CN103540313B - Novel electroluminescent material and application thereof - Google Patents

Novel electroluminescent material and application thereof Download PDF

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CN103540313B
CN103540313B CN201310504322.5A CN201310504322A CN103540313B CN 103540313 B CN103540313 B CN 103540313B CN 201310504322 A CN201310504322 A CN 201310504322A CN 103540313 B CN103540313 B CN 103540313B
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compound
quinoline
naphtho
organic electroluminescence
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CN103540313A (en
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盛磊
高自良
周银波
艾文
李子澍
张陆峰
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Valiant Co Ltd
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Yantai Valiant Fine Chemicals Co Ltd
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Abstract

The invention relates to a novel electroluminescent material and an application thereof. The material takes naphtho-[1, 2-h] chinoline as the center and has a molecular structure according to a formula (I). The material has better film stability and proper molecular energy level, and can be used as luminescent materials or carrier transport materials to be applied in the field of organic electroluminescence.

Description

A kind of electroluminescent material and application thereof
Technical field
The present invention relates to a kind of novel materials for electroluminescence, and the application in organic electroluminescence device, belong to ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field.
Background technology
Organic light emitting diode (OLED) results from the eighties in last century, because it has luminous, wide viewing angle, fast response time, can realize the plurality of advantages such as Flexible Displays, just advance with the swift and violent impetus at present, and very likely become the best candidate person of flat panel display of future generation, be subject to people and pay close attention to greatly.
OLED is divided into small molecule devices and polymer device, wherein small molecule devices often has multilayer sandwiched structure, and every layer has different functions respectively, this feature, for in material development process, successively improve and bring conveniently, but simultaneously, in order to the OLED of excellent, in each functional layer material of consideration, while self property, also will ensure coupling between layers, this brings challenge also to the exploitation of small molecule devices.
Exploitation has the functional layer material of premium properties, and being the important foundation of OLED technical development, is also the important directions that people make great efforts.Fused ring compound " is bent ", because having suitable conjugate length and stable closed-loop structure, is just receiving the concern of people, and patent WO2008150872, WO2008150940, WO2010107037 are structure constructions centered by bending.
Naphtho-[1,2-h] quinoline to bend there is similar closed-loop structure, the introducing of atom N, be conducive to the molecular entergy level regulating center ring, improve carrier transmission performance, at naphtho-[1,2-h] 6 and 12 of quinoline, introduce different substituting groups, be conducive to the fluorescence spectrum color of Molecular regulator, be also conducive to the thin film stability promoting molecule.We imagine, and by carrying out suitable chemically modified to naphtho-[1,2-h] quinoline, will be hopeful the novel materials for electroluminescence of acquisition one class excellent property.
Summary of the invention
Technical problem to be solved by this invention is, provide a kind of novel materials for electroluminescence centered by naphtho-[1,2-h] quinoline, this material as luminescent material or electron transport material, can be applied in organic electroluminescence device.
The invention provides a kind of novel materials for electroluminescence, there is structure as shown in the formula (I):
Wherein, R1 ~ R9 is independently selected from hydrogen atom, halogen atom, cyano group, the alkyl of C1 ~ C40 or alkoxyl group, can be identical, also can be different, Ar1 and Ar2 independently is selected from the aromatic condensed ring of molecular weight between 60 ~ 600 or nitrogen heterocyclic ring, further independent preferably uncertainly, containing substituting group or not containing substituent naphthalene, luxuriant and rich with fragrance, pyrene, fluorenes, biphenyl, phenylnaphthalene, substituted ethylene base, N-substituted carbazole, pyridine, quinoline, [1,8] naphthyridines, imidazoles and the minor structure unit derived by above structure, described Ar1 with Ar2 can be identical, also can be different.
Described being independently selected from refers to and structure does not depend on, is not subordinate to, and arbitrary structural unit belonging to being independently selected from, can be identical, also can be different.
The invention provides the novel materials for electroluminescence of a class centered by naphtho-[1,2-h] quinoline, and provide the synthetic method of such material:
Take quinoline-8-formaldehyde as raw material, through Wittig reaction, hydrolysis, Guan Huan, oxidation, bromo five step is reacted, and obtains intermediate 6,12-bis-bromo-naphtho-[1,2-h] quinoline (5);
Reaction formula is as follows:
Then with the bromo-naphtho-of 6,12-bis-[1,2-h] quinoline (5) for raw material, carry out Suzuki linked reaction from the boric acid of different substrate structure or boric acid ester, obtain novel materials for electroluminescence.
The boric acid of described different substrate structure or boric acid ester refer to the difference according to substrate structure, the boric acid that this substrate grows or the corresponding also difference of boric acid ester structure.
Listed Compound C-01 ~ C-39 below, being the representative structure meeting the present invention's spirit and principle, should be appreciated that and list following compound structure, just in order to explain the present invention better, is not limitation of the present invention.
The molecular entergy level that a kind of novel materials for electroluminescence provided by the invention has good thin film stability and is applicable to, can as the luminescent layer of organic electroluminescence device or electron transfer layer.
Prepared organic electroluminescence device generally comprises the ITO Conducting Glass that superposes successively as anode, hole transmission layer (NPB), luminescent layer (MADN or Alq3), electron transfer layer (TPBI), electron injecting layer (LiF) and cathode layer (Al).All functions layer all adopts vacuum evaporation process to make.
Wherein, at least one deck in the luminescent layer of described organic electroluminescence device, electron transfer layer comprises the compound with following formula (I) structural formula.
The molecular structural formula of other organic compound used in described organic electroluminescence device is as follows.
In the present invention, the functional layer of described organic electroluminescence device is not limited to use above-mentioned materials, and as hole transmission layer can also with replacements such as TPD, electron transfer layer can also with replacements such as BCP, and the molecular structural formula of these materials is as follows:
Figure explanation
Fig. 1 is in device embodiments 1, using Compound C-20 as the luminescent layer of organic electroluminescence device, and the voltage-current density curve of device;
Fig. 2 is in device embodiments 1, using Compound C-20 as the luminescent layer of organic electroluminescence device, and the voltage-brightness curve of device;
Fig. 3 is in device embodiments 1, using Compound C-20 as the luminescent layer of organic electroluminescence device, and the current density-current efficiency curve of device;
Fig. 4 is in device embodiments 1, and using Compound C-20 as the luminescent layer of organic electroluminescence device, device is 100cd/m in brightness 2time electroluminescent spectrum figure;
Fig. 5 is in device embodiments 2, with (Compound C-20:MADN=4:1, the W/W) luminescent layer as organic electroluminescence device, and the voltage-current density curve of device;
Fig. 6 is in device embodiments 2, with (Compound C-20:MADN=4:1, the W/W) luminescent layer as organic electroluminescence device, and the voltage-brightness curve of device;
Fig. 7 is in device embodiments 2, with (Compound C-20:MADN=4:1, the W/W) luminescent layer as organic electroluminescence device, and the current density-current efficiency curve of device;
Fig. 8 is in device embodiments 2, and with (Compound C-20:MADN=4:1, the W/W) luminescent layer as organic electroluminescence device, device is 100cd/m in brightness 2time electroluminescent spectrum figure;
Fig. 9 is in device embodiments 3, using Compound C-36 as the luminescent layer of organic electroluminescence device and electron transfer layer, and the voltage-current density curve of device;
Figure 10 is in device embodiments 3, using Compound C-36 as the luminescent layer of organic electroluminescence device and electron transfer layer, and the voltage-brightness curve of device;
Figure 11 is in device embodiments 3, using Compound C-36 as the luminescent layer of organic electroluminescence device and electron transfer layer, and the current density-current efficiency curve of device;
Figure 12 is in device embodiments 3, and using Compound C-36 as the luminescent layer of organic electroluminescence device and electron transfer layer, device is 100cd/m in brightness 2time electroluminescent spectrum figure;
Figure 13 is in device embodiments 4, using Alq3 as the luminescent layer of organic electroluminescence device, Compound C-36 as electron transfer layer, the voltage-current density curve of device;
Figure 14 is in device embodiments 4, using Alq3 as the luminescent layer of organic electroluminescence device, Compound C-36 as electron transfer layer, the voltage-brightness curve of device;
Figure 15 is in device embodiments 4, using Alq3 as the luminescent layer of organic electroluminescence device, Compound C-36 as electron transfer layer, the current density-current efficiency curve of device;
Figure 16 is in device embodiments 4, and using Alq3 as the luminescent layer of organic electroluminescence device, Compound C-36 is as electron transfer layer, and device is 100cd/m in brightness 2time electroluminescent spectrum figure;
Embodiment
Be described principle of the present invention and feature below, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Compou nd synthesis embodiment:
Embodiment 1
8-(2-Methoxy-vinyl) synthesis of quinoline (compound 1)
In 2L there-necked flask, add quinoline-8-formaldehyde (78.5g, 0.5mol), methoxyl methyl triphenyl phosphine dichloride (205.5g, 0.6mol), toluene (825g), N 2protection, is cooled to interior temperature <-5 DEG C, is dissolved in by potassium tert.-butoxide (67.2g, 0.6mol) in 250g THF, and slowly in instillation there-necked flask, warm <5 DEG C in controlling, about 0.5h dropwises ,-5 DEG C ~ 5 DEG C insulation reaction 2h.Add 400g deionized water, stir 10min, separatory, 400mL X2 washes organic phase to neutral, removes toluene, adds 800g sherwood oil, stir 0.5h, suction filtration, the drip washing of 200g sherwood oil, collects filtrate, slough sherwood oil, obtain 8-(2-Methoxy-vinyl) quinoline 82.2g, yield 88.8%, MS(m/s): 185.1.
Embodiment 2
The synthesis of quinoline-8-acetaldehyde (compound 2)
In 1L there-necked flask, add 8-(2-Methoxy-vinyl) quinoline (74g, 0.4mol), 170gTHF, N 2protection, stirs 20min, 190g concentrated hydrochloric acid is joined 150g dilution with water, then slowly instills in there-necked flask; warm <30 DEG C in controlling, about 15min dropwises, and is warming up to interior temperature 40 DEG C, insulation reaction 2h; stop reaction, be down to room temperature, add 300g CH 2cl 2, stir 5min, separatory, 150mLX2 washes organic phase, 40g anhydrous Na 2sO 4drying, filter, slough solvent, obtain quinoline-8-acetaldehyde 69g, yield 101%, products obtained therefrom does not carry out purifying, is directly used in next step reaction.
Embodiment 3
The synthesis of 7,8,9,10-tetrahydrochysene naphtho-[1,2-h] quinoline (compound 3)
In 3L there-necked flask, add quinoline-8-acetaldehyde (69g) prepared by previous step, cyclohexenyl trimethylsilyl ethers (81.5g, 0.48mol), methylene dichloride (2000g), be cooled to interior temperature <-85 DEG C, by anhydrous titanium tetrachloride (453g, 2.4mol) be dissolved in 670g methylene dichloride, then slowly instill in there-necked flask, warm <-80 DEG C in controlling, about 2h dropwises, insulation reaction 2h, move into room temperature, insulation reaction 36h, react complete, by in reaction solution slowly impouring 1L frozen water, a large amount of hydrogen chloride gas is had to release, separatory, collect organic phase, 100g anhydrous Na 2sO 4drying, filters, and collect filtrate, filtrate is quickly through 100g alkali alumina post, collected post liquid, desolventizing, obtained thick product, with ethyl acetate: sherwood oil=1:1 was eluent, silica gel column chromatography, obtains target compound 32.5g, yield 34.8%, MS(m/s): 233.1.
Embodiment 4
The synthesis of naphtho-[1,2-h] quinoline (compound 4)
In 1L there-necked flask, add 7,8,9,10-tetrahydrochysene naphtho-[1,2-h] quinoline (31g, 0.13mol), DDQ (60g, 0.26mol), toluene (300g), is warming up to backflow, insulation reaction 24h, slough solvent, add 300g dehydrated alcohol, stirring at room temperature 0.5h, suction filtration, collects filter cake, obtains target compound naphtho-[1,2-h] quinoline 26.5g, yield 89.2%, MS(m/s): 229.1.
Embodiment 5
The synthesis of the bromo-naphtho-of 6,12-bis-[1,2-h] quinoline (compound 5)
In 2L there-necked flask, add naphtho-[1,2-h] quinoline (25g, 0.11mol), oil of mirbane (980g), Br 2(65g, 0.40mol), is warming up to interior temperature 160 DEG C, insulation reaction 24h, stops reaction, is down to room temperature, adds 500g water, 21g NaHSO 3, stir 10min, suction filtration, the drip washing of 500mL dehydrated alcohol, collect filter cake, be solvent recrystallization with toluene, obtain target compound 27.8g, yield 65%.
High resolution mass spectrum, ESI source, positive ion mode, molecular formula C 17h 9br 2n, theoretical value 386.9081, test value 386.9083.Ultimate analysis (C 17h 9br 2n), theoretical value C:52.75, H:2.34, Br:41.29, N:3.62, measured value C:52.73, H:2.32, Br:41.31, N:3.64.
Embodiment 6
The synthesis of 6,12-, bis--(1-naphthyl)-naphtho-[1,2-h] quinoline (Compound C-01)
In 100mL there-necked flask, add the bromo-naphtho-of 6,12-bis-[1,2-h] quinoline (1.54g, 4mmol), 1-naphthalene boronic acids (1.51g, 8.8mmol), K 2cO 3(2.2g, 16mmol), THF(60mL), deionized water (26mL), N 2protection, adds Pd (PPh 3) 4(220mg), back flow reaction 36 hours, stops reaction, filters, the drip washing of 50mL deionized water, the drip washing of 50mL dehydrated alcohol, collects filter cake, toluene heat of solution, while hot quickly through 20g layer of silica gel, collected post liquid, left at room temperature over night, product is separated out, suction filtration, the drip washing of 20mL toluene, collects filter cake, air-dry, obtain crude product 1.4g, use the further sublimation purification of chemical gas-phase deposition system, sublimation temperature 280 DEG C, obtains 1.1g target compound C-01, yield 57.3%.
High resolution mass spectrum, ESI source, positive ion mode, molecular formula C 37h 23n, theoretical value 481.1830, test value 481.1832.Ultimate analysis (C 37h 23n), theoretical value C:92.28, H:4.81, N:2.91, measured value C:92.26, H:4.83, N:2.91.
Embodiment 7
The synthesis of 6,12-, bis--(2-naphthyl)-naphtho-[1,2-h] quinoline (Compound C-03)
With the bromo-naphtho-of 6,12-bis-[1,2-h] quinoline (compound 5) and 2-naphthalene boronic acids for raw material, according to the preparation of method described in embodiment 6, yield 41%.
High resolution mass spectrum, ESI source, positive ion mode, molecular formula C 37h 23n, theoretical value 481.1830, test value 481.1831.Ultimate analysis (C 37h 23n), theoretical value C:92.28, H:4.81, N:2.91, measured value C:92.25, H:4.82, N:2.93.
Embodiment 8
The synthesis of 6,12-bis--(9-is luxuriant and rich with fragrance)-naphtho-[1,2-h] quinoline (Compound C-05)
With the luxuriant and rich with fragrance boric acid of the bromo-naphtho-of 6,12-bis-[1,2-h] quinoline (compound 5) and 9-for raw material, according to the preparation of method described in embodiment 6, yield 51.3%.
High resolution mass spectrum, ESI source, positive ion mode, molecular formula C 45h 27n, theoretical value 581.2143, test value 581.2145.Ultimate analysis (C 45h 27n), theoretical value C:92.91, H:4.68, N:2.41, measured value C:92.92, H:4.66, N:2.42.
Embodiment 9
The synthesis of 6,12-, bis--(4-biphenyl)-naphtho-[1,2-h] quinoline (Compound C-11)
With the bromo-naphtho-of 6,12-bis-[1,2-h] quinoline (compound 5) and 4-biphenylboronic acid for raw material, according to the preparation of method described in embodiment 6, yield 38.2%.
High resolution mass spectrum, ESI source, positive ion mode, molecular formula C 41h 27n, theoretical value 533.2143, test value 533.2144.Ultimate analysis (C 41h 27n), theoretical value C:92.28, H:5.10, N:2.62, measured value C:92.26, H:5.11, N:2.63.
Embodiment 10
6,12-bis--(4-(9-carbazole) phenyl) synthesis of-naphtho-[1,2-h] quinoline (Compound C-16)
In 250mL there-necked flask, add the bromo-naphtho-of 6,12-bis-[1,2-h] quinoline (1.54g, 4mmol), 4-(9-carbazole) phenylo boric acid (2.5g, 8.8mmol), K 2cO 3(6.0g, 43mmol), DMAc(80mL), deionized water (24mL), N 2protection, adds Pd (PPh 3) 4(320mg), interior temperature 100 DEG C, react 36 hours, stop reaction, cooling, add 120mL deionized water, stir 0.5h, filter, 50mL deionized water drip washing filter cake once, 50mL dehydrated alcohol drip washing filter cake once, collect filter cake, be placed in 250mL single port bottle, add 120mL acetone, stirring at room temperature 1h, suction filtration, collect filter cake, add 250mL orthodichlorobenzene, the lower heat of solution of backflow, while hot quickly through the layer of silica gel that 15cm is thick, collected post liquid, kept at room temperature overnight, solid product is had to separate out, suction filtration, the drip washing of 20mL normal hexane, obtain target compound 2.1g, use the further sublimation purification of chemical gas-phase deposition system, sublimation temperature 330 DEG C, obtain 1.8g target compound C-16, yield 63.3%.
High resolution mass spectrum, ESI source, positive ion mode, molecular formula C 53h 33n 3, theoretical value 711.2674, test value 711.2677.Ultimate analysis (C 53h 33n 3), theoretical value C:89.42, H:4.67, N:5.90, measured value C:89.41, H:4.68, N:5.91.
Embodiment 11
6,12-bis--(3-(N-phenyl) carbazole) synthesis of-naphtho-[1,2-h] quinoline (Compound C-20)
With the bromo-naphtho-of 6,12-bis-[1,2-h] quinoline (compound 5) and N-phenyl carbazole-3-boric acid for raw material, according to the preparation of method described in embodiment 10, yield 51.7%.
High resolution mass spectrum, ESI source, positive ion mode, molecular formula C 53h 33n 3, theoretical value 711.2674, test value 711.2675.Ultimate analysis (C 53h 33n 3), theoretical value C:89.42, H:4.67, N:5.90, measured value C:89.39, H:4.63, N:5.98.
Embodiment 12
The synthesis of 6,12-, bis--(4-pyridine)-naphtho-[1,2-h] quinoline (Compound C-24)
In 100mL there-necked flask, add the bromo-naphtho-of 6,12-bis-[1,2-h] quinoline (1.54g, 4mmol), pyridine-4-pinacol borate (1.8g, 8.8mmol), K 2cO 3(4.0g, 29mmol), THF(50mL), deionized water (20mL), N 2protection, adds Pd (PPh 3) 4(210mg), back flow reaction 24 hours, stops reaction, and cooling, adds 120mL ethyl acetate, separatory, 50mL deionized water wash organic phase, collects organic phase, anhydrous Na 2sO 4drying, filters, desolventizing, and thick product uses silica gel column chromatography, and eluent is normal hexane: ethyl acetate=1:1, collects target compound, and use the further sublimation purification of chemical gas-phase deposition system, sublimation temperature 250 DEG C, obtains 0.8g target compound C-24, yield 52.2%.
High resolution mass spectrum, ESI source, positive ion mode, molecular formula C 27h 17n 3, theoretical value 383.1422, test value 383.1426.Ultimate analysis (C 27h 17n 3), theoretical value C:84.57, H:4.47, N:10.96, measured value C:84.55, H:4.43, N:11.02.
Embodiment 13
6,12-bis--(4-(4-pyridine) phenyl) synthesis of-naphtho-[1,2-h] quinoline (Compound C-31)
With the bromo-naphtho-of 6,12-bis-[1,2-h] quinoline (compound 5) and 4-(4-pyridine)-phenylo boric acid pinacol ester for raw material, according to the preparation of method described in embodiment 12, yield 31.7%.
High resolution mass spectrum, ESI source, positive ion mode, molecular formula C 39h 25n 3, theoretical value 535.2048, test value 535.2043.Ultimate analysis (C 39h 25n 3), theoretical value C:87.45, H:4.70, N:7.84, measured value C:87.41, H:4.71, N:7.88.
Embodiment 14
6,12-bis--(3-(3,5-bis--(3-pyridine)) phenyl) synthesis of-naphtho-[1,2-h] quinoline (Compound C-36)
In 100mL there-necked flask, add the bromo-naphtho-of 6,12-bis-[1,2-h] quinoline (1.54g, 4mmol), 3,5-bis--(3-pyridine) phenylo boric acid pinacol ester (3.15g, 8.8mmol), K 2cO 3(8.0g, 56mmol), DMAc(50mL), deionized water (20mL), N 2protection, adds Pd (PPh 3) 4(410mg), back flow reaction 24 hours, stops reaction, cooling, pours in 120mL deionized water by reaction solution, stir 5min, suction filtration, the drip washing of 50mL deionized water, the drip washing of 50mL dehydrated alcohol, collect solids crude product, use silica gel column chromatography, eluent is normal hexane: ethyl acetate=1:2, collect target compound, use the further sublimation purification of chemical gas-phase deposition system, sublimation temperature 360 DEG C, obtain 1.5g target compound C-36, yield 54.3%.
High resolution mass spectrum, ESI source, positive ion mode, molecular formula C 49h 31n 5, theoretical value 689.2579, test value 689.2581.Ultimate analysis (C 49h 31n 5), theoretical value C:85.32, H:4.53, N:10.15, measured value C:85.31, H:4.55, N:10.14.
Embodiment 15
6,12-bis--(3-(3,5-bis--(4-pyridine)) phenyl) synthesis of-naphtho-[1,2-h] quinoline (Compound C-37)
With the bromo-naphtho-of 6,12-bis-[1,2-h] quinoline (compound 5) and 3,5-bis--(4-pyridine) phenylo boric acid pinacol ester for raw material, according to the preparation of method described in embodiment 14, yield 33.3%.
High resolution mass spectrum, ESI source, positive ion mode, molecular formula C 49h 31n 5, theoretical value 689.2579, test value 689.2577.Ultimate analysis (C 49h 31n 5), theoretical value C:85.32, H:4.53, N:10.15, measured value C:85.37, H:4.56, N:10.07.
Organic electroluminescence device embodiment:
The present invention chooses Compound C-20 and is manufactured with organic electroluminescence devices with Compound C-36, should be appreciated that device implementation process and result, just in order to explain the present invention better, and not limitation of the present invention.
Embodiment 1
The application one of Compound C-20 in organic electroluminescence device
The present embodiment prepares organic electroluminescence device by the following method:
A) ITO(tin indium oxide is cleaned) glass: clean ito glass each 30 minutes with deionized water, acetone, EtOH Sonicate respectively, then in plasma cleaner, process 5 minutes;
B) vacuum evaporation hole transmission layer NPB on anode ito glass, thickness is 50nm;
C) on hole transmission layer, vacuum evaporation is as the Compound C-20 of luminescent layer, and thickness is 30nm;
D) on luminescent layer, vacuum evaporation is as the TPBI of electron transfer layer, and thickness is 30nm;
E) on electron transfer layer, vacuum evaporation electron injecting layer LiF, thickness is 1nm;
F) on electron injecting layer, vacuum evaporation negative electrode Al, thickness is 100nm.
The structure of device is ITO/NPB (50nm)/Compound C-20 (30nm)/TPBI (30nm)/LiF (1nm)/Al (100nm).Using Compound C-20 as the luminescent layer of this device, as shown in Figure 1, as shown in Figure 2, as shown in Figure 3, the bright voltage that opens of device is 6.0V, high-high brightness 1160cd/m to current density-current efficiency curve to voltage-brightness curve to the voltage-current density curve of this device 2, maximum current efficiency 0.98cd/A.Fig. 4 is this device is 100cd/m in brightness 2time electroluminescent spectrum figure, CIE coordinate is positioned at (0.160,0.063).
Embodiment 2
The application two of Compound C-20 in organic electroluminescence device
The present embodiment prepares organic electroluminescence device by the following method:
A) ITO(tin indium oxide is cleaned) glass: clean ito glass each 30 minutes with deionized water, acetone, EtOH Sonicate respectively, then in plasma cleaner, process 5 minutes;
B) vacuum evaporation hole transmission layer NPB on anode ito glass, thickness is 50nm;
C) on hole transmission layer, vacuum mixing evaporation as the Compound C-20 of luminescent layer and MADN, the mass ratio 4:1 of Compound C-20 and MADN, thickness is 30nm;
D) on luminescent layer, vacuum evaporation is as the TPBI of electron transfer layer, and thickness is 30nm;
E) on electron transfer layer, vacuum evaporation electron injecting layer LiF, thickness is 1nm;
F) on electron injecting layer, vacuum evaporation negative electrode Al, thickness is 100nm.
The structure of device is ITO/NPB (50nm)/Compound C-20:MADN=4:1, (W/W, 30nm)/TPBI (30nm)/LiF (1nm)/Al (100nm).With (Compound C-20:MADN=4:1, the W/W) luminescent layer as this device, the voltage-current density curve of this device as shown in Figure 5, voltage-brightness curve as shown in Figure 6, as shown in Figure 7, the bright voltage that opens of device is 6.0V, high-high brightness 4900cd/m to current density-current efficiency curve 2, maximum current efficiency 2.3cd/A.Fig. 8 is this device is 100cd/m in brightness 2time electroluminescent spectrum figure, CIE coordinate is positioned at (0.158,0.180).
Embodiment 3
The application one of Compound C-36 in organic electroluminescence device
The present embodiment prepares organic electroluminescence device by the following method:
A) ITO(tin indium oxide is cleaned) glass: clean ito glass each 30 minutes with deionized water, acetone, EtOH Sonicate respectively, then in plasma cleaner, process 5 minutes;
B) vacuum evaporation hole transmission layer NPB on anode ito glass, thickness is 50nm;
C) on hole transmission layer, vacuum evaporation is 60nm as Compound C-36 thickness of luminescent layer and electron transfer layer;
D) on Compound C-36, vacuum evaporation electron injecting layer LiF, thickness is 1nm;
E) on electron injecting layer, vacuum evaporation negative electrode Al, thickness is 100nm.
The structure of device is ITO/NPB (50nm)/Compound C-36 (60nm)/LiF (1nm)/Al (100nm).Using Compound C-36 as the luminescent layer of this device and electron transfer layer, as shown in Figure 9, as shown in Figure 10, current density-current efficiency curve as shown in figure 11 for voltage-brightness curve for the voltage-current density curve of this device, the bright voltage that opens of device is 7.0V, high-high brightness 2600cd/m 2, maximum current efficiency 0.42cd/A.Figure 12 is this device is 100cd/m in brightness 2time electroluminescent spectrum figure, CIE coordinate is positioned at (0.155,0.074).
Embodiment 4
The application two of Compound C-36 in organic electroluminescence device
The present embodiment prepares organic electroluminescence device by the following method:
A) ITO(tin indium oxide is cleaned) glass: clean ito glass each 30 minutes with deionized water, acetone, EtOH Sonicate respectively, then in plasma cleaner, process 5 minutes;
B) vacuum evaporation hole transmission layer NPB on anode ito glass, thickness is 50nm;
C) on hole transmission layer, vacuum evaporation is as the Alq3 of luminescent layer, and thickness is 30nm;
D) on luminescent layer, vacuum evaporation is as the Compound C-36 of electron transfer layer, and thickness is 30nm;
E) on electron transfer layer, vacuum evaporation electron injecting layer LiF, thickness is 1nm;
F) on electron injecting layer LiF, vacuum evaporation negative electrode Al, thickness is 100nm.
The structure of device is ITO/NPB (50nm)/Alq3 (30nm)/Compound C-36 (30nm)/LiF (1nm)/Al (100nm).Using Alq3 as the luminescent layer of this device, Compound C-36 is as electron transfer layer, and the voltage-current density curve of this device as shown in figure 13, voltage-brightness curve as shown in figure 14, as shown in figure 15, the bright voltage that opens of device is 6.5V, high-high brightness 9500cd/m to current density-current efficiency curve 2, maximum current efficiency 1.34cd/A.Figure 16 is this device is 100cd/m in brightness 2time electroluminescent spectrum figure, be green fluorescence.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.As used other material to replace NPB as hole transmission layer, with other blue emitting material mixing evaporation as luminescent layer etc., similar improvement all should be understood to, belongs to protection category of the present invention.

Claims (3)

1. an electroluminescent material, is characterized in that, has such as formula the structure shown in (I):
Wherein, described R1 ~ R9 is hydrogen atom; Described Ar1 and Ar2 is identical substituting group, for not containing substituent naphthyl, phenanthryl, pyrenyl, fluorenyl, xenyl, phenyl napthyl, N-substituted carbazole base, pyridyl, quinolyl, [1,8] naphthyridinyl, imidazolyl.
2. a kind of electroluminescent material according to claim 1, it is characterized in that, synthetic method is as follows:
Take quinoline-8-formaldehyde as raw material, through Wittig reaction, hydrolysis, Guan Huan, oxidation, bromo five step is reacted, and obtains intermediate 6,12-bis-bromo-naphtho-[1,2-h] quinoline (5),
Reaction formula is as follows:
Then with the bromo-naphtho-of 6,12-bis-[1,2-h] quinoline (5) for raw material, carry out Suzuki linked reaction from the boric acid of different substrate structure or boric acid ester, obtain electroluminescent material.
3. an organic electroluminescence device, is characterized in that, adopts electroluminescent material as claimed in claim 1 as the luminescent layer of organic electroluminescence device or electron transfer layer.
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WO2008150940A1 (en) * 2007-06-01 2008-12-11 E. I. Du Pont De Nemours And Company Chrysenes for green luminescent applications
WO2010107037A1 (en) * 2009-03-16 2010-09-23 Canon Kabushiki Kaisha Novel chrysene compound and organic light-emitting device having the compound
CN102827078A (en) * 2011-06-16 2012-12-19 三星显示有限公司 Condensed-cyclic compound and organic light-emitting diode comprising the same

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KR101971198B1 (en) * 2011-10-19 2019-04-23 삼성디스플레이 주식회사 Heterocyclic compound, organic light-emitting diode comprising the same, and flat display device comprising the organic light-emitting diode

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Publication number Priority date Publication date Assignee Title
WO2008150872A1 (en) * 2007-06-01 2008-12-11 E.I. Du Pont De Nemours And Company Chrysenes for deep blue luminescent applications
WO2008150940A1 (en) * 2007-06-01 2008-12-11 E. I. Du Pont De Nemours And Company Chrysenes for green luminescent applications
WO2010107037A1 (en) * 2009-03-16 2010-09-23 Canon Kabushiki Kaisha Novel chrysene compound and organic light-emitting device having the compound
CN102827078A (en) * 2011-06-16 2012-12-19 三星显示有限公司 Condensed-cyclic compound and organic light-emitting diode comprising the same

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