CN111217715A - Diarylamine substituted spirobifluorene compound and application thereof in OLED device - Google Patents

Diarylamine substituted spirobifluorene compound and application thereof in OLED device Download PDF

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CN111217715A
CN111217715A CN201811416425.5A CN201811416425A CN111217715A CN 111217715 A CN111217715 A CN 111217715A CN 201811416425 A CN201811416425 A CN 201811416425A CN 111217715 A CN111217715 A CN 111217715A
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CN111217715B (en
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钱晓春
蒋建兴
马培培
孙杰
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Changzhou Tronly New Electronic Materials Co Ltd
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Changzhou Tronly Eray Optoelectronics Material Co ltd
Changzhou Tronly New Electronic Materials Co Ltd
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Priority to PCT/CN2019/120526 priority patent/WO2020108422A1/en
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Abstract

The invention discloses an organic compound containing a diarylamine substituted spirobifluorene structure, which has a structure shown in a chemical formula (1). The compound has higher glass transition temperature, proper HOMO and LUMO energy levels, higher Eg (energy gap), high thermal stability, capability of sublimating under the conditions of no decomposition and no residue, good application effect in an OLED device, capability of effectively improving the luminous performance of the device and the service life of the device.

Description

Diarylamine substituted spirobifluorene compound and application thereof in OLED device
Technical Field
The invention belongs to the technical field of organic chemistry and photoelectric devices, and particularly relates to a compound containing a diarylamine substituted Spirobifluorene (9,9' -Spirobifluorene) structure and application thereof in an OLED device.
Background
Compared with the conventional Liquid Crystal Display (LCD) panel, the organic electroluminescent (OLED) device has the advantages of self-luminescence, high contrast, light weight, good color saturation, wide viewing angle, fast response speed, and the like, and is called as a third generation display. With the wide application of the OLED screen in smart phones, televisions and automobile electronic markets, the shipment of the OLED panel is in a rapidly increasing state, and the shipment of the LCD panel starts to go down a slope, so that many manufacturers mainly engaged in the production of the LCD panel stop production or even fall over. According to the latest data display of the HISMarkit, the sales volume of the liquid crystal display is reduced due to the fact that the smart phone market enters a lag period, and the good situation of the OLED display market is caused. The demand for OLEDs will continue to grow as many manufacturers will push flexible display devices to attract more buyers. The industrial prospect of the OLED is very wide in China, and enterprises in the industry are also striving to accumulate development experience, but factors such as a weak upstream link of an industrial chain in China and a lack of matching capability of the industry create a large development obstacle for manufacturers. With the increasing demand of the OLED, the development of the upstream link of the industrial chain is stimulated inevitably.
The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, the OLED device structure applied in industry generally comprises a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an emitting layer (EML), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL) and other various film layers, namely the photoelectric functional material applied to the OLED device at least comprises a hole injection material, a hole transport material, a light emitting material, an electron transport material and the like, and the material type and the matching form have the characteristics of richness and diversity. In addition, for the collocation of OLED devices with different structures, the used photoelectric functional material has stronger selectivity, and the performance of the same material in the devices with different structures can be completely different.
The fluorene compound has high thermal stability and chemical stability due to the rigid in-plane biphenyl unit, and has high fluorescence quantum efficiency in a solid state, so that the fluorene compound can be used in an OLED device to improve the thermal stability, morphological stability, carrier migration stability, good intersolubility and the like of materials. Spirobifluorene serving as a common fluorene derivative can be used as a luminescent material in an OLED device, and the structural advantages of spirobifluorene are utilized to improve the performance of the OLED device and prolong the service life of the OLED device.
Disclosure of Invention
The invention aims to provide an organic compound containing a diarylamine substituted spirobifluorene structure. The compound has higher glass transition temperature, proper HOMO and LUMO energy levels, higher Eg (energy gap), high thermal stability, capability of sublimating under the condition of no decomposition and no residue, good application effect in an OLED device, capability of effectively improving the luminous performance and the service life of the device, suitability for the OLED device of phosphorescence and fluorescence, and particularly the condition when the compound is used as a hole injection layer material and/or a hole transport layer material.
In order to achieve the above object, an organic compound containing a diarylamine-substituted spirobifluorene structure according to the present invention has a structure represented by the following chemical formula (1):
Figure BDA0001879582930000021
wherein the content of the first and second substances,
Ar1、Ar2、Ar3、Ar4each independently represents a substituted or unsubstituted aryl or heteroaryl group, and Ar1And Ar2Can pass through E1Are linked to each other to form a ring, Ar3And Ar4Can pass through E2Are connected with each other to form a ring;
E1and E2Each independently represents a direct bond, CRR ', NR, O or S, wherein R and R' each independently represents C1-C8Straight or branched alkyl of (2), C1-C8Alkoxy group of (C)7-C14Aralkyl group of (1);
S1and S2Each independently represents a direct bond, a substituted or unsubstituted arylene, a substituted or unsubstituted heteroarylene;
m and n each independently represent an integer of 0 to 3;
R1and R2Each independently represents hydrogen, deuterium, halogen, a nitrile group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted aralkenyl group, or a substituted or unsubstituted heterocyclic group;
provided that Ar is1(Ar2)N-(S1)m-and- (S)2)n-NAr3(Ar4) Different.
As a preferred embodiment of the present invention, S in the structure represented by formula (1)1、S2Is a direct bond, namely, N atoms on two sides are directly connected with a spirobifluorene structure, and the structure is shown as the following chemical formula (2):
Figure BDA0001879582930000031
further preferably, R1And R2All represent hydrogen, i.e., the structure is shown in the following chemical formula (3):
Figure BDA0001879582930000032
more preferably, in the structures represented by the above chemical formulae (1), (2) and (3), Ar1、Ar2、Ar3、Ar4Each independently has 6 to 60C atoms and each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl groupSubstituted or unsubstituted terphenyl group, substituted or unsubstituted quaterphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted phenanthryl group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted spirobifluorenyl group, substituted or unsubstituted dibenzothienyl group, substituted or unsubstituted dibenzofuranyl group, or substituted or unsubstituted carbazolyl group.
Particularly preferably, Ar1、Ar2、Ar3、Ar4Each independently selected from the following structures:
Figure BDA0001879582930000041
wherein the dotted line represents a linking site bonded to nitrogen; r3Each independently represents methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, cycloheptyl, n-octyl, phenyl, 4-tert-butylphenyl, cycloalkyl.
Without limitation, some preferred examples of the organic compounds of the present invention are listed below, including:
Figure BDA0001879582930000051
Figure BDA0001879582930000061
Figure BDA0001879582930000071
Figure BDA0001879582930000081
Figure BDA0001879582930000091
Figure BDA0001879582930000101
Figure BDA0001879582930000111
after determining the above-described organic compounds of the present invention and their structural characteristics, it is easy for those skilled in the art of organic chemistry to determine how to prepare the compounds. Typically, the target compound can be obtained by performing addition reaction on dihalofluorenone and bromobiphenyl, performing Buchwald-Hartwig coupling reaction (C-N coupling reaction) between the dihalofluorenone and the bromobiphenyl in sequence after cyclization, and introducing diarylamino groups step by step. Among these, the synthesis of dihalofluorenones is referred to the prior art, such as CN107075089A, which is incorporated herein by reference in its entirety.
Illustratively, the synthesis process is represented by the compound represented by the synthetic chemical formula (3):
Figure BDA0001879582930000121
bromo-biphenyl is added with dihalo-fluorenone A under the action of an N-butyllithium reagent to obtain intermediate alcohol B, the intermediate alcohol B is hydrolyzed and cyclized to generate dihalo-spirobifluorene C, and the dihalo-spirobifluorene C is coupled with different diarylamines through C-N coupling to obtain a mono-diarylamine substituted compound D and then obtain a target compound.
In addition, other similar processes based on the same reaction principles can also be used to synthesize the target compounds. E.g. for-NAr3(Ar4) The compound of formula (3) having a group at the 2-substituted position can also be synthesized by the following process:
Figure BDA0001879582930000122
bromo-fluorenone and diarylamine are subjected to C-N coupling to obtain mono-diarylamine substituted fluorenone, then the mono-diarylamine substituted fluorenone is reacted with NBS to obtain bromo-mono-diarylamine substituted fluorenone, … … is reacted with bromo-biphenyl under the action of an N-butyllithium reagent to obtain intermediate alcohol, the intermediate alcohol is hydrolyzed and cyclized to generate mono-diarylamine substituted bromo-spirobifluorene, and finally the intermediate alcohol and diarylamine are subjected to C-N coupling to obtain the target compound.
The invention also aims to provide application of the organic compound in an OLED device and the OLED device containing the organic compound.
As an exemplary embodiment, the OLED device includes: a first electrode; a second electrode disposed to face the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein one or more of the organic material layers comprise a compound represented by chemical formula (1).
The organic material layer may be formed of a single layer structure or a multi-layer structure in which two or more organic material layers are stacked. For example, the OLED device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like as organic material layers. The device structure is not limited thereto, and may include a smaller number of organic layers.
As an exemplary embodiment, the organic material layer includes a hole injection layer, and the hole injection layer includes the compound of formula (1).
As an exemplary embodiment, the organic material layer includes a hole injection layer including a compound of formula (1) and including a P-type dopant material doped at a doping concentration of 1 to 20 wt%, the P-type dopant material having a chemical structural formula as follows:
Figure BDA0001879582930000131
as an exemplary embodiment, the organic material layer includes a hole injection layer, a hole transport layer, and the hole transport layer includes the compound of formula (1).
As an exemplary embodiment, the organic material layer includes a hole injection layer, a hole transport layer, and when the hole transport layer includes the compound of formula (1), the hole injection layer uses only the compound HAT-CN having the following structural formula:
Figure BDA0001879582930000141
as an exemplary embodiment, the organic material layer further includes an electron blocking layer using a compound HT2 of the following chemical structure:
Figure BDA0001879582930000142
as an exemplary embodiment, the organic material layer further includes a light emitting layer, and the light emitting layer uses a compound EB as a host light emitter and a compound BD as a guest light emitter, wherein the doping ratio of the guest light emitter is 1 to 10 wt%, and the chemical structural formulas of both are as follows:
Figure BDA0001879582930000143
as an exemplary embodiment, the organic material layer further includes an electron transport layer using a compound ET of the following chemical structure and containing Lithium quinolate (abbreviated as LiQ) doped with 5 wt%:
Figure BDA0001879582930000151
as an exemplary embodiment, the organic material layer further includes an electron injection layer using a compound of lithium fluoride (LiF).
The OLED device of the present invention may be a top emission type, a bottom emission type, or a bi-directional emission type, depending on the material used.
The beneficial technical effects of the invention are as follows: when the organic compound is used for an OLED device, the compound has a large conjugated system, good rigidity coplanarity, high glass transition temperature and high thermal stability, so that the amorphous thin film of the compound can be prevented from being converted into a crystalline thin film, and the service life of the OLED device is prolonged. In addition, the compound has different HOMO and LOMO energy levels, and can be applied to different functional layers of an OLED device. Meanwhile, the compound provided by the invention has high triplet energy (characteristics of a spiro material), so that the device has better stability and service life.
Drawings
FIG. 1 is a schematic structural diagram of an OLED device in the characterization of device application performance; wherein the content of the first and second substances,
1. transparent substrate, 2, ITO anode layer, 3, hole injection layer, 4, hole transport layer, 5, electron blocking layer, 6, luminescent layer, 7, electron transport layer, 8, electron injection layer, 9, cathode layer.
Detailed Description
The invention is illustrated in more detail by the following examples, without wishing to be restricted thereby. On the basis of these teachings, the person skilled in the art will be able to carry out the invention and to prepare further compounds according to the invention within the full scope of the disclosure without inventive effort, and to use these compounds in electronic devices or to use the method according to the invention.
Preparation examples
Unless otherwise specified, reaction conditions not explicitly described in the following preparation examples may be carried out with reference to conditions suggested in the description of the apparatus or conditions conventional in the art, which are easily determined by those skilled in the art.
1. Synthesis of intermediates
1.1 Synthesis of intermediate C (homolateral substituted dihalospirobifluorenes)
Figure BDA0001879582930000161
(1) Example C1: synthesis of 2-bromo-6-chloro-9, 9' -spirobifluorene
Figure BDA0001879582930000162
Fully drying an experimental device, adding 35g of 2-bromo-1, 1' -biphenyl (152mmo1) and 400mL of dried tetrahydrofuran into a 1L four-neck flask under nitrogen, stirring to dissolve, cooling to below-78 ℃ by using liquid nitrogen, and slowly dropwise adding 61mL2.5M (152mmol) n-BuLi n-hexane solution; after the dropwise addition, the mixture was stirred at-78 ℃ for 1 hour, and then 45g (152mmo1) of 2-bromo-6-chloro-9-fluorenone solid was added in portions at that temperature, and after the addition, the mixture was kept at-78 ℃ for 1 hour, and then stirred at room temperature for 12 hours. After the reaction is finished, 4M hydrochloric acid solution is dripped to quench the reaction, ethyl acetate is used for extraction, the organic phase is washed by saturated saline solution, and the solvent is removed by spin drying to obtain intermediate alcohol B1.
In the absence of any purification, a 1L dry three-necked flask was charged with acetic acid 160mL and hydrochloric acid 5g 36%, and the reaction was terminated by heating and refluxing for 3 hours. After cooling to room temperature, filtration, washing twice with water, drying and purification by column chromatography gave 36.6g of off-white solid product C1 in 56% yield.
The structure of intermediate C1 was characterized and the results are shown below.
1H NMR(CDCl3,400MHz)δ:7.89(d,J＝7.5Hz,2H),7.83(s,1H),7.77(d,J＝8.1Hz,1H),7.61(s,1H),7.54(d,J＝7.5Hz,2H),7.44(d,J＝8.1Hz,1H),7.39-7.27(m,6H)；
IR(KBr)ν:3057,3028,1593,1516,1483,1450,1279,758,694cm-1；
MS[M+H]+＝428.99.
(2) Intermediate C2-C10
Referring to the preparation method of intermediate C1, intermediates C2-C10 were synthesized by using different starting materials. As shown in table 1 below.
TABLE 1
Figure BDA0001879582930000171
Figure BDA0001879582930000181
1.2 Synthesis of intermediate D (chloro spirobifluorene monosubstituted diaryl derivative)
Figure BDA0001879582930000191
(1) Example D1: synthesis of N- ([1,1 '-biphenyl-4-yl) -6-chloro-N- (9-9-dimethyl-9-fluoren-2-yl) -9,9' -spirobifluorenyl-2-amine ]
Figure BDA0001879582930000192
The experimental setup was dried thoroughly and 19.3g (45mmol) and 17.9g (49.5mmol) of N- [1,1 '-biphenyl-4-yl ] -9, 9-dimethyl-9H-fluoren-2-amine were added to a 500mL four-necked flask under nitrogen, dried and degassed toluene was added as solvent, 6.5g (67.5mmol) of sodium tert-butoxide, 1.2g (2.25mmol) of the catalyst 1,1' -bis (diphenylphosphino) ferrocene were added and the temperature was raised to 100-105 ℃ for 16H. After the reaction was complete, the reaction was cooled to room temperature, diluted with toluene, filtered over silica gel, and the filtrate was evaporated in vacuo to give a crude which was purified by column chromatography to give 18.6g of product D1 in 58% yield.
MS[M+H]+＝710.23。
(2)D2-D10
Referring to the preparation of intermediate D1, intermediates D2-D10 were synthesized by using different starting materials. Specifically, as shown in table 2 below.
TABLE 2
Figure BDA0001879582930000193
Figure BDA0001879582930000201
Figure BDA0001879582930000211
2. Synthesis of target Compound
Figure BDA0001879582930000212
The following examples prefer a portion of intermediate D to synthesize the corresponding target compound.
(1) Synthesis of compounds 1-192:
Figure BDA0001879582930000213
the experimental apparatus was thoroughly dried, and D1(32.0g, 45mmol) and 12.1g (49.5mmol) of N-phenyl-4-benzidine were added to a 500mL four-necked flask under nitrogen, dried and degassed toluene was added as a solvent, and 6.5g (67.5mmol) of sodium tert-butoxide, 0.88g (0.96mmol) of catalyst Pd were added2(dba)3The temperature is raised to 80 ℃, and 4.5mL of tri-tert-butylphosphine toluene solution with the mass concentration of 10 percent is slowly dropped. After the dropwise addition, the temperature is raised to 100-105 ℃ for reaction for 6 h. After the reaction is finished, cooling to room temperature, diluting with toluene, filtering with silica gel, evaporating the solvent from the filtrate in vacuum to obtain a crude product, and purifying the crude product by column chromatography to obtain 23.6g of products 1-192, wherein the yield is 57%.
The structural characterization data for the product compounds 1-192 are shown below.
1H NMR(CDCl3,400MHz)δ:7.90-7.84(m,5H),7.74(d,J＝7.5Hz,4H),7.61-7.54(m,8H),7.47(t,J＝7.5Hz,4H),7.41-7.35(m,10H),7.33-7.27(m,4H),7.25-7.20(m,3H),7.14(d,J＝7.5Hz,1H),7.09-7.04(m,4H),6.99(t,J＝7.5Hz,1H),1.68(s,6H)；
IR(KBr)ν:3067,3034,1595,1494,1468,1332,1273,807,761,696cm-1；
MS[M+H]+＝919.42.
(2) According to the preparation method of the compounds 1-192, D2-D10 and different diarylamines are used as raw materials to synthesize corresponding target compounds. As shown in table 3 below.
TABLE 3
Figure BDA0001879582930000221
Figure BDA0001879582930000231
Figure BDA0001879582930000241
Performance characterization
3. Physical properties of the compound
The thermal properties, HOMO level and LUMO level of the organic compounds of the present invention were tested using some of the compounds as examples. The detection target and the results thereof are shown in table 4.
TABLE 4
Compound (I) Tg(℃) Td(℃) HOMO(eV) LUMO(eV) Functional layer suitable for use
1-192 185 497 5.56 2.30 HIL，HTL
1-92 178 489 5.47 2.26 HIL，HTL
1-164 175 483 5.23 2.15 HIL，HTL，EBL
1-197 197 519 5.34 2.28 HIL，HTL
1-202 191 505 5.55 2.32 HIL，HTL
Wherein the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC25 differential scanning calorimeter of TA company in USA), and the heating rate is 10 ℃/min; the thermal weight loss temperature Td is the temperature at which 1% of weight is lost in a nitrogen atmosphere, and is measured on a TGA55 thermogravimetric analyzer of the company TA of America, and the nitrogen flow is 20 mL/min; the highest occupied molecular orbital HOMO energy level and the lowest unoccupied molecular orbital LUMO energy level are measured by cyclic voltammetry.
As can be seen from the data in Table 4, the compound of the present invention has a higher glass transition temperature, and can ensure the thermal stability of the compound, thereby preventing the amorphous thin film of the compound from being transformed into a crystalline thin film, and improving the lifetime of the OLED device containing the organic compound of the present invention. Meanwhile, the compound has different HOMO and LOMO energy levels, and can be applied to different functional layers of OLED devices.
OLED device applications
The organic compounds of the invention are particularly suitable for use in Hole Injection Layers (HILs), Hole Transport Layers (HTLs) and/or Electron Blocking Layers (EBLs) in OLED devices. They may be provided as individual layers or as mixed components in the HIL, HTL or EBL.
The effect of the organic compounds of the present invention as materials for different functional layers in OLED devices is detailed by examples 1-10 and comparative examples 1-2 in conjunction with FIG. 1.
The structural formula of the organic materials used therein is as follows, and they are all known compounds on the market and obtained from market purchase:
Figure BDA0001879582930000261
p-type doped material
Example 1
Referring to the structure shown in fig. 1, the OLED device is manufactured by the following specific steps: ultrasonically washing a glass substrate (Corning glass 50mm x 0.7mm) plated with ITO (indium tin oxide) with the thickness of 130nm with isopropanol and pure water for 5 minutes respectively, then cleaning with ultraviolet ozone, and then conveying the glass substrate into a vacuum deposition chamber; the hole injection material HAT-CN was evacuated to a thickness of 5nm (about 10 nm)-7Torr) thermal deposition on a transparent ITO electrode, thereby forming a hole injection layer; vacuum-depositing 110nm thick compounds 1 to 192 synthesized in the above preparation examples on the hole injection layer to form a hole transport layer; depositing HT2 with the thickness of 20nm on the hole transport layer in vacuum to form an electron blocking layer; as a light emitting layer, a host EB and 4% of a guest dopant BD were vacuum-deposited to a thickness of 25 nm; forming an electron transport layer using an ET compound comprising 5% doped LiQ (8-hydroxyquinoline lithium) to a thickness of 25 nm; finally, lithium fluoride (an electron injection layer) with the thickness of 1nm and aluminum with the thickness of 150nm are deposited in sequence to form a cathode; the device was transferred from the deposition chamber into a glove box and then encapsulated with a UV curable epoxy and a glass cover plate containing a moisture absorber to produce an OLED device.
In the above manufacturing steps, the deposition rates of the organic material, lithium fluoride and aluminum used were maintained at 0.1nm/s, 0.05nm/s and 0.2nm/s, respectively.
The resulting OLED device emitted blue light and had a light emitting area of 9 square millimeters.
Example 2
An experiment was performed in the same manner as in example 1 except that: as the hole transport layer, compounds 1 to 92 were used in place of compounds 1 to 192 in example 1.
Example 3
An experiment was performed in the same manner as in example 1 except that: as the hole transport layer, compounds 1 to 164 were used in place of compounds 1 to 192 in example 1.
Example 4
An experiment was performed in the same manner as in example 1 except that: as the hole transporting layer, compounds 1 to 197 were used in place of compounds 1 to 192 in example 1.
Example 5
An experiment was performed in the same manner as in example 1 except that: as the hole transporting layer, compounds 1 to 202 were used in place of compounds 1 to 192 in example 1.
Comparative example 1
An experiment was performed in the same manner as in example 1 except that: as the hole transport layer, HT1 was used instead of compounds 1 to 192 in example 1.
The structures of the OLED devices fabricated in examples 1 to 5 and comparative example 1 are shown in table 5, and the test results are shown in table 6.
TABLE 5
Figure BDA0001879582930000281
The devices obtained in examples 1 to 5 and comparative example 1 were mixed at 10mA/cm2And (5) carrying out performance test at the current density. Wherein the emission color is represented by CIEx,yJudging and defining chromaticity coordinates; the driving voltage is 1cd/m in luminance2Voltage of (d); current efficiency refers to the current per unit current densityBrightness; luminous efficiency refers to the luminous flux produced by consuming a unit of electric power; external Quantum Efficiency (EQE) refers to the ratio of the number of photons exiting the surface of the component in the observation direction to the number of injected electrons. LT97@1000nits refers to the time for the device to decrease from the initial luminance (100%) to 97% for more than 1000h of continuous use.
The results are shown in Table 6.
TABLE 6
Figure BDA0001879582930000291
As shown in the above table, the compounds used in examples 1 to 5, which were used as a hole transport layer in an OLED device, had excellent hole transport ability to exhibit low voltage and high efficiency characteristics, as compared to a benzidine-type material, and at the same time, exhibited better stability and lifetime based on high triplet energy (characteristics of a spiro ring material). It can be seen that the OLED device containing the invention has low driving voltage and long service life, and shows high-stability device performance.
To further verify the performance advantages of the present invention, OLED devices having the structure shown in table 7 were fabricated in the manner described above with reference to example 1.
TABLE 7
Figure BDA0001879582930000301
Compared with comparative example 2, the device manufacturing processes in examples 6 to 10 are completely the same, the same substrate and electrode material are used, the film thickness of the electrode material is also kept consistent, except that the hole injection material and the hole transport material in the device are replaced, and the hole injection layer is doped with 2 wt% of P-type doping material.
The devices obtained in examples 6 to 10 and comparative example 2 were mixed at 10mA/cm2And (5) carrying out performance test at the current density. The results are shown in Table 8.
TABLE 8
Figure BDA0001879582930000311
As shown in the above table, the compounds used in examples 6 to 10, which were used as a host material for a hole injection layer and a hole transport layer in an organic light emitting device, and a P-type dopant compound was doped in the hole injection layer, had superior hole transport ability and exhibited low voltage and high efficiency characteristics, and also exhibited better stability and lifetime, compared to a benzidine-type material. It can be seen that the organic light emitting device including the present invention has low driving voltage and long service life, and exhibits high-stability device performance.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (19)

1. An organic compound containing a diarylamine-substituted spirobifluorene structure, having a structure represented by the following chemical formula (1):
Figure FDA0001879582920000011
wherein the content of the first and second substances,
Ar1、Ar2、Ar3、Ar4each independently represents a substituted or unsubstituted aryl or heteroaryl group, and Ar1And Ar2Can pass through E1Are linked to each other to form a ring, Ar3And Ar4Can pass through E2Are connected with each other to form a ring;
E1and E2Each independently represents a direct bond, CRR ', NR, O or S, wherein R and R' each independently represents C1-C8Straight or branched alkyl of (2), C1-C8Alkoxy group of (C)7-C14Aralkyl group of (1);
S1and S2Each independently represents a direct bond, a warpSubstituted or unsubstituted arylene, substituted or unsubstituted heteroarylene;
m and n each independently represent an integer of 0 to 3;
R1and R2Each independently represents hydrogen, deuterium, halogen, a nitrile group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted aralkenyl group, or a substituted or unsubstituted heterocyclic group;
provided that Ar is1(Ar2)N-(S1)m-and- (S)2)n-NAr3(Ar4) Different.
2. The organic compound according to claim 1, having a structure represented by the following chemical formula (2):
Figure FDA0001879582920000021
3. the organic compound according to claim 1 or 2, characterized by having a structure represented by the following chemical formula (3):
Figure FDA0001879582920000022
4. an organic compound according to any one of claims 1 to 3, characterized in that: ar (Ar)1、Ar2、Ar3、Ar4Each independently having 6 to 60C atoms and each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted quaterphenyl group, a substituted or unsubstituted naphthyl groupA substituted or unsubstituted fluorenyl group, a substituted or unsubstituted spirobifluorenyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted carbazolyl group.
5. The organic compound of claim 4, wherein Ar is Ar1、Ar2、Ar3、Ar4Each independently selected from the following structures:
Figure FDA0001879582920000031
wherein the dotted line represents a linking site bonded to nitrogen; r3Each independently represents methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, cycloheptyl, n-octyl, phenyl, 4-tert-butylphenyl, cycloalkyl.
6. A method for producing the organic compound described in any one of claims 1 to 3, comprising: and (3) adding dihalofluorenone and brominated biphenyl, cyclizing, sequentially carrying out C-N coupling reaction with diarylamines with different structures, and introducing diarylamino groups step by step to obtain the target compound.
7. A method for producing the organic compound according to claim 3, comprising:
bromobiphenyl and dihalofluorenone A are added under the action of an N-butyllithium reagent to obtain an intermediate alcohol B, the intermediate alcohol B is hydrolyzed and cyclized to generate dihalogenated spirobifluorene C, and the dihalogenated spirobifluorene C and different diarylamines are subjected to C-N coupling to obtain a compound D substituted by the monodiallylamine and then obtain a target compound;
the synthesis process comprises the following steps:
Figure FDA0001879582920000041
8. a method for producing the organic compound according to claim 3, comprising:
carrying out C-N coupling on bromo-fluorenone and diarylamine to obtain mono-diarylamine substituted fluorenone, then reacting with NBS to obtain bromo-mono-diarylamine substituted fluorenone, then reacting with bromo-biphenyl under the action of an N-butyllithium reagent to obtain intermediate alcohol, hydrolyzing and cyclizing to generate mono-diarylamine substituted bromo-spirobifluorene, and finally carrying out C-N coupling on the bromo-diarylamine and diarylamine to obtain a target compound;
the synthesis process comprises the following steps:
Figure FDA0001879582920000042
9. use of an organic compound according to any one of claims 1 to 5 in an OLED device.
10. An OLED device comprising: a first electrode; a second electrode disposed to face the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein one or more of the organic material layers comprises the organic compound of any one of claims 1-5.
11. The OLED device of claim 10, wherein: the organic material layer includes a hole injection layer, and the hole injection layer contains the organic compound according to any one of claims 1 to 5.
12. The OLED device of claim 10, wherein: the organic material layer includes a hole injection layer comprising the organic compound of any one of claims 1 to 5, and comprising a P-type dopant material doped at a doping concentration of 1 to 20 wt%.
13. The OLED device of claim 10, wherein: the organic material layer includes a hole injection layer, a hole transport layer, and the hole transport layer contains the organic compound according to any one of claims 1 to 5.
14. The OLED device of claim 13, wherein the hole injection layer uses only the compound HAT-CN having the following structural formula:
Figure FDA0001879582920000051
15. the OLED device of any one of claims 10-14, wherein the organic material layer further comprises an electron blocking layer, the electron blocking layer being formed using the compound HT2 of the following chemical structure:
Figure FDA0001879582920000061
16. the OLED device according to any one of claims 10 to 14, wherein the organic material layer further includes a light-emitting layer, and the light-emitting layer uses compound EB as a host light-emitting body and compound BD as a guest light-emitting body, wherein the doping ratio of the guest light-emitting body is 1 to 10 wt%, and the chemical structures of both are as follows:
Figure FDA0001879582920000062
17. the OLED device according to any one of claims 10 to 14, characterized in that the organic material layer further comprises an electron transport layer, which uses compound ET of the following chemical structure and comprises quinoline lithium doped with 5% by weight:
Figure FDA0001879582920000071
18. the OLED device according to any one of claims 10 to 14, wherein the organic material layer further comprises an electron injection layer, and a compound used for the electron injection layer is lithium fluoride.
19. The OLED device of any one of claims 10-18, wherein: the OLED device is of a top emission type, a bottom emission type, or a bi-directional emission type.
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