Compound, organic electronic device comprising the same, and display device and lighting device comprising the same
11539001 · 2022-12-27
Assignee
Inventors
- Steffen Runge (Dresden, DE)
- Benjamin Schulze (Dresden, DE)
- Omrane Fadhel (Dresden, DE)
- Gregor Schwartz (Dresden, DE)
- Volodymyr Senkovskyy (Dresden, DE)
- Chao Wu (Dresden, DE)
Cpc classification
H10K2101/30
ELECTRICITY
H10K85/6572
ELECTRICITY
C07D401/10
CHEMISTRY; METALLURGY
H10K85/636
ELECTRICITY
C07D401/04
CHEMISTRY; METALLURGY
International classification
C07D401/10
CHEMISTRY; METALLURGY
Abstract
The present invention relates to compounds that include a nitrogen heteroatom, including a compound of the formula (I). Also provided herein is an organic electronic device comprising the compound and a display device or lighting device comprising the organic electronic device.
Claims
1. Compound of the Formula (I) ##STR00034## wherein all of R.sup.1 to R.sup.11, except one, are independently selected from the group consisting of H, D, F, substituted or unsubstituted C.sub.1 to C.sub.18 alkyl, substituted or unsubstituted C.sub.6 to C.sub.42 aryl, substituted or unsubstituted C.sub.3 to C.sub.42 heteroaryl; and adjacent groups R.sup.1 to R.sup.11 may be linked to each other to form a fused ring, wherein the one of R.sup.1 to R.sup.11 not selected from the above groups is a group G, wherein the group G comprises one atom A having an electron pair in a p-orbital thereof; the group G comprises two 6-membered aryl rings which are attached to the atom A, wherein each of the two 6-membered aryl rings is attached to the atom A via a single bond respectively; and wherein the two 6-membered aryl rings attached to the atom A may be connected with each other via a single bond; the group G comprises 12 to 66 carbon atoms in total; the group G is attached to the benzoacridine part of the compound of formula (I) via a single bond or via a C.sub.6 to C.sub.18 arylene group, wherein the C.sub.6 to C.sub.18 arylene group is part of the group G; and the group G is unsubstituted or substituted with one or more substituents independently selected from the group consisting of D, F, C.sub.1 to C.sub.18 alkyl, C.sub.6 to C.sub.42 aryl, C.sub.6 to C.sub.42 heteroaryl, (R.sup.12).sub.2P═O, CN or G′, wherein the group G′ is defined likewise group G with the exception that the group G′ is not attached to the benzoacridine part of the compound of formula (I) but to the group G via a single bond or via a C.sub.6 to C.sub.18 arylene group, wherein the C.sub.6 to C.sub.18 arylene group is part of the group G′ provided that in case that the group G is attached to the benzoacridine part of the compound of formula (I) via the C.sub.6 to C.sub.18 arylene group, substituents which may be attached to the C.sub.6 to C.sub.18 arylene group are only selected from the group consisting of C.sub.1 to C.sub.18 alkyl, C.sub.6 to C.sub.42 aryl, (R.sup.12).sub.2P═O and CN; wherein in case that at least one of R.sup.1 to R.sup.11, which is not the group G, is substituted, the respective substituent or substituents are independently selected from the group consisting of D, F, C.sub.1 to C.sub.18 alkyl, C.sub.6 to C.sub.36 aryl, C.sub.6 to C.sub.42 heteroaryl, (R.sup.12).sub.2P═O, CN; and wherein R.sup.12 are independently selected from the group consisting of C.sub.1 to C.sub.18 alkyl and C.sub.6 to C.sub.24 aryl; wherein the group G comprises the following structural element ##STR00035## wherein the group G is attached to the benzoacridine part of the compound of Formula (I) at the position indicated by “#”, wherein the two 6-membered aryl rings may be linked with each other via a single bond.
2. Compound according to claim 1, wherein the group G comprises 1 to 5 heteroatoms selected from the group consisting of N, S and O.
3. Compound according to claim 1, wherein the atom A is.
4. Compound according to claim 1, wherein the total number of aromatic rings comprised in the compound of Formula (I) is from 6 to 21.
5. Compound according to claim 1, wherein R.sup.1 and R.sup.2; or R.sup.2 and R.sup.3; or R.sup.3 and R.sup.4; are linked to form an aryl ring structure.
6. Compound according to claim 1, wherein R.sup.5 or R.sup.10 is the group G.
7. Organic electronic device comprising an organic semiconducting layer, wherein the organic semiconducting layer comprises the compound of the Formula (I) according to claim 1.
8. Organic electronic device according to claim 7 further comprising a first electrode and a second electrode, wherein the organic semiconducting layer is arranged between the first electrode and the second electrode.
9. Organic electronic device according to claim 7, wherein the organic semiconducting layer is an emission layer.
10. Organic electronic device according to claim 7, wherein the organic semiconducting layer is a hole blocking layer.
11. Organic electronic device according to claim 7, wherein the organic semiconducting layer is an electron transport layer.
12. Organic electronic device according to claim 7, wherein the organic semiconducting layer further comprises at least one second compound which is not a compound of formula (I).
13. Display device comprising the organic electronic device according to claim 7.
14. Lighting device comprising the organic electronic device according to claim 7.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) These and/or other aspects and advantages of the present invention will become apparent and more readily appreciated from the following description of the exemplary embodiments, taken in conjunction with the accompanying drawings, of which:
(2)
(3)
(4)
DETAILED DESCRIPTION
(5) Reference will now be made in detail to the exemplary embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the like elements throughout. The exemplary embodiments are described below, in order to explain the aspects of the present invention, by referring to the figures.
(6) Herein, when a first element is referred to as being formed or disposed “on” or “onto” a second element, the first element can be disposed directly on the second element, or one or more other elements may be disposed there between. When a first element is to referred to as being formed or disposed “directly on” or “directly onto” a second element, no other elements are disposed there between.
(7)
(8) Instead of a single electron transport layer 160, optionally an electron transport layer stack (ETL) can be used.
(9)
(10) Referring to
(11) Preferably, the organic semiconducting layer comprising a compound of Formula (I) or consisting of a compound of Formula (I) may be an EML, an HBL or an ETL.
(12)
(13) Referring to
(14) Preferably, the organic semiconducting layer comprising a compound of Formula (I) or consisting of a compound of Formula (I) may be the first EML, first HBL, first ETL, n-type CGL and/or second EML, second HBL, second ETL.
(15) While not shown in
(16) Hereinafter, one or more exemplary embodiments of the present invention will be described in detail with, reference to the following examples. However, these examples are not intended to limit the purpose and scope of the one or more exemplary embodiments of the present invention.
Experimental Part
(17) The invention is furthermore illustrated by the following examples which are illustrative only and non-binding.
(18) Synthesis of Compounds of Formula (I)
(19) ##STR00017##
9-(3-(dibenzo[c,h]acridin-7-yl)phenyl)-9H-carbazole-3-carbonitrile (Compound 5)
(20) ##STR00018##
(21) A flask was flushed with nitrogen and charged with 7-chlorodibenzo[c,h]acridine (12 g, 38.4 mmol), 9-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole-3-carbonitrile (15.9 g, 40 mmol), Pd(PPh.sub.3).sub.4 (1.3 g, 1.15 mmol), and K.sub.2CO.sub.3 (15.9 g, 115 mmol). A mixture of deaerated 1,4-dioxane/water (3:1, 240 mL) was added and the reaction mixture was heated to 95° C. under a nitrogen atmosphere for 16 h. After cooling down to room temperature, the formed precipitate was collected by suction filtration and washed with 1,4-dioxane, water and methanol. The obtained solid was dissolved in hot dichloromethane and filtered through a pad of silica gel. After rinsing with additional hot dichloromethane, the filtrate was concentrated under reduced pressure and n-hexane was added. The obtained precipitate was collected by suction filtration and washed with n-hexane. After drying, 19.2 g (91%) of a pale yellow solid were obtained. HPLC/ESI-MS: 100%, m/z=546 ([M+H].sup.+).
(22) ##STR00019##
7-(4-(3,6-diphenyl-9H-carbazol-9-yl)phenyl)dibenzo[c,h]acridine (Compound 4)
(23) ##STR00020##
(24) A flask was flushed with nitrogen and charged with tris(dibenzylidenacetone)dipalladium(0) (211 mg, 0.23 mmol), tri-tert-butylphosphine (186 mg, 0.92 mmol) and deaerated o-xylene (30 mL). After stirring for 30 min under a nitrogen atmosphere at ambient temperature, 7-(4-bromophenyl)dibenzo[c,h]acridine (10 g, 23 mmol), 3,6-diphenyl-9H-carbazole (8.8 g, 27.6 mmol), K.sub.2CO.sub.3 (9.5 g, 69 mmol), 18-crown-6 (1.2 g, 0.46 mmol), and additional deaerated o-xylene (200 mL) were added. The resulting reaction mixture was heated to reflux under a nitrogen atmosphere for 48 h. After cooling down to 10° C., the formed precipitate was collected by suction filtration and washed with n-hexane. The obtained solid was dissolved in chloroform and extracted with water five times. After drying over MgSO.sub.4, the organic phase was filtered, concentrated under reduced pressure and n-hexane was added. The obtained precipitate was collected by suction filtration and washed with n-hexane. Further purification was achieved by recrystallization from toluene. After drying, 11.7 g (76%) of a pale yellow solid were obtained. Final purification was achieved by sublimation. HPLC/ESI-MS: 99.6%, m/z=673 ([M+H].sup.+).
(25) ##STR00021##
7-(9′-phenyl-9H,9′H-[3,3′-bicarbazol]-9-yl)dibenzo[c,h]acridine (Compound 6)
(26) ##STR00022##
(27) A flask was flushed with nitrogen and charged with sodium hydride (616 mg, 25.7 mmol) and anhydrous dimethylformamide (135 mL). The suspension was stirred at 0° C. for 30 minutes. Then 9-phenyl-9H,9′H-3,3′-bicarbazole (10.0 g, 24.5 mmol) was added portionwise and the reaction mixture was stirred at room temperature for 90 minutes. 7-chlorodibenzo[c,h]acridine (8.5 g, 26.9 mmol) was added and the reaction mixture was stirred at 110° C. for 4 hours. The reaction was quenched with methanol (100 mL) and the precipitate formed was filtered and washed with methanol. The obtained solid was dissolved in chloroform/toluene 1/1 (500 mL) and filtered through a pad of silica gel. After rinsing with additional chloroform/toluene 1/1, the filtrate was concentrated under reduced pressure and the suspension was stirred at room temperature overnight. The obtained precipitate was collected by suction filtration and washed with toluene. The crude solid was dissolved in hot THF, ethanol was slowly added and the suspension was stirred overnight at room temperature. The precipitate was collected by suction filtration and further purified by column chromatography (eluting with dichloromethane/hexane 1/3 to pure dichloromethane at the end). The solid was dissolved in hot THF, ethanol was slowly added and the suspension was stirred overnight at room temperature, then solid was filtered. After drying, 8.8 g (52%) of a solid were obtained. Final purification was achieved by sublimation. HPLC/ESI-MS: 100%, m/z=686 ([M+H].sup.+).
(28) ##STR00023##
N-(3-(dibenzo[c,h]acridin-7-yl)phenyl)-N-phenylnaphthalen-2-amine (Compound 7)
(29) ##STR00024##
(30) A flask was flushed with nitrogen and charged with 7-(3-bromophenyl)dibenzo[c,h]acridine (10.0 g, 23.0 mmol), N-phenylnaphthalen-2-amine (5.6 g, 25.33 mmol), KO.sup.tBu (7.75 g, 69.1 mmol), Bis(dibenzylidenaceton)palladium (278 mg, 0.46 mmol), tri-tert-butylphosphine (140 mg, 0.69 mmol) and deaerated toluene (230 mL). The resulting reaction mixture was heated to 80° C. under a nitrogen atmosphere for 5 hours. After cooling down to room temperature, the formed precipitate was collected by suction filtration and washed with toluene. The obtained solid was stirred in water for 30 minutes at room temperature, then it was filtered, washed with water and dried. Crude solid was dissolved in toluene and filtered through a pad of silica gel. After rinsing with additional toluene, the filtrate was concentrated under reduced pressure and the suspension was stirred at room temperature overnight. The obtained precipitate was collected by suction filtration and washed with n-hexane. Further purification was achieved by recrystallization from acetone. Finally, the solid was dissolved in hot toluene, n-hexane was slowly added and the suspension was stirred overnight at room temperature, then solid was filtered. After drying, 8.5 g (64%) of a solid were obtained. Final purification was achieved by sublimation. HPLC/ESI-MS: 100%, m/z=573 ([M+H].sup.+).
(31) Procedure for Fabrication of OLEDs
(32) For top emission OLED devices types A and B (top emission devices) a glass substrate with dimensions of 150 mm×150 mm×0.7 mm was ultrasonically cleaned with a 2% aquatic solution of Deconex FPD 211 for 7 minutes and then with pure water for 5 minutes, and dried for 15 minutes in a spin rinse dryer. Subsequently, 100 nm Ag were deposited as anode at a pressure of 10-5 to 10-7 mbar. For bottom emission OLED device, OLED device type C, a UV-Ozone cleaned ITO/glass substrate was used instead of a glass substrate.
(33) Then, HT-1 and D-1 were vacuum co-deposited at a wt % ratio of 92:8 on the anode to form a HIL. Then, HT-1 was vacuum deposited on the HIL, to form an HTL. Then, HT-2 was vacuum deposited on the HTL to form an electron blocking layer (EBL).
(34) Afterwards the emission layer was formed on the EBL by co-deposition of HOST-1 and EMITTER-1 in the wt % ratio of 97:3.
(35) Then, for top emission OLED devices type A, ET-1 was vacuum deposited onto the emission layer to form the hole blocking layer (HBL). Then, the electron transporting layer is formed on the hole blocking layer by co-deposition of the compounds of Formula (I), or the comparative compound-1, and lithium quinolate (LiQ) in a wt % ratio of 1:1.
(36) For top emission OLED devices type B, the compounds of Formula (I) were vacuum deposited onto the emission layer to form the hole blocking layer. Then, the electron transporting layer is formed on the hole blocking layer by co-deposition ET-2 and lithium quinolate (LiQ) in a wt % ratio of 1:1.
(37) Then, for both top emission OLED devices of type A and B the electron injection layer is formed on the electron transporting layer by deposing Yb.
(38) Ag is evaporated at a rate of 0.01 to 1 Å/s at 10-7 mbar to form a cathode.
(39) A cap layer of N-([1,1′-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine is formed on the cathode.
(40) For bottom emission OLED device, OLED device type C, HT-1 and D-1 were vacuum co-deposited at a wt % ratio of 97:3 on the ITO to form a HIL. Then, HT-1 was vacuum deposited on the HIL to form an HTL. Then, HT-3 was vacuum deposited on the HTL form an electron blocking layer (EBL).
(41) Afterwards the emission layer was deposited by co-deposition of HOST-2:compound of Formula (I):EMITTER-2 in a wt % ratio of 49:49:2 and the emission layer.
(42) Afterwards, ET-1 was vacuum deposited onto the emission layer to form the hole blocking layer. Then, the electron transporting layer is formed on the hole blocking layer by co-deposition ET-2 and lithium quinolate (LiQ) in a wt % ratio of 1:1.
(43) Then, the electron injection layer is formed on the electron transporting layer by depositing LiQ.
(44) Then, Ag is evaporated at a rate of 0.01 to 1 Å/s at 10-7 mbar to form a cathode.
Examples
(45) Table 1: Performance of an organic electroluminescent device comprising an a compound of formula 1 in the emission layer ETL, in the auxiliary ETL or in the EML.
(46) OLED devices of 3 types (A, B and C) were prepared in order to test the inventive compounds of Formula (I). The details of the layer stack in the OLED devices are given below. A slash “/” separates individual layers. Layer thicknesses are given in squared brackets [ . . . ], mixing ratios in wt % given in round brackets ( . . . ):
(47) OLED device type A: The compound of Formula (I) or the comparative compound is comprised in the electron transport layer. Layer stack: silver [100 nm]/HT-1:D-1 (92:8) [10 nm]/HT-1 [118 nm]/HT-2 [5 nm]/HOST-1:EMITTER-1 (97:3) [20 nm]/ET-1 [5 nm]/compound of Formula (I):LiQ or the comparative compound:LiQ (1:1) [31 nm]/Yb [2 nm]/silver [11 nm]
(48) OLED device type B: The compound of Formula (I) is comprised in the hole blocking layer. Layer stack: silver [100 nm]/HT-1:D-1 (92:8) [10 nm]/HT-1 [125 nm]/HT-2 [5 nm]/HOST-1:EMITTER-1 (97:3) [20 nm]/compound of Formula (I) [5 nm]/ET-2:LiQ (1:1) [31 nm]/Yb [2 nm]/silver [11 nm]
(49) OLED device type C: The compound of Formula (I) is comprised in the emission layer. Layer stack: ITO/HT-1:D-1 (97:3) [10 nm]/HT-1 [144 nm]/HT-3 [70 nm]/HOST-2:compound of Formula (I):EMITTER-2 (49:49:2) [40 nm]/ET-1 [5 nm]/ET-2:LiQ (1:1) [31 nm]/LiQ [2 nm]/silver [100 nm]
(50) Technical Effect of the Invention
(51) In Table 1 below, material properties of compounds of Formula (I) and the comparative compounds are shown.
(52) In Table 2 below, dipole moment, HOMO energy level and LUMO energy level and the energy gap LUMO—HOMO of compounds of Formula (I) are shown. Compounds of Formula (I) have an energy gap LUMO—HOMO which is lower than 3.89 eV.
(53) In Table 3 below operating voltage and lifetime LT97 at 30 mA/cm2 (h) are shown of an OLED comprising a compound of Formula (I).
(54) It is evident from Table 3, that the operating lifetime LT97 at 30 mA/cm2 (h) is improved for all examples 1 to 9 compared to comparative examples by at least 28% or more. Without being bound by theory, the improvement in LT may be due to reduced degradation of the compound of Formula (I) during fabrication of the OLED.
(55) List of Compounds Used
(56) TABLE-US-00001 IUPAC name Reference HT-1 Biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4- US2016322581 (9-phenyl-9H-carbazol-3-yl)phenyl]-amine (CAS 1242056-42-3) HT-2 N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)- JP2014096418 [1,1′:4′,1″-terphenyl]-4-amine (CAS 1198399-61-9) HT-3 N,N-di([1,1′-biphenyl]-4-yl)-7,7-dimethyl-7H- US2015280136 fluoreno[4,3-b]benzofuran-10-amine (CAS 1616706-52-5) D-1 4,4′,4″-((1E,1′E,1″E)-cyclopropane-1,2,3- US2008265216 triylidenetris(cyanomethanylylidene))tris(2,3,5,6- tetrafluorobenzonitrile) HOST-1 H09 (Fluorescent-blue host material) Commercially available from Sun Fine Chemicals, Inc, S. Korea HOST-2 5,8-di([1,1′-biphenyl]-4-yl)-5,8- dihydroindolo[2,3-c]carbazole (CAS 222044-79- 3) EMITTER-1 BD200 (Fluorescent-blue emitter material) Commercially available from Sun Fine Chemicals, Inc, S. Korea EMITTER-2 Bis(2-(3,5- dimethylphenyl)quinolinato)(acetylaceton- ate)iridium(III) (CAS 1056874-46-4) ET-1 2,4-diphenyl-6-(4′,5′,6′-triphenyl- WO2O16171358 [1,1′:2′,1″:3″,1″′:3″′,1″″-quinquephenyl]-3″″-yl)- 1,3,5-triazine (CAS 2032364-64-8) ET-2 2-([1,1′-biphenyl]-4-yl)-4-(9,9-diphenyl-9H- KR101537500 fluoren-4-yl)-6-phenyl-1,3,5-triazine (CAS 1801992-44-8) LiQ 8-Hydroxyquinolinolato-lithium (CAS 850918- WO2013079217 68-2)
(57) TABLE-US-00002 TABLE 1 Properties of compounds of Formula (I) and comparative compounds. mp Tg T.sub.RO Structure (° C.) (° C.) (° C.) Comparative-1 reference: EP3312899 A1
(58) TABLE-US-00003 TABLE 2 Dipole moment, HOMO and LUMO energy levels, Energy gap LUMO − HOMO of compounds of Formula (I) and comparative compounds, simulated by DFT (B3LYP_Gaussian/6-31G*, gas phase) Energy gap Dipole moment HOMO LUMO LUMO − HOMO [Debye] [eV] [eV] [eV] Comparative-1 1.89 −5.63 −1.74 3.89 Comparative-2 2.59 −5.67 −1.78 3.89 Compound 1 0.05 −5.43 −1.84 3.59 Compound 2 1.40 −5.42 −1.83 3.59 Compound 3 1.63 −5.26 −1.84 3.42 Compound 4 0.40 −5.28 −1.86 3.42 Compound 5 6.88 −5.84 −1.97 3.87 Compound 6 1.30 −5.04 −1.99 3.05 Compound 7 2.08 −5.05 −1.71 3.34
(59) TABLE-US-00004 TABLE 3 OLED devices comprising compounds of fomula 1 and comparative compounds. Ratio of Compounds in compounds in Operating OLED device OLED layer comprising layer comprising voltage at LT97 at 30 example device a compound of compound of 10 mA/cm.sup.2 mA/cm.sup.2 name type Formula (I) Formula (I) (V) (h) Comparative A Comparative-1:LiQ 1:1 3.51 32 example 1 Comparative A Comparative-2:LiQ 1:1 3.61 30 example 2 Example-1 A Compound 1:LiQ 1:1 3.47 41 Example-2 A Compound 2:LiQ 1:1 3.62 43 Example-3 A Compound 3:LiQ 1:1 3.71 49 Example-4 A Compound 4:LiQ 1:1 3.66 50 Example-5 A Compound 5:LiQ 1:1 3.98 101 Example-6 A Compound 6:LiQ 1:1 3.48 42 Example-7 B Compound 3 1 3.69 73 Example-8 B Compound 4 1 3.72 97 Example-9 C Compound 6:HOST- 49:49:2 3.69 63 2:EMITTER-2
(60) The features disclosed in the foregoing description and in the dependent claims may, both separately and in any combination thereof, be material for realizing the aspects of the disclosure made in the independent claims, in diverse forms thereof.