Organic light emitting device and display device including same

Abstract

The present invention relates to an organic light emitting device, to a display device comprising the organic light emitting device, and to a compound.

Description

[0001] This invention relates to an organic light-emitting device and a display device comprising the organic light-emitting device. Background Technology

[0002] Organic semiconductor devices, such as organic light-emitting diodes (OLEDs), are self-emissive devices that possess wide viewing angles, excellent contrast ratios, fast response times, high brightness, superior operating voltage characteristics, and excellent color reproduction. A typical OLED comprises an anode, a hole transport layer (HTL), an emissive layer (EML), an electron transport layer (ETL), and a cathode, which are sequentially stacked on a substrate. In this regard, the HTL, EML, and ETL are thin films formed from organic compounds.

[0003] When a voltage is applied to the anode and cathode, holes injected from the anode move to the EML via the HTL, and electrons injected from the cathode move to the EML via the ETL. Holes and electrons recombine in the EML to generate excitons. When the excitons descend from the excited state to the ground state, light is emitted. The injection and flow of holes and electrons should be balanced so that OLEDs with the above structure exhibit excellent efficiency and / or long lifetime.

[0004] The performance of organic light-emitting diodes can be affected by the characteristics of the organic semiconductor layer, which in turn can be affected by the characteristics of the organic materials in the organic semiconductor layer.

[0005] In particular, there is a need to develop organic semiconductor layers that can improve electron mobility while simultaneously increasing electrochemical stability, so that organic semiconductor devices such as organic light-emitting diodes can be applied to large flat panel displays.

[0006] Therefore, one object of the present invention is to provide an organic light-emitting diode (OLED) that overcomes the disadvantages of the prior art and a compound for preparing the OLED, particularly a compound for use in an OLED that contributes to improving its performance, especially in terms of efficiency. Summary of the Invention

[0007] This objective is achieved by an organic light-emitting device comprising an anode, a cathode, a light-emitting layer, an electron injection layer, and a first electron transport layer; in - The light-emitting layer, the electron injection layer, and the first electron transport layer are arranged between the anode and the cathode; - An electron injection layer and a first electron transport layer are arranged between the light-emitting layer and the cathode; - The first electron transport layer is arranged between the light-emitting layer and the electron injection layer; - The first electron transport layer includes compounds of formula (I) and silicon-containing compounds; (Ar 2 ) m-(Z k -G) n (I); - m and n are 1 or 2 independently; - k is independently 0, 1, or 2; - Ar 2 Independently selected from C2 to C 42 heteroaryl and C6 to C 60 Aryl, - where each Ar 2 It can be substituted by one or two independent substituents selected from the following: C6 to C6. 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 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 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; - Among them Ar 2 Each C6 to C 12 Aryl substituents and Ar 2 Each C3 to C 11 The heteroaryl substituents can be replaced by C1 to C4 alkyl groups or halogens; - Z is independently selected from C6 to C 30 Aryl, - where each Z can be substituted by one or two substituents independently selected from the following: C6 to C6 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 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 Independently selected from C6 to C 12 Aryl, C3 to C12 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; - where each C6 to C on Z 12 The aryl substituents can be replaced by C1 to C4 alkyl groups or halogens; - Choose G such that the dipole moment of the compound G-phenyl is ≥1 D; - Silicon-containing compounds contain at least two Si atoms; and - The first electron transport layer contains no electrical dopants.

[0008] This objective is also achieved by an apparatus comprising an organic light-emitting device according to the invention, wherein the apparatus is a display device or a lighting device.

[0009] First electron transport layer

[0010] The first electron transport layer includes compounds of formula (I).

[0011] (Ar 2 ) m -(Z k -G) n (I)

[0012] And silicon-containing compounds.

[0013] The first electron transport layer may consist of a compound of formula (I) and a silicon-containing compound. Alternatively, the first electron transport layer may consist of a compound of formula (I) and a silicon-containing compound, as well as one or more other compounds, provided that the other compounds are not electrodopers. The first electron transport layer may contain more than one compound of formula (I). The first electron transport layer may consist of a compound of formula (I) or a mixture of different compounds of formula (I) and a silicon-containing compound or a mixture of different silicon-containing compounds.

[0014] The first electron transport layer may contain a compound of formula (I) in an amount of 10% or more but less than 99% or more, 20% or more but less than 95% or more, 30% or more but less than 90% or more, 40% or more but less than 90% or more, or 50% or more but less than 85% or more based on the total volume of the first electron transport layer.

[0015] The first electron transport layer may contain a silicon-containing compound in an amount of 1% to 70% of the total volume of the first electron transport layer, 5% to 65% of the total volume of the first electron transport layer, 10% to 60% of the total volume of the total volume of the first electron transport layer, or 15% to 50% of the total volume of the first electron transport layer.

[0016] The first electron transport layer can be disposed between the hole blocking layer and the electron injection layer. The first electron transport layer can be disposed in direct contact with the hole blocking layer. The first electron transport layer can be disposed in direct contact with the electron injection layer. The first electron transport layer can be disposed in a "contact-sandwiched" manner between the hole blocking layer and the electron injection layer.

[0017] The first electron transport layer may have a thickness of <100 nm, optionally between 10 nm and 90 nm, optionally between 10 nm and 60 nm, or optionally between 10 nm and 50 nm.

[0018] Compound of formula (I)

[0019] In the compound of formula (I), the group "Z" is the linker (if present, i.e., in the case of k>1) of the group Ar. 2 The spacer portion between G and [other compound]. Compounds of formula (I) contain more than one group (Z). k In the case of -G), the group may independently contain or may independently not contain the spacer group Z.

[0020] In equation (I), m and n are independently 1 or 2. In equation (I), m and n can both be 1.

[0021] In equation (I), k is independently 0, 1, or 2. In equation (I), k can be independently 1 or 2.

[0022] Ar 2 Can be independently selected from C2 to C 39 heteroaryl and C6 to C 54 Aryl, optionally selected from C2 to C 36 heteroaryl and C6 to C 48 Aryl, optionally selected from C3 to C 30 heteroaryl and C6 to C 42 Aryl, optionally selected from C3 to C 27 heteroaryl and C6 to C 36 Aryl, optionally selected from C3 to C 24 heteroaryl and C6 to C 30 Aryl, optionally selected from C3 to C 21 heteroaryl and C6 to C 24 Aryl.

[0023] Ar 2 Can be independently selected from C2 to C 39 Contains N-heteroaryl and C6 to C 54 Aryl, optionally selected from C2 to C 36 Contains N-heteroaryl and C6 to C 48 Aryl, optionally selected from C3 to C30 Contains N-heteroaryl and C6 to C 42 Aryl, optionally selected from C3 to C 27 Contains N-heteroaryl and C6 to C 36 Aryl, optionally selected from C3 to C 24 Contains N-heteroaryl and C6 to C 30 Aryl, optionally selected from C3 to C 21 Contains N-heteroaryl and C6 to C 24 Aryl. In this respect, the corresponding N-containing heteroaryl group may be specified to contain one or more N atoms as the only heteroatom.

[0024] Ar 2 It can contain at least two 5- or 6-membered rings with increasing rings.

[0025] Ar 2 It may be independently selected from pyridyl, triazinyl, 1,2-diazinyl, 1,3-diazinyl, 1,4-diazinyl, quinazolinyl, benzoquinazolinyl, benzimidazolyl, quinolinyl, benzoquinolinyl, benzoacridyl, dibenzoacridyl, fluoranthyl, anthraceneyl, naphthyl, biphenylideneyl, phenanthrolinel, and dinaphthofuranyl, wherein the groups may be substituted or unsubstituted.

[0026] Ar 2 It can be independently selected from dibenzo-acridyl, 1,3-diazinyl, 1,4-diazinyl, anthraceneyl, triazinyl, phenanthrolinel, biphenylideneyl, pyridyl, and dinaphthofuranyl.

[0027] Ar 2 It may be selected from one of the following groups or independently contain one of the following groups. ; ; ; ; ; ; ;

[0028] The asterisk symbol " "" respectively represent the binding positions with Z in equation (I).

[0029] In Ar 2 In the case of being replaced, Ar 2 Each substituent may be independently selected from phenyl, naphthyl, optionally β-naphthyl, pyridyl, and biphenyl, and the groups may be substituted or unsubstituted, respectively.

[0030] In Ar 2 In the case of being replaced, Ar 2Each substituent may be independently selected from phenyl, pyridyl, and biphenyl, and optionally from p-biphenyl.

[0031] Z can be independently selected from C6 to C6. 24 Aryl, or C6 to C 18 Aryl, or C6 to C 12 Aryl group, which may or may not be substituted.

[0032] Z can be independently selected from phenylene, naphthylene, phenylene-naphthylene, biphenylene, and terphenylene, and the groups can be substituted or not substituted, respectively.

[0033] Z can be independently selected from one of the following groups. ; ; ; ;

[0034] Among them, with Ar 2 The binding position of G can be freely chosen.

[0035] When Z is substituted, each substituent on Z can be independently selected from phenyl and C1 to C4 alkyl groups.

[0036] Choosing G enables the use of hybrid functionals B3LYP and Gaussian 6-31G via the TURBOMOLE V6.5 package. The dipole moment of the compound G-phenyl calculated by basis set is ≥1 D but ≤7 D. The unit of dipole moment, "Debye," is abbreviated as "D." The inventors have found that it is advantageous for the compound of formula (I) to contain a group with a specific polarity, i.e., a group with a specific dipole moment within the ranges described above or below. It has also been found that it is still advantageous for the compound of formula (I) to contain another polar group (a second polar group), which is suitable for balancing the dipole moment of the first polar group, so that the total dipole moment of the compound of formula (I) is low; for example, when the compound is a symmetrical molecule containing the same first and second polar groups, the dipole moment can be 0 Debye. Therefore, the compound of formula (I) cannot be characterized by referring to the total dipole moment of the compound. Instead, a simulated compound containing the polar group "G" and the nonpolar group "phenyl" is referenced. In this respect, the dipole moment of a compound containing N atoms It is given by the following formula:

[0037] in and It represents the partial charge and position of atom i in the molecule. The dipole moment is determined by a semi-empirical molecular orbital method. As implemented in the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany), it uses the hybrid functional B3LYP with 6-31G in the gas phase. The basis set is used to optimize the geometry of the molecular structure. If more than one conformation is feasible, the conformation with the lowest total energy is chosen to determine the bond lengths of the molecule. In this respect, the entire G part includes all possible substituents that can be included.

[0038] 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 ≥2.5 D, optionally ≥3 D, optionally ≥3.5 D. G can also 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, optionally ≤5 D. If more than one conformational isomer of the compound G-phenyl is feasible, 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 isomers can be converted to each other only by rotation of formally single bonds.

[0039] By selecting G such that the dipole moment of the compound G-phenyl is within the aforementioned range, electron injection from adjacent different electron injection layers (EILs) is improved, and the voltage of the OLED device can be reduced, while the cd / A efficiency of the OLED device can be increased.

[0040] Exemplary compounds “G-phenyl” are listed in Table 1 below, wherein the portion of the corresponding compound is described in the table.

[0041] The instruction is "G- Phenyl The "phenyl" part in "".

[0042] Table 1:

[0043] G can be selected from dialkylphosphine oxide (-P(=O)alkyl2), diarylphosphine oxide (-P(=O)aryl2), alkylarylphosphine oxide (-P(=O)alkyl2), diheteroarylphosphine oxide (-P(=O)heteroaryl2), arylheteroarylphosphine oxide (-P(=O)aryl,heteroaryl), cyclic diaryloxyphosphine, phosphine oxide, aryl-containing phosphine oxide, heteroaryl-containing phosphine oxide, cyclic arylheteroaryloxyphosphine, phosphine oxide containing cyclic heteroaryl, nitriles, benzonitrile, nicotinic nitrile, amides, ureas, and C2 to C3. 42 Heteroaryl; wherein G may contain one or more substituents attached to said group, wherein the one or more substituents are selected from C6 to C6. 18 Aryl, C1 to C 10 Alkyl, C2 to C 14 Heteroaryl groups. In this respect, "cyclic" refers to the "P=O" of phosphine oxide, which is part of a ring formed with the other parts of the group.

[0044] G can be selected from C1 to C. 10 -alkylphosphine oxide, di-C6 to C 10 -Arylphosphine oxide, C 10 -C 42 Dihexarylphosphine oxide, C7-C 42 aryl heteroaryl phosphine oxide, C8-C 42 Phosphorus oxide, containing C8-C 42 Aryl phosphine oxides, C8-C 63 heteroaryl phosphine oxide, C 12 -C 63 Cyclic arylphosphine oxide, C7-C 42 Cyclic aryl heteroaryl phosphine oxide, containing C7-C 42 Cyclic heteroaryl phosphine oxides, 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 contain one or more substituents attached to said group, wherein the one or more substituents are selected from C6 to C6. 12 Aryl, C1 to C6 alkyl, C2 to C 11 Mixed aromatic compounds.

[0045] G can be selected from di-C1 to C4-alkylphosphine oxide, di-C6 to C 10-Arylphosphine oxide, C 10 Dihexarylphosphine oxide, C7-C 25 aryl heteroaryl phosphine oxide, C8-C 42 Phosphorus oxide, containing C8-C 42 Aryl phosphine oxides, C8-C 24 heteroaryl phosphine oxide, C 12 -C 42 Cyclic arylphosphine oxide, C7-C 25 Cyclic aryl heteroaryl phosphine oxide, containing C7-C 25 Circular heteroaryl phosphine oxides and C2 to C 25 Heteroaryl; wherein the corresponding G may contain one or more substituents attached to said group, wherein the one or more substituents are selected from C6 to C6. 10 Aryl, C1 to C4 alkyl, C2 to C5 heteroaryl.

[0046] G is selected from dialkylphosphine oxide, diarylphosphine oxide, alkylarylphosphine oxide, diheteroarylphosphine oxide, arylheteroarylphosphine oxide, cyclic diarylphosphine oxide, phosphine oxide, aryl-containing phosphine oxide, heteroaryl-containing phosphine oxide, cyclic arylheteroarylphosphine oxide, cyclic heteroarylphosphine oxide, nitriles, benzonitrile, nicotinic nitrile, amide group, urea group, and C2 to C3 groups. 17 Heteroaryl; wherein the corresponding G may contain one or more substituents attached to the group, wherein the one or more substituents are selected from phenyl, methyl, ethyl and pyridyl.

[0047] G can be independently selected from dimethylphosphine oxide, diphenylphosphine oxide, nitriles, benzonitrile, nicotinic nitrile, dihydrobenzimidazolone, diphenyl-propane, etc. N,N -Dimethylacetamide, amide, urea, imidazole, phenylbenzimidazolyl, ethylbenzimidazolyl, phenylbenzimidazolyl, phenylbenzimidazolyl, phenylbenzimidazolyl, pyridyl, bipyridyl, pyridylmethyl, dimethylpyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triphenyl-pyrazinyl, benzoquinolinyl, phenanthrolinel, phenylphenanthrolinel, quinazolinyl, benzo[a]azolyl, benzimidazolyl, pyridyl-imidazopyridyl; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ;

[0048] The asterisk symbol " "" indicates the position that is associated with Z in equation (I), and is not shown in it. In the formula, the combination position can be freely chosen.

[0049] G can be independently selected from dimethylphosphine oxide, diphenylphosphine oxide, 2-phenyl-1H-benzo[d]imidazolyl, 2-ethyl-1H-benzo[d]imidazolyl, 2-phenylbenzo[h]quinolinyl, pyridyl, 2,2'-bipyridyl, 5-phenylbenzo[4,5]imidazo[1,2-a]quinolinyl, 9-phenyl-1,10-phenanthrolinel, 2-quinazolinyl, 4-quinazolinyl, 4-phenyl-2-quinazolinyl and (pyridin-2-yl)imidazo[1,5-a]pyridyl; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ;

[0050] The asterisk symbol " " indicates the position where it is combined with Z in equation (I).

[0051] In one implementation, in equation (I), Ar 2 It is C3 to C 21 heteroaryl; Z is C6 to C 12 Aryl; G is C2 to C 42 heteroaryl; m is 1; k is 1; n is 1.

[0052] In one implementation, in equation (I), Ar 2 It is C3 to C 21 Contains N-heteroaryl; Z is phenylene group; G is C2 to C3. 25 heteroaryl; m is 1; k is 1; n is 1.

[0053] In one implementation, in equation (I), Ar 2 It is a triazine group substituted with phenyl and / or a phenyl group substituted with pyridyl, preferably a m-phenylene-3-pyridyl group as in formula B-27; Z is a phenylene group; G is C2 to C3. 25 heteroaryl; m is 1; k is 1; n is 1.

[0054] In one implementation, in equation (I), Ar 2 It is C3 to C 21 Contains N-heteroaryl; Z is m-phenyleneide; G is C2 to C3. 25 heteroaryl; m is 1; k is 1; n is 1.

[0055] In one implementation, in equation (I), Ar 2 It is C3 to C 21 It contains N-heteroaryl; Z is phenylene group; G is triphenyl-pyrazinyl; m is 1; k is 1; n is 1.

[0056] In one implementation, in equation (I), Ar 2It is a triazine group substituted with phenyl and / or a phenyl group substituted with pyridinyl, preferably a m-phenylene-3-pyridinyl group as in formula B-27; Z is a phenylene group; G is a triphenyl-pyrazine group; m is 1; k is 1; n is 1.

[0057] The compounds of formula (I) may be selected from compounds B-1 to B-28 in Table 2 below.

[0058] Table 2:

[0059] In one implementation, the hybrid functionals B3LYP and Gaussian6-31G are used via the TURBOMOLE V6.5 package. Basis set calculations show that, on an absolute scale with the vacuum level at zero, the LUMO level of the compound of formula (I) is in the range of -2.30 eV to -1.20 eV, preferably -2.10 eV to -1.28 eV.

[0060] Compounds of formula (I) may comprise 8 to 13 aromatic or heteroaromatic rings, optionally 8 to 11 aromatic or heteroaromatic rings, optionally 8 to 10 aromatic or heteroaromatic rings, wherein one or more of said aromatic or heteroaromatic rings may be substituted with C1 to C4 alkyl groups. In this respect, the aromatic rings, and correspondingly the heteroaromatic rings, are monoaromatic rings, such as 6-membered aromatic rings like phenyl; 6-membered heteroaromatic rings like pyridyl; 5-membered heteroaromatic rings like pyrroleyl, etc. In systems of fused (hetero)aromatic rings, each ring is considered a monoaromatic ring in this respect. For example, naphthalene comprises two aromatic rings.

[0061] The compound of formula (I) may contain at least one heteroaromatic ring, optionally 1 to 5 heteroaromatic rings, optionally 1 to 4 heteroaromatic rings, optionally 1 to 3 heteroaromatic rings, optionally 1 or 2 heteroaromatic rings.

[0062] The aromatic or heteroaromatic ring of the compound of formula (I) can be a 6-membered ring.

[0063] The heteroaromatic ring of the compound of formula (I) can be an N-containing heteroaromatic ring, optionally all heteroaromatic rings are N-containing heteroaromatic rings, optionally all heteroaromatic rings contain N as the only type of heteroatom.

[0064] The compound of formula (I) may contain at least one 6-membered heteroaromatic ring, each heteroaromatic ring containing one to three N atoms, optionally containing one to three 6-membered heteroaromatic rings, each heteroaromatic ring containing one to three N atoms.

[0065] At least one 6-membered heteroaromatic ring contained in the compound of formula (I) may be an azine. At least one 6-membered heteroaromatic ring contained in compound (I) may be a triazine, a diazine, or a pyrazine.

[0066] If compound (I) contains two or more heteroaromatic rings, the heteroaromatic rings may be separated from each other by at least one aromatic ring that does not contain heteroatoms.

[0067] In one embodiment, the compound of formula (I) contains a polar group "G".

[0068] It may be specified that the compound of formula (I) does not contain the P=O moiety. It may be specified that the compound of formula (I) does not contain P(=O)aryl2. It may be specified that the compound of formula (I) does not contain P(=O)alkyl2. It may be specified that the compound of formula (I) does not contain P(=O)Ph2. It may be specified that the compound of formula (I) does not contain P(=O)(CH3)2. It may be specified that the compound of formula (I) does not contain R'P(=O)R'', wherein R' and R'' are linked to each other to form a ring, i.e., it does not contain cyclophosphine oxide. It may be specified that the compound of formula (I) does not contain R'P(=O)R'', wherein R' and R'' are linked to each other to form a 7-membered ring.

[0069] It can be specified that the compound of formula (I) does not contain two P=O moieties. It can be specified that the compound of formula (I) does not contain two P(=O)aryl 2-membered compounds. It can be specified that the compound of formula (I) does not contain two P(=O)alkyl 2-membered compounds. It can be specified that the compound of formula (I) does not contain two P(=O)Ph 2-membered compounds. It can be specified that the compound of formula (I) does not contain two P(=O)(CH 3) 2-membered compounds. It can be specified that the compound of formula (I) does not contain CN.

[0070] It may be specified that one or more of the following formulas are not included in the scope of compounds of formula (I). ; ; ; ; ; ; ; ; .

[0071] In one embodiment, the compound of formula (II) is not a compound of formula (I).

[0072] Silicon compounds

[0073] In addition to the compound of formula (I), the first electron transport layer also comprises a silicon-containing compound. The silicon-containing compound contains at least two Si atoms.

[0074] Silicon-containing compounds can be sesquioxanes, arylsilanes, or mixtures of two or more of them.

[0075] Silicon-containing compounds can be sesquioxanes.

[0076] Silsesquioxanes employ cage-like or polymeric structures with Si-O-Si connections and tetrahedral Si vertices.

[0077] Silsesquioxanes can have formula (II)

[0078] Si x R S x O 1.5x (II)

[0079] in

[0080] - R S Independently selected from C1 to C 30 hydrocarbon group, - where each C1 to C 30 The hydrocarbon group can be independently substituted by one or more halogens, preferably by one or more F groups; and - x is selected from 6, 8, 10, 12, 14 and 16.

[0081] One or more halogens may be independently selected from F, Cl, Br, and I. Each of the one or more halogens may be F.

[0082] R S Can be independently selected from C1 to C 28 Hydrocarbon group, C1 to C 26 Hydrocarbon group, C1 to C 24 Hydrocarbon group, C1 to C 22 Hydrocarbon group, C1 to C 20 Hydrocarbon group, C1 to C 18 Hydrocarbon group, C1 to C 16 Hydrocarbon group, C1 to C 14 Hydrocarbon group, C1 to C 12 Hydrocarbon group, C1 to C 10 Hydrocarbon group, C1 to C8 hydrocarbon group, C2 to C8 hydrocarbon group, C3 to C8 hydrocarbon group, or C3 to C4 hydrocarbon group, wherein the corresponding hydrocarbon group is unsubstituted or substituted with one or more halogens, preferably substituted with one or more F.

[0083] R SCan be independently selected from C1 to C 28 Alkyl, C1 to C 28 Aryl, C1 to C 28 alkylaryl, or C1 to C 28 arylalkyl, C1 to C 26 Alkyl, C1 to C 26 Aryl, C1 to C 26 alkylaryl, or C1 to C 26 arylalkyl, C1 to C 24 Alkyl, C1 to C 24 Aryl, C1 to C 24 alkylaryl, or C1 to C 24 arylalkyl, C1 to C 22 Alkyl, C1 to C 22 Aryl, C1 to C 22 alkylaryl, or C1 to C 22 arylalkyl, C1 to C 20 Alkyl, C1 to C 20 Aryl, C1 to C 20 alkylaryl, or C1 to C 20 arylalkyl, C1 to C 18 Alkyl, C1 to C 18 Aryl, C1 to C 18 alkylaryl, or C1 to C 18 arylalkyl, C1 to C 16 Alkyl, C1 to C 16 Aryl, C1 to C 16 alkylaryl, or C1 to C 16 arylalkyl, C1 to C 14 Alkyl, C1 to C 14 Aryl, C1 to C 14 alkylaryl, or C1 to C 14 arylalkyl, C1 to C 12 Alkyl, C1 to C 12 Aryl, C1 to C 12 alkylaryl, or C1 to C 12 arylalkyl, C1 to C 10 Alkyl, C1 to C 10 Aryl, C1 to C 10 alkylaryl, or C1 to C 10arylalkyl, C1 to C8 alkyl, C1 to C8 aryl, C1 to C8 alkylaryl, or C1 to C8 arylalkyl, C2 to C8 alkyl, C2 to C8 aryl, C2 to C8 alkylaryl, or C2 to C8 arylalkyl, C3 to C8 alkyl, C3 to C8 aryl, C3 to C8 alkylaryl, or C3 to C8 arylalkyl, or C3 to C4 alkyl, wherein the corresponding hydrocarbon group is unsubstituted or substituted with one or more halogens, preferably substituted with one or more F.

[0084] R S Can be independently selected from C1 to C 28 Alkyl, C1 to C 26 Alkyl, C1 to C 24 Alkyl, C1 to C 22 Alkyl, C1 to C 20 Alkyl, C1 to C 18 Alkyl, C1 to C 16 Alkyl, C1 to C 14 Alkyl, C1 to C 12 Alkyl, C1 to C 10 Alkyl, C1 to C8 alkyl, C2 to C8 alkyl, C3 to C8 alkyl, or C3 to C4 alkyl, wherein the corresponding hydrocarbon group is unsubstituted or substituted with one or more halogens, preferably substituted with one or more F.

[0085] R S It can be independently selected from n-propyl, isobutyl, and 2-phenylethyl, wherein the corresponding group can be substituted with one or more F. It can be specified that all R in a silsesquioxane... s Choose the same option for all.

[0086] R S (Including all substituents) can be independently selected from R S -1 to R S -3, preferably all are selected as the same. R S -1、 R S -2、 R S -3, in" "" indicates the position where it binds to the remaining structure of the sesquioxane.

[0087] R S (Including all substituents) can be independently selected from R S -1 to R S -3, preferably all are selected as the same. R S -1、 RS -2 in" "" indicates the position where it binds to the remaining structure of the sesquioxane.

[0088] x can be selected from 8, 10, and 12. x can be either 8 or 12.

[0089] Silsesquioxanes have formulas S-1 to S-3 S-1 S-2 S-3 Silsesquioxanes may have the formula S-1 or S-2.

[0090] Silicon-containing compounds can be arylsilanes, that is, arylsilanes containing at least two Si atoms. Silicon-containing compounds can be arylsilanes containing two to four Si atoms. Silicon-containing compounds can be arylsilanes containing two or three Si atoms. Silicon-containing compounds can be arylsilanes containing exactly two Si atoms.

[0091] According to this disclosure, arylsilanes can be considered as compounds composed of Si and aryl groups, preferably compounds composed only of Si and a 6-membered aryl ring, that is, they preferably do not contain any other components, such as other heteroatoms, alkyl groups, etc. (however, this does not exclude the substitution by deuterium).

[0092] Arylsilanes can have formula (III), (III) in Ar S1 To Ar S7 Independently selected from C6 to C 24 Aryl. S1 To Ar S7 Independently selected from C6 to C 18 Aryl.

[0093] Ar S1 To Ar S3 and Ar S5 To Ar S7 Can be independently selected from C6 to C 18 Aryl, C6 to C 12 Aryl or C6 to C 10 Aryl. S1 To Ar S3 and Ar S5 To Ar S7 Each can be a phenyl group.

[0094] Ar S4 It can be C12 To C 24 Aryl, C 12 To C 18 Aryl, C 18 To C 24 Aryl or C 18 Aryl. S4 It can be selected from phenyl, biphenyl, and terphenyl.

[0095] The arylsilane of formula (III) may contain 6 to 12 six-membered aryl rings, 7 to 11 six-membered aryl rings, 8 to 10 six-membered aryl rings, or 9 six-membered aryl rings.

[0096] Ar S4 It could be Ar S4 -1 Ar S4 -1 in" "1" indicates the position where the substance binds to the following groups:

[0097] and" 2” is the position where it binds to the following groups: .

[0098] Ar S4 Optional from Ar S4 -2 to Ar S4 -7 Ar S4 -2、 Ar S4 -3、 Ar S4 -4、 Ar S4 -5、 Ar S4 -6、 Ar S4 -7, in" "1" indicates the position where the substance binds to the following groups:

[0099] and" 2” is the position where it binds to the following groups: .

[0100] Arylsilanes can have the formula S-4 S-4.

[0101] Electro-doped

[0102] The first electron transport layer does not contain any electrical dopants, that is, it does not contain electrical dopants such as n-type dopants, especially redox n-type dopants.

[0103] In this regard, the term "free of" does not exclude impurities. Impurities have no technical impact on the objectives achieved by this invention. During processing, impurities are not intentionally added to the layers.

[0104] The term “free of” a compound means that such a compound is not intentionally added to the layer during processing.

[0105] Electro-dopers, especially n-type dopers, should be understood as compounds that, when embedded in an electron transport matrix, can improve the electronic properties of the resulting organic material compared to a pure matrix under the same physical conditions, particularly improving electronic properties in terms of electron injection and / or electronic conductivity.

[0106] In the context of this invention, "embedded in the electron transport matrix" means uniformly mixed with the electron transport matrix.

[0107] The electrodopers discussed in this article are selected in particular from elemental metals, metal salts, metal complexes, and organic groups.

[0108] In one embodiment, the electrodoperbating agent is selected from alkali metal salts and alkali metal complexes; preferably from lithium salts and lithium organo-complexes; more preferably from lithium halides and lithium organo-chelates; even more preferably from lithium fluoride, lithium quinoline, lithium borate, lithium phenolate, lithium pyridyl alcohol, or from lithium complexes having Schiff base ligands; most preferably, - Lithium complexes have formula II, III, or IV:

[0109] in

[0110] A1 to A6 are selected from CH, CR, N, and O, either identically or independently; R is selected, either identically or independently, from hydrogen, halogen, alkyl, aryl, or heteroaryl groups having 1 to 20 carbon atoms; more preferably, A1 to A6 are CH. - The boronic ester / salt organic ligand is tetrakis(1H-pyrazol-1-yl)boronic ester / salt. - Phenolic esters / salts are 2-(pyridin-2-yl)phenolic esters / salts, 2-(diphenylphosphoyl)phenolic esters / salts, imidazole phenolic esters / salts, 2-(pyridin-2-yl)phenolic esters / salts, or 2-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenolic esters / salts. - Pyridine alcohol ester / salt is 2-(diphenylphospho)pyridine-3-ol ester / salt, - Lithium Schiff bases have structures 100, 101, 102, or 103:

[0111] According to one embodiment of the present invention, the first electron transport layer of the present invention does not contain lithium organic complexes or lithium 8-hydroxyquinoline (=LiQ).

[0112] According to one embodiment of the present invention, the first electron transport layer is metal-free, wherein the metal is preferably selected from alkali metals, alkaline earth metals, rare earth metals, and metals of the first transition period, such as Ti, V, Cr, and Mn, particularly selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sm, Eu, Tm, and Yb; more preferably selected from Li, Na, K, Rb, Cs, Mg, and Yb; even more preferably selected from Li, Na, Cs, and Yb; and most preferably selected from Li, Na, and Yb.

[0113] The most practical benchmark for the strength of n-type dopants is their redox potential. There are no particular restrictions on how negative the redox potential can be.

[0114] Since the reduction potential of the typical electron transport matrix used in organic semiconductors is generally in the range of about -0.8 V to about -3.1 V if measured by cyclic voltammetry relative to a ferrocene / ferrocene cation reference redox pair, the practically applicable range of the redox potential of the n-type dopant that can effectively n-type dope such a matrix is ​​a slightly wider range, namely about -0.5 V to about -3.3 V.

[0115] The measurement of redox potential is actually performed on the corresponding redox pairs composed of the reduced and oxidized forms of the same compound.

[0116] When the n-type dopant is an electrically neutral metal complex and / or an electrically neutral organic radical, its redox potential is actually measured against a redox pair formed by: (i) Electroneutral metal complexes and their cationic radicals formed by the separation of an electron from an electron in an electronneutral metal complex, or (ii) Electroneutral organic radicals and the cations formed by the separation of an electron from an electron-neutral organic radical.

[0117] Preferably, for the corresponding redox pairs consisting of the following, if measured by cyclic voltammetry relative to a ferrocene / ferrocene cation reference redox pair, the redox potential of the electrically neutral metal complex and / or the electrically 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, even more preferably more negative than -2.1 V, and most preferably more negative than -2.5 V: (i) Electroneutral metal complexes and their cationic radicals formed by the separation of an electron from an electron in an electronneutral metal complex, or (ii) Electroneutral organic radicals and the cations formed by the separation of an electron from an electron-neutral organic radical.

[0118] In a preferred embodiment, the redox potential of the n-type dopant is between a value that is about 0.5 V more positive than the reduction potential of the selected electron transport matrix and a value that is about 0.5 V more negative than it.

[0119] Suitable electrically neutral metal complexes as n-type dopants can be, for example, strongly reducing complexes of certain low oxidation state transition metals. As described in more detail in WO 2005 / 086251, particularly strong n-type dopants can be selected from, for example, Cr(II), Mo(II) and / or W(II) guanidine complexes, such as W2(hpp)4.

[0120] As described in more detail in EP 1 837 926 B1, WO 2007 / 107306, or WO 2007 / 107356, a 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. Elemental metal should be understood as a metal in a pure metallic state, a metallic alloy state, or a state of free atoms or metal clusters. It should be understood that a metal deposited from a metallic phase, such as a pure bulk metal, by vacuum thermal evaporation vaporizes in its elemental form. It should also be understood that if the vaporized 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 should be understood that any metal-doped covalent material prepared by vacuum thermal evaporation contains at least partially a metal in its elemental form.

[0121] For use in user electronic products, only metals containing stable nuclides or nuclides with extremely long radioactive decay half-lives are suitable. The nuclear stability of natural potassium is an acceptable level.

[0122] In one embodiment, the electroactive dopant may be selected from an electropositive metal, which is selected from alkali metals, alkaline earth metals, rare earth metals, and first transition period metals Ti, V, Cr, and Mn. Preferably, the n-type dopant may be selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sm, Eu, Tm, and Yb; more preferably from Li, Na, K, Rb, Cs, Mg, and Yb; even more preferably from Li, Na, Cs, and Yb; and most preferably from Li, Na, and Yb.

[0123] Specific implementation methods

[0124] In one embodiment, the organic light-emitting device includes an anode, a cathode, a light-emitting layer, an electron injection layer, and a first electron transport layer; in - The light-emitting layer, the electron injection layer, and the first electron transport layer are arranged between the anode and the cathode; - An electron injection layer and a first electron transport layer are arranged between the light-emitting layer and the cathode; - The first electron transport layer is arranged between the light-emitting layer and the electron injection layer; - The first electron transport layer includes compounds of formula (I) and silicon-containing compounds; (Ar 2 ) m -(Z k -G) n (I); - m and n are 1 or 2 independently; - k is independently 0, 1, or 2; - Ar 2 Independently selected from C2 to C 42 heteroaryl and C6 to C 60 Aryl, - where each Ar 2 It can be substituted by one or two independent substituents selected from the following: C6 to C6. 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 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 Independently selected from C6 to C 12 Aryl, C3 to C 12Heteroaryl, 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; - Among them Ar 2 Each C6 to C 12 Aryl substituents and Ar 2 Each C3 to C 11 The heteroaryl substituents can be replaced by C1 to C4 alkyl groups or halogens; - Z is independently selected from C6 to C 30 Aryl, - where each Z can be substituted by one or two substituents independently selected from the following: C6 to C6 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 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 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; - where each C6 to C on Z 12 The aryl substituents can be replaced by C1 to C4 alkyl groups or halogens; - Choose G such that the dipole moment of the compound G-phenyl is ≥1 D; - Silicon-containing compounds contain at least two Si atoms; - The silicon-containing compound is a sesquioxane; and - The first electron transport layer contains no electrical dopants.

[0125] In this embodiment, the compound of formula (I) and the sesquioxane can be as detailed above.

[0126] In one embodiment, the organic light-emitting device includes an anode, a cathode, a light-emitting layer, an electron injection layer, and a first electron transport layer; in - The light-emitting layer, the electron injection layer, and the first electron transport layer are arranged between the anode and the cathode; - An electron injection layer and a first electron transport layer are arranged between the light-emitting layer and the cathode; - The first electron transport layer is arranged between the light-emitting layer and the electron injection layer; - The first electron transport layer includes compounds of formula (I) and silicon-containing compounds; (Ar 2 ) m -(Z k -G) n (I); - m and n are 1 or 2 independently; - k is independently 0, 1, or 2; - Ar 2 Independently selected from C2 to C 42 heteroaryl and C6 to C 60 Aryl, - where each Ar 2 It can be substituted by one or two independent substituents selected from the following: C6 to C6. 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 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 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; - Among them Ar 2 Each C6 to C 12 Aryl substituents and Ar 2 Each C3 to C 11 The heteroaryl substituents can be replaced by C1 to C4 alkyl groups or halogens; - Z is independently selected from C6 to C 30 Aryl, - where each Z can be substituted by one or two substituents independently selected from the following: C6 to C6 12Aryl 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 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 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; - where each C6 to C on Z 12 The aryl substituents can be replaced by C1 to C4 alkyl groups or halogens; - Choose G such that the dipole moment of the compound G-phenyl is ≥1 D; - Silicon-containing compounds contain at least two Si atoms; - The silicon-containing compound is an arylsilane; and - The first electron transport layer contains no electrical dopants.

[0127] In this embodiment, the compound of formula (I) and the arylsilane may be as detailed above.

[0128] Cavity barrier

[0129] Organic light-emitting devices may further include a hole-blocking layer. in - A hole blocking layer is disposed between the light-emitting layer and the first electron transport layer; - Hole-blocking layer containing (IV) compounds (Ar 1 -A c ) a -X b (IV); - a and b are 1 or 2 independently; - c is either 0 or 1 independently; - Ar 1 Independently selected from C6 to C 60 Aryl or C2 to C 42 Mixed aromatics, - where each Ar 1 It can be substituted by one or two independent substituents selected from the following: C6 to C6. 12 Aryl, C3 to C11 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 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 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; - Among them Ar 1 Each C6 to C 12 Aryl substituents and Ar 1 Each C3 to C 11 The heteroaryl substituents can be replaced by C1 to C4 alkyl groups or halogens; - A is independently selected from C6 to C 30 Aryl, - Each A may be substituted by one or two substituents independently selected from the following: C6 to C6 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 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 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; - where each C6 to C on A 12 The aryl substituents can be replaced by C1 to C4 alkyl groups or halogens; - X is independently selected from C2 to C 42 heteroaryl and C6 to C 60 Aryl, - where each X can be substituted by one or two substituents independently selected from the following: C6 to C6 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 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 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; - where each C6 to C on X 12 aryl substituents and each C3 to C on X 11 The heteroaryl substituents can be replaced by C1 to C4 alkyl groups or halogens; and - The molecular dipole moment of the compound of formula (IV) is ≥0 D but ≤4 D.

[0130] A hole-blocking layer, if present, comprising a compound of formula (IV).

[0131] (Ar 1 -A c ) a -X b (IV).

[0132] The hole blocking layer may be composed of a compound of formula (IV). Alternatively, the hole blocking layer may be composed of a compound of formula (IV) and a mixture of one or more other compounds, provided that the other compounds are not electrodopers. The hole blocking layer may contain more than one compound of formula (IV). In particular, the hole blocking layer may be composed of a compound of formula (IV) and a mixture of other compounds known in the art as electron transport matrix compounds. Exemplary other electron transport matrix compounds that may be included are disclosed below.

[0133] A hole blocking layer can be disposed between the light-emitting layer and the first electron transport layer. The hole blocking layer can be disposed in direct contact with the light-emitting layer. Alternatively, the hole blocking layer can be disposed in a "contact-sandwiched" configuration between the light-emitting layer and the first electron transport layer.

[0134] The hole blocking layer may have a thickness of <50 nm, optionally between 1 nm and 30 nm, optionally between 1 nm and 10 nm, or optionally between 1 nm and 5 nm.

[0135] In the compound of formula (IV), the group "A" is a linker (if present, i.e., in the case of c>1) to the group Ar. 1 The spacer portion between X and ... Compounds of formula (IV) contain more than one group (Ar ... 1 -A c In the case of ), the group may independently contain or may independently not contain spacer group A.

[0136] In the compound of formula (IV), a and b are independently 1 or 2. Alternatively, a and b can both be 1.

[0137] In the compounds of formula (IV), c is independently 0 or 1.

[0138] Ar 1 Independently selected from C6 to C 60 Aryl or C2 to C 42 heteroaryl, or 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 Mixed aromatic compounds.

[0139] Ar 1 It can be C6 to C independently. 54 Aryl, optionally C6 to C 48 Aryl, optionally C6 to C 42 Aryl, optionally C6 to C 36 Aryl, optionally C6 to C 30 Aryl, optionally C6 to C 24 Aryl.

[0140] Ar 1 It can be C2 to C independently 42 heteroaryl, optionally C2 to C 40 heteroaryl, optionally C2 to C 36 heteroaryl, optionally C2 to C 30 heteroaryl, optionally C2 to C3 24 Mixed aromatic compounds.

[0141] In one implementation, Ar 1 Unlike X.

[0142] Ar 1 The system may contain two or more cyclic aromatic rings, preferably three or more cyclic aromatic rings.

[0143] Ar 1 It may contain at least one sp 3 - Hybridized carbon atoms.

[0144] Ar 1 It may contain at least one carbon-carbon sp that is not integrated into the aromatic ring structure. 2 Olefin bond. In the embodiment, Ar 1 Independently selected from unsubstituted C2 to C 42 Heteroaryl groups, where heteroatoms are bonded to Ar via single bonds. 1 In the molecular structure.

[0145] Ar 1 It may be independently selected from phenyl, naphthyl, anthraceneyl, fluoranthyl, xanthyl, spiro-xanthyl, fluorenyl, spiro-fluorenyl, triphenylsilyl, tetraphenylsilyl, dibenzofuranyl, di-dibenzofuranyl, pyrimidinyl, pyrazinyl, aryl-alkenyl or a group having formula (IIa). (IIa) in - Asterisk symbol " The group representing formula (IIa) is used for the binding site with A; and - R 1 To R 5 Independently selected from H, C6 to C 12 Aryl, and C3 to C 10 Or C4 to C5 heteroaryl groups.

[0146] Ar 1 It can be independently selected from phenyl, anthracene, fluorenyl or groups of formula (IIa). (IIa) Where R 1 To R 5 It is independently selected from H and phenyl.

[0147] Ar 1 It can be a group of formula (IIa) (IIa) And R 1 To R 5 At least two of them are not H.

[0148] In the group of formula (IIa), R 1 To R 5 At least two of the elements that are not H can be adjacent to each other. 1 To R 5 At least one of which is not H can be in the position of The two groups are adjacent to each other if they are respectively bonded to adjacent carbon atoms of the benzene ring in formula (IIa).

[0149] Ar 1 It can be independently selected from one of the following groups. ; ; ; ; ; ; ; ; ; ; ; ; ; ; The asterisk symbol " "These represent the binding sites used to bind with A."

[0150] In Ar 1 When substituted, each substituent may be independently selected from phenyl, naphthyl, biphenyl, pyridyl, methylpyridyl, dimethylpyridyl, dibenzofuranyl, dibenzothiophenyl, and benzothiophenyl.

[0151] A can be independently selected from C6 to C6, whether substituted or unsubstituted. 30 Aryl, or C6 to C 24 Aryl, or C6 to C 18 Aryl.

[0152] A can be independently selected from phenylene, naphthylene, biphenylene, and terphenylene, and the group can be substituted or not substituted, respectively.

[0153] A can be independently selected from one or a combination of the following groups. ; ; ; ; Among them, it is used to bind to Ar 1 The binding position of X can be freely chosen, preferably ; ; ; ; ; ; ; When A is substituted, each substituent on A can be independently selected from phenyl and C1 to C4 alkyl groups.

[0154] X can 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, optionally C3 to C 21 heteroaryl and C6 to C 24 Aryl groups, wherein the corresponding groups may or may not be substituted.

[0155] X can be independently selected from C2 to C. 39 Contains N-heteroaryl, C2 to C 39 Contains O-heteroaryl and C6 to C 54 Aryl, optionally C2 to C 36 Contains N-heteroaryl, C2 to C 36 Contains O-heteroaryl and C6 to C 48 Aryl, optionally C3 to C 30 Contains N-heteroaryl, C3 to C 30 Contains O-heteroaryl and C6 to C 42 Aryl, optionally C3 to C 27 Contains N-heteroaryl, C3 to C 27 Contains O-heteroaryl and C6 to C 36 Aryl, optionally C3 to C 24 Contains N-heteroaryl, C3 to C 24 Contains O-heteroaryl and C6 to C 30 Aryl, optionally C3 to C 21 Contains N-heteroaryl, C3 to C 21 Contains O-heteroaryl and C6 to C 24 Aryl.

[0156] X can be independently selected from C2 to C. 39 Contains N-heteroaryl and C6 to C 54 Aryl, optionally C2 to C36 Contains N-heteroaryl and C6 to C 48 Aryl, optionally C3 to C 30 Contains N-heteroaryl and C6 to C 42 Aryl, optionally C3 to C 27 Contains N-heteroaryl and C6 to C 36 Aryl, optionally C3 to C 24 Contains N-heteroaryl and C6 to C 30 Aryl, optionally C3 to C 21 Contains N-heteroaryl and C6 to C 24 Aryl. In this respect, the corresponding N-containing heteroaryl group may be specified to contain one or more N atoms as the only one or more heteroatoms.

[0157] X may be independently selected from triazinyl, 1,2-diazinyl, 1,3-diazinyl, 1,4-diazinyl, quinazolinyl, benzoquinazolinyl, benzimidazolyl, quinolinyl, benzoquinolinyl, benzoacridyl, dibenzoacridyl, fluoranthyl, anthraceneyl, naphthyl, biphenylideneyl, phenanthrolinel, and dinaphthofuranyl, wherein the groups may be substituted or unsubstituted.

[0158] X may be independently selected from triazinyl, 1,2-diazinyl, 1,3-diazinyl, 1,4-diazinyl, quinazolinyl, benzoquinazolinyl, benzoacridyl, dibenzoacridyl, fluoranthyl, anthraceneyl, naphthyl, biphenylpyrimidine, phenanthrolinel, and dinaphthofuranyl, wherein the groups may be substituted or unsubstituted.

[0159] X may be independently selected from triazinyl, 1,2-diazinyl, 1,3-diazinyl, 1,4-diazinyl, quinazolinyl, benzoquinazolinyl, benzoacridyl, dibenzoacridyl, and fluoranthyl, wherein the groups may be substituted or not substituted.

[0160] X can be independently selected from one of the following groups. ; ; ;

[0161] The asterisk symbol " "" respectively indicate the binding positions of the groups used to bind with A.

[0162] When X is substituted, each substituent on X can be independently selected from phenyl, naphthyl, and biphenyl.

[0163] When X is substituted, the corresponding substituted X group can be ; ; ; .

[0164] The asterisk symbol " "" respectively indicate the binding positions of the groups used to bind with A.

[0165] It may be specified that the compound of formula (IV) does not contain the P=O moiety. It may be specified that the compound of formula (IV) does not contain P(=O)aryl2. It may be specified that the compound of formula (IV) does not contain P(=O)alkyl2. It may be specified that the compound of formula (IV) does not contain P(=O)Ph2. It may be specified that the compound of formula (IV) does not contain P(=O)(CH3)2. It may be specified that the compound of formula (IV) does not contain R'P(=O)R'', wherein R' and R'' are linked to each other to form a ring, i.e., it does not contain cyclophosphine oxide. It may be specified that the compound of formula (IV) does not contain R'P(=O)R'', wherein R' and R'' are linked to each other to form a 7-membered ring.

[0166] It can be specified that the compound of formula (IV) does not contain two P=O moieties. It can be specified that the compound of formula (IV) does not contain two P(=O)aryl 2-membered compounds. It can be specified that the compound of formula (IV) does not contain two P(=O)alkyl 2-membered compounds. It can be specified that the compound of formula (IV) does not contain two P(=O)Ph 2-membered compounds. It can be specified that the compound of formula (IV) does not contain two P(=O)(CH 3) 2-membered compounds. It can be specified that the compound of formula (IV) does not contain CN.

[0167] It may be specified that one or more of the following formulas are not included in the scope of compounds of formula (IV). ; ; ; ; ; ; .

[0168] Compounds of formula (IV) may contain 6 to 14 aromatic or heteroaromatic rings, optionally 7 to 13 aromatic or heteroaromatic rings, optionally 7 to 12 aromatic or heteroaromatic rings, optionally 9 to 11 aromatic or heteroaromatic rings. In this respect, the aromatic rings, and correspondingly the heteroaromatic rings, are monoaromatic rings, such as 6-membered aromatic rings like phenyl; 6-membered heteroaromatic rings, an example of which would be pyridyl; 5-membered heteroaromatic rings, an example of which would be pyrrole, etc. In systems of fused (hetero)aromatic rings, each ring is considered to be a monoaromatic ring in this respect. For example, naphthalene contains two aromatic rings.

[0169] Using the hybrid functionals B3LYP and Gaussian 6-31G via the TURBOMOLE V6.5 package Basis set calculations show that the molecular dipole moment of compounds of formula (IV) can be ≥0 D but ≤4 D; or ≥0 D but ≤3.5 D; or ≥0 D but ≤3.0 D; or ≥0 D but ≤2.5 D; or ≥0 D but ≤2.0 D. In this respect, the dipole moment of molecules containing N atoms... It is given by the following formula:

[0170] in and The partial charge and position of atom i in the molecule. The dipole moment is determined by a semi-empirical molecular orbital method. This is implemented in the gas phase using a hybrid functional B3LYP with 6-31G, as implemented in the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). Basis sets are used to optimize the geometry of the molecular structure. If more than one conformation is feasible, the conformation with the lowest total energy is selected to determine the bond lengths of the molecule.

[0171] In one implementation, the hybrid functionals B3LYP and Gaussian6-31G are used via the TURBOMOLE V6.5 package. Basis set calculations show that, on an absolute scale with the vacuum level at zero, the LUMO level of the compound of formula (IV) is in the range of -1.90 eV to -1.60 eV, preferably -1.87 eV to -1.65 eV, preferably -1.85 eV to -1.65 eV.

[0172] The compounds of formula (IV) may be selected from compounds A-1 to A-29 in Table 4 below.

[0173] Table 4:

[0174] In one implementation, the hybrid functionals B3LYP and Gaussian6-31G are used via the TURBOMOLE V6.5 package. Basis set calculations show that, on an absolute scale with the vacuum level at zero, the LUMO level of the compound of formula (IV) is in the range of -1.90 eV to -1.60 eV, preferably -1.85 eV to -1.65 eV.

[0175] Other layers

[0176] According to the present invention, in addition to the layers already mentioned above, the organic light-emitting device may also include other layers. Exemplary embodiments of each layer are described below: base The substrate can be any substrate commonly used to manufacture electronic devices such as organic light-emitting diodes (OLEDs). If light is emitted through the substrate, it should be a transparent or translucent material, such as a glass substrate or a transparent plastic substrate. If light is emitted through the top surface, the substrate can be a transparent or opaque material, such as a glass substrate, a plastic substrate, a metal substrate, or a silicon substrate. It may be specified that the substrate is opaque.

[0177] Anode electrode

[0178] The organic light-emitting device of the present invention includes an anode (anode electrode). The anode electrode can be formed by deposition or sputtering of a material used to form the anode electrode. The material used to form the anode electrode can be a high work function material to facilitate 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 (AlZnO), and zinc oxide (ZnO) can be used to form the anode electrode. The anode electrode can also be formed using metals, typically silver (Ag), gold (Au), or metal alloys.

[0179] Hole injection layer

[0180] Hole-injected layers (HILs) can be formed on the anode electrode via vacuum deposition, spin coating, printing, casting, slot die coating, and Langmuir-Blodgett (LB) deposition. When using vacuum deposition to form HILs, 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, typically, vacuum deposition conditions can include deposition temperatures ranging from 100°C to 500°C, and 10... -8 Up to 10 -3 The pressure was 1 Torr (1 Torr equals 133.322 Pa) and the deposition rate was 0.1 nm / s to 10 nm / s.

[0181] When spin coating or printing is used to form HILs, 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, coating conditions may 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.

[0182] HILs can be formed from any compound commonly used to form HILs. Examples of compounds that can be used to form HILs 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-ethimidedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), and polyaniline / poly(4-styrenesulfonate) (PANI / PSS).

[0183] HILs may contain or be composed of p-type dopants, and the p-type dopants may be selected from, but are not limited to, tetrafluorotetracyanoquinone dimethyl ether (F4TCNQ), 2,2'-(perfluoronaphthalene-2,6-diethylenedipropylene nitrile) or 2,2',2''-(cyclopropane-1,2,3-triethylenedipropylene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile). HILs may be selected from hole transport matrix compounds doped with p-type dopants. Typical examples of known doped hole transport materials are: copper phthalocyanine (CuPc) with a HOMO level of approximately -5.2 eV; tetrafluorotetracyanoquinone dimethane (F4TCNQ) doped with a LUMO level of approximately -5.2 eV; zinc phthalocyanine (ZnPc) doped with F4TCNQ (HOMO = -5.2 eV); α-NPD (N,N'-bis(naphthyl-1-yl)-N,N'-bis(phenyl)-benzidine) doped with F4TCNQ; and α-NPD doped with 2,2'-(perfluoronaphthyl-2,6-diethylenediamine)dimalonitrile. The concentration of the p-type dopant can be selected from 1 wt% to 20 wt%, more preferably from 3 wt% to 10 wt%.

[0184] The thickness of the HIL can range from about 1 nm to about 100 nm, for example, from about 1 nm to about 25 nm. When the thickness of the HIL is within this range, the HIL can have excellent hole injection characteristics without substantially impairing the driving voltage.

[0185] Hole transport layer

[0186] Hole transport layers (HTLs) can be formed on hollow inlets (HILs) via vacuum deposition, spin coating, slot die coating, printing, casting, and Langmuir-Blodgett (LB) deposition. When forming HTLs via vacuum deposition or spin coating, the deposition and coating conditions can be similar to those for HIL formation. However, the conditions for vacuum or solution deposition can vary depending on the compound used to form the HTL.

[0187] HTLs can be formed from any compound commonly used to form HTLs. Suitable compounds are disclosed, for example, in Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953-1010, which are incorporated herein by reference. Examples of compounds that can be used to form HTLs 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'-di(naphthyl-1-yl)-N,N'-diphenylbenzidine (α-NPD); and triphenylamine compounds, such as 4,4',4''-tris(N-carbazolyl)triphenylamine (TCTA). In these compounds, TCTA can transport holes and inhibit exciton diffusion into the EML.

[0188] 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, and further about 120 nm to about 140 nm. The preferred thickness of the HTL can be from 170 nm to 200 nm.

[0189] When the thickness of the HTL is within this range, the HTL can have excellent hole transport characteristics without substantially damaging the driving voltage.

[0190] Electron blocking layer

[0191] The function of the electron blocking layer (EBL) is to prevent electrons from transferring from the emissive layer to the hole transport layer, thereby confining electrons within the emissive layer. This improves efficiency, operating voltage, and / or lifetime. Typically, the electron blocking layer contains a triarylamine compound. The LUMO level of the triarylamine compound can be closer to the vacuum level than the LUMO level of the hole transport layer. Compared to the HOMO level of the hole transport layer, the electron blocking layer can have a HOMO level further away from the vacuum level. The thickness of the electron blocking layer can be selected between 2 nm and 20 nm.

[0192] If an electron blocking layer has a high triplet energy level, it can also be described as a triplet control layer.

[0193] If a phosphorescent green or blue emitting layer is used, the function of the triplet control layer is to reduce triplet quenching. This allows for higher luminous efficiency from the phosphorescent emitting layer. The triplet control layer is selected from triarylamine compounds whose triplet energy level is higher than that of the phosphorescent emitter in the adjacent emitting layer. EP 2 722 908 A1 describes compounds suitable for triplet control layers, particularly triarylamine compounds.

[0194] Emissive Layer (EML)

[0195] The light-emitting layer in the organic light-emitting device according to the present invention can be a blue light-emitting layer or a green light-emitting layer.

[0196] EML can be formed on HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When using vacuum deposition or spin coating to form EML, the deposition and coating conditions can be similar to those for HIL formation. However, the deposition and coating conditions can vary depending on the compound used to form the EML.

[0197] It can be specified that the luminescent layer does not contain compounds of formula (I).

[0198] The luminescent layer (EML) can be formed by a combination of a host and a luminescent dopant. Examples of hosts are Alq3, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,10-bis(naphthyl-2-yl)anthracene (ADN), 4,4',4"-tris(carbazole-9-yl)triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-bis-2-naphthylanthracene (TBADN), stilbeneyl arylene (DSA), and bis(2-(2-hydroxyphenyl)benzothiazolic acid)zinc (Zn(BTZ)2).

[0199] The luminescent dopant can be a phosphorescent or fluorescent luminescent material. Phosphorescent luminescent materials and those emitting light via thermally activated delayed fluorescence (TADF) are preferred due to their higher efficiency. The luminescent material can be a small molecule or a polymer.

[0200] Examples of red-emitting dopants include PtOEP, Ir(piq)3, and Btp2Ir(acac), but are not limited to these. These compounds are phosphorescent; however, fluorescent red-emitting dopants can also be used.

[0201] Examples of phosphorescent green luminescent dopants are Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2(acac), and Ir(mpyp)3.

[0202] Examples of phosphorescent blue emitting electron dopants are F₂Irpic, (F₂ppy)₂Ir(tmd), and Ir(dfppz)₃, as well as terfluorene. Examples of fluorescent blue emitting electron dopants are 4,4'-bis(4-diphenylaminostyryl)biphenyl (DPAVBi) and 2,5,8,11-tetratert-butylperylene (TBPe).

[0203] Based on 100 parts by weight of the host, the amount of luminescent dopant can range from about 0.01 parts by weight to about 50 parts by weight. Alternatively, the luminescent layer can be composed of a luminescent 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 exhibit excellent luminescence without substantially impairing the driving voltage.

[0204] Hole blocking layer (HBL)

[0205] Hole blocking layers (HBLs) can be formed on the EML using methods such as vacuum deposition, spin coating, slot die coating, printing, casting, and LB deposition to prevent holes from diffusing into the ETL. When the EML contains phosphorescent dopants, the HBL can also have triplet exciton blocking functionality.

[0206] HBL can also be referred to as auxiliary ETL or a-ETL.

[0207] When forming HBLs using vacuum deposition or spin coating, the deposition and coating conditions can be similar to those for forming HILs. However, the deposition and coating conditions can vary depending on the compound used to form the HBL. Any compound commonly used to form HBLs can be used. Examples of compounds used to form HBLs include diazole derivatives, triazole derivatives, and phenanthrene derivatives.

[0208] HBLs can have a thickness in the range of about 5 nm to about 100 nm, for example, in the range of about 10 nm to about 30 nm. When the thickness of the HBL is within this range, the HBL can have excellent hole blocking properties without substantially impairing the driving voltage.

[0209] According to this disclosure, HBL can be a hole blocking layer.

[0210] Hole blocking layers may not contain silicon compounds.

[0211] Electron Transport Layer (ETL)

[0212] The OLED according to the invention includes an electron transport layer (ETL), particularly a first electron transport layer as described herein. The OLED according to the invention may include one or more other electron transport layers (ETLs).

[0213] By appropriately adjusting the energy levels of specific ETL layers, electron injection and transport can be controlled, and holes can be effectively blocked. Therefore, OLEDs can have a long lifespan.

[0214] The electron transport layer may comprise ETM materials known in the art. There are no particular limitations on compounds suitable for use in ETMs.

[0215] It can be specified that ETL includes an electron transport matrix compound and an electric dopant.

[0216] In one embodiment, the electron transport matrix compound consists of covalently bonded atoms. Preferably, the electron transport matrix compound comprises a conjugated system with at least 6 delocalized electrons, more preferably at least 10 delocalized electrons. In one embodiment, as disclosed, for example, in documents EP 1 970 371 A1 or WO 2013 / 079217 A1, the conjugated system with delocalized electrons may be contained in an aromatic or heteroaromatic structural moiety.

[0217] The ETL, in addition to the first electron transport layer, may contain electric dopants, such as n-type dopants, especially redox n-type dopants.

[0218] Electro-dopers, especially n-type dopers, should be understood as compounds that, when embedded in an electron transport matrix, improve the electronic properties of the resulting organic material compared to a pure matrix under the same physical conditions, particularly improving electronic properties in terms of electron injection and / or electronic conductivity.

[0219] In the context of this invention, "embedded in the electron transport matrix" means uniformly mixed with the electron transport matrix.

[0220] Electrodopers can be selected from elemental metals, metal salts, metal complexes, and organic groups.

[0221] In one embodiment, the electrodoperbating agent is selected from alkali metal salts and alkali metal complexes; preferably from lithium salts and lithium organo-complexes; more preferably from lithium halides and lithium organo-chelates; even more preferably from lithium fluoride, lithium quinoline, lithium borate, lithium phenolate, lithium pyridyl alcohol, or from lithium complexes having Schiff base ligands; most preferably, - Lithium complexes have formula II, III, or IV:

[0222] in

[0223] A1 to A6 are selected from CH, CR, N, and O, either identically or independently; R is selected, either identically or independently, from hydrogen, halogen, alkyl, aryl, or heteroaryl groups having 1 to 20 carbon atoms; more preferably, A1 to A6 are CH. - The boronic ester / salt organic ligand is tetrakis(1H-pyrazol-1-yl)boronic ester / salt. - Phenolic esters / salts are 2-(pyridin-2-yl)phenolic esters / salts, 2-(diphenylphosphoyl)phenolic esters / salts, imidazole phenolic esters / salts, 2-(pyridin-2-yl)phenolic esters / salts, or 2-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenolic esters / salts. - Pyridine alcohol ester / salt is 2-(diphenylphospho)pyridine-3-ol ester / salt, - Lithium Schiff bases have structures 100, 101, 102, or 103:

[0224] According to one embodiment of the present invention, the electrodopermeable is a lithium organic complex, such as lithium 8-hydroxyquinoline (=LiQ).

[0225] It can be specified that the ETL, except for the first electron transport layer, does not contain compounds of formula (I).

[0226] Electron Injection Layer (EIL)

[0227] An electron transport layer (EIL) that facilitates electron injection from the cathode into the electron transport layer stack can be formed on, preferably directly on, the electron transport layer. Examples of materials used to form the EIL or materials included in the EIL include lithium 8-hydroxyquinoline (LiQ), LiF, NaCl, CsF, Li₂O, BaO, Ca, Ba, Yb, and Mg, known in the art. The deposition and coating conditions for forming the EIL are similar to those for forming a high-level electron transport layer (HIL), but the deposition and coating conditions may vary depending on the material used to form the EIL. The EIL may contain an organic matrix material doped with an n-type dopant. The matrix material may be selected from materials conventionally used as matrix materials for electron transport layers.

[0228] An EIL can be composed of multiple individual EIL sublayers. When an EIL is composed of multiple individual EIL sublayers, the number of sublayers is preferably two. Each individual EIL sublayer can contain different materials used to form the EIL.

[0229] The thickness of the EIL can 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 impairing the driving voltage.

[0230] It can be specified that the electron injection layer does not contain compounds of formula (I).

[0231] It can be specified that the electron injection layer is made of Yb.

[0232] cathode electrode

[0233] The cathode (cathode) is formed on the electron transport layer (EIL, if present) or on the electron transport layer (ETL), preferably directly on the EIL, and preferably in direct contact with the EIL. In the context of this invention, the cathode and EIL can be considered as a functional component enabling the injection of electrons into the electron transport layer stack. The cathode electrode can be formed from a metal, alloy, conductive compound, or mixture thereof. The cathode electrode can have a low work function. For example, the cathode electrode can be formed from lithium (Li), magnesium (Mg), aluminum (Al), aluminum (Al)-lithium (Li), calcium (Ca), barium (Ba), ytterbium (Yb), magnesium (Mg)-indium (In), magnesium (Mg)-silver (Ag), etc., for example, from an alloy of Ag and Mg, such as Ag:Mg 90:10 weight / weight. Alternatively, the cathode electrode can be formed from a transparent conductive oxide such as ITO or IZO.

[0234] The thickness of the cathode electrode can range from about 5 nm to about 1000 nm, for example, from about 10 nm to about 100 nm. When the thickness of the cathode electrode is in the range of about 5 nm to about 50 nm, it can be transparent or translucent even if the cathode electrode is formed of metal or metal alloy. A transparent or translucent cathode can promote the emission of light through the cathode.

[0235] Charge generation layer (CGL)

[0236] 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 arranged between the p-CGL and the n-CGL.

[0237] Typically, the charge generation layer is a pn junction connecting the n-type charge generation layer (electron generation layer) and the hole generation layer. Electrons are generated on the n-side of the pn junction and injected into the adjacent layer in the direction of the anode. Similarly, holes are generated on the p-side of the pn junction and injected into the adjacent layer in the direction of the cathode.

[0238] The charge-generating layer is used in series and stacked devices, such as in series or stacked OLEDs containing two or more light-emitting layers between two electrodes. In a series or stacked OLED containing two light-emitting layers, the n-type charge-generating layer provides electrons to a first light-emitting layer disposed near the anode, while the hole-generating layer provides holes to a second light-emitting layer disposed between the first light-emitting layer and the cathode.

[0239] The matrix material suitable for the hole generation layer can be any material conventionally used as a matrix material for hole injection and / or hole transport. Furthermore, the p-type dopant used for the hole generation layer can be a conventional material. For example, the p-type dopant can be selected from one of the following: tetrafluoro-7,7,8,8-tetracyanoquinone dimethyl ether (F4-TCNQ), derivatives of tetracyanoquinone dimethyl ether, axialene derivatives, iodine, FeCl3, FeF3, and SbCl5. Additionally, the host material can be selected from one of the following: N,N'-di(naphthyl-1-yl)-N,N-diphenyl-benzidine (NPB), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1-biphenyl-4,4'-diamine (TPD), and N,N',N'-tetranaphthyl-benzidine (TNB). The p-type charge generation layer can be composed of CNHAT.

[0240] The n-type charge generation layer may be a layer comprising a compound of formula (I). The n-type charge generation layer may be a pure n-type dopant layer, such as a metal layer, or may consist of an organic matrix material doped with an n-type dopant. In one embodiment, the n-type dopant may 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 may be selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Sm, Eu, Tb, Dy, and Yb. More specifically, the n-type dopant may be selected from the group consisting of Li, Cs, K, Rb, Mg, Na, Ca, Sr, Eu, and Yb. The matrix material suitable for the electron generation layer may be a material conventionally used as a matrix material for electron injection or electron transport layers. The matrix material may be, for example, selected from the group consisting of triazine compounds, hydroxyquinoline derivatives such as tris(8-hydroxyquinoline)aluminum, benzo[a]azole derivatives, and silanecyclopentane derivatives.

[0241] According to one aspect of the invention, an electron transport layer comprising a compound of formula (I) is disposed between a first light-emitting layer and a second light-emitting layer, and an electron transport layer comprising a compound of formula (I) is disposed between the second light-emitting layer and the cathode.

[0242] According to another aspect of the present invention, an OLED is provided, the 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, an auxiliary electron transport layer, an electron transport layer comprising a compound of formula (I); and a cathode electrode.

[0243] According to another aspect of the present invention, an OLED is provided, the 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, an auxiliary electron transport layer, an electron transport layer comprising a compound of formula (I), an electron injection layer; and a cathode electrode.

[0244] According to various embodiments of the present invention, OLED layers can be provided disposed between the aforementioned layers, on a substrate, or on a top electrode.

[0245] In one embodiment, the organic light-emitting device according to the invention further comprises a layer containing an axialene compound and / or a quinone dimethane compound.

[0246] In one embodiment, the axial alkene compound and / or quinone dimethane compound may be substituted with one or more halogen atoms and / or with one or more electron-withdrawing groups. The electron-withdrawing group may be selected from a nitrile group, a haloalkyl group, a perhaloalkyl group, or a perfluoroalkyl group. Other examples of the electron-withdrawing group may be an acyl group, a sulfonyl group, or a phosphoryl group.

[0247] Alternatively, the acyl group, sulfonyl group, and / or phosphoryl group may comprise a halogenated and / or a perhalogenated hydrocarbon group. In one embodiment, the perhalogenated hydrocarbon group may be a perfluorohydrocarbon group. Examples of perfluorohydrocarbon groups may be perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorophenyl, and perfluorotolyl; examples of sulfonyl groups comprising halogenated hydrocarbon groups may be trifluoromethylsulfonyl, pentafluoroethylsulfonyl, pentafluorophenylsulfonyl, heptafluoropropylsulfonyl, nonafluorobutylsulfonyl, etc.

[0248] In one embodiment, the hole injection layer, hole transport layer, and / or hole generation layer may contain axial ene compounds and / or quinone dimethane compounds.

[0249] In one embodiment, the axial ene compound may have formula (XX) and / or the quinone dimethane compound may have formula (XXIa) or (XXIb): (XX) (XXIa) (XXIb), 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 15R 16 R 20 R 21 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 It is independently selected from H, halogens and the above-mentioned electron-withdrawing groups.

[0250] Methods for fabricating organic light-emitting devices

[0251] According to another aspect, the present invention relates to a method for preparing an organic light-emitting device according to the invention, wherein the method includes the step of depositing a compound of formula (I) according to the invention onto a solid support.

[0252] Methods for deposition may include: - Deposition via vacuum thermal evaporation; - Deposition via solution processing, preferably the processing being selected from spin coating, printing, casting; and / or - Slit-type die coating.

[0253] Device

[0254] According to another aspect, the present invention relates to a display device or lighting device comprising an organic light-emitting device according to the invention, preferably comprising at least two organic light-emitting devices according to the invention.

[0255] The display device can be a television, tablet computer, or mobile phone.

[0256] General definition

[0257] Unless otherwise explicitly stated, the parts of the compounds described herein, especially the parts of the compounds of formulas (I) to (IV), may be substituted with one or more D (deuterium).

[0258] In this specification, unless otherwise defined, "alkyl group" may refer to an aliphatic hydrocarbon group. An alkyl group may refer to a "saturated alkyl group" without any double or triple bonds. As used herein, the term "alkyl" should encompass straight-chain as well as branched and cyclic alkyl groups. For example, C3-alkyl may be selected from n-propyl and isopropyl. Similarly, C4-alkyl encompasses n-butyl, sec-butyl, and tert-butyl. Likewise, C6-alkyl encompasses n-hexyl and cyclohexyl.

[0259] Unless otherwise explicitly stated, as indicated by the asterisk used in this article. "" indicates the bonding position where the corresponding marked part is bonded to another part.

[0260] As used herein, the term "aryl" or "arylene" shall encompass phenyl (C6-aryl), fused aromatic hydrocarbons such as naphthalene, anthracene, phenanthrene, and tetraphenylene. It also encompasses biphenyl and oligophenyl or polyphenylene such as terphenyl, phenyl-substituted biphenyl, phenyl-substituted terphenyl (e.g., tetraphenylphenyl group), etc. "Arylene," and correspondingly "heteroarylene," refers to a group connected to two additional moieties. In this specification, the term "aryl group" or "arylene group" may refer to a group comprising at least one hydrocarbon aromatic moiety, and all elements of said hydrocarbon aromatic moiety may have conjugated p orbitals, such as phenyl groups, naphthyl groups, anthracene groups, phenanthryl groups, pyrene groups, fluorene groups, etc. It also encompasses spirocyclic compounds in which two aromatic moieties are connected to each other via spiro atoms, such as 9,9'-spirodi[9H-fluorene]yl. Aryl or arylene groups may contain monocyclic or polycyclic (i.e., linked by sharing adjacent carbon atom pairs) functional groups.

[0261] 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" can refer to an aromatic heterocycle having at least one heteroatom, and all elements of the hydrocarbon heteroaromatic moiety may have conjugated p orbitals. The heteroatom may be selected from N, O, S, B, Si, P, Se, preferably from N, O, and S. The heteroaromatic alkyl ring may contain at least 1 to 3 heteroatoms. Preferably, the heteroaromatic alkyl ring may contain at least 1 to 3 heteroatoms independently selected from N, S, and / or O. As in the case of "aryl" / "aromatic alkyl alkyl," the term "heteroaryl" includes, for example, a spirocyclic compound in which two aromatic moieties are linked to each other, such as spiro[fluorene-9,9'-xanthine]. Other exemplary heteroaryl groups are diazine, triazine, dibenzofuran, dibenzothiofuran, acridine, benzoacridine, dibenzoacridine, etc.

[0262] As used herein, the term "alkenyl" refers to a group containing a carbon-carbon double bond -CR 1 =CR 2 R 3 .

[0263] As used herein, the term "fully halogenated" refers to a hydrocarbon group in which all hydrogen atoms in the hydrocarbon group are replaced by halogen (F, Cl, Br, I) atoms.

[0264] As used herein, the term "alkoxy" refers to a structural segment of the formula –OR, where R is a hydrocarbon group, preferably an alkyl or cycloalkyl group.

[0265] As used herein, the term "thioalkyl" refers to a structural segment of formula -SR, where R is a hydrocarbon group, preferably an alkyl or cycloalkyl group.

[0266] C n - The subscript 'n' in a heteroaryl group refers only to the number of carbon atoms, excluding the number of heteroatoms. In this context, it is clear that C3 heteroaryl groups are aromatic compounds containing three carbon atoms, such as pyrazoles, imidazoles, thiazoles, etc.

[0267] As used herein, the term "heteroaryl" should encompass pyridine, quinoline, benzoquinoline, quinazoline, benzoquinazoline, pyrimidine, pyrazine, triazine, benzimidazole, benzothiazole, benzo[4,5]thieno[3,2-d]pyrimidine, carbazole, xanthan, phenazine, benzo[acridine], dibenzo[acridine], etc.

[0268] In this specification, the term single bond refers to a direct bond.

[0269] As used herein, the term "fluorinated" refers to a hydrocarbon group in which at least one hydrogen atom of the hydrocarbon group is replaced by a fluorine atom. A fluorinated group in which all hydrogen atoms are replaced by fluorine atoms is called a perfluorinated group, and is specifically referred to by the term "fluorinated".

[0270] According to the present invention, if one of the hydrogen atoms contained in the group is replaced by another group, the group is "replaced" by another group, wherein the other group is a substituent.

[0271] According to this disclosure, as an exemplary example, the use of any group A in the formula illustrates the following binding scenarios:

[0272] Group A can bind to any suitable bonding site. This applies when the bond of A crosses more than one ring.

[0273] Group A can bind to any suitable bonding site on any of the rings through which the bond passes.

[0274] According to the present invention, the expression "between" regarding a layer being between two other layers does not preclude the existence of an additional layer that may be arranged between one of the two other layers. According to the present invention, the expression "direct contact" regarding two layers in direct contact with each other means that no other layer is arranged between the two layers. A layer deposited on top of another layer is considered to be in direct contact with that layer.

[0275] The term "contact sandwich" refers to a three-layer arrangement in which the middle layer is in direct contact with the two adjacent layers.

[0276] Regarding the first electron transport layer of the present invention, the compound mentioned in the experimental section is the most preferred.

[0277] Lighting devices can be any device used for illumination, irradiation, signal transmission, or projection. They are correspondingly classified as lighting devices, irradiation devices, signal transmission devices, and projection devices. Lighting devices typically consist of the following components: a light radiation source, a device that transmits radiant flux into space in the desired direction, and a housing that connects the components into a single unit and protects the radiation source and light transmission system from environmental damage and influences.

[0278] According to another aspect, the organic electroluminescent device according to the invention comprises two, three, or more light-emitting layers. OLEDs comprising more than one light-emitting layer are also described as tandem OLEDs or stacked OLEDs.

[0279] Organic light-emitting devices (OLEDs) can be bottom-emitting or top-emitting devices. OLEDs can emit light through a transparent anode or a transparent cathode.

[0280] Another aspect relates to a device comprising at least one organic light-emitting device (OLED).

[0281] Devices that include organic light-emitting diodes are, for example, displays or lighting panels.

[0282] In this invention, unless otherwise defined in the claims or elsewhere in this specification, the terms defined below shall be used with those definitions.

[0283] In the context of this specification, the terms “different” or “different from” in relation to matrix materials mean that the matrix material is different in its structural formula.

[0284] The terms “OLED” and “organic light-emitting diode” are used together and have the same meaning. As used herein, the term “organic electroluminescent device” can include both organic light-emitting diodes and organic light-emitting transistors (OLETs).

[0285] As used herein, “percentage by weight,” “% by weight,” “percentage by weight,” “% by weight,” and variations thereof mean the weight of a composition, component, substance, or reagent expressed as the weight of the component, substance, or reagent of the corresponding electron transport layer divided by the total weight of the corresponding electron transport layer and multiplied by 100. It should be understood that the total weight percentage of all components, substances, and reagents of the corresponding electron transport layer and electron injection layer is selected so that it does not exceed 100% by weight.

[0286] As used herein, “volume percentage,” “volume %,” “percentage by volume,” “%volume,” and variations thereof mean the volume of a composition, component, substance, or reagent expressed as the volume of the component, substance, or reagent in the corresponding electron transport layer divided by the total volume of the corresponding electron transport layer and multiplied by 100. It should be understood that the total volume percentage of all components, substances, and reagents in the cathode layer is selected such that it does not exceed 100% volume.

[0287] Whether explicitly stated or not, this document assumes that all numerical values ​​are modified by the term "about". As used herein, the term "about" refers to a possible variation in quantity. Whether or not modified by the term "about", the claims include equivalents of the stated quantity.

[0288] It should be noted that, unless otherwise expressly stated, the singular forms “a,” “an,” “the,” and “the” used in this specification and claims include plural indicators.

[0289] The terms "does not contain," "does not contain," and "does not include" do not exclude impurities. Impurities have no technical impact on the objectives achieved by this invention.

[0290] In the context of this specification, the terms "substantially non-luminescent" or "non-luminescent" mean that the contribution of the compound or layer to the visible emission spectrum from the device is less than 10%, preferably less than 5%, relative to the visible emission spectrum. A visible emission spectrum is an emission spectrum having a wavelength of about ≥380 nm to about ≤780 nm.

[0291] Preferably, the hole-blocking layer comprising the compound of formula (I) is substantially non-luminescent or non-luminescent.

[0292] The operating voltage, also known as U, is 10 milliamperes per square centimeter (mA / cm²). 2 The following measurements are in volts (V).

[0293] Candela / Ampere efficiency is also known as cd / A efficiency or C eff At 10 mA / cm² 2 The following measurements are in units of candelas per ampere.

[0294] External quantum efficiency, also known as EQE, is measured as a percentage (%).

[0295] Color spaces are described using coordinates CIE-x and CIE-y (International Commission on Illumination 1931). CIE-y is particularly important for blue light emission. A smaller CIE-y value indicates a deeper blue. Efficiency values ​​are compared at the same CIE-y value.

[0296] The highest occupied molecular orbital, also known as the HOMO, and the lowest unoccupied molecular orbital, also known as the LUMO, are measured in electron volts (eV).

[0297] The terms “OLED,” “organic light-emitting diode,” “organic light-emitting device,” “organic optoelectronic device,” and “organic light-emitting diode” are used together and have the same meaning.

[0298] The terms “lifespan” and “service life” are used together and have the same meaning.

[0299] The anode and cathode can be described as an anode electrode / cathode, or an anode electrode / cathode, or an anode electrode layer / cathode electrode layer.

[0300] Room temperature, also known as ambient temperature, is 23°C.

[0301] In the following description, the implementation methods will be illustrated with reference to embodiments. However, the present invention is not limited to the following embodiments. Exemplary aspects will now be referred to in detail. Detailed Implementation

[0302] In the described embodiments, the components described above, as well as the claimed components and the components used according to the invention, have no particular exceptions in terms of their size, shape, material selection, and technical concept, thereby allowing the application of selection criteria known in the relevant field without limitation.

[0303] Further details, features, and advantages of the invention are disclosed in the dependent claims and the following description of the various accompanying drawings, which illustrate preferred embodiments of the invention by way of example. However, any embodiment is not necessarily representative of the full scope of the invention, and therefore the scope of the invention is to be interpreted with reference to the claims and this document. It should be understood that the foregoing general description and the following detailed description are merely exemplary and explanatory, and are intended to provide further explanation of the claimed invention.

[0304] Figure 1 This is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention.

[0305] Figure 2 This is a schematic cross-sectional view of an OLED comprising a charge generation layer and two light-emitting layers according to an exemplary embodiment of the present invention.

[0306] Figure 3 The refractive indices of the pure layer and the mixed layer are shown.

[0307] The accompanying drawings will be described in more detail below with reference to embodiments. However, the present invention is not limited to the following drawings.

[0308] In this document, when a first element is referred to as being formed or arranged "on" or "above" a second element, the first element may be arranged directly on the second element, or one or more other elements may be arranged therebetween. When a first element is referred to as being "directly" formed or arranged "on" or "above" a second element, no other elements are arranged therebetween.

[0309] Figure 1 This is a 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, an electron blocking layer (EBL) 145, an emissive layer (EML) 150, a hole blocking layer 155, and a first electron transport layer (ETL) 160. The first electron transport layer (ETL) 160 is formed on the hole blocking layer 155. The first electron transport layer (ETL) 160 includes a compound of formula (I) and a Si-containing compound. An electron injection layer (EIL) 180 is disposed on the first electron transport layer (ETL) 160. A cathode 190 is directly disposed on the electron injection layer (EIL) 180.

[0310] Figure 2 This is a schematic cross-sectional view of an OLED 100 according to another exemplary embodiment of the present invention. Figure 2 and Figure 1 The difference is that, Figure 2 The OLED 100 also includes a charge generation layer (CGL) and a second light-emitting layer (151).

[0311] refer to Figure 2 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 light-emitting layer (EML) 150, a first hole blocking layer (HBL) 155, a first electron transport layer (ETL) 160, 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 light-emitting layer (EML) 151, a second hole blocking layer (HBL) 156, and a second electron transport layer (ETL) 161, a second electron injection layer (EIL) 181, and a cathode 190, comprising a compound of formula (I) and a Si-containing compound.

[0312] Despite Figure 1 and Figure 2Not shown, but a sealing layer may be additionally formed on the cathode electrode 190 to seal the OLED 100. Furthermore, various other modifications may be made thereto.

[0313] Figure 3 The refractive indices of the pure layer and the hybrid layer are shown in the wavelength range of 400 nm to 800 nm. The pure layer consists of a compound of formula (I). The hybrid layer contains a compound of formula (I) and a silicon-containing compound. Compared with the pure layer, the hybrid layer exhibits a lower refractive index.

[0314] The following describes the implementation in more detail with reference to the embodiments. However, this disclosure is not limited to the following embodiments.

[0315] Experimental Section

[0316] Melting point

[0317] The melting point (mp) was determined as the peak temperature based on the DSC curve measured by TGA-DSC as described above or a separate DSC measurement (MettlerToledo DSC822e, where the sample was heated from room temperature to complete melting at a heating rate of 10 K / min under a pure nitrogen flow. Samples of 4 to 6 mg were placed in a 40 µL covered Mettler Toledo aluminum dish with a <1 mm hole punched in the cover).

[0318] Glass transition temperature

[0319] As described in DIN EN ISO 11357 published in March 2010, the glass transition temperature (Tg) is measured in a Mettler Toledo DSC 822e differential scanning calorimeter under nitrogen atmosphere and with a heating rate of 10 K / min.

[0320] Standard starting temperature

[0321] Standard starting temperature (T) RO The concentration was determined by loading 100 mg of the compound into a VTE source. As a VTE source, a point source of organic materials provided by Kurt J. Lesker Company (www.Lesker.com) or CreaPhys GmbH (http: / / www.creaphys.com) can be used. In amounts less than 10 mg... -5 The VTE source was heated at a constant rate of 15 K / min under a pressure of millibars, and the internal temperature of the source was measured using thermocouples. The evaporation of the compound was detected using a QCM detector, which also detected the deposition of the compound on a quartz crystal of the detector. The deposition rate on the quartz crystal was... Measurements were taken in units of / s. To determine the standard onset temperature, the deposition rate was plotted against the VTE source temperature. The standard onset is the temperature at which significant deposition occurs on the QCM detector. To obtain accurate results, the VTE source was heated and cooled three times, and only the results from the second and third runs were used to determine the standard onset temperature.

[0322] To effectively control the evaporation rate of organic compounds, a standard onset temperature can be set within the range of 200 to 255°C. If the standard onset temperature is below 200°C, evaporation may be too rapid and therefore difficult to control. If the standard onset temperature is above 255°C, the evaporation rate may be too low, which could result in a low cycle time, and the organic compounds in the VTE source may decompose due to prolonged exposure to high temperatures.

[0323] The standard onset temperature is an indirect measure of a compound's volatility. The higher the standard onset temperature, the lower the compound's volatility.

[0324] reduction potential

[0325] The redox potential was determined by cyclic voltammetry using a Metrohm PGSTAT30 potentiostat and MetrohmAutolab GPES software at room temperature. The redox potential given for a specific compound was measured as follows: in an argon-degassed, dry 0.1 M THF solution of the experimental material, under an argon atmosphere, with a 0.1 M tetrabutylammonium hexafluorophosphate supporting electrolyte between platinum working electrodes, and using an Ag / AgCl pseudo-standard electrode (Metrohm silver rod electrode) composed of silver wire coated with silver chloride and directly immersed in the measurement solution at a scan rate of 100 mV / s. The first run was performed within the widest range of potentials set on the working electrodes, and the range was adjusted appropriately in subsequent runs. The last three runs were performed by adding ferrocene (0.1 M concentration) as a standard. The average potential corresponding to the cathode and anodic peaks of the compound under study, after subtracting the value for the standard Fc, was calculated. + The values ​​reported above were finally obtained by averaging the observed cathode and anodic potentials of the / Fc redox couple. All the compounds studied, as well as the reported comparative compounds, exhibited well-defined reversible electrochemical behavior.

[0326] dipole moment

[0327] The dipole moment of a molecule containing N atoms It is given by the following formula:

[0328] in and It represents the partial charge and position of atom i in the molecule.

[0329] The dipole moment is determined by the semi-empirical molecular orbital method.

[0330] As implemented in the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany), the hybrid functionals B3LYP and 6-31G are used in the gas phase. Basis sets are used to optimize the geometry of the molecular structure. If more than one conformation is feasible, the conformation with the lowest total energy is selected to determine the bond lengths of the molecule.

[0331] Calculated HOMO and LUMO

[0332] HOMO and LUMO were calculated using the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardststrasse 19, 76135 Karlsruhe, Germany). The results were obtained by applying hybrid functionals B3LYP and 6-31G in the gas phase. The basis set determines the optimal geometry of the molecular structure, as well as the HOMO and LUMO energy levels. If more than one conformation is feasible, the conformation with the lowest total energy is selected.

[0333] Refractive index measurement of thin films

[0334] In a vacuum system (Cluster Tool, Sunic System Ltd.) at a deposition rate of 1 Å / s and approximately 3e -7 Films of 70 nm thickness were prepared on a silicon substrate (0.5 nm natural SiO2, 675 µm thickness, Siegert Wafer GmbH) under millibar pressures, with the pure layer prepared by thermal evaporation and the mixed layer by thermal co-evaporation. Samples were stored in a glove box with a pure nitrogen atmosphere until measurement (maximum air exposure of 1 hour). Reflectance was measured in the spectral range of 380 nm to 1050 nm using a Filmmetrics F10-RT spectrometer. A silicon reference sample from Filmmetrics was used as a reflectance standard. The measured reflectance data were then modeled using the Cauchy model in FILMeasure software to obtain the refractive index in the range of 420 nm to 1020 nm.

[0335] Material details

[0336] Device Experiment

[0337] General steps for manufacturing OLEDs

[0338] For top-emitting OLED devices, a substrate measuring 150 mm × 150 mm × 0.7 mm was ultrasonically cleaned for 7 minutes with a 2% aqueous solution of Deconex FPD 211, then rinsed with pure water for 5 minutes, and dried in a rotary rinse-dryer for 15 minutes. Subsequently, it was subjected to 10 -5 Up to 10 -7 Ag was deposited under millibar pressure to serve as an anode.

[0339] Then, HT-1 and D-1 are vacuum co-deposited on the anode to form the HIL. Then, HT-1 is vacuum deposited on the HIL to form the HTL. Then, HT-2 is vacuum deposited on the HTL to form the electron blocking layer (EBL).

[0340] Then, a luminescent layer is formed on the EBL by co-deposition of HOST-1 and EMITTER-1.

[0341] Then, ET-1 is vacuum deposited onto the light-emitting layer to form the HBL. Next, a first electron transport layer is formed on the HBL by depositing a compound of formula (I) and a silicon-containing compound. For the comparative examples in Table 7, the first electron transport layer is formed on the HBL by depositing a compound of formula (I) and a Si-containing compound and Yb. For the comparative examples in Table 8, the first electron transport layer is formed on the HBL by depositing only a compound of formula (I).

[0342] Then, by first depositing LiQ or ET-2:Li according to Tables 7 and 8, followed by depositing Yb, an electron injection layer as a double layer is formed on the first electron transport layer.

[0343] Then in 10 -7 Ag:Mg was evaporated at a rate of 0.01 Å / s to 1 Å / s under millibars to form a cathode.

[0344] An HT-3 capping layer is formed on the cathode.

[0345] The following details the stacking in a top-emitting OLED device. Individual layers are separated by forward slashes " / ". Layer thicknesses are given in square brackets [...], and mixing ratios (...) are given in parentheses (...). HT-1:D-1 (8%), 10 nm / HT-1, 133 nm HT-2, 5 nm / HOST-1 H09: EMITTER-1BD200 (3%), 20 nm / ET-1, 5 nm / Comparative or Inventive First ETL, 30 nm / LiQ (1 nm) or ET-2:Li (1%, 15 nm) / Yb, 2 nm / Ag:Mg (10%), 13 nm / HT-3, 75 nm Table 5: Silicon-containing compounds tested

[0346] The compound of formula (I) was tested B-11 B-27 B-28 B-1 Table 6: Other compounds used in device fabrication

[0347] Table 7: The influence of the absence of electrodops in the first electron transport layer

[0348] Table 8: Effects of adding silicon-containing compounds to compounds of formula (I) used to form the first electron transport layer

[0349] As can be seen from Tables 7 and 8, the combination of the compound of formula (I) with a Si-containing compound containing at least two Si atoms in the undoped first electron transport layer leads to an improvement in OLED efficiency.

[0350] The features disclosed in the foregoing specification and dependent claims may be used individually and in any combination thereof, thereby fulfilling the aspects of this disclosure set forth in the independent claims as material in various forms.

Claims

1. An organic light-emitting device, the organic light-emitting device comprising an anode, a cathode, a light-emitting layer, an electron injection layer, and a first electron transport layer; in - The light-emitting layer, the electron injection layer, and the first electron transport layer are disposed between the anode and the cathode; - The electron injection layer and the first electron transport layer are disposed between the light-emitting layer and the cathode; - The first electron transport layer is disposed between the light-emitting layer and the electron injection layer; - The first electron transport layer comprises a compound of formula (I) and a silicon-containing compound; (Ar 2 ) m -(Z k -G) n (I) - m and n are 1 or 2 independently; - k is independently 0, 1, or 2; - Ar 2 independently selected from C2 to C 42 heteroaryl and C6 to C 60 aryl, - where each Ar 2 It can be substituted by one or two independent substituents selected from the following: C6 to C6. 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 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 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; - Among them Ar 2 Each C6 to C 12 Aryl substituents and Ar 2 Each C3 to C 11 The heteroaryl substituents can be replaced by C1 to C4 alkyl groups or halogens; - Z is independently selected from C6 to C 30 Aryl, - where each Z can be substituted by one or two substituents independently selected from the following: C6 to C6 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 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 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; - where each C6 to C on Z 12 The aryl substituents can be replaced by C1 to C4 alkyl groups or halogens; - Choose G such that the dipole moment of the compound G-phenyl is ≥1 D; - The silicon-containing compound contains at least two Si atoms; and - The first electron transport layer does not contain electrical dopants.

2. The organic light-emitting device according to claim 1, wherein the silicon-containing compound is a silsesquioxane, an arylsilane, or a mixture of two or more thereof.

3. The organic light-emitting device according to claim 2, wherein the silsesquioxane has formula (II). Si x R x O 1.5x (II) in - R is independently selected from C1 to C 30 hydrocarbon group, - where each C1 to C 30 The hydrocarbon group can be independently substituted by one or more halogens; and - x is selected from 6, 8, 10, 12, 14 and 16.

4. The organic light-emitting device according to claim 3, wherein R is independently selected from C1 to C2. 12 alkyl.

5. The organic light-emitting device according to claim 3 or 4, wherein the halogen is F.

6. The organic light-emitting device according to any one of claims 3 to 5, wherein x is 8 or 12.

7. The organic light-emitting device according to any one of claims 3 to 6, wherein the silsesquioxane has formula S-1 or S-2. S-1 S-2。 8. The organic light-emitting device according to claim 2, wherein the arylsilane has formula (III), (III) in Ar S1 To Ar S7 Independently selected from C6 to C 24 Aryl.

9. The organic light-emitting device according to claim 8, wherein Ar S1 To Ar S3 and Ar S5 To Ar S7 Independently selected from C6 to C 10 Aryl.

10. The organic light-emitting device according to claim 8 or 9, wherein Ar S4 It is C 12 To C 24 Aryl.

11. The organic light-emitting device according to any one of claims 8 to 10, wherein the arylsilane has formula S-4 S-4。 12. The organic light-emitting device according to any one of the preceding claims, wherein... - G is selected from dialkylphosphine oxide, diarylphosphine oxide, alkylarylphosphine oxide, nitriles, benzonitrile, nicotinic nitrile, amide groups, urea groups, and C2 to C3 groups. 17 Mixed aromatics; - Each G may contain one or more substituents attached to the group, wherein the one or more substituents are selected from phenyl, methyl, ethyl and pyridyl.

13. The organic light-emitting device according to any one of the preceding claims, wherein the organic light-emitting device further comprises a hole-blocking layer. in - The hole blocking layer is disposed between the light-emitting layer and the first electron transport layer; - The hole-blocking layer comprises a compound of formula (IV). (Ar 1 -A c ) a -X b (IV); - a and b are 1 or 2 independently; - c is either 0 or 1 independently; - Ar 1 Independently selected from C6 to C 60 Aryl or C2 to C 42 Mixed aromatics, - where each Ar 1 It can be substituted by one or two independent substituents selected from the following: C6 to C6. 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 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 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; - Among them Ar 1 Each C6 to C 12 Aryl substituents and Ar 1 Each C3 to C 11 The heteroaryl substituents can be replaced by C1 to C4 alkyl groups or halogens; - A is independently selected from C6 to C 30 Aryl, - Each A may be substituted by one or two substituents independently selected from the following: C6 to C6 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 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 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; - where each C6 to C on A 12 The aryl substituents can be replaced by C1 to C4 alkyl groups or halogens; - X is independently selected from C2 to C 42 heteroaryl and C6 to C 60 Aryl, - where each X can be substituted by one or two substituents independently selected from the following: C6 to C6 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 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 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; - where each C6 to C on X 12 aryl substituents and each C3 to C on X 11 The heteroaryl substituents can be replaced by C1 to C4 alkyl groups or halogens; and - The molecular dipole moment of the compound of formula (IV) is ≥0 D but ≤4 D.

14. The organic light-emitting device according to any one of the preceding claims, wherein the first electron transport layer is in direct contact with the electron injection layer.

15. An apparatus comprising an organic light-emitting device according to any one of the preceding claims, wherein the apparatus is a display device or a lighting device.

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