CN108586352A - A kind of organic material and its application in organic electroluminescence device - Google Patents

A kind of organic material and its application in organic electroluminescence device Download PDF

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CN108586352A
CN108586352A CN201711396317.1A CN201711396317A CN108586352A CN 108586352 A CN108586352 A CN 108586352A CN 201711396317 A CN201711396317 A CN 201711396317A CN 108586352 A CN108586352 A CN 108586352A
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organic
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electroluminescence device
organic electroluminescence
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CN108586352B (en
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班全志
杭德余
马天凯
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Beijing Yanshan Gicom Photoelectric Technology Co Ltd
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Abstract

The present invention relates to organic electroluminescent (OLED) display fields, more particularly to a kind of organic material and its application in organic electroluminescence device, novel OLED material provided by the invention has the structure as shown in general formula I, it is centered on fused aromatic compounds, using the benzimidazole containing fluorine atom as end group, by in the active position of fused aromatic compounds, the substituent group (2 (3 fluorophenyl) phenylimidazole) with electronic transmission performance is introduced, a kind of novel OLED material with electronic transmission performance is obtained.Such material has high electron mobility, preferable thin film stability and suitable molecular entergy level, can be used in field of organic electroluminescence, be used as electron transport material.

Description

A kind of organic material and its application in organic electroluminescence device
Technical field
The present invention relates to a kind of new organic materials, and its application in organic electroluminescence device, belong to Organic Electricity Photoluminescence display technology field.
Background technology
Application of organic electroluminescent (OLED) material in the fields such as presentation of information material, organic optoelectronic material has Great researching value and fine application prospect.With the development of multimedia information technology, to flat-panel display device performance It is required that higher and higher.Current main display technology has plasma display apparatus, field emission display and organic electroluminescent Display device (OLED).Wherein, OLED has itself luminous, low-voltage direct-current driving, all solidstate, the wide, various colors in visual angle etc. Series of advantages, compared with liquid crystal display device, OLED does not need backlight, and visual angle is wider, low in energy consumption, and response speed is liquid 1000 times of crystal display device, therefore, OLED have broader practice foreground.
The electron transport material reported at present is since molecular weight is generally smaller, and the glass transition temperature of material is relatively low, in material During use, charging and discharging, material are easy crystallization repeatedly, and the homogeneity of film is destroyed, to influence the materials'use service life. Therefore, the electron transport material for developing stability and high efficiency improves device light emitting efficiency to reduce driving voltage, extends the device longevity Life has critically important actual application value.
Invention content
The purpose of the present invention is to provide can carry out low voltage drive, the long-life and the OLED element of high efficiency, And the compound of such OLED element can be provided.
In order to develop the compound with aforesaid properties and use the OLED element of such compound, as a result, it has been found that, lead to The compound that profit is represented by the general formula (1) expression is crossed, above-mentioned purpose is can reach.
That is, the present invention proposes that a kind of novel organic material, general structure are as follows：
In above formula, Ar is selected from：
M is selected from 1 to 4 integer.
Indicate substitution position.
Preferably, in general formula I：
Ar is selected from：
And/or m 1,2 or 3.
Preferably, when m is 1, structure one kind chosen from the followings shown in general formula I：
When m is 2, structure one kind chosen from the followings shown in general formula I：
When m is 3, structure one kind chosen from the followings shown in general formula I：
As further preferred technical solution, the organic material is selected from one kind of following compound：
Above-mentioned organic material on the benzimidazole of end due to containing fluorine atom, so as to increase intermolecular distance, prevents The only association between compound reduces the probability of molecule piled up.It is less likely to occur to crystallize when vapor deposition, is applied to OLED devices OLED yield rates can be effectively improved in part, are reduced driving voltage, are improved luminous efficiency, increase the service life.
Invention also provides the preparation methods of above-mentioned organic material, are related to two concomitant regimens altogether.
As one of scheme, when Ar is：
When, the reaction mechanism mechanism of reaction is as follows：
Specifically comprise the following steps：
(a) using compound I-1 as starting material first with n-BuLi lithiation reagent is obtained by the reaction, afterwards with unsaturation ring diketone Lithiation occurs and obtains compound I-2 under the action of sodium hypophosphite and potassium iodide through conventional treatment after acidification；
(b) compound I-2 withCoupling reaction obtains compound I；
Wherein, the integer (consistent with the restriction in above-mentioned organic material) that m is 1 to 4.
Known common approach can be used to realize in 2 above-mentioned step those skilled in the art, and such as selection is suitably urged Agent, solvent determine suitable reaction temperature, time etc..
Preferably, above-mentioned preparation method includes the following steps：
(a) using compound I-1 as starting material, tetrahydrofuran is solvent, is reacted at -90 DEG C~-80 DEG C with n-BuLi, - 90 DEG C~-80 DEG C addition unsaturation ring diketone of temperature control afterwards, are stirred 20 ± 2 hours.Acid is acidified, and is with acetic acid after conventional treatment Solvent obtains compound I-2 with sodium hypophosphite and potassium iodide back flow reaction 20 ± 2 hours；
(b) using compound I-2 as starting material, withThrough piperidinecarboxylic acid and cuprous iodide catalyzed coupling reaction, it obtains To compound I.
Wherein, the integer (consistent with the restriction in above-mentioned organic material) that m is 1 to 4.
As the two of scheme, when Ar is：
When, the reaction mechanism mechanism of reaction is as follows：
Include the following steps：
(e) using compound I-1 as starting material, first withCoupling reaction obtains compound I-3；
(f) first with n-BuLi lithiation occurs for compound I-3, reacts with trimethylborate, is obtained after acidified afterwards Compound I-4；
(g) with dibromo condensed-nuclei aromatics SUZUKI coupling reactions occur for compound I-4, obtain compound I；
Wherein, the integer that m is 1 to 4.
It is highly preferred that described method includes following steps：
(e) using compound I-1 as starting material, withThrough piperidinecarboxylic acid and cuprous iodide catalyzed coupling reaction, obtain Compound I-3；
(f) using compound I-3 as starting material, tetrahydrofuran is solvent, first with n-BuLi at -90 DEG C~-80 DEG C Lithiation is reacted with trimethylborate afterwards, and hydrochloric acid acidification obtains compound I-4；
(g) using toluene, ethyl alcohol, water as solvent, it is catalyst that four triphenylphosphines, which close palladium, and sodium carbonate is alkali, and nitrogen protection is returned It flows down, with dibromo condensed-nuclei aromatics SUZUKI coupling reactions occur for compound I-4, obtain compound I；
Wherein, the integer that m is 1 to 4.
It is above-mentionedTrimethylborate, piperidinecarboxylic acid and n-BuLi etc. can pass through disclosure Method known per se synthesizes to obtain in commercial sources or document.
Invention further provides application of the above-mentioned organic material in organic electroluminescence device.
Preferably, organic material of the present invention is used as electron transfer layer in organic electroluminescence device.
The present invention also provides a kind of organic electroluminescence device, organic function layer includes above-mentioned general formula compound, Such compound is used as the electron transport material in organic function layer.
Preferably, above-mentioned organic electroluminescence device from the bottom to top successively by transparent substrate, anode layer, hole transmission layer, Organic luminous layer, electron transfer layer, electron injecting layer and cathode layer composition.
The material for constituting the transparent substrate is glass substrate or flexible substrate；
Substrate can use the substrate in conventional organic luminescence device, such as：Glass or plastics.In the device system of the present invention Glass substrate, ITO is selected to make anode material in work.
The material for constituting the anode layer is inorganic material；Wherein, the inorganic material be specially tin indium oxide (ITO), At least one of zinc oxide, zinc tin oxide, gold, silver or copper, preferably tin indium oxide (ITO)；
The material for constituting the hole transmission layer is selected from various tri-arylamine group materials.It is selected in the element manufacturing of the present invention Hole mobile material is at least one of compound shown in NPB and TPD：
The material for constituting the organic luminous layer is made of material of main part；
Wherein, the material of main part is any one in following compound：
The material for constituting the electron transfer layer is Formulas I compound represented；
The material for constituting the electron injecting layer is selected from LiF, Li2O, MgO or Al2O3, preferably LiF.
The material for constituting the cathode is selected from lithium, magnesium, silver, calcium, strontium, aluminium, indium, copper, Jin Heyin, preferably aluminium.
Specifically,
The thickness of the hole transmission layer is 5-10nm, specially 6nm；
The thickness of the organic luminous layer is 10-80nm, specially 40nm；
The thickness of the electron transfer layer is 10-30nm, specially 20nm；
The thickness of the electron injecting layer is 2-30nm, specially 5nm；
Al layers of the thickness is 30-110nm, specially 50nm.
Novel OLED material provided by the invention is centered on fused aromatic compounds, with the benzimidazole containing fluorine atom For end group, by the active position of fused aromatic compounds, introducing substituent group (2- (the 3- fluorine with electronic transmission performance Phenyl) phenylimidazole), obtain a kind of novel OLED material with electronic transmission performance.Such material has high electronics Mobility, preferable thin film stability and suitable molecular entergy level, can be used in field of organic electroluminescence, as electronics Transmission material uses.
Specific implementation mode
Various phenylbenzimidazol boric acid used in the present invention, various bromo anthracenes, bromo, bromo pyrene, anthraquinone, benzo The basic chemical industries such as anthraquinone raw material can conveniently be bought in chemical products market at home, and various phenyl benzimidazole groups boric acid are available Common organic procedures synthesis.
Compound synthesis in the present invention all can refer to embodiment 1, embodiment 2 and 3 method of embodiment and carry out.It explains below State the synthetic method of part main compound in the present invention.
Embodiment 1
The synthesis of (compound 1)
Synthetic route is as follows：
1) synthesis of compound 1-1
1000 milliliters of there-necked flasks, match magnetic agitation, press above-mentioned amount after argon gas displacement successively and the bromo- 4- iodobenzenes 26.49g of 1- are added (purity 99%, 0.094mol), THF500ml.N-BuLi38ml (concentration 2.5M, 0.095mol) is added dropwise at -90 DEG C, it is rear to add Enter 8.4g anthraquinones (purity 99%, 0.04mol), after adding, warms naturally to room temperature, solution is in glassy yellow, is stirred to react 20h. The hydrolysis of 500m water is added, liquid separation, water phase is extracted with dichloromethane, merges organic layer, and acetic acid 600ml, 36g is added in solvent evaporated KI and 36g sodium hypophosphite, reflux, react 20 hours, cool down, filtering, with water wash it, obtain 17.49g yellow production Object, purity 99.5%, yield 90%.
2) synthesis of compound 1
N2Under gas shielded, 9,10- bis--(4- bromophenyls) anthracene 16.53g (purity is added in a 500mL there-necked flasks 94.5%, 0.034mol), 2- (3- fluorophenyls) benzimidazolyl 21.63g (purity 99%0.102mol), cupric iodide 2.6g is (pure Spend AR 0.0136mol), piperidinecarboxylic acid 5.4g (purity AR 0.0136mol), potassium carbonate 35g (purity AR 0.254mol).DMF With 500ml, magnetic agitation flows back 20 hours, lets cool filtering, crude yellow solid is boiled several times repeatedly with ethyl alcohol, is obtained yellow Color solid 13.22g, purity 99.4%, yield 80%.
Product MS (m/e)：750.26；
Elemental analysis (C52H32F2N4)：Theoretical value C：83.18%, H：4.30%, F：5.06%, N：7.46%；Measured value C：83.15%, H：4.33%, F：5.02%, N：7.50%.
Technical solution according to embodiment 1, it is only necessary to the corresponding raw material of simple replacement does not change any substantive operations, Following compound can be synthesized.
Embodiment 2
The synthesis of (compound 2)
Synthetic route is as follows：
1) synthesis of compound 2-1
N2Under gas shielded, 4- bromo-iodobenzenes 9.58g (0.034mol), 2- (3- fluorophenyls) are added in a 500mL there-necked flasks Benzimidazolyl 7.21g (0.034mol), cupric iodide 2.6g (purity AR0.0136mol), piperidinecarboxylic acid 5.4g (purity AR 0.0136mol), potassium carbonate 35g (purity AR0.254mol).DMF 600ml, magnetic agitation flow back 30 hours, let cool filtering, Crude yellow solid is boiled several times repeatedly with ethyl alcohol, obtains yellow solid 9.96g, purity 99.6%, yield 80%.
2) synthesis of compound 2-2
73.20g 4- (2- (3- fluorophenyls) benzimidazolyl) bromobenzene (compound is added in the there-necked flask of 2L dried and cleans 1-1,0.2mol), 1000ml tetrahydrofurans, nitrogen protection, for liquid nitrogen cooling to -80 DEG C, it is anti-to drip complete temperature control for dropwise addition 80ml butyl lithiums 1h is answered, 32g trimethylborates (0.30mol) are added dropwise, drop finishes, and warms naturally to -20 DEG C after the reaction 30 minutes of -80 DEG C of temperature control, drop Add 600ml aqueous hydrochloric acid solutions.Liquid separation, water phase are extracted twice with the ethyl acetate of 400ml × 2, merge organic phase, be spin-dried for white solid Body, liquid phase purity (LC) 99.1%, theoretical yield 66.42g, actual production 63.10g, yield 95%；
3) synthesis of compound 2
N2Under gas shielded, 1,6-, bis--bromine pyrenes 7.34g (purity 98%, 0.02mol) is added in a 1000mL there-necked flasks, 4- (2- (3- fluorophenyls) benzimidazolyl) phenyl boric acid 16.61g (purity 98%, 0.050mol), tetra-triphenylphosphine palladium 0.46g (purity AR, 0.0004mol), potassium carbonate 17.3g (purity AR, 0.125mol), toluene 300ml, ethyl alcohol 300ml, water 100ml. Above-mentioned material, is heated to reflux.Stop reaction after 15 hours, let cool, filters, obtain yellow solid, solid is tied again with 16 times of THF Crystalline substance repeats secondary.Obtain the faint yellow products of 13.63g, purity 99.80%, yield 88%.
Product MS (m/e)：774.26.；Elemental analysis (C54H32F2N4)：Theoretical value C：83.70%, H：4.16%, F： 4.90%, N：7.23%；Measured value C：83.68%, H：4.18%, F：4.87%, N：7.27%
Embodiment 3：The synthesis of compound 3
N2Under gas shieldeds, 6,12- dibromos are added in a 1000mL there-necked flasks and bend 11.52g (purity 98%, 0.03mol), 4- (2- (3- fluorophenyls) benzimidazolyl) phenyl boric acid 24.91g (purity 99%, 0.075mol), tetra-triphenylphosphine palladium 0.69g (purity AR, 0.0006mol), potassium carbonate 25.88g (purity AR, 0.188mol), toluene 300ml, ethyl alcohol 50ml, water 50ml.On Material is stated, is heated to reflux.Stop reaction after 30 hours, let cool, yellow solid is obtained by filtration, solid is recrystallized with THF, repeats two Time.Obtain the faint yellow products of 19.21g, purity 99.80%, yield 80%.
Product MS (m/e)：800.28；Elemental analysis (C56H34F2N4)：Theoretical value C：83.98%, H：4.28%, F： 4.74%, N：7.00%；Measured value C：83.97%, H：4.29%, F：4.72%, N：7.02%
Technical solution according to embodiment 2 and embodiment 3, it is only necessary to which the corresponding raw material of simple replacement does not change any reality Matter operates, and can synthesize following compound.
Embodiment 4 prepares device OLED-1~OLED-4
1) glass substrate for being coated with ITO conductive layer is ultrasonically treated 30 minutes in cleaning agent, is rushed in deionized water It washes, it is 30 minutes ultrasonic in acetone/ethanol in the mixed solvent, it is baked to is completely dried under a clean environment, use ultraviolet rays cleaning Machine irradiates 10 minutes, and low energy cation beam bombarded surface is used in combination.
2) the above-mentioned ito glass substrate handled well is placed in vacuum chamber, is evacuated to
1×10-5~9 × 10-4Pa, it is hole transmission layer, evaporation rate that compound N PB is deposited on above-mentioned anode tunic For 0.2nm/s, vapor deposition film thickness is 6nm；
3) continue to be deposited ADN on the hole transport layer as material of main part, as the organic luminous layer of device, evaporation rate Film thickness for 0.2nm/s, vapor deposition gained organic luminous layer is 40nm；
4) continue the compound 1 of ownership Formulas I obtained by one layer of preparation of embodiment 1 of vapor deposition on organic luminous layer as device Electron transfer layer, evaporation rate 0.2nm/s, vapor deposition film thickness are 20nm；
5) continue that electron injecting layers of the one layer of LiF as device is deposited on electron transfer layer, evaporation rate is 0.2nm/s, vapor deposition film thickness are 5nm；
6) continue that cathodes of the one layer of Al as device, evaporation rate 0.2nm/s, vapor deposition is deposited on electron injecting layer Film thickness is 50nm；OLED device provided by the invention is obtained, OLED-1 is denoted as；
According to upper identical step, by the compound 1 in step 4) replace with embodiment 2 prepare gained compound 2, obtain To OLED-2 provided by the invention；
According to upper identical step, by the compound 1 in step 4) replace with embodiment 3 prepare gained compound 3, obtain To OLED-3 provided by the invention；
According to upper identical step, the compound 1 in step 4) is replaced with into ET1, obtains comparative device OLED-4；
ET1 (control compounds 1)
The performance test results of obtained device OLED-1 to OLED-4 are as shown in table 1.
The performance test results of table 1OLED-1 to OLED-4
From the foregoing, it will be observed that the device OLED-1 being prepared into using organic material shown in Formulas I provided by the invention is to OLED-4's Bright voltage is lower, brightness under the same conditions, the apparent device OLED-4 than ET1 as electron transport material of current efficiency It is much higher, and the service life of device be obviously prolonged very much.
Although the present invention is described in conjunction with the embodiments, the invention is not limited in above-described embodiments, should manage Solution, under the guiding of present inventive concept, those skilled in the art can carry out various modifications and improve, and appended claims summarise The scope of the present invention.

Claims (10)

1. a kind of organic material, it is characterised in that：Its structure is as shown in general formula I：
Wherein, Ar is selected from：
M is selected from 1 to 4 integer；
Indicate substitution position.
2. organic material according to claim 1, it is characterised in that：In general formula I, Ar is selected from：
And/or m is 1 or 2 or 3；
Preferably, when m is 1, structure one kind chosen from the followings shown in general formula I：
When m is 2, structure one kind chosen from the followings shown in general formula I：
When m is 3, structure one kind chosen from the followings shown in general formula I：
3. organic material according to claim 1 or 2, it is characterised in that：The organic material is selected from following compound It is a kind of：
4. the preparation method of claim 1-3 any one of them organic materials, it is characterised in that：When Ar is：
When, the reaction mechanism mechanism of reaction is as follows：
Specifically comprise the following steps：
(a) lithiation reagent first is obtained by the reaction with n-BuLi using compound I-1 as starting material, occurs afterwards with unsaturation ring diketone Lithiation after acidification, obtains compound I-2 under the action of sodium hypophosphite and potassium iodide；
(b) compound I-2 withCoupling reaction obtains compound I；
Wherein, the reference of m is the same as described in claim any one of 1-3.
5. the preparation method of claim 1-3 any one of them organic materials, it is characterised in that：When Ar is：
When, the reaction mechanism mechanism of reaction is as follows：
Include the following steps：
(e) using compound I-1 as starting material, first withCoupling reaction obtains compound I-3；
(f) first with n-BuLi lithiation occurs for compound I-3, is reacted afterwards with trimethylborate, chemical combination is obtained after acidified Object I-4；
(g) with dibromo condensed-nuclei aromatics SUZUKI coupling reactions occur for compound I-4, obtain compound I；
Wherein, the reference of m is the same as described in claim any one of 1-3.
6. application of the claim 1-3 any one of them organic materials in organic electroluminescence device.
7. application according to claim 6, it is characterised in that：The organic material is in the organic electroluminescence device As electron transfer layer.
8. a kind of organic electroluminescence device, it is characterised in that：Including by claim 1-3 any one of them organic material systems At electron transfer layer.
9. organic electroluminescence device according to claim 8, it is characterised in that：The organic electroluminescence device is under It is supreme successively by transparent substrate, anode layer, hole transmission layer, organic luminous layer, electron transfer layer, electron injecting layer and cathode layer Composition；
It is preferred that：
The material for constituting the transparent substrate is glass substrate or flexible substrate；
And/or；The material for constituting the anode layer is at least one in tin indium oxide, zinc oxide, zinc tin oxide, gold, silver or copper Kind；
And/or；The material for constituting the hole transmission layer is at least one of compound shown in NPB and TPD：
And/or；The material for constituting the organic luminous layer is any one in following compound：
And/or；The material for constituting the electron injecting layer is selected from LiF, Li2O, MgO or Al2O3In one kind；
And/or；Constitute the one kind of the material of the cathode in lithium, magnesium, silver, calcium, strontium, aluminium, indium, copper, gold and silver.
10. organic electroluminescence device according to claim 9, it is characterised in that：
The thickness of the hole transmission layer is 5-10nm；The thickness of the organic luminous layer is 10-80nm；The electron transfer layer Thickness be 10-30nm；The thickness of the electron injecting layer is 2-30nm；Al layers of the thickness is 30-110nm.
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