Organic electronic device, display and lighting apparatus including the same

Abstract

The invention relates to an organic electronic device, and a display and lighting apparatus including the same. Specifically, the present invention relates to an organic electronic device comprising at least one electron transport, electron injection or electron generation layer comprising a compound of formula (I), a compound of formula (I), and a display and lighting device comprising said organic electronic device, wherein all positions at the "*" position that are not linked to the-(A) a-L moiety can be bound to another substituent; a is selected from substituted or unsubstituted aryl or heteroaryl; l is selected from substituted or unsubstituted aryl or heteroaryl or groups (II) and (III); "A" is an integer from 0 to 2.

Description

[0001] This patent application is a divisional application of the patent application with the international application number PCT / EP2019 / 054031, the international filing date of 19 February 2019, the entering Chinese national phase application number of 201980015720.6, and the invention patent application name of “Organic electronic device, display and illumination device comprising an organic electronic device”. TECHNICAL FIELD

[0002] The present invention relates to organic electronic devices, display and illumination devices comprising organic electronic devices. In particular, the present invention relates to an organic electronic device, a compound which can be comprised in said organic electronic device, an organic semiconducting layer comprising said compound and a display or illumination device comprising said organic electronic device. BACKGROUND

[0003] An organic light emitting diode (OLED) as a self-light emitting device has a wide viewing angle, an excellent contrast, a fast response, a high luminance, an excellent driving voltage characteristic and a color reproducibility. A typical OLED comprises an anode, a hole transport layer (HTL), an emission layer (EML), an electron transport layer (ETL) and a cathode, which are sequentially stacked on a substrate. In this regard, the HTL, the EML and the ETL are thin films formed of organic compounds and / or organometallic compounds.

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

[0005] Triazine and pyrimidine compounds are widely used for organic electronic applications, in particular as electron transport materials. Derivatives of triazines and pyrimidines typically show low glass transition temperature values (Tg). Low Tg compounds are not preferred as materials in organic electronic products, as low Tg has an adverse effect on the durability and performance of devices comprising such compounds. Large molecular fragments are required to provide amorphous character to the electron transport material and increase Tg. However, large molecular fragments severely interfere with charge carrier mobility, thus reducing the overall device performance.

[0006] It is therefore an object of the present invention to provide novel organic electronic devices and compounds for use therein which overcome the disadvantages of the prior art, in particular to provide novel compounds suitable for improving the performance of organic electronic devices, in particular the cd / A efficiency of OLED devices, in particular when used in an electron transport layer which can further comprise an additive. SUMMARY

[0007] The above object is achieved by an organic electronic device comprising at least one layer selected from an electron transport layer, an electron injection layer or an electron generation layer between an anode and a cathode, said layer comprising a compound of formula (I),

[0008]

[0009] wherein in the above formula (I) all positions not bound to -(A) a -L moiety at the position marked with "*" can be bound to hydrogen or a substituent selected from the group consisting of deuterium, fluorine, RF, C1-C 20 linear alkyl, C3-C 20 branched alkyl, C1-C 12 linear fluorinated alkyl, CN, RCN, C6-C 20 aryl, C2-C 20 heteroaryl, (P=0)R2; wherein each R is independently selected from the group consisting of C1-C 20 linear alkyl, C1-C 20 alkoxy, C1-C 20 thioalkyl, C3-C 20 branched alkyl, C3-C 20 cyclic alkyl, C3-C 20 branched alkoxy, C3-C 20 cyclic alkoxy, C3-C 20 branched thioalkyl, C3-C 20 cyclic thioalkyl, C6-C 20 aryl and C2-C 20 heteroaryl; A is selected from the group consisting of substituted or unsubstituted C6-C 24 aryl or substituted or unsubstituted C2-C 20 heteroaryl, wherein in case of A being substituted, the respective substituents are independently selected from the group consisting of deuterium, fluorine, C1-C 20 linear alkyl, C3-C 20 branched alkyl, linear fluorinated C1-C 12 alkyl, CN, C6-C 20 aryl, C2-C 20 heteroaryl; L is selected from the group consisting of substituted or unsubstituted C2-C 42 heteroaryl, substituted or unsubstituted C6-C 24 aryl, or a group selected from wherein, in case of L being substituted, the respective substituents are selected from the group consisting of: deuterium, fluorine, C1-C 20 linear alkyl, C3-C 20 branched alkyl, C3-C 20 cyclic alkyl, C1-C20 linear alkoxy, C3-C 20 branched alkoxy, linear fluorinated C1-C 12 alkyl, linear fluorinated C1-C 12 alkoxy, C3-C 12 branched fluorinated cyclic alkyl, C3-C 12 fluorinated cyclic alkyl, C3-C 12 fluorinated cyclic alkoxy, CN, RCN, C6-C 20 aryl, C2-C 20 heteroaryl, OR, SR, (C=0)R, (C=0)NR2, SiR3, (S=0)R, (S=0)2R, (P=0)R2; wherein each R is independently selected from C1-C 20 linear alkyl, C1-C 20 alkoxy, C1-C 20 thioalkyl, C3-C 20 branched alkyl, C3-C 20 cyclic alkyl, C3-C 20 branched alkoxy, C3-C 20 cyclic alkoxy, C3-C 20 branched thioalkyl, C3-C 20 cyclic thioalkyl, C6-C 20 aryl and C2-C 20 heteroaryl; and "a" is an integer from 0 to 2.

[0010] Surprisingly, it has been found that by using a compound of formula (I) as electron transport material in an OLED device, better OLED device performance can be generated. The compound of formula (I) comprises a spiro[benzo[de]anthracene-7,9'-fluorene] structural unit. This unit promotes a sufficiently high glass transition temperature and at the same time a sufficiently high charge carrier mobility of the electron transport material, to enable an enhancement of the performance of an organic electronic device comprising this material of formula (I). The use of a compound of formula (I) in an electron transport layer as pure material or as host material in combination with additives (metals, salts, complexes) can improve the device performance, especially in terms of lifetime and durability.

[0011] In the electronic device of the present application, A can be unsubstituted. In this way, a fine tuning of the electronic structure of the compound of formula (I) can be achieved to further improve its usability in an organic semiconducting layer of an organic electronic device, in particular in an electron transport layer.

[0012] In the electronic device of the present application, in case L is substituted, the respective substituents can be independently selected from the group consisting of phenyl, naphthyl, pyridyl, biphenyl, dibenzofuranyl, dibenzothiophenyl and carbazolyl. In this way, a fine tuning of the electronic structure of the compound of formula (I) can be achieved to further improve its usability in the organic semiconducting layer, in particular in the electron transport layer, of an organic electronic device.

[0013] In the electronic device of the present application, in case L is C2-C 42 heteroaryl, said C2-C 42 heteroaryl can be selected from the group consisting of triazine, pyrimidine, benzacridine, dibenzacridine, pyridine, bipyridine, benzimidazole, phenanthroline, benzonitrile, phenanthridine, benzo thiazole, phenanthridinone, naphtho-benzofuran, dinaphthofuran, benzo-naphtho-thiophene, dinaphthothiophene. In this way, a fine tuning of the electronic structure of the compound of formula (I) can be achieved to further improve its usability in the organic semiconducting layer, in particular in the electron transport layer, of an organic electronic device.

[0014] In the electronic device of the present application, in case L is C6-C 24 heteroaryl, said C2-C 24 heteroaryl can be selected from the group consisting of triazine, pyrimidine, benzacridine, dibenzacridine, pyridine, bipyridine, benzimidazole, phenanthroline, benzonitrile, phenanthridine, benzo

[0015] In the electronic device of the present application, L can be selected from the group consisting of:

[0016]

[0017] In this way, a fine tuning of the electronic structure of the compound of formula (I) can be achieved to further improve its usability in the organic semiconducting layer, in particular in the electron transport layer, of an organic electronic device.

[0018] In the electronic device of the present application, in case L is substituted, the respective substituents can be independently selected from the group consisting of:

[0019]

[0020] In this way, a fine tuning of the electronic structure of the compound of formula (I) can be achieved to further improve its usability in the organic semiconducting layer, in particular in the electron transport layer, of an organic electronic device.

[0021] In the organic electronic device according to the present application, the layer comprising the compound of formula (I) can consist of at least one compound of formula (I). This embodiment is particularly suitable for realizing an organic electronic device in which the layer comprising the compound of formula (I) is a charge injection layer (respectively an electron injection layer).

[0022] Alternatively, in the electronic device according to the present application, the layer comprising the compound of formula (I) can further comprise a metal, a metal salt or an organometallic complex, or an alkali metal additive or a rare earth metal additive, or a rare earth metal or alkali metal complex or alkali metal salt, or Yb or LiQ or an alkali metal borate or alkali metal phenate, or LiQ. This embodiment is suitable for realizing an organic electronic device in which the layer comprising the compound of formula (I) is an electron transport layer.

[0023] The organic electronic device according to the present application can further comprise an emitting layer, wherein the layer comprising the compound of formula (I) is arranged between the emitting layer and the cathode. In case of this arrangement, a particularly good effect is obtained with respect to improving the performance of the organic electronic device.

[0024] In the organic electronic device according to the present application, the device can further comprise an electron transport layer, and the layer comprising the compound of formula (I) is arranged between the electron transport layer and the cathode. Also in case of this arrangement, a particularly pronounced improvement of the device performance is observed.

[0025] The object is further achieved by a compound of general formula (I),

[0026]

[0027] wherein in the above formula (I) all positions not bound to -(A) a -L moiety at the position marked with "*" can be bound to hydrogen or a substituent selected from the group consisting of deuterium, fluorine, RF, C1-C 20 linear alkyl, C3-C 20 branched alkyl, C1-C 12 linear fluorinated alkyl, CN, RCN, C6-C 20 aryl, C2-C 20 heteroaryl, (P=O)R2; wherein each R is independently selected from the group consisting of C1-C 20 linear alkyl, C1-C 20 alkoxy, C1-C 20 thioalkyl, C3-C 20 branched alkyl, C3-C 20 cyclic alkyl, C3-C 20 branched alkoxy, C3-C 20 cyclic alkoxy, C3-C 20 branched thioalkyl, C3-C 20cyclic alkyl, C6-C 20 aryl and C2-C 20 heteroaryl; A can be selected from substituted or unsubstituted C6-C 24 aryl or substituted or unsubstituted C2-C 20 heteroaryl, wherein in case of substitution of the group A, the respective substituents are independently selected from the group consisting of deuterium, fluorine, C1-C 20 linear alkyl, C3-C 20 branched alkyl, linear fluorinated C1-C 12 alkyl, CN, C6-C 20 aryl, C2-C 20 heteroaryl; L can be selected from substituted or unsubstituted C2-C 42 heteroaryl, substituted or unsubstituted C6-C 24 aryl, or from the group consisting of wherein, in case L can be substituted, the respective substituents can be selected from the group consisting of: deuterium, fluorine, C1-C 20 linear alkyl, C3-C 20 branched alkyl, C3-C 20 cyclic alkyl, C1-C 20 linear alkoxy, C3-C 20 branched alkoxy, linear fluorinated C1-C 12 alkyl, linear fluorinated C1-C 12 alkoxy, C3-C 12 branched fluorinated cyclic alkyl, C3-C 12 fluorinated cyclic alkyl, C3-C 12 fluorinated cyclic alkoxy, CN, RCN, C6-C 20 aryl, C2-C 20 heteroaryl, OR, SR, (C=O)R, (C=O)NR2, SiR3, (S=O)R, (S=O)2R, (P=O)R2; wherein each R is independently selected from C1-C 20 linear alkyl, C1-C 20 alkoxy, C1-C 20 thioalkyl, C3-C 20 branched alkyl, C3-C 20 cyclic alkyl, C3-C 20 branched alkoxy, C3-C 20 cyclic alkoxy, C3-C 20 branched thioalkyl, C3-C 20 cyclic thioalkyl, C6-C 20 aryl and C2-C 20 heteroaryl; and

[0028] "a" can be an integer from 0 to 2,

[0029] a) wherein in case "a" is 0, L is selected from C2 to C 42 heteroaryl and said formula (I) comprises only one moiety -(A) a -L; in case L is a N-containing heteroaryl, said C2-C 42 The heteroaryl can be selected from triazine, benzacridine, dibenzacridine, bipyridine, benzimidazole, phenanthroline, phenanthridine, benzothiazole, phenanthridone;

[0030] b) wherein in case "a" is 1

[0031] (i) if A is aryl and L is a N-containing heteroaryl, said N-containing heteroaryl can be a substituted or unsubstituted triazine, pyrimidine, benzacridine, dibenzacridine, pyridine, bipyridine, phenanthroline, phenanthridine or phenanthridone;

[0032] (ii) if A is heteroaryl and L is aryl, A can be selected from triazine, pyrimidine, benzacridine, dibenzacridine, pyridine, bipyridine, benzimidazole, phenanthroline, benzonitrile, phenanthridine, benz thiazole, phenanthridone, naphtho-benzofuran, dinaphthofuran, benzo-naphtho-thiophene and dinaphthothiophene;

[0033] (iii) if A is heteroaryl and L is heteroaryl, A can be selected from triazine, pyrimidine, benzacridine, dibenzacridine, bipyridine, benzimidazole, phenanthroline, benzonitrile, phenanthridine, benz thiazole, phenanthridone, naphtho-benzofuran, dinaphthofuran, benzo-naphtho-thiophene and dinaphthothiophene;

[0034] c) wherein in case "a" is 2, i.e. in case the compound of formula (I) comprises two A moieties, in case both A and L are aryl, the A directly connected to the group L is an anthracenyl; in case A is a sulfur-containing heteroaryl, said heteroaryl can be selected from benzo-naphtho-thiophene, dinaphthothiophene and benzothiazole. These compounds are found to be particularly advantageous for use in organic electronic devices and for improving their performance.

[0035] In the compound of formula (I), the group *-(A) a -L can be connected to each of the three ring positions indicated with "*", or only to two of the three ring positions indicated with "*", or only to one of the three ring positions indicated with "*". In case the group *-(A) a -L is connected to two or three of the ring positions indicated with "*", the plurality of groups *-(A) a -L are independently selected and can be the same or different.

[0036] The compounds of formula (I) can have a HOMO energy level of -5.50 eV to -3.99 eV. The corresponding HOMO energy level was found to be particularly advantageous for the use of the compounds of formula (I) in organic electronic devices.

[0037] The compounds of formula (I) can have a LUMO energy level of -2.72 eV to -1.30 eV. The corresponding LUMO energy level was found to be particularly advantageous for the use of the compounds of formula (I) in organic electronic devices. In this regard, a LUMO energy level of -2.1 eV to -1.8 eV was found to be particularly advantageous for the use of the compounds of formula (I) in an electron transport layer, in particular in an n-ETL, together with an additive. Furthermore, a LUMO energy level in the range of -1.9 to -1.7 eV was found to be particularly advantageous for the use of the compounds of formula (I) in a hole blocking layer, in particular without an additive.

[0038] The compounds of formula (I) can have a dipole moment of 0.18 Debye to 5.66 Debye. Such a dipole moment was found to be particularly advantageous for the use of the compounds of formula (I) in organic electronic devices.

[0039] The compounds of formula (I) can be selected from the group consisting of structures A-1 to A-86.

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053] The HOMO and LUMO energy levels (eV) and the dipole moment (Debye) of the compounds of formula (1 ) are calculated using the program package TURBOMOLE V6.5 and the hybrid functional B3LYP with the 6-31G* basis set.

[0054] The object is further achieved by an organic semiconductor layer comprising a compound according to the present application.

[0055] The object is further achieved by a display device comprising an organic electronic device according to the present application.

[0056] Finally, the object is achieved by a lighting device comprising an organic electronic device according to the present application.

[0057] Further layers

[0058] According to the present application, the organic electronic device can comprise further layers besides the layers already mentioned above. Exemplary embodiments of the respective layers are described below:

[0059] Substrate

[0060] The substrate can be any substrate commonly used in the manufacture of electronic devices, for example organic light emitting diodes. If light is to be emitted through the substrate, the substrate should be a transparent or semi-transparent material, for example a glass substrate or a transparent plastic substrate. If light is to be emitted through the top side, the substrate can be either a transparent material or a non-transparent material, for example a glass substrate, a plastic substrate, a metal substrate or a silicon substrate.

[0061] Anode

[0062] The first electrode or the second electrode can be an anode. The anode can be formed by deposition or sputtering of a material used to form the anode. The material used to form the anode can be a high work function material in order to facilitate hole injection. The anode material can also be selected from low work function materials (i.e. aluminum). The anode can be a transparent or reflective electrode. The anode can be formed using transparent conductive oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (Sn02), aluminum zinc oxide (AlZO) and zinc oxide (ZnO). The anode can also be formed using a metal, which is typically silver (Ag), gold (Au) or a metal alloy.

[0063] Hole injection layer

[0064] The hole injection layer (HIL) can be formed on the anode by vacuum deposition, spin coating, printing, casting, slot-die coating, Langmuir-Blodgett (LB) deposition or the like. When the HIL is formed using vacuum deposition, the deposition conditions can vary depending on the compound used to form the HIL and the desired structure and thermal properties of the HIL. However, generally, the conditions for vacuum deposition can include a deposition temperature of 100 °C to 500 °C, a pressure of 10-8 Torr to 10 -3 The pressure of the Torr (1 Torr is equal to 133.322 Pa) and the deposition rate of 0.1 nm / s to 10 nm / s.

[0065] When the HIL is formed using spin coating or printing, the coating conditions can vary depending on the compound used to form the HIL and the desired structure and thermal properties of the HIL. For example, the coating conditions can include a coating speed of about 2000 rpm to about 5000 rpm, and a heat treatment temperature of about 80 °C to about 200 °C. After the coating is performed, heat treatment removes the solvent.

[0066] The HIL can be formed from any compound typically used to form an HIL. Examples of compounds that can be used to form the HIL include phthalocyanine compounds such as copper phthalocyanine (CuPc), 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA), TDATA, 2T-NATA, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphor sulfonic acid (Pani / CSA), and polyaniline / poly(4-styrenesulfonate) (PANI / PSS).

[0067] The HIL can be a pure p-type dopant layer, and the p-type dopant can be selected from tetrafluoro-tetracyanoquinodimethane (F4TCNQ), 2,2'-(perfluoronaphthalene-2,6-diylidene)dimalononitrile, or 2,2',2"-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile), but is not limited thereto. The HIL can be selected from a hole transport matrix compound doped with a p-type dopant. Typical examples of known doped hole transport materials are: copper phthalocyanine (CuPc) with a HOMO level of about -5.2 eV, doped with tetrafluoro-tetracyanoquinodimethane (F4TCNQ) with a LUMO level of about -5.2 eV; zinc phthalocyanine (ZnPc) doped with F4TCNQ (HOMO = -5.2 eV); alpha-NPD (N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-benzidine) doped with F4TCNQ; alpha-NPD doped with 2,2'-(perfluoronaphthalene-2,6-diylidene)dimalononitrile; alpha-NPD doped with 2,2',2"-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile). The dopant concentration can be selected from 1 wt% to 20 wt%, more preferably 3 wt% to 10 wt%.

[0068] The thickness of the HIL can be in the range of about 1 nm to about 100 nm, and for example, in the range of about 1 nm to about 25 nm. When the thickness of the HIL is in this range, the HIL can have excellent hole-injection properties without substantial damage to the driving voltage.

[0069] Hole transport layer

[0070] The hole transport layer (HTL) can be formed on the HIL by vacuum deposition, spin coating, slot-die coating, printing, casting, Langmuir-Blodgett (LB) deposition, or the like. When the HTL is formed by vacuum deposition or spin coating, the conditions of deposition and coating can be similar to those used for forming the HIL. However, the conditions of vacuum or solution deposition can vary depending on the compound used to form the HTL.

[0071] The HTL can be formed from any compound typically used to form an HTL. Compounds that can be suitably used are disclosed in, for example, Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953-1010, and incorporated herein by reference. Examples of compounds that can be used to form the HTL are: carbazole derivatives, such as N-phenylcarbazole or polyvinylcarbazole; phenylenediamine derivatives, such as N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1- biphenyl]-4,4'-diamine (TPD) or N,N'-di(naphthalen-1-yl)-N,N'-diphenylphenylenediamine (a-NPD); and triphenylamine-based compounds, such as 4,4',4"-tris(N-carbazolyl)triphenylamine (TCTA). Among these compounds, TCTA can transport holes and suppress exciton diffusion into the EML.

[0072] The thickness of the HTL can be in the range of about 5 nm to about 250 nm, preferably about 10 nm to about 200 nm, further about 20 nm to about 190 nm, further about 40 nm to about 180 nm, further about 60 nm to about 170 nm, further about 80 nm to about 160 nm, further about 100 nm to about 160 nm, further about 120 nm to about 140 nm. The preferred thickness of the HTL can be 170 nm to 200 nm.

[0073] When the thickness of the HTL is in this range, the HTL can have excellent hole-transport properties without substantial damage to the driving voltage.

[0074] Electron transport layer

[0075] The function of the electron blocking layer (EBL) is to prevent the transfer of electrons from the light-emitting layer to the hole-transporting layer, thereby confining the electrons to the light-emitting layer. Thereby, the efficiency, operating voltage and / or lifetime is improved. Typically, the electron blocking layer comprises a triarylamine compound. The LUMO level of the triarylamine compound can be closer to the vacuum level than the LUMO level of the hole-transporting layer. The electron blocking layer can have a HOMO level further away from the vacuum level than the HOMO level of the hole-transporting layer. The thickness of the electron blocking layer can be selected from 2 nm to 20 nm.

[0076] If the electron blocking layer has a high triplet energy level, it can also be described as a triplet control layer.

[0077] The function of the triplet control layer is to reduce the quenching of triplets in case a green or blue phosphorescent light-emitting layer is used. Thereby, a higher light-emitting efficiency from the phosphorescent light-emitting layer can be achieved. The triplet control layer is selected from a triarylamine compound having a triplet energy level higher than the triplet energy level of the phosphorescent emitter in the adjacent light-emitting layer. Suitable compounds, in particular triarylamine compounds, for the triplet control layer are described in EP 2 722 908 Al.

[0078] Light-emitting layer (EML)

[0079] The EML can be formed on the HTL by vacuum deposition, spin coating, slot-die coating, printing, casting, LB deposition, etc. When the EML is formed using vacuum deposition or spin coating, the conditions of deposition and coating can be similar to those used for forming the HIL. However, the conditions of deposition and coating can vary depending on the compounds used to form the EML.

[0080] The light-emitting layer (EML) can be formed from a combination of a host and an emitter dopant. Examples of hosts are Alq3, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,10-di(naphthalen-2-yl)anthracene (ADN), 4,4',4"-tris(carbazol-9-yl)- triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzoimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-di-2-naphthylanthracene (TBADN), diphenylstyrylarene (DSA), and bis(2-(2-hydroxyphenyl)benzothiazole)zinc (Zn(BTZ)2).

[0081] The emitter dopant can be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters that emit light via the thermally activated delayed fluorescence (TADF) mechanism can be preferred due to the higher efficiency. The emitter can be a small molecule or a polymer.

[0082] Examples of red phosphorescent dopants are PtOEP, Ir(piq)3, and Btp2Ir(acac), but are not limited thereto. These compounds are phosphorescent emitters, but red fluorescent dopants can also be used.

[0083] Examples of green phosphorescent dopants are Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2(acac), Ir(mpyp)3.

[0084] Examples of blue phosphorescent dopants are F2Irpic, (F2ppy)2Ir(tmd), and Ir(dfppz)3, and triphenylfluorene. 4,4'-Bis(4-diphenylaminostyryl)biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butylperylene (TBPe) are examples of blue fluorescent dopants.

[0085] The amount of the emitter dopant can be in the range of about 0.01 to about 50 parts by weight, based on 100 parts by weight of the host. Alternatively, the EML can consist of an emitting polymer. The EML can have a thickness of about 10 nm to about 100 nm, for example, about 20 nm to about 60 nm. When the thickness of the EML is in this range, the EML can have excellent emission without substantial damage to the driving voltage.

[0086] Hole blocking layer (HBL)

[0087] The hole blocking layer (HBL) can be formed on the EML by using vacuum deposition, spin coating, slot-die coating, printing, casting, LB deposition, etc., to prevent the diffusion of holes into the ETL. When the EML contains a phosphorescent dopant, the HBL can also have a function of blocking triplet excitons. The hole blocking layer can be an organic semiconductor layer of the present application comprising a compound of the present application represented by the general formula (I) as defined above.

[0088] When the HBL is formed using vacuum deposition or spin coating, the conditions of deposition and coating can be similar to those used for forming the HIL. However, the conditions of deposition and coating can vary depending on the compound used for forming the HBL. Any compound commonly used for forming the HBL can be used. Examples of the compound for forming the HBL include oxadiazole derivatives, triazole derivatives, and phenanthroline derivatives.

[0089] The thickness of the HBL can be in the range of about 5 nm to about 100 nm, for example, about 10 nm to about 30 nm. When the thickness of the HBL is in this range, the HBL can have excellent hole blocking properties without substantial damage to the driving voltage.

[0090] Electron transport layer (ETL)

[0091] The OLED of the present application can comprise an electron transport layer (ETL). According to the present application, the electron transport layer can be an organic semiconducting layer of the present application comprising a compound of the present application represented by the general formula (I) as defined above.

[0092] According to various embodiments, the OLED can comprise an electron transport layer or an electron transport layer stack structure comprising at least a first electron transport layer and at least a second electron transport layer.

[0093] By properly adjusting the energy level of the specific layers of the ETL, the injection and transport of electrons can be controlled and holes can be effectively blocked. Thus, the OLED can have a long lifetime.

[0094] The electron transport layer of the organic electronic device can comprise a compound represented by the general formula (I) as defined above as an organic electron transport matrix (ETM) material. In addition to the compound represented by the general formula (I), the electron transport layer can further comprise other ETM materials known in the art. Likewise, the electron transport layer can comprise the compound represented by the general formula (I) as the only electron transport matrix material. In case the organic electronic device of the present application comprises more than one electron transport layer, the compound represented by the general formula (I) can be comprised in only one electron transport layer, in more than one electron transport layer or in all electron transport layers. According to the present application, the electron transport layer can comprise at least one additive as defined below in addition to the ETM material. Furthermore, the electron transport layer can comprise one or more n-type dopants. The additive can be an n-type dopant. The additive can be an alkali metal, an alkali metal compound, an alkaline earth metal, an alkaline earth metal compound, a transition metal, a transition metal compound or a rare earth metal. In another embodiment, the metal can be one selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Sm, Eu, Tb, Dy and Yb. In another embodiment, the n-type dopant can be one selected from the group consisting of Cs, K, Rb, Mg, Na, Ca, Sr, Eu and Yb. In one embodiment, the alkali metal compound can be lithium 8-hydroxyquinolinate (LiQ), lithium tetrakis(1 H-pyrazol-1 -yl)borate or lithium 2-(diphenylphosphoryl)phenolate. Suitable compounds for use in the ETM (which can be used in addition to the compound of the present application represented by the general formula (I) as defined above) are not particularly limited. In one embodiment, the electron transport matrix compound consists of covalently bound atoms. Preferably, the electron transport matrix compound comprises a conjugated system of at least 6, more preferably at least 10 delocalized electrons. In one embodiment, the conjugated system of delocalized electrons can be comprised in an aromatic or heteroaromatic structural moiety, as for example disclosed in the literature EP 1 970 371 A1 or WO 2013 / 079217 A1.

[0095] Electron injection layer (EIL)

[0096] An optional EIL that can facilitate injection of electrons from the cathode can be formed on the ETL, preferably directly on the electron transport layer. Examples of materials forming the EIL include lithium 8-hydroxyquinolinate (LiQ), LiF, NaCl, CsF, Li2O, BaO, Ca, Ba, Yb, Mg known in the art. The deposition and coating conditions for forming the EIL are similar to those for forming the HIL, but the deposition and coating conditions can vary depending on the material used to form the EIL. The EIL can be a layer comprising a compound of Formula (I).

[0097] 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 in this range, the EIL can have satisfactory electron injection properties without causing substantial damage to the driving voltage.

[0098] Cathode

[0099] The cathode is formed on the EIL, if present. The cathode can be formed of a metal, an alloy, a conductive compound, or a mixture thereof. The cathode can have a low work function. For example, the cathode can be formed of lithium (Li), magnesium (Mg), aluminum (Al), aluminum (Al)-lithium (Li), calcium (Ca), barium (Ba), ytterbium (Yb), magnesium (Mg)-indium (In), magnesium (Mg)-silver (Ag), or the like. Alternatively, the cathode can be formed of a transparent conductive oxide such as ITO or IZO.

[0100] The thickness of the cathode can be in the range of about 5 nm to about 1000 nm, for example, in the range of about 10 nm to about 100 nm. When the thickness of the cathode is in the range of about 5 nm to about 50 nm, the cathode can be transparent or semi-transparent even if formed of a metal or a metal alloy.

[0101] It should be understood that the cathode is not part of the electron injection layer or the electron transport layer.

[0102] Charge generation layer / hole generation layer

[0103] The charge generation layer (CGL) can be composed of a double layer.

[0104] In general, the charge generation layer is a pn junction that connects an n-type charge generation layer (electron generation layer) and a hole generation layer. The n-side of the pn junction generates electrons and injects the electrons into a layer adjacent in the direction of the anode. Similarly, the p-side of the p-n junction generates holes and injects the holes into a layer adjacent in the direction of the cathode.

[0105] The charge generation layer is used in a tandem device, for example, in a tandem OLED comprising two or more light-emitting layers between two electrodes. In a tandem OLED comprising two light-emitting layers, the n-type charge generation layer provides electrons to a first light-emitting layer disposed near the anode, while the hole generation layer provides holes to a second light-emitting layer disposed between the first light-emitting layer and the cathode.

[0106] A suitable host material for the hole generation layer can be a material conventionally used as a hole injection and / or hole transport host material. In addition, the p-type dopant for the hole generation layer can employ a conventional material. For example, the p-type dopant can be one selected from the group consisting of tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), a derivative of tetracyanoquinodimethane, an acetylene derivative, iodine, FeCl3, FeF3, and SbCl5. In addition, the host can be one selected from the group consisting of N,N'-di(naphthalen-1-yl)-N,N-diphenylbenzidine (NPB), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1-biphenyl-4,4'-diamine (TPD), and N,N',N'-tetranaphthyl-benzidine (TNB).

[0107] The n-type charge generation layer can substantially comprise a compound of Formula (I). The n-type charge generation layer can be a layer of a pure n-type dopant, such as a positive metal, or can consist of an organic host material doped with an n-type dopant. In one embodiment, the n-type dopant can be an alkali metal, an alkali metal compound, an alkaline earth metal, an alkaline earth metal compound, a transition metal, a transition metal compound, or a rare earth metal. In another embodiment, the metal can be one selected from the 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 can be one selected from the group consisting of Cs, K, Rb, Mg, Na, Ca, Sr, Eu, and Yb. A suitable host material for the electron generation layer can be a material conventionally used as a host material for an electron injection or electron transport layer. The host material can be, for example, one selected from the group consisting of a triazine compound, a hydroxyquinoline derivative such as tris(8-hydroxyquinoline)aluminum, a benzoxazole derivative, and a silacyclophane derivative.

[0108] In one embodiment, the n-type charge generation layer can comprise a compound of the following chemical formula X,

[0109]

[0110] wherein A 1 to A 6each of which can be hydrogen, a halogen atom, a nitrile group (-CN), a nitro group (-N02), a sulfonyl group (-S02R), a sulfoxide group (-SOR), a sulfonamide group (-S02NR), a sulfonate group (-S03R), a trifluoromethyl group (-CF3), an ester (-COOR), an amide (-CONHR or -CONRR'), a substituted or unsubstituted linear or branched C1-C 12 alkoxy group, a substituted or unsubstituted linear or branched C1-C 12 alkyl group, a substituted or unsubstituted linear or branched C2-C 12 alkenyl group, a substituted or unsubstituted aromatic or non-aromatic heterocycle, a substituted or unsubstituted aryl group, a substituted or unsubstituted mono- or di- aryl amine, a substituted or unsubstituted aralkyl amine, etc. Here, each of the above R and R' can be a substituted or unsubstituted C1-C 60 alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted 5- to 7-membered heterocycle, etc.

[0111] One example of such an n-type charge generation layer can be a layer comprising CNHAT.

[0112]

[0113] The hole generation layer is disposed on the n-type charge generation layer.

[0114] Organic light emitting diode (OLED)

[0115] The organic electronic device of the present application can be an organic light emitting device.

[0116] According to one aspect of the present application, there is provided an organic light emitting diode (OLED) comprising: a substrate; an anode formed on the substrate; a hole injection layer, a hole transport layer, a light emitting layer, and a cathode.

[0117] According to another aspect of the present application, there is provided an OLED comprising: a substrate; an anode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, and a cathode.

[0118] According to another aspect of the present application, there is provided an OLED comprising: a substrate; an anode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and a cathode.

[0119] According to another aspect of the present application, there is provided an OLED comprising: a substrate; an anode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode.

[0120] According to various embodiments of the present application, an OLED layer can be provided which is arranged between the above-mentioned layers, on the substrate or on the top electrode.

[0121] According to one aspect, the OLED can comprise a layer structure of a substrate arranged adjacent to an anode, the anode arranged adjacent to a first hole injection layer, the first hole injection layer arranged adjacent to a first hole transport layer, the first hole transport layer arranged adjacent to a first electron blocking layer, the first electron blocking layer arranged adjacent to a first emission layer, the first emission layer arranged adjacent to a first electron transport layer, the first electron transport layer arranged adjacent to an n-type charge generation layer, the n-type charge generation layer arranged adjacent to a hole generation layer, the hole generation layer arranged adjacent to a second hole transport layer, the second hole transport layer arranged adjacent to a second electron blocking layer, the second electron blocking layer arranged adjacent to a second emission layer, between the second emission layer and a cathode an optional electron transport layer and / or an optional injection layer is arranged.

[0122] For example, Figure 2 The OLED of Formula (I) can be formed by a method, wherein

[0123] On a substrate (110), an anode (120), a hole injection layer (130), a hole transport layer (140), an electron blocking layer (145), an emission layer (150), a hole blocking layer (155), an electron transport layer (160), an electron injection layer (180) and a cathode (190) are formed in this order.

[0124] Organic electronic device

[0125] The organic electronic device of the present application comprises an organic semiconductor layer comprising a compound of Formula I.

[0126] The organic electronic device according to one embodiment can comprise a substrate, an anode layer, an organic semiconductor layer comprising a compound of Formula (I) and a cathode layer.

[0127] The organic electronic device according to one embodiment comprises at least one organic semiconductor layer comprising at least one compound of Formula I, at least one anode layer, at least one cathode layer and at least one emission layer, wherein the organic semiconductor layer is preferably arranged between the emission layer and the cathode layer.

[0128] The organic light emitting diode (OLED) of the present application can comprise an anode, a hole transport layer (HTL), an emission layer (EML), an electron transport layer (ETL) comprising at least one compound of Formula (I) and a cathode, which are stacked in this order on a substrate. In this regard, the HTL, the EML and the ETL are thin films formed from organic compounds.

[0129] The organic electronic device according to one embodiment can be a light-emitting device, a thin film transistor, a battery, a display device or a photovoltaic cell, and is preferably a light-emitting device.

[0130] According to another aspect of the present application, there is provided a method of manufacturing an organic electronic device, said method using:

[0131] - at least one deposition source, preferably two deposition sources, more preferably at least three deposition sources.

[0132] Suitable deposition methods can include:

[0133] - deposition by vacuum thermal evaporation;

[0134] - deposition by solution processing, preferably said processing is selected from spin-coating, printing, casting; and / or

[0135] - slot-die coating.

[0136] According to various embodiments of the present application, there is provided a method using:

[0137] - a first deposition source to release a compound of formula (I) of the present application, and

[0138] - a second deposition source to release an alkali metal halide or alkali metal organic complex, preferably lithium halide or lithium organic complex;

[0139] The method comprises the step of forming an electron transport layer stack; wherein for an organic light-emitting diode (OLED):

[0140] - forming a first electron transport layer by releasing a compound of formula (I) of the present application from the first deposition source, and releasing an alkali metal compound, preferably an alkali metal halide or alkali metal organic complex, preferably lithium halide or lithium organic complex, from the second deposition source.

[0141] According to various embodiments of the present application, the method can further comprise forming a light-emitting layer on the anode, and forming at least one layer selected from a hole injection layer, a hole transport layer or a hole blocking layer between the anode and the first electron transport layer.

[0142] According to various embodiments of the present application, the method can further comprise steps for forming an organic light-emitting diode (OLED), wherein

[0143] - forming a first anode on a substrate,

[0144] - forming a light-emitting layer on the first anode,

[0145] - forming an electron transport layer stack on the light-emitting layer, preferably forming a first electron transport layer on the light-emitting layer, and optionally forming a second electron transport layer,

[0146] - finally forming a cathode,

[0147] - optionally forming a hole injection layer, a hole transport layer and a hole blocking layer in this order between the first anode and the light emitting layer,

[0148] - optionally forming an electron injection layer between the electron transport layer and the cathode.

[0149] According to various embodiments of the present application, the method can further comprise forming an electron injection layer on the first electron transport layer. However, according to various embodiments of the OLED of the present application, the OLED can not comprise an electron injection layer.

[0150] According to various embodiments, the OLED can have the following layer structure, wherein the layers have the following order:

[0151] anode, hole injection layer, first hole transport layer, second hole transport layer, light emitting layer, optional second electron transport layer, first electron transport layer comprising a compound of formula (I) of the present application, optional electron injection layer and cathode.

[0152] According to another aspect of the present application, there is provided an electronic device comprising at least one organic light emitting device according to any of the embodiments described throughout the present application, preferably the electronic device comprises an organic light emitting diode according to one of the embodiments described throughout the present application. More preferably, the electronic device is a display device.

[0153] In one embodiment, the organic electronic device of the present application comprising an organic semiconductor layer comprising a compound of formula (I) can further comprise a layer comprising an axi compound and / or a quinonedimethane compound.

[0154] In one embodiment, the axi compound and / or the quinonedimethane compound can be substituted by one or more halogen atoms and / or one or more electron withdrawing groups. The electron withdrawing group can be selected from a nitrile group, a halogenated alkyl group, or from a perhalogenated alkyl group, or from a perfluorinated alkyl group. Other examples of electron withdrawing groups can be acyl groups, sulfonyl groups or phosphoryl groups.

[0155] Alternatively, the acyl group, the sulfonyl group and / or the phosphoryl group can comprise a halogenated and / or a perhalogenated hydrocarbon group. In one embodiment, the perhalogenated hydrocarbon group can be a perfluorinated hydrocarbon group. Examples of perfluorinated hydrocarbon groups can be perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorophenyl, perfluorotolyl; examples of sulfonyl groups comprising a halogenated hydrocarbon group can be trifluoromethylsulfonyl, pentafluoroethylsulfonyl, pentafluorophenylsulfonyl, heptafluoropropylsulfonyl, nonafluorobutylsulfonyl and the like.

[0156] In one embodiment, the fulvene compound and / or the quinodimethane compound can be comprised in a hole injection, hole transport and / or hole generation layer.

[0157] In one embodiment, the fulvene compound can have formula (XX) and / or the quinodimethane compound can have formula (XXIa) or (XXIb):

[0158]

[0159] wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 11 , R 12 , R 15 , R 16 , R 20 , R 21 are independently selected from the above-mentioned electron- withdrawing groups, and R 9 , R 10 , R 13 , R 14 , R 17 , R 18 , R 19 , R 22 , R 23 and R 24 are independently selected from H, halogen and the above-mentioned electron- withdrawing groups.

[0160] In the following, embodiments will be explained in more detail with reference to examples. However, the present disclosure is not limited to the following examples. Reference will now be made in detail to exemplary aspects.

[0161] Details and definitions of the invention

[0162] In formula (I), the “*” marks the possible positions where a -(A) a -L can bind. In each of the aromatic rings marked with “*”, a -(A) a -L moiety can bind at each position which does not already have four binders. The respective binding is by replacement of a hydrogen by the respective moiety. In this regard, the compound of formula (I) can comprise only one -(A) a -L moiety. Likewise, the compound of formula (I) can comprise more than one -(A) a -L moiety, unless explicitly mentioned otherwise. In this regard, the -(A) a -L moiety is only attached to the respective marked ring, and the remaining aromatic rings do not comprise a respective -(A)a - moiety L.

[0163] In the present specification, the term "alkyl group" can refer to an aliphatic hydrocarbon group, when no definition is provided otherwise. The alkyl group can refer to a "saturated alkyl group" without any double or triple bonds. The term "alkyl" as used herein shall encompass straight chain as well as branched and cyclic alkyl groups. For example, a C3 alkyl group can be selected from n-propyl and i-propyl. Likewise, a C4 alkyl group includes n-butyl, sec-butyl and t-butyl. Likewise, a C6 alkyl group includes n-hexyl and cyclohexyl.

[0164] C n The lower index number n relates to the total number of carbon atoms in the respective alkyl, arylene, heteroarylene or aryl group.

[0165] The term "aryl" as used herein shall encompass phenyl (C6 aryl) or fused aromatic compounds, such as naphthyl, anthryl, phenanthryl, naphthacene, etc. Further encompassed are any other aromatic hydrocarbon substituents, such as fluorenyl, etc. The term "aryl" as used herein is also used for "arylene" moieties. For example, a group A, which can be an aryl group, is bound to two different moieties, namely the spiro moiety of formula (I) and the moiety L. In the present specification, the term "aryl group" can refer to a group comprising at least one hydrocarbon aromatic moiety, and all elements of the hydrocarbon aromatic moiety can have p-orbitals forming a conjugation, such as phenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, pyrenyl groups, fluorenyl groups, etc. Arylene groups can include monocyclic or fused ring polycyclic (i.e. rings sharing pairs of adjacent carbon atoms) functional groups.

[0166] The term "heteroaryl" as used herein refers to an aryl group, wherein at least one carbon atom is replaced by a heteroatom, preferably selected from N, O, S, B or Si.

[0167] C n The index number n in a heteroaryl refers only to the number of carbon atoms, excluding the number of heteroatoms. In this context, it is clear that a C3 heteroarylene is an aromatic compound comprising three carbon atoms, such as pyrazole, imidazole, oxazole, thiazole, etc.

[0168] The term "heteroaryl" can refer to an aromatic heterocycle having at least one heteroatom, and all elements of the hydrocarbon heteroaromatic moiety can have p-orbitals forming a conjugation. The heteroatom can be selected from N, O, S, B, Si, P, Se, preferably from N, O and S. The heteroarylene ring can comprise at least 1 to 3 heteroatoms. Preferably, the heteroarylene ring can comprise at least 1 to 3 heteroatoms independently selected from N, S and / or O.

[0169] The term "heteroaryl" as used herein shall encompass pyridine, quinoline, quinazoline, pyridine, triazine, benzimidazole, benzothiazole, benzo[4,5]thieno[3,2-d]pyrimidine, carbazole, xanthene, phenoxazine, phenothiazine, dibenzoacridine, and the like. The term "heteroaryl" as used herein shall encompass pyridine, quinoline, quinazoline, pyridine, triazine, benzimidazole, benzothiazole, benzo[4,5]thieno[3,2-d]pyrimidine, carbazole, xanthene, phenoxazine, phenothiazine, dibenzoacridine, and the like.

[0170] In the present description, a single bond means a direct bond.

[0171] As used herein, the term "fluorinated" refers to a hydrocarbyl group in which at least one hydrogen atom contained in the hydrocarbyl group is replaced by a fluorine atom. A fluorinated group in which all hydrogen atoms are replaced by fluorine atoms is referred to as a perfluorinated group and is in particular crowned with the term "fluorinated".

[0172] According to the present application, a group is "substituted" by another group if one hydrogen atom contained in this group is replaced by the other group, wherein the other group is a substituent.

[0173] According to the present application, the expression "between" with respect to one layer between two other layers does not exclude that further layers can be arranged between said one layer and one of the two other layers. According to the present application, the expression "direct contact" with respect to two layers in direct contact with each other means that no further layer is arranged between these two layers. A layer deposited on top of another layer is considered to be in direct contact with this layer.

[0174] For the organic semiconducting layer of the present application as well as for the compounds of the present application, most preferred are the compounds mentioned in the experimental part.

[0175] The organic electronic device of the present application can be an organic electroluminescent device (OLED), an organic photovoltaic device (OPV), a lighting device or an organic field effect transistor (OFET). Lighting devices can be any device for illumination, irradiation, signaling or projection. They are accordingly classified as illumination, irradiation, signaling and projection devices. Lighting devices generally consist of a source of light radiation, a means of transmitting the radiation flux in the desired direction into the space, and a housing that connects the parts into a single device and protects the radiation source and the light transmission system from damage and the environment.

[0176] According to another aspect, the organic electroluminescent device of the present application can comprise more than one light-emitting layer, preferably two or three light-emitting layers. OLEDs comprising more than one light-emitting layer are also described as tandem OLEDs or stacked OLEDs.

[0177] The organic electroluminescent device (OLED) can be a bottom or a top emitting device.

[0178] Another aspect relates to a device comprising at least one organic electroluminescent device (OLED). A device comprising organic light emitting diodes is for example a display or lighting panel.

[0179] In the present application, the following defined terms are to be used with the definitions given herein, unless a different definition is given in the claims or elsewhere in the specification.

[0180] In the context of the present specification, the term "different" in relation to a matrix material means that the structural formula of the matrix material is different.

[0181] The energy levels of the highest occupied molecular orbital (also referred to as HOMO) and the lowest unoccupied molecular orbital (also referred to as LUMO) are measured indirectly against ferrocene (in electron volts (eV)) by cyclic voltammetry or can be calculated. Such DFT calculations can be performed using the program package TURBOMOLE V6.5 (Supplier: TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The best geometry of the molecular structure and the HOMO / LUMO energy levels are determined using the hybrid functional B3LYP with the 6-31G* basis set. If more than one conformation is feasible, the conformation with the lowest total energy is selected. The terms "OLED" and "organic light-emitting diode" are used simultaneously and have the same meaning. The term "organic electroluminescent device" as used herein can encompass organic light-emitting diodes as well as organic light-emitting transistors (OLETs).

[0182] As used herein, "weight percent," "wt. %," "percent by weight," "% by weight," and variations thereof refer to the composition, component, substance or agent as a weight of the composition, component, substance or agent of the respective electron transport layer divided by the total weight of the respective electron transport layer, and multiplied by 100. It is understood that the total weight percent amounts of all components, substances and agents of the respective electron transport layer and electron injection layer should be selected such that they do not exceed 100 wt. %.

[0183] As used herein, "volume percent," "vol. %," "percent by volume," "% by volume," and variations thereof refer to the composition, component, substance or agent as a volume of the composition, component, substance or agent of the respective electron transport layer divided by the total volume of the respective electron transport layer, and multiplied by 100. It is understood that the total volume percent amounts of all components, substances and agents of the respective electron transport layer should be selected such that they do not exceed 100 vol. %.

[0184] All numerical values herein are assumed to be modified by the term "about," whether explicitly indicated or not. As used herein, the term "about" means a quantity that can vary by up to 10%. The claims include the quantitative amounts of the recited amounts, whether or not modified by the term "about."

[0185] It should be noted that the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise.

[0186] The terms "free of," "not including," "not comprising," do not exclude impurities.

[0187] In the context of the present specification, the term "essentially not emitting light" or "not emitting light" means 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. The visible emission spectrum is the emission spectrum having a wavelength of about > 380 nm to about < 780 nm.

[0188] Preferably, the organic semiconducting layer comprising the compound of formula I is essentially not emitting light or not emitting light.

[0189] Operating voltage, also called U, is measured in Volt (V) at 10 milliampere per square centimeter (mA / cm 2 ) and is measured in Candela per Ampere (cd / A).

[0190] Candela per Ampere efficiency, also called cd / A efficiency, is measured in Candela per Ampere (cd / A) at 10 milliampere per square centimeter (mA / cm 2 ) and is measured in percent (%).

[0191] External quantum efficiency (also called EQE) is measured in percent (%).

[0192] The color space is described by the coordinates CIE-x and CIE-y (Commission Internationale de l'Eclairage 1931). For blue light emission, CIE-y is of particular importance. The smaller CIE-y is, the deeper the blue color is.

[0193] Highest occupied molecular orbital (also called HOMO) and lowest unoccupied molecular orbital (also called LUMO) are measured in electron volt (eV).

[0194] The terms "OLED", "organic light emitting diode", "organic light emitting device", "organic optoelectronic device" and "organic light emitting diode" are used simultaneously and have the same meaning.

[0195] The term "transition metal" means and includes any element in the d-block of the periodic table, which includes elements from group 3 to 12 in the periodic table.

[0196] The term "group III to VI metal" means and includes any metal from group III to VI of the periodic table.

[0197] The terms "lifetime period" and "lifetime" are used simultaneously and have the same meaning.

[0198] All numerical values herein are assumed to be modified by the term "about", whether expressly indicated or not. As used herein, the term "about" means a numerical variation that can occur.

[0199] The claims include the equivalent amounts of the recited quantities, whether or not modified by the term "about".

[0200] It should be noted that the singular forms "a", "an", and "the" include plural referents unless the content clearly dictates otherwise.

[0201] An anode and a cathode can be described as an anode / cathode or an anode electrode / cathode electrode or an anode layer / cathode layer.

[0202] Dipole moment of a molecule containing N atoms is given by:

[0203]

[0204] where q i and are the local charges and positions of the atoms in the molecule.

[0205] The dipole moments were determined by a semi-empirical molecular orbital method.

[0206] The local charges and atomic positions in the gas phase were obtained using the hybrid functional B3LYP with the 6-31G* basis set implemented in the program package TURBOMOLE V6.5. If more than one conformation was feasible, the conformation with the lowest total energy was chosen to determine the dipole moment.

[0207] The reduction potential can be determined by cyclic voltammetry with a potentiostat device Metrohm PGSTAT30 and the software Metrohm Autolab GPES at room temperature. The redox potential is measured in anhydrous 0.1 M THF solution of the compound of formula I degassed with argon, under an argon atmosphere, between platinum working electrodes with 0.1 M tetrabutylammonium hexafluorophosphate as supporting electrolyte and using an Ag / AgCl pseudo-standard electrode consisting of a silver wire covered with silver chloride and directly immersed in the solution under test, with a scan rate of 100 mV / s. The first run is performed in the widest potential range set on the working electrodes, then the range is adjusted appropriately in the subsequent runs. The last three runs are performed with the addition of ferrocene (concentration 0.1 M) as a standard. The average of the potentials corresponding to the cathodic and anodic peaks of the compound is determined by subtracting the average of the cathodic and anodic potentials observed for the Fc + / Fc redox couple.

[0208] Room temperature (also referred to as ambient temperature) is 23 °C. Attached Figure Description

[0209] These and / or other aspects and advantages of the present invention will become clear and more readily understood from the following description of exemplary embodiments in conjunction with the accompanying drawings, wherein:

[0210] Figure 1 This is a schematic cross-sectional view of an organic light-emitting diode (OLED) according to an exemplary embodiment of the present invention.

[0211] Figure 2 This is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention.

[0212] Figure 3 This is a schematic cross-sectional view of a tandem OLED including a charge generation layer according to an exemplary embodiment of the present invention. Detailed Implementation

[0213] Reference will now be made in detail to exemplary embodiments of the invention, embodiments of which are illustrated in the accompanying drawings, wherein the same reference numerals denote the same elements throughout. Exemplary embodiments are described below with reference to the accompanying drawings to explain aspects of the invention.

[0214] Here, when the first element is referred to as being formed or disposed "on" the second element, the first element may be directly disposed on the second element, or one or more other elements may be disposed therein. When the first element is referred to as being "directly" formed or disposed on the second element, there are no other elements therein.

[0215] 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 emissive layer (EML) 150, and an electron transport layer (ETL) 160. The electron transport layer (ETL) 160 is formed on the EML 150. An electron injection layer (EIL) 180 is disposed on the electron transport layer (ETL) 160. A cathode 190 is directly disposed on the electron injection layer (EIL) 180.

[0216] Instead of a single electron transport layer 160, an electron transport layer stack (ETL) structure can be optionally used.

[0217] 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 2The OLED 100 of FIG. 1 includes an electron blocking layer (EBL) 145 and a hole blocking layer (HBL) 155.

[0218] Referring to Figure 2 , 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 emission layer (EML) 150, a hole blocking layer (HBL) 155, an electron transport layer (ETL) 160, an electron injection layer (EIL) 180, and a cathode 190.

[0219] Figure 3 is a schematic cross-sectional view of a tandem OLED 200 according to another exemplary embodiment of the present application. Figure 3 Unlike Figure 2 , Figure 3 The OLED 100 of FIG. 1 further includes a charge generation layer (CGL) and a second emission layer (151).

[0220] Referring to Figure 3 , the OLED 200 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 emission 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 emission layer (EML) 151, a second hole blocking layer (EBL) 156, a second electron transport layer (ETL) 161, a second electron injection layer (EIL) 181, and a cathode 190.

[0221] Although not shown in Figure 1 , Figure 2 and Figure 3 , a sealing layer can be further formed on the cathode 190 to seal the OLEDs 100 and 200. In addition, various other modifications can be made thereto.

[0222] Hereinafter, one or more exemplary embodiments of the present application will be described in detail with reference to the following examples. However, these examples are not intended to limit the purpose and scope of one or more exemplary embodiments of the present application.

[0223] The features disclosed in the foregoing description, in the claims, and / or in the accompanying drawings can be, both separately and in any combination thereof, material for realizing the application in various forms thereof.

[0224] Experimental Section

[0225] Synthesis of compounds of formula 1

[0226] 3-bromo-spiro[benzo[de]anthracene-7,9'-fluorene] was synthesized according to literature procedure (J.-Y. Kim et al., Dyes and Pigments 2012, 94, 304-313). 4,4,5,5-tetramethyl-2-(spiro[benzo[de]anthracene-7,9'-fluorene]-3-yl)-1,3,2- dioxaborolane 2-(dibenzo[b,d]furan-3-yl)-4-phenyl-6-(spiro[benzo[de]anthracene-7,9'-fluorene]-3-yl)- 1,3,5-triazine (compound A-2)

[0227]

[0228] 5-triazine (compound A-1)

[0229]

[0230] The flask was purged with nitrogen and charged with 3-bromo-spiro[benzo[de]anthracene-7,9'-fluorene (34.2 g, 76.8 mmol), bis(pinacolato)diboron (29.2 g, 115.2 mmol), potassium acetate (22.6 g, 230.4 mmol) and Pd(dppf)Cl2(2.2 g, 3.0 mmol). Degassed 1,4-dioxane (700 mL) was added and the reaction mixture was heated to 100 °C under a nitrogen atmosphere for 18 hours. After cooling to room temperature, ethyl acetate was added and the organic layer was filtered through a pad of celite. The organic solvent was removed under reduced pressure, the solid was dissolved in dichloromethane and filtered through a pad of silica gel. After rinsing with a mixture of dichloromethane / n-hexane (4:6), the combined filtrates were concentrated under reduced pressure. The obtained solid was triturated with a mixture of dichloromethane / n-hexane (5:95), isolated by suction filtration, washed with n-hexane and dried under vacuum to give 26.8 g (71%) of a light yellow solid. HPLC: 99%. The flask was purged with nitrogen and charged with 3-bromo-spiro[benzo[de]anthracene-7,9'-fluorene (34.2 g, 76.8 mmol), bis(pinacolato)diboron (29.2 g, 115.2 mmol), potassium acetate (22.6 g, 230.4 mmol) and Pd(dppf)Cl2(2.2 g, 3.0 mmol). Degassed 1,4-dioxane (700 mL) was added and the reaction mixture was heated to 100 °C under a nitrogen atmosphere for 18 hours. After cooling to room temperature, ethyl acetate was added and the organic layer was filtered through a pad of celite. The organic solvent was removed under reduced pressure, the solid was dissolved in dichloromethane and filtered through a pad of silica gel. After rinsing with a mixture of dichloromethane / n-hexane (4:6), the combined filtrates were concentrated under reduced pressure. The obtained solid was triturated with a mixture of dichloromethane / n-hexane (5:95), isolated by suction filtration, washed with n-hexane and dried under vacuum to give 26.8 g (71%) of a light yellow solid. HPLC: 99%.

[0231] 2,4-diphenyl-6-(4-(spiro[benzo[de]anthracene-7,9'-fluorene]-3-yl]phenyl)-1,3,5- triazine (compound A-3) Melting point

[0232]

[0233] The flask was purged with nitrogen and charged with 3-bromo-spiro[benzo[de]anthracene-7,9'-fluorene (34.2 g, 76.8 mmol), bis(pinacolato)diboron (29.2 g, 115.2 mmol), potassium acetate (22.6 g, 230.4 mmol) and Pd(dppf)Cl2(2.2 g, 3.0 mmol). Degassed 1,4-dioxane (700 mL) was added and the reaction mixture was heated to 100 °C under a nitrogen atmosphere for 18 hours. After cooling to room temperature, ethyl acetate was added and the organic layer was filtered through a pad of celite. The organic solvent was removed under reduced pressure, the solid was dissolved in dichloromethane and filtered through a pad of silica gel. After rinsing with a mixture of dichloromethane / n-hexane (4:6), the combined filtrates were concentrated under reduced pressure. The obtained solid was triturated with a mixture of dichloromethane / n-hexane (5:95), isolated by suction filtration, washed with n-hexane and dried under vacuum to give 26.8 g (71%) of a light yellow solid. HPLC: 99%. A mixture of alkyl / water (4.5:1, 245 mL) was used, and the reaction mixture was heated to 90 °C for 18 hours under a nitrogen atmosphere. After cooling to room temperature, ethyl acetate was added, the organic layer was washed with water, dried over Na₂SO₄, and the organic solvent was removed under reduced pressure. The crude product was dissolved in dichloromethane and filtered through a silica gel pad. After washing with a mixture of dichloromethane and n-hexane (gradient from 10% to 30%), the combined filtrates were concentrated under reduced pressure. The obtained precipitate was ground with n-hexane, separated by filtration, and washed again with n-hexane. After recrystallization from THF and drying under vacuum, 14.7 g (69%) of a pale yellow solid was given. Final purification was achieved by sublimation. HPLC / ESI-MS: 100%, m / z = 688 ([M+H)). + ).

[0234] Glass transition temperature A-5)

[0235]

[0236] The flask was rinsed with nitrogen and then filled with 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (3.6 g, 9.2 mmol), 4,4,5,5-tetramethyl-2-(3',4',5'-triphenyl-[1,1':2',1”-terphenyl]-4-yl)-1,3,2-dioxane (5.0 g, 10.1 mmol), K₂CO₃ (3.8 g, 27.7 mmol), and Pd(PPh₃)₄ (0.3 g, 0.3 mmol). Degassed 1,4-dioxane was added. A mixture of alkane and water (2.8:1, 54 mL) was prepared, and the reaction mixture was heated to 90 °C for 18 hours under a nitrogen atmosphere. After cooling to room temperature, the precipitate was separated by vacuum filtration. The crude product was dissolved in toluene, the organic phase was washed with water, and dried over MgSO4. The resulting filtrate was filtered through a silica gel pad, and the solvent was removed under reduced pressure. The solid obtained was dried under vacuum to give 3.4 g (56%) of white solid. Final purification was achieved by sublimation. HPLC / ESI-MS: 99.9%, m / z = 674 ([M+H)). + ).

[0237] Reduction potential

[0238] The melting point (mp) is determined from the peak temperature of the DSC curve measured by TGA-DSC as described above or from a separate DSC measurement (Mettler Toledo DSC822e, sample heated from room temperature to complete melting at a heating rate of 10 K / min under a stream of pure nitrogen. A sample amount of 4 to 6 mg is placed in a 40 μL crimped Mettler-Toledo aluminum pan with lid, a <1 mm hole is punched into the lid).

[0239] Dipole moment, LUMO level, HOMO level

[0240] The glass transition temperature (Tg) is measured in a Mettler Toledo DSC 822e differential scanning calorimeter under nitrogen and at a heating rate of 10 K per minute as described in DIN EN ISO 11357, March 2010.

[0241] General procedure for the fabrication of OLEDs

[0242] The reduction potential is determined by cyclic voltammetry with a potentiostat device Metrohm PGSTAT30 and software Metrohm Autolab GPES at room temperature. The redox potential for a particular compound is measured in an anhydrous 0.1 M THF solution of the measured substance degassed with argon, under an argon atmosphere, between platinum working electrodes with a 0.1 M tetrabutylammonium hexafluorophosphate supporting electrolyte and using an Ag / AgCl pseudo-standard electrode consisting of a silver wire covered with silver chloride and directly immersed in the measured solution (Metrohm silver rod electrode), at a scan rate of 100 mV / s. The first run is performed in the widest potential range set on the working electrode, then the range is adjusted appropriately in the subsequent runs. The last three runs are performed with the addition of ferrocene (concentration 0.1 M) as a standard. The average of the potentials corresponding to the cathodic and anodic peaks of the studied compound, after subtracting the cathodic and anodic potentials of the Fc + After the average of the cathodic and anodic potentials observed with respect to the Fc

[0243] Summary of compounds used (non-inventive and non-comparative)

[0244] The dipole moment of a molecule containing N atoms is given by:

[0245]

[0246] where q i and is the local charge and position of atom i in the molecule.

[0247] The dipole moment was determined by a semi-empirical molecular orbital method.

[0248] The geometry of the molecular structure was optimized using the hybrid functional B3LYP with the 6-31G* basis set implemented in the program package TURBOMOLE V6.5. If more than one conformation was feasible, the conformation with the lowest total energy was chosen to determine the bond lengths of the molecule.

[0249] The DFT calculations were also performed using the program package TURBOMOLE V6.5 and used in combination with the optimized molecular geometry to determine the HOMO and LUMO energy levels of the molecular structure using the hybrid functional B3LYP with the 6-31G* basis set. If more than one conformation was feasible, the conformation with the lowest total energy was chosen.

[0250] Supplier: TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany

[0251] Technical effects of the invention

[0252] For the top-emitting OLED devices, embodiments and comparative examples of the present invention, a glass substrate was cut to a size of 50 mm x 50 mm x 0.7 mm, first cleaned ultrasonically with isopropanol for 5 minutes, then cleaned ultrasonically with pure water for 5 minutes, and then cleaned with ultraviolet ozone for 30 minutes to prepare a first electrode. A 10 nm thick layer of 4,4'-bis(N-(naphthalen-1-yl)-N-phenyl-amino) biphenyl (CAS 1198399-61-9) was vacuum deposited onto the first electrode to form a hole injection layer (HIL). -5 to 10 -7 A 100 nm thick layer of Ag was deposited as an anode at a pressure of 10

[0253] Then, 92 vol% of biphen-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine (CAS 1242056-42-3) and 8 vol% of 2,2',2"-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile) were vacuum deposited onto the ITO electrode to form a HIL with a thickness of 10 nm. Then, biphen-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine was vacuum deposited onto the HIL to form a HTL with a thickness of 118 nm.

[0254] Then, N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1 ':4',1 "-terphenyl]-4-amine (CAS 1198399-61-9) was vacuum deposited onto the HTL to form an electron blocking layer (EBL) with a thickness of 5 nm.

[0255] Then, a light-emitting layer was deposited. On the EBL, 97 vol% of H09 (blue fluorescent host material, Sun Fine Chemicals) was deposited as EML host, and 3 vol% of BD200 (Sun Fine Chemicals) as blue fluorescent dopant, forming a blue-emitting EML with a thickness of 20 nm on the EBL.

[0256] Then, on the light-emitting layer, 2,4-diphenyl-6-(4',5',6'-triphenyl-[1,1':2',1 ":3",1 ":3",1 ":3"-penta phenyl]-3"-yl)-1,3,5-triazine (CAS 2032364-64-8) was deposited with a thickness of 5 nm. Then, for Example 2, according to Table 4, the compound of Formula 1 was co-deposited with lithium quinolate (LiQ) in a weight % ratio of 1 :1 on the light-emitting layer to form an electron transport layer with a thickness of 31 nm. For Comparative Example 2, according to Table 4, Comparative Compound-1 was co-deposited with lithium quinolate (LiQ) in a weight % ratio of 1 :1 on the light-emitting layer to form an electron transport layer with a thickness of 31 nm.

[0257] Then, for both top-emitting OLED devices of configuration A and B, an electron injection layer was formed on the electron transport layer by deposition of Yb with a thickness of 2 nm.

[0258] At 10 -7 millibar, Ag was evaporated at a rate of 0.01 to 11 nm to form a cathode with a thickness of 11 nm.

[0259] On the cathode, a capping layer of diphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9- phenyl-9H-carbazol-3-yl)phenyl]amine was formed with a thickness of 75 nm.

[0260] Material properties

[0261]

[0262] By using a glass slide encapsulation of the device, the OLED stack was protected from environmental conditions. Thereby, a chamber was formed, containing a getter material for further protection.

[0263] To evaluate the performance of the embodiments of the present application compared to the prior art, the current efficiency was measured at 20 °C. The current-voltage characteristics were determined by providing a voltage in V and measuring the current in mA flowing through the device under test using a Keithley 2635 source measurement unit. The voltage applied to the device was varied in steps of 0.1 V in the range from 0 V to 10 V. Likewise, the luminance-voltage characteristics and the CIE coordinates were determined by measuring the luminance in cd / m2 using an Instrument Systems CAS-140CT array spectrometer, which was calibrated by Deutsche Akkreditierungsstelle (DAkkS) for each voltage value. The cd / A efficiency at 10 mA / cm2 was determined by interpolating the luminance-voltage and current-voltage characteristics, respectively. 2 The current-voltage characteristics were determined by providing a voltage in V and measuring the current in mA flowing through the device under test using a Keithley 2635 source measurement unit. The voltage applied to the device was varied in steps of 0.1 V in the range from 0 V to 10 V. Likewise, the luminance-voltage characteristics and the CIE coordinates were determined by measuring the luminance in cd / m2 using an Instrument Systems CAS-140CT array spectrometer, which was calibrated by Deutsche Akkreditierungsstelle (DAkkS) for each voltage value. The cd / A efficiency at 10 mA / cm 2 The current-voltage characteristics were determined by providing a voltage in V and measuring the current in mA flowing through the device under test using a Keithley 2635 source measurement unit. The voltage applied to the device was varied in steps of 0.1 V in the range from 0 V to 10 V. Likewise, the luminance-voltage characteristics and the CIE coordinates were determined by measuring the luminance in cd / m2 using an Instrument Systems CAS-140CT array spectrometer, which was calibrated by Deutsche Akkreditierungsstelle (DAkkS) for each voltage value. The cd / A efficiency at 10 mA / cm

[0264] In top-emitting devices, the light emission is a forward non-Lambertian emission and is also highly dependent on the microcavity. Therefore, the external quantum efficiency (EQE) and the power efficiency (in lm / W) will be higher compared to bottom-emitting devices.

[0265] Top-emitting device

[0266] Compound name

[0267] The Tg values are in a range suitable for use in organic electronic devices. Higher Tg values of materials used in organic electronic devices are generally preferred for the durability and robustness of the devices. The Tg of compounds A-1 and A-5 (Table 2) are significantly increased compared to the Tg of comparative compound-1 (Table 1).

[0268] Table 3 shows the HOMO and LUMO energy levels and the dipole moment of compound A-1 and compound A-5 of formula 1 and comparative compound-1. The values are in a range suitable for use as hole blocking material or electron transport material in organic electronic devices.

[0269] HOMO (eV)*

[0270] Surprisingly, the lifetime of top-emitting OLED devices is increased when using compound A-1 of formula 1 mixed with additive LiQ (instead of comparative compound-1) as electron transport layer. At the same time, the operating voltage of top-emitting OLED devices is improved when using compound A-5 instead of comparative compound-1 in the electron transport layer; or the level of operating voltage is comparable when using compound A-1 of formula 1 as electron transport host material mixed 1 : 1 with LiQ.

[0271] Table 4 shows the operating voltage and lifetime (97% value) of top-emitting OLED devices comprising an electron transport layer with a 1 :1 wt% mixture of a compound of Formula 1 and LiQ.

[0272] In summary, an improvement in the performance of top-emitting OLED devices was achieved by using a compound of Formula 1.

[0273] Experimental data (overview)

[0274] Table 1 : Properties of comparative compounds

[0275]

[0276] Table 2: Properties of compounds of Formula 1

[0277]

[0278] Table 3: Energy levels and dipole moments of comparative compounds and compounds of Formula 1

[0279] LUMO (eV)* Dipole moment (Debye)* Comparative compound 1 Compound A-1 Compound A-5 -5.80 -1.85 0.51 ​ -5.42 -2.02 1.27 ​ -5.30 -1.91 0.60

[0280] * Values calculated with B3LYP_Gaussian / 6-31G*, gas phase

[0281] Table 4: Operating voltage of top-emitting organic electroluminescent devices comprising a 1 :1 wt% mixture of a compound of Formula 1 and LiQ in an electron transport layer with a layer thickness of 31 nm.

[0282]

Claims

1. An organic electronic device comprising at least one layer selected from an electron transport layer, an electron injection layer, or an electron generation layer between an anode and a cathode, said layer comprising a compound of formula (I): in In equation (I) above, the position marked with "*" is not related to -(A). a All positions connected to the -L portion can be combined with hydrogen or substituents selected from: deuterium, fluorine, RF, C1-C. 20 Straight-chain alkyl, C3-C 20 Branched alkyl, C1-C 12 Straight-chain fluorinated alkyl groups, CN, RCN, C6-C 20 Aryl, C2-C 20 Heteroaryl, (P=O)R2; wherein each R is independently selected from C1-C 20 Straight-chain alkyl, C1-C 20 Alkoxy, C1-C 20 Thioalkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C3-C 20 Branched alkoxy groups, C3-C 20 Cyclic alkoxy groups, C3-C 20 Branched thioalkyl, C3-C 20 Cyclic thioalkyl, C6-C 20 Aryl and C2-C 20 Mixed aromatics; A is selected from substituted or unsubstituted C6-C. 24 Aryl or substituted or unsubstituted C2-C 20 Heteroaryl groups, wherein when group A is substituted, the corresponding substituents are independently selected from deuterium, fluorine, C1-C... 20 Straight-chain alkyl, C3-C 20 Branched alkyl groups, straight-chain fluorinated C1-C 12 Alkyl, CN, C6-C 20 Aryl, C2-C 20 Mixed aromatics; L is selected from substituted or unsubstituted C2-C. 42 heteroaryl, substituted or unsubstituted C6-C 24 Aryl, or selected from The groups, wherein, When L is substituted, the corresponding substituents are selected from: deuterium, fluorine, C1-C. 20 Straight-chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C1-C 20 Straight-chain alkoxy groups, C3-C 20 Branched alkoxy groups, straight-chain fluorinated C1-C 12 Alkyl, straight-chain fluorinated C1-C 12 Alkoxy, C3-C 12 Branched fluorinated cyclic alkyl groups, C3-C 12 Fluorinated cyclic alkyl groups, C3-C 12 Fluorinated cyclic alkoxy groups, CN, RCN, C6-C 20 Aryl, C2-C 20 Heteroaryl, OR, SR, (C=O)R, (C=O)NR2, SiR3, (S=O)R, (S=O)2R, (P=O)R2; wherein each R is independently selected from C1-C 20 Straight-chain alkyl, C1-C 20 Alkoxy, C1-C 20 Thioalkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C3-C 20 Branched alkoxy groups, C3-C 20 Cyclic alkoxy groups, C3-C 20 Branched thioalkyl, C3-C 20 Cyclic thioalkyl, C6-C 20 Aryl and C2-C 20 heteroaryl; and "a" is an integer from 0 to 2.

2. The organic electronic device according to claim 1, wherein A is unsubstituted.

3. The organic electronic device according to claim 1, wherein, When L is substituted, the corresponding substituent is independently selected from phenyl, naphthyl, pyridyl, biphenyl, dibenzofuranyl, dibenzothiophenyl, and carbazoyl.

4. The organic electronic device according to claim 1, wherein L is C2-C 42 In the case of heteroaryl groups, the C2-C 42 The heteroaryl group is selected from triazine, pyrimidine, benzo[a]acryl, dibenzo[a]acryl, pyridine, bipyridine, benzimidazole, phenanthrene, benzonitrile, phenanthridine, benzo[a] Azole, benzothiazole, phenanthridine, naphtho-benzofuran, dinaphthofuran, benzo-naphtho-thiophene, dinaphthothiophene.

5. The organic electronic device according to claim 1, wherein L is C6-C 24 In the case of aryl, the C6-C 24 The aryl group is selected from anthracene, phenanthrene, pyrene, fluoranthene, and biphenylene.

6. The organic electronic device according to claim 1, wherein when L is substituted, the substituent is independently selected from:

7. The organic electronic device according to claim 1, wherein the layer comprising the compound of formula (I) is composed of at least one compound of formula (I).

8. The organic electronic device according to claim 1, wherein the layer comprising the compound of formula (I) further comprises a metal, a metal salt, or an organometallic complex.

9. The organic electronic device according to claim 1, further comprising a light-emitting layer, wherein the layer comprising the compound of formula (I) is disposed between the light-emitting layer and the cathode.

10. The organic electronic device according to claim 1, wherein, The device further includes an electron transport layer, and the layer containing the compound of formula (I) is disposed between the electron transport layer and the cathode.

11. A compound of general formula (I), in In equation (I) above, the position marked with "*" is not related to -(A). a All positions connected to the -L portion can be combined with hydrogen or substituents selected from: deuterium, fluorine, RF, C1-C. 20 Straight-chain alkyl, C3-C 20 Branched alkyl, C1-C 12 Straight-chain fluorinated alkyl groups, CN, RCN, C6-C 20 Aryl, C2-C 20 Heteroaryl, (P=O)R2; wherein each R is independently selected from C1-C 20 Straight-chain alkyl, C1-C 20 Alkoxy, C1-C 20 Thioalkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C3-C 20 Branched alkoxy groups, C3-C 20 Cyclic alkoxy groups, C3-C 20 Branched thioalkyl, C3-C 20 Cyclic thioalkyl, C6-C 20 Aryl and C2-C 20 Mixed aromatics; A is selected from substituted or unsubstituted C6-C. 24 Aryl or substituted or unsubstituted C2-C 20 Heteroaryl groups, wherein when group A is substituted, the corresponding substituents are independently selected from deuterium, fluorine, C1-C... 20 Straight-chain alkyl, C3-C 20 Branched alkyl groups, straight-chain fluorinated C1-C 12 Alkyl, CN, C6-C 20 Aryl, C2-C 20 Mixed aromatics; L is selected from substituted or unsubstituted C2-C. 42 heteroaryl, substituted or unsubstituted C6-C 24 Aryl, or selected from The groups, wherein, When L is substituted, the corresponding substituents are selected from: deuterium, fluorine, C1-C. 20 Straight-chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C1-C 20 Straight-chain alkoxy groups, C3-C 20 Branched alkoxy groups, straight-chain fluorinated C1-C 12 Alkyl, straight-chain fluorinated C1-C 12 Alkoxy, C3-C 12 Branched fluorinated cyclic alkyl groups, C3-C 12 Fluorinated cyclic alkyl groups, C3-C 12 Fluorinated cyclic alkoxy groups, CN, RCN, C6-C 20 Aryl, C2-C 20 Heteroaryl, OR, SR, (C=O)R, (C=O)NR2, SiR3, (S=O)R, (S=O)2R, (P=O)R2; wherein each R is independently selected from C1-C 20 Straight-chain alkyl, C1-C 20 Alkoxy, C1-C 20 Thioalkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C3-C 20 Branched alkoxy groups, C3-C 20 Cyclic alkoxy groups, C3-C 20 Branched thioalkyl, C3-C 20 Cyclic thioalkyl, C6-C 20 Aryl and C2-C 20 heteroaryl; and "a" is an integer between 0 and 2. a) Where "a" is 0, L is selected from C2 to C 42 Heteroaryl groups, and formula (I) contains only one part - (A). a -L; where L is a nitrogen-containing heteroaryl group, the C2-C 42 The heteroaryl group is selected from triazine, benzo[a]acryl, dibenzo[a]acryl, bipyridine, benzimidazole, phenanthrene, phenanthridine, benzothiazole, and phenanthridine ketone; b) Where "a" is 1 (i) If A is aryl and L is N-containing heteroaryl, then the N-containing heteroaryl is a substituted or unsubstituted triazine, pyrimidine, benzo[a]acryl, dibenzo[a]acryl, pyridine, bipyridine, phenanthrene, phenanthrene, or phenanthrene ketone; (ii) If A is a heteroaryl group and L is an aryl group, then A is selected from triazine, pyrimidine, benzo[a]acrylidine, dibenzo[a]acrylidine, pyridine, bipyridine, benzimidazole, phenanthrene, benzonitrile, phenanthridine, benzo[a] azole, benzothiazole, phenanthridine, naphtho-benzofuran, dinaphthofuran, benzo-naphtho-thiophene, dinaphthothiophene; (iii) If A is a heteroaryl group and L is a heteroaryl group, then A is selected from triazine, pyrimidine, benzo[a]acrylidine, dibenzo[a]acrylidine, bipyridine, benzimidazole, phenanthrene, benzonitrile, phenanthridine, benzo[a]acrylidine, etc. azoles, benzothiazoles, phenanthridine, naphtho-benzofuran, dinaphthofuran, benzo-naphtho-thiophene, and dinaphthothiophene; c) Where "a" is 2, and both A and L are aryl groups, A directly connected to group L is an anthracene group; where A is a sulfur-containing heteroaryl group, the heteroaryl group is selected from benzo-naphtho-thiophene, dinaphthothiophene, and benzothiazole.

12. An organic semiconductor layer comprising the compound according to claim 11.

13. A display device comprising an organic electronic device according to any one of claims 1 to 10.

14. A lighting device comprising an organic electronic device according to any one of claims 1 to 10.

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