Organic light emitting diode, device comprising same, and compound

Abstract

The invention relates to an organic light emitting diode and a device comprising the same. The invention also relates to a compound which can be used in the organic light emitting diode.

Description

Technical Field

[0001] The present invention relates to an organic light-emitting diode and a device including the same. The present invention also relates to a compound that can be used in the organic light-emitting diode. Background of the Invention

[0003] Organic semiconductor devices such as organic light-emitting diodes (OLEDs) as self-emitting devices have a wide viewing angle, excellent contrast, fast response, high brightness, excellent operating voltage characteristics, and color reproduction. A typical OLED includes an anode, a hole transport layer (HTL), a light-emitting layer (EML), an electron transport layer (ETL), and a cathode sequentially stacked on a substrate. In this regard, the HTL, EML, and ETL are thin films formed of organic compounds.

[0004] When a voltage is applied between the anode and the cathode, holes injected from the anode move through the HTL to the EML, and electrons injected from the cathode move through the ETL to the EML. The holes and electrons recombine in the EML to generate excitons. When the excitons decay from the excited state to the ground state, light is emitted. The injection and flow of holes and electrons should be balanced so that the OLED having the above structure has excellent efficiency and / or a long lifespan.

[0005] The performance of an organic light-emitting diode is affected by the characteristics of the organic semiconductor layer, and among them, is affected by the characteristics of the organic material of the organic semiconductor layer.

[0006] In particular, it is necessary to develop an organic semiconductor layer that can increase the electron mobility and at the same time increase the electrochemical stability so that an organic semiconductor device such as an organic light-emitting diode can be applied to a large-size flat panel display.

[0007] Accordingly, an object of the present invention is to provide an organic light-emitting diode and a compound for preparing the organic light-emitting diode that overcome the disadvantages of the prior art, and in particular, to provide a compound for use in an organic light-emitting diode, thereby contributing to improving its performance, especially improving its performance in terms of efficiency, and the organic light-emitting diode includes the compound. Summary of the Invention

[0008] The above object is achieved by an organic light-emitting diode including an anode, a cathode, a light-emitting layer, and an electron transport layer,

[0009] wherein

[0010] - the electron transport layer is disposed between the light-emitting layer and the cathode;

[0011] - the electron transport layer does not contain an electrical dopant;

[0012] - the electron transport layer includes a compound of formula (I),

[0013] (Ar 2 ) m -(Z k -G) n (I);

[0014] Wherein in formula (I),

[0015] -m and n are independently 1 or 2;

[0016] -k is independently 0, 1 or 2;

[0017] -Ar 2 is independently selected from C2 to C 42 heteroaryl and C6 to C 60 aryl,

[0018] -Wherein each Ar 2 may be substituted by one or two substituents, and the one or two substituents are independently selected from: C6 to C 12 aryl, C3 to C 11 heteroaryl and C1 to C6 alkyl, D, 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 fully fluorinated C1 to C6 alkyl, partially or fully fluorinated C1 to C6 alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy, halogen, CN or PY(R 10 )2, wherein Y is selected from O, S or Se, preferably O, and R 10 is independently selected from C6 to C 12 aryl, C3 to C 12 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, partially or fully fluorinated C1 to C6 alkyl, partially or fully fluorinated C1 to C6 alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy;

[0019] -Wherein each C6 to C 2 aryl substituent on Ar 12 and each C3 to C 2 heteroaryl substituent on Ar 11 may be substituted by C1 to C4 alkyl or halogen;

[0020] -Z is independently selected from C6 to C 30 aryl,

[0021] -Wherein each Z may be substituted by one or two substituents, and the one or two substituents are independently selected from: C6 to C 12Aryl and C1-C6 alkyl, D, C1-C6 alkoxy, C3-C6 branched alkyl, C3-C6 cyclic alkyl, C3-C6 branched alkoxy, C3-C6 cyclic alkoxy, partially or perfluorinated C1-C6 alkyl, partially or perfluorinated C1-C6 alkoxy, partially or perdeuterated C1-C6 alkyl, partially or perdeuterated C1-C6 alkoxy, halogen, CN or PY(R 10 )2, where Y is selected from O, S or Se, preferably O, and R 10 independently selected from C6-C 12 aryl, C3-C 12 heteroaryl, C1-C6 alkyl, C1-C6 alkoxy, partially or perfluorinated C1-C6 alkyl, partially or perfluorinated C1-C6 alkoxy, partially or perdeuterated C1-C6 alkyl, partially or perdeuterated C1-C6 alkoxy;

[0022] - Each C6-C 12 aryl substituent on Z may be substituted by C1-C4 alkyl or halogen;

[0023] - G is selected such that the dipole moment of the compound G-phenyl is ≥1 D and ≤7 D;

[0024] - The electron transport layer further comprises a compound of formula (II) and / or a compound of formula (III),

[0025]

[0026] wherein in formula (II) and formula (III), respectively,

[0027] - Ar 1 independently selected from C6-C 19 aryl and C2-C 19 heteroaryl;

[0028] - Wherein Ar 1 may be substituted by one or two substituents independently selected from: C1-C6 alkyl, D, C1-C6 alkoxy, C3-C6 branched alkyl, C3-C6 cyclic alkyl, C3-C6 branched alkoxy, C3-C6 cyclic alkoxy, partially or perfluorinated C1-C6 alkyl, partially or perfluorinated C1-C6 alkoxy, partially or perdeuterated C1-C6 alkyl, partially or perdeuterated C1-C6 alkoxy, halogen, CN or PY(R 10 )2, where Y is selected from O, S or Se, preferably O, and R 10 independently selected from: C6-C 12 aryl, C3-C 12Heteroaryl, C1-C6 alkyl, C1-C6 alkoxy, partially or perfluorinated C1-C6 alkyl, partially or perfluorinated C1-C6 alkoxy, partially or perdeuterated C1-C6 alkyl, partially or perdeuterated C1-C6 alkoxy;

[0029] -Ar 3 Independently selected from C6-C 19 Aryl;

[0030] -Wherein Ar 3 May be substituted by one or two substituents independently selected from: C1-C6 alkyl, D, C1-C6 alkoxy, C3-C6 branched alkyl, C3-C6 cyclic alkyl, C3-C6 branched alkoxy, C3-C6 cyclic alkoxy, partially or perfluorinated C1-C6 alkyl, partially or perfluorinated C1-C6 alkoxy, partially or perdeuterated C1-C6 alkyl, partially or perdeuterated C1-C6 alkoxy, halogen, CN or PY(R 10 )2, wherein Y is selected from O, S or Se, preferably O, and R 10 Independently selected from C6-C 12 Aryl, C3-C 12 Heteroaryl, C1-C6 alkyl, C1-C6 alkoxy, partially or perfluorinated C1-C6 alkyl, partially or perfluorinated C1-C6 alkoxy, partially or perdeuterated C1-C6 alkyl, partially or perdeuterated C1-C6 alkoxy;

[0031] -ET is independently selected from C6-C 60 Aryl and C2-C 60 Heteroaryl;

[0032] -Wherein ET may be substituted by one or two substituents independently selected from: C6-C 20 Aryl, C3-C 20 Heteroaryl and C1-C6 alkyl, D, C1-C6 alkoxy, C3-C6 branched alkyl, C3-C6 cyclic alkyl, C3-C6 branched alkoxy, C3-C6 cyclic alkoxy, partially or perfluorinated C1-C6 alkyl, partially or perfluorinated C1-C6 alkoxy, partially or perdeuterated C1-C6 alkyl, partially or perdeuterated C1-C6 alkoxy, halogen, CN or PY(R 10 )2, wherein Y is selected from O, S or Se, preferably O, and R 10 Independently selected from C6-C 12 Aryl, C3-C 12Heteroaryl, C1-C6 alkyl, C1-C6 alkoxy, partially or perfluorinated C1-C6 alkyl, partially or perfluorinated C1-C6 alkoxy, partially or perdeuterated C1-C6 alkyl, partially or perdeuterated C1-C6 alkoxy;

[0033] - wherein each C6-C 20 aryl substituent on ET and each C3-C 20 heteroaryl substituent on ET may be substituted by C1-C4 alkyl or halogen;

[0034] -L 1 has formula (IIa),

[0035]

[0036] wherein L 1 is bonded to the triazine moiety in formula (II) at *1; and L 1 is bonded to Ar 1 at *2; and p is 0 or 1;

[0037] -L 2 has formula (IIb),

[0038]

[0039] wherein L 2 is bonded to the triazine moiety in formula (II) at *3; and L 2 is bonded to ET at *4; and

[0040] -L 3 has formula (IIIa.1) or (IIIa.2),

[0041]

[0042] wherein L 3 is bonded to the triazine moiety in formula (III) at *5; and L 3 is bonded to ET at *6.

[0043] The object is also achieved by a device comprising an organic light-emitting diode according to the invention, wherein the device is a display device or a lighting device.

[0044] The object is also achieved by a compound of formula (IV) or formula (V),

[0045]

[0046] wherein in formula (IV) and formula (V), respectively,

[0047] -Ar 4Selected from C6 to C 19 aryl and C2 to C 19 heteroaryl;

[0048] - wherein Ar 4 may be substituted by one or two substituents independently selected from: C1 to C6 alkyl, D, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cycloalkyl, C3 to C6 branched alkoxy, C3 to C6 cycloalkoxy, partially or fully fluorinated C1 to C6 alkyl, partially or fully fluorinated C1 to C6 alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy, halogen, CN or PY(R 10 )2, where Y is selected from O, S or Se, preferably O, and R 10 is independently selected from C6 to C 12 aryl, C3 to C 12 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, partially or fully fluorinated C1 to C6 alkyl, partially or fully fluorinated C1 to C6 alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy;

[0049] - Ar 5 is selected from C6 to C 19 aryl;

[0050] - wherein Ar 5 may be substituted by one or two substituents independently selected from: C1 to C6 alkyl, D, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cycloalkyl, C3 to C6 branched alkoxy, C3 to C6 cycloalkoxy, partially or fully fluorinated C1 to C6 alkyl, partially or fully fluorinated C1 to C6 alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy, halogen, CN or PY(R 10 )2, where Y is selected from O, S or Se, preferably O, and R 10 is independently selected from C6 to C 12 aryl, C3 to C 12 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, partially or fully fluorinated C1 to C6 alkyl, partially or fully fluorinated C1 to C6 alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy;

[0051] - ET' is selected from pyrazinyl, triphenylpyrazinyl, pyridine-anthryl, acridine, benzoacridine, dibenzoacridine, phenylanthryl and compounds of formula ET'-i,

[0052]

[0053] wherein R 1 to R 5 are independently H or phenyl, provided that at least two, preferably at least three, most preferably four of R 1 to R 5 are phenyl and the remaining R 1 to R 5 are H; and ET'-i is bonded to L 5 or R 6 at * respectively;

[0054] -L 4 has the formula (IVa),

[0055]

[0056] wherein L 4 is bonded to the triazine moiety in formula (IV) at *7; and L 4 is bonded to Ar 4 at *8; and p' is 0 or 1;

[0057] -L 5 has the formula (IVb),

[0058]

[0059] wherein L 5 is bonded to the triazine moiety in formula (IV) at *9; and L 5 is bonded to ET' at *10; and

[0060] -L 6 has the formula (Va.1) or (Va.2),

[0061]

[0062] wherein L 6 is bonded to the triazine moiety in formula (V) at *11; and L 6 is bonded to ET' at *12.

[0063] Compound of formula (I)

[0064] The electron transport layer contains a compound of formula (I),

[0065] (Ar 2 ) m -(Z k -G) n (I).

[0066] The electron transport layer may be composed of a mixture of a compound of formula (I), a compound of formula (II) and / or a compound of formula (III), provided that none of the other compounds is an electrical dopant. The electron transport layer may contain more than one compound of formula (I). The electron transport layer may be composed of a mixture of a compound of formula (I) and a compound of formula (II). Exemplary other electron transport matrix compounds that may be contained are disclosed hereinafter.

[0067] In the compound of formula (I), the group "Z" is a spacer moiety connecting (if present, i.e., when k>1) the groups Ar 2 and G. In the case where the compound of formula (I) contains more than one group (Z k -G), the groups may or may not independently contain the spacer Z.

[0068] In formula (I), m and n are independently 1 or 2. In formula (I), m and n can be 1.

[0069] In formula (I), k is independently 0, 1 or 2. In formula (I), k can be independently 1 or 2.

[0070] Ar 2 may be independently selected from C2 to C 39 heteroaryl and C6 to C 54 aryl, optionally C2 to C 36 heteroaryl and C6 to C 48 aryl, optionally C3 to C 30 heteroaryl and C6 to C 42 aryl, optionally C3 to C 27 heteroaryl and C6 to C 36 aryl, optionally C3 to C 24 heteroaryl and C6 to C 30 aryl and optionally C3 to C 21 heteroaryl and C6 to C 24 aryl.

[0071] Ar 2 may be independently selected from C2 to C 39 N-containing heteroaryl and C6 to C 54 aryl, optionally C2 to C 36 N-containing heteroaryl and C6 to C 48 aryl, optionally C3 to C 30 N-containing heteroaryl and C6 to C 42 aryl, optionally C3 to C 27 N-containing heteroaryl and C6 to C 36 aryl, optionally C3 to C 24 N-containing heteroaryl and C6 to C 30 aryl and optionally C3 to C21 Containing an N - heteroaryl and a C6 - C 24 aryl. In this regard, each N - heteroaryl may contain one or more N atoms as the only heteroatoms.

[0072] Ar 2 may contain at least two fused 5 - or 6 - membered rings.

[0073] Ar 2 may be independently selected from: pyridyl, triazinyl, 1,2 - diazinyl, 1,3 - diazinyl, 1,4 - diazinyl, quinazolinyl, benzoquinazolinyl, benzimidazolyl, quinolinyl, benzoquinolinyl, benzacridinyl, dibenzacridinyl, fluoranthenyl, anthryl, naphthyl, terphenylidene, phenanthrolinyl, and dinaphthofuranyl, which may be optionally substituted or unsubstituted.

[0074] Ar 2 may be independently selected from dibenzacridinyl, 1,3 - diazinyl, 1,4 - diazinyl, anthryl, triazinyl, phenanthrolinyl, terphenylidene, pyridyl, dinaphthofuranyl.

[0075] Ar 2 may be independently selected from one of the following groups:

[0076]

[0077] wherein the asterisk “*” represents the bonding position bonded to Z respectively.

[0078] In the case where Ar 2 is substituted, each substituent on Ar 2 may be independently selected from phenyl, naphthyl, optionally β - naphthyl, pyridyl, and biphenyl, which may be optionally substituted or unsubstituted.

[0079] In the case where Ar 2 is substituted, each substituent on Ar 2 may be independently selected from phenyl, pyridyl, and biphenyl, optionally biphenyl.

[0080] Z may be independently selected from C6 - C 24 aryl, or C6 - C 18 aryl, or C6 - C 12 aryl, which may be substituted or unsubstituted.

[0081] Z may be selected from benzylidene, naphthylidene, benzylidene - naphthylidene, biphenylidene, and terphenylidene, which may be optionally substituted or unsubstituted.

[0082] Z may be independently selected from one of the following groups:

[0083]

[0084] Among them, the bonding position that can freely select the bonding with Ar 2 and the G bond can be selected.

[0085] In the case where Z is substituted, each substituent on Z can be independently selected from phenyl and C1-C4 alkyl.

[0086] G is selected in such a way that the dipole moment of the compound G-phenyl is ≥1 D and ≤7 D, and the dipole moment is calculated using the hybrid functional B3LYP and the Gaussian 6-31G* basis set through the TURBOMOLE V6.5 program package. The unit of dipole moment "Debye" is abbreviated as the symbol "D". The inventors have found that it is advantageous if the compound of formula (I) contains a group with a specific polarity, i.e., a specific dipole moment within the above range or the following range. It has also been found that if the compound of formula (I) additionally contains other polar groups (second polar groups), it is still advantageous for the compound of formula (I) to contain such polar groups (first polar groups), which is suitable for balancing the dipole moment of the first polar group in such a way that the total dipole moment of the compound of formula (I) is relatively low. For example, in the case where the compound is a symmetric molecule containing the same first polar group and second polar group, the dipole moment can be 0 Debye. Therefore, the compound of formula (I) cannot be characterized as referring to the total dipole moment of the compound. Instead, it refers to an artificial compound containing a polar group "G" and a non-polar group "phenyl". In this regard, the dipole moment of a compound containing N atoms is given by the following formula:

[0087]

[0088] where q i and are the partial charge and position of atom i in the molecule. The dipole moment is determined by the semi-empirical molecular orbital method. As implemented in the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany), the geometry of the molecular structure is optimized using the hybrid functional B3LYP and the 6-31G* basis set in the gas phase. If more than one conformation is feasible, the conformation with the lowest total energy is selected to determine the bond length of the molecule. In this regard, the entire part G includes all possible substituents.

[0089] G can be selected such that the dipole moment of the compound G-phenyl is > 1 D, optionally ≥ 2 D, optionally ≥ 2.5 D, optionally ≥ 3 D, and optionally ≥ 3.5 D. G can be selected such that the dipole moment of the compound G-phenyl is ≤ 7 D, optionally ≤ 6.5 D, optionally ≤ 6 D, optionally ≤ 5.5 D, and optionally ≤ 5 D. If more than one conformational isomer of the compound G-phenyl is possible, the average dipole moment of the conformational isomers of G-phenyl is selected to be within this range. Conformational isomerism is a form of stereoisomerism in which the isomers can be interconverted only by the rotation of formally single bonds.

[0090] By selecting G such that the dipole moment of the compound G-phenyl lies within the above range, electron injection from adjacent different electron injection layers (EILs) is improved, and the voltage of the OLED device is reduced, and the cd / A efficiency of the OLED device is increased.

[0091] The exemplary compound "G-phenyl" is listed in Table 1 below, where the following part in the corresponding compound is specified as the "phenyl" part in "G- Phenyl ".

[0092]

[0093] Table 1:

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105] G may be selected from: dialkyloxyphosphino, diaryloxyphosphino, alkylaryloxyphosphino, diheteroaryloxyphosphino, arylheteroaryloxyphosphino, cyclic diaryloxyphosphino, phosphine oxide, aryl-containing phosphine oxide, heteroaryl-containing phosphine oxide, cyclic arylheteroaryloxyphosphino, cyclic heteroaryl-containing phosphine oxide, nitrile, benzonitrile, nicotinonitrile, amide, urea, and C2 to C 42 heteroaryl; wherein G may comprise one or more substituents attached to said group, wherein said one or more substituents are selected from C6 to C 18 aryl, C1 to C 10 alkyl, C2 to C 14 heteroaryl. In this regard, "cyclic" means that the phosphorus atom of the oxyphosphino, the corresponding phosphine oxide, the corresponding "P=O" group is part of a ring formed with the other part of said group G.

[0106] G may be selected from: di-C1 to C 10 alkyloxyphosphino, di-C6 to C 10 aryloxyphosphino, C 10 -C 42 diheteroaryloxyphosphino, C7-C 42 arylheteroaryloxyphosphino, C8-C 42 phosphine oxide, C8-C 42 aryl-containing phosphine oxide, C8-C 63 heteroaryl-containing phosphine oxide, C 12 -C 63 cyclic aryloxyphosphino, C7-C 42 cyclic arylheteroaryloxyphosphino, C7-C 42 cyclic heteroaryl-containing phosphine oxide; and C2 to C 39 heteroaryl, optionally C2 to C 35 heteroaryl, optionally C2 to C 32 heteroaryl, optionally C2 to C 29 heteroaryl, optionally C2 to C 25 heteroaryl; G may comprise one or more substituents attached to said group, wherein said one or more substituents are selected from C6 to C 12 aryl, C1 to C6 alkyl, C2 to C 11 heteroaryl.

[0107] G may be selected from: di-C1 to C4 alkyloxyphosphino, di-C6 to C 10 aryloxyphosphino, C 10 diheteroaryloxyphosphino, C7-C 25 arylheteroaryloxyphosphino, C8-C 42 phosphine oxide, C8-C 42 aryl-containing phosphine oxide, C8-C 24 heteroaryl-containing phosphine oxide, C 12 -C42 Cyclic arylphosphinyloxy, C7-C 25 Cyclic arylheteroarylphosphinyloxy, containing C7-C 25 Phosphine oxides of cyclic heteroaryl and C2-C 25 Heteroaryl; wherein the corresponding G may contain one or more substituents attached to said group, and wherein said one or more substituents are selected from C6 to C 10 Aryl, C1-C4 alkyl, C2-C5 heteroaryl.

[0108] G is selected from: dialkylphosphinyloxy, diarylphosphinyloxy, alkylarylphosphinyloxy, diheteroarylphosphinyloxy, arylheteroarylphosphinyloxy, cyclic diarylphosphinyloxy, phosphine oxide, aryl-containing phosphine oxide, heteroaryl-containing phosphine oxide, cyclic arylheteroarylphosphinyloxy, cyclic heteroaryl-containing phosphine oxide, nitrile, benzonitrile, nicotinonitrile, amido, ureido and C2-C 17 Heteroaryl; wherein the corresponding G may contain one or more substituents attached to said group, and wherein said one or more substituents are selected from phenyl, methyl, ethyl and pyridyl.

[0109] G may independently be selected from: dimethylphosphinyloxy, diphenylphosphinyloxy, nitrile, benzonitrile, nicotinonitrile, dihydrobenzimidazolone, diphenylpropyl, N,N-dimethylacetamide, amide, urea, imidazolyl, phenylbenzimidazolyl, ethylbenzimidazolyl, phenylbenzoquinolyl, phenylbenzimidazoquinolyl, pyridyl, bipyridyl, picolyl, dimethylpyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triphenyl-pyrazinyl, benzoquinolyl, phenanthrolyl, phenylphenanthrolyl, quinazolinyl, benzo Oxazolyl, benzimidazolyl, pyridyl-imidazopyridyl;

[0110]

[0111]

[0112]

[0113]

[0114] Wherein the asterisk "*" represents the bonding position.

[0115] G can be independently selected from: dimethyloxyphosphino, diphenyloxyphosphino, 2-phenyl-1H-benzo[d]imidazolyl, 2-ethyl-1H-benzo[d]imidazolyl, 2-phenylbenzo[h]quinolyl, pyridyl, 2,2'-bipyridyl, 5-phenylbenzo[4,5]imidazo[1,2-a]quinolyl, 9-phenyl-1,10-phenanthrolinyl, 2-quinazolinyl, 4-quinazolinyl, 4-phenyl-2-quinazolinyl, and (pyridin-2-yl)imidazo[1,5-a]pyridyl;

[0116]

[0117]

[0118]

[0119]

[0120]

[0121] wherein the asterisk "*" represents the bonding position.

[0122] The compound of formula (I) can be selected from Compounds B-1 to B-26 in Table 2 below.

[0123] Table 2:

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130] In one embodiment, the LUMO energy level of the compound of formula (I) can be in the range of -2.30 eV to -1.20 eV, preferably -2.10 eV to -1.28 eV, on an absolute scale with the vacuum energy level as zero, and the LUMO energy level is calculated by the TURBOMOLE V6.5 program package using the hybrid functional B3LYP and the Gaussian 6-31G* basis set.

[0131] In one embodiment, the compound of formula (I) contains a polar group "G".

[0132] The compound of formula (I) may not contain a P=O moiety. The compound of formula (I) may not contain P(=O)aryl₂. The compound of formula (I) may not contain P(=O)alkyl₂. The compound of formula (I) may not contain P(=O)Ph₂. The compound of formula (I) may not contain P(=O)(CH₃)₂. The compound of formula (I) may not contain R'P(=O)R", where R' and R" are linked to form a ring, i.e., it does not contain a cyclic phosphine oxide. The compound of formula (I) may not contain R'P(=O)R", where R' and R" are linked to form a 7-membered ring.

[0133] The compound of formula (I) may not contain two P=O moieties. The compound of formula (I) may not contain two P(=O)aryl₂. The compound of formula (I) may not contain two P(=O)alkyl₂. The compound of formula (I) may not contain two P(=O)Ph₂. The compound of formula (I) may not contain two P(=O)(CH₃)₂. The compound of formula (I) may not contain CN.

[0134] One or more of the following formulas may not be included within the scope of the compound of formula (I):

[0135]

[0136]

[0137] Compound of formula (II) and compound of formula (III)

[0138] The electron transport layer further contains a compound of formula (II) and / or a compound of formula (III),

[0139]

[0140] The electron transport layer may be composed of a mixture of a compound of formula (I), a compound of formula (II) and / or a compound of formula (III), and one or more other compounds, provided that the other compounds are not electrical dopants. The electron transport layer may contain more than one compound of formula (II). The electron transport layer may contain more than one compound of formula (III). The electron transport layer may contain one or more compounds of formula (II) and one or more compounds of formula (III). The electron transport layer may be composed of a mixture of a compound of formula (I) and a compound of formula (II) and / or (III). Exemplary other electron transport matrix compounds that may be included are disclosed below.

[0141] Ar 1 may be independently selected from C₆ to C 12 aryl and C₃ to C 10 heteroaryl. Ar 1 may be independently selected from C₆ to C 10 aryl and C₃ to C₅ heteroaryl. Ar 1 may be independently selected from C₆ and C₃ to C₅ heteroaryl.

[0142] Ar 1 may be independently selected from C6 to C 19 aryl. Ar 1 may be independently selected from C6 to C 12 aryl. Ar 1 may be independently selected from C6 to C 10 aryl. Ar 1 may be phenyl.

[0143] Ar 3 may be independently selected from C6 to C 12 aryl and C3 to C 10 heteroaryl. Ar 3 may be independently selected from C6 to C 10 aryl and C3 to C5 heteroaryl. Ar 3 may be independently selected from C6 and C3 to C5 heteroaryl.

[0144] Ar 3 may be independently selected from C6 to C 19 aryl. Ar 3 may be independently selected from C6 to C 12 aryl. Ar 3 may be independently selected from C6 to C 10 aryl. Ar 3 may be phenyl.

[0145] ET may be independently selected from C6 to C 54 aryl or C2 to C 39 heteroaryl, or C6 to C 48 aryl or C2 to C 36 heteroaryl, or C6 to C 42 aryl or C2 to C 36 heteroaryl, or C6 to C 36 aryl or C2 to C 30 heteroaryl, or C6 to C 30 aryl or C2 to C 24 heteroaryl, or C6 to C 20 aryl or C2 to C 22 heteroaryl, or C 12 to C 20 aryl or C7 to C 22 heteroaryl, or C 14 to C 20 aryl such as C 20 aryl or C 19 to C 22 heteroaryl.

[0146] ET can be independently selected from triphenylpyrazinyl, dibenzoacridinyl, pyridyl, anthryl, pyridylanthryl, phenylanthryl, and the compound of formula ET-i:

[0147]

[0148] wherein R 1 to R 5 are independently H or phenyl, provided that at least two, preferably at least three, and most preferably four of R 1 to R 5 are phenyl, and the remaining R 1 to R 5 are H; and ET-i is bonded to L 2 or L 3 at * respectively.

[0149] ET can be independently selected from the moieties of the following formula:

[0150]

[0151] wherein the corresponding moiety ET is bonded to L 2 or L 3 at "*" respectively.

[0152] L 1 has the formula (Iia),

[0153]

[0154] L 1 is bonded to the triazine moiety in formula (II) at *1 and to Ar 2 at *2, that is, the following connection is formed:

[0155]

[0156] p is 0 or 1.

[0157] In the case where p is 0, L 1 has the following formula:

[0158]

[0159] In the case where p is 1, L 1 has the following formula:

[0160]

[0161] p can be 0.

[0162] L 3 has the formula (IIIa.1) or (IIIa.2),

[0163]

[0164] L 3 is bonded to the triazine moiety in formula (III) at *5; and L 3 is bonded to ET at *6, i.e., the following linkage is formed (taking IIIa.1 as an example):

[0165]

[0166] In one embodiment, the electron transport layer comprises a compound of formula (I) and a compound of formula (II), and "p" in formula (IIa) is 0.

[0167] The compound of formula (II) and / or (III) may comprise 8 to 13 aromatic or heteroaromatic rings, optionally 8 to 11 aromatic or heteroaromatic rings, optionally 9 to 11 aromatic or heteroaromatic rings and optionally 9 to 10 aromatic or heteroaromatic rings.

[0168] The compound of formula (II) and / or (III) may comprise 8 to 13 aromatic or heteroaromatic rings, wherein 1 to 3 aromatic or heteroaromatic rings are N-containing rings; optionally comprise 8 to 11 aromatic or heteroaromatic rings, wherein 1 to 3 aromatic or heteroaromatic rings are N-containing rings; optionally comprise 9 to 11 aromatic or heteroaromatic rings, wherein 1 or 2 aromatic or heteroaromatic rings are N-containing rings; and optionally comprise 9 to 10 aromatic or heteroaromatic rings, wherein 1 or 2 aromatic or heteroaromatic rings are N-containing rings.

[0169] The compound of formula (II) and / or (III) may comprise 8 to 13 aromatic or heteroaromatic rings, wherein 6 to 10 aromatic or heteroaromatic rings are aryl rings; optionally comprise 8 to 11 aromatic or heteroaromatic rings, wherein 6 to 10 aromatic or heteroaromatic rings are aryl rings; optionally comprise 9 to 11 aromatic or heteroaromatic rings, wherein 7 to 9 aromatic or heteroaromatic rings are aryl rings; and optionally comprise 9 to 10 aromatic or heteroaromatic rings, wherein 7 to 9 aromatic or heteroaromatic rings are N-containing rings.

[0170] The ratio of aryl rings to N-containing rings in the compound of formula (II) and / or (III) may be from 10:1 to 3:1, such as from 9:1 to 3.5:1.

[0171] The LUMO of the compound of formula (II) and / or (III) may be in the range of -2.0 eV to -1.5 eV, or -1.9 eV to -1.6 eV, such as -1.86 eV to -1.69 eV.

[0172] The refractive index of the compound of formula (II) and / or (III) at a wavelength of 633 nm may be in the range of 1.5 to 2.0, or 1.6 to 1.9, or 1.7 to 1.8, such as 1.72 to 1.78.

[0173] The corresponding compound of formula (III) of formula (II) can be selected from compounds E-1 to E-9:

[0174]

[0175]

[0176]

[0177]

[0178] Exemplary embodiments

[0179] According to one embodiment, an organic light-emitting diode is provided, which comprises an anode, a cathode, a light-emitting layer, and an electron transport layer,

[0180] wherein

[0181] - the electron transport layer is disposed between the light-emitting layer and the cathode;

[0182] - the electron transport layer does not contain an electrical dopant;

[0183] - the electron transport layer contains a compound of formula (I),

[0184] (Ar 2 ) m -(Z k -G) n (I);

[0185] wherein in formula (I),

[0186] - m and n are independently 1 or 2;

[0187] - k is independently 0, 1, or 2;

[0188] - Ar 2 is independently selected from C3 to C 30 heteroaryl and C6 to C 42 aryl,

[0189] - wherein each Ar 2 can be substituted by one or two substituents, and the one or two substituents are independently selected from: C6 to C 12 aryl, C3 to C 11 heteroaryl, C1 to C6 alkyl, D, 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 fully fluorinated C1 to C6 alkyl, partially or fully fluorinated C1 to C6 alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy, halogen, CN, or PY(R10 ) 2, where Y is selected from O, S or Se, preferably O, and R 10 is independently selected from C6 to C 12 aryl, C3 to C 12 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy;

[0190] - wherein each C6 to C 2 aryl substituent on Ar 12 and each C3 to C 2 heteroaryl substituent on Ar 11 can be substituted by C1 to C4 alkyl or halogen;

[0191] - Z is independently selected from C6 to C 18 aryl,

[0192] - wherein each Z can be substituted by one or two substituents independently selected from: C6 to C 12 aryl and C1 to C6 alkyl, D, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cycloalkyl, C3 to C6 branched alkoxy, C3 to C6 cycloalkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy, halogen, CN or PY(R 10 ) 2, where Y is selected from O, S or Se, preferably O, and R 10 is independently selected from C6 to C 12 aryl, C3 to C 12 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy;

[0193] - wherein each C6 to C 12 aryl substituent on Z

[0194] - Select G such that the dipole moment of the compound G - phenyl is ≥ 2D and ≤ 6D;

[0195] - The electron transport layer further comprises a compound of formula (II) and / or a compound of formula (III),

[0196]

[0197] wherein in Formula (II) and Formula (III), respectively,

[0198] -Ar 1 is independently selected from C6-C 12 aryl and C3-C 10 heteroaryl;

[0199] -Ar 3 is independently selected from C6-C 12 aryl and C3-C 10 heteroaryl;

[0200] -ET is independently selected from C6-C 30 aryl or C2-C 24 heteroaryl;

[0201] -L 1 has Formula (IIa),

[0202]

[0203] wherein L 1 is bonded to the triazine moiety in Formula (II) at *1; and L 1 is bonded to Ar 1 at *2; and p is 0 or 1;

[0204] -L 2 has Formula (IIb),

[0205]

[0206] wherein L 2 is bonded to the triazine moiety in Formula (II) at *3; and L 2 is bonded to ET at *4; and

[0207] -L 3 has Formula (IIIa.1) or (IIIa.2),

[0208]

[0209] wherein L 3 is bonded to the triazine moiety in Formula (III) at *5; and L 3 is bonded to ET at *6.

[0210] According to one embodiment, there is provided an organic light-emitting diode comprising an anode, a cathode, a light-emitting layer, and an electron transport layer,

[0211] wherein

[0212] - the electron transport layer is disposed between the light-emitting layer and the cathode;

[0213] - The electron transport layer does not contain an electrical dopant;

[0214] - The electron transport layer contains a compound of formula (I),

[0215] (Ar 2 ) m -(Z k -G) n (I);

[0216] Wherein in formula (I),

[0217] - m and n are independently 1 or 2;

[0218] - k is independently 1 or 2;

[0219] - Ar 2 is independently selected from C3 to C 21 N-containing heteroaryl and C6 to C 24 aryl,

[0220] - Wherein each Ar 2 can be independently substituted by one or two substituents selected from phenyl, pyridyl and biphenyl, optionally biphenyl;

[0221] - Z is independently selected from phenylene, naphthylene, phenylene-naphthylene, biphenylene and terphenylenylene,

[0222] - Wherein each Z is independently substituted by one or two substituents selected from phenyl and C1 to C4 alkyl;

[0223] - G is selected from C2 to C 25 heteroaryl; G may contain one or more substituents attached to said group, wherein said one or more substituents are selected from C6 to C 12 aryl, C1 to C6 alkyl, C2 to C 11 heteroaryl;

[0224] - The electron transport layer further contains a compound of formula (II) and / or a compound of formula (III):

[0225]

[0226] Wherein in formula (II) and formula (III), respectively,

[0227] - Ar 1 is independently selected from C6 to C 19 aryl;

[0228] - Ar 3 is independently selected from C6 to C 19 aryl;

[0229] - ET is independently selected from C14 to C 30 An aryl such as C 20 to C 30 An aryl or C 19 to C 22 A heteroaryl;

[0230] -L 1 Having formula (IIa),

[0231]

[0232] wherein L 1 Is bonded to the triazine moiety in formula (II) at *1; and L 1 Is bonded to Ar 1 at *2; and p is 0 or 1;

[0233] -L 2 Having formula (IIb),

[0234]

[0235] wherein L 2 Is bonded to the triazine moiety in formula (II) at *3; and L 2 Is bonded to ET at *4; and

[0236] -L 3 Having formula (IIIa.1) or (IIIa.2),

[0237]

[0238] wherein L 3 Is bonded to the triazine moiety in formula (III) at *5; and L 3 Is bonded to ET at *6.

[0239] According to one embodiment, there is provided an organic light-emitting diode comprising an anode, a cathode, a light-emitting layer, and an electron transport layer,

[0240] wherein

[0241] - The electron transport layer is disposed between the light-emitting layer and the cathode;

[0242] - The electron transport layer does not contain an electrical dopant;

[0243] - The electron transport layer contains a compound of formula (I),

[0244] (Ar 2 ) m -(Z k -G) n (I);

[0245] Wherein in formula (I),

[0246] -m and n are independently 1 or 2;

[0247] -k is independently 1 or 2;

[0248] -Ar 2 is independently selected from dibenzoacridinyl, 1,3-diazinyl, 1,4-diazinyl, anthracenyl, triazinyl, phenanthrolinyl, terphenylidene, pyridyl, dinaphthofuranyl,

[0249] -wherein each Ar 2 may be independently substituted by one or two substituents selected from phenyl, pyridyl and biphenyl, optionally biphenyl;

[0250] -Z is independently selected from phenylene, naphthylene, phenylene-naphthylene, biphenylene and terphenylene,

[0251] -wherein each Z may be independently substituted by one or two substituents selected from phenyl and C1-C4 alkyl;

[0252] -G is selected from: dimethyloxyphosphino, diphenyloxyphosphino, nitrile, benzonitrile, nicotinonitrile, dihydrobenzimidazolone, diphenylpropyl, N,N-dimethylacetamide, amide, urea, imidazolyl, phenylbenzimidazolyl, ethylbenzimidazolyl, phenylbenzoquinolyl, phenylbenzimidazoquinolyl, pyridyl, bipyridyl, picolyl, dimethylpyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triphenylpyrazinyl, benzoquinolyl, phenanthrolinyl, phenylphenanthrolinyl and pyridyl-imidazopyridyl;

[0253] -The electron transport layer further comprises a compound of formula (II) and / or a compound of formula (III),

[0254]

[0255] wherein in formula (II) and formula (III), respectively,

[0256] -Ar 1 is phenyl;

[0257] -Ar 3 is phenyl;

[0258] -ET is independently selected from: triphenylpyrazinyl, dibenzoacridinyl, pyridyl, anthracenyl, pyridylanthracenyl, phenylanthracenyl and a compound of formula ET-i:

[0259]

[0260] wherein R 1 to R 5Independently H or phenyl, provided that R 1 to R 5 at least two, preferably at least three, most preferably four of which are phenyl, and the remaining R 1 to R 5 are H; and ET-i is bonded to L 2 or L 3 at *;

[0261] -L 1 has the formula (IIa),

[0262]

[0263] wherein L 1 is bonded to the triazine moiety in formula (II) at *1; and L 1 is bonded to Ar 1 at *2; and p is 0 or 1;

[0264] -L 2 has the formula (IIb),

[0265]

[0266] wherein L 2 is bonded to the triazine moiety in formula (II) at *3; and L 2 is bonded to ET at *4; and

[0267] -L 3 has the formula (IIIa.1) or (IIIa.2),

[0268]

[0269] wherein L 3 is bonded to the triazine moiety in formula (III) at *5; and L 3 is bonded to ET at *6.

[0270] Compound of formula (IV) or (V)

[0271] The present invention also relates to compounds having formula (IV) or formula (V):

[0272]

[0273] Ar 4 can be independently selected from C6 to C 12 aryl and C3 to C 10 heteroaryl. Ar 4 can be independently selected from C6 to C 10 aryl and C3 to C5 heteroaryl. Ar 4It may be independently selected from C6 and C3-C5 heteroaryl.

[0274] Ar 4 It may be independently selected from C6-C 19 aryl. Ar 5 It may be independently selected from C6-C 12 aryl. Ar 4 It may be independently selected from C6-C 10 aryl. Ar 4 It may be phenyl.

[0275] Ar 5 It may be independently selected from C6-C 12 aryl and C3-C 10 heteroaryl. Ar 5 It may be independently selected from C6-C 10 aryl and C3-C5 heteroaryl. Ar 5 It may be independently selected from C6 and C3-C5 heteroaryl.

[0276] Ar 5 It may be independently selected from C6-C 19 aryl. Ar 5 It may be independently selected from C6-C 12 aryl. Ar 5 It may be independently selected from C6-C 10 aryl. Ar 5 It may be phenyl.

[0277] ET' is selected from triphenylpyrazinyl, pyridine-anthryl, acridine, benzacridine, dibenzacridine, phenylanthryl and a compound of formula ET'-i:

[0278]

[0279] wherein R 1 to R 5 are independently H or phenyl, provided that at least two, preferably at least three, most preferably four of R 1 to R 5 are phenyl, and the remaining R 1 to R 5 are H; and ET'-i is bonded to L 5 or R 6 at *.

[0280] ET' may be selected from triphenylpyrazinyl, pyridine-anthryl, acridine, benzacridine and dibenzacridine.

[0281] ET may be independently selected from moieties of the following formula:

[0282]

[0283] wherein the corresponding group ET' is bonded to L at "*". 5 or L 6 by a bond.

[0284] ET can be independently selected from the moieties of the following formulae:

[0285]

[0286] wherein the corresponding group ET' is bonded to L at "*". 5 or L 6 by a bond.

[0287] L 4 has the formula (IVa):

[0288]

[0289] L 4 is bonded to the triazine moiety in formula (IV) at *7 and to Ar 4 by a bond, i.e., forming the following linkage:

[0290]

[0291] p' is 0 or 1.

[0292] In the case where p' is 0, L 4 has the following formula:

[0293]

[0294] In the case where p' is 1, L 4 has the following formula:

[0295]

[0296] p' can be 0.

[0297] L 6 has the formula (Va.1) or (Va.2):

[0298]

[0299] L 6 is bonded to the triazine moiety in formula (V) at *11; and L 6 is bonded to ET' at *12, i.e., forming the following linkage (taking Va.1 as an example):

[0300]

[0301] In one embodiment, the electron transport layer comprises a compound of formula (IV), and "p'" in formula (IVa) is 0.

[0302] The compounds of formula (IV) and / or (V) may contain from 8 to 13 aromatic or heteroaromatic rings, optionally from 8 to 11 aromatic or heteroaromatic rings, optionally from 9 to 11 aromatic or heteroaromatic rings, and optionally from 9 to 10 aromatic or heteroaromatic rings.

[0303] The compounds of formula (IV) and / or (V) may contain: from 8 to 13 aromatic or heteroaromatic rings, wherein 1 to 3 aromatic or heteroaromatic rings are N-containing rings; optionally from 8 to 11 aromatic or heteroaromatic rings, wherein 1 to 3 aromatic or heteroaromatic rings are N-containing rings; optionally from 9 to 11 aromatic or heteroaromatic rings, wherein 1 or 2 aromatic or heteroaromatic rings are N-containing rings; and optionally from 9 to 10 aromatic or heteroaromatic rings, wherein 1 or 2 aromatic or heteroaromatic rings are N-containing rings.

[0304] The compounds of formula (IV) and / or (V) may contain: from 8 to 13 aromatic or heteroaromatic rings, wherein 6 to 10 aromatic or heteroaromatic rings are aryl rings; optionally from 8 to 11 aromatic or heteroaromatic rings, wherein 6 to 10 aromatic or heteroaromatic rings are aryl rings; optionally from 9 to 11 aromatic or heteroaromatic rings, wherein 7 to 9 aromatic or heteroaromatic rings are aryl rings; and optionally from 9 to 10 aromatic or heteroaromatic rings, wherein 7 to 9 aromatic or heteroaromatic rings are N-containing rings.

[0305] The ratio of aryl rings to N-containing rings in the compounds of formula (IV) and / or (V) may be from 10:1 to 3:1, such as from 9:1 to 3.5:1.

[0306] The LUMO of the compounds of formula (IV) and / or (V) may be in the range of -2.0 eV to -1.5 eV, or -1.9 eV to -1.6 eV, such as -1.86 eV to -1.69 eV.

[0307] When measured as a single layer composed of the corresponding compounds of formula (IV) and / or (V) shown in Table 1, the refractive index of the compounds of formula (IV) and / or (V) at a wavelength of 633 nm may be in the range of 1.5 to 2.0, or 1.6 to 1.9, or 1.7 to 1.8, such as 1.72 to 1.78.

[0308] When measured as a single layer containing the corresponding compounds of formula (II) and / or formula (III) shown in Table 1, the refractive index of the electron transport layer containing the compounds of formula (II) and / or formula (III) at a wavelength of 633 nm may be in the range of 1.5 to 2.0, or 1.6 to 1.9, or 1.7 to 1.8, such as 1.70 to 1.78.

[0309] The compounds of formula (IV), the corresponding compounds of formula (V) may be selected from Compounds E-1, E-2, E-4 and E-7:

[0310]

[0311]

[0312] Electron transport layer

[0313] The electron transport layer does not contain an electrical dopant, such as an n-type dopant, especially a redox n-type dopant. The term "does not contain" does not exclude impurities in this regard. The impurities do not have a technical effect for the purposes achieved by the present invention. During processing, impurities are not deliberately added to the layer.

[0314] The term "does not contain" a compound means that such a compound is not deliberately added to the layer during processing. An electrical dopant, especially an n-type dopant, should be understood as a compound as described below: if it is embedded in an electron transport matrix, it can improve the electronic properties of the resulting organic material compared to the pure matrix under the same physical conditions, especially in terms of electron injection and / or electron conductivity.

[0315] In the context of the present invention, "embedded in the electron transport matrix" means being uniformly mixed with the electron transport matrix.

[0316] The electrical dopants referred to herein are particularly selected from elemental metals, metal salts, metal complexes, and organic radicals.

[0317] In one embodiment, the electrical dopant is selected from alkali metal salts and alkali metal complexes; preferably selected from lithium salts and lithium organic complexes; more preferably selected from lithium halides and lithium organic chelates; still more preferably selected from lithium fluoride, lithium quinolate, lithium borate, lithium phenolate, lithium pyridinolate, or a lithium complex having a Schiff base ligand; most preferably,

[0318] - The lithium complex has formula II, III, or IV:

[0319]

[0320] where

[0321] A1 to A6 are the same or independently selected from CH, CR, N, O;

[0322] R is the same or independently selected from hydrogen, halogen, an alkyl or aryl or heteroaryl having 1 to 20 carbon atoms; more preferably A1 to A6 are CH,

[0323] - The organic ligand of the borate anion is a tetrakis(1H-pyrazol-1-yl)borate anion,

[0324] - The phenolate anion is 2-(pyridin-2-yl)phenolate anion, 2-(diphenylphosphoryl)phenolate anion, imidazolophenolate anion, 2-(pyridin-2-yl)phenolate anion or 2-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenolate anion,

[0325] - The pyridinol anion is 2-(diphenylphosphoryl)pyridin-3-olate anion,

[0326] - The lithium Schiff base has structure 100, 101, 102 or 103:

[0327]

[0328] According to an embodiment of the present invention, the electron transport layer of the present invention does not contain a lithium organic complex or does not contain lithium 8-hydroxyquinoline (=LiQ).

[0329] According to an embodiment of the present invention, the electron transport layer does not contain a metal, and the metal is preferably selected from alkali metals, alkaline earth metals, rare earth metals and metals Ti, V, Cr and Mn in the first transition period, especially selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sm, Eu, Tm, Yb; more preferably selected from Li, Na, K, Rb, Cs, Mg and Yb, still more preferably selected from Li, Na, Cs and Yb, and most preferably selected from Li, Na and Yb.

[0330] The most practical benchmark for measuring the strength of an n-dopant is its redox potential value. There is no particular limitation in terms of the negative degree of the redox potential.

[0331] The reduction potential of an electron transport matrix commonly used in organic semiconductors, when measured by cyclic voltammetry with respect to the ferrocene / ferrocenium reference redox couple, is generally in the range of about -0.8V to about -3.1V; the practical applicable range of the redox potential of an n-type dopant capable of effectively n-doping this matrix is in a slightly wider range from about -0.5 to about -3.3V.

[0332] The measurement of the redox potential is actually carried out on the corresponding redox couple composed of the reduced state and the oxidized state of the same compound.

[0333] In the case where the n-type dopant is a neutral metal complex and / or a neutral organic radical, the measurement of its redox potential is actually carried out on the redox couple formed by:

[0334] (i) a neutral metal complex and its cation radical formed by extracting one electron from the neutral metal complex; or

[0335] (ii) A neutral organic radical and its cation formed by extracting an electron from the neutral organic radical.

[0336] Preferably, for the corresponding redox couple consisting of the following, if measured by cyclic voltammetry relative to the ferrocene / ferrocenium reference redox couple, the redox potential of the neutral metal complex and / or the neutral organic radical may have a value more negative than -0.5 V, preferably more negative than -1.2 V, more preferably more negative than -1.7 V, still more preferably more negative than -2.1 V, and most preferably more negative than -2.5 V:

[0337] (i) A neutral metal complex and its cation radical formed by extracting an electron from the neutral metal complex; or

[0338] (ii) A neutral organic radical and its cation formed by extracting an electron from the neutral organic radical.

[0339] In a preferred embodiment, the redox potential of the n-dopant is between a value approximately 0.5 V more positive than the reduction potential value of the selected electron transport matrix and a value approximately 0.5 V more negative than it.

[0340] The neutral metal complex suitable as an n-type dopant can be, for example, a strongly reducing complex of certain transition metals in a low oxidation state. As described in more detail in WO2005 / 086251, particularly strong n-type dopants can be selected, for example, from Cr(II), Mo(II), and / or W(II) guanidine complexes such as W2(hpp)4.

[0341] As described in more detail in EP 1 837 926 B1, WO2007 / 107306, or WO2007 / 107356, the neutral organic radical suitable as an n-type dopant can be, for example, an organic radical generated by supplying additional energy from its stable dimer, oligomer, or polymer. An elemental metal should be understood to be in the state of a pure metal, a metal alloy, or in the state of free atoms or metal clusters. It can be understood that a metal deposited by vacuum thermal evaporation from a metal phase, such as from a pure bulk metal, volatilizes in its elemental form. It should also be understood that if the volatilized elemental metal is deposited together with a covalent matrix, the metal atoms and / or clusters are embedded in the covalent matrix. In other words, it can be understood that any metal-doped covalent material prepared by vacuum thermal evaporation contains at least partially the metal in its elemental form.

[0342] For use in consumer electronics products, only metals containing stable nuclides or nuclides with a very long radioactive decay half-life are applicable. As an acceptable level of nuclear stability, the nuclear stability of natural potassium can be adopted.

[0343] In one embodiment, the electrical dopant may be selected from electropositive metals, and the electropositive metals are selected from: alkali metals; alkaline earth metals; rare earth metals; and metals Ti, V, Cr, and Mn in the first transition period. Preferably, the n-dopant may be selected from: Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sm, Eu, Tm, Yb; more preferably selected from Li, Na, K, Rb, Cs, Mg, and Yb, still more preferably selected from Li, Na, Cs, and Yb, and most preferably selected from Li, Na, and Yb.

[0344] Organic light emitting diode

[0345] The organic light-emitting layer may further include a hole-blocking layer, where the hole-blocking layer is disposed between the light-emitting layer and the electron-transporting layer. The hole-blocking layer may also be referred to as an auxiliary electron-transporting layer (a-ETL).

[0346] The hole-blocking layer may be in direct contact with the electron-transporting layer. The hole-blocking layer may be in direct contact with the light-emitting layer. The hole-blocking layer may be sandwiched between and in contact with the light-emitting layer and the electron-transporting layer.

[0347] The organic light-emitting diode may further include an electron-injecting layer, where the electron-injecting layer is disposed between the cathode and the electron-transporting layer, and the electron-injecting layer may be in direct contact with the electron-transporting layer. The electron-injecting layer may be in direct contact with the cathode. The electron-injecting layer may be sandwiched between and in contact with the electron-transporting layer and the cathode.

[0348] The electron-injecting layer may not include the compound of formula (I). The electron-injecting layer may not include the compound of formula (II). The electron-injecting layer may not include the compound of formula (III). The electron-injecting layer may not include any one of the compounds of formula (I) to (III).

[0349] The electron-injecting layer may include a first electron-injecting sub-layer and a second electron-injecting sub-layer, where the first electron-injecting sub-layer and the second electron-injecting sub-layer are in direct contact with each other.

[0350] The first electron-injecting sub-layer may be in direct contact with the electron-transporting layer, and the first electron-injecting sub-layer may include: a metal salt or a metal complex, preferably a lithium salt or a lithium organic complex; more preferably a compound selected from lithium halides and lithium organic chelates; still more preferably selected from lithium fluoride, lithium quinolate, lithium borate, lithium phenolate, lithium pyridinolate, or a lithium complex having a Schiff base ligand; most preferably,

[0351] - the lithium complex has formula II, III, or IV:

[0352]

[0353] where

[0354] A1 to A6 are the same or independent and are each selected from CH, CR, N, O;

[0355] R is the same or independent and is each selected from hydrogen, halogen, an alkyl, aryl or heteroaryl group having 1 to 20 carbon atoms; more preferably, A1 to A6 are CH,

[0356] - The borate anion-based organic ligand is a tetrakis(1H-pyrazol-1-yl)borate anion,

[0357] - The phenolate anion is a 2-(pyridin-2-yl)phenolate anion, 2-(diphenylphosphoryl)phenolate anion, imidazolophenolate anion, 2-(pyridin-2-yl)phenolate anion or 2-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenolate anion,

[0358] - The pyridinol anion is a 2-(diphenylphosphoryl)pyridin-3-ol anion,

[0359] - The lithium Schiff base has structures 100, 101, 102 or 103:

[0360]

[0361] Preferably, the first electron injection sublayer contains lithium 8-hydroxyquinoline (=LiQ).

[0362] The second electron injection sublayer contains a metal selected from alkali metals, alkaline earth metals and rare earth metals. Preferably, the metal can be selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sm, Eu, Tm, Yb; more preferably selected from Li, Na, K, Rb, Cs, Mg and Yb, still more preferably selected from Li, Na, Cs and Yb, most preferably selected from Li, Na and Yb, and most preferably Yb.

[0363] The second electron injection sublayer can be in direct contact with the cathode.

[0364] According to the present invention, the organic light-emitting diode may further include other layers in addition to the layers mentioned above. Next, exemplary embodiments of each layer will be described:

[0365] Substrate

[0366] The substrate can be any substrate commonly used for manufacturing electronic devices such as organic light-emitting diodes. If light is to be emitted through the substrate, the substrate should be a transparent or translucent material, such as a glass substrate or a transparent plastic substrate. If light is to be emitted through the top surface, the substrate can be either a transparent material or an opaque material, such as a glass substrate, a plastic substrate, a metal substrate or a silicon substrate.

[0367] Anode electrode

[0368] Either the first electrode or the second electrode included in the organic electronic device of the present invention can be an anode electrode. The anode electrode can be formed by depositing or sputtering a material for forming the anode electrode. The material for forming the anode electrode can be a high work function material, which helps hole injection. The anode material can also be selected from low work function materials (i.e., aluminum). The anode electrode can be a transparent or reflective electrode. Transparent conductive oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), aluminum zinc oxide (AlZO), and zinc oxide (ZnO) can be used to form the anode electrode. The anode electrode can also be formed using a metal or metal alloy, and the metal is usually silver (Ag), gold (Au).

[0369] Hole injection layer

[0370] The hole injection layer (HIL) can be formed on the anode electrode by vacuum deposition, spin coating, printing, casting, slot die coating, Langmuir-Blodgett (LB) deposition, etc. When forming the HIL by vacuum deposition, the deposition conditions can vary depending on the compound used to form the HIL and the desired structure and thermal properties of the HIL. However, generally, the deposition conditions for vacuum deposition can include a deposition temperature of 100 °C to 500 °C, a pressure of 10 -8 to 10 -3 torr (1 torr is equal to 133.322 Pa), and a deposition rate of 0.1 nm / second to 10 nm / second.

[0371] When forming the HIL by spin coating or printing, the coating conditions can vary depending on the compound used to form the HIL and the desired structure and thermal properties of the HIL. For example, the coating conditions can include a coating speed of about 2000 rpm to about 5000 rpm and a heat treatment temperature of about 80 °C to about 200 °C. After coating, heat treatment is performed to remove the solvent.

[0372] The HIL can be formed from any compound commonly used to form the HIL. Examples of compounds that can be used to form the HIL include phthalocyanine compounds such as copper phthalocyanine (CuPc), 4,4',4”-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA), TDATA, 2T-NATA, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), and polyaniline / poly(4-styrenesulfonate) (PANI / PSS).

[0373] The HIL may contain or consist of a p-type dopant, and the p-type dopant may be selected from, but not limited to: tetrafluoro-tetracyanoquinodimethane (F4TCNQ), 2,2'-(perfluoronaphthalene-2,6-diylidene) dipropanedinitrile, or 2,2',2''-(cyclopropane-1,2,3-triylidene) tris(2-(p-cyanotetrafluorophenyl)acetonitrile). The HIL may be selected from hole-transporting matrix compounds doped with a p-type dopant. Typical examples of known doped hole-transporting materials are: copper phthalocyanine (CuPc) doped with tetrafluoro-tetracyanoquinodimethane (F4TCNQ), the HOMO energy level of the copper phthalocyanine (CuPc) being about -5.2 eV and the LUMO energy level of the tetrafluoro-tetracyanoquinodimethane (F4TCNQ) being about -5.2 eV; zinc phthalocyanine (ZnPc) doped with F4TCNQ (HOMO = -5.2 eV); α-NPD (N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-benzidine) doped with F4TCNQ; α-NPD doped with 2,2'-(perfluoronaphthalene-2,6-diylidene) dipropanedinitrile. The concentration of the p-type dopant may be selected from 1 wt% to 20 wt%, more preferably from 3 wt% to 10 wt%.

[0374] The thickness of the HIL may be in the range of about 1 nm to about 100 nm, and for example in the range of about 1 nm to about 25 nm. When the thickness of the HIL is in this range, the HIL may have excellent hole injection characteristics without causing substantial damage to the driving voltage.

[0375] Hole transport layer

[0376] 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, etc. When the HTL is formed by vacuum deposition or spin coating, the deposition and coating conditions may be similar to those for forming the HIL. However, the vacuum or solution deposition conditions may vary depending on the compound used to form the HTL.

[0377] The HTL can be formed from any compound commonly used to form an HTL. For example, compounds that can be suitably used are disclosed in Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, pp. 953 - 1010 and are incorporated herein by reference. Examples of compounds that can be used to form the HTL are: carbazole derivatives such as N - phenylcarbazole or polyvinylcarbazole; benzidine derivatives such as N,N'-bis(3 - methylphenyl)-N,N'-diphenyl-[1,1 - biphenyl]-4,4'-diamine (TPD) or N,N'-bis(naphthalen - 1 - yl)-N,N'-diphenylbenzidine (α - NPD); and triphenylamine compounds such as 4,4',4”-tris(N - carbazolyl)triphenylamine (TCTA). Among these compounds, TCTA can transport holes and inhibit exciton diffusion into the EML.

[0378] The thickness of the HTL can 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 160 nm, further about 100 nm to about 160 nm, further about 120 nm to about 140 nm. The preferred thickness of the HTL can be 170 nm to 200 nm.

[0379] When the thickness of the HTL is within this range, the HTL can have excellent hole - transporting properties without causing substantial damage to the driving voltage.

[0380] Electron blocking layer

[0381] The function of the electron blocking layer (EBL) is to prevent electrons from transferring from the light - emitting layer to the hole - transporting layer, thereby confining electrons in the light - emitting layer. Thereby, the efficiency, operating voltage, and / or lifetime are improved. Generally, the electron blocking layer contains a triarylamine compound. The LUMO energy level of the triarylamine compound is closer to the vacuum energy level than the LUMO energy level of the hole - transporting layer. Compared with the HOMO energy level of the hole - transporting layer, the electron blocking layer can have a HOMO energy level that is further from the vacuum energy level. The thickness of the electron blocking layer can be selected between 2 nm and 20 nm.

[0382] If the electron blocking layer has a high triplet energy level, it can also be described as a triplet control layer.

[0383] If a phosphorescent green or blue light-emitting layer is used, the function of the triplet control layer is to reduce the quenching of triplets. Thereby, a higher luminous efficiency derived from the phosphorescent light-emitting layer can be achieved. The triplet control layer is selected from triarylamine compounds having a triplet energy level higher than that of the phosphorescent emitter in the adjacent light-emitting layer. Suitable compounds for the triplet control layer, in particular triarylamine compounds, are described in EP 2 722 908 A1.

[0384] Emission layer (EML)

[0385] The EML can be formed on the HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When vacuum deposition or spin coating is used to form the EML, the deposition and coating conditions can be similar to those for forming the HIL. However, the deposition and coating conditions can vary depending on the compound used to form the EML.

[0386] The emission layer may not contain the compound of formula (I).

[0387] The emission layer (EML) can be formed by a combination of a host and a luminescent dopant. Examples of the host are Alq3, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,10-bis(naphthalen-2-yl)anthracene (ADN), 4,4',4”-tris(carbazol-9-yl)-triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-di-2-naphthylanthracene (TBADN), distyrylarylene (DSA), and bis(2-(2-hydroxyphenyl)benzothiazole)zinc (Zn(BTZ)2).

[0388] The luminescent dopant can be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters that emit light via the thermally activated delayed fluorescence (TADF) mechanism can be preferred because of their higher efficiency. The emitter can be a small molecule or a polymer.

[0389] Examples of red luminescent dopants are PtOEP, Ir(piq)3, and Btp2Ir(acac), but are not limited thereto. These compounds are phosphorescent emitters; however, fluorescent red luminescent dopants can also be used.

[0390] Examples of phosphorescent green luminescent dopants are Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2(acac), Ir(mpyp)3.

[0391] Examples of phosphorescent blue light-emitting dopants are: F2Irpic, (F2ppy)2Ir(tmd), and Ir(dfppz)3, as well as truxene. 4,4'-Bis(4-diphenylaminostyryl)biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butylperylene (TBPe) are examples of fluorescent blue light-emitting dopants.

[0392] Based on 100 parts by weight of the host, the amount of the light-emitting dopant can be in the range of about 0.01 part by weight to about 50 parts by weight. Alternatively, the light-emitting layer can be composed of a light-emitting polymer. The EML can have a thickness of about 10 nm to about 100 nm, for example, about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML can have excellent light emission without causing substantial damage to the driving voltage.

[0393] Hole blocking layer (HBL)

[0394] The hole blocking layer (HBL) can be formed on the EML by using vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. to prevent holes from diffusing into the ETL. When the EML contains a phosphorescent dopant, the HBL can also have a triplet exciton blocking function. The hole blocking layer can be the organic semiconductor layer of the present invention, and the organic semiconductor layer contains the compound represented by the general formula (I) defined above or is composed of the compound represented by the general formula (I) defined above.

[0395] The HBL can also be named as an auxiliary ETL or a-ETL.

[0396] When the HBL is formed by using vacuum deposition or spin coating, the deposition and coating conditions can be similar to those for forming the HIL. However, the deposition and coating conditions can vary with the compound used to form the HBL. Any compound commonly used to form the HBL can be used. Examples of the compound used to form the HBL include diazole derivatives, triazole derivatives, and phenanthroline derivatives.

[0397] The thickness of the HBL can be in the range of about 5 nm to about 100 nm, for example, about 10 nm to about 30 nm. When the thickness of the HBL is within this range, the HBL can have excellent hole blocking performance without causing substantial damage to the driving voltage.

[0398] The hole blocking layer can also be described as a-ETL or auxiliary ETL.

[0399] According to one embodiment, the hole blocking layer is disposed between at least one light-emitting layer and an electron transport layer, and the electron transport layer contains a compound of formula (I) and a compound of formula (II) and / or a compound of formula (III).

[0400] Electron Transport Layer (ETL)

[0401] An OLED according to the present invention includes one or more electron transport layers (ETLs). According to the present invention, at least one electron transport layer is the electron transport layer of the present invention comprising a compound of formula (I), a compound of formula (II), and / or a compound of formula (III) as defined herein.

[0402] According to various embodiments, an OLED may include an electron transport layer or a stack of electron transport layers, the stack of electron transport layers comprising at least a first electron transport layer and at least a second electron transport layer.

[0403] By appropriately adjusting the energy levels of specific ETL layers, the injection and transport of electrons can be controlled, and holes can be effectively blocked. Thus, the OLED can have a long lifespan.

[0404] In addition to comprising a compound of formula (I), a compound of formula (II), and / or a compound of formula (III), the electron transport layer may further comprise other ETM materials known in the art. Similarly, the electron transport layer may comprise a compound of formula (I), a compound of formula (II), and / or a compound of formula (III) as the only electron transport matrix material. In the case where the organic electronic device of the present invention includes more than one electron transport layer, the compound of formula (I), the compound of formula (II), and / or the compound of formula (III) may be included in only one electron transport layer, included in more than one electron transport layer, or included in all electron transport layers.

[0405] Electron Injection Layer (EIL)

[0406] On the ETL, preferably directly on the electron transport layer, an optional EIL may be formed, which promotes the injection of electrons from the cathode. Examples of materials for forming the EIL include lithium 8-hydroxyquinoline (LiQ), LiF, NaCl, CsF, Li2O, BaO, Li, Ca, Ba, Yb, Mg known in the art. The deposition and coating conditions for forming the EIL are similar to those for forming the HIL, but the deposition and coating conditions may vary with the materials used to form the EIL.

[0407] The thickness of the EIL may be in the range of about 0.1 nm to about 10 nm, for example, in the range of about 0.5 nm to about 9 nm. When the thickness of the EIL is within this range, the EIL can have satisfactory electron injection performance without substantially damaging the driving voltage.

[0408] Charge Generation Layer (CGL)

[0409] The charge generation layer (CGL) may comprise a p-type charge generation layer (p-CGL) and an n-type charge generation layer (n-CGL). An intermediate layer may be disposed between the p-CGL and the n-CGL.

[0410] Typically, the charge generation layer is a p-n junction that connects an n-type charge generation layer (electron generation layer) and a hole generation layer. Electrons are generated on the n-side of the p-n junction and are injected into the layer adjacent in the anode direction. Similarly, holes are generated on the p-side of the p-n junction and are injected into the layer adjacent in the cathode direction.

[0411] The charge generation layer is used in tandem and stacked devices, such as in a tandem or stacked OLED that includes two or more light-emitting layers between two electrodes. In a tandem or stacked OLED that includes two light-emitting layers, the n-type charge generation layer provides electrons to the first light-emitting layer disposed near the anode, while the hole generation layer provides holes to the second light-emitting layer disposed between the first light-emitting layer and the cathode.

[0412] Suitable matrix materials for the hole generation layer can be materials that are conventionally used as hole injection and / or hole transport matrix materials. Moreover, p-type dopants for the hole generation layer can employ conventional materials. For example, the p-type dopant can be one selected from the following: tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), derivatives of tetracyanoquinodimethane, annulene derivatives, iodine, FeCl3, FeF3, and SbCl5. In addition, the host can be one selected from the following: N,N'-bis(naphthalen-1-yl)-N,N-diphenylbenzidine (NPB), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1-biphenyl-4,4'-diamine (TPD), and N,N',N'-tetranaphthylbenzidine (TNB). The p-type charge generation layer can be composed of CNHAT.

[0413] The n-type charge generation layer can be a layer containing a compound of formula (I). The n-type charge generation layer can be a layer of a pure n-type dopant such as a metal, or can be composed of an organic matrix material doped with an n-type dopant. In one embodiment, the n-type dopant can be an alkali metal, an alkali metal compound, an alkaline earth metal, an alkaline earth metal compound, a transition metal, a transition metal compound, or a rare earth metal. In another embodiment, the metal can be one selected from the following: Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Sm, Eu, Tb, Dy, and Yb. More specifically, the n-type dopant can be one selected from the following: Li, Cs, K, Rb, Mg, Na, Ca, Sr, Eu, and Yb. Suitable matrix materials for the electron generation layer can be materials that are conventionally used as matrix materials for electron injection or electron transport layers. The matrix material can be, for example, one selected from the following: triazine compounds, hydroxyquinoline derivatives such as tris(8-hydroxyquinoline)aluminum, indole derivatives, and silafluorene derivatives.

[0414] The hole generation layer is arranged to be in direct contact with the n-type charge generation layer.

[0415] According to one aspect of the present invention, the electron transport layer is arranged between the first light-emitting layer and the second light-emitting layer.

[0416] According to one aspect of the present invention, the electron transport layer containing the compound of formula (I) and the compound of formula (II) and / or the compound of formula (III) is arranged between the first light-emitting layer and the second light-emitting layer, and the electron transport layer containing the compound of formula (I) and the compound of formula (II) and / or the compound of formula (III) is arranged between the second light-emitting layer and the cathode.

[0417] According to one aspect of the present invention, there is provided an organic light-emitting diode (OLED) comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer containing the compound of formula (I) and the compound of formula (II) and / or the compound of formula (III), and a cathode electrode.

[0418] According to another aspect of the present invention, there is provided an OLED comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer containing the compound of formula (I) and the compound of formula (II) and / or the compound of formula (III), and a cathode electrode.

[0419] According to another aspect of the present invention, there is provided an OLED comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer containing the compound of formula (I) and the compound of formula (II) and / or the compound of formula (III), an electron injection layer, and a cathode electrode.

[0420] According to various embodiments of the present invention, the OLED layers can be arranged between the above layers, on the substrate or on the top electrode.

[0421] According to one aspect, an OLED can include the following layer structure: a substrate disposed adjacent to an anode electrode, the anode disposed adjacent to a first hole injection layer, the first hole injection layer disposed adjacent to a first hole transport layer, the first hole transport layer disposed adjacent to a first electron blocking layer, the first electron blocking layer disposed adjacent to a first light-emitting layer, the first light-emitting layer disposed adjacent to a first electron transport layer, the first electron transport layer disposed adjacent to an n-type charge generation layer, the n-type charge generation layer disposed adjacent to a hole generation layer, the hole generation layer disposed adjacent to a second hole transport layer, the second hole transport layer disposed adjacent to a second electron blocking layer, the second electron blocking layer disposed adjacent to a second light-emitting layer, and an optional electron transport layer and / or an optional injection layer disposed between the second light-emitting layer and the cathode electrode.

[0422] For example, according to Figure 2 the OLED can be formed by the following method: an anode (120), a hole injection layer (130), a hole transport layer (140), an electron blocking layer (145), a light-emitting layer (150), a hole blocking layer (155), an electron transport layer (160), an electron injection layer (180), and a cathode electrode (190) are sequentially formed on a substrate (110).

[0423] According to another aspect of the present invention, there is provided an electronic device, the electronic device including at least one organic light-emitting device according to any embodiment described throughout this application, preferably, the electronic device including an organic light-emitting diode in one embodiment described throughout this application. More preferably, the electronic device is a display device or a light-emitting device, and more preferably a display device.

[0424] In one embodiment, the organic light-emitting diode according to the present invention further includes a layer containing an annulene compound and / or a quinodimethane compound.

[0425] In one embodiment, the annulene compound and / or the quinodimethane compound can be substituted with one or more halogen atoms and / or one or more electron-withdrawing groups. The electron-withdrawing group can be selected from a nitrile group, a haloalkyl group, or a perhaloalkyl group, or a perfluoroalkyl group. Other examples of the electron-withdrawing group can be an acyl group, a sulfonyl group, or a phosphoryl group.

[0426] Alternatively, the acyl group, the sulfonyl group, and / or the phosphoryl group can include a halogenated and / or perhalogenated hydrocarbon group. In one embodiment, the perhalogenated hydrocarbon group can be a perfluorinated hydrocarbon group. Examples of the perfluorinated hydrocarbon group can be perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorophenyl, perfluorotolyl; examples of the sulfonyl group containing a halogenated hydrocarbon group can be trifluoromethylsulfonyl, pentafluoroethylsulfonyl, pentafluorophenylsulfonyl, heptafluoropropylsulfonyl, nonafluorobutylsulfonyl, etc.

[0427] In one embodiment, the [n]radialene and / or quinodimethane compound may be included in a hole injection layer, a hole transport layer, and / or a hole generation layer.

[0428] In one embodiment, the [n]radialene compound may have the formula (XX) and / or the quinodimethane compound may have the formula (XXIa) or (XXIb):

[0429]

[0430] wherein (as an exception to the above description) R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 11 、R 12 、R 15 、R 16 、R 20 、R 21 are independently selected from the above electron-withdrawing groups, and R 9 、R 10 、R 13 、R 14 、R 17 、R 18 、R 19 、R 22 、R 23 and R 24 are independently selected from H, halogen, and the above electron-withdrawing groups.

[0431] According to one embodiment of the present invention, the organic semiconductor layer containing the compound of formula (1) is adjacent to the layer containing the compound of formula (XX), (XXIa), or (XXIb).

[0432] According to one embodiment of the present invention, the organic semiconductor layer containing the compound of formula (1) is in direct contact with the layer containing the compound of formula (XX), (XXIa), or (XXIb).

[0433] Display device

[0434] The present invention also relates to a display device including the organic electronic device according to the present invention.

[0435] Method for manufacturing an organic electronic device

[0436] According to another aspect of the present invention, there is provided a method for manufacturing an organic light-emitting diode, the method using:

[0437] - At least one deposition source, preferably two deposition sources, more preferably at least three deposition sources.

[0438] Suitable deposition methods include:

[0439] - Deposition by vacuum thermal evaporation;

[0440] - Deposition by solution processing, preferably, the processing is selected from spin coating, printing, casting; and / or

[0441] - Slot-die coating.

[0442] According to various embodiments of the present invention, a method is provided that uses:

[0443] - A first deposition source to release a compound of formula (I) according to the present invention; and

[0444] - A second deposition source to release a compound of formula (II) and / or a compound of formula (III);

[0445] The method includes the step of forming an organic semiconductor layer; wherein for an organic light-emitting diode (OLED):

[0446] - An electron transport layer is formed by releasing a compound of formula (I) according to the present invention from the first deposition source and releasing a compound of formula (II) and / or a compound of formula (III) from the second deposition source.

[0447] According to various embodiments of the present invention, the method may further include forming a light-emitting layer on the anode electrode and forming at least one layer selected from a hole injection layer, a hole transport layer, or a hole blocking layer between the anode electrode and the first electron transport layer.

[0448] According to various embodiments of the present invention, the method may further include the step of forming an organic light-emitting diode (OLED), wherein

[0449] - A first anode electrode is formed on a substrate,

[0450] - A light-emitting layer is formed on the first anode electrode,

[0451] - An electron transport layer stack is formed on the light-emitting layer, optionally a hole blocking layer is formed on the light-emitting layer and an organic semiconductor layer is formed,

[0452] - Finally, a cathode electrode is formed,

[0453] - An optional hole injection layer, a hole transport layer, and a hole blocking layer are sequentially formed between the first anode electrode and the light-emitting layer,

[0454] - An electron transport layer is formed between the light-emitting layer and the cathode electrode;

[0455] - An optional electron injection layer is formed between the organic semiconductor layer and the cathode electrode.

[0456] According to various embodiments of the present invention, the method may further include forming an electron injection layer on the electron transport layer. However, according to various embodiments of the OLED of the present invention, the OLED may not include an electron injection layer.

[0457] According to various embodiments, the OLED may have the following layer structure, wherein the layers have the following order:

[0458] Anode, hole injection layer, first hole transport layer, second hole transport layer, light emitting layer, optional hole blocking layer, electron transport layer, and cathode.

[0459] General definitions

[0460] In this specification, when no other definition is provided, an "alkyl group" may refer to an aliphatic hydrocarbon group. The alkyl group may refer to a "saturated alkyl group" without any double or triple bonds. As used herein, the term "alkyl" shall cover straight-chain as well as branched-chain and cyclic alkyls. For example, C3-alkyl may be selected from n-propyl and isopropyl. Similarly, C4-alkyl includes n-butyl, sec-butyl, and tert-butyl. Similarly, C6-alkyl includes n-hexyl and cyclohexyl.

[0461] As used herein, if not otherwise explicitly mentioned, the asterisk "*" indicates the bonding position of the corresponding marked part to another part.

[0462] C n The subscript number n in C refers to the total number of carbon atoms in the corresponding alkyl, arylene, heteroarylene, or aryl group.

[0463] As used herein, the term "aryl" or "arylene" shall cover: phenyl (C6-aryl); fused aromatic compounds such as naphthalene, anthracene, phenanthrene, tetracene, etc. It also covers biphenyl and oligophenyls or polyphenyls such as terphenyl, phenyl-substituted biphenyl, phenyl-substituted terphenyl (e.g., a phenyl group with four phenyls). "Arylene", correspondingly "heteroarylene", refers to a group connected to two other parts. In this specification, the term "aryl group" or "arylene group" may refer to a group containing at least one hydrocarbon aromatic moiety, and all elements of the hydrocarbon aromatic moiety may have p-orbitals forming conjugation, such as phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, fluorenyl group, etc. It also includes spiro compounds in which two aromatic moieties are connected to each other through a spiro atom, such as 9,9'-spirobi[9H-fluorene] group. The aryl or arylene group may include monocyclic or fused polycyclic (i.e., sharing adjacent carbon atom pairs) functional groups.

[0464] As used herein, the term "heteroaryl" refers to an aryl group in which at least one carbon atom is replaced by a heteroatom. The term "heteroaryl" may refer to an aromatic heterocycle having at least one heteroatom, and all elements of the hydrocarbon heteroaromatic moiety may have p-orbitals that form conjugation. The heteroatom may be selected from N, O, S, B, Si, P, Se, preferably selected from N, O and S. The heteroarylene ring may contain at least 1 to 3 heteroatoms. Preferably, the heteroarylene ring may contain at least 1 to 3 heteroatoms independently selected from N, S and / or O. As in the case of "aryl" / "arylene", the term "heteroaryl" includes, for example, spiro compounds in which two aromatic moieties are connected to each other, such as spiro[fluorene-9,9'-xanthene]. Other exemplary heteroaryl groups are diazine, triazine, dibenzofuran, dibenzothiophene, acridine, benzoacridine and dibenzoacridine, etc.

[0465] As used herein, the term "alkenyl" refers to a group -CR 1 =CR 2 R 3 .

[0466] As used herein, the term "perhalogenated" refers to a hydrocarbon group in which all hydrogen atoms of the hydrocarbon group are replaced by halogen (F, Cl, Br, I) atoms.

[0467] As used herein, the term "alkoxy" refers to a structural moiety of the formula -OR, where R is a hydrocarbon group, preferably an alkyl or cycloalkyl group.

[0468] As used herein, the term "thioalkyl" refers to a structural moiety of the formula -SR, where R is a hydrocarbon group, preferably an alkyl or cycloalkyl group.

[0469] C n The subscript number n in -heteroaryl only refers to the number of carbon atoms other than the number of heteroatoms. In this context, it is obvious that a C3 heteroarylene group is an aromatic compound containing three carbon atoms such as pyrazole, imidazole, azole, thiazole, etc.

[0470] As used herein, the term "heteroaryl" shall include pyridine, quinoline, benzoquinoline, quinazoline, benzoquinazoline, pyrimidine, pyrazine, triazine, benzimidazole, benzothiazole, benzo[4,5]thieno[3,2-d]pyrimidine, carbazole, xanthene, phen azine, benzoacridine, dibenzoacridine, etc.

[0471] In this specification, the term single bond refers to a direct bond.

[0472] As used herein, the term "fluorinated" refers to a hydrocarbon group in which at least one hydrogen atom contained in the hydrocarbon group is replaced by a fluorine atom. A fluorinated group in which all of its hydrogen atoms are replaced by fluorine atoms is called a perfluorinated group, and is specifically denoted by the term "fluorinated".

[0473] According to the present invention, if one hydrogen atom contained in a group is replaced by another group, the group is "substituted" by the other group, where the other group is a substituent.

[0474] According to the present invention, in a formula showing the following bonding conditions,

[0475]

[0476] Group A can be bonded to any suitable bonding position. In the case where the bond of A spans more than one ring,

[0477]

[0478] Group A can be bonded to any suitable bonding position of each ring spanned by the bond.

[0479] According to the present invention, the expression "between" with respect to one layer between two other layers does not exclude the existence of other layers that may be disposed between one layer and one of the two other layers. According to the present invention, the expression "in direct contact" with respect to two layers in direct contact with each other means that no other layers are disposed between the two layers. A layer deposited on top of another layer is considered to be in direct contact with that layer.

[0480] The term "contact sandwiched" refers to an arrangement of three layers, where the middle layer is in direct contact with two adjacent layers.

[0481] Regarding the electron transport laminate of the present invention, the compounds mentioned in the experimental section are most preferred.

[0482] The lighting device can be any device for lighting, radiation, signaling, or projection. They are accordingly classified as lighting, radiation, signaling, and projection devices. A lighting device generally consists of the following elements: a light radiation source; a device for transmitting the radiation flux in a desired direction into space; and a housing that connects the components into a single device and protects the radiation source and the light transmission system from environmental damage and influence.

[0483] According to another aspect, the organic electroluminescent device according to the present invention includes two or three or more light-emitting layers. An OLED including more than one light-emitting layer is also called a tandem OLED or a stacked OLED.

[0484] An organic light-emitting device (OLED) can be a bottom- or top-emitting device. The organic light-emitting device (OLED) can emit light through a transparent anode or through a transparent cathode.

[0485] Another aspect relates to a device comprising at least one organic light-emitting device (OLED).

[0486] Devices comprising organic light-emitting diodes are, for example, displays or lighting panels.

[0487] In the present invention, for the terms defined below, unless a different definition is given elsewhere in the claims or in this specification, these definitions shall apply.

[0488] In the context of this specification, the term "different" in relation to a host material means that the host materials are different in terms of their structural formulas.

[0489] The terms "OLED" and "organic light-emitting diode" are used interchangeably and have the same meaning. As used herein, the term "organic light-emitting device" may include organic light-emitting diodes as well as organic light-emitting transistors (OLET).

[0490] As used herein, "weight percentage", "wt%", and variations thereof refer to expressing a composition, component, substance, or reagent as the weight of the corresponding component, substance, or reagent of the electron transport layer divided by the total weight of its corresponding electron transport layer, and multiplying by 100. It should be understood that the amounts of the total weight percentages of all components, substances, and reagents of the corresponding electron transport layer and electron injection layer are selected in such a way that they do not exceed 100 wt%.

[0491] As used herein, "volume percentage", "vol%", and variations thereof refer to expressing a composition, component, substance, or reagent as the volume of the corresponding component, substance, or reagent of the electron transport layer divided by the total volume of its corresponding electron transport layer, and multiplying by 100. It should be understood that the amounts of the total volume percentages of all components, substances, and reagents of the cathode layer are selected in such a way that they do not exceed 100 vol%.

[0492] Whether or not explicitly stated, all numerical values herein are assumed to be modified by the term "about". As used herein, the term "about" refers to variations in the quantities that can occur. Whether or not modified by the term "about", the claims include equivalents of the recited quantities.

[0493] It should be noted that as used in this specification and the claims, singular forms of the expressions "a", "an", "the", and "said" include plural referents unless the context clearly dictates otherwise.

[0494] The terms "free of", "does not contain", "does not include" do not exclude impurities. The impurities have no technical impact on the purposes achieved by the present invention.

[0495] In the context of this specification, the term "substantially non-luminescent" or "non-luminescent" means that, relative to the visible light emission spectrum, the contribution of a compound or layer to the visible light emission spectrum from the device is less than 10%, preferably less than 5%. The visible light emission spectrum is an emission spectrum having a wavelength of about ≥380 nm to about ≤780 nm.

[0496] Preferably, the organic semiconductor layer comprising the compound of formula (1) is substantially non-luminescent or non-luminescent.

[0497] The operating voltage, also referred to as U, is measured in volts (V) at 10 milliamperes per square centimeter (mA / cm 2 ).

[0498] The candela per ampere efficiency, also referred to as the cd / A efficiency, is measured in candela per ampere at 10 milliamperes per square centimeter (mA / cm 2 ).

[0499] The external quantum efficiency, also referred to as EQE, is measured in percentage (%).

[0500] The color space is described by the coordinates CIE-x and CIE-y (International Commission on Illumination 1931). For blue emission, CIE-y is particularly important. The smaller the CIE-y, the deeper the blue. The efficiency values are compared at the same CIE-y.

[0501] The highest occupied molecular orbital (also referred to as HOMO) and the lowest unoccupied molecular orbital (also referred to as LUMO) are measured in electron volts (eV).

[0502] The terms "OLED", "organic light-emitting diode", "organic light-emitting device", "organic optoelectronic device" and "organic light-emitting diode" are used interchangeably and have the same meaning.

[0503] The terms "lifetime" and "service life" are used interchangeably and have the same meaning.

[0504] The anode and cathode can be described as anode electrode / cathode electrode or anode electrode / cathode electrode or anode electrode layer / cathode electrode layer.

[0505] Room temperature, also referred to as ambient temperature, is 23 °C.

[0506] Hereinafter, the embodiments will be described in more detail in conjunction with the examples. However, the present invention is not limited to the following examples. Now, the exemplary aspects will be referred to in detail. BRIEF DESCRIPTION OF THE DRAWINGS

[0507] The above components, as well as the claimed components and the components used in the described embodiments according to the present invention, are not limited by any special exceptions in terms of their size, shape, material selection, and technical concept, and thus the selection criteria known in the relevant fields can be applied without limitation.

[0508] Other details, features, and advantages of the subject matter of the present invention are disclosed in the dependent claims and the description of the following respective drawings, which show, by way of example, preferred embodiments according to the present invention. However, any embodiment does not necessarily represent the entire scope of the present invention, and thus reference is made to the claims and the present text to interpret the scope of the present invention. It should be understood that the above general description and the following detailed description are merely exemplary and explanatory and are intended to further explain the claimed present invention.

[0509] Figure 1 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention;

[0510] Figure 2 is a schematic cross-sectional view of an organic light-emitting diode (OLED) according to an exemplary embodiment of the present invention;

[0511] Figure 3 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention;

[0512] Figure 4 is a schematic cross-sectional view of an OLED including a charge generation layer and two light-emitting layers according to an exemplary embodiment of the present invention.

[0513] Hereinafter, the drawings will be described in more detail in conjunction with the embodiments. However, the present invention is not limited to the following drawings.

[0514] Here, when a first element is referred to as being formed or disposed "on" a second element, the first element can be directly disposed on the second element, or one or more other elements can be disposed therebetween. When a first element is referred to as being "directly" formed or disposed on a second element, no other elements are disposed therebetween.

[0515] Figure 1Schematic cross-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 120, a light-emitting layer (EML) 125, and an electron transport layer 160 containing a compound of formula (I) and a compound of formula (II) and / or a compound of formula (III). The electron transport layer 160 containing the compound of formula (I) and the compound of formula (II) and / or the compound of formula (III) is formed on the EML 125. A cathode 190 is provided on the electron transport layer 160 containing the compound of formula (I) and the compound of formula (II) and / or the compound of formula (III).

[0516] Figure 2 Schematic cross-sectional view of an organic light-emitting diode (OLED) 100 according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate 110, an anode 120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140, a light-emitting layer (EML) 150, and an electron transport layer (ETL) 160. The electron transport layer (ETL) 160 is formed on the EML 150. An electron injection layer (EIL) 180 is provided on the electron transport layer (ETL) 160. The cathode 190 is directly provided on the electron injection layer (EIL) 180.

[0517] Figure 3 Schematic cross-sectional view of the OLED 100 according to another exemplary embodiment of the present invention. Figure 3 Differing from Figure 2 is that Figure 3 the OLED 100 in

[0518] Reference Figure 3 , the OLED 100 includes a substrate 110, an anode 120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140, an electron blocking layer (EBL) 145, a light-emitting layer (EML) 150, a hole blocking layer (HBL) 155, an electron transport layer 160 containing a compound of formula (I) and a compound of formula (II) and / or a compound of formula (III), an electron injection layer (EIL) 180, and a cathode 190.

[0519] Figure 4 Schematic cross-sectional view of the OLED 100 according to another exemplary embodiment of the present invention. Figure 4 Differing from Figure 3 is that Figure 4 the OLED 100 in

[0520] Reference Figure 4, the OLED 100 includes a substrate 110, an anode 120, a first hole injection layer (HIL) 130, a first hole transport layer (HTL) 140, a first electron blocking layer (EBL) 145, a first emitting layer (EML) 150, a first hole blocking layer (HBL) 155, a first electron transport layer 160 containing a compound of formula (I) and a compound of formula (II) and / or a compound of formula (III), an n-type charge generation layer (n-type CGL) 185, a hole generation layer (p-type charge generation layer; p-type GCL) 135, a second hole transport layer (HTL) 141, a second electron blocking layer (EBL) 146, a second emitting layer (EML) 151, a second hole blocking layer (EBL) 156, a second electron transport layer 161 containing a compound of formula (I) and a compound of formula (II) and / or a compound of formula (III), a second electron injection layer (EIL) 181, and a cathode 190.

[0521] Although not shown in Figure 1 , Figure 2 , Figure 3 and Figure 4 , a sealing layer may also be formed on the cathode electrode 190 to seal the OLED 100. In addition, various other variations may also be applied thereto.

[0522] Hereinafter, the embodiments will be described in more detail with reference to the examples. However, the present invention is not limited to the following examples. Detailed Description

[0523] The present invention is further illustrated by the following examples, which are merely illustrative and not binding.

[0524] Experimental Section

[0525] Melting point

[0526] The melting point (mp) was determined as the peak temperature according to the DSC curve measured by the above TGA-DSC measurement or a separate DSC measurement (Mettler Toledo DSC822e, the sample was heated from room temperature to complete melting at a heating rate of 10 K / min under a pure nitrogen gas flow. A sample with a quantity of 4 to 6 mg was placed in a 40 μL covered Mettler Toledo aluminum pan, and a <1 mm hole was punched in the cover).

[0527] Glass transition temperature

[0528] As described in DIN EN ISO 11357 published in March 2010, the glass transition temperature (Tg) was measured in a Mettler Toledo DSC 822e differential scanning calorimeter under nitrogen and using a heating rate of 10 K / min.

[0529] Standard onset temperature

[0530] The standard starting temperature (TRO) was determined by loading 100 mg of the compound into a VTE source. As the VTE source, an organic material point source provided by Kurt J. Lesker Company (www.Lesker.com) or CreaPhys GmbH (http: / / www.creaphys.com) could be used. At a pressure of less than 10 -5 mbar, the VTE source was heated at a constant rate of 15 K / min, and the temperature inside the source was measured with a thermocouple. The evaporation of the compound was detected with a QCM detector, which detected the deposition of the compound on the quartz crystal of the detector. The deposition rate on the quartz crystal was measured in units. To determine the standard starting temperature, the deposition rate was plotted against the VTE source temperature. The standard starting was the temperature at which significant deposition occurred on the QCM detector. To obtain accurate results, the VTE source was heated and cooled 3 times, and only the results of the second and third runs were used to determine the standard starting temperature.

[0531] To well control the evaporation rate of the organic compound, the standard starting temperature can be in the range of 200 °C to 255 °C. If the standard starting temperature is lower than 200 °C, the evaporation may be too fast and thus difficult to control. If the standard starting temperature is higher than 255 °C, the evaporation rate may be too low, which may result in a low beat time, and the organic compound in the VTE source may decompose due to long exposure to high temperature.

[0532] The standard starting temperature is an indirect measure of the volatility of the compound. The higher the standard starting temperature, the lower the volatility of the compound.

[0533] Reduction potential

[0534] The reduction potential was determined at room temperature by cyclic voltammetry using a potentiostat Metrohm PGSTAT30 and software Metrohm Autolab GPES. The redox potential given for a particular compound was measured as follows: in a dry 0.1 M THF solution of the experimental substance degassed with argon, under an argon atmosphere, using 0.1 M tetrabutylammonium hexafluorophosphate supporting electrolyte between platinum working electrodes, and measured at a scan rate of 100 mV / s with an Ag / AgCl pseudo-reference electrode (Metrohm silver rod electrode) consisting of a silver wire covered with silver chloride and directly immersed in the measurement solution. The first run was done within the widest range of potentials set on the working electrode, and then the range was adjusted appropriately in subsequent runs. The last three runs were done by adding ferrocene (0.1 M concentration) as a standard. The average of the potentials corresponding to the cathodic and anodic peaks of the compound under study, after subtracting the average of the cathodic and anodic potentials observed for the standard Fc + / Fc redox couple, finally gave the values reported above. All the compounds studied as well as the comparative compounds reported showed well-defined reversible electrochemical behavior.

[0535] Dipole moment

[0536] The dipole moment of a molecule containing N atoms is given by:

[0537]

[0538] where q i and are the partial charge and position of atom i in the molecule.

[0539] The dipole moment was determined by semi-empirical molecular orbital methods.

[0540] As implemented in the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany), the geometry of the molecular structure was optimized in the gas phase using the hybrid functional B3LYP and the 6-31G* basis set. If more than one conformation was feasible, the conformation with the lowest total energy was selected to determine the bond lengths of the molecule.

[0541] Calculated HOMO and LUMO

[0542] The HOMO and LUMO were calculated using the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The optimal geometry of the molecular structure and the HOMO and LUMO energy levels were determined by applying the hybrid functional B3LYP and the 6-31G* basis set in the gas phase. If more than one conformation was feasible, the conformation with the lowest total energy was selected.

[0543] Measurement of thin film refractive index

[0544] At the deposition rate of about 3×10 -7 mbar, a pure film of the host material with a thickness of 70 nm was prepared on a silicon substrate (0.5 nm native SiO2, 675 μm thick, Siegert Wafer GmbH) by thermal evaporation in a vacuum system (Cluster Tool, Sunic System Ltd.). The samples were stored in a glove box under a pure nitrogen atmosphere until measurement (exposed to air for at most 1 hour). A Filmetrics F10-RT spectrometer with a spectral range of 380 nm to 1050 nm was used to measure the reflectivity. A silicon reference sample from Filmetrics was used as the reflectivity standard. Then, the measured reflectivity data were modeled using the Cauchy model in the FILMeasure software to obtain the refractive index in the range of 420 nm to 1020 nm.

[0545] Table 1.

[0546]

[0547] Synthesis procedure

[0548] Compound E-1

[0549]

[0550] 2-(3-chlorophenyl)-4-phenyl-6-(3-(10-phenylanthracen-9-yl)phenyl)-1,3,5-triazine (30.0 g, 50.3 mmol) and 2-biphenylboronic acid (12.0 g, 60.4 mmol) were suspended in tetrahydrofuran (200 ml) in a Schlenk flask. A solution of potassium phosphate (21.2 g, 100 mmol) in water (50 ml) was added, and the mixture was purged with N2. Chloride (crotyl)(2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl)palladium(II) (611 mg, 1.00 mmol) was added under a stream of N2, and the mixture was heated to 52 °C for 60 h. An additional portion of 2-biphenylboronic acid (10 g, 50.5 mmol) and chloride (crotyl)(2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl)palladium(II) (600 mg, 988 mg) were added, and the mixture was heated at 52 °C for an additional 16 h. Subsequently, the solvent was removed under reduced pressure, and the residue was dissolved in dichloromethane and water. After filtration, the phases were separated. The organic phase was washed again with water, dried over MgSO4, and filtered through a silica gel pad. The filtrate was concentrated under reduced pressure to 100 ml, and 500 ml of cyclohexane was added. Another 200 ml of solvent was removed under reduced pressure to give a pale yellow solid precipitate. The solid was recrystallized from hot toluene, filtered off, dissolved in dichloromethane and reprecipitated with n-hexane, and washed with n-hexane to give the pure product (17.6 g, 49%).

[0551] ESI-MS—m / z = 714 ([M] + )

[0552] Compound E-2

[0553]

[0554] 2'-(3,5,6-triphenylpyrazin-2-yl)-[1,1'-biphenyl]-3-carbaldehyde (46.0 g, 94.2 mmol), benzamidine hydrochloride (29.5 g, 118.3 mmol), and cesium carbonate (61.4 g, 118.3 mmol) were placed in a Schlenk flask and suspended in dimethyl sulfoxide (300 ml) under N2. The mixture was heated to 90 °C for 20 h. After cooling to room temperature, the off-white precipitate was collected by filtration and washed with water and ethanol. The solid was then dissolved in dichloromethane (200 ml), and methanol (300 ml) was added to precipitate it. It was filtered and dried under reduced pressure at 100 °C to give the desired product (24.5 g, 38%).

[0555] ESI-MS—m / z = 692 ([M] + )

[0556] Compound E-4

[0557]

[0558] Dissolve 3-(10-bromoanthracen-9-yl)pyridine (14.6 g, 43.7 mmol), 2-([1,1'-biphenyl]-2-yl)-4-phenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine (29.1 g, 56.8 mmol) and [1,1'-bis(diphenylphosphino)ferrocene]-dichloropalladium(II) (159 mg, 218 mmol) in tetrahydrofuran (180 ml) in a Schlenk flask, and purge the solution with N2. Then dissolve potassium carbonate (12.1 g, 87.4 mmol) in water (43 ml) and add it to the above Schlenk flask. Heat the mixture to 55 °C and stir for 16 h. Subsequently, add water (250 ml) to the reaction mixture, separate the phases, and evaporate the organic phase to dryness under reduced pressure. Dissolve the residue in chlorobenzene at 60 °C and filter through a silica gel pad. Concentrate the solution to 150 ml, add n-hexane to precipitate a solid, and wash it with n-hexane and methanol. Recrystallize from ethyl acetate / hexane to obtain the pure product (12.0 g, 43%).

[0559] ESI-MS—m / z=639([M] + )

[0560] Compound E-7

[0561]

[0562] Combine potassium carbonate (16.0 g, 115 mmol) with 1,4-di Alkane (230 ml) and water (58 ml) were placed together in a Schlenk flask, and the resulting mixture was purged with N2. Subsequently, 2,3,5-triphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrazine (21.3 g, 41.7 mmol), 2-(2-bromophenyl)-4,6-diphenyl-1,3,5-triazine (18.0 g, 46.4 mmol) and tetrakis(triphenylphosphine)palladium(0) (1.07 g, 0.93 mmol) were added under a stream of N2, and the mixture was heated to reflux for 60 h. An additional portion of 2,3,5-triphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrazine (2.40 g, 4.17 mmol) and tetrakis(triphenylphosphine)palladium(0) (300 mg, 0.259 mmol) was added, and the mixture was refluxed for an additional 16 h. The resulting precipitate was separated by precipitation and washed with 1,4-d alkane and water. The solid was then dissolved in CHCl3, dried over MgSO4 and filtered through a silica gel pad. The solution was concentrated under reduced pressure to 500 ml, and acetonitrile (100 ml) was added to precipitate a colorless solid product, which was washed with acetonitrile and hexane and dried in vacuo (25.4 g, 78%).

[0563] ESI-MS—m / z = 692 ([M] + )

[0564] General procedure for manufacturing an OLED

[0565] For the top-emitting OLED device, a substrate with dimensions of 150 mm × 150 mm × 0.7 mm was ultrasonically cleaned in a 2% aqueous solution of Deconex FPD211 for 7 min, then washed with pure water for 5 min and dried in a spin-rinse dryer for 15 min. Subsequently, Ag was deposited as the anode at a pressure of 10 -5 mbar to 10 -7 mbar.

[0566] Then, HT-1 and D-1 were co-deposited in vacuo on the anode to form the HIL. Then, HT-1 was deposited in vacuo on the HIL to form the HTL. Then, HT-2 was deposited in vacuo on the HTL to form the electron blocking layer (EBL).

[0567] Subsequently, the light-emitting layer was formed by co-depositing HOST-1 and EMITTER-1 on the EBL.

[0568] Then, ET-1 was deposited in vacuo on the light-emitting layer to form the HBL.

[0569] Then, for Comparative Example 1 and Comparative Example 2, an electron transport layer was formed by co-depositing a mixture of ET-3 and ET-5 on HBL. For OLED Examples OLED-1 to OLED-5 of the present invention, an electron transport layer was formed by co-depositing a mixture of ET-3 and a compound of Formula (II) or Formula (III) on HBL. For OLED Examples OLED-12 and OLED-13 of the present invention, an electron transport layer was formed by co-depositing a mixture of ET-4 and a compound of Formula (II) or Formula (III) on HBL. The mixing ratios are shown in Table 3.

[0570] Then, a double-layer electron injection layer was formed on the electron transport layer by depositing LiQ as the first EIL (for Comparative Example 1 and for OLED-1 to OLED-5) or a mixture of ET-2:Li [99:1 vol%] (for OLED-6 to OLED-13), and then depositing Yb as the second EIL.

[0571] Then, at a pressure of 10 -7 mbar, Ag:Mg was evaporated at a rate of to to form the cathode.

[0572] A covering layer of HT-3 was formed on the cathode.

[0573] Details of the lamination in the top-emitting OLED device are given below. The individual layers are separated by a slash " / ". The layer thicknesses are given in square brackets […], and the mixing ratios in weight % are given in round brackets (…):

[0574] Details of the lamination for the OLED device examples in Table 3

[0575] Ag [100 nm] / HT-1:D-1 (vol% 92:8) [10 nm] / HT-1 [130 nm] / HT-2 [5 nm] / H09:BD200 (vol% 97:3) [20 nm] / ET-1 [5 nm] / ET-3:ET-5 (vol% 20:80) or ET-3:compound of Formula (II) or Formula (III) (wt% 20:80) or ET-4:compound of Formula (II) or Formula (III) (vol% 30:70) [30 nm] / LiQ [1 nm] or ET-2:Li (vol% 99:1) [15 nm] / Yb [2 nm] / Ag:Mg (vol% 90:10) [13 nm] / HT-3 [75 nm]

[0576] Table 2: List of compounds used

[0577]

[0578]

[0579] Table 3. Performance data of an organic electroluminescent device containing a mixture of the compound of formula (I) and the compound of formula (II) and / or the compound of formula (III) in an electron transport layer.

[0580]

[0581] Examples OLED-1 to OLED-13 show that if the compound of formula (I): the compound of formula (II) or (III) is used instead of ET-5, the cd / A efficiency will increase at a comparable voltage.

[0582] Table 4:

[0583]

[0584]

[0585]

[0586] Examples OLED-14 and OLED-13 show that if the compound of formula (I): the compound of formula (II) or (III) is used instead of C-1, the cd / A efficiency will also increase at a lower voltage.

[0587] The features disclosed in the foregoing description and the dependent claims can be used singly and in any combination thereof in two ways as materials for realizing the subject matter disclosed in the independent claims in its various forms.

Claims

1. An organic light-emitting diode, which comprises an anode, a cathode, a light-emitting layer and an electron transport layer, wherein - the electron transport layer is disposed between the light-emitting layer and the cathode; - the electron transport layer does not contain an electrical dopant; - the electron transport layer contains a compound of formula (I), (Ar 2 ) m -(Z k -G) n (I); wherein in formula (I), - m and n are independently 1 or 2; - k is independently 0, 1 or 2; -Ar 2 independently selected from C2 to C 42 heteroaryl and C6 to C 60 aryl, - wherein each Ar 2 may be substituted with one or two substituents independently selected from: C6 to C 12 aryl, C3 to C 11 heteroaryl, and C1 to C6 alkyl, D, 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 C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy, halogen, CN or PY(R 10 )2, wherein Y is selected from O, S or Se, preferably O, and R 10 is independently selected from C6 to C 12 aryl, C3 to C 12 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy; - wherein Ar 2 each C6 to C 12 aryl substituent on and Ar 2 each C3 to C 11 heteroaryl substituent may be substituted by a C1 to C4 alkyl or a halogen; -Z is independently selected from C6 to C 30 aryl, - wherein each Z may be substituted by one or two substituents independently selected from: C6 to C 12 aryl and C1 to C6 alkyl, D, 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 C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy, halogen, CN or PY(R 10 )2, wherein Y is selected from O, S or Se, preferably O, and R 10 is independently selected from C6 to C 12 aryl, C3 to C 12 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy; - wherein each C6 to C on Z 12 aryl substituent may be substituted by C1 to C4 alkyl or halogen; - G is selected such that the dipole moment of the compound G-phenyl is ≥1 D and ≤7 D; - the electron transport layer further contains a compound of formula (II) and / or a compound of formula (III), wherein in formula (II) and formula (III), respectively, -Ar 1 independently selected from C6 to C 19 aryl and C2 to C 19 heteroaryl; - wherein Ar 1 may be substituted with one or two substituents independently selected from: C1-C6 alkyl, D, C1-C6 alkoxy, C3-C6 branched alkyl, C3-C6 cycloalkyl, C3-C6 branched alkoxy, C3-C6 cycloalkoxy, partially or perfluorinated C1-C6 alkyl, partially or perfluorinated C1-C6 alkoxy, partially or perdeuterated C1-C6 alkyl, partially or perdeuterated C1-C6 alkoxy, halogen, CN or PY(R 10 )2, wherein Y is selected from O, S or Se, preferably O, and R 10 is independently selected from: C6-C 12 aryl, C3-C 12 heteroaryl, C1-C6 alkyl, C1-C6 alkoxy, partially or perfluorinated C1-C6 alkyl, partially or perfluorinated C1-C6 alkoxy, partially or perdeuterated C1-C6 alkyl, partially or perdeuterated C1-C6 alkoxy; -Ar 3 independently selected from C6 to C 19 aryl; - wherein Ar 3 may be substituted by one or two substituents independently selected from: C1-C6 alkyl, D, C1-C6 alkoxy, C3-C6 branched alkyl, C3-C6 cyclic alkyl, C3-C6 branched alkoxy, C3-C6 cyclic alkoxy, partially or perfluorinated C1-C6 alkyl, partially or perfluorinated C1-C6 alkoxy, partially or perdeuterated C1-C6 alkyl, partially or perdeuterated C1-C6 alkoxy, halogen, CN or PY(R 10 )2, wherein Y is selected from O, S or Se, preferably O, and R 10 is independently selected from C6-C 12 aryl, C3-C 12 heteroaryl, C1-C6 alkyl, C1-C6 alkoxy, partially or perfluorinated C1-C6 alkyl, partially or perfluorinated C1-C6 alkoxy, partially or perdeuterated C1-C6 alkyl, partially or perdeuterated C1-C6 alkoxy; -ET is independently selected from C6 to C 60 aryl and C2 to C 60 heteroaryl; - wherein ET may be substituted by one or two substituents independently selected from: C6 to C 20 aryl, C3 to C 20 heteroaryl, and C1 to C6 alkyl, D, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cycloalkyl, C3 to C6 branched alkoxy, C3 to C6 cycloalkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy, halogen, CN or PY(R 10 )2, wherein Y is selected from O, S or Se, preferably O, and R 10 is independently selected from C6 to C 12 aryl, C3 to C 12 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy; - wherein each of the C6 to C on ET 20 aryl substituents and each of the C3 to C on ET 20 heteroaryl substituents may be substituted by a C1 to C4 alkyl or a halogen; -L 1 having the formula (IIa), wherein L 1 is bonded to the triazine moiety in formula (II) at *1; and L 1 is bonded to Ar 1 at *2; and p is 0 or 1; -L 2 having the formula (IIb), wherein L 2 is bonded to the triazine moiety in formula (II) at *3; and L 2 is bonded to ET at *4; and -L 3 having the formula (IIIa.1) or (IIIa.2), wherein L 3 is bonded to the triazine moiety in formula (III) at *5; and L 3 is bonded to ET at *6.

2. The organic light emitting diode according to claim 1, wherein Ar 2 is independently selected from pyridyl, triazinyl, 1,2-diazinyl, 1,3-diazinyl, 1,4-diazinyl, quinazolinyl, benzoquinazolinyl, benzimidazolyl, quinolinyl, benzoquinolinyl, benzacridinyl, dibenzoacridinyl, fluoranthenyl, anthracenyl, naphthyl, terphenylidene, phenanthrolinyl and dinaphthofuranyl, and the groups may be optionally substituted or unsubstituted, respectively.

3. The organic light-emitting diode according to claim 1 or 2, wherein -G is selected from dialkyloxyphosphino, diaryloxyphosphino, alkylaryloxyphosphino, nitrile, benzonitrile, nicotinonitrile, amido, urea group and C2 to C 17 heteroaryl; - each G may contain one or more substituents attached to the group, and the one or more substituents are selected from phenyl, methyl, ethyl and pyridyl.

4. The organic light emitting diode according to any one of the preceding claims, wherein Ar 1 is a substituted or unsubstituted C6 to C 19 aryl group.

5. The organic light emitting diode according to any one of the preceding claims, wherein Ar 3 is a substituted or unsubstituted phenyl group.

6. The organic light-emitting diode according to any one of the preceding claims, wherein ET is selected from triphenylpyrazinyl, dibenzoacridinyl, pyridyl, anthracenyl, pyridylanthracenyl, phenylanthracenyl and the group of formula ET-i: wherein R 1 to R 5 are independently H or phenyl, provided that at least two of R 1 to R 5 are phenyl and the remaining R 1 to R 5 are H; and ET-i is bonded to L 2 or L 3 at * respectively.

7. The organic light-emitting diode according to any one of the preceding claims, wherein the electron transport layer contains a compound of formula (I) and a compound of formula (II), and "p" in formula (IIa) is 0.

8. The organic light-emitting diode according to any one of the preceding claims, wherein the organic light-emitting layer further contains a hole blocking layer, and the hole blocking layer is disposed between the light-emitting layer and the electron transport layer.

9. The organic light-emitting diode according to any one of the preceding claims, wherein the organic light-emitting diode further contains an electron injection layer, and the electron injection layer is disposed between the cathode and the electron transport layer and the electron injection layer is in direct contact with the electron transport layer.

10. The organic light-emitting diode according to claim 9, wherein the electron injection layer contains a first electron injection sublayer and a second electron injection sublayer, and the first electron injection sublayer and the second electron injection sublayer are in direct contact with each other.

11. The organic light-emitting diode according to claim 10, wherein the first electron injection sublayer is in direct contact with the electron transport layer, and the first electron injection sublayer contains a metal salt or a metal complex, preferably contains LiQ.

12. The organic light-emitting diode according to claim 10 or 11, wherein the second electron injection sublayer contains a metal selected from alkali metals, alkaline earth metals and rare earth metals, preferably consists of Yb.

13. A device, which comprises the organic light-emitting diode according to any one of the preceding claims, wherein the device is a display device or a lighting device.

14. A compound of formula (IV) or formula (V), wherein in formula (IV) and formula (V), respectively, -Ar 4 Selected from C6 to C 19 aryl and C2 to C 19 heteroaryl; - wherein Ar 4 may be substituted by one or two substituents independently selected from: C1-C6 alkyl, D, C1-C6 alkoxy, C3-C6 branched alkyl, C3-C6 cycloalkyl, C3-C6 branched alkoxy, C3-C6 cycloalkoxy, partially or fully fluorinated C1-C6 alkyl, partially or fully fluorinated C1-C6 alkoxy, partially or fully deuterated C1-C6 alkyl, partially or fully deuterated C1-C6 alkoxy, halogen, CN or PY(R 10 )2, wherein Y is selected from O, S or Se, preferably O, and R 10 is independently selected from C6-C 12 aryl, C3-C 12 heteroaryl, C1-C6 alkyl, C1-C6 alkoxy, partially or fully fluorinated C1-C6 alkyl, partially or fully fluorinated C1-C6 alkoxy, partially or fully deuterated C1-C6 alkyl, partially or fully deuterated C1-C6 alkoxy; -Ar 5 Selected from C6 to C 19 aryl; - wherein Ar 5 may be substituted by one or two substituents independently selected from: C1-C6 alkyl, D, C1-C6 alkoxy, C3-C6 branched alkyl, C3-C6 cyclic alkyl, C3-C6 branched alkoxy, C3-C6 cyclic alkoxy, partially or perfluorinated C1-C6 alkyl, partially or perfluorinated C1-C6 alkoxy, partially or perdeuterated C1-C6 alkyl, partially or perdeuterated C1-C6 alkoxy, halogen, CN or PY(R 10 )2, wherein Y is selected from O, S or Se, preferably O, and R 10 is independently selected from C6-C 12 aryl, C3-C 12 heteroaryl, C1-C6 alkyl, C1-C6 alkoxy, partially or perfluorinated C1-C6 alkyl, partially or perfluorinated C1-C6 alkoxy, partially or perdeuterated C1-C6 alkyl, partially or perdeuterated C1-C6 alkoxy; - ET' is selected from pyrazinyl, triphenylpyrazinyl, pyridine-anthracenyl, acridine, benzacridine, dibenzoacridine, phenylanthracenyl and a compound of formula ET'-i; wherein R 1 to R 5 are independently H or phenyl, provided that at least two, preferably at least three, most preferably four of R 1 to R 5 are phenyl and the remaining R 1 to R 5 are H; and ET'-i is bonded to L 5 or R 6 at * respectively; -L 4 having the formula (IVa), wherein L 4 is bonded to the triazine moiety in formula (IV) at *7; and L 4 is bonded to Ar 4 at *8; and p' is 0 or 1; -L 5 having the formula (IVb), where L 5 is bonded to the triazine moiety in formula (IV) at *9; and L 5 is bonded to ET' at *10; and -L 6 having the formula (Va.1) or (Va.2), wherein L 6 is bonded to the triazine moiety in formula (V) at *11; and L 6 is bonded to ET' at *12.

15. A compound of the following formula:

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