CN106467551A - A kind of photoelectric material with equal benzene as core and its application - Google Patents

A kind of photoelectric material with equal benzene as core and its application Download PDF

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CN106467551A
CN106467551A CN201610797543.XA CN201610797543A CN106467551A CN 106467551 A CN106467551 A CN 106467551A CN 201610797543 A CN201610797543 A CN 201610797543A CN 106467551 A CN106467551 A CN 106467551A
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photoelectric material
luminescent device
oled
compound
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CN106467551B (en
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于凯朝
李崇
张兆超
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Jiangsu Sunera Technology Co Ltd
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Jiangsu Sanyue Optoelectronic Technology Co Ltd
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Abstract

The invention discloses a kind of photoelectric material with equal benzene as core and its application, this photoelectric material has higher triplet, higher glass transition temperature, good film forming stability and wider energy gap, it is used in organic luminescent device substantially reducing voltage as hole transport/electron-blocking materials or emitting layer material, improve device efficiency.The current efficiency of the device that application photoelectric material of the present invention is made, power efficiency and external quantum efficiency are all greatly improved；Lifted clearly simultaneously for device lifetime.

Description

A kind of photoelectric material with equal benzene as core and its application
Technical field
The present invention relates to optoelectronic materials technology, especially relate to one kind with equal benzene as core, the 1 of benzene, 3,5 difference The photoelectric material being connected with C-C key and C-N key side chain and its application on device.
Background technology
Compared with liquid crystal display (LCD), it is low that organic electroluminescence device (OLED) has driving voltage；Luminosity and send out Light efficiency is high；Luminous visual angle width, fast response time；In addition also ultra-thin, the advantages of being produced on flexible panel.For OLED Luminescent device proposes high performance research and includes：Reduce the driving voltage of device, improve the luminous efficiency of device, improve making of device With life-span etc..In order to realize the continuous lifting of the performance of OLED, not only need from OLED structure and processing technology Innovation, constantly studies with greater need for oled light sulfate ferroelectric functional material and innovates, formulate out the functional material of higher performance OLED.
The oled light sulfate ferroelectric functional material being applied to OLED can be divided into two big class from purposes, i.e. electric charge injection transmission Material and luminescent material, further, also can inject charge into transmission material and be divided into electron injection transmission material, electronic blocking material Luminescent material can also be divided into main body luminescent material and dopant material by material, hole injection transmission material and hole barrier materials.
In order to make high performance OLED luminescent device it is desirable to various organic functional material possesses good photoelectric characteristic, Such as, as charge transport materials it is desirable to have good carrier mobility, high-vitrification conversion temperature etc., as luminous The material of main part of layer requires material to have good bipolarity, suitable HOMO/LUMO energy level etc..
The oled light sulfate ferroelectric functional material film layer constituting OLED at least includes the above structure of two-layer, application in industry OLED structure, then include hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electronics biography Multiple film layer such as defeated layer, electron injecting layer is that is to say, that the photoelectric functional material being applied to OLED includes at least hole note Enter material, hole mobile material, luminescent material, electron injection material etc., material type and collocation form have rich and many The feature of sample.In addition, for the OLED of different structure is arranged in pairs or groups, the photoelectric functional material that used has stronger Selectivity, performance in different structure device for the identical material is it is also possible to completely totally different.
Therefore, for the industry application requirement of current OLED, and the difference in functionality film layer of OLED, device Photoelectric characteristic demand, it is necessary to select to be more suitable for, has high performance OLED functional material or combination of materials, just enables device The overall characteristic of high efficiency, long-life and low-voltage.For the actual demand that current OLED shows Lighting Industry, current OLED The development of material is also far from enough, lags behind the requirement of panel manufacturing enterprise, organic as material enterprise development higher performance The exploitation of functional material is particularly important.
Content of the invention
For prior art exist the problems referred to above, the applicant provide a kind of photoelectric material with equal benzene as core and Its application.In the present invention, the compound with equal benzene as core has a higher triplet, higher glass transition temperature, Good film forming stability and wider energy gap.Designed compound as hole mobile material, electron-blocking materials or luminous Layer material is used for substantially reducing voltage in organic luminescent device, improves device efficiency.
Technical scheme is as follows：
The applicant provides a kind of photoelectric material with equal benzene as core, the structure such as formula (1) of described photoelectric material Shown：
In formula (1),
X1For oxygen atom, sulphur atom, selenium atom, ethenylidene, C1-10The alkylidene of straight or branched alkyl replacement, alkyl One of or the tertiary amine groups of aryl replacement；
X2It is expressed as oxygen atom, sulphur atom, C1-10The alkylidene that straight or branched alkyl replaces, alkyl or aryl replace One of tertiary amine groups；
R1、R2Selection hydrogen independently or structure shown in formula (2)：
A isX3、X4It is respectively oxygen atom, sulphur atom, selenium atom, C1-10Straight chain or One of tertiary amine groups that the alkylidene of branched alkyl replacement, the alkylidene of aryl replacement, alkyl or aryl replace；
A passes through CL1-CL2Key, CL2-CL3Key or CL3-CL4On the bonded relevant position in formula (1)；Or a passes through CM1- CM2Key, CM2-CM3Key or CM3-CM4On the bonded relevant position in formula (1)；
Ar represents phenyl, C1-10Phenyl, dibiphenylyl, terphenyl, naphthyl or anthracene that straight or branched alkyl replaces Base.
Preferably, R in described formula (1)1、R2It is asynchronously hydrogen.
Preferably, the concrete structure formula of described photoelectric material is：
In any one.
The applicant additionally provides a kind of luminescent device containing described photoelectric material, and described photoelectric material passes as hole Defeated layer or electronic blocking layer material, for preparing OLED.
The applicant additionally provides another kind of luminescent device containing described photoelectric material, and described photoelectric material is as luminous Layer material, for preparing OLED.
The applicant additionally provides a kind of method preparing described photoelectric material, the reaction equation occurring in preparation process It is：
Specifically preparation process is：
(1) weigh 3- bromo- 5- chlorine aryl benzene withWith volume ratio for 1:1.0～1.5:1.0～ 1.5 toluene, the mixed solvent dissolving of second alcohol and water；Add Pd2(dba)3, sodium carbonate；Under an inert atmosphere, will be above-mentioned anti- Answer the mixed solution of thing in 75～80 DEG C of reaction temperature, react 10～24 hours, cooling, filtering reacting solution, filtrate revolving, mistake Silicagel column, obtains intermediate A；
Described 3- bromo- 5- chlorine aryl benzene withMol ratio be 1:1.0～1.5；Pd2(dba)3 The mol ratio of 5- chlorine aryl benzene bromo- with 3- is 0.006～0.04:1, sodium carbonate is 3.0 with the mol ratio of 3- bromo- 5- chlorine aryl benzene ～5.0:1；
(2) intermediate A withAs reaction substrate, with toluene as solvent；Add Pd2(dba)3, tertiary fourth Sodium alkoxide；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in 105～110 DEG C of reaction temperature, react 10～24 hours, Cooling, filtering reacting solution, filtrate revolving, cross silicagel column, obtain target product；
Described intermediate A withMol ratio be 1:1.0～1.5, Pd2(dba)3With intermediate A mole Than for 0.006～0.04:1, sodium tert-butoxide and intermediate A mol ratio are 1.0～1.5:1.
Beneficial the having technical effect that of the present invention：
With equal benzene as core, equal benzene-like compounds have a high-vitrification transition temperature to the compounds of this invention, good stability, Higher triplet.Designed compound is distributed in the 1 of benzene, 3,5, is replaced using three kinds of different branched groups, is formed Dissymmetrical structure, puies forward high molecular stability and triplet.Designed molecule has good cavity transmission ability, high by three Line state energy level, wide energy gap, and good heat stability.
Compound of the present invention is applied to OLED luminescent device as hole transport or electron-blocking materials and makes, permissible Obtain good device to show, the current efficiency of device, power efficiency and external quantum efficiency are all greatly improved；Meanwhile, right Lifted clearly in device lifetime.
Compound of the present invention is applied to OLED luminescent device as emitting layer material and makes, it is possible to obtain good device Part shows, the current efficiency of device, and power efficiency and external quantum efficiency are all greatly improved；Carry simultaneously for device lifetime Rise clearly.
The special construction of compound of the present invention designs so that material also has while having high decomposition temperature Low sublimation temperature or vacuum evaporation temperature, have higher temperature difference window between sublimation temperature or evaporation temperature and decomposition temperature Mouth, so that material has higher operation controllability in commercial Application, is applied beneficial to material volume production.
Compound of the present invention has good application effect in OLED luminescent device, before having good industrialization Scape.
Brief description
Fig. 1 is the device architecture schematic diagram using the compounds of this invention；
Wherein, 1 is transparent substrate layer, and 2 is ito anode layer, and 3 is hole injection layer, and 4 is hole transmission layer, and 5 is electronics resistance Barrier, 6 is luminescent layer, and 7 is electron transfer layer, and 8 is electron injecting layer, and 9 is negative electrode reflection electrode layer.
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is specifically described.
Embodiment 1：The synthesis of compound 3
(1) synthesis of intermediate
1- phenyl -3- chloro- 5- bromobenzene (3.5g, 10mmol), dibenzofurans -4- boric acid (2.3g, 11mmol), sodium carbonate (5.1g, 48mmol), Pd2(dba)3(0.4g, 0.4mmol), toluene, ethanol, each 50ml of water sequentially adds in reaction bulb, nitrogen The lower back flow reaction of protection 10 hours, is cooled to room temperature, point liquid, and aqueous layer with ethyl acetate extracts, and merges organic layer, uses saturation respectively Saline solution and washing, organic layer is dried with magnesium sulfate, filters, and filtrate is spin-dried for, and crosses silicagel column, obtains 3g product, HPLC purity 99.2%.
(2) synthesis of compound 3
Raw material S1 (3.5g, 10.0mmol), raw material S2 (3.1g, 10.2mmol) add in reaction bulb, sodium tert-butoxide (1.2g, 12mmol), Pd2(dba)3(0.1g, 0.1mmol), toluene 50ml sequentially adds in reaction bulb, and nitrogen protection is lower to flow back Reaction 10 hours, is cooled to room temperature, addition 100ml water, point liquid, aqueous layer with ethyl acetate extracts, and merges organic layer, respectively with satisfying With saline solution and washing, organic layer is dried with magnesium sulfate, filters, and filtrate is spin-dried for, and crosses silicagel column, obtains 2.9g product, HPLC is pure Degree 99.5%.
Identify this compound, molecular formula C using DEI-MS45H31NO2, detected value [M+1]+=617.40, value of calculation 617.24.
Embodiment 2：The synthesis of compound 9
(1) synthesis of intermediate
1- phenyl -3- chloro- 5- bromobenzene (3.5g, 10mmol), dibenzofurans -4- boric acid (2.3g, 11mmol), sodium carbonate (5.1g, 48mmol), Pd2(dba)3(0.4g, 0.4mmol), toluene, ethanol, each 50ml of water sequentially adds in reaction bulb, nitrogen The lower back flow reaction of protection 10 hours, is cooled to room temperature, point liquid, and aqueous layer with ethyl acetate extracts, and merges organic layer, uses saturation respectively Saline solution and washing, organic layer is dried with magnesium sulfate, filters, and filtrate is spin-dried for, and crosses silicagel column, obtains 3g product, HPLC purity 99.2%
(2) synthesis of compound 9
Raw material S1 (3.5g, 10.0mmol), raw material S3 (3.1g, 10.2mmol) add in reaction bulb, sodium tert-butoxide (1.2g, 12mmol), Pd2(dba)3(0.1g, 0.1mmol), toluene 50ml sequentially adds in reaction bulb, and nitrogen protection is lower to flow back Reaction 10 hours, is cooled to room temperature, addition 100ml water, point liquid, aqueous layer with ethyl acetate extracts, and merges organic layer, respectively with satisfying With saline solution and washing, organic layer is dried with magnesium sulfate, filters, and filtrate is spin-dried for, and crosses silicagel column, obtains 2.8g product, HPLC is pure Degree 99.6%.
Identify this compound, molecular formula C using DEI-MS45H31NO2, detected value [M+1]+=617.36, value of calculation 617.24.
Embodiment 3：The synthesis of compound 12
(1) synthesis of intermediate
1- phenyl -3- chloro- 5- bromobenzene (3.5g, 10mmol), dibenzofurans -4- boric acid (2.3g, 11mmol), sodium carbonate (5.1g, 48mmol), Pd2(dba)3(0.4g, 0.4mmol), toluene, ethanol, each 50ml of water sequentially adds in reaction bulb, nitrogen The lower back flow reaction of protection 10 hours, is cooled to room temperature, point liquid, and aqueous layer with ethyl acetate extracts, and merges organic layer, uses saturation respectively Saline solution and washing, organic layer is dried with magnesium sulfate, filters, and filtrate is spin-dried for, and crosses silicagel column, obtains 3g product, HPLC purity 99.2%
(2) synthesis of compound 12
Raw material S1 (3.5g, 10.0mmol), raw material S4 (3.1g, 10.2mmol) add in reaction bulb, sodium tert-butoxide (1.2g, 12mmol), Pd2(dba)3(0.1g, 0.1mmol), toluene 50ml sequentially adds in reaction bulb, and nitrogen protection is lower to flow back Reaction 10 hours, is cooled to room temperature, addition 100ml water, point liquid, aqueous layer with ethyl acetate extracts, and merges organic layer, respectively with satisfying With saline solution and washing, organic layer is dried with magnesium sulfate, filters, and filtrate is spin-dried for, and crosses silicagel column, obtains 3.0g product, HPLC is pure Degree 99.5%.
Identify this compound, molecular formula C using DEI-MS45H31NO2, detected value [M+1]+=617.30, value of calculation 617.24.
Embodiment 4：The synthesis of compound 24
(1) synthesis of intermediate
1- phenyl -3- chloro- 5- bromobenzene (3.5g, 10mmol), dibenzofurans -4- boric acid (2.3g, 11mmol), sodium carbonate (5.1g, 48mmol), Pd2(dba)3(0.4g, 0.4mmol), toluene, ethanol, each 50ml of water sequentially adds in reaction bulb, nitrogen The lower back flow reaction of protection 10 hours, is cooled to room temperature, point liquid, and aqueous layer with ethyl acetate extracts, and merges organic layer, uses saturation respectively Saline solution and washing, organic layer is dried with magnesium sulfate, filters, and filtrate is spin-dried for, and crosses silicagel column, obtains 3g product, HPLC purity 99.2%
(2) synthesis of compound 24
Raw material S1 (3.5g, 10.0mmol), raw material S5 (3.1g, 10.2mmol) add in reaction bulb, sodium tert-butoxide (1.2g, 12mmol), Pd2(dba)3(0.1g, 0.1mmol), toluene 50ml sequentially adds in reaction bulb, and nitrogen protection is lower to flow back Reaction 10 hours, is cooled to room temperature, addition 100ml water, point liquid, aqueous layer with ethyl acetate extracts, and merges organic layer, respectively with satisfying With saline solution and washing, organic layer is dried with magnesium sulfate, filters, and filtrate is spin-dried for, and crosses silicagel column, obtains 2.7g product, HPLC is pure Degree 99.6%.
Identify this compound, molecular formula C using DEI-MS45H31NO2, detected value [M+1]+=617.38, value of calculation 617.24.
Embodiment 5：The synthesis of compound 33
(1) synthesis of intermediate
1- phenyl -3- chloro- 5- bromobenzene (3.5g, 10mmol), dibenzothiophenes -4- boric acid (2.5g, 11mmol), sodium carbonate (5.1g, 48mmol), Pd2(dba)3(0.4g, 0.4mmol), toluene, ethanol, each 50ml of water sequentially adds in reaction bulb, nitrogen The lower back flow reaction of protection 10 hours, is cooled to room temperature, point liquid, and aqueous layer with ethyl acetate extracts, and merges organic layer, uses saturation respectively Saline solution and washing, organic layer is dried with magnesium sulfate, filters, and filtrate is spin-dried for, and crosses silicagel column, obtains 3.1g product, HPLC purity 99.4%.
(2) synthesis of compound 33
Raw material S6 (3.7g, 10.0mmol), raw material S7 (2.8g, 10.2mmol) add in reaction bulb, sodium tert-butoxide (1.2g, 12mmol), Pd2(dba)3(0.1g, 0.1mmol), toluene 50ml sequentially adds in reaction bulb, and nitrogen protection is lower to flow back Reaction 10 hours, is cooled to room temperature, addition 100ml water, point liquid, aqueous layer with ethyl acetate extracts, and merges organic layer, respectively with satisfying With saline solution and washing, organic layer is dried with magnesium sulfate, filters, and filtrate is spin-dried for, and crosses silicagel column, obtains 2.7g product, HPLC is pure Degree 99.5%.
Identify this compound, molecular formula C using DEI-MS42H25NO2S, detected value [M+1]+=607.24, value of calculation 607.16.
Embodiment 6：The synthesis of compound 44
Synthetic route：
Referring in particular to embodiment 4, difference is to be replaced with raw material dibenzothiophenes -4- boric acid the synthetic method of compound 44 Change dibenzofurans -4- boric acid.
Embodiment 7：The synthesis of compound 63
Synthetic route：
Referring in particular to embodiment 1, difference is with raw material 3- boric acid -9,9- dimethyl fluorene the synthetic method of compound 63 Replace dibenzofurans -4- boric acid, with raw material 6,6- dimethyl -6,11- dihydro -13- oxa- -11- azepine-indole [1,2-b] Anthracene replaces 8,8- dimethyl -5,8- dihydro -13- oxa- -5- azepine-indole [1,2-a] anthracene.
Embodiment 8：The synthesis of compound 92
Synthetic route：
Referring in particular to embodiment 1, difference is with raw material 6,6- dimethyl -6,11- bis- synthetic method of compound 92 Hydrogen -13- oxa- -11- azepine-indole [1,2-b] anthracene replaces 8,8- dimethyl -5,8- dihydro -13- oxa- -5- azepine-indole [1,2-a] anthracene, substitutes the chloro- 5- bromobenzene of 1- phenyl -3- with the bromo- 5- of raw material 3- chloro- [1,1 ', 2 ', 1 "] terphenyl.
Embodiment 9：The synthesis of compound 96
Synthetic route：
Referring in particular to embodiment 1, difference is with raw material 13,13- dimethyl -5,13- the synthetic method of compound 96 Dihydro -8- oxa- -5- azepine-indole [1,2-a] anthracene replaces 8,8- dimethyl -5,8- dihydro -13- oxa- -5- azepine-indole [1,2-a] anthracene, substitutes the chloro- 5- bromobenzene of 1- phenyl -3- with the bromo- 5- of raw material 3- chloro- [1,1 ', 2 ', 1 "] terphenyl, uses raw material hexichol Bithiophene -4- boric acid replaces dibenzofurans -4- boric acid.
Embodiment 10：The synthesis of compound 98
Synthetic route：
Referring in particular to embodiment 2, difference is with raw material 2- (3- bromo- 5- chlorphenyl) naphthalene the synthetic method of compound 98 Replace the chloro- 5- bromobenzene of 1- phenyl -3-.
The compounds of this invention uses in luminescent device, can be as hole transport/electronic blocking layer material it is also possible to make Use for luminescent layer material of main part.The compounds of this invention has high operability and practicality in application, is mainly reflected in There is high glass transition temperature, low sublimation temperature, high decomposition temperature and film forming stability.
Hot property and the test of HOMO energy level are carried out to the compounds of this invention 3, compound 24, current material TCTA, measures Result is as shown in table 1.
Table 1
Note：Vitrification point Tg is by differential scanning calorimetry (DSC, German Nai Chi company DSC204F1 differential scanning calorimetry Instrument) measure, 10 DEG C/min of heating rate；Evaporation temperature is using SUNIC evaporated device, vacuum ＜ 1E-5Pa, material rate ForWhen evaporation temperature；Thermal weight loss temperature Td is in nitrogen atmosphere weightless 1% temperature, in Japanese Shimadzu Corporation It is measured on TGA-50H thermogravimetric analyzer, nitrogen flow is 20mL/min；Film forming stability refers to, using SUNIC evaporator Platform, is deposited with to glass substrate 100nm thickness thin film material, envelope in glove box environment (water oxygen content equal ＜ 1PPm) Dress, after encapsulation, glass sample under the conditions of double 80 (humidity 80%, 80 DEG C of temperature) places test 240 hours, uses micro- sem observation The crystal property of sample film；Highest occupied molecular orbital HOMO energy level and minimum occupied molecular orbital lumo energy are by photoelectron Transmitting spectrometer (AC-2 type PESA) test, tests as atmospheric environment.
From upper table data, the compounds of this invention has adjustable HOMO energy level, is suitable as difference in functionality layer material Use；Low evaporation temperature can make material in commercial Application, reduces heat radiation to Fine-mask influence of crust deformation in evaporation board, Improve OLED PPI grade, improve producing line yield；High film forming stability energy, ensure that material is being applied to OLED device During use after part, keep film morphology, do not formed local-crystalized, cause device electrode short circuit, improving OLED makes Use the life-span；
Hereinafter, by the compound that embodiment 11～20 and comparative example 1 describe present invention synthesis in detail be used as hole transport/ Application effect on device for the electronic barrier layer.Embodiment 12～20 with comparative example 1 compared with embodiment 11, the system of described device Make technique identical, and employed identical baseplate material and electrode material, the thickness of electrode material is also consistent, Except that the portion of material used in device has been carried out with some adjustment.The performance test knot of each embodiment obtained device Fruit is as shown in table 2.
Embodiment 11
Photoetching and etching are carried out to the ito anode layer 2 (thickness of ito anode layer 2 is 220nm) with transparent substrate layer 1, Form the figure of the ito anode layer 2 of rule needing, immediately above-mentioned glass transparent substrate layer 1 is washed, carry out successively Neutralizing treatment, pure water, be dried after carry out again ultraviolet-ozone wash to remove the organic residue on ito anode layer 2 surface.
On the ito anode layer 2 having carried out after above-mentioned washing, using vacuum deposition apparatus (molybdenum crucible, evaporation rate 0.1nm/s, vacuum about 5.0x10-5Pa), evaporation, as the NPB of hole-injecting material, makes the layer that thickness is 60nm, this layer For hole injection layer 3.
On hole injection layer 3, by vacuum deposition apparatus, (molybdenum crucible, evaporation rate 0.1nm/s, vacuum is about 5.0x10-5Pa), evaporation structural compounds material (TAPC), its thickness is 10nm, and this layer of organic material is as luminescent device Hole transmission layer 4 uses.
On hole transmission layer 4, by vacuum deposition apparatus, (molybdenum crucible, evaporation rate 0.1nm/s, vacuum is about 5.0x10-5Pa), evaporation embodiment 1 structural compounds material (compound 3), its thickness is 10nm, this layer of organic material conduct The electronic barrier layer 5 of luminescent device uses.
After above-mentioned electron-blocking materials, make the luminescent layer 6 of OLED luminescent device, its structure includes OLED luminescent layer institute It is used material C BP as material of main part, phosphorescence dopant material is Ir (PPy) 3, phosphor material doping ratio is 7% weight ratio, sends out Photosphere thickness is 30nm.
After above-mentioned luminescent layer, continue vacuum evaporation and made OLED luminescent device electron transfer layer, this electric transmission Layer material is TPBI.The vacuum evaporation thickness of this material is 30nm, and this layer is electron transfer layer 7.
On electron transfer layer 7, by vacuum deposition apparatus, make lithium fluoride (LiF) layer that thickness is 1nm, this layer is Electron injecting layer 8.
On electron injecting layer 8, by vacuum deposition apparatus, make aluminum (Al) layer that thickness is 150nm, this layer is reflection Electrode layer 9 uses.
In embodiment, common used material structural formula used is as follows：
After OLED luminescent device accomplished as described above, with known drive circuit, anode and negative electrode are coupled together, survey The I-E characteristic of the luminous efficiency of metering device, luminescent spectrum and device.The measurement of the above-mentioned device characteristics of luminescence adopts brightness Degree determinator (Co., Ltd.'s TOPCON system, trade name BM7) measures.Its test result is as shown in table 2.
Embodiment 12
The present embodiment is with embodiment 11 difference：OLED luminescent device electron-blocking materials change into embodiment 2 The material (compound 9) of described structure.The test result of made OLED luminescent device is shown in Table 2.
Embodiment 13
The present embodiment is with embodiment 11 difference：OLED luminescent device electron-blocking materials change into embodiment 3 The material (compound 12) of described structure.The test result of made OLED luminescent device is shown in Table 2.
Embodiment 14
The present embodiment is with embodiment 11 difference：OLED luminescent device electron-blocking materials change into embodiment 4 The material (compound 24) of described structure.The test result of made OLED luminescent device is shown in Table 2.
Embodiment 15
The present embodiment is with embodiment 11 difference：OLED luminescent device electron-blocking materials change into embodiment 5 The material (compound 33) of described structure.The test result of made OLED luminescent device is shown in Table 2.
Embodiment 16
The present embodiment is with embodiment 11 difference：OLED luminescent device electron-blocking materials change into embodiment 6 The material (compound 44) of described structure.The test result of made OLED luminescent device is shown in Table 2.
Embodiment 17
The present embodiment is with embodiment 11 difference：OLED luminescent device electron-blocking materials change into embodiment 7 The material (compound 63) of described structure.The test result of made OLED luminescent device is shown in Table 2.
Embodiment 18
The present embodiment is with embodiment 11 difference：OLED luminescent device electron-blocking materials change into embodiment 8 The material (compound 92) of described structure.The test result of made OLED luminescent device is shown in Table 2.
Embodiment 19
The present embodiment is with embodiment 11 difference：OLED luminescent device electron-blocking materials change into embodiment 9 The material (compound 96) of described structure.The test result of made OLED luminescent device is shown in Table 2.
Embodiment 20
The present embodiment is with embodiment 11 difference：OLED luminescent device electron-blocking materials change into embodiment 10 The material (compound 98) of described structure.The test result of made OLED luminescent device is shown in Table 2.
Comparative example 1
Comparative example 1 with embodiment 11 except that：The electron-blocking materials of OLED luminescent device are by the structure of embodiment 1 Compound changes following structural formula electron-blocking materials TCTA into；The test result of made OLED luminescent device is shown in Table 2.
Table 2
Device code name Luminous efficiency Color CIE coordinate (x；y) The LT95 life-span
Embodiment 11 1.3 Green glow 0.34,0.62 1.6
Embodiment 12 1.2 Green glow 0.35,0.61 1.4
Embodiment 13 1.4 Green glow 0.35,0.62 1.5
Embodiment 14 1.3 Green glow 0.33,0.63 1.4
Embodiment 15 1.4 Green glow 0.34,0.64 1.5
Embodiment 16 1.2 Green glow 0.35,0.64 1.3
Embodiment 17 1.3 Green glow 0.34,0.63 1.4
Embodiment 18 1.3 Green glow 0.34,0.62 1.4
Embodiment 19 1.3 Green glow 0.34,0.62 1.3
Embodiment 20 1.4 Green glow 0.35,0.65 1.4
Comparative example 1 1 Green glow 0.33,0.63 1
Note：Luminous efficiency and driving life-span are on the basis of comparative example 1.Comparative example 1 luminous efficiency is 60.2cd/A, the LT95 longevity Order as 6.8 hours, chromaticity coordinates (0.33,0.63).
Compound of the present invention be can be seen that by the result of table 2 and can be applicable to the making of OLED luminescent device, and permissible Obtain good performance, embodiment 1 arrives material described in embodiment 10 as the electron-blocking materials of OLED luminescent device no matter It is efficiency or life-span all ratio known OLED material larger changes of acquisition, the life-span that drives of particularly device obtains larger proposing Rise.The compounds of this invention has good application effect as electron-blocking materials in OLED luminescent device, has good Industrialization prospect.
Above-described electron-blocking materials also have the performance of hole transport, usual in some those skilled in the art Occasion, often calls it " electronic blocking/hole transport " material.
Hereinafter, luminescent layer material is used as by the compound that embodiment 21～27 and comparative example 2 describe present invention synthesis in detail Application effect on device for the material., with comparative example 2 compared with embodiment 21, the processing technology of described device is complete for embodiment 22～27 Exactly the same, and employed identical baseplate material and electrode material, the thickness of electrode material is also consistent, different It is that the portion of material used in device has been carried out with some adjustment.
Embodiment 21
Photoetching and etching are carried out to the ito anode layer 2 (thickness of ito anode layer 2 is 220nm) with transparent substrate layer 1, Form the figure of the ito anode layer 2 of rule needing, immediately above-mentioned glass transparent substrate layer 1 is washed, carry out successively Neutralizing treatment, pure water, be dried after carry out again ultraviolet-ozone wash to remove the organic residue on ito anode layer 2 surface.
On the ito anode layer 2 having carried out after above-mentioned washing, using vacuum deposition apparatus (molybdenum crucible, evaporation rate 0.1nm/s, vacuum about 5.0x10-5Pa), evaporation, as the NPB of hole-injecting material, makes the layer that thickness is 60nm, this layer For hole injection layer 3.
On hole injection layer 3, by vacuum deposition apparatus, (molybdenum crucible, evaporation rate 0.1nm/s, vacuum is about 5.0x10-5Pa), it is deposited with structural compounds material TAPC, its thickness is 10nm, and this layer of organic material is as the sky of luminescent device Cave transport layer 4 uses.
On hole transmission layer 4, by vacuum deposition apparatus, (molybdenum crucible, evaporation rate 0.1nm/s, vacuum is about 5.0x10-5Pa), it is deposited with compound-material TCTA, its thickness is 10nm, this layer of organic material hinders as the electronics of luminescent device Barrier 5 uses.
After above-mentioned electronic blocking layer material, make the luminescent layer 6 of OLED luminescent device, its structure includes OLED luminescent layer In used material C BP and embodiment 1, as material of main part, ratio is 7 to compound 3:3 weight ratios, phosphorescence dopant material is Ir (PPy) 3, phosphor material doping ratio is 7% weight ratio, and luminescent layer thickness is 30nm.
After above-mentioned luminescent layer, continue vacuum evaporation and made OLED luminescent device electron transfer layer, this electric transmission Layer material is TPBI.The vacuum evaporation thickness of this material is 30nm, and this layer is electron transfer layer 7.
On electron transfer layer 7, by vacuum deposition apparatus, make lithium fluoride (LiF) layer that thickness is 1nm, this layer is Electron injecting layer 8.
On electron injecting layer 8, by vacuum deposition apparatus, make aluminum (Al) layer that thickness is 150nm, this layer is reflection Electrode layer 9 uses.
In embodiment, common used material structural formula used is as follows：
After OLED luminescent device accomplished as described above, with known drive circuit, anode and negative electrode are coupled together, survey The I-E characteristic of the luminous efficiency of metering device, luminescent spectrum and device.The measurement of the above-mentioned device characteristics of luminescence adopts brightness Degree determinator (Co., Ltd.'s TOPCON system, trade name BM7) measures.Its test result is as shown in table 3.
Embodiment 22
The present embodiment is with embodiment 21 difference：OLED luminescent device luminescent layer material of main part change into CBP and The material (compound 9) of structure described in embodiment 2, weight is than for 7:3.The test result of made OLED luminescent device is shown in Table 3.
Embodiment 23
The present embodiment is with embodiment 21 difference：OLED luminescent device luminescent layer material of main part change into CBP and The material (compound 12) of structure described in embodiment 3, weight is than for 7:3.The test result of made OLED luminescent device is shown in Table 3.
Embodiment 24
The present embodiment is with embodiment 21 difference：OLED luminescent device luminescent layer material of main part change into CBP and The material (compound 24) of structure described in embodiment 4, weight is than for 7:3.The test result of made OLED luminescent device is shown in Table 3.
Embodiment 25
The present embodiment is with embodiment 21 difference：OLED luminescent device luminescent layer material of main part change into CBP and The material (compound 33) of structure described in embodiment 5, weight is than for 7:3.The test result of made OLED luminescent device is shown in Table 3.
Embodiment 26
The present embodiment is with embodiment 21 difference：OLED luminescent device luminescent layer material of main part change into CBP and The material (compound 44) of structure described in embodiment 6, weight is than for 7:3.The test result of made OLED luminescent device is shown in Table 3.
Embodiment 27
The present embodiment is with embodiment 21 difference：OLED luminescent device luminescent layer material of main part change into CBP and The material (compound 63) of structure described in embodiment 7, weight is than for 7:3.The test result of made OLED luminescent device is shown in Table 3.
Comparative example 2
Comparative example 2 with embodiment 21 except that：The luminescent layer material of main part of OLED luminescent device is single CBP； The test result of made OLED luminescent device is shown in Table 3.
Table 3
Device code name Luminous efficiency Color CIE coordinate (x；y) The LT95 life-span
Embodiment 21 1.5 Green glow 0.34,0.62 1.6
Embodiment 22 1.4 Green glow 0.35,0.61 1.4
Embodiment 23 1.3 Green glow 0.35,0.62 1.7
Embodiment 24 1.5 Green glow 0.33,0.63 1.4
Embodiment 25 1.4 Green glow 0.34,0.64 1.5
Embodiment 26 1.5 Green glow 0.35,0.64 1.6
Embodiment 27 1.3 Green glow 0.34,0.63 1.4
Comparative example 2 1 Green glow 0.33,0.63 1
Note：Luminous efficiency and driving life-span are on the basis of comparative example 2.Comparative example 2 luminous efficiency is 60.2cd/A, the LT95 longevity Order as 6.8 hours, chromaticity coordinates (0.33,0.63).
Compound of the present invention be can be seen that by the result of table 3 and can be applicable to the making of OLED luminescent device, and permissible Obtain good performance, embodiment 21 arrives material described in the embodiment 27 and CBP luminescent layer collectively as OLED luminescent device Material of main part, either efficiency or life-span all ratio known OLED material larger changes of acquisition, the particularly driving life-span of device Obtain larger lifting.The compounds of this invention has good application effect as luminescent layer material of main part in OLED luminescent device Really, there is good industrialization prospect.
Hereinafter, luminescent layer is used as by the compound that embodiment 28～30 and comparative example 3 describe present invention synthesis in detail auxiliary Help application effect on device for the material of main part.Embodiment 29～30 with comparative example 3 compared with embodiment 28, the system of described device Make technique identical, and employed identical baseplate material and electrode material, the thickness of electrode material is also consistent, Except that the portion of material used in device has been carried out with some adjustment.
Embodiment 28
Photoetching and etching are carried out to the ito anode layer 2 (thickness of ito anode layer 2 is 220nm) with transparent substrate layer 1, Form the figure of the ito anode layer 2 of rule needing, immediately above-mentioned glass transparent substrate layer 1 is washed, carry out successively Neutralizing treatment, pure water, be dried after carry out again ultraviolet-ozone wash to remove the organic residue on ito anode layer 2 surface.
On the ito anode layer 2 having carried out after above-mentioned washing, using vacuum deposition apparatus (molybdenum crucible, evaporation rate 0.1nm/s, vacuum about 5.0x10-5Pa), evaporation, as the NPB of hole-injecting material, makes the layer that thickness is 60nm, this layer For hole injection layer 3.
On hole injection layer 3, by vacuum deposition apparatus, (molybdenum crucible, evaporation rate 0.1nm/s, vacuum is about 5.0x10-5Pa), it is deposited with structural compounds material TAPC, its thickness is 10nm, and this layer of organic material is as the sky of luminescent device Cave transport layer 4 uses.
On hole transmission layer 4, by vacuum deposition apparatus, (molybdenum crucible, evaporation rate 0.1nm/s, vacuum is about 5.0x10-5Pa), it is deposited with compound-material TCTA, its thickness is 10nm, this layer of organic material hinders as the electronics of luminescent device Barrier 5 uses.
After above-mentioned electronic blocking layer material, make the luminescent layer 6 of OLED luminescent device, its structure includes OLED luminescent layer As compound 92 in material of main part and embodiment 8 as co-host material, ratio is 5 to used material H1:5 weight ratios, Phosphorescence dopant material is Ir (PPy) 3, and phosphor material doping ratio is 12% weight ratio, and luminescent layer thickness is 30nm.
After above-mentioned luminescent layer, continue vacuum evaporation and made OLED luminescent device electron transfer layer, this electric transmission Layer material is TPBI.The vacuum evaporation thickness of this material is 30nm, and this layer is electron transfer layer 7.
On electron transfer layer 7, by vacuum deposition apparatus, make lithium fluoride (LiF) layer that thickness is 1nm, this layer is Electron injecting layer 8.
On electron injecting layer 8, by vacuum deposition apparatus, make aluminum (Al) layer that thickness is 150nm, this layer is reflection Electrode layer 9 uses.
In embodiment, common used material structural formula used is as follows：
After OLED luminescent device accomplished as described above, with known drive circuit, anode and negative electrode are coupled together, survey The I-E characteristic of the luminous efficiency of metering device, luminescent spectrum and device.The measurement of the above-mentioned device characteristics of luminescence adopts brightness Degree determinator (Co., Ltd.'s TOPCON system, trade name BM7) measures.Its test result is as shown in table 4.
Embodiment 29
The present embodiment is with embodiment 28 difference：OLED luminescent device luminescent layer co-host material changes embodiment The material (compound 96) of structure described in 9.The test result of made OLED luminescent device is shown in Table 4.
Embodiment 30
The present embodiment is with embodiment 28 difference：OLED luminescent device luminescent layer co-host material changes embodiment The material (compound 98) of structure described in 10.The test result of made OLED luminescent device is shown in Table 4.
Comparative example 3
Comparative example 3 with embodiment 28 except that：The luminescent layer co-host material of OLED luminescent device is changed to following Structural formula H2；The test result of made OLED luminescent device is shown in Table 4.
Table 4
Device code name Luminous efficiency Color CIE coordinate (x；y) The LT95 life-span
Embodiment 28 1.5 Green glow 0.34,0.62 1.6
Embodiment 29 1.4 Green glow 0.35,0.63 1.4
Embodiment 30 1.3 Green glow 0.35,0.62 1.7
Comparative example 3 1 Green glow 0.34,0.64 1
Note：Luminous efficiency and driving life-span are on the basis of comparative example 3.Comparative example 3 luminous efficiency is 62.5cd/A, the LT95 longevity Order as 7.8 hours, chromaticity coordinates (0.34,0.64).
Compound of the present invention be can be seen that by the result of table 4 and can be applicable to the making of OLED luminescent device, and permissible Obtain good performance, embodiment 28 arrives material described in embodiment 30 as luminescent layer co-host material, either efficiency Or the life-span all obtains larger change than known OLED material, the life-span that drives of particularly device obtains larger lifting.This Bright compound has good application effect as luminescent layer co-host material in OLED luminescent device, has good product Industry prospect.
Although the present invention has been disclosed by embodiment and preferred implementation it should be appreciated that the invention is not restricted to institute's public affairs The embodiment opened.On the contrary, it will be understood by those skilled in the art that it is intended to various modifications and similar arrangement.Therefore, institute The scope of attached claim should arrangement to cover all such modifications and be similar to consistent with explanation the widest.

Claims (6)

1. a kind of photoelectric material with equal benzene as core is it is characterised in that the structure such as formula (1) of described photoelectric material is shown：
In formula (1),
X1For oxygen atom, sulphur atom, selenium atom, ethenylidene, C1-10Alkylidene, alkyl or virtue that straight or branched alkyl replaces One of tertiary amine groups that base replaces；
X2It is expressed as oxygen atom, sulphur atom, C1-10The tertiary amine that the alkylidene of straight or branched alkyl replacement, alkyl or aryl replace One of base；
R1、R2Selection hydrogen independently or structure shown in formula (2)：
A isX3、X4It is respectively oxygen atom, sulphur atom, selenium atom, C1-10Straight or branched One of tertiary amine groups that the alkylidene of alkyl replacement, the alkylidene of aryl replacement, alkyl or aryl replace；
A passes through CL1-CL2Key, CL2-CL3Key or CL3-CL4On the bonded relevant position in formula (1)；Or a passes through CM1-CM2 Key, CM2-CM3Key or CM3-CM4On the bonded relevant position in formula (1)；
Ar represents phenyl, C1-10Phenyl, dibiphenylyl, terphenyl, naphthyl or anthryl that straight or branched alkyl replaces.
2. photoelectric material according to claim 1 is it is characterised in that R in described formula (1)1、R2It is asynchronously hydrogen.
3. photoelectric material according to claim 1 is it is characterised in that the concrete structure formula of described photoelectric material is：
In any one.
4. a kind of luminescent device of photoelectric material described in any one containing claims 1 to 3 is it is characterised in that described photoelectric material As hole transmission layer or electronic blocking layer material, for preparing OLED.
5. a kind of luminescent device of photoelectric material described in any one containing claims 1 to 3 is it is characterised in that described photoelectric material As emitting layer material, for preparing OLED.
6. a kind of method preparing photoelectric material described in any one of claims 1 to 3 it is characterised in that in preparation process occur Reaction equation is：
Specifically preparation process is：
(1) weigh 3- bromo- 5- chlorine aryl benzene withWith volume ratio for 1:1.0～1.5:1.0～1.5 Toluene, second alcohol and water mixed solvent dissolving；Add Pd2(dba)3, sodium carbonate；Under an inert atmosphere, by above-mentioned reactant Mixed solution in 75～80 DEG C of reaction temperature, react 10～24 hours, cooling, filtering reacting solution, filtrate revolving, cross silica gel Post, obtains intermediate A；
Described 3- bromo- 5- chlorine aryl benzene withMol ratio be 1:1.0～1.5；Pd2(dba)3With 3- The mol ratio of bromo- 5- chlorine aryl benzene is 0.006～0.04:1, the mol ratio of sodium carbonate and 3- bromo- 5- chlorine aryl benzene is 3.0～ 5.0:1；
(2) intermediate A withAs reaction substrate, with toluene as solvent；Add Pd2(dba)3, the tert-butyl alcohol Sodium；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in 105～110 DEG C of reaction temperature, react 10～24 hours, cold But, filtering reacting solution, filtrate revolving, cross silicagel column, obtain target product；
Described intermediate A withMol ratio be 1:1.0～1.5, Pd2(dba)3With intermediate A mol ratio it is 0.006～0.04:1, sodium tert-butoxide and intermediate A mol ratio are 1.0～1.5:1.
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CN106883218A (en) * 2017-03-29 2017-06-23 江苏三月光电科技有限公司 A kind of organic compound with equal benzene as core and its application on organic electroluminescence device
CN106967021A (en) * 2017-03-29 2017-07-21 江苏三月光电科技有限公司 A kind of organic compound and its application using equal benzene as core
KR20190133360A (en) * 2018-05-23 2019-12-03 (주)피엔에이치테크 An electroluminescent compound and an electroluminescent device comprising the same
CN110903294A (en) * 2018-09-18 2020-03-24 江苏三月光电科技有限公司 Compound with benzo [1,2-b:5, 4-b' ] dibenzofuran as core and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140020208A (en) * 2012-08-07 2014-02-18 주식회사 동진쎄미켐 Organic electroluminescent compound comprising acridine derivative and organic electroluminescent device comprising same
KR20140076520A (en) * 2012-12-12 2014-06-20 에스에프씨 주식회사 An electroluminescent compound and an electroluminescent device comprising the same
WO2014104515A1 (en) * 2012-12-31 2014-07-03 제일모직 주식회사 Compound for organic optoelectric device, organic light emitting diode comprising same, and display apparatus comprising organic light emitting diode
CN105315265A (en) * 2014-07-09 2016-02-10 环球展览公司 Organic electroluminescent materials and devices
WO2016089080A1 (en) * 2014-12-02 2016-06-09 주식회사 두산 Organic luminescent compound and organic electroluminescent device comprising same
KR20160079514A (en) * 2014-12-26 2016-07-06 (주)피엔에이치테크 An electroluminescent compound and an electroluminescent device comprising the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140020208A (en) * 2012-08-07 2014-02-18 주식회사 동진쎄미켐 Organic electroluminescent compound comprising acridine derivative and organic electroluminescent device comprising same
KR20140076520A (en) * 2012-12-12 2014-06-20 에스에프씨 주식회사 An electroluminescent compound and an electroluminescent device comprising the same
WO2014104515A1 (en) * 2012-12-31 2014-07-03 제일모직 주식회사 Compound for organic optoelectric device, organic light emitting diode comprising same, and display apparatus comprising organic light emitting diode
CN105315265A (en) * 2014-07-09 2016-02-10 环球展览公司 Organic electroluminescent materials and devices
WO2016089080A1 (en) * 2014-12-02 2016-06-09 주식회사 두산 Organic luminescent compound and organic electroluminescent device comprising same
KR20160079514A (en) * 2014-12-26 2016-07-06 (주)피엔에이치테크 An electroluminescent compound and an electroluminescent device comprising the same

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106883218A (en) * 2017-03-29 2017-06-23 江苏三月光电科技有限公司 A kind of organic compound with equal benzene as core and its application on organic electroluminescence device
CN106967021A (en) * 2017-03-29 2017-07-21 江苏三月光电科技有限公司 A kind of organic compound and its application using equal benzene as core
KR20190133360A (en) * 2018-05-23 2019-12-03 (주)피엔에이치테크 An electroluminescent compound and an electroluminescent device comprising the same
KR102665301B1 (en) * 2018-05-23 2024-05-10 (주)피엔에이치테크 An electroluminescent compound and an electroluminescent device comprising the same
CN110903294A (en) * 2018-09-18 2020-03-24 江苏三月光电科技有限公司 Compound with benzo [1,2-b:5, 4-b' ] dibenzofuran as core and application thereof
WO2020057480A1 (en) * 2018-09-18 2020-03-26 江苏三月光电科技有限公司 Compound with benzo[1,2-b: 5,4-b'] dibenzofuran core and application thereof
CN110903294B (en) * 2018-09-18 2022-06-03 江苏三月科技股份有限公司 Compound with benzo [1,2-b:5, 4-b' ] dibenzofuran as core and application thereof

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