CN100569750C - The organic electroluminescence device of dendroid material of main part and this compound - Google Patents
The organic electroluminescence device of dendroid material of main part and this compound Download PDFInfo
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- CN100569750C CN100569750C CNB2007100559311A CN200710055931A CN100569750C CN 100569750 C CN100569750 C CN 100569750C CN B2007100559311 A CNB2007100559311 A CN B2007100559311A CN 200710055931 A CN200710055931 A CN 200710055931A CN 100569750 C CN100569750 C CN 100569750C
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Abstract
The present invention relates to the organic electroluminescence device of a kind of dendroid material of main part and this compound, belong to technical field of organic electroluminescence.This compound is made of branch and surface group three parts that intercalated nucleus, carbazole unit constitute.This dendrimer is a branch with the carbazole unit with cavity transmission ability, has the good carrier transmittability.Simultaneously, have good morphological stability and high triplet, can be used as the material of main part of phosphor material, particularly the material of main part of blue light phosphor material is applied in the organic electroluminescence device.The maximum luminous efficiency of prepared El element is 8.6cd/A, and maximum power efficiency is 4.11m/W, high-high brightness 6450cd/m
2, chromaticity coordinates CIE value x=0.15, y=0.30.
Description
Technical field
The invention belongs to technical field of organic electroluminescence, relate to the organic electroluminescence device of dendroid material of main part and this compound.
Technical background
Electroluminescent organic material and device are current international forward position research fields.At present, the commercialization of many electroluminescent organic materials, part organic display spare has also obtained application at aspects such as mobile phone, automobile audios.
According to the difference of principle of luminosity, electroluminescent organic material can be divided into fluorescent material and phosphor material two big classes.For phosphor material, owing to can make full use of all form of energy that comprise singlet and triplet state, increase substantially the efficient of device, can make the internal quantum efficiency of device reach 100% in theory.Therefore, utilize transition metal complex to become a kind of good methods that improves device efficiency as luminescent material.
Yet this class phosphor material has very strong concentration quenching effect.To obtain high efficient, in the preparation of devices process, phosphor material generally is diluted in the material of main part with certain proportion and uses for fear of this effect.This is higher than the triplet of phosphor material with regard to the triplet that requires material of main part.Otherwise triplet energy state can be transferred to material of main part from phosphor material, discharges in the mode of non-radiative decay, thereby causes the reduction of device efficiency.For this reason, material of main part with high triplet of design and exploitation has become a major challenge of academia and industrial community.
Summary of the invention
For solving above-mentioned technical problem, the present invention is based on the characteristics of dendrimer, be branch with carbazole unit with cavity transmission ability, develop a kind of dendroid material of main part, and be used to prepare organic electroluminescence device with high triplet.
One of purpose of the present invention provides the dendroid material of main part of phosphor material.
Two of purpose of the present invention provides the organic electroluminescence device of the dendroid material of main part of this phosphor material.
In order to reach one of purpose of the present invention, provide the dendroid material of main part of phosphor material.A kind of dendroid material of main part with phosphor material of chemical formula (1), this compound is made of branch and surface group three parts that 9-phenyl carbazole intercalated nucleus, carbazole unit constitute, and it is characterized in that its structural formula is as follows:
Wherein, R is a surface group, is independently selected from the alkyl of C1-C30, the alkenyl of C2-C20 or the alkoxyl group of C1-C20; The position of substitution of R can be the 1-4 position and the 5-8 position of carbazole, preferred 3 and 6; N is the algebraically of branch, is independently selected from 1,2 and 3.
The preferred embodiment of the dendroid material of main part of the phosphor material of described above-mentioned chemical formula (1) is for having the compound of following chemical formula (2) to (3).
The preparation method of the dendroid material of main part of chemical formula (1) is described below.The dendroid material of main part adopts convergence method synthetic, promptly peripheral branch D
nReact by classical high temperature Ullmann with the iodo product 3I-Core of 9-phenyl carbazole intercalated nucleus, obtain the compound of chemical formula (1).Peripheral branch D
nWith the mol ratio of iodo product 3I-Core be 3~9, preferred 3~6; Temperature of reaction is 160 ℃~230 ℃, and the reaction times is 24~144 hours; Reaction solvent uses high boiling solvent, selects 1 for use, 3-dimethyl-3,4,5,6-tetrahydrochysene-2-pyrimidone (DMPU), oil of mirbane, tert.-butylbenzene or dichlorobenzene, preferred DMPU; Metal catalyst is selected cuprous iodide, cuprous chloride, cuprous bromide or copper powder for use, preferred cuprous iodide, and basic catalyst is selected salt of wormwood, yellow soda ash, potassium hydroxide or sodium hydroxide for use, preferred salt of wormwood; In order to add the speed of fast response, can add 0~10% phase-transfer catalyst 18-hat-6.
In order to realize two of purpose of the present invention, provide the organic electroluminescence device of the dendroid material of main part of a kind of above-mentioned chemical formula of use (1).
As shown in Figure 1, a kind of organic electroluminescence device, between first electrode 102 that is connected with substrate 101 and second electrode 108, one or more layers organic layer is arranged, it is characterized in that, wherein having one deck organic layer at least is emission layer 104, it includes the dendroid material of main part of described chemical formula (1), or this dendroid material of main part and phosphorescent dopants, described phosphorescent dopants is Ir (III) title complex, Pt (II) title complex, Ru (II) title complex, Os (II) title complex, Re (I) title complex or Cu (I) title complex.
A kind of organic electroluminescence device, it is characterized in that, described have the multilayer organic layer to be between first electrode 102 that is connected with substrate 101 and second electrode 108: hole injection layer 103, emission layer 104, hole blocking layer 105, electron transfer layer 106, electron injecting layer 107, they connect formation successively, described first electrode 102 connects with hole injection layer 103, and electron injecting layer 107 connects with second electrode 108.
Described substrate 101 is glass or transparent, flexible plastics; First electrode 102 is indium tin oxide (ITO), indium-zinc oxide (IZO), nickel (Ni), platinum (Pt) or the gold (Au) of the metal oxide of the conducting metal that is easy to the hole and injects or conduction; The material of hole injection layer (HIL) 103 is water miscible PEDOT (poly-(3, the 4-Ethylenedioxy Thiophene)) or PSS (poly styrene sulfonate); Emission layer (EML) 104 contains dendroid material of main part or this dendroid material of main part and the phosphorescent dopants of described chemical formula (1); Phosphorescent dopants is Ir (III) title complex, Pt (II) title complex, Ru (II) title complex, Os (II) title complex, Re (I) title complex or Cu (I) title complex; In order to improve the transmission performance of current carrier, in EML104, add chemical formula (4) any one electron transport material to chemical formula (7):
The material of HBL105 is the phenanthroline derivative, and it is preferably 2,9-dimethyl-4,7-phenylbenzene-1,10-phenanthroline (BCP), triazole derivative, oxadiazole derivative or aluminium complex; Suitable material Wei oxazole, oxadiazole, isoxazole, triazole, thiadiazoles, imidazoles or the aluminium complex of ETL106; The material of EIL107 is LiF, NaCl, NaOH, CsF, Cs
2CO
3, Ca (acac)
3The material of second electrode 108 is generally low work function metal: Ca, Ba, Al, Mg or Ag.
Organic EL device structure of the present invention as shown in Figure 1, wherein HIL103, HBL105, ETL106 or EIL107 can select to use or do not use.
Below, will describe the method for making organic EL device in detail.
With reference to the accompanying drawings 1, at first form first electrode 102 of figure on the surface of substrate 101.General material as substrate be transparent, be easy to handle and waterproof and surface glass substrate or transparent, flexible plastic uniformly.Substrate 101 preferably has the thickness of 0.3~0.7mm.
Cleaning has the substrate 101 of first electrode 102, with an organic solvent, and as Virahol, acetone etc.After the cleaning, substrate 101 is carried out ultraviolet ray/ozonize.
Then, on first electrode 102 of substrate 101, optionally form hole injection layer (HIL) 103.HIL103 can reduce the contact resistance between first electrode 102 and the emission layer (EML) 104, increases the injectability in hole.The material that preferably is suitable for HIL103 is water miscible PEDOT (poly-(3, the 4-Ethylenedioxy Thiophene) or PSS (poly styrene sulfonate).When applying first electrode 102, answer heat drying to form HIL103 with this material.Wherein, when PEDOT is used for HIL103, preferred dry coating under 100~250 ℃ temperature.
Then, on HIL103, form emission layer (EML) 104.Emission layer (EML) 104 is made by the dendroid material of main part and the phosphorescent dopants combination of above-mentioned chemical formula (1).The phosphorescent dopants that is fit to is Ir (III) title complex, Pt (II) title complex, Ru (II) title complex, Os (II) title complex, Re (I) title complex or Cu (I) title complex.
In order to improve the transmission performance of current carrier, also can in EML104, add electron transport material.The electron transport material that is fit to comprises the compound of chemical formula (4) to chemical formula (7);
Emission layer EML104 adopts the method preparation of solution spin coating, and organic solvent can use chloroform, toluene, chlorobenzene etc.Then, emission layer can be heat-treated under vacuum condition, the preferred 60-100 of thermal treatment temp ℃.
On EML104,, form hole blocking layer (HBL) 105 by vacuum-deposited method.HBL105 can prevent that exciton or hole migration are in electron transfer layer (ETL) 106.The material that is applicable to HBL105 is the BCP of phenanthroline derivative; Triazole, oxadiazole derivative or aluminium complex.
On HBL105,, form electron transfer layer (ETL) 106 by vacuum-deposited method.The suitable material Wei oxazole, oxadiazole, isoxazole, triazole, thiadiazoles, imidazoles or the aluminium complex that are used for ETL106.
Then, forming the material that electron injecting layer (EIL) 107. is used for EIL107 on ETL106 is LiF, NaCl, NaOH, CsF, Cs
2CO
3, Ca (acac)
3, the thickness of preferred EIL107 is 1-
At last, deposition second electrode 108 is finished the manufacturing of organic EL device on EIL107.The material that is suitable for second electrode 108 is generally low work function metal: Ca, Ba, Al, Mg or Ag.The thickness of preferred second electrode 108 is 800-
Beneficial effect: design of the present invention and synthetic dendroid material of main part have good morphological stability and high triplet, can be used as the material of main part of phosphor material, particularly the material of main part of blue light phosphor material is applied in the organic electroluminescence device.As material of main part, the performance of prepared El element is as follows: maximum luminous efficiency is 8.6cd/A with the compound of preferred embodiment chemical formula (2), and maximum power efficiency is 4.1lm/W, high-high brightness 6450cd/m
2, chromaticity coordinates CIE value x=0.15, y=0.30.
Description of drawings
Fig. 1 is the structural representation of the organic electroluminescence device of dendroid material of main part.
Fig. 2 provides the current density-voltage-luminosity response of the organic EL device of embodiment 1 manufacturing;
Fig. 3 provides the change curve of the luminous efficiency of the organic EL device that embodiment 1 makes with current density;
Fig. 4 provides the change curve of the power efficiency of the organic EL device that embodiment 1 makes with current density;
Fig. 5 provides the EL spectrum of the organic EL device of embodiment 1 manufacturing.
Embodiment
Embodiment 1: the compound of chemical formula (2) synthetic
Reaction formula 1:
Under the nitrogen protection; compound 3.1g (5.0mmol) with chemical formula (8); peripheral branch D1 4.6g (16.5mmol), salt of wormwood 4.2g (30.0mmol), cuprous iodide 300mg (1.5mmol); 18-is preced with-6 211mg (0.8mmol) and 1; 3-dimethyl-3,4,5; the mixture heating up to 170 of 6-tetrahydrochysene-2-pyrimidone (DMPU) 2mL ℃; reacted 24 hours, in the dilute hydrochloric acid and remaining salt of wormwood, dichloromethane extraction; ammoniacal liquor flush away cupric ion; saturated common salt is washed to neutrality, and anhydrous sodium sulfate drying is after the decompression rotary evaporation falls solvent; post separates the compound 4.4g that obtains chemical formula (2), productive rate 82%.
Embodiment 2: the compound of chemical formula (3) synthetic
Reaction formula 2:
Under the nitrogen protection, with the compound 1.6g (2.5mmol) of chemical formula (8), peripheral branch D
25.9g (8.2mmol), salt of wormwood 2.1g (15.0mmol), cuprous iodide 150mg (0.75mmol), 18-is preced with-6 106mg (0.4mmol) and 1,3-dimethyl-3,4,5, the mixture heating up to 190 of 6-tetrahydrochysene-2-pyrimidone (DMPU) 5mL ℃, reacted 48 hours, in the dilute hydrochloric acid and remaining salt of wormwood, dichloromethane extraction, ammoniacal liquor flush away cupric ion, saturated common salt is washed to neutrality, and anhydrous sodium sulfate drying is after the decompression rotary evaporation falls solvent, post separates the compound 3.3g that obtains chemical formula (3), productive rate 55%.
El element prepares embodiment 1:
For the embodiment that provides, blue light complex of iridium FIrpic is entrained in the dendroid material of main part of chemical formula (2), and adds electron transport material OXD-star, form emission layer, three's weight ratio is 1: 8: 2.The structure of device is: the dendroid material of main part of ITO/PEDOT (70nm)/chemical formula (2): OXD-star:FIrpic (8: 2: 1)/Ca (10nm)/Al (100nm).The packaging technology of device is as follows:
1, to have 100 Ω/cm
2Indium tin oxide (ITO) substrate as anode.Water miscible polythiofuran derivative (PEDOT) is spin-coated on the anode, dries by the fire 30min down at 120 ℃, forms the thick hole injection layer of 70nm.
2, the dendroid material of main part of chemical formula (2), electron transport material OXD-star and blue light complex of iridium FIrpic are dissolved in the chlorobenzene, are made into the solution of 22 mg/ml, are spin-coated on PEDOT with 1500 rev/mins speed and go up the formation emission layer.This emission layer is under vacuum condition, in 80 ℃ of thermal treatment 30min.
3, the thick Al electrode of Ca that 10nm is thick on evaporation on the emission layer successively and 100nm is finished the preparation of organic EL device.
The performance of the El element of gained is as follows: maximum luminous efficiency is 8.6cd/A, and maximum power efficiency is 4.1lm/W, high-high brightness 6450cd/m
2, chromaticity coordinates CIE value x=0.15, y=0.30.
El element embodiment 2:
For this embodiment, blue light complex of iridium FIrpic is entrained in the dendroid material of main part of chemical formula (3), and adds electron transport material OXD-star, form emission layer, three's weight ratio is 1: 8: 2.The structure of device is: the dendroid material of main part of ITO/PEDOT (70nm)/chemical formula (3): OXD-star:FIrpic (8: 2: 1)/Ca (10nm)/Al (100nm).The processing condition of device assembling are with embodiment 1.
The performance of the El element of gained is as follows: maximum luminous efficiency is 5.0cd/A, and maximum power efficiency is 1.9lm/W, high-high brightness 3200cd/m
2, chromaticity coordinates CIE value x=0.16, y=0.32.
Claims (8)
1, dendroid material of main part, this compound is made of branch and surface group three parts that 9-phenyl carbazole intercalated nucleus, carbazole unit constitute, it is characterized in that, structural formula as the formula (1):
Wherein, R is a surface group, is independently selected from the alkyl of C1-C30, the alkenyl of C2-C20 or the alkoxyl group of C1-C20; The position of substitution of R is the 1-4 position and the 5-8 position of carbazole; N is the algebraically of branch, is independently selected from 1,2 and 3.
4, a kind of organic electroluminescence device, between first electrode (102) that is connected with substrate 101 and second electrode (108), one or more layers organic layer is arranged, it is characterized in that, wherein having one deck organic layer at least is emission layer (104), it includes the dendroid material of main part according to the described chemical formula of claim 1 (1), or this dendroid material of main part and phosphorescent dopants;
Described phosphorescent dopants is Ir (III) title complex, Pt (II) title complex, Ru (II) title complex, Os (II) title complex, Re (I) title complex or Cu (I) title complex.
6, as claim 4 or 5 described a kind of organic electroluminescence devices, it is characterized in that, described have the multilayer organic layer to be between first electrode (102) that is connected with substrate (101) and second electrode (108): hole injection layer (103), emission layer (104), hole blocking layer (105), electron transfer layer (106), electron injecting layer (107), they connect formation successively, described first electrode (102) connects with hole injection layer (103), and electron injecting layer (107) connects with second electrode (108).
7, a kind of organic electroluminescence device as claimed in claim 6 is characterized in that, described substrate (101) is glass or transparent, flexible plastics; First electrode (102) is indium tin oxide, indium-zinc oxide, nickel, platinum or the gold of the metal oxide of the conducting metal that is easy to the hole and injects or conduction; The material of hole injection layer (103) is water miscible poly-(3, the 4-Ethylenedioxy Thiophene) or poly styrene sulfonate; Emission layer (104) contains dendroid material of main part or this dendroid material of main part and the phosphorescent dopants of above-mentioned chemical formula (1), and phosphorescent dopants is Ir (III) title complex, Pt (II) title complex, Ru (II) title complex, Os (II) title complex, Re (I) title complex or Cu (I) title complex; The material of hole blocking layer (105) is phenanthroline derivative, triazole derivative, oxadiazole derivative or aluminium complex; Material Wei oxazole, oxadiazole, isoxazole, triazole, thiadiazoles, imidazoles or the aluminium complex of electron transfer layer (106); The material of electron injecting layer (107) is LiF, NaCl, NaOH, CsF, Cs
2CO
3, Ca (acac)
3The material of second electrode (108) is low work function metal Ca, Ba, Al, Mg or Ag.
8, a kind of organic electroluminescence device as claimed in claim 7 is characterized in that, the material phenanthroline derivative of described hole blocking layer (105) is 2,9-dimethyl-4,7-phenylbenzene-1,10-phenanthroline.
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EP2337785A1 (en) * | 2008-10-16 | 2011-06-29 | Solvay SA | N-phenyl carbazole-based host material for light-emitting diodes |
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KR101211471B1 (en) * | 2010-06-29 | 2012-12-12 | 단국대학교 산학협력단 | Highly Efficient Carbazole Type Compound and Organic Light Emitting Device Including the Same |
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