CN103087103A - Organic semiconductor material for organic electroluminescence device as well as preparation method and application thereof - Google Patents
Organic semiconductor material for organic electroluminescence device as well as preparation method and application thereof Download PDFInfo
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 57
- 238000005401 electroluminescence Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- SCHRRICRQNJJKN-UHFFFAOYSA-N P.[O] Chemical group P.[O] SCHRRICRQNJJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003852 triazoles Chemical class 0.000 claims abstract description 11
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000003205 fragrance Substances 0.000 claims description 10
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- 125000003118 aryl group Chemical group 0.000 claims description 6
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- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
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- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 claims description 2
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- Plural Heterocyclic Compounds (AREA)
Abstract
The present invention relates to the organic semiconducting materials and its preparation method and application for organic electroluminescence device, relate more specifically to the material of main part in a kind of ternary organic semiconducting materials as well as organic electroluminescence device containing triazole, carbazole and phosphine oxygen groups. Ternary organic semiconducting materials of the invention have the general structure such as formula (I), wherein Cz is the carbazole or carbazole derivates of nitrogen atom; 1Ar, 2Ar and 3Ar are aromatic monocyclic or polycyclic or including the heteroatomic aromatic heterocycle such as nitrogenous, oxygen, sulphur. 1Ar, 2Ar and 3Ar can be the same or different, and n is the integer selected from 1~5. Ternary organic semiconducting materials in invention can be used as the critical material in organic electroluminescence device, there is more excellent electron mobility and cavity transmission ability than traditional material, the efficiency that can be improved organic electroluminescence device, is with a wide range of applications
Formula (I).
Description
Technical field
The present invention relates to the organic optoelectronic Material Field, be specifically related to the organic semiconductor material for organic electroluminescence device, relate more specifically to ternary organic semiconductor material that contains carbazole, triazole and phosphine oxygen groups and preparation method thereof, and these organic semiconductor material are in the application in organic optoelectronic field.
Background technology
Display and lighting technology based on organic electroluminescent diode (OLED), due to have low driving voltage, high luminosity, large visual angle, fast-response time, ultra-thin and can make on flexible substrate have can bending, the advantage such as chip-proof novel display panel, and more and more receive the very big concern of academia, industrial community and national governments.
Organic electroluminescence device is made of the multilayer organic materials, and luminescent layer is wherein selected the subject and object material of suitable blending ratio usually.Be about to guest materials (fluorescence dopant material or have the more phosphorescence dopant material of high-quantum efficiency) with certain doped in concentrations profiled in having the organic semiconductor material of main part of carrier transport ability, improve the luminous efficiency of organic electroluminescence device.Metallic phosphorescence dopant material is used widely in red emission and green ballistic device structure because efficient is higher.The green glow electroluminescent device of reports such as Forrrest in 1999 and Thompson, luminescent layer is with 4,4 '-N, N '-two carbazole biphenyl (CBP) monobasic carbazoles organic semiconductor material is material of main part, and the 6 percent green glow phosphorescent light-emitting materials three (2-phenylpyridine) that adulterate close iridium (II) (Ir (ppy)
3), the power efficiency figure of device reaches 31lm/w.Forrest in 2000 etc. have reported monobasic triazole class material of main part 3-phenyl-4-(1 ' naphthyl)-5-phenyl-1,2,4-triazole (TAZ) doping green phosphorescent light-emitting materials Ir (ppy)
3, obtained higher power efficiency (40lm/w).
But these organic semiconductor material of main parts or take hole transport as main the monobasic organic semiconductor material CBP of carbazole (as contain), take electric transmission as main the monobasic organic semiconductor material TAZ of triazole (as contain), cause electronics and hole concentration imbalance in luminescent layer, thereby can affect performance of devices and efficient, especially performance is more outstanding in the blue light electroluminescent device, and its power efficiency is difficult to higher than 15lm/w.
subsequently, contain carbazole/triazole, carbazole/oxadiazole, carbazole/phosphine oxygen groups, triazole/triphenylamine, carbazole/benzoglyoxaline, carbazole/triazine, binary organic semiconductor material and the ternary organic semiconductor material phosphine oxygen groups/tetraphenyl-silicon/carbazoles such as carbazole/tetraphenyl-silicon, phosphine oxygen groups/fluorenes/triphenylamine, phosphine oxygen groups/fluorenes/carbazole, phenylimidazole group/tetraphenyl-silicon/triphenylamine, oxadiazole/tetraphenyl-silicon/triphenylamine (exemplary configuration sees Table lattice one) is developed is used for improving the electronics of current carrier and the performance that hole pair transmission performances are come boost device, organic semiconductor material for electroluminescent device of the prior art is as shown in table 1 below:
Table 1: the monobasic of patent and bibliographical information, binary, ternary organic semiconductor material
Although above these material systems are arranged, the practical application of blu-ray emission device still is subject to does not have better Subjective and Objective material, causes present blue light material system to become the bottleneck of OLED technical development.
Summary of the invention
In order to overcome the problems referred to above of the prior art, the invention provides the different organic semiconductor material that is used for organic electroluminescence device of a kind of and above monobasic, binary and ternary chemical structure.
the present invention will have 1 of good electric transmission and hole barrier ability, 3, 4-triazole unit, have the carbazole unit of high triplet energy state high hole transmittability and have and effectively to block the phosphine oxygen groups specific fixed ratio connection combination in a particular manner that the pi-conjugated system maintenance high triplet energy state of material (high triplet is to ensure the high efficiency key factor of organic electroluminescence devices) can effectively be improved the material electronics transmission performance simultaneously, prepared the ternary organic semiconductor material that a class has new texture, they can be used for the material of main part of electroluminescent device luminescent layer, and show through the carrier transmission performance test, this type of organic semiconductor material has electronics and the hole transport performance of balance more, can be used as the critical material in organic optoelectronic device, especially as the material of main part of OLED device.
Structure and the feature of the organic semiconductor material for electroluminescent device provided by the present invention are as shown in table 1 below:
Table 2: ternary organic semiconductor material structure of the present invention and feature
One object of the present invention is, is connected combination with ratio by triazole, carbazole and phosphine oxygen groups are connected, and provides a kind of carrier transmission performance the more efficient organic semiconductor material of balance more.
Another object of the present invention is that the preparation method of above-mentioned organic semiconductor material is provided.
Another purpose of the present invention is, the purposes in efficient organic electroluminescence devices such as above-mentioned organic semiconductor material being applied to Organic Light Emitting Diode as the material of main part of luminescent layer is provided.
The technical solution adopted in the present invention is: a kind of organic semiconductor material for organic electroluminescence device, contain triazole, carbazole and phosphine oxygen groups in the structure of this organic semiconductor material, and its general structure is as shown in the formula shown in (I),
Formula (I)
Wherein, Cz is carbazole or the carbazole derivative of nitrogen atom;
1Ar,
2Ar and
3Ar is independently selected from fragrant monocycle, the many rings of fragrance, and this fragrance monocycle, the many rings of fragrance comprise aromatic heterocycle;
N is integer, and n=1～5.
Preferably, above-mentioned aromatic heterocycle comprises nitrogen or oxygen or sulfur heteroatom.
Preferably, in formula (I) compound the structure of Cz be:
Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Be independently selected from hydrogen or alkyl or aryl; R
9Be selected from alkyl or aryl.More preferably, above-mentioned formula (1) compound
1Ar,
2Ar and
3Ar is independently selected from following aromatic group or derivatives thereof:
Again preferably, the represented organic semiconductor material of formula (I) compound be selected from following formula (II) to formula (compound of (XII):
Formula (II);
Formula (III);
Formula (IV);
Formula V;
Formula (VI);
Formula (VII);
Formula (VIII);
Formula (IX);
Formula (X);
Formula (XI);
Formula (XII).
Another aspect of the present invention also provides the preparation method of above-mentioned organic semiconductor material, wherein, can utilize suzuki reaction (that is, Suzuki linked reaction) or introduce carbazole by ullmann reaction (that is, Ullmann linked reaction); Utilize two hydrazides and arylamine reaction to introduce the triazole heterocycle; Utilize the aryl halogen to introduce the phosphine oxygen groups at organic bases as the triaryl phosphine oxidation that the reaction with the diaryl phosphonium chloride generates, concrete synthetic route is as follows:
Wherein: X is Cl, Br or I;
Cz is carbazole or the carbazole derivative of nitrogen atom;
1Ar,
2Ar and
3Ar is independently selected from fragrant monocycle, the many rings of fragrance, and this fragrance monocycle, the many rings of fragrance comprise aromatic heterocycle;
N is integer, and n=1～5.
Preferably, this aromatic heterocycle comprises nitrogen or oxygen or sulfur heteroatom.
Preferably, above-mentioned organic bases is butyllithium.
Another aspect of the invention also provides above-mentioned organic semiconductor material to be used for being manufactured with the purposes of organic electroluminescence devices.
Further, this invention provides above-mentioned organic semiconductor material to can be used as the purposes that material of main part be used for to be made Organic Light Emitting Diode (OLED) that display and lighting uses etc.
Due to the enforcement of above technical scheme, compared with prior art, the present invention has following advantage:
Organic semiconductor material for organic electroluminescence device provided by the present invention is ternary system, contain simultaneously triazole unit, carbazole and phosphine oxygen unit, have more excellent electronic mobility, electronics and the cavity transmission ability of balance more than traditional material of main part (as CBP) that is used for organic electroluminescence device, therefore also more be conducive to the lifting of organic electroluminescence device efficient.
Description of drawings
Fig. 1 is the structural representation of the device 1 of making according to the present invention;
Fig. 2 is the current density-voltage-brightness curve figure of the device 1 made according to the present invention;
Fig. 3 is the current efficiency-voltage-power efficiency graphic representation of the device 1 made according to the present invention;
Fig. 4 is the structural representation of the device 2 of making according to the present invention;
Fig. 5 be the device 2 made according to the present invention current density-voltage-brightness curve figure;
Fig. 6 is the current efficiency-voltage-power efficiency graphic representation of the device 2 made according to the present invention;
Fig. 7 is the structural representation of the device 3 of making according to the present invention;
Fig. 8 is the current density-voltage-brightness curve figure of the device 3 made according to the present invention;
Fig. 9 is the current efficiency-voltage-power efficiency graphic representation of the device 3 made according to the present invention;
Figure 10 is the structural representation of the device 4 of making according to the present invention;
Figure 11 is the current density-voltage-brightness curve figure of the device 4 made according to the present invention;
Figure 12 is the current efficiency-voltage-power efficiency graphic representation of the device 4 made according to the present invention;
Figure 13 is the structural representation of the device 5 of making according to the present invention;
Figure 14 is the current density-voltage-brightness curve figure of the device 5 made according to the present invention;
Figure 15 is the current efficiency-voltage-power efficiency graphic representation of the device 5 made according to the present invention;
Figure 16 is the structural representation of the device 6 of making according to the present invention;
Figure 17 is the current density-voltage-brightness curve figure of the device 6 made according to the present invention;
Figure 18 is the current efficiency-voltage-power efficiency graphic representation of the device 6 made according to the present invention;
Embodiment
The present invention will be further described in detail below in conjunction with specific embodiment, but the present invention is not limited to these embodiment.
The synthetic organic semiconductor material with formula (II) structure that contains carbazole group, concrete synthetic route is seen following reaction equation 1:
Concrete operation step is as follows:
(1) under argon shield, add successively 3-iodo-benzoic acid methyl esters (180g in the 5L there-necked flask, 0.69mol), carbazole (172.2g, 1.03mol), copper powder (436.82g, 6.87mol), the 18-hat-6(2.3g), salt of wormwood (949.23g, 6.87mol) and orthodichlorobenzene 1.5L, mechanical stirring is even, then be warming up to gradually 180 ℃, back flow reaction 52h, then reaction solution is cooled to room temperature, add tetrahydrofuran (THF) 3L, suction filtration, filtrate decompression boils off THF and a small amount of orthodichlorobenzene, put into-28 ℃ of refrigerators, remove by filter the raw material carbazole of separating out, filtrate decompression distillation desolventizing, gained residuum methanol/ethyl acetate (300mL/50mL) mixed solution recrystallization.Get compound a (104g, productive rate 50%).
(2) add compound a (104g in the 5L there-necked flask, 0.345mol), ethanol 700mL, Isosorbide-5-Nitrae-dioxane 700mL, 85% hydrazine hydrate 186mL, back flow reaction 48h, vacuum rotary steam is removed most of solvent to thick, and pour in 2L water and separate out white solid, the silica gel column chromatography separation (hexane/EtOAc4/1), get compound b(68g, productive rate 72%).
1H?NMR(400MHz，CDCl
3)δppm：：8.16(d，2H)，7.99(s，1H)，7.82(d，1H)，7.72(d，1H)，7.65-7.59(m，1H)，7.42-7.33(m，4H)，7.32-7.27(m，2H)，4.64-3.32(br，2H)。
(3) under argon shield; add b(17.06g in the 500mL three-necked bottle; 56.61mmol), salt of wormwood (1.96g; 14.15mmol) and N-Methyl pyrrolidone 150mL; stirring and dissolving; then dropwise add 4-bromo-benzoyl chloride (12.51g with constant pressure funnel; 57.00mmol); reaction is spent the night; then reaction solution is poured into water; generate immediately gray precipitate, suction filtration gained crude product is purified with dichloromethane/ethyl acetate (10: 1) column chromatography for separation and is obtained compd A (22.7g, 83%).Ultimate analysis calculated value C
26H
18BrN
3O
2: C, 64.47; H, 3.75; N, 8.68; Measured value: C, 64.48; H, 3.72; N, 8.70.
(4) under argon shield, add aniline (24.9g, 0.27mmol) and 150mL orthodichlorobenzene in the three-necked bottle of 500mL, after being heated to 100 ℃, gained solution dropwise adds PCl
3(9.2g, 0.07mmol) reacts and adds compd A (21.6g, 0.05mmol) after 1 hour, then is warming up to 180 ℃ of reaction overnight; Filter, repeatedly wash insolubles with methylene dichloride, merge washing lotion and be spin-dried for solvent, with dichloromethane/ethyl acetate (10: 1) column chromatography for separation purification residuum, obtain midbody compound B(15.5g, 0.03), productive rate: 60%.
1H?NMR(400MHz，CDCl
3)δppm：8.13-8.04(d，2H)，7.78-7.55(dt，1H)，7.65-7.55(m，3H)，7.54-7.46(m，3H)，7.45-7.40(m，2H)，7.34-7.27(m，4H)，7.26-7.20(m，4H)，7.05-6.97(d，2H)；
13C?NMR(100MHz，CDCl3，δ)：155.69，155.62，141.78，139.20，136.21，133.20，131.95，131.80，131.55，131.51，130.08，129.45，129.20，128.46，127.42，127.08，125.88，124.81，121.68，121.60，110.90。MS (ESI, m/z) [(M+H)
+] calculated value: 541.0950; Measured value: 541.0948.
(5) under argon shield, add compd B (13.2g in the three-necked bottle of 500mL, 24.4mmol) and the THF of 250mL drying, stirring and dissolving is placed in the low-temp reaction device, dropwise adds n-Butyl Lithium (n-BuLi) (2.40M at-78 ℃ of temperature, 11.18mL, 26.8mmol), reacted 3 hours under-78 ℃ after dropwising, and then add diphenyl phosphine chloride (4.97mL, 26.8mmol), continue reaction and return to gradually the ambient temperature overnight reaction after 2 hours; Add methyl alcohol (3mL) termination reaction in reaction system, after being spin-dried for the solvent in reaction solution, add the 280mL methylene dichloride to dissolve, then dropwise add 30% hydrogen peroxide (7.5mL), reaction overnight under normal temperature with pure water (100mL * 3) washing, is used the anhydrous sodium sulfate drying organic phase, be spin-dried for solvent, with methylene chloride/methanol (20: 1) column chromatography separating-purifying crude product, obtain target product, i.e. formula (II) compound (4.57g, 6.9mmol), productive rate: 28.3%.
1H?NMR(400MHz，CDCl
3)δppm：8.10-8.06(d，2H)，7.77-7.72(dt，1H)，7.68-7.42(m，21H)，7.34-7.27(m，3H)，7.24-7.20(m，2H)，7.06-6.98(d，2H)；
13C?NMR(100MHz，CDCl
3)δppm：154.46，154.13，140.34，137.81，134.82，134.62，134.31，134.29，133.80，132.34，132.25，132.17，132.15，132.08，131.98，131.30，130.59，130.36，130.19，130.12，130.10，128.66，128.58，128.54，128.51，128.46，128.32，127.98，127.69，127.03，125.99，123.38，120.24，120.17，109.45；
31P?NMR(400MHz，CDCl
3)δppm：28.55。MS (ESI, m/z) [(M+H)
+] calculated value: 663.2235; Measured value: 663.2237.
Synthetic organic semiconductor material with formula (VII) structure wherein contains carbazole derivative (2,7-Dimethylcarbazole), the concrete following reaction equation 2 of synthetic route:
Concrete operation step is as follows:
(1) add successively 4 in the 5L reaction vessel that stirring, condensation and nitrogen protection device are housed; 4 ' dimethyl diphenyl (93.7g; 0.51mol) and Glacial acetic acid (2.5L); then increase the temperature to 70 ℃; slowly drip nitric acid (750mL); TLC monitors reaction, stopped reaction when raw material reaction is complete.Reaction solution is poured in 10L water, filtration drying, get yellow solid intermediate 4,4 '-dimethyl-2-nitro-1,1 '-biphenyl (105g, 0.46mol), productive rate 91%.
(2) add successively gained intermediate 4 in the 2L reaction flask with condensation, stirring and nitrogen protection device; 4 '-dimethyl-2-nitro-1,1 '-biphenyl (105g, 0.46mol) and triethyl-phosphite (650mL); then the temperature that slowly raises is to refluxing; and keep reflux state reaction 24h, and reaction solution is poured in 10L water, filter and obtain faint yellow solid; obtain white-yellowish solid intermediate 2 through ethyl alcohol recrystallization; 7-Dimethylcarbazole (63g, 0.32mmol), productive rate 70%.
1H?NMR(400MHz，CDCl
3)δppm：7.92(d，2H)，7.18(m，2H)，7.06(d，2H)，2.53(s，6H)。
(3) according to the synthetic method described in embodiment 1, drop into 2,7-Dimethylcarbazole (60g, 0.31mol), obtain Compound C (47g, three step total recoverys 30%) by intermediate c and d.The ultimate analysis calculated value C of Compound C
28H
22BrN
3O
2: C, 65.63; H, 4.33; N, 8.20; Measured value: C, 65.61; H, 4.32; N, 8.21.
(4) according to the described synthetic method of embodiment 1, drop into Compound C (28.5g, 0.05mmol), obtain midbody compound D(27.6g, 0.04mmol final the separation), productive rate: 80%.
MS (ESI, m/z) [(M+H)+] calculated value: 569.1263; Measured value: 569.1260.
(5) according to the synthetic method described in embodiment 1, drop into Compound D (17.1g, 30mmol), obtain target product (5.2g, 7.5mmol), productive rate: 25% final the separation.
MS (ESI, m/z) [(M+H)+]: calculated value C
46H
35N
4OP:691.2548; Measured value 691.2551.
Embodiment 3
Synthetic organic semiconductor material with formula (IX) structure wherein contains carbazole derivative (3,6-di-t-butyl carbazole), the concrete following reaction equation 3 of synthetic route:
Reaction equation 3
Concrete operation step is as follows:
(1) carbazole (33g, 0.20mmol), zinc chloride (81g, 0.59mmol) and 100mL Nitromethane 99Min. are added in the reaction flask of 250mL, drip 2-chloro-2 methylpropane (65mL under nitrogen protection, 0.59mmol), after dropwising, room temperature reaction spends the night under nitrogen protection; Then reaction solution is joined termination reaction in 100mL water, extract with DCM, merge organic phase and drying and be spin-dried for, cross post and get white products, intermediate 3,6-di-t-butyl carbazole (33.5g, 0.12mmol), productive rate 60%.
1H?NMR(400MHz，CDCl
3)δppm：8.08(d，2H)，7.48(dd，2H)，7.34(d，2H)，1.45(s，18H)。
(2) according to the described synthetic method of embodiment 1, drop into 3,6-di-t-butyl carbazole (30g, 0.11mol), obtain compd E (32g, three step total recoverys 49%) by intermediate e and f.The ultimate analysis calculated value C of compd E
34H
34BrN
3O
2: C, 68.45; H, 5.74; N, 7.04; Measured value: C, 68.46; H, 5.71; N, 7.06.
(3) according to the described synthetic method of embodiment 1, drop into compd E (29.8g, 0.05mmol), obtain compound F 17-hydroxy-corticosterone (22.9g, 0.035mmol), productive rate: 70% final the separation.
MS (ESI, m/z) [(M+H)+]: calculated value C
40H
37BrN
4: 653.2202; Measured value 653.2208.
(4) according to the synthetic method described in embodiment 1, drop into compound F 17-hydroxy-corticosterone (19.6g, 30mmol), separate obtaining target product, i.e. formula (IX) compound (6.7g, 8.7mmol), productive rate: 29%.
MS (ESI, m/z) [(M+H)+]: calculated value C
52H
47N
4OP:775.3487; Measured value: 775.3484.
Synthetic organic semiconductor material with formula (XII) structure wherein contains carbazole derivative (3,6-phenylbenzene carbazole), the concrete following reaction equation 4 of synthetic route:
Concrete operation step is as follows:
(1) according to the described synthetic method of embodiment 1, drop into 3,6-phenylbenzene carbazole (30g, 0.09mol), obtain compound G(14g by intermediate g and h, three step total recoverys 25%).The ultimate analysis calculated value C of compound G
38H
26BrN
3O
2: C, 71.70; H, 4.12; N, 6.60; Measured value: C, 71.71; H, 4.10; N, 6.66.
(2) according to the described synthetic method of embodiment 1, drop into compound G(10g, 0.016mol), obtain compound H (8g, 0.011mol), productive rate: 72% final the separation.
MS (ESI, m/z) [(M+H)+] calculated value: 693.1576; Measured value 692.1578.
(3) according to the synthetic method described in embodiment 1, drop into compound H (8g, 0.011mol), separate obtaining target product, i.e. formula (XII) compound (3.3g, 4mmol), productive rate: 37%.
MS (ESI, m/z) [(M+H)+] calculated value: 815.2861; Measured value: 815.2860.
Synthetic organic semiconductor material with formula (X) structure, the concrete following reaction equation 5 of synthetic route:
Concrete operation step is as follows:
(1) according to the described synthetic method of embodiment 1, drop into compd A (20g, 0.041mol), obtain compound J(15g, 0.028mol final the separation), productive rate: 68%.
MS (ESI, m/z) [(M+H)+] calculated value: 543.0855; Measured value: 543.0857.
(2) according to the synthetic method described in embodiment 1, drop into compound J(15g, 0.028mol), separate obtaining target product, i.e. formula (X) compound (7.6g, 0.011mmol), productive rate: 41%.
MS (ESI, m/z) [(M+H)+] calculated value: 665.2140; Measured value: 665.2141.
Synthetic organic semiconductor material with formula (XI) structure, the concrete following reaction equation 6 of synthetic route:
Concrete operation step is as follows:
(1) under argon shield, add successively 3-iodo-benzoic acid methyl esters (180g in the 5L there-necked flask, 0.69mol), N-phenyl-3-carbazole boric acid (198g, 0.69mol), palladium (1.5g, 6.9mmol), three (o-methyl-phenyl-phosphorus) (4.2g, 13.8mmol), toluene (700mL), ethanol (150mL) and salt of wormwood (2mol/L, 350mL), mechanical stirring is even, then be warming up to gradually 80 degree, back flow reaction 24h, then reaction solution is cooled to room temperature, add toluene 2L, suction filtration, filtrate decompression distillation desolventizing, the gained residuum column chromatography compound m(182g that purifies to get, 0.48mol), productive rate: 70%.
MS (ESI, m/z) [(M+H)+] calculated value: 378.1416; Measured value: 378.1415.
(2) according to the described synthetic method of embodiment 1, drop into compound m(180g, 0.48mol), obtain compound n(136g, 0.36mol final the separation), productive rate: 75%.
MS (ESI, m/z) [(M+H)+] calculated value: 378.1528; Measured value: 378.1530.
(3) according to the synthetic method described in embodiment 1, drop into compound n(120g, 0.32mol), by intermediate M and N, separate obtaining target product, i.e. formula (X) compound (24g, 0.032mmol), three step productive rates: 10%.
MS (ESI, m/z) [(M+H)+] calculated value: 739.2548; Measured value: 739.2546.
In above embodiment 2-6, omitted to embodiment 1 in the specific descriptions of relevant similar operations step, all cardinal principle is identical with embodiment 1 like parameters such as the reagent that uses in operation, the reaction conditionss that feeds intake when for respective class in these embodiment, difference is, the starting compound that uses in reaction is similar compound, and the committed step thing that namely uses in embodiment 2-6 is the derivative of the corresponding committed step thing in embodiment 1.About these embodiment, those skilled in the art fully can be according to method and the concrete operation step thereof described in embodiment 1, each intermediate and final product in Preparation Example 2-6, this is readily appreciated that and realizes, thereby omitted corresponding repeatability at this and described, these methods, operation steps, and result it will be apparent to those skilled in the art that.
Embodiment 7
With the material of main part of the organic semiconductor material with formula (II) structural compounds as blue light OLED device luminescent layer.
[1-(2 for the blue emitting phosphor metal iridium complex three that adopts US Patent No. 20110204333A1 to report, 4-di-isopropyl dibenzo [b, d] furans-3-yl)-2-phenyl-1H-imidazoles] [tris[1-(2 for iridium (III), 4-diisopropyldibenzo[b, d] furan-3-yl)-2-phenyl-1H-imidazole] iridium (III), (Ir (dbi)
3)] as the dopant material of blue light OLED device luminescent layer, doping content is 15%, adopts tin indium oxide (ITO) as anode, TAPC is as hole mobile material, and BCP is as electron transport material, and LiF is electron injection material, Al is negative electrode, makes blue emission OLED device (device 1).
Concrete device architecture is: ITO/TAPC (30nm)/EML
1(30nm)/BCP (30nm)/LiF (1nm)/Al, wherein, EML
1=formula (II) compound: Ir (dbi)
3(15wt%), the structure of device 1 as shown in Figure 1.
Adopt vacuum deposition method to make device 1,5 * 10
-4Make under the vacuum condition of Pa, ito glass used is through processing 15 minutes under ultraviolet-ozone environment after ultrasonic cleaning, and in the cavity of then directly packing into, evaporation is until finish whole device successively.Testing power supply adopts the KEITHLEY2400 system, and spectrograph adopts PR655.Test is carried out under atmospheric environment, does not make encapsulation process, and the test result of the device 1 of made is seen Fig. 2 and Fig. 3.
The performance of device 1: brightness reaches 100cdm
-2Voltage be 3.6V, 1000cdm
-2Voltage be 4.9V, high-high brightness is 6990cdm
-2Voltage be 4.9V, maximum current efficient is 41.6cdA
-1, maximum power efficiency is 43.0lmW
-1The spectrum peak of photoluminescence is 474nm, and is in full accord with the spectrum of this luminous dopant material, and do not find that unnecessary peak occurs.
With the material of main part of the organic semiconductor material with formula (VII) structure as blue light OLED device luminescent layer.
[1-(3 for the blue emitting phosphor metal iridium complex three of employing US Patent No. 20070088167 reports, 5-diisopropyl biphenyl base-4-yl)-2-phenyl-1H-imidazoles] iridium (III), [tris[1-(3,5-diisopropylbiphenyl-4-yl)-2-phenyl-1H-imidazole], (Ir (dbpi)
3)] as the dopant material of blue light OLED device luminescent layer, doping content is 10%, adopts ITO as anode, TAPC is as hole mobile material, and BCP is as electron transport material, and LiF is electron injection material, Al is negative electrode, makes blue emission OLED device (device 2).
Concrete device architecture is: ITO/TAPC (30nm)/EML
2(30nm)/BCP (30nm)/LiF (1nm)/Al, wherein, EML
2=formula (VII) compound: Ir (dbpi)
3(10wt%), the structure of device 2 as shown in Figure 4.
Adopt vacuum deposition method to make device, 5 * 10
-4Make under the vacuum condition of Pa, ito glass used is through processing 15 minutes under ultraviolet-ozone environment after ultrasonic cleaning, and in the cavity of then directly packing into, evaporation is until finish whole device successively.Testing power supply adopts the KEITHLEY2400 system, and spectrograph adopts PR655.Test is carried out under atmospheric environment, does not make encapsulation process, and the test result of the device 2 of made is seen Fig. 5 and Fig. 6.
The performance of device 2: brightness reaches 100cdm
-2Voltage be 4.3V, 1000cdm
-2Voltage be 5.6V, high-high brightness is 17784cdm
-2Voltage be 9.9V, maximum current efficient is 31.0cdA
-1, maximum power efficiency is 26.5lmW
-1The spectrum peak of photoluminescence is 474nm, and is in full accord with the spectrum of this luminous dopant material, and do not find that unnecessary peak occurs.
Embodiment 9
With the material of main part of the organic semiconductor material with formula (IX) structure as blue light OLED device luminescent layer.
[1-(2 for the blue emitting phosphor metal iridium complex three that adopts U.S. Patent application US20070088167 to report, the 6-diisopropyl phenyl)-2-phenyl-1H-imidazoles] [tris[1-(2 for iridium (III), 6-diisopropylphenyl)-2-phenyl-1H-imidazole] iridium (III), (Ir (dppi)
3)] as the dopant material of blue light OLED device luminescent layer, doping content is 14%, adopts ITO as anode, TAPC is as hole mobile material, and BCP is as electron transport material, and LiF is electron injection material, Al is negative electrode, makes blue emission OLED device (device 3).
Concrete device architecture is ITO/TAPC (30nm)/EML
3(30nm)/BCP (30nm)/LiF (1nm)/Al, wherein, EML
3=formula (IX) compound: Ir (dppi)
3(14wt%), the structure of device 3 as shown in Figure 7.
Adopt vacuum deposition method to make device, 5 * 10
-4Make under the vacuum condition of Pa, ito glass used is through processing 15 minutes under ultraviolet-ozone environment after ultrasonic cleaning, and in the cavity of then directly packing into, evaporation is until finish whole device successively.Testing power supply adopts KEITHLEY 2400 systems, and spectrograph adopts PR655.Test is carried out under atmospheric environment, does not make encapsulation process, and the test result of the device 3 of made is seen Fig. 8 and Fig. 9
The performance of device 3: brightness reaches 100cdm
-2Voltage be 6.4V, 1000cdm
-2Voltage be 8.6V, high-high brightness is 11857cdm
-2Voltage be 14V, maximum current efficient is 35.7cdA
-1, maximum power efficiency is 28.2lmW
-1The spectrum peak of photoluminescence is 474nm, and is in full accord with the spectrum of this luminous dopant material, and do not find that unnecessary peak occurs.
With the material of main part of the organic semiconductor material with formula (XI) structure as blue light OLED device luminescent layer.
[1-(2 for the blue emitting phosphor metal iridium complex three of employing US Patent No. 20070088167 reports, the 6-3,5-dimethylphenyl)-2-phenyl-1H-imidazoles] [tris[1-(2 for iridium (III), 6-dimethylphenyl)-2-phenyl-1H-imidazole] iridium (III), (Ir (dmpi)
3)] as the dopant material of blue light OLED device luminescent layer, doping content is 12%, adopts ITO as anode, TAPC is as hole mobile material, and BCP is as electron transport material, and LiF is electron injection material, Al is negative electrode, makes blue emission OLED device (device 4).
Concrete device architecture is: ITO/TAPC:(30nm)/EML
4(30nm)/BCP (30nm)/LiF (1nm)/Al, wherein, EML
4The compound of=formula (XI): Ir (dmpi)
3(12wt%), the structure of device 4 as shown in figure 10.
Adopt vacuum deposition method to make device, 5 * 10
-4Make under the vacuum condition of Pa, ito glass used is through processing 15 minutes under ultraviolet-ozone environment after ultrasonic cleaning, and in the cavity of then directly packing into, evaporation is until finish whole device successively.Testing power supply adopts the KEITHLEY2400 system, and spectrograph adopts PR655.Test is carried out under atmospheric environment, does not make encapsulation process, and the test result of the device 4 of made is seen Figure 11 and Figure 12.
The performance of device 4: brightness reaches 100cdm
-2Voltage be 8.6V, 1000cdm
-2Voltage be 11.0V, high-high brightness is 8827cdm
-2Voltage be 16V, maximum current efficient is 31.1cdA
-1, maximum power efficiency is 17.4lmW
-1The spectrum peak of photoluminescence is 474nm, and is in full accord with the spectrum of this luminous dopant material, and do not find that unnecessary peak occurs.
Embodiment 11
With the material of main part of the organic semiconductor material with formula (X) structure as green glow OLED device luminescent layer.
Adopt research phosphorescent metal complex of iridium three (2-phenylpyridine-C commonly used
2, N]] iridium (III) [tris (2-phenylpyridine-C
2, N]] iridium (III), (Ir (ppy)
3)] as the dopant material of green glow OLED device luminescent layer, doping content is 10%, adopts ITO as anode, TAPC is as hole mobile material, and BCP is as electron transport material, and LiF is electron injection material, Al is negative electrode, makes green emission OLED device (device 5).
Concrete device architecture is: ITO/TAPC (30nm)/EML
5(30nm)/BCP (30nm)/LiF (1nm)/Al, wherein, EML
5=formula (X) compound: Ir (ppy)
3(10wt%), the structure of device 5 as shown in figure 13.
Element manufacturing adopts vacuum deposition method, 5 * 10
-4Make under the vacuum condition of Pa, ito glass used is through processing 15 minutes under ultraviolet-ozone environment after ultrasonic cleaning, and in the cavity of then directly packing into, evaporation is until finish whole device successively.Testing power supply adopts the KEITHLEY2400 system, and spectrograph adopts PR655.Test is carried out under atmospheric environment, does not make encapsulation process, the test result of the device 5 of made such as Figure 14 and shown in Figure 15.
The performance of device 5: brightness reaches 100cdm
-2Voltage be 4.1V, 1000cdm
-2Voltage be 5.6V, high-high brightness is 12844cdm
-2Voltage be 10.8V, maximum current efficient is 31.3cdA
-1, maximum power efficiency is 27.4lmW
-1The spectrum peak of photoluminescence is 512nm, and is in full accord with the spectrum of this luminous dopant material, and do not find that unnecessary peak occurs.
With the material of main part of the organic semiconductor material with formula (XII) structure as orange light OLED device luminescent layer.
Adopt the orange light phosphorescent metal complex of iridium three [2-phenylquinoline-C of US Patent No. 20060223997 reports
2, N]] iridium (III) [tris[2-phenylquinoline-C2, N]] iridium (III), (Ir (2-phq)
3)] as the dopant material of orange light OLED device luminescent layer, doping content is 10%, adopts ITO as anode, TAPC is as hole mobile material, and BCP is as electron transport material, and LiF is electron injection material, Al is negative electrode, makes green emission OLED device (device 6).
Concrete device architecture is: ITO/TAPC (30nm)/EML
6(30nm)/BCP (30nm)/LiF (1nm)/Al, wherein, EML
6=formula (XII) compound: Ir (2-phq)
3(10wt%), the structure of device 6 as shown in figure 16.
Adopt vacuum deposition method to make device, 5 * 10
-4Make under the vacuum condition of Pa, ito glass used is through processing 15 minutes under ultraviolet-ozone environment after ultrasonic cleaning, and in the cavity of then directly packing into, evaporation is until finish whole device successively.Testing power supply adopts the KEITHLEY2400 system, and spectrograph adopts PR655.Test is carried out under atmospheric environment, does not make encapsulation process, and the test result of the device 6 of made is seen Figure 17 and Figure 18.
The performance of device 6: brightness reaches 100cdm
-2Voltage be 4.9V, 1000cdm
-2Voltage be 6.3V, high-high brightness is 17693cdm
-2Voltage be 10.8V, maximum current efficient is 12.4cdA
-1, maximum power efficiency is 9.1lmW
-1The spectrum peak of photoluminescence is 588nm, and is in full accord with the spectrum of this luminous dopant material, and do not find that unnecessary peak occurs.
Characterization data such as following table 3 according to the device 1-6 of embodiment 6-12 made:
Table 3:OLED device 1-6 characterization data gathers
Annotate: CE: current efficiency; PE: power efficiency
Above the present invention has been done detailed description; its purpose is to allow the person skilled in the art can understand content of the present invention and be implemented; can not limit protection scope of the present invention with this; the equivalence that all spirit according to the present invention are done changes or modifies, and all should be encompassed in protection scope of the present invention.
Claims (9)
1. organic semiconductor material that is used for organic electroluminescence device is characterized in that: contain triazole, carbazole and phosphine oxygen groups in the structure of described organic semiconductor material, its structure is as shown in the formula shown in (I),
Formula (I)
Wherein, Cz is carbazole or the carbazole derivative of nitrogen atom;
1Ar,
2Ar and
3Ar is independently selected from fragrant monocycle, the many rings of fragrance, and described fragrant monocycle, the many rings of fragrance comprise aromatic heterocycle;
N is integer, and n=1～5.
2. the organic semiconductor material for organic electroluminescence device according to claim 1, it is characterized in that: described aromatic heterocycle comprises nitrogen or oxygen or sulfur heteroatom.
3. the organic semiconductor material for organic electroluminescence device according to claim 1 and 2 is characterized in that the structure of the Cz in formula (I) is:
Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Be independently selected from hydrogen or alkyl or aryl; R
9Be selected from alkyl or aryl.
4. the organic semiconductor material for organic electroluminescence device according to claim 1, is characterized in that: formula (1) compound
1Ar,
2Ar and
3Ar is independently selected from following aromatic group or derivatives thereof:
5. the organic semiconductor material for organic electroluminescence device according to claim 1 is characterized in that: the represented organic semiconductor material of formula (1) is for to be selected from the compound of following formula (II) to formula (XII):
Formula (II);
Formula (III);
Formula (IV);
Formula V;
Formula (VIII);
Formula (IX);
Formula (X);
Formula (XII).
6. the preparation method of the described organic semiconductor material for organic electroluminescence device of any one in claim 1～5 is characterized in that: the carbazole in described organic semiconductor material is by suzuki reaction or introduce by ullmann reaction; Triazole is introduced by two hydrazides and arylamine reaction; The phosphine oxygen groups is introduced by the triaryl phosphine oxidation that reaction generates with the diaryl phosphonium chloride under the organic bases effect of aryl halogen, and concrete reaction scheme is as follows
Wherein: X is Cl, Br or I;
Cz is carbazole or the carbazole derivative of nitrogen atom;
1Ar,
2Ar and
3Ar is independently selected from fragrant monocycle, the many rings of fragrance, and fragrant monocycle, the many rings of fragrance comprise aromatic heterocycle;
N is integer, and n=1～5.
7. the preparation method of the organic semiconductor material for organic electroluminescence device according to claim 6, it is characterized in that: described organic bases is butyllithium.
8. in claim 1～5, the described organic semiconductor material for organic electroluminescence device of any one is used for being manufactured with the purposes of organic electroluminescence devices.
9. purposes according to claim 8 is characterized in that: described organic semiconductor material for organic electroluminescence device is used for making as material of main part the organic light emitting diode device that display and lighting is used.
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| CN110437134A (en) * | 2019-07-24 | 2019-11-12 | 苏州络森生物科技有限公司 | A kind of synthetic method of 2,7- Dimethylcarbazole |
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| CN112928220B (en) * | 2021-01-25 | 2023-08-08 | 中国科学院长春应用化学研究所 | Organic electroluminescent diode containing crystalline solid solution as light-emitting layer and application thereof |
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