CN112457201A

CN112457201A - Compound, organic electroluminescent device and display device

Info

Publication number: CN112457201A
Application number: CN202011270988.5A
Authority: CN
Inventors: 王占奇; 郭林林; 李志强; 陆金波
Original assignee: Beijing Sineva Technology Co ltd; Beijing Xinyihua Material Technology Co ltd; Fuyang Sineva Material Technology Co Ltd
Current assignee: Beijing Sineva Technology Co ltd; Beijing Xinyihua Material Technology Co ltd; Fuyang Sineva Material Technology Co Ltd
Priority date: 2020-11-13
Filing date: 2020-11-13
Publication date: 2021-03-09
Also published as: CN114478270B; CN114478270A; CN117185941A; WO2022100704A1; CN117800850A

Abstract

The application relates to the field of electroluminescence, and discloses a compound, an organic electroluminescent device and a display device. The structural formula of the compound is shown as the formula (I):

the organic electroluminescent device using the material of the compound has lower driving voltage and higher current efficiency, and simultaneously, the compound can be used for preparing a transmission layer or an injection layer of the organic electroluminescent device by a solution method.

Description

Compound, organic electroluminescent device and display device

Technical Field

The application relates to the field of electroluminescence, in particular to a compound, an organic electroluminescent device and a display device.

Background

Currently, organic electroluminescent (OLED) display technology has been applied in the fields of smart phones, tablet computers, and the like, and further will be expanded to large-size application fields such as televisions. In the development process of the last 30 years, various OLED materials with excellent performance are developed, and the commercialization process of the OLED is accelerated by different designs of the device structure and optimization of the device life, efficiency and other properties, so that the OLED is widely applied in the fields of display and illumination.

However, since there is a great gap between the external quantum efficiency and the internal quantum efficiency of the OLED, the development of the OLED is greatly restricted, and one of the most important factors is that the efficiency of the device still does not reach a desired level. This is because most of light is confined inside the light emitting device due to mode loss of the substrate, loss of surface plasmon, and waveguide effect, thereby reducing the light emitting efficiency of the device. Improving the light emitting efficiency of the device, and using light extraction materials is one of the effective methods. The light extraction Layer (CPL) can adjust the light extraction direction and the light extraction efficiency by reducing the surface plasma effect of the metal electrode, and can effectively improve the light extraction efficiency of the device, thereby improving the luminous efficiency of the device. At present, the light extraction material is of a single type and has an unsatisfactory effect, and developing a more effective light extraction material is one of the more serious challenges facing OLED workers.

In addition, the selection of the materials of the light emitting layer and other organic functional layers also has a great influence on the current efficiency and driving voltage of the device, and functional layer materials with higher performance are still being explored.

Therefore, in order to meet the higher requirements of people for OLED devices, the development of more various and higher-performance OLED materials is urgently needed in the art.

Disclosure of Invention

The application discloses a compound, an organic electroluminescent device and a display device, wherein the organic electroluminescent device made of the material of the compound has lower driving voltage and higher current efficiency, and the compound provided by the application can be used for preparing a transmission layer or an injection layer of the organic electroluminescent device by a solution method.

In order to achieve the purpose, the application provides the following technical scheme:

a compound has a structural formula shown as a formula (I),

wherein a, b, c, d are each independently selected from 0,1, 2, 3 or 4; p is selected from 0 or 1;

R₁～R₄each independently selected from hydrogen, deuterium, F, CN, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 40 carbon atoms; the hydrogen in the aryl group containing 6-40 carbon atoms can be substituted by R;

Ar、Ar₁each independently selected from aromatic groups containing 6 to 40 carbon atoms, wherein hydrogen in the aromatic groups containing 6 to 40 carbon atoms can be substituted by R; wherein R may form a ring with spirofluorene, and Ar may form a ring with Ar₁、 Ar₂Looping;

Ar₂one selected from the structures shown in A-1 to A-8:

wherein represents Ar₂And the position to which the N atom in formula (I) is attached;

R₅～R₁₄each independently selected from an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 40 carbon atoms; the hydrogen in the aryl group containing 6-40 carbon atoms can be substituted by R; wherein R is bound to the same carbon atom or to adjacent carbon atoms₅～R₁₄Can be connected into a ring;

e, f are selected from 0 or 1, and e, f are not 0 at the same time;

r is selected from F, CN or alkyl containing 1-20 carbon atoms, alkoxy containing 1-20 carbon atoms or aryl containing 6-40 carbon atoms.

Further, R₁～R₄When the alkyl group is selected from aryl groups having 6 to 40 carbon atoms, which are substituted with an alkyl group having 1 to 20 carbon atoms, the alkyl group having 1 to 20 carbon atoms may be substituted with a spiro groupThe fluorene group forms a ring.

The application also provides a synthetic method of the compound shown in the formula (I):

the application also provides another synthesis method of the compound shown in the formula (I):

wherein X is selected from Cl, Br and I.

The present application also provides the following intermediates useful in the synthesis of compounds of formula (I):

wherein X is selected from Cl, Br and I.

Further, the structure of the compound is selected from one of the following structures:

further, in the compounds II-1 to II-9, Ar₁Ar is selected from benzene, biphenyl, naphthalene, phenanthrene, fluorene, carbazole, dibenzofuran, dibenzothiophene, triphenylene, fluoranthene or Ar₂And Ar is₁The hydrogen in Ar can be substituted by alkyl with 1-20 carbon atoms and aryl with 6-40 carbon atoms.

Wherein, Ar₁When hydrogen in the group is substituted by an aromatic group having 6 to 40 carbon atoms, Ar₁Can form a ring with an aromatic group containing 6-40 carbon atoms through carbon atoms, can also form a ring through N-R, and can also form a ring through O, S, wherein R is selected from alkyl with 1-20 carbon atoms and an aromatic group containing 6-40 carbon atoms; ar may be cyclized with a substituent and spirofluorene.

Further, in the compound II-1 to the compound II-9: p is selected from 1; ar (Ar)₁Selected from benzene, biphenyl, naphthalene, phenanthrene, fluorene, carbazole, dibenzofuran, dibenzothiophene, triphenylene, fluoranthene, and Ar₁The hydrogen in the aromatic hydrocarbon can be substituted by an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms;

ar is selected from benzene, biphenyl, spirofluorene, naphthalene, phenanthrene, fluorene, carbazole, dibenzofuran, dibenzothiophene, triphenylene and fluoranthene, and hydrogen in Ar can be substituted by alkyl with 1-6 carbon atoms and aryl with 6-12 carbon atoms.

Further, in the compound II-1 to compound II-9, p is selected from 0; ar (Ar)₁Selected from benzene, biphenyl, naphthalene, phenanthrene, fluorene, carbazole, dibenzofuran, dibenzothiophene, triphenylene, fluoranthene, and Ar₁The hydrogen in the aromatic hydrocarbon can be substituted by an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms.

Further, the compound is selected from one of the following P-1 to P-108 structures and P-1 to P-108 structural isomers:

wherein, in the present application, the structural isomers of P-1 to P-108 refer to various connection modes between aromatic rings constituting Ar in the specific structures of P-1 to P-108, constituting Ar₁Different connection modes between aromatic rings of Ar₂Position of SP2 hybridized carbon atom attached to N atom, Ar₂And Ar₂The different connecting positions of the substituents belong to P-1 to P-108 structural isomers.

Examples are as follows:

for P-3, where a biphenyl group and a tetramethyldihydrophenanthrene group are attached to the N, when two benzene rings on the biphenyl group are linked in any manner and/or any one SP2 hybridized carbon atom on the tetramethyldihydrophenanthrene group is linked to the N, both are considered structural isomers of P-3, including, but not limited to, the following structures:

the structural isomers of P-1 to P-108 can be understood by reference to the above explanation of P-3.

A compound intermediate selected from one of the following structures:

intermediates of the above compounds, each useful for preparing a portion of the compounds of the present application.

An organic electroluminescent device comprising a compound as described herein.

Further, the material of the hole transport layer or the hole injection layer of the organic electroluminescent device is a compound of the present application.

Further, the compounds of the present application can be used in solution processes to prepare hole transport layers or hole injection layers for electroluminescent devices.

A display device includes the organic electroluminescent device provided by the application.

By adopting the technical scheme of the application, the beneficial effects are as follows:

the application provides a compound shown in formula (I), wherein spirofluorene is used as a mother nucleus, the selection range of each substituent group is limited, and the film forming property and the light transmittance of the material are improved, so that the material is greatly improved compared with the existing material. Meanwhile, the structure of the compound is changed, the solubility of the material in an organic solvent is correspondingly changed, the organic solvent with better viscosity performance can be obtained after the compound solution is dissolved in the solvent, and the film-forming performance of the residual organic material is excellent after the solvent is volatilized, so that the material is more suitable for being prepared by a solution method when being used for preparing an OLED device. Meanwhile, the change of the compound structure improves the HOMO and LOMO energy levels of the material, so that the material has higher luminous efficiency and lower driving voltage when being used as a host material, a Hole Injection Layer (HIL) material or a Hole Transport Layer (HTL) material and applied to an OLED device.

Drawings

FIG. 1 is a mass spectrometric detection of compound P-5 provided in the examples herein;

figure 2 is a mass spectrometric detection of compound P-6 provided in the examples herein.

Detailed Description

The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

It should be noted that: in the present application, all embodiments and preferred methods mentioned herein can be combined with each other to form new solutions, if not specifically stated. In the present application, all the technical features mentioned herein as well as preferred features may be combined with each other to form new technical solutions, if not specifically stated. In the present application, percentages (%) or parts refer to percent by weight or parts by weight relative to the composition, unless otherwise specified. In the present application, the components referred to or the preferred components thereof may be combined with each other to form new embodiments, if not specifically stated. In this application, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "6 to 22" means that all real numbers between "6 to 22" have been listed herein, and "6 to 22" is simply a shorthand representation of the combination of these values. The "ranges" disclosed herein may be in the form of lower limits and upper limits, and may be one or more lower limits and one or more upper limits, respectively. In the present application, unless otherwise indicated, the individual reactions or process steps may or may not be performed in sequence. Preferably, the reaction processes herein are carried out sequentially.

Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present application.

Synthesis example 1

Synthesis of P-1

Step S1) Synthesis of 4-bromo-9, 9,10, 10-tetramethyl-9, 10-dihydrophenanthrene and 2-bromo-9, 9,10, 10-tetramethyl-9, 10-dihydrophenanthrene

Adding 0.01mol (2.36g) of 9,9,10, 10-tetramethyl-9, 10-dihydrophenanthrene, 30 ml of dichloromethane, 5 ml of glacial acetic acid and 0.2 g of iron powder into a 250 ml three-neck flask, then controlling the temperature to be 20-25 ℃, slowly dropwise adding 5 ml of dichloromethane solution of 0.012mol (1.92 g) of liquid bromine, controlling the temperature to be 20-25 ℃ after the addition to react for 4 hours, adding water and stirring, filtering insoluble substances, separating mother liquor, washing organic layer sodium bisulfite solution, then washing silica gel column to be neutral, concentrating to be dry, carrying out chromatographic separation, and eluting with petroleum ether to obtain the products of 4-bromo-9, 9,10, 10-tetramethyl-9, 10-dihydrophenanthrene 0.81 g, 2-bromo-9, 9,10, 10-tetramethyl-9, 10-dihydrophenanthrene 0.92 g and the total yield of 54.9%.

The obtained 4-bromo-9, 9,10, 10-tetramethyl-9, 10-dihydrophenanthrene is subjected to mass spectrometric detection, and the molecular m/z is determined as follows: 314, 316, determining the molecular formula of the product as C₁₈H₁₉Br。

The obtained 4-bromo-9, 9,10, 10-tetramethyl-9, 10-dihydrophenanthrene was subjected to nuclear magnetic detection, and the data were analyzed as follows: 1H-NMR (Bruker, Switzerland, Avance II 400MHz NMR spectrometer, CDCl3), delta 7.71(m, 1H), delta 7.66(m, 1H), delta 7.55(m, 1H), delta 7.48(m, 1H), delta 7.34-7.28 (m, 2H), delta 7.21(t, 1H), delta 1.33(s, 12H).

The obtained 2-bromo-9, 9,10, 10-tetramethyl-9, 10-dihydrophenanthrene is subjected to mass spectrometric detection, and the molecular m/z is determined as follows: 314, 316, determining the molecular formula of the product as C₁₈H₁₉Br。

The obtained 2-bromo-9, 9,10, 10-tetramethyl-9, 10-dihydrophenanthrene was subjected to nuclear magnetic detection, and the data were analyzed as follows: 1H-NMR (Bruker, Switzerland, Avance II 400MHz NMR spectrometer, CDCl3), delta 7.71(m, 1H), delta 7.67(d, 1H), delta 7.61-7.53 (m, 2H), delta 7.46(m, 1H), delta 7.35-7.26 (m, 2H), delta 1.33(s, 12H).

Step S2) Synthesis of 2- (9,9,10, 10-tetramethyl-9, 10-dihydrophenanthren-4-yl) -2-propanol

Adding 0.01mol (3.15 g) of 4-bromo-9, 9,10, 10-tetramethyl-9, 10-dihydrophenanthrene and 100 ml of tetrahydrofuran into a 250 ml three-neck flask, replacing with nitrogen, cooling to-78 ℃, then dropwise adding 0.012mol of butyl lithium n-hexane solution (7.5 ml, with the concentration of 1.6M), keeping at-70 to-78 ℃ for 30min, then adding 0.02mol (1.16g) of acetone at one time, slowly heating to 25 ℃, adding ammonium chloride solution for hydrolysis, then adding dichloromethane for separating liquid, washing an organic layer to be neutral, concentrating and reducing the pressure to be dry to obtain a yellow oily substance, and directly carrying out the next reaction without separation.

Step S3) Synthesis of 4,4,8,8,9, 9-hexamethyl-8, 9-dihydro-4H-cyclopenta [ def ] phenanthrene

Under the protection of nitrogen, 20 ml of dichloromethane is added into unseparated 2- (9,9,10, 10-tetramethyl-9, 10-dihydrophenanthrene-4-yl) -2-propanol obtained in the previous step, after stirring and dissolving, 3 ml of glacial acetic acid is added, then, the temperature is reduced to 0 ℃, 2g of methanesulfonic acid is slowly dropped at 0-5 ℃, after the addition, the temperature is raised to 25 ℃ under stirring, then, the reaction is carried out for 4 hours, 30 ml of methanol is added, solid is separated out, filtered, washed by methanol and dried, and white-like solid 4,4,8,8,9, 9-hexamethyl-8, 9-dihydro-4H-cyclopenta [ def ] phenanthrene, 1.88 g is obtained, and the total yield is 68% calculated from the previous step.

Mass spectrometry detection was performed on 4,4,8,8,9, 9-hexamethyl-8, 9-dihydro-4H-cyclopenta [ def ] phenanthrene to determine the molecular m/z as: 276.

step S4) Synthesis of 2-bromo-4, 4,8,8,9, 9-hexamethyl-8, 9-dihydro-4H-cyclopenta [ def ] phenanthrene

Adding 0.01mol (2.76g) of 4,4,8,8,9, 9-hexamethyl-8, 9-dihydro-4H-cyclopenta [ def ] phenanthrene, 40 ml of dichloromethane, 15 ml of glacial acetic acid and 0.2 g of iron powder into a 250 ml three-neck flask, then controlling the temperature to be 20-25 ℃, slowly dropwise adding 5 ml of dichloromethane solution of 0.012mol (1.92 g) of liquid bromine, controlling the temperature to be 35-40 ℃ after the addition for reaction for 4 hours, adding water for stirring, filtering insoluble substances, separating mother liquor, washing an organic layer sodium bisulfite solution, then washing the organic layer sodium bisulfite solution to be neutral, concentrating the solution to be dry, carrying out silica gel column chromatography separation, and eluting with petroleum ether to obtain 2.18 g of a product, namely 2-bromo-4, 4,8,8,9, 9-hexamethyl-8, 9-dihydro-4H-cyclopenta [ def ] phenanthrene.

P-2-bromo-4, 4,8,8,9, 9-hexamethyl-8, 9-dihydro-4H-cyclopenta [ def]Performing mass spectrum detection on phenanthrene, and determining that the molecular m/z is as follows: 354, 356, determining the molecular formula of the product as: c₂₁H₂₃Br。

Step S5) Synthesis of P-1

250 ml of three-necked flask, nitrogen protection, 150 ml of dry toluene, 4.84 g (0.01mol) of N- ([1,1 '-biphenyl ] -3-yl) -9,9' -spirobifluorene-2-amine, 3.91 g (0.011mol) of 2-bromo-4, 4,8,8,9, 9-hexamethyl-8, 9-dihydro-4H-cyclopenta [ def ] phenanthrene, 0.0575 g (0.0001mol) of Pd (dba)2 (bis (dibenzylideneacetone palladium), 0.4 g (0.0002mol) of toluene solution containing 10% of tri-tert-butylphosphine, 1.44 g (0.015 mol) of sodium tert-butoxide, heating to reflux reaction for 6 hours, cooling, adding water for liquid separation, washing the organic layer with water to neutrality, drying magnesium sulfate, filtering to remove magnesium sulfate, concentrating to dryness, mixing chloroform and methanol to dissolve and recrystallizing to obtain 6.12 g of the compound represented by P-1, the yield thereof was found to be 80.74%.

Performing mass spectrum detection on the compound shown as the P-1, and determining that the molecular m/z is as follows: 757.

the nuclear magnetic detection is carried out on the compound shown as P-1, and the data are analyzed as follows: 1H-NMR (Bruker, Switzerland, Avance II 400MHz NMR spectrometer, CDCl3), δ 7.93-7.84 (m, 4H), δ 7.77 (m, 2H), δ 7.65(m, 2H), δ 7.59-7.46 (m, 5H), δ 7.45-7.31 (m, 7H), δ 7.28-7.21 (m, 6H), δ 7.20-7.13 (m, 3H), δ 1.70(s, 6H), δ 1.34(s, 12H).

Synthesis example 2

Synthesis of P-5

The synthesis method refers to the synthesis of P-1, and is different from the synthesis method of a compound P-1 in that N- ([1,1 '-biphenyl ] -3-yl) -9,9' -spirobifluorene-2-amine is replaced by N- ([1,1 '-biphenyl ] -4-yl) -9,9' -spirobifluorene-2-amine, and 2-bromo-4, 4,8,8,9, 9-hexamethyl-8, 9-dihydro-4H-cyclopenta [ def ] phenanthrene is replaced by 9-bromo-7, 7-dimethyl-7H-benzo [ c ] fluorene to obtain the compound shown in P-5.

Performing mass spectrum detection on the compound shown in P-5, wherein the spectrum is shown in the attached figure 1, and the molecular m/z is determined as follows: 725.

synthesis example 3

Synthesis of P-6

The synthesis method refers to the synthesis of P-1, and is different from the synthesis method of a compound P-1 in that N- ([1,1' -biphenyl ] -3-yl) -9,9' -spirobifluorene-2-amine in the synthesis method is changed into N- (9, 9-dimethyl-9H-fluorene-2-yl) -9,9' -spirobifluorene-2-amine, and 2-bromo-4, 4,8,8,9, 9-hexamethyl-8, 9-dihydro-4H-cyclopenta [ def ] phenanthrene in the synthesis method is changed into 9-bromo-7, 7-dimethyl-7H-benzo [ c ] fluorene to obtain the compound shown in P-6.

Performing mass spectrum detection on the compound shown as P-6, wherein the spectrum is shown in the attached figure 2, and the molecular m/z is determined as follows: 765.

synthesis example 4

Synthesis of P-17

The synthesis method refers to the synthesis of P-1, and is different from the synthesis method of a compound P-1 in that N- ([1,1' -biphenyl ] -3-yl) -9,9' -spirobifluorene-2-amine in the synthesis method is replaced by N- (4-fluorophenyl) -9,9' -spirobifluorene-2-amine, and 2-bromo-4, 4,8,8,9, 9-hexamethyl-8, 9-dihydro-4H-cyclopenta [ def ] phenanthrene in the synthesis method is replaced by 3-bromo-7, 7-dimethyl-7H-benzo [ de ] anthracene to obtain the compound shown in P-17.

Performing mass spectrum detection on the compound shown as P-17, and determining that the molecular m/z is as follows: 667.

synthesis example 5

Synthesis of P-44

1) Firstly, 9' -spirobifluorene-2-amine and 5-bromo-7, 7-dimethyl-7H-benzo [ c ] fluorene are reacted to generate a compound shown as P-44-1.

Performing mass spectrum detection on the compound shown in the P-44-1, and determining that the molecular m/z is as follows: 573.

2) the compound shown as P-44-1 and the compound shown as P-44-2 react to generate the compound shown as P-44.

Performing mass spectrum detection on the compound shown as P-44, and determining that the molecular m/z is as follows: 890.

synthesis example 6

Synthesis of P-79

The compound shown as P-79-1 and the compound shown as 3-bromo-7, 7-dimethyl-7H-benzo [ de ] anthracene react to generate the compound shown as P-79.

Performing mass spectrum detection on the compound shown as P-79, and determining that the molecular m/z is as follows: 801.

the synthesis of products not shown in the above synthesis examples can be achieved by conventional methods using methods known in the art.

Device embodiments

The specific structures of several materials used in this application are as follows:

device example 1

The examples used the compounds of the present application as hole transport materials in organic electroluminescent devices, and the comparative examples used HT-1 to HT-4 as hole transport materials in organic electroluminescent devices.

The organic electroluminescent device has the following structure: ITO/HIL02(100 nm)/hole transport material (40nm)/EM1(30nm)/TPBI (30nm)/LiF (0.5nm)/Al (150 nm).

The preparation process of the organic electroluminescent device is as follows:

carrying out ultrasonic treatment on the glass substrate coated with the ITO transparent conductive layer (serving as an anode) in a cleaning agent, then washing the glass substrate in deionized water, ultrasonically removing oil in a mixed solvent of acetone and ethanol, baking the glass substrate in a clean environment until the water is completely removed, cleaning the glass substrate by using ultraviolet light and ozone, and bombarding the surface by using low-energy cation beams to improve the surface property and improve the binding capacity with a hole injection layer;

placing the glass substrate in a vacuum chamber, and vacuumizing to 1 × 10^-5～9×10^-3Pa, vacuum evaporation of HIL02 on the anodeAs a hole injection layer, the evaporation rate is 0.1nm/s, and the evaporation film thickness is 100 nm;

respectively carrying out vacuum evaporation on the compound and the contrast material on the hole injection layer to form a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 40 nm;

vacuum evaporating EM1 on the hole transport layer to serve as an organic light emitting layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness is 30 nm;

vacuum evaporating TPBI on the organic light-emitting layer to be used as an electron transport layer of the organic electroluminescent device; the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 30 nm;

LiF with the thickness of 0.5nm and Al with the thickness of 150nm are evaporated on the electron transport layer in vacuum to be used as an electron injection layer and a cathode.

The luminance, driving voltage, and current efficiency of the prepared organic electroluminescent device were measured.

The organic electroluminescent device properties are shown in table 1 below. OLED-1000 multichannel accelerated aging life and photochromic performance analysis system test using Hangzhou remote production

TABLE 1

Hole transport material	Required luminance cd/m²	Drive voltage V	Current efficiency cd/A
				HT-1	1000	6.19	1.60
HT-2	1000	6.22	1.77
				HT-3	1000	6.36	1.68
HT-4	1000	6.05	1.88
				P-1	1000	5.88	1.99
P-2	1000	5.66	2.01
				P-5	1000	5.51	2.11
P-6	1000	5.52	1.98
				P-60	1000	5.72	2.21
P-76	1000	5.37	2.09
				P-79	1000	6.01	2.13
P-103	1000	5.98	2.22

Device example 2

Examples the compound of the present application was selected as a hole transport material in an organic electroluminescent device, and comparative example HT-1 was selected as a hole transport material in an organic electroluminescent device, and in this example, a hole transport layer was prepared using a solution method.

The organic electroluminescent device has the following structure: ITO/HIL02(100 nm)/hole transport material/EM 1(30nm)/TPBI (30nm)/LiF (0.5nm)/Al (150 nm).

The preparation process of the organic electroluminescent device is as follows:

placing the glass substrate in a vacuum chamber, and vacuumizing to 1 × 10^-5～9×10^-3Pa, performing vacuum evaporation on the anode to form HIL02 as a hole injection layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 100 nm;

the glass substrate with the evaporated hole injection layer is transferred to a glove box filled with nitrogen, chlorobenzene solutions of the compound and the comparative compound are respectively spin-coated on the hole injection layer, the spin-coating rotation speed is 1000 rpm, the time is 60 seconds, the concentration of the compound and the comparative compound in a solvent is adjusted to enable the thickness of the obtained hole transmission layer to be 45-55 nm, then the glass substrate is placed at 80 ℃ for heating for 2 hours, the solvent is removed in vacuum, and the film thickness of the spin-coated hole transmission layer is measured by a step profiler (model Amibios XP-2surface profiler), and the following table shows the film thickness of the spin-coated hole transmission layer.

Transferring the glass substrate which is spin-coated with the hole transport layer into a vacuum chamber, and performing vacuum evaporation on the hole transport layer to obtain an EM1 (effective organic light emitting layer) serving as an organic light emitting layer of the device, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 30 nm;

The organic electroluminescent device properties are shown in table 2 below. And testing by using an OLED-1000 multichannel accelerated aging life and light color performance analysis system produced in Hangzhou distance.

TABLE 2

Device example 3

The compound of the present application was selected as a hole transport material in an organic electroluminescent device in the examples, and HT-1 was selected as a hole transport material in an organic electroluminescent device in the comparative examples.

The preparation process of the organic electroluminescent device is as follows:

respectively carrying out vacuum evaporation on the compound and the contrast material on the hole injection layer to form a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is shown in the following table;

The organic electroluminescent device properties are shown in table 3 below. And testing by using an OLED-1000 multichannel accelerated aging life and light color performance analysis system produced in Hangzhou distance.

TABLE 3

By the above data, when the compound is used as a hole transport layer of an organic electroluminescent device, when the film thickness of the hole transport layer changes, the voltage and current efficiency changes of the device are smaller than those of a contrast compound, so that when the compound is used for preparing the organic electroluminescent device, the influence on the performance of a product is smaller due to the fluctuation of a production process when the film thickness changes, the compound has higher adaptability, and the production process for preparing the organic electroluminescent device is easier to control.

Device example 4

The compound of the application is used as a green light host material in an organic electroluminescent device in the examples, and GH-1 and GH-2 are used as green light host materials in the organic electroluminescent device in the comparative examples.

The structure of the organic electroluminescent device is as follows: ITO/NPB (20 nm)/Green host Material (30 nm): ir (ppy)3[ 7% ]/TPBI (10nm)/Alq3(15nm)/LiF (0.5nm)/Al (150 nm). Wherein "Ir (ppy)3[ 7% ]" refers to the doping ratio of the green dye, i.e., the weight ratio of the green host material to Ir (ppy)3 is 100: 7.

The preparation process of the organic electroluminescent device is as follows: the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;

placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10^-5～9×10^-3Pa, vacuum evaporating a hole transport layer NPB on the anode layer film, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 20 nm;

vacuum evaporating a green light main material and a dye Ir (ppy)3 on the hole transport layer to be used as a light emitting layer of the organic electroluminescent device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 30 nm; (ii) a

Sequentially vacuum evaporating an electron transport layer TPBI and an electron transport layer Alq3 on the light-emitting layer, wherein the evaporation rates are both 0.1nm/s, and the evaporation film thicknesses are respectively 10nm and 15 nm;

and (3) evaporating LiF with the thickness of 0.5nm and Al with the thickness of 150nm on the electron transport layer in vacuum to be used as an electron injection layer and a cathode.

All the organic electroluminescent devices are prepared by the method, and the differences only lie in the selection of green light main body materials, and the details are shown in the following table 4.

And (3) performance testing:

the brightness, the driving voltage and the current efficiency of the prepared organic electroluminescent device are measured by using a Hangzhou remote production OLED-1000 multichannel accelerated aging life and photochromic performance analysis system test, and the test results are shown in the following table.

TABLE 4

As can be seen from the above table, compared to the comparative compound, the compound provided by the present application as a green host material of an organic electroluminescent device can improve the light emitting efficiency and reduce the driving voltage.

It will be apparent to those skilled in the art that various changes and modifications may be made in the embodiments of the present application without departing from the spirit and scope of the application. Thus, if such modifications and variations of the present application fall within the scope of the claims of the present application and their equivalents, the present application is intended to include such modifications and variations as well.

Claims

1. A compound is characterized in that the structural formula of the compound is shown as a formula (I),

R₁～R₄each independently selected from hydrogen, deuterium, F, CN, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aromatic group having 6 to 40 carbon atomsA group; the hydrogen in the aryl group containing 6-40 carbon atoms can be substituted by R;

Ar、Ar₁each independently selected from aromatic groups containing 6 to 40 carbon atoms, wherein hydrogen in the aromatic groups containing 6 to 40 carbon atoms can be substituted by R;

Ar₂one selected from the structures shown in A-1 to A-8:

R₅～R₁₄each independently selected from an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 40 carbon atoms; the hydrogen in the aryl group containing 6-40 carbon atoms can be substituted by R;

e, f are selected from 0 or 1, and e, f are not 0 at the same time;

2. A compound of claim 1, wherein R is₁～R₄When the alkyl group is an aryl group having 6 to 40 carbon atoms substituted with an alkyl group having 1 to 20 carbon atoms, the alkyl group having 1 to 20 carbon atoms may form a ring with a spirofluorene group.

3. The compound of claim 1, wherein the structure of the compound is selected from one of the following structures:

4. the compound of claim 3, wherein in the compounds II-1 to II-9, Ar₁Ar is selected from benzene, biphenyl, naphthalene, phenanthrene, fluorene, carbazole, dibenzofuran, dibenzothiophene, triphenylene, fluoranthene or Ar₂And Ar is₁The hydrogen in Ar can be substituted by alkyl with 1-20 carbon atoms and aryl with 6-40 carbon atoms.

5. The compound of claim 3, wherein in the compounds II-1 to II-9:

p is selected from 1;

Ar₁selected from benzene, biphenyl, naphthalene, phenanthrene, fluorene, carbazole, dibenzofuran, dibenzothiophene, triphenylene, fluoranthene, and Ar₁The hydrogen in the aromatic hydrocarbon can be substituted by an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms;

6. A compound according to claim 3, wherein in the compounds II-1 to II-9, p is selected from 0; ar (Ar)₁Selected from benzene, biphenyl, naphthalene, phenanthrene, fluorene, carbazole, dibenzofuran, dibenzothiophene, triphenylene, fluoranthene, and Ar₁The hydrogen in the aromatic hydrocarbon can be substituted by an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms.

7. The compound of claim 1, wherein said compound is selected from the group consisting of one of P-1 to P-108 and one of P-1 to P-108 structural isomers:

8. a compound intermediate, wherein the compound intermediate is selected from one of the following structures:

9. an organic electroluminescent device, characterized in that it comprises a compound according to any one of claims 1 to 7.

10. A display device comprising the organic electroluminescent device according to claim 9.