layer by depositing 50 wt.-% 4'-(4-(4-(4,6-diphenyl-1,3,5-triazin-2- yl)phenyl)naphthalen-1-yl)-[1,1'-biphenyl]-4-carbonitrile and 50 wt.-% of LiQ.
Then Ag:Mg (90:10 vol.-%) was evaporated at a rate of 0.01 to 1 A/s at 10 -7 mbar to form a cathode layer with a thickness of 13 nm on the electron transporting layer.
Then, F3 was deposited on the cathode layer to form a capping layer with a thickness of 75 nm.
The OLED stack is protected from ambient conditions by encapsulation of the device with a glass slide. Thereby, a cavity is formed, which includes a getter material for further protection.
Comparative example 1
For comparative example 1 in Table 3, a 15Ω /cm 2 glass substrate with 90 nm ITO (available from Coming Co.) was cut to a size of 50 mm x 50 mm x 0.7 mm, ultrasonically washed with water for 60 minutes and then with isopropanol for 20 minutes. The liquid film was removed in a nitrogen stream, followed by plasma treatment in nitrogen atmosphere at a power of 100 W for 75 seconds to prepare the anode layer.
Then, 90 vol.-% F3 and 10 vol.-% MC-1 were co-deposited in vacuum on the anode layer, to form a hole injection layer (HIL) having a thickness of 10 nm.
Then, F3 was vacuum deposited on the HIL, to form a HTL having a thickness of 123 nm.
Then, the EBL, EML, HBL and ETL are deposited in this order on the HTL, as described for example 1 above.
Then Al was evaporated at a rate of 0.01 to 1 Å/s at 10 -7 mbar to form a cathode layer with a thickness of 100 nm on the electron transporting layer. The OLED stack is protected from ambient conditions by encapsulation of the device with a glass slide. Thereby, a cavity is formed, which includes a getter material for further protection.
Comparative example 2
For comparative example 2 in Table 3, a glass substrate was cut to a size of 50 mm x 50 mm x 0.7 mm, ultrasonically washed with water for 60 minutes and then with isopropanol for 20 minutes. The liquid film was removed in a nitrogen stream, followed by plasma treatment in nitrogen atmosphere at a power of 100 W for 75 seconds, to prepare the substrate.
Then, 100 nm Ag was deposited in vacuum on the substrate to form the anode layer.
Then, 90 vol.-% F3 and 10 vol.-% MC-1 were co-deposited in vacuum on the anode layer, to form a hole injection layer (HIL) having a thickness of 10 nm.
Then, F3 was vacuum deposited on the HIL, to form a HTL having a thickness of 123 nm.
Then, the EBL, EML, HBL and ETL, cathode layer and capping layer are deposited in this order on the HTL, as described for example 1 above.
The OLED stack is protected from ambient conditions by encapsulation of the device with a glass slide. Thereby, a cavity is formed, which includes a getter material for further protection.
To assess the performance of the inventive examples compared to the prior art, the current efficiency is measured at 20°C. The current-voltage characteristic is determined using a Keithley 2635 source measure unit, by sourcing a voltage in V and measuring the current in mA flowing through the device under test. The voltage applied to the device is varied in steps of 0.1V in the range between 0V and 10V. Likewise, the luminance-voltage characteristics and CIE coordinates are determined by measuring the luminance in cd/m 2 using an Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungsstelle (DAkkS)) for each of the voltage values. The cd/A efficiency at 10 mA/cm 2 is determined by interpolating the luminance-voltage and current-voltage characteristics, respectively.
In bottom emission devices, the emission is predominately Lambertian and quantified in percent external quantum efficiency (EQE). The light is emitted through the anode layer. To determine the efficiency EQE in % the light output of the device is measured using a calibrated photodiode at 10 mA/cm2.
In top emission devices, the emission is forward directed through the cathode layer, non- Lambertian and also highly dependent on the mirco-cavity. Therefore, the efficiency EQE will be higher compared to bottom emission devices. To determine the efficiency EQE in % the light output of the device is measured using a calibrated photodiode at 10 mA/cm 2 . Lifetime LT of the device is measured at ambient conditions (20°C) and 30 mA/cm 2 , using a Keithley 2400 sourcemeter, and recorded in hours.
The brightness of the device is measured using a calibrated photo diode. The lifetime LT is defined as the time till the brightness of the device is reduced to 97 % of its initial value.
To determine the voltage stability over time U(100h)-(lh), a current density of at 30 mA/cm 2 was applied to the device. The operating voltage was measured after 1 hour and after 100 hours, followed by calculation of the voltage stability for the time period of 1 hour to 100 hours. A low value for U(100h)-(lh) denotes an improvement in stability of operating voltage over time.
Technical Effect of the invention
In Table 1 are shown the decomposition temperatures Tdec and rate onset temperatures TRO for metal complexes of formula (I) and formulae (la) to (Id).
Table 1: Metal complexes of formula (I) and formulae (la) to (Id)
As can be seen in Table 1, the metal complexes of formula (I) and formulae (la) to (Id) have decomposition temperatures and/or rate onset temperatures suitable for mass production of organic electronic devices.
Matrix compounds in the hole injection layer and/or hole transport layer
In Table 2 are shown the HOMO levels and rate onset temperatures TRO for matrix compounds of formula (I). HOMO levels were calculated using TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany) by applying the hybrid functional B3LYP with a 6-31G* basis set in the gas phase.
Table 2: Matrix compounds for hole injection layers
As can be seen in Table 2, the matrix compound of formula (Illa) or (Illb) have rate onset temperatures suitable for mass production of organic electronic devices.
In Table 3 are shown data for organic electronic devices comprising a hole injection layer comprising a metal complex of formula (I) or formula (la) to (Id).
In comparative example 1, the anode layer consists of ITO. As can be seen in Table 3, the operating voltage is 5.06 V, the voltage increase over time is 1.87 V and the lifetime is 32 hours.
In comparative example 2, the anode layer consists of Ag. As can be seen in Table 3, the operating voltage is very high at > 10 V. Therefore, the volate stability over time and the lifetime have not been determined.
In example 1, the organic electronic device comprises an anode layer according to invention. As can be seen in Table 3, the operating voltage is improved to 3.93 V, the voltage stability over time has been improved to 0.06 V and the lifetime is 115 hours.
In example 2, the hole injection layer comprises the same metal complex as in example 1. However, the doping concentration has been reduced from 10 vol.-% in example 1 to 5 vol.-% in example 2. As can be seen in Table 3, the operating voltage is 4.01 V, the voltage stability over time is 0.16 V and the lifetime is improved to 120 hours.
In example 3, the hole injection layer comprises metal complex MC-2. As can be seen in Table 3, the operating voltage is improved to 3.84 V, the voltage stability over time is improved to 0.08 V and the lifetime is still high at 107 hours.
In examples 4 and 5, the hole injection layer comprises metal complex MC-2 at higher concentration. As can be seen in Table 3, the operating voltage is improved further to 3.62 V, the voltage stability over time is improved to 0.01 V and the lifetime is still high at 107 and 111 hours, respectively. In examples 6 to 11, the hole injection layer comprises metal complex MC-1 and matrix compound F18 at a range of concentrations. The HOMO of the matrix compound is -4.73 eV, see Table 2. As can be seen in Table 3, the operating voltage, voltage stability over time and lifetime are improved over comparative example 1.
In examples 12 to 19, the hole injection layer comprises metal complex MC-2 and matrix compound F 18 at a range of concentrations. As can be seen in Table 3, the operating voltage, voltage stability over time and lifetime are improved over comparative example 1.
In examples 20 to 22, the hole injection layer comprises metal complex MC-1 and matrix compound F4 at a range of concentrations. The HOMO of the matrix compound is -4.82 eV, see Table 2. As can be seen in Table 3, the operating voltage, voltage stability over time and lifetime are improved over comparative example 1.
In examples 23 to 25, the hole injection layer comprises metal complex MC-2 and matrix compound F4 at a range of concentrations. As can be seen in Table 3, the operating voltage, voltage stability over time and lifetime are improved over comparative example 1.
In summary, an improvement in operating voltage, voltage stability overtime and/or lifetime has been obtained.
A lower operating voltage may be important for the battery life of organic electronic devices, in particular mobile devices.
An improvement in voltage stability over time and/or lifetime may be important for the longterm stability of organic electronic devices.
Table 3: Organic electronic devices comprising a hole injection layer comprising a metal complex and a matrix compound
The particular combinations of elements and features in the above detailed embodiments are exemplary only; the interchanging and substitution of these teachings with other teachings in this and the patents/applications incorporated by reference are also expressly contemplated. As those skilled in the art will recognize, variations, modifications, and other implementations of what is described herein can occur to those of ordinary skill in the art without departing from the spirit and the scope of the invention as claimed. Accordingly, the foregoing description is by way of example only and is not intended as limiting. In the claims, the word "comprising" does not exclude other elements or steps, and the indefinite article "a" or "an" does not exclude a plurality. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measured cannot be used to advantage. The invention's scope is defined in the following claims and the equivalents thereto. Furthermore, reference signs used in the description and claims do not limit the scope of the invention as claimed.