CN104326967A - Organic electroluminescent semiconductor material and preparation method and application thereof - Google Patents

Organic electroluminescent semiconductor material and preparation method and application thereof Download PDF

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CN104326967A
CN104326967A CN201310309648.2A CN201310309648A CN104326967A CN 104326967 A CN104326967 A CN 104326967A CN 201310309648 A CN201310309648 A CN 201310309648A CN 104326967 A CN104326967 A CN 104326967A
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semiconductor material
organic electroluminescent
organic
electroluminescent semiconductor
compd
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周明杰
梁禄生
王平
张娟娟
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E10/549—Organic PV cells

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Abstract

The invention discloses an organic electroluminescent semiconductor material and a preparation method and application thereof, the organic electroluminescent semiconductor material has the molecular structural formula as shown in (I), wherein R is H or C1-C4 alkyl group. The preparation method includes the step of providing a compound A and a compound B for Suzuki coupling reaction of the compound A and the compound B to prepare the organic electroluminescent semiconductor material, the organic electroluminescent semiconductor material has excellent thermal stability, and the film recrystallization phenomenon can be avoided. At the same time, the organic electroluminescent semiconductor material has excellent charge carrier transport properties and solubility, good film-forming property, and wide application range. The preparation method is mature in process and high in yield.

Description

Organic electroluminescent semiconductor material and its preparation method and application
Technical field
The invention belongs to photoelectric material technical field, relate to a kind of organic electroluminescent semiconductor material and its preparation method and application specifically.
Background technology
Organic electroluminescence device (Organic Light Emission Diode, hereinafter referred to as OLED) is a kind of current mode light emitting semiconductor device based on organic materials.Under the principle of luminosity of OLED is based on the effect of extra electric field, electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Meet at luminescent layer in electronics and hole, compound, formation exciton, and exciton moves under electric field action, and by transmission ofenergy to luminescent material, and excitation electron is from ground state transition to excited state, and excited energy, by Radiation-induced deactivation, produces photon, release luminous energy.
OLED has that luminous efficiency is high, material selection range is wide, driving voltage is low, all solidstate active illuminating, the advantage such as light, thin, have high-resolution, wide viewing angle, fast response time, low cost and the advantage such as bright in luster simultaneously, a kind of technique of display and light source of great potential, meet the development trend of information age mobile communication and information displaying, and the requirement of green lighting technique, therefore, thought to be most likely at the device of new generation following illumination and display device market occupying dominance by insider.Just because of this OLED, there is this advantage, along with the development of information age, there is the concern that the organic EL display (OLEDs) of efficient, energy-conservation, lightweight and big area white-light illuminating are more and more subject to people, higher requirement is proposed to the material of preparation OLED simultaneously.
1987, Tang and VanSlyke of Eastman Kodak company of the U.S. reported the breakthrough in organic electroluminescent research.But realize the application purpose such as total colouring and illumination, luminescent device must have certain efficiency and life-span.There is efficient, stable blue light material at present comparatively lack, have impact on the lifting in OLED efficiency and life-span.
Anthracene single crystal is the blue organic electroluminescent material used the earliest, but makes device unstable due to its easy crystallization.In order to prevent its recrystallize, improve thermostability, the improvement of those skilled in the art to the carrying out of organic anthracene single crystal blue organic electroluminescent material on molecular structure and exploration, but still there is following problems in the blue organic electroluminescent material of preparation, constrain as the application of one of OLED three primary colours material blue light material in OLED: 1. to work long hours under the electric field or in intensification tempering program, the still unstable and easily crystallization of the film morphology of blue light material, is difficult to form unbodied film; 2. carrier transmission performance is poor, and fluorescence quantum efficiency is not high.Therefore, during as existing blue organic electroluminescent material is applied to OLED, cause OLED poor stability, light efficiency is low, and the life-span is short.
Summary of the invention
The object of the invention is to the above-mentioned deficiency overcoming prior art, a kind of organic electroluminescent semiconductor material is provided, to solve the technical problem of existing electroluminescent organic material thermostability and carrier transmission performance difference.
Another object of the present invention is to provide a kind of productive rate high, the preparation method of the organic electroluminescent semiconductor material be easy to operate and control.
Further aim of the present invention is the application providing above-mentioned organic electroluminescent semiconductor material.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A kind of organic electroluminescent semiconductor material, its general formula of molecular structure is following (I):
In formula, R is H or C 1~ C 4alkyl.
And a kind of method preparing above-mentioned organic electroluminescent semiconductor material, comprises the steps:
Compd A, the B of following structural formula general formula are provided:
In anaerobic, alkaline environment and organo-metallic catalyst, under organic solvent existent condition, described compd A and B are carried out Suzuki linked reaction, and obtaining following general structure is the organic electroluminescent semiconductor material that (I) represents:
Wherein, the R in compd A, general structure (I) is H or C 1~ C 4alkyl.
And, above-mentioned organic electroluminescent semiconductor material at organic photoelectrical material, polymer solar battery, organic electroluminescence device, organic field effect tube, organic light storage device, organic non-linear optical properties or/and application in organic laser apparatus.
Above-mentioned organic electroluminescent semiconductor material passes through 1,3, the sec.-propyl position of 5-tri-(sec.-propyl) benzene connects respectively three carbazoles, whole material structure is had configuration that plane founds structure, give the thermal stability that this organic electroluminescent semiconductor material is high.Meanwhile, this carbazole is nitrogenous electron rich group, is a kind of carrier transport group of excellence, therefore, gives the carrier transmission performance of this organic electroluminescent semiconductor material excellence.In addition, organic electroluminescent semiconductor material also has excellent solvability and film-forming properties.Just because of this organic electroluminescent semiconductor material, there is the excellent performance such as thermostability, carrier transport, widened the range of application of this organic electroluminescent semiconductor material.
Above-mentioned organic electroluminescent method for preparing semi-conducting material adopts ripe Suzuki linked reaction, compd A and B are carried out coupling, thus makes the productive rate of target product high, and its linked reaction is easy to operate and control, and is suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the schema of embodiment of the present invention organic electroluminescent method for preparing semi-conducting material;
The OLED structure schematic diagram that Fig. 2 utilizes embodiment of the present invention organic electroluminescent semiconductor material to prepare;
In Fig. 3 Application Example 1, the OLED of preparation carries out spectroscopic analysis figure when 6.5V.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The invention provides a kind of organic electroluminescent semiconductor material with superior heat-stability and carrier transmission performance.The general formula of molecular structure of this organic electroluminescent semiconductor material is following (I):
Particularly, the R in logical formula I formula is H or C 1~ C 4alkyl.Wherein, the solvability that this organic electroluminescent semiconductor material can be improved of this R group existence.Accordingly, in a preferred embodiment, this R group is C 4alkyl, is more preferably tertiary butyl groups.
In a particular embodiment, the R in logical formula I formula is C 1~ C 4alkyl time, this R can be methane or tertiary butyl groups.
Like this, above-mentioned organic electroluminescent semiconductor material by connecting three carbazoles respectively on the sec.-propyl position of 1,3,5-tri-(sec.-propyl) benzene, whole material structure is had configuration that plane founds structure, gives the thermal stability that this organic electroluminescent semiconductor material is high.Meanwhile, this carbazole is nitrogenous electron rich group, is a kind of carrier transport group of excellence, therefore, gives the carrier transmission performance of this organic electroluminescent semiconductor material excellence.Particularly, the thermostability of this organic electroluminescent semiconductor material refers to hereafter table 1, and carrier transmission performance refers to hereafter table 2.In addition, according to the Molecular Structure Design of this organic electroluminescent semiconductor material, phenyl ring links many support arms, effective increasing is macromolecular sterically hindered, interaction between Inhibitory molecules chain and accumulation, organic electroluminescent semiconductor material crystallinity is suppressed, improves its film forming properties.Secondly, R group, except improving except carrier transmission performance, effectively can also improve the solvability of this organic electroluminescent semiconductor material, improves the film forming properties in the course of processing further.Further, by the selection of the R in mutual-through type (I) formula, dissolving and the film forming properties of this organic electroluminescent semiconductor material can be improved further.
Correspondingly, the embodiment of the present invention additionally provides the method that one prepares the organic electroluminescent semiconductor material of above-mentioned general formula of molecular structure (I), and its preparation method flow process as shown in Figure 1.This organic electroluminescent method for preparing semi-conducting material comprises the steps:
S01., compd A, the B of following structural formula general formula are provided:
S02. compd A, B are carried out Suzuki linked reaction and generate organic electroluminescent semiconductor material: in anaerobic, alkaline environment and organo-metallic catalyst, under organic solvent existent condition, compd A in step S01 and B are carried out Suzuki linked reaction, and obtaining following general structure is the organic electroluminescent semiconductor material that (I) represents:
Particularly, in above-mentioned steps S01, be H or C about the R in compd B molecular structural formula 1~ C 4alkyl, this R is preferably butyl, is more preferably tertiary butyl groups.In addition, compd A, compd B can be directly commercial or according to the record of document or prepare according to organic chemical reactions principle.
In above-mentioned steps S02, the Suzuki coupled reaction chemical formula between compd A, B is as follows:
In this Suzuki coupled reaction, the condition of this Suzuki coupled reaction can directly be arranged according to the condition of the Suzuki coupled reaction of existing routine, in the present invention in order to improve the Suzuki coupled reaction speed between compd A, B, improve the productive rate of organic electroluminescent semiconductor material, in a preferred embodiment, the condition setting of this Suzuki coupled reaction is: the temperature of Suzuki linked reaction is 75 ~ 120 DEG C, and the reaction times is 24 ~ 48 hours.
In step S02, the consumption of reactant compound A, B can directly add according to ratio in both chemical equation.In the present invention, carry out to forward to impel the Suzuki linked reaction between compd A, B, improve Suzuki coupled reaction speed, improve the productive rate of organic electroluminescent semiconductor material, in a preferred embodiment, the mol ratio of reactant compound A, B consumption is 1:(2 ~ 3).
In step S02, organo-metallic catalyst is preferably organic palladium catalyzer, in further preferred embodiment, this organic palladium catalyzer is tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, at least one of three (dibenzalacetone) two in palladium.
In step S02, as preferred embodiment, the consumption of this organo-metallic catalyst and the mol ratio of compd A consumption are (0.001 ~ 0.1): 1.
As further preferred embodiment, organic palladium catalyzer is tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, at least one of three (dibenzalacetone) two in palladium, and the mol ratio of the consumption of organic palladium catalyzer and compd A consumption is (0.001 ~ 0.1): 1.
The catalyzer of above-mentioned preferred kind and consumption can provide Suzuki linked reaction speed, improve the productive rate of embodiment of the present invention target product, certainly the condition of Suzuki linked reaction can also be reduced, as made above-mentioned organic electroluminescent method for preparing semi-conducting material embodiment Suzuki linked reaction can be 75 ~ 120 DEG C in temperature, the reaction times be carry out smoothly under condition for 24 ~ 48 hours.
By above-mentioned, in above-mentioned organic electroluminescent method for preparing semi-conducting material embodiment, the Suzuki linked reaction condition between reactant compound A, B can be at least following preferred implementation:
As a preferred embodiment, the mol ratio of compd A, B consumption is 1:(2 ~ 3); The Suzuki linked reaction temperature of compd A, B is 75 ~ 120 DEG C, and the reaction times is 24 ~ 48 hours; Organo-metallic catalyst is organic palladium catalyzer.
As another preferred embodiment, the mol ratio of compd A, B consumption is 1:(2 ~ 3); The Suzuki linked reaction temperature of compd A, B is 75 ~ 120 DEG C, and the reaction times is 24 ~ 48 hours; Organo-metallic catalyst is the organic palladium catalyzer of tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, three (dibenzalacetone) two at least one in palladium.
As another preferred embodiment, the mol ratio of compd A, B consumption is 1:(2 ~ 3); The Suzuki linked reaction temperature of compd A, B is 75 ~ 120 DEG C, and the reaction times is 24 ~ 48 hours; Organo-metallic catalyst is the organic palladium catalyzer of tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, three (dibenzalacetone) two at least one in palladium, while the mol ratio of the consumption of organic palladium catalyzer and compd A consumption is (0.001 ~ 0.1): 1.
In this step S02, in each embodiment of above-mentioned organic electroluminescent method for preparing semi-conducting material, Suzuki linked reaction need be carried out in the presence of alkali, in Suzuki linked reaction, the power of alkali (negative ion) is not only depended in the impact of alkali, and cationic character will be taken into account, if positively charged ion too little being unfavorable for generates middle transition state ylide (Pd) intermediate, the speed that conductively-closed is reacted when positively charged ion is too little and efficiency will significantly decline, suitably large cationic alkali, can accelerate the speed of Suzuki reaction.Therefore, in the present invention, this alkali Cs 2cO 3, K 2cO 3, Na 2cO 3in one or more mixture, its addition is 8 ~ 12 times of compd A mole dosage.
In this step S02, in each embodiment of above-mentioned organic electroluminescent method for preparing semi-conducting material, Suzuki linked reaction must be reacted in oxygen-free environment, this is because the organo-metallic catalyst of Suzuki reaction is all be afraid of oxygen, if the existence of aerobic in reaction system, can catalyst deactivation be caused, thus cause Suzuki coupling reaction to carry out.Oxygen-free environment in reaction system can adopt vacuum or be full of rare gas element to realize, and is preferably full of rare gas element to realize oxygen-free environment, and this rare gas element is the rare gas element that the art is commonly used, such as nitrogen, argon gas etc., preferred nitrogen.
In this step S02, in each embodiment of above-mentioned organic electroluminescent method for preparing semi-conducting material, the reaction solvent of Suzuki linked reaction directly can select the solvent of Suzuki linked reaction routine.As preferred embodiment, the solvent of above-mentioned Suzuki linked reaction is organic solvent.Particularly, this organic solvent is the double solvents of any one or more in tetrahydrofuran (THF), glycol dimethyl ether, toluene.This preferred solvent can effectively dissolve each reactive component, thus improves the above-mentioned speed of reaction of Suzuki linked reaction and the yield of target product.
After Suzuki linked reaction in above-mentioned steps S02, generation such as above-mentioned general structure is the organic electroluminescent semiconductor material of (I).In this general structure (I), R is H or C 1~ C 4alkyl, R is preferably butyl, is more preferably tertiary butyl groups.That is, the R group in this general structure (I) in R group and above-mentioned steps S01 in compd B molecular structure is one to one.
In addition, in the nature of things, as other organic syntheses, the purification step of the organic electroluminescent semiconductor material to general structure (I) is also comprised.This purification step preferably carries out as follows: pour in saturated aqueous ammonium chloride by the reaction solution of gained after Suzuki linked reaction, with dichloromethane extraction, organic phase sodium chloride aqueous solution is washed, dry, revolve to steam and obtain crude product except after desolventizing, subsequently crude product is carried out silica gel column chromatography separating-purifying, finally obtain pure organic electroluminescent semiconductor material.
By above-mentioned, above-mentioned organic electroluminescent method for preparing semi-conducting material adopts ripe Suzuki linked reaction, compd A and B are carried out coupling, thus make the productive rate of target product high, and its linked reaction is easy to operate and control, without the need to special equipment and environmental requirement, its preparation method technique is simple, and mild condition, be easy to operate and control, be suitable for suitability for industrialized production.
In addition, if be not identical group by two R settings in organic electroluminescent semiconductor material general formula of molecular structure (I) mentioned above simultaneously, and this group is phenyl or C 1~ C 4alkyl or C 4during above alkyl, also in scope disclosed by the invention.This can be prepared by the compd B set in organic electroluminescent method for preparing semi-conducting material mentioned above the organic electroluminescent semiconductor material that R group changes.
Correspondingly, the embodiment of the present invention additionally provides the Application Areas of organic electroluminescent semiconductor material mentioned above.Have as the thermostability of above-mentioned excellence, carrier transport, solvability and film forming properties just because of organic electroluminescent semiconductor material mentioned above, the thermal stability of its excellence can avoid its film recrystallization phenomenon to occur, and excellent carrier transmission performance improves the luminous efficiency of organic electroluminescent semiconductor material.Therefore, this organic electroluminescent semiconductor material can at organic photoelectrical material, polymer solar battery, organic electroluminescence device, organic field effect tube, organic light storage device, organic non-linear optical properties or/and application in organic laser apparatus.As in application process, using this organic electroluminescent semiconductor material as blue-ray organic electroluminescent material.
In concrete Application Example, this organic electroluminescent semiconductor material is utilized to prepare as organic electroluminescence device.As shown in Figure 2, it comprises anode layer 1, organic function layer 2, cathode layer 3 to this organic electroluminescence device structure.Wherein, organic function layer 2 comprises the hole transmission layer 21, luminescent layer 22 and the electron transfer layer 23 that stack gradually, and electron transfer layer 23 and the stacked combination of cathode layer 3, hole transmission layer 21 and the stacked combination of anode layer 1, luminescent layer 22 material is organic electroluminescent semiconductor material mentioned above.In addition, anode layer 1, cathode layer 3, hole transmission layer 21, electron transfer layer 23 layers of material material that this area all can be selected conventional.The thickness of each layer also can be arranged according to the thickness of this area routine.
Certainly, as the advantageous applications embodiment of this organic electroluminescent semiconductor material, this organic function layer 2 can also comprise hole injection layer and electron injecting layer (figure does not show), or comprises electronic barrier layer, hole blocking layer (figure does not show) further.This hole injection layer preferably contained, electron injecting layer, electronic barrier layer, hole blocking layer each layer lamination order are carried out stacked according to the structure of this area organic electroluminescence device routine, do not specially require in the present invention.
Certainly, as the advantageous applications embodiment of this organic electroluminescent semiconductor material, organic electroluminescence device also comprises substrate (figure do not show), and this substrate can be bonded inversion organic electroluminescence device with cathode layer 3 outside surface is stacked, or with the stacked combination of anode layer 1 outside surface.
Now in conjunction with the embodiments, the present invention is further elaborated.
Embodiment 1
A kind of organic electroluminescent semiconductor material 9-(4-(2-(3 containing carbazole, two (2-(4-(9H-carbazole-9-base) phenyl) propane-2-base) phenyl of 5-) propane-2-base) phenyl)-9H-carbazole (called after TCzIPB), its molecular structural formula is as following I 1shown in:
This organic electroluminescent semiconductor material I 1preparation method comprise the steps:
(1) compd A (1,3,5-tri-(1-bromine sec.-propyl) benzene) providing following structural formula to represent respectively and compd B (4-(9H-carbazole-9-base) phenylo boric acid),
(2) by compd A (1, 3, 5-tri-(1-bromine sec.-propyl) benzene) 4.0mmol, compd B (4-(9H-carbazole-9-base) phenylo boric acid) 8.0mmol, catalyzer (tetrakis triphenylphosphine palladium) 0.4mmol joins in reaction flask, vacuumizes, after logical nitrogen circulation 3 times, makes reaction system be in anaerobic state, under nitrogen protection, add the Na of tetrahydrofuran solution 55mL, 2mol/L 2cO 3aqueous solution 40ml, Suzuki coupling reaction is carried out in mixed solution heating, 75 ~ 80 DEG C of back flow reaction 24h, obtained containing the organic semiconductor material 9-(4-(2-(3 containing carbazole, two (2-(4-(9H-carbazole-9-base) phenyl) propane-2-base) phenyl of 5-) propane-2-base) phenyl) reaction solution of-9H-carbazole, described reaction solution is poured in the aqueous solution of saturated ammonium chloride, dichloromethane extraction three times, organic phase sodium chloride aqueous solution is washed, dry, revolve to steam and obtain crude product except after desolventizing, through silica gel column chromatography separating-purifying, finally obtain the (4-(2-(3 of the solid product 9-after purifying, two (2-(4-(9H-carbazole-9-base) phenyl) propane-2-base) phenyl of 5-) propane-2-base) phenyl)-9H-carbazole.The productive rate of this 9-(4-(2-(two (2-(4-(9H-carbazole-9-base) phenyl) propane-2-base) phenyl of 3,5-) propane-2-base) phenyl)-9H-carbazole is 60%.
9-(4-(2-(3 prepared by the present embodiment 1, two (2-(4-(9H-carbazole-9-base) phenyl) propane-2-base) phenyl of 5-) propane-2-base) phenyl)-9H-carbazole compound carries out mass spectroscopy and ultimate analysis, and analytical results is as follows:
Mass spectrometric measurement result is: MS:m/z929 (M +);
Ultimate analysis: C 69h 57n 3, C, 89.35; H, 6.17; N, 4.56.
Embodiment 2:
A kind of organic electroluminescent semiconductor material 9-(4-(2-(3 containing carbazole, two (2-(the 4-(3 of 5-, 6-dimethyl-9H-carbazole-9-base) phenyl) propane-2-base) phenyl) propane-2-base) phenyl)-3,6-dimethyl-9H-carbazole (in the present invention called after TMCzIPB), its molecular structural formula is as shown in following I 2:
This organic electroluminescent semiconductor material I 2preparation method comprise the steps:
(1) compd A (1,3,5-tri-(1-bromine sec.-propyl) benzene) providing following structural formula to represent respectively and compd B (4-(3,6-dimethyl-9H-carbazole-9-base) phenylo boric acid),
(2) by compd A (1, 3, 5-tri-(1-bromine sec.-propyl) benzene) 4.0mmol, compd B (4-(3,6-dimethyl-9H-carbazole-9-base) phenylo boric acid) 8.5mmol, catalyzer (three (dibenzalacetone) two palladium) 0.12mmol joins in reaction flask, vacuumize, after logical nitrogen circulation 3 times, make reaction system be in anaerobic state, under nitrogen protection, add the K of glycol dimethyl ether 70mL, 2mol/L 2cO 3aqueous solution 45ml, Suzuki coupling reaction is carried out in mixed solution heating, 95 DEG C of back flow reaction 40h, obtained containing the organic semiconductor material 9-(4-(2-(3 containing carbazole, two (2-(the 4-(3 of 5-, 6-dimethyl-9H-carbazole-9-base) phenyl) propane-2-base) phenyl) propane-2-base) phenyl)-3, the reaction solution of 6-dimethyl-9H-carbazole, described reaction solution is poured in the aqueous solution of saturated ammonium chloride, dichloromethane extraction three times, organic phase sodium chloride aqueous solution is washed, dry, revolve to steam and obtain crude product except after desolventizing, through silica gel column chromatography separating-purifying, finally obtain the (4-(2-(3 of the solid product 9-after purifying, two (2-(the 4-(3 of 5-, 6-dimethyl-9H-carbazole-9-base) phenyl) propane-2-base) phenyl) propane-2-base) phenyl)-3, 6-dimethyl-9H-carbazole.This 9-(4-(2-(3, two (2-(the 4-(3 of 5-, 6-dimethyl-9H-carbazole-9-base) phenyl) propane-2-base) phenyl) propane-2-base) phenyl) productive rate of-3,6-dimethyl-9H-carbazoles is 64%.
9-(4-(2-(3 prepared by the present embodiment 2, two (2-(the 4-(3 of 5-, 6-dimethyl-9H-carbazole-9-base) phenyl) propane-2-base) phenyl) propane-2-base) phenyl)-3,6-dimethyl-9H-carbazole compound carries out mass spectroscopy and ultimate analysis, and analytical results is as follows:
Mass spectrometric measurement result is: MS:m/z1012 (M +).
Ultimate analysis: C 75h 69n 3, C, 88.91; H, 6.82; N, 4.14.
Embodiment 3:
A kind of organic electroluminescent semiconductor material 9-(4-(2-(3 containing carbazole, two (2-(the 4-(3 of 5-, 6-di-t-butyl-9H-carbazole-9-base) phenyl) propane-2-base) phenyl) propane-2-base) phenyl)-3,6-di-t-butyl-9H-carbazole (in the present invention called after TtBuCzIPB), its molecular structural formula is as shown in following I 3:
This organic electroluminescent semiconductor material I 3preparation method comprise the steps:
(1) compd A (1,3,5-tri-(1-bromine sec.-propyl) benzene) providing following structural formula to represent respectively and compd B (4-(3,6-di-t-butyl-9H-carbazole-9-base) phenylo boric acid),
(2) by compd A (1, 3, 5-tri-(1-bromine sec.-propyl) benzene) 4.0mmol, compd B (4-(3,6-di-t-butyl-9H-carbazole-9-base) phenylo boric acid) 12.0mmol, catalyzer (two (triphenylphosphine) palladium chloride) 0.004mmol joins in reaction flask, vacuumize, after logical nitrogen circulation 3 times, make reaction system be in anaerobic state, under nitrogen protection, add the Cs of toluene solution 60mL, 2mol/L 2cO 3aqueous solution 50ml, Suzuki coupling reaction is carried out in mixed solution heating, 120 DEG C of back flow reaction 48h, obtained containing the organic semiconductor material 9-(4-(2-(3 of P3 containing carbazole, two (2-(the 4-(3 of 5-, 6-di-t-butyl-9H-carbazole-9-base) phenyl) propane-2-base) phenyl) propane-2-base) phenyl)-3, the reaction solution of 6-di-t-butyl-9H-carbazole, described reaction solution is poured in the aqueous solution of saturated ammonium chloride, dichloromethane extraction three times, organic phase sodium chloride aqueous solution is washed, dry, revolve to steam and obtain crude product except after desolventizing, through silica gel column chromatography separating-purifying, finally obtain the (4-(2-(3 of the solid product 9-after purifying, two (2-(the 4-(3 of 5-, 6-di-t-butyl-9H-carbazole-9-base) phenyl) propane-2-base) phenyl) propane-2-base) phenyl)-3, 6-di-t-butyl-9H-carbazole.This 9-(4-(2-(3, two (2-(the 4-(3 of 5-, 6-di-t-butyl-9H-carbazole-9-base) phenyl) propane-2-base) phenyl) propane-2-base) phenyl) productive rate of-3,6-di-t-butyl-9H-carbazoles is 79%.
9-(4-(2-(3 prepared by the present embodiment 3, two (2-(the 4-(3 of 5-, 6-di-t-butyl-9H-carbazole-9-base) phenyl) propane-2-base) phenyl) propane-2-base) phenyl)-3,6-di-t-butyl-9H-carbazole compound carries out mass spectroscopy and ultimate analysis, and analytical results is as follows:
Mass spectrometric measurement result is: MS:m/z1264 (M +).
Ultimate analysis: C 93h 105n 3, C, 88.24; H, 8.41; N, 3.35.
Performance test:
TCzIPB, TMCzIPB, TtBuCzIPB compound prepared by above-described embodiment 1-3 carries out the mensuration of following performance respectively, records result as follows respectively:
1. thermal stability determination:
Adopt thermogravimetric analyzer (TGA) to detect, analysis condition is nitrogen atmosphere, and when sweep velocity is 10 DEG C/min, analytical results is as shown in table 1:
The heat decomposition temperature of organic semiconductor material prepared by table 1 embodiment 1-3
As shown in Table 1, embodiment of the present invention organic electroluminescent semiconductor material has high heat decomposition temperature, its heat decomposition temperature is up to 400 DEG C more than (5% thermal weight loss), wherein, the heat decomposition temperature of the organic electroluminescent semiconductor material as embodiment 1 preparation that heat decomposition temperature is minimum is up to 401 DEG C, the heat decomposition temperature of organic electroluminescent semiconductor material prepared by embodiment 3 is up to 426 DEG C, and thermostability is high.
2. carrier transmission performance measures:
Adopt time of flight method (Time of Flight, TOF) to detect, record result as shown in table 2 below:
The hole mobility of organic semiconductor material prepared by table 2 embodiment 1-3
As shown in Table 2, be 8 × 10 at electric field 5vcm -1time, the hole mobility of embodiment of the present invention organic semiconductor material is 1.4 × 10 -5cm 2(Vs) -1above, illustrate that embodiment of the present invention organic electroluminescent semiconductor material has good hole transport performance.
Application Example 1:
9-(4-(the 2-(3 utilizing above-described embodiment 1 to prepare, two (2-(4-(9H-carbazole-9-base) phenyl) propane-2-base) phenyl of 5-) propane-2-base) phenyl)-9H-carbazole (called after TCzIPB) prepares OLED, this OLED structure is with reference to Fig. 2, and it comprises glass substrate/ito anode layer (150nm)/NPB hole transmission layer (40nm)/TCzIPB luminescent layer (25nm)/TPBI electron transfer layer (20nm)/LiF buffer layer (the 1nm)/Al cathode layer (120nm) stacking gradually combination.
Wherein, anode layer ITO(tin indium oxide) square resistance be the ITO of 10-20 Ω/mouth.The each layer of OLED adopts the method preparation of vacuum evaporation, and the technique of vacuum evaporation is according to existing processing parameter setting, and Preparation equipment is: high vacuum coating system (scientific instrument development center, Shenyang company limited).
OLED prepared by above-mentioned this application embodiment is carried out electroluminescent spectrum, Electrical.Wherein, spectroscopic analysis adopts the USB4000 fiber spectrometer of U.S. ocean optics Ocean Optics to test; Electrical adopts the Keithley2400 test of Keithley company of the U.S..Spectroscopic analysis as shown in Figure 3.As shown in Figure 3, should in the electroluminescent device of the use-case luminescent spectrum when voltage is 6.5V, its maximum emission wavelength, at 436nm, belongs to blue light electroluminescent scope.
At room temperature, test under atmospheric environment, this Nan dian Yao achieves the current efficiency of 9.4cd/A to OLED this application embodiment prepared.Illustrate that organic electroluminescent semiconductor material (as TCzIPB) prepared by the embodiment of the present invention has excellent stability and carrier transmission performance, give stability and the luminous efficiency of this OLED excellence, effectively extend the work-ing life of this device.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. an organic electroluminescent semiconductor material, its general formula of molecular structure is following (I):
In formula, R is H or C 1~ C 4alkyl.
2. organic electroluminescent semiconductor material according to claim 1, is characterized in that: described C 1~ C 4alkyl be methyl or the tertiary butyl.
3. prepare a method for organic electroluminescent semiconductor material as claimed in claim 1 or 2, comprise the steps:
Compd A, the B of following structural formula general formula are provided:
In anaerobic, alkaline environment and organo-metallic catalyst, under organic solvent existent condition, described compd A and B are carried out Suzuki linked reaction, and obtaining following general structure is the organic electroluminescent semiconductor material that (I) represents:
Wherein, the R in compd B, general structure (I) is H or C 1~ C 4alkyl.
4. the method preparing organic electroluminescent semiconductor material according to claim 3, is characterized in that: the temperature of described Suzuki linked reaction is 75 ~ 120 DEG C, and the reaction times is 24 ~ 48 hours.
5. the method preparing organic electroluminescent semiconductor material according to claim 3, is characterized in that: the mol ratio of described compd A and B is 1:(2 ~ 3).
6. the method preparing organic electroluminescent semiconductor material according to claim 3, is characterized in that: the consumption of described organo-metallic catalyst and the mol ratio of compd A consumption are (0.001 ~ 0.1): 1.
7., according to the arbitrary described method preparing organic electroluminescent semiconductor material of claim 3 ~ 6, it is characterized in that: described organo-metallic catalyst is organic palladium.
8. the method preparing organic electroluminescent semiconductor material according to claim 7, is characterized in that: described organic palladium is tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, three (dibenzalacetone) two at least one in palladium.
9. the organic electroluminescent semiconductor material according to any one of claim 1 to 2 at organic photoelectrical material, polymer solar battery, organic electroluminescence device, organic field effect tube, organic light storage device, organic non-linear optical properties or/and application in organic laser apparatus.
10. the application of organic electroluminescent semiconductor material according to claim 9, it is characterized in that: described organic electroluminescence device comprises the anode layer, organic function layer, the cathode layer that stack gradually combination, wherein, the luminescent layer that described organic function layer is luminous under being included in the driving of additional power source, and described emitting layer material is the organic electroluminescent semiconductor material as described in any one of claim 1 to 2.
CN201310309648.2A 2013-07-22 2013-07-22 Organic electroluminescent semiconductor material and preparation method and application thereof Pending CN104326967A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113563254A (en) * 2021-09-24 2021-10-29 季华实验室 Organic electroluminescent compound, preparation method thereof and organic electroluminescent device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113563254A (en) * 2021-09-24 2021-10-29 季华实验室 Organic electroluminescent compound, preparation method thereof and organic electroluminescent device

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