CN113292488B - Cyano-containing aza-benzene compound, application thereof and organic electroluminescent device containing compound - Google Patents

Cyano-containing aza-benzene compound, application thereof and organic electroluminescent device containing compound Download PDF

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CN113292488B
CN113292488B CN202110395678.4A CN202110395678A CN113292488B CN 113292488 B CN113292488 B CN 113292488B CN 202110395678 A CN202110395678 A CN 202110395678A CN 113292488 B CN113292488 B CN 113292488B
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organic electroluminescent
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CN113292488A (en
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王彦杰
朱运会
张其胜
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Zhejiang Hongwu Technology Co ltd
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Abstract

The invention discloses a cyano-group aza-benzene compound, application thereof and organic electroluminescence containing the compoundA light-emitting device, the cyanoazabenzenes have the structure of formula (1) wherein X 1 ～X 5 Each independently represents C or N; and X 1 ～X 5 1-3 are selected to be N; cyano radicals being only in X 1 ～X 5 Substituted by carbon atoms, and cyano radicals at X 1 ～X 5 The number of (A) is 1 to 3 integers; meanwhile, the sum of the number of nitrogen atoms and the number of cyano groups is less than or equal to 5; the formula (2) represents an Ar structure. The compound provided by the invention is used as a main body material, an electron transport material, a hole blocking material or an electron injection material of an organic electroluminescent device, and has asymmetric structure, so that the energy levels of HOMO and LUMO can be easily adjusted, other layer materials can be effectively matched, and the asymmetric energy level distribution can avoid energy loss caused by molecular accumulation, thereby improving the efficiency of the device.
Figure DDA0003018510460000011

Description

Cyano-containing aza-benzene compound, application thereof and organic electroluminescent device containing compound
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to a novel organic compound, application thereof and an organic electroluminescent device containing the compound.
Background
An Organic Light Emitting Device (OLED) is a current-driven thin film device with a sandwich-like structure, and a single layer or multiple layers of Organic functional material are sandwiched between an anode and a cathode. Under the action of an electric field, holes generated by an anode and electrons generated by a cathode move to be respectively injected into a hole transport layer and an electron transport layer and migrate to a light emitting layer, and when the holes and the electrons meet and are combined at the light emitting layer, energy excitons are generated, so that light emitting molecules are excited to finally generate visible light. The OLED has the characteristics of self-luminescence, wide visual angle, wide color gamut, short response time, high luminous efficiency, low working voltage, low cost, simple production process and the like, can be manufactured into a large-size and/or flexible ultrathin panel, is a novel display technology with rapid development and higher process integration level, is widely applied to display products such as televisions, smart phones, tablet computers, vehicle-mounted display, illumination and the like at present, and is further applied to creative display products such as large-size display, flexible screens and the like.
The organic photoelectric material applied to the OLED device can be divided into a light emitting layer material and an auxiliary functional layer material in terms of application, wherein the light emitting layer material includes a guest material (also called a light emitting material or a doping material) and a host material (also called a host material), the light emitting material is divided into a fluorescent material, a phosphorescent material and a thermal activation delayed fluorescent material according to different energy transfer modes, and the auxiliary functional layer material is divided into an electron injection material, an electron transport material, a hole blocking material, an electron blocking material, a hole transport material and a hole injection material according to the property of different electron or hole transport speeds.
The electron transport material generally has a proper HOMO/LUMO value, so that the driving voltage can be reduced due to a smaller electron injection barrier, and meanwhile, higher electron transport rate, higher glass transition temperature and higher thermal stability are required.
Therefore, there is a need in the art to develop a class of OLED functional materials that are low in cost and can produce an organic electroluminescent device with high efficiency, long lifetime, and high stability under low driving voltage.
Disclosure of Invention
In order to solve the technical problems, the invention provides a novel cyano-containing aza-benzene organic compound which has a structure shown in a formula (1):
Figure BDA0003018510440000021
wherein the content of the first and second substances,
X 1 ～X 5 each independently represents C or N; and X 1 ～X 5 Has 1 to 3 choices ofN；
Cyano radicals being only in X 1 ～X 5 Is substituted by a carbon atom, and cyano radicals being present at X 1 ～X 5 The number of (A) is 1 to 3 integers;
meanwhile, the sum of the number of nitrogen atoms and the number of cyano groups is less than or equal to 5;
preferably, when R in formula (1) 1 ～R 5 Independently selected as cyano and X 1 ～X 5 Independently selected as a nitrogen atom, specifically as shown below:
Figure BDA0003018510440000031
l in the formula (1) is independently selected from a single bond, a substituted or unsubstituted alkylene group with 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkylene group with 3 to 30 ring carbon atoms, a substituted or unsubstituted cycloalkylene oxy group with 2 to 30 ring carbon atoms, a substituted or unsubstituted arylene group with 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroarylene group with 2 to 30 ring carbon atoms, a substituted or unsubstituted fused aryl ring with 10 to 50 ring carbon atoms, and a substituted or unsubstituted fused heterocyclic ring with 6 to 50 ring carbon atoms;
preferably, L is independently selected from the group consisting of substituted or unsubstituted, but not limited to:
Figure BDA0003018510440000032
Figure BDA0003018510440000041
ar in the formula (1) has a structure shown in a formula (2):
Figure BDA0003018510440000042
in the formula (2), the reaction mixture is,
formula (2) is bonded to L of formula (1) by a-may be at X of formula (2) 6～ X 11 (iii) optionally substituted in position;
X 6 ～X 11 each independently represents C or N; and the number of N atoms is an integer of 0 to 3;
Y 1 ～Y 2 each independently represents a single bond, a hydrogen bond, or CR 12 R 13 、CR 14 CR 15 、SiR 16 R 17 、NR 18 、O、S；
Preferably, ar may be independently selected from the following substituted or unsubstituted groups, but is not limited to the following:
Figure BDA0003018510440000051
in the formulae (1) and (2), R 1 ～R 18 Each of the substituent groups is independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, a substituted amino group, a substituted silyl group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring carbon atoms;
adjacent R 1 ～R 18 The substituent groups can be bonded with each other to form a substituted or unsubstituted saturated or unsaturated ring, and can also form a substituted or unsubstituted saturated or unsaturated condensed ring with an adjacent aromatic ring or heteroaromatic ring;
preferably, R 1 ～R 18 The substituent groups are respectively and independently selected from any one or more of the following groups:
hydrogen atom, deuterium atom, halogen atom, cyano group, nitro group, substituted amine group, substituted silicon group, substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or unsubstituted n-propyl group, substituted or unsubstituted isopropyl group, or a substituted or unsubstituted alkyl groupSubstituted or unsubstituted n-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, or a pharmaceutically acceptable salt thereof substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted indenyl substituted or unsubstituted fluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted indenofluorenyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted perylenyl, substituted or unsubstituted fluorenyl
Figure BDA0003018510440000062
A phenyl group, a substituted or unsubstituted tetracenyl group, a substituted or unsubstituted benzothiophene group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted dibenzothiapyrrol group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzoselenophene group, a substituted or unsubstituted carbazolyl group.
The term "substituted" in the above-mentioned compounds which is "substituted or unsubstituted" means that the substituents are independently selected from deuterium atom, halogen atom, cyano group, nitro group, hydroxyl group, 1-valent arylamine group having 7 to 30 carbon atoms, 1-valent silicon group having 3 to 30 carbon atoms, 1-valent alkyl group or cycloalkyl group having 1 to 10 carbon atoms, 1-valent monocyclic aryl group or condensed ring aryl group having 6 to 30 carbon atoms, 1-valent heterocyclic group or condensed ring heteroaryl group having 2 to 50 carbon atoms;
preferably, the "substituted" groups in "substituted or unsubstituted" are independently any one or more selected from the following groups:
deuterium atom, halogen atom, cyano group, nitro group, hydroxyl group, dimethyltriarylamine group, diphenyltriarylamine group, trimethylsilyl group, triphenylsilyl group, methyl group, methoxy group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-methylbutyl group, cyclohexyl group, adamantyl group, 2-ethylhexyl group, trifluoromethyl group, pentafluoroethyl group, 2-trifluoroethyl group, phenyl group, deuterated phenyl group, fluorophenyl group, methylphenyl group, n-propylphenyl group, tert-butylphenyl group, trimethylphenyl group, triphenylphenyl group, tetraphenylphenyl group, cyanophenyl group, naphthyl group, anthracenyl group, biphenyl group, biphenylyl group, terphenyl group, fluorenyl group, spirobifluorenyl group, furyl group, benzofuryl group, dibenzofuryl group, azabenzofuryl group, thienyl group, benzothienyl group, dibenzothienyl group, azadibenzothienyl group, carbazolyl group, phenylcarbazolyl group, azacarbazolyl group;
further, the following specific structural compounds 1 to 220 can be preferably selected from the formula (1) protected by the present invention, and the compounds are only representative:
Figure BDA0003018510440000061
Figure BDA0003018510440000071
Figure BDA0003018510440000081
Figure BDA0003018510440000091
Figure BDA0003018510440000101
Figure BDA0003018510440000111
Figure BDA0003018510440000121
Figure BDA0003018510440000131
Figure BDA0003018510440000141
the second objective of the present invention is to provide an organic electroluminescent device. The organic electroluminescent device comprises an anode, a cathode and at least one layer of organic thin film positioned between the anode and the cathode, wherein the organic thin film contains one or more organic electroluminescent compounds represented by the formula (1). The organic layer includes a light emitting layer and a functional layer, and the compound represented by formula (1) may be used as a host material, an electron transport material, a hole blocking material, or an electron injection material, alone or in combination.
It is a further object of the present invention to provide an organic electroluminescent device. When the compound represented by the formula (1) is applied to a device, a high-thermal-stability organic electroluminescent device with higher luminous efficiency and longer service life under low driving voltage is obtained by optimizing the structure of the device.
The beneficial effects of the invention include:
the compound protected by the invention is a cyano-group aza-benzene material, the molecular structure of the material is simple and easy to design, the synthesis is easy, the raw material is cheap, and the material has stronger pi-conjugation effect, so that the triplet state energy level of the material is improved, the material has higher glass transition temperature, the thermal stability of a device is improved, and the service life of the device is further prolonged;
when the compound is applied to an organic electroluminescent device, the energy levels of HOMO and LUMO can be easily adjusted due to the asymmetric structure, and other layer materials (such as a main body material and an injection layer material) can be effectively matched, so that the driving voltage of the device is reduced, and the efficiency of the device is improved. In addition, the mobility of the material can be effectively adjusted by adjusting the number and the positions of the cyano groups and the nitrogen atoms, so that electrons are effectively transmitted to the light-emitting layer, the accumulation of the electrons is avoided, and the service life of the device is prolonged.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:
FIG. 1 is a schematic diagram of the structure of an organic electroluminescent device to which the compound of the present invention is applied, wherein the structure of each layer of the device represents the following meanings:
1. transparent substrate layer, 2, ITO anode layer, 3, hole injection layer, 4, hole transport layer A,5, hole transport layer B (or electron blocking layer), 6, luminescent layer, 7, electron transport layer B (or hole blocking layer), 8, electron transport layer A,9, electron injection layer, 10, cathode reflection electrode layer.
Detailed Description
The principles and features of this invention will be further illustrated by the following examples of synthesis, which are provided for the purpose of illustration only and are not intended to limit the scope of the invention.
The synthesis of the specific compounds of formula (1) listed below, unless otherwise indicated, is carried out in an anhydrous solvent under a protective gas atmosphere.
Synthesis example 1: synthesis of formula 2
Figure BDA0003018510440000151
10.0g (48mmol, 1.00eq) of chalcone (2 a), 4.44g (52.8mmol, 1.10eq) of chloroacetamide (2 b), and 500mL of tert-butanol were weighed and charged into a flask, and dissolved by stirring, and 21.5g (19.2mmol, 4.0eq) of potassium tert-butoxide was added thereto, and reacted at 30 ℃ for 24 hours, whereupon a solid precipitated, followed by filtration. Pulping with n-hexane, and filtering to obtain a product 2c which is directly used for the next synthesis.
250mL of phosphorus oxychloride was added to the flask, followed by slow addition of intermediate 2c in portions, which was dissolved with stirring. And (3) pumping gas for three times to the reaction system, reacting for 6 hours at 100 ℃ under the protection of nitrogen, performing rotary evaporation to remove the solvent, separating by using a silica gel column, eluting by using ethyl acetate/petroleum ether (1.
5.22g (18.0mmol, 1.0eq) of intermediate 2e, 8.36g (18.9mmol, 1.05eq) of 2-boronic acid pinacol-9, 9-spirofluorene (2 e) were added with 0.50g (0.54mmol, 0.03eq) of tris (dibenzylideneacetone) dipalladium and 3.44g (36mmol, 2.00eq) of sodium tert-butoxide. The reaction system was purged three times with nitrogen, and 2.16mL (2.16mmol, 0.12eq) of tri-tert-butylphosphine in toluene (1 mol/L) and 150mL of xylene were added via a syringe. Heating and stirring under the protection of nitrogen, and carrying out reflux reaction at 120 ℃ for 12h. The reaction was stopped, cooled to room temperature, 100ml of deionized water was added and extracted three times with ethyl acetate. The solvent was removed by rotary evaporation, separated on a silica gel column, rinsed with ethyl acetate/petroleum ether (1.
In a similar reaction, the following compounds can be prepared:
TABLE 1
Figure BDA0003018510440000161
Figure BDA0003018510440000171
Synthetic example 16: synthesis of formula 4
Figure BDA0003018510440000172
4.30g (20.0 mmol,1.0 eq) of 5-bromo-2-chloronicotinonitrile (4 a), 2.56g (20.10 mmol, 1.05eq) of phenylboronic acid, 5.53g (40.0 mmol, 2eq) of potassium carbonate, 30ml of xylene and 10ml of water were charged into a reaction flask, dissolved by stirring, the reaction system was degassed three times, protected with nitrogen, and 0.92g (0.8 mmol, 0.04eq) was added. And refluxing and reacting for 12h under the protection of nitrogen. The reaction was stopped, cooled to room temperature, 200ml of deionized water was added, and extracted three times with ethyl acetate. The solvent was removed by rotary evaporation, separated by a silica gel column, rinsed with n-hexane, solvent dried by rotary evaporation, and dried under vacuum to give 3.64g of intermediate product with 85% yield. White solid 4c, molecular weight M/z =215.0 (M + H) + mass spectrometry.
3.21g (15.0mmol, 1.0eq) of intermediate 4c, 7.43g (18.9mmol, 1.05eq) of 4d, and then 0.42g (0.45mmol, 0.03eq) of tris (dibenzylideneacetone) dipalladium and 2.87g (30mmol, 2.00eq) of sodium tert-butoxide were added to the reaction flask. The reaction system was purged three times with nitrogen, and 1.8mL (1.8mmol, 0.12eq) of a toluene solution of tri-tert-butylphosphine (1 mol/L) and 120mL of xylene were added through a syringe. Under the protection of nitrogen, the mixture is heated and stirred and refluxed for reaction for 12 hours at 120 ℃. The reaction was stopped, cooled to room temperature, 100ml of deionized water was added and extracted three times with ethyl acetate. The solvent was removed by rotary evaporation, separated on a silica gel column, rinsed with ethyl acetate/petroleum ether (1.
In a similar reaction, the following compounds can be prepared:
TABLE 2
Figure BDA0003018510440000181
Figure BDA0003018510440000191
Figure BDA0003018510440000201
The function of the film layer of the organic electroluminescent device according to the preferred embodiment of the present invention will be described below.
The organic electroluminescent device comprises an anode layer, a cathode layer and at least one organic layer between the anode and the cathode. Alternatively, the organic layer is a film layer formed by stacking a plurality of organic compounds. The organic layer may further contain an inorganic compound.
At least one of the organic layers of the organic electroluminescent device of the scheme of the invention is a light-emitting layer. The organic layer may contain other functional layers in addition to the light-emitting layer, for example, one or more hole injection layers, hole transport layers, or electron blocking layers may be present between the anode layer and the light-emitting layer, an exciton blocking layer or an intermediate layer having a similar function may be present between the two light-emitting layers, and one or more hole blocking layers, electron transport layers, or electron injection layers may be present between the light-emitting layer and the cathode layer. Note that these functional layers are not necessarily present.
The organic electroluminescent device can be a fluorescent or phosphorescent device, and can also be a fluorescent and phosphorescent mixed device; the light emitting device may be a device having a single light emitting element or a tandem device having a plurality of light emitting cells; further, the light emitting device may be a single color light emitting device, a mixed color light emitting device, or a white light emitting device.
The light emitting layer may include a plurality of guest materials and a plurality of host materials. The guest material may be a fluorescent material, a phosphorescent material, or a thermally activated delayed fluorescence material. The host material is a host material that occupies most of the constituent components in the light-emitting layer, and the host material doped with a fluorescent material is referred to as a "fluorescent host" and the host material doped with a phosphorescent material is referred to as a "phosphorescent host". The host material is selected not depending on the molecular structure thereof but depending on the host material as the guest material.
The compounds according to the invention according to the above embodiments can be used in different organic layers. The organic electroluminescent device is preferably used as an electron transport material and/or a hole blocking material and a phosphorescent host material. The use of the compounds of the invention of the above embodiments is equally applicable to organic electronic devices.
In a preferred embodiment of the present invention, the compounds according to the invention are used as hole-blocking layer materials in organic electroluminescent devices. The light-emitting layer in this embodiment may be a fluorescent material, a phosphorescent material, or a thermally activated delayed fluorescent material, or a mixture of a fluorescent material and a phosphorescent material in the light-emitting layer.
In a further preferred embodiment of the present invention, the compounds according to the invention are used as electron transport layer materials in organic electroluminescent devices. The light-emitting layer in this embodiment may be a fluorescent material, a phosphorescent material, or a thermally activated delayed fluorescent material, or a mixture of a fluorescent material and a phosphorescent material in the light-emitting layer.
In this embodiment, the compound of the present invention is used as an electron transport layer material, and can be doped and mixed with other electron transport layer materials. Other electron transport layer materials may be other compounds of the present invention, and may be electron transport layer materials known in the art or other disclosed or undisclosed electron transport layer materials. The use mode can adopt a pre-mixing mode or a co-evaporation mode.
In another preferred embodiment of the present invention, the compound of the present invention is used as a phosphorescent host material in an organic electroluminescent device, and the light-emitting layer of the organic electroluminescent device described herein may be a single layer or a plurality of layers, wherein at least one layer comprises the compound of the present invention.
In a preferred embodiment of the present invention, the compound of the present invention is used as a phosphorescent host material in an organic electroluminescent device, and one or more phosphorescent materials may be selected for use in combination with the host material in the light-emitting layer of the organic electroluminescent device described herein.
When the compound of the present invention is used as a host material, the compound of the present invention may be used singly or in combination of a plurality of host materials in the light-emitting layer of the organic electroluminescent device described herein. When a plurality of host materials are used together, at least one host material is the compound of the present invention, and other host materials may be other compounds of the present invention, or may be known host materials in the art or other disclosed or undisclosed host materials. The use mode can adopt a pre-mixing mode or a co-evaporation mode.
In a preferred embodiment of the present invention, the mixture doping ratio of the light emitting material and the host material in the light emitting layer of the organic electroluminescent device is preferably 0.1 wt% to 30 wt%.
These methods are generally known to those skilled in the art and can be applied without inventive step to organic electroluminescent devices comprising the compounds of the present invention.
The following detailed description of the effect of the compounds of the present invention in the application of organic electroluminescent devices is provided by device examples 1 to 30 and device comparative examples 1 to 6 to demonstrate the technical progress and advantageous effects of the compounds of the present invention in the art. The examples and comparative examples are intended to illustrate the present invention in further detail, but the present invention is not limited to the technical conditions.
Device example 1: manufacture of organic electroluminescent devices as hole blocking layer materials
A glass substrate with an Indium Tin Oxide (ITO) transparent electrode (anode) having a thickness of 25mm × 75mm × 1.1mm was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then subjected to Ultraviolet (UV) -ozone cleaning for 30 minutes. The thickness of the ITO film was 130nm. The cleaned glass substrate was mounted on a substrate holder of a vacuum deposition apparatus, and the substrate holder was evacuated to 1X 10 -5 ～1×10 -6 Pa, depositing a Hole Injection Layer (HIL) HATCN on the ITO transparent conductive layer, and the thickness is 15nm. A hole transport layer A (HTL) was deposited on the hole injection layer to a thickness of 60nm. Then, an Electron Blocking Layer (EBL) was deposited on the hole transport layer A to a thickness of 5nm. Then, an emission layer (EML) was co-evaporated on the electron blocking layer to a film thickness of 20nm. The light-emitting layer (EML) adopts a multi-source co-evaporation mode to evaporate the light-emitting material BD and the main body material BH of the light-emitting layer, wherein the doping concentration of the light-emitting material is 2 wt%. In order to ensure the accuracy of the doping concentration of the luminescent material, the shielding partition plate needs to be opened again after the evaporation rate of the luminescent material and the main body material is stable, and multi-source co-evaporation is carried out. Then, a Hole Blocking Layer (HBL) was deposited on the light-emitting layer to form a layer 7, and the thickness was 5nm. Then, an electron transport material (ETL-1) and 8-hydroxyquinoline lithium (Liq) were deposited on the hole blocking layer, with a film thickness of 30nm and a doping ratio of 1. An electron injection Electrode (EIL) was deposited on the ETL to a thickness of 1nm. Then, metal cathode aluminum (Al) was deposited on the EIL to a film thickness of 100nm. Organic electroluminescence of example 1The structure of the optical device is shown in fig. 1, and fig. 1 also shows the stacking sequence and the function of each functional layer.
The OLEDs have in principle the following layer structure: substrate/Hole Injection Layer (HIL)/hole injection layer (HTL)/Electron Blocking Layer (EBL)/emission layer (EML)/Hole Blocking Layer (HBL)/Electron Transport Layer (ETL)/Electron Injection Layer (EIL) and finally a cathode. The cathode is formed from a 100nm thick layer of aluminum. The molecular structure of the material for OLED is shown in table 3.
TABLE 3 materials for OLEDs
Figure BDA0003018510440000221
Figure BDA0003018510440000231
Device examples 1 to 9: manufacture of organic electroluminescent devices as hole blocking layer materials
The device structure of device example 1 is specifically: ITO (130)/HATCN (15)/HTL (60)/EBL-1 (5)/BH: BD (20, 2% by weight)/conversion 4 (5)/ETL-1 Liq (30, 50% by weight)/Liq (1)/Al (100), and the number in parentheses indicates the film thickness (unit: nm).
Device examples 10 to 18: manufacture of organic electroluminescent devices as electron transport layers
The device structure of device example 10 is specifically: ITO (130)/HATCN (15)/HTL (60)/EBL-1 (5)/BH BD (20, 2% by weight)/HBL-1 (5)/oxidized 2 Liq (30, 50% by weight)/Liq (1)/Al (100).
Device examples 19 to 22: manufacture of organic electroluminescent devices as hole blocking layer materials and electron transport layers
The device structure of device example 19 is specifically: ITO (130)/HATCN (15)/HTL (60)/EBL-1 (5)/BH BD (20, 2% by weight)/conversion 4 (5)/conversion 2 Liq (30, 50% by weight)/Liq (1)/Al (100).
Comparative example 1:
this comparative example is different from example 1 in that the hole blocking material in the organic electroluminescent device was changed to HBL-1, and the resulting device performance test data is shown in table 4.
Comparative example 2:
this comparative example is different from example 1 in that the hole blocking material in the organic electroluminescent device was changed to HBL-2, and the resulting device performance test data is shown in table 4.
Comparative example 3:
the comparative example is different from comparative example 10 in that the electron transport material in the organic electroluminescent device was changed to ETL-2, and the resulting device performance test data is shown in table 4.
The OLEDs were characterized by standard methods. For this purpose, the electroluminescence spectrum, the current efficiency (measured in cd/a), the power efficiency (measured in lm/W) and the external quantum efficiency (EQE, measured in%) are determined, which are calculated as a function of the luminous density from current/voltage/luminous density characteristic lines (IUL characteristic lines) which exhibit lambertian emission characteristics. At 1000cd/m 2 Determines the required voltage V1000 at the luminance of (c). CE1000 is expressed at 1000cd/m 2 The current efficiency achieved. Finally, EQE1000 is shown at 1000cd/m 2 External quantum efficiency at an operating luminance of (1), T95 denotes that the device is at 1000cd/m 2 The device luminance decreases to 95% of the on time at the initial luminance of (a).
TABLE 4
Figure BDA0003018510440000232
Figure BDA0003018510440000241
As can be seen from table 4, compared with the prior art, the device examples 1 to 22 of the present invention can maintain a slight reduction in the driving voltage of the OLED, and improve the lifetime of the device, such as the CE1000 of the device example 12 in the chemical formula 9 is improved by 37.6% compared with the comparative example 4, and more importantly, when the material protected by the present invention is used as an ETL and HBL material in combination, the efficiency is improved significantly, such as the CE1000 of the device example 21 in the chemical formula 7 and the chemical formula 5 is improved by 16.5% compared with the comparative example 4. This is probably because the cyanazabenzene protected by the present invention has asymmetric structure, the energy level of HOMO and LUMO can be easily adjusted, and other layer materials (such as host material and injection layer material) can be effectively matched. Meanwhile, the energy loss caused by molecular accumulation can be avoided due to asymmetric energy level distribution, and the device efficiency of the material is improved. In addition, the mobility of the material can be effectively adjusted by adjusting the number and the positions of the cyano groups and the nitrogen atoms, so that electrons are effectively transmitted to the light-emitting layer, the accumulation of the electrons is avoided, and the service life of the device is prolonged.
Device examples 23 to 30: manufacture of organic electroluminescent device used as phosphorescent host material of green light-emitting layer
Device examples 23 to 27:
the device structure of device example 23 is specifically: ITO (130)/HATCN (15)/HTL (60)/EBL-2 (5)/chemo-21 GD (30, 6% by weight)/HBL-1 (5)/ETL-1 Liq (20, 50% by weight)/Liq (1)/Al (100).
Device examples 28 to 30:
the device structure of device example 28 is specifically: ITO (130)/HATCN (15)/HTL (60)/EBL-2 (5)/chemo-21, GH-3.
Comparative example 4:
this comparative example is different from example 23 in that the host material of the light emitting layer in the organic electroluminescent device was changed to GH-1, which is a phosphorescent host material known in the art and commercially used, and the resulting device performance test data are shown in Table 5.
Comparative example 5:
this comparative example is different from example 23 in that the host material of the light emitting layer in the organic electroluminescent device is changed to GH-2, which is a phosphorescent host material known in the art and commercially used, and the resulting device performance test data are shown in Table 5.
Comparative example 6:
the present comparative example is different from example 28 in that a phosphorescent mixed host material GH-1: GH-3, the resulting device performance test data is shown in Table 5.
TABLE 5
Figure BDA0003018510440000251
Figure BDA0003018510440000261
The device performances of examples 23 to 30 of the present invention and comparative examples 4 to 6 as green host GH are summarized in table 5. It can be seen that the efficiency can be improved while the driving voltage is kept lower by using the material of the present invention compared with the prior art (comparative examples 4-6), e.g. CE1000 in example 26 is improved by 25.3% compared with comparative example 4, and more importantly, the service life of the OLED is significantly improved, e.g. T95 in example 30 is improved by 38.5% compared with the device in comparative example 6. It can also be seen from table 5 that device performance of device examples 28 to 30 using a mixed host is improved by nearly one time compared with device examples 23, 24 and 27 using a single host, the compound protected by the present invention and GH-3 as a partial hole type are used in combination as a host material of a light emitting layer, which balances the transport speed of electrons and holes, and meanwhile, the triplet state energy level of the protection material is improved by a strong pi-conjugation effect, so that the material has a higher glass transition temperature, the thermal stability of the device is improved, and the device lifetime is improved compared with comparative examples 4 to 6.

Claims (4)

1. A cyanoazepine compound selected from the group consisting of:
Figure DEST_PATH_IMAGE001
chemical 9
Figure 296337DEST_PATH_IMAGE002
Chemical reaction 23
Figure DEST_PATH_IMAGE003
And (5) melting the mixture to 35.
2. An organic electroluminescent device comprising an anode, a cathode, and at least one organic thin film between the anode and the cathode, wherein the organic thin film comprises the compound according to claim 1.
3. The organic electroluminescent device according to claim 2, wherein the compound is selected for use as a host material, an electron transport material, a hole blocking material, or an electron injection material in an organic electroluminescent device.
4. The organic electroluminescent device according to claim 2 or 3, wherein the compound is used as a host material, an electron transport material, a hole blocking material or an electron injection material in the organic electroluminescent device.
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CN104072405A (en) * 2013-03-29 2014-10-01 海洋王照明科技股份有限公司 Electron transport material as well as preparation method and organic electroluminescence device thereof
CN106083825A (en) * 2016-06-07 2016-11-09 石家庄诚志永华显示材料有限公司 Pyrazines derivatives and the application in organic electroluminescence device thereof
CN108779103A (en) * 2016-03-17 2018-11-09 默克专利有限公司 With the fluorene structured compound of spiral shell two

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CN104072405A (en) * 2013-03-29 2014-10-01 海洋王照明科技股份有限公司 Electron transport material as well as preparation method and organic electroluminescence device thereof
CN108779103A (en) * 2016-03-17 2018-11-09 默克专利有限公司 With the fluorene structured compound of spiral shell two
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