CN1395454A - organic electroluminescent device - Google Patents
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- CN1395454A CN1395454A CN 02120837 CN02120837A CN1395454A CN 1395454 A CN1395454 A CN 1395454A CN 02120837 CN02120837 CN 02120837 CN 02120837 A CN02120837 A CN 02120837A CN 1395454 A CN1395454 A CN 1395454A
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Abstract
The invention relates to the electroluminescence (EL) device with high performances. The special ramification of anthracene as the principal part is adopted in the device. The principal part is suitable to the dopant material in all colors region. When ramification of coumarin is utilized as the color dopant material of the ramification of anthracene in the EL device. The device possesses the ideal luminous efficiency and tolerance. Using ramification of anthracene with IV strural formula as the material of the electric transport layer improves the performances of the device further. Display devices can be manufactured from the invented organic EL device.
Description
Technical field
The present invention relates to a kind of high performance electroluminescent organic device containing specific electroluminescent organic material, more specifically, the present invention relates to the folder for organic electroluminescence device between the anode and cathode as the electroluminescent organic material of organic luminous layer, organic electroluminescence device containing this electroluminescent organic material can be emitted in the light of a variety of optical wavelength in limit of visible spectrum, and with higher electroluminescent efficiency, excellent durability and relatively low driving voltage.
Background technology
Organic electroluminescent (EL) device is typically made up of the single or multiple lift organic material being added between transparency electrode and metal electrode.Organic electroluminescent technology is just to have emerged in recent years and the novel flat-plate Display Technique with very big potential market competitiveness, compared with liquid crystal display (LCD) popular in the market, LCD shortcoming is overcome completely, there is low-voltage current driving, actively luminous, visual angle is big, fast response time and low cost.The manufacture of organic EL device is also relatively easy and cost is relatively low.In addition the light produced by organic EL device is enough to use under the conditions of various indoor lights.Therefore, organic EL device has potential huge applications market in full color flat-panel displays and miniscope product ask the fields such as pager, portable phone, two-way radio, data base set and other electrooptical devices.
Continuing to develop for organic electroluminescent technology has made it possible that organic EL device is applied in extensive field in recent years, but the performance level of general commercially available device is still below expected requirement.In addition, for visually displaying that application, luminous organic material should provide the color that is satisfied with limit of visible spectrum, the blue and green light and feux rouges of maximum can be typically launched in the nanometers of about 460,550 and 630.The metal complex of 8-hydroxyquinoline is often used, such as aluminium three (8-hydroxyquinoline), what it typically sent is the fluorescence in green and longer wavelength region.However, for the El element of blue light-emitting, the use of these electron transport materials is restricted.Although some organic materials of prior art can send the fluorescence of blue light range, such as United States Patent (USP) US5151629；US5432014, but the performance of obtained El element still has many shortcomings, and such as operational stability is poor.1,8- naphthoyl imide compounds are another electroluminescent materials widely studied at present, but its luminosity is only 35cd/m2, luminous efficiency is only 0.221m/W, and heat resistance and stability are poor, it is impossible to the need for meeting practical application.
Kodak once developed a kind of using 8-hydroxyquinoline (AlQ3) as organic fluorescence materials, and the organic EL device that the DC low-voltage (＜ 10) that triphenylamine is made as hole mobile material drives, its luminescence peak is positioned at 520nm, and luminous quantum efficiency is only 10%.
Japanese patent application publication No. 210790/1990 discloses a kind of organic EL device, and wherein luminescent layer includes a kind of while having the organic compound of hole transport performance and electronic transmission performance, but the organic EL device with this type compound is difficult to obtain high brightness.In addition, the heat resistance and durability of these compounds are also not good enough.Another problem that the device is present is that if Continuous Drive, compound therein is easily crystallized, and this would generally reduce the brightness of the device.
Sum it up, the electroluminescent material of high comprehensive performance is considerably less, it has also become the total colouring of organic electroluminescent and a last industrialized obstacle.Therefore the electroluminescent material for developing or finding function admirable is extremely important.In order to improve luminosity, efficiency and the life-span of organic EL device, it is necessary to which further research and development have the more suitably material and the organic EL device containing this material of electroluminescent properties.
The content of the invention
It is an object of the invention to provide a kind of organic electroluminescence device of performance improvement, it can satisfactorily be emitted in blueness to the visible ray of longer wavelength, at the same there is high-luminous-efficiency, excellent luminescent lifetime, high brightness and low driving voltage.
The present inventor by studying and testing for many years, it was found that specific class anthracene derivant, especially when this kind of anthracene derivant as material of main part and adulterate a small amount of greening or feux rouges fluorescent dye as organic EL device electroluminescent organic material when, unexpectedly realize the purpose of the present invention, so that the organic EL device containing this electroluminescent organic material has a variety of advantages of the present invention, i.e. it can satisfactorily be emitted in blueness to the visible ray of longer wavelength, improve the operational stability and durability of organic EL device, and enhance the charge transport quality of organic EL device, thus reduce driving voltage.
Specifically, the invention provides a kind of improved organic electroluminescence device, it includes at least one layer in anode, negative electrode and the Organic electroluminescent media being clipped between the anode and negative electrode layer, Organic electroluminescent media layer and contains one or more anthracene derivants.The anthracene derivant electroluminescent organic material has excellent carrier injection and transmittability, and excellent heat endurance, its can easily vacuum evaporation into film so that for organic electroluminescence device.
Furthermore, the invention provides a kind of improved organic electroluminescence device, it includes anode, negative electrode and the Organic electroluminescent media layer being clipped between the anode and negative electrode, luminescence medium layer includes hole injection and transport layer, luminescent layer, electron injection and transport layer, wherein Organic electroluminescent media layer contains one or more anthracene derivants as material of main part and the one or more greenings or the fluorescent dye of feux rouges as dopant material, the concentration of the dopant material is 0.1-5 moles of % of material of main part, the organic EL device can send the color of preferably full vision coverage area, this is the principle based on guest host energy transfer, and influence the spectral displacement from main body to object.
Embodiment of the present invention described in detail below.
In one embodiment, the present invention relates to a kind of organic electroluminescence device, it includes an anode, a negative electrode and the Organic electroluminescent media being clipped between the anode and negative electrode layer, luminescence medium layer includes hole injection and transport layer, luminescent layer, electron injection and transport layer, wherein the luminescent layer includes one or more structural formula I anthracene derivant：
Wherein R1, R2, R3And R4It is respectively hydrogen, alkyl or alkoxy containing 1-16 carbon atom, the alkenyl containing at least one carbon-to-carbon double bond, aryl or substituted aryl containing 6-24 carbon atom, heteroaryl or substituted heteroaryl, amino, N- alkyl aminos, N- arylaminos, N containing 5-24 carbon atom, N- dialkyl amidos, N, N- diaryl, cyano group, the perfluoroalkyl containing 1-8 carbon atom, chlorine, bromine and fluorine；
R5It is alkyl or perfluoroalkyl containing 1-16 carbon atom；Containing 6-40, the aryl or substituted aryl of preferably 6-24 carbon atom；Containing 5-40, the heteroaryl or substituted heteroaryl of preferably 5-24 carbon atom, cyano group, chlorine, bromine and fluorine；
X is methylene, dialkyl methylene radical and Diarylmethylidene, hetero atom such as oxygen, sulphur or the amino or dialkyl group or the silicyl or carbonyl of diaryl substitution of alkyl or aryl substitution.
According to the present invention, it was found that because the energy transfer process of decay can produce suitable organic EL device color or color, including white, so that the anthracene derivant of these types is particularly useful to produce panchromatic organic EL panel and shown.For example, green or red EL transmittings can be produced by adulterating a small amount of green or red fluorescence dyestuff for being referred to as dopant material into anthracene derivant.
It is used as one or more coumarin derivatives that the material of doping includes being represented by lower formula II in the organic EL device luminescent layer of the present invention：
Wherein R is hydrogen, the alkyl containing 1-24 carbon atom, aryl, heteroaryl or carbocyclic ring system；
R1, R2, R3, R4, R5, R6, R7, R8And R9Alkyl, aryl or the carbocyclic ring system of respectively 1-20 carbon atom；
EDG is the aryl or electron donating group of hydrogen, the alkyl of 1-24 carbon atom, 5-24 carbon atom, more specifically：
-OR10
Wherein：R10, R11And R12It is respectively the alkyl, aryl or carbocyclic ring system of 1-20 carbon atom；R11And R1, R11And R12, and R12And R2It may then bond together to form member ring systems, such as piperidines, julolidine or tetramethyl julolidine.
Include one or more anthracene derivants for being represented by lower formula II I as the another kind of material of doping in organic EL device luminescent layer of the present invention：
Wherein R1It is the alkyl containing 1-20 carbon atom；R and R2It is respectively hydrogen, the alkyl containing 1-24 carbon atom, aryl or heteroaryl containing 5-24 carbon atom.
According to the present invention, it was found that when the electron transport material that the anthracene derivant represented by following formula I V is used as organic EL device of the present invention constitutes electron transfer layer, more preferably, the electron transfer layer is while the also effect of hole blocking layer for the performance of organic EL device of the present invention：
Wherein：
R1, R2, R3, R4And R5Respectively hydrogen, alkyl or alkoxy containing 1-16 carbon atom, aryl or substituted aryl containing 6-24 carbon atom, heteroaryl or substituted heteroaryl containing 5-24 carbon atom；
X is methylene, dialkyl methylene radical and Diarylmethylidene, S, and O or NR, wherein R are hydrogen, alkyl or alkoxy containing 1-16 carbon atom, aryl or substituted aryl containing 6-24 carbon atom.
The organic EL device of the present invention can make the device produce the emission spectrum of gamut and the stability of extended operation in luminescent layer using above-mentioned organic material.
Accompanying drawing is described
Accompanying drawing is to be used to illustrate embodiment of the present invention, and it does not mean that the limitation constituted in any way to the scope of the invention or objective.
Accompanying drawing 1 represents the El element of five parts.
Accompanying drawing 3 represents the El element of seven parts.
Embodiment of the present invention is described in detail below in conjunction with accompanying drawing.More specifically, accompanying drawing 1 illustrates a kind of organic EL device of the present invention, the negative electrode 6 that the hole injection of its being made up of arylamine described below on such as glass of load substrate 2, anode 3, vacuum evaporation and transport layer 4, electron injection and electric transmission 5, low work function metal are made is constituted.The luminous or dielectric layer of the device includes hole transmission layer 4 and/or electron transfer layer 5, wherein electronics-hole-recombination, then launches light.Alternatively property, can add the fluorescent material that can be lighted after electronics-hole-recombination in luminescent layer.Anthracene derivative host of the present invention is in electron transfer layer.
In another embodiment as described in accompanying drawing 2, organic hole transmission range 4, organic electronic transmission range 5 that organic EL device of the present invention is constituted by load substrate 2 such as glass, anode 3, by the arylamine of chemical formula described herein, and the negative electrode 6 contacted are constituted.Device architecture with single layer transmission area shown in Fig. 1 is on the contrary, in the device architecture shown in Fig. 2, transmission range is made up of one or more transport layers.Specifically, Fig. 2 hole transport area 4 is by contributing to the floor 4a of hole injection and the arylamine isomer mixture floor 4b of transporting holes carrier to constitute.Electric transmission area 5 is by contributing to the floor 5a of electron injection and the floor 5b of transmission electronics to constitute.
In another embodiment as shown in Figure 3, organic EL device of the present invention is that organic hole transmission range 4, luminescent layer 5b, organic electronic transmission range 5a and the negative electrode 6 that contacts constituted by load substrate 2 such as glass, anode 3, by the arylamine of chemical formula described herein is constituted, and wherein luminescent layer is by pure luminescent material is deposited or luminous material of main part and another luminescent material co-evaporation as dopant material are made.
Carrying the illustrative example of substrate includes polymeric composition, glass etc., polyester such as MYLAR.RTM., makrolon, polyacrylate, HPMC, polysulfones, quartz etc..Other substrates also may be selected, for example they are substantially other non-functional and sustainable layers.The thickness of substrate for example can be about 25 to about 1000 microns, more specifically, about 50-6000 microns, this is the structural requirement according to such as device.
The example of anode includes conductive carbon, conjugated polymer polyaniline, polypyrrole of positive charge injecting electrode indium oxide-tin, tin oxide, gold, platinum or other materials etc., they are based on for example being equal to or greater than about 4 electron-volts, more specifically, greater than about 4-6 electron-volts of work content.The thickness of anode can be at about 10-5000 angstroms, and scope preferably is determined by the optical constant of anode material.It is preferred that a kind of thickness range be about 20-1000 angstroms.
The hole mobile material often used is triaryl amine or its mixture, such as：
Constituted for preparing the arylamine isomer mixture that the hole injection of El element of the present invention and another preferred material of transmission range are represented by following formula (1) 54：
[(A1)a+(A2)b+------+(An)x] (1) wherein：A1, A2... and AnRepresent each composition in arylamine isomer mixture；These amine isomers contain at least 24 carbon atoms, and with general molecular formula (2)：Wherein：Ar1It is aryl or substituted aryl containing at least 18 carbon atoms；Ar2And Ar3It is respectively the aryl containing at least six carbon atom or substituted aryl；Each composition (A in the mixture1, A2... .. and An) there is identical molecular formula, the difference of each composition be they atomic order or substituent the position of substitution；
A, b, --- and x is each composition A in the mixture1, A2... ..AnRatio, its scope is 0-100%, a, b, --- x summation is 1.
The mixture for following example illustrating the arylamine isomers used in organic EL device of the present invention is NPPX and NPBX mixture.
Wherein：
A, b and c are the ratios of each composition in the isomer mixture, and its scope is 0 to 100%.A, b and c summation are 1.
These arylamine isomer mixtures have the advantages that improvement film morphology property, and as a result the pin hole in organic EL device can obviously reduce.
Electron injection and transmission range in organic EL device of the present invention can be made up of any conventional electron injection and transport compound.The example of useful electron transport compound includes anthracene, Bi, perylenes described in fused rings luminescent material United States Patent (USP) 3172862 etc.；Butadiene Isosorbide-5-Nitrae as described in United States Patent (USP) 4356429 and 5516577-diphenyl diethylene and tetraphenylbutadiene and stilbene etc.；Those of fluorescent whitening agent such as described in United States Patent (USP) 4539507, all these documents are hereby incorporated by reference.
The luminescent layer of organic EL device of the present invention is by lighting or fluorescent material is constituted, and electroluminescent therein is due to electronics-hole to producing the area is compound.In the present invention is implemented, simplest structure includes single component material and constitutes luminescent layer, and it includes the anthracene derivant or its mixture represented by following general structure Formulas I：
Wherein R1, R2, R3And R4It is respectively hydrogen, alkyl or alkoxy containing 1-16 carbon atom, the alkenyl containing at least one carbon-carbon double bond, aryl or substituted aryl containing 6-24 carbon atom, heteroaryl or substituted heteroaryl, amino, N- alkyl aminos, N- arylaminos, N containing 5-24 carbon atom, N- dialkyl amidos, N, N- diaryl, cyano group, the perfluoroalkyl containing 1-8 carbon atom, chlorine, bromine and fluorine；
R5It is alkyl or perfluoroalkyl containing 1-16 carbon atom；Aryl or substituted aryl containing 6-40 carbon atom；Heteroaryl or substituted heteroaryl containing 5-40 carbon atom, cyano group, chlorine, bromine and fluorine；
X is methylene, dialkyl methylene radical and Diarylmethylidene, hetero atom such as oxygen, sulphur or the amino or dialkyl group or the silicyl of diaryl substitution of alkyl or aryl substitution.
These as follows are included according to the representative example of the anthracene derivant of the present invention.Following example is the various anthracene materials for further illustrating the present invention.It should be noted that these examples are to be used to illustrate, it is not limitation the scope of the present invention.When X is methylene, dialkyl methylene radical or Diarylmethylidene, the structural formula preferred scheme is with shown in following formula I a：Compound R1 R2, R3 R4 R5 R6 R7Ia-1, , H, , H, , , H, ,-Ph, ,-Me,-MeIa-2, , H, , H, , , H, ,-Ph, ,-Et,-EtIa-3, , H, , H, , , t-Bu,-Ph, ,-Me,-MeIa-4, , H, , H, , , t-Bu,-Ph, ,-Et,-EtIa-5, , H, , H, , , H, , 2- naphthyls,-Me,-MeIa-6, , H, , H, , , H, , 2- naphthyls,-Et,-EtIa-7, , H, , H, , , t-Bu, 2- naphthyls,-Me,-MeIa-8, , H, , H, , , t-Bu, 2- naphthyls,-Et,-EtIa-9, , H, , H, , , H, , CF3, ,-Me,-MeIa-10, H, , H, , , H, , CF3, ,-Et,-EtIa-11, H, , H, , , t-Bu, CF3, ,-Me,-MeIa-12, H, , H, , , t-Bu, CF3, ,-Et,-EtIa-13, H, , H, , , H, , CN, ,-Me,-MeIa-14, H, , H, , , H, , CN, ,-Et,-EtIa-15, H, , H, , , t-Bu, CN, ,-Me,-MeIa-16, H, , H, , , t-Bu, CN, ,-Et,-EtIa-17, NPh2 H H CF3 -Me -MeIa-18 NPh2 H H CF3 -Et -EtIa-19 NPh2 H t-Bu CF3 -Me -MeIa-20 NPh2 H t-Bu CF3 -Et -EtIa-21 NPh2 H H CN -Me -MeIa-22 NPh2 H H CN -Et -EtIa-23 NPh2 H t-Bu CN -Me -MeIa-24 NPh2 H t-Bu CN -Et -EtIa-25 NPh2 H H -Ph -Me -MeIa-26 NPh2 H H -Ph -Et -EtIa-27 NPh2 H t-Bu -Ph -Me -MeIa-28 NPh2 H t-Bu -Ph -Et -EtIa-29 NPh2H H 2- naphthyl-Me-MeIa-30 NPh2H H 2- naphthyl-Et-EtIa-31 NPh2H t-Bu 2- naphthyl-Me-MeIa-32 NPh2H t-Bu 2- naphthyl-Et-EtIa-33 H H H-Ph-Bu-BuIa-34 H H t-Bu-Ph-Bu-BuIa-35 H H H 2- naphthyl-Bu-BuIa-36 H H t-Bu 2- naphthyl-Bu-BuIa-37 H H H CF3-Bu-BuIa-38 H H t-Bu CF3-Bu-BuIa-39 H H H CN-Bu-BuIa-40 H H t-Bu CN-Bu-BuIa-41 NPh2 H H CF3 -Bu -BuIa-42 NPh2 H t-Bu CF3 -Bu -BuIa-43 NPh2 H H CN -Bu -BuIa-44 NPh2 H t-Bu CN -Bu -BuIa-45 NPh2 H H -Ph -Bu -BuIa-46 NPh2 H t-Bu -Ph -Bu -BuIa-47 NPh2H H 2- naphthyl-Bu-BuIa-48 NPh2H t-Bu 2- naphthyl-Bu-Bu
Work as R5It isWhen, the structure of Formulas I turns into more generally Formulas I b：
Compound R1 R2, R3 R4 R6 R7Ib-1 H H H -Me -MeIb-2 H H H -Et -EtIb-3 H H t-Bu -Me -MeIb-4 H H t-Bu -Et -EtIb-5 NPh2 H H -Me -MeIb-6 NPh2 H H -Et -EtIb-7 NPh2 H t-Bu -Me -MeIb-8 NPh2 H t-Bu -Et -EtIb-9 Ph H H -Me -MeIb-10 Ph H H -Et -EtIb-11 Ph H t-Bu -Me -MeIb-12 Ph H t-Bu -Et -EtIb-13 H H H -Bu -BuIb-14 H H t-Bu -Bu -BuIb-15 NPh2 H H -Bu -BuIb-16 NPh2 H t-Bu -Bu -BuIb-17 Ph H H -Bu -BuIb-18 Ph H t-Bu -Bu -BuIb-19
H H -Me -MeIb-20
H H -Et -EtIb-21
H t-Bu -Me -MeIb-22
H t-Bu -Et -EtIb-23
H H -Bu -BuIb-24
H t-Bu -Bu -Bu
When X is the amino of alkyl or aryl substitution, R5It is：When, the molecular structure of Formulas I is changed into more generally Formulas I c：Compound R1 R2, R3 R4 R8Ic-1 H H H-EtIc-2 H H H-PhIc-3 H H H 1- naphthyl Ic-4 H H H 2- naphthyl Ic-5 H H t-Bu-EtIc-6 H H t-Bu-PhIc-7 H H t-Bu 1- naphthyl Ic-8 H H t-Bu 2- naphthyl Ic-9 H NPh2 H -EtIc-10 H NPh2 H -PhIc-11 H NPh2H 1- naphthyl Ic-12 H NPh2H 2- naphthyl Ic-13 H NPh2 t-Bu -EtIc-14 H NPh2 t-Bu -PhIc-15 H NPh2T-Bu 1- naphthyl Ic-16 H NPh2T-Bu 2- naphthyls Ic-17
H H -EtIc-18
H H -PhIc-19
H H 1- naphthyls Ic-20
H H 2- naphthyls Ic-21
H t-Bu -EtIc-22
H t-Bu -PhIc-23
H t-Bu 1- naphthyls Ic-24
H t-Bu 2- naphthyl Ic-25 H
H -EtIc-26 H
H -PhIc-27 H
H 1- naphthyl Ic-28 H
H 2- naphthyl Ic-29 H
t-Bu -EtIc-30 H
t-Bu -PhIc-31 H
T-Bu 1- naphthyl Ic-32 H
T-Bu 2- naphthyls
The preferred scheme of luminescent layer includes by material of main part and adulterates and one or more fluorescent dyes or catch the multi-component material that electrophile is constituted.Make in this way, efficient El element can be constructed.Meanwhile, the color of the tunable organic EL device of fluorescent dye of different emission is used in material of main part.
The anthracene derivant of the present invention has sufficiently large band gap, and effective energy migration is carried out with the various fluorescent dyes as dopant material.The example of blue dopant material includes the benzenoid form of arylamine, cumarin, stilbene, distyrene stilbene, anthracene derivant, aphthacene, perylenes and other conjugation in tool.Other dopant materials of the El element lighted at longer wavelength include the fluorescent dye of rubrene, quinacridone and other greenings and feux rouges.
In the present invention, the preferred embodiment of dopant material is the coumarin derivative represented by Formula Il：
Wherein：
R is hydrogen, the alkyl containing 1-24 carbon atom, aryl, heteroaryl or carbocyclic ring system；
R1, R2, R3, R4, R5, R6, R7, R8And R9It is respectively alkyl, aryl or the carbocyclic ring system of 1-20 carbon atom；
EDG is the aryl or electron donating group of hydrogen, the alkyl of 1-24 carbon atom, 5-24 carbon atom, more specifically：
-OR10
Wherein：R10, R11And R12It is respectively the alkyl, aryl or carbocyclic ring system of 1-20 carbon atom；R11And R1, R11And R12, and R12And R2It may then bond together to form member ring systems, such as piperidines, julolidine or tetramethyl julolidine.
It is the expected catalogue that can be used in the present invention the fluorescent dye as dopant material in list below.Those as follows are included according to the representative example of the coumarin derivative of the present invention.Following examples are to be used to further illustrate the present invention, are not limit the scope of the invention：
Compound number R R1~R6 R7 R8 R9 R10IIa-1, ,-Me, , H, , H, , H, , H, ,-MeIIa-2, ,-Me, , H, , H, , H, , H, ,-EtIIa-3, ,-Me, , H, , H, , H, , H, ,-isopropyl IIa-4, ,-Me, , H, , H, , H, , H, ,-butyl IIa-5, ,-Me, , H, , H, , H, , H, ,-tert-butyl group IIa-6, ,-Me, , H, , H, , H, , H, , PhIIa-7, ,-Et, , H, , H, , H, , H, ,-MeIIa-8, ,-Et, , H, , H, , H, , H, ,-EtIIa-9, ,-Et, , H, , H, , H, , H, ,-isopropyl IIa-10, ,-Et, , H, , H, , H, , H, ,-butyl IIa-11, ,-Et, , H, , H, , H, , H, ,-tert-butyl group IIa-12, ,-Et, , H, , H, , H, , H, , PhIIa-13, , Ph, , , H, , H, , H, , H, ,-MeIIa-14, , Ph, , , H, , H, , H, , H, ,-EtIIa-15, , Ph, , , H, , H, , H, , H, ,-isopropyl IIa-16, , Ph, , , H, , H, , H, , H, ,-butyl IIa-17, , Ph, , , H, , H, , H, , H, ,-tert-butyl group IIa-18, , Ph, , , H, , H, , H, , H, , PhIIa-19, , 1- naphthyls, , H, , H, , H, , H, ,-MeIIa-20, , 1- naphthyls, , H, , H, , H, , H, ,-EtIIa-21, , 1- naphthyls, , H, , H, , H, , H, ,-isopropyl IIa-22, , 1- naphthyls, , H, , H, , H, , H, ,-butyl IIa-23, , 1- naphthyls, , H, , H, , H, , H, ,-tert-butyl group IIa-24, , 1- naphthyls, , H, , H, , H, , H, , PhIIa-25, , p- xenyl, H, , H, , H, , H, ,-MeIIa-26, , p- xenyl, H, , H, , H, , H, ,-EtIIa-27, , p- xenyl, H, , H, , H, , H, ,-isopropyl IIa-28, , p- xenyl, H, , H, , H, , H, ,-butyl IIa-29, , p- xenyl, H, , H, , H, , H, ,-tert-butyl group IIa-30, , p- xenyl, H, , H, , H, , H, , PhIIa-31,-Me, , H, , ,-the tert-butyl group, H, H, , ,-MeIIa-32,-Me, , H, , ,-the tert-butyl group, H, H, , ,-EtIIa-33,-Me, , H, , ,-the tert-butyl group, H, H, , ,-isopropyl IIa-34,-Me, , H, , ,-the tert-butyl group, H, H, , ,-butyl IIa-35,-Me, , H, , ,-the tert-butyl group, H, H, , ,-tert-butyl group IIa-36,-Me, , H, , ,-the tert-butyl group, H, H, , , PhIIa-37,-Et, , H, , , H, , , H,-the tert-butyl group,-MeIIa-38,-Et, , H, , , H, , , H,-the tert-butyl group,-EtIIa-39,-Et, , H, , , H, , , H,-the tert-butyl group,-isopropyl IIa-40,-Et, , H, , , H, , , H,-the tert-butyl group,-butyl IIa-41,-Et, , H, , , H, , , H,-the tert-butyl group,-tert-butyl group IIa-42,-Et, , H, , , H, , , H,-the tert-butyl group, PhIIa-43, Ph, , , H, , ,-the tert-butyl group, H,-the tert-butyl group,-MeIIa-44, Ph, , , H, , ,-the tert-butyl group, H,-the tert-butyl group,-EtIIa-45, Ph, , , H, , ,-the tert-butyl group, H,-the tert-butyl group,-isopropyl IIa-46, Ph, , , H, , ,-the tert-butyl group, H,-the tert-butyl group,-butyl IIa-47, Ph, , , H, , ,-the tert-butyl group, H,-the tert-butyl group,-tert-butyl group IIa-48, Ph, , , H, , ,-the tert-butyl group, H,-the tert-butyl group, Ph
Compound R R1~R6 R7 R8 R9 R11 R12Numbering IIb-1, , between tolyl, H, , , H, H, H,-Me, , ,-MeIIb-2, , between tolyl, H, , , H, H, H,-Et, , ,-EtIIb-3, , between tolyl, H, , , H, H, H,-butyl, ,-butyl IIb-4, , between tolyl, H, , , H, H, H,-Me, , , PhIIb-5, , between tolyl, H, , , H, H, H, Ph, , , PhIIb-6, , between tolyl, H, , , H, H, H, p-methylphenyl, p-methylphenyl IIb-7, ,-Et, , H, , , H, H, H,-Me, , ,-MeIIb-8, ,-Et, , H, , , H, H, H,-Et, , ,-EtIIb-9, ,-Et, , H, , , H, H, H,-butyl, ,-butyl IIb-10,-Et, , H, , , H, H, H,-Me, , , PhIIb-11,-Et, , H, , H, , H, H, , Ph, , , PhIIb-12,-Et, , H, , H, , H, H, , p-methylphenyl, p-methylphenyl IIb-13, Ph, , H, , H, , H, H, ,-Me, ,-MeIIb-14, Ph, , H, , H, , H, H, ,-Et, ,-EtIIb-15, Ph, , H, , H, , H, H, ,-butyl, ,-butyl IIb-16, Ph, , H, , H, , H, H, ,-Me, , PhIIb-17, Ph, , H, , H, , H, H, , Ph, , , PhIIb-18, Ph, , H, , H, , H, H, , p-methylphenyl, p-methylphenyl IIb-19, 1- naphthyls, H, , H, , H, H, ,-Me, ,-MeIIb-20, 1- naphthyls, H, , H, , H, H, ,-Et, ,-EtIIb-21, 1- naphthyls, H, , H, , H, H, ,-butyl, ,-butyl IIb-22, 1- naphthyls, H, , H, , H, H, ,-Me, , PhIIb-23, 1- naphthyls, H, , H, , H, H, , Ph, , , PhIIb-24, 1- naphthyls, H, , H, , H, H, , p-methylphenyl, p-methylphenyl IIb-25, p- xenyl, H, , H, , H, H, ,-Me, ,-MeIIb-26, p- xenyl, H, , H, , H, H, ,-Et, ,-EtIIb-27, p- xenyl, H, , H, , H, H, ,-butyl, ,-butyl IIb-29, p- xenyl, H, , H, , H, H, , Ph, , , PhIIb-30, p- xenyl, H, , H, , H, H, , p-methylphenyl, p-methylphenyl IIb-31,-butyl, , H, , tert-butyl group H, H, ,-Me, ,-MeIIb-32,-butyl, , H, , tert-butyl group H, H, ,-Et, ,-EtIIb-33,-butyl, , H, , tert-butyl group H, H, ,-butyl, ,-butyl IIb-34,-butyl, , H, , tert-butyl group H, H, ,-Me, , PhIIb-35,-butyl, , H, , tert-butyl group H, H, , Ph, , , PhIIb-36,-butyl, , H, , tert-butyl group H, H, , p-methylphenyl, p-methylphenyl IIb-37, p-methylphenyl, H, , H, , H, the tert-butyl group,-Me, ,-MeIIb-38, p-methylphenyl, H, , H, , H, the tert-butyl group,-Et, ,-EtIIb-39, p-methylphenyl, H, , H, , H, the tert-butyl group,-butyl, ,-butyl IIb-40, p-methylphenyl, H, , H, , H, the tert-butyl group,-Me, , PhIIb-41, p-methylphenyl, H, , H, , H, the tert-butyl group, Ph, , , PhIIb-42, p-methylphenyl, H, , H, , H, the tert-butyl group, p-methylphenyl, p-methylphenyl IIb-43, Ph, , H, , tert-butyl group H, the tert-butyl group,-Me, ,-MeIIb-44, Ph, , H, , tert-butyl group H, the tert-butyl group,-Et, ,-EtIIb-45, Ph, , H, , tert-butyl group H, the tert-butyl group,-butyl, ,-butyl IIb-46, Ph, , H, , tert-butyl group H, the tert-butyl group,-Me, , PhIIb-47, Ph, , H, , tert-butyl group H, the tert-butyl group, Ph, , , PhIIb-48, Ph, , H, , tert-butyl group H, the tert-butyl group, p-methylphenyl, p-methylphenylCompound number R R1~R6 R7 R8 R9, , nIIc-1, , between tolyl, H, H, , , H, , , H, , , 1IIc-2, , between tolyl, H, the tert-butyl group, , H, , , H, , , 1IIc-3, , between tolyl, H, H, , , the tert-butyl group, , H, , , 1IIc-4, , between tolyl, H, H, , , H, , , H, , , 2IIc-5, , between tolyl, H, the tert-butyl group, , H, , , H, , , 2IIc-6, , between tolyl, H, H, , , the tert-butyl group, , H, , , 2IIc-7, ,-Et, , , H, H, , , H, , , H, , , 1IIc-8, ,-Et, , , H, the tert-butyl group, , H, , , H, , , 1IIc-9, ,-Et, , , H, H, , , the tert-butyl group, , H, , , 1IIc-10, ,-Et, , , H, H, , , H, , , H, , , 2IIc-11, ,-Et, , , H, the tert-butyl group, , H, , , H, , , 2IIc-12, ,-Et, , , H, H, , , the tert-butyl group, , H, , , 2IIc-13, , Ph, , , H, H, , , H, , , H, , , 1IIIc-14, , Ph, , , H, the tert-butyl group, , H, , , H, , , 1IIc-15, , Ph, , , H, H, , , the tert-butyl group, , H, , , 1IIc-16, , Ph, , , H, H, , , H, , , H, , , 2IIc-1, 7, , Ph, , , H, the tert-butyl group, , H, , , H, , , 2IIc-18, , Ph, , , H, H, , , the tert-butyl group, , H, , , 2IIc-19, , 1- naphthyls, , H, H, , , H, , , H, , , 1IIc-20, , 1- naphthyls, , H, the tert-butyl group, , H, , , H, , , 1IIc-21, , 1- naphthyls, , H, H, , , the tert-butyl group, , H, , , 1IIc-22, , 1- naphthyls, , H, H, , , H, , , H, , , 2IIc-23, , 1- naphthyls, , H, the tert-butyl group, , H, , , H, , , 2IIc-24, , 1- naphthyls, , H, H, , , the tert-butyl group, , H, , , 2IIc-25, , to xenyl, H, H, , , H, , , H, , , 1IIc-26, , to xenyl, H, the tert-butyl group, , H, , , H, , , 1IIc-27, , to xenyl, H, H, , , the tert-butyl group, , H, , , 1IIc-28, , to xenyl, H, H, , , H, , , H, , , 2IIc-29, , to xenyl, H, the tert-butyl group, , H, , , H, , , 2IIc-30, , to xenyl, H, H, , , the tert-butyl group, , H, , , 2IIc-31, ,-butyl, , H, , H, , , H, , , H, , , 1IIc-32, ,-butyl, , H, , the tert-butyl group, H, , , H, , , 1IIc-33, ,-butyl, , H, , H, , ,-the tert-butyl group, H, , , 1IIc-34, ,-butyl, , H, , H, , , H, , , H, , , 2IIc-35, ,-butyl, , H, ,-the tert-butyl group, H, , , H, , , 2IIc-36, ,-butyl, , H, , H, , ,-the tert-butyl group, H, , , 2IIc-37, , p-methylphenyl, H, , H, , , H, , , H, , , 1IIc-38, , p-methylphenyl, H, ,-the tert-butyl group, H, , , H, , , 1IIc-39, , p-methylphenyl, H, , H, , ,-the tert-butyl group, H, , , 1IIc-40, , p-methylphenyl, H, , H, , , H, , , H, , , 2IIc-41, , p-methylphenyl, H, ,-the tert-butyl group, H, , , H, , , 2IIc-42, , p-methylphenyl, H, , H, , ,-the tert-butyl group, H, , , 2
Compound number R R3~R6 R7 R8 R9 R13~R16IId-1, , between tolyl, H, , H, , , H, , , H, , , HIId-2, , between tolyl, H, , the tert-butyl group, H, , , H, , , HIId-3, , between tolyl, H, , H, , , the tert-butyl group, H, , , HIId-4, , between tolyl, H, , H, , , H, , , H, , , MeIId-5, , between tolyl, H, , the tert-butyl group, H, , , H, , , MeIId-6, , between tolyl, H, , H, , , the tert-butyl group, H, , , MeIId-7, ,-Et, , , H, , H, , , H, , , H, , , HIId-8, ,-Et, , , H, , the tert-butyl group, H, , , H, , , HIId-9, ,-Et, , , H, , H, , , the tert-butyl group, H, , , HIId-10, ,-Et, , , H, , H, , , H, , , H, , , MeIId-11, ,-Et, , , H, , the tert-butyl group, H, , , H, , , MeIId-12, ,-Et, , , H, , H, , , the tert-butyl group, H, , , MeIId-13, Ph, , , H, H, , , H, , , H, , HIId-14, Ph, , , H, the tert-butyl group, , H, , , H, , HIId-15, Ph, , , H, H, , , the tert-butyl group, , H, , HIId-16, Ph, , , H, H, , , H, , , H, , MeIId-17, Ph, , , H, the tert-butyl group, , H, , , H, , MeIId-18, Ph, , , H, H, , , the tert-butyl group, , H, , MeIId-19, 1- naphthyls, , H, H, , , H, , , H, , HIId-20, 1- naphthyls, , H, the tert-butyl group, , H, , , H, , HIId-21, 1- naphthyls, , H, H, , , the tert-butyl group, , H, , HIId-22, 1- naphthyls, , H, H, , , H, , , H, , MeIId-23, 1- naphthyls, , H, the tert-butyl group, , H, , , H, , MeIId-24, 1- naphthyls, , H, H, , , the tert-butyl group, , H, , MeIId-25, to xenyl, H, H, , , H, , , H, , HIId-26, to xenyl, H, the tert-butyl group, , H, , , H, , HIId-27, to xenyl, H, H, , , the tert-butyl group, , H, , HIId-28, to xenyl, H, H, , , H, , , H, , MeIId-29, to xenyl, H, the tert-butyl group, , H, , , H, , MeIId-30, to xenyl, H, H, , , the tert-butyl group, , H, , MeIId-3, 1,-butyl, , H, H, , , H, , , H, , HIId-32,-butyl, , H,-the tert-butyl group, H, , , H, , HIId-33,-butyl, , H, H, , ,-the tert-butyl group, H, , HIId-34,-butyl, , H, H, , , H, , , H, , MeIId-35,-butyl, , H,-the tert-butyl group, H, , , H, , MeIId-36,-butyl, , H, H, , ,-the tert-butyl group, H, , MeIId-37, p-methylphenyl, H, H, , , H, , , H, , HIId-38, p-methylphenyl, H,-the tert-butyl group, H, , , H, , HIId-39, p-methylphenyl, H, H, , ,-the tert-butyl group, H, , HIId-40, p-methylphenyl, H, H, , , H, , , H, , MeIId-41, p-methylphenyl, H,-the tert-butyl group, H, , , H, , MeIId-42, p-methylphenyl, H, H, , ,-the tert-butyl group, H, , MeCompound number R R1~R6 R7 R8 R9 R10~R11IIe-1, , between tolyl, H, , H, , , H, , H, HIIe-2, , between tolyl, H, , the tert-butyl group, H, , H, HIIe-3, , between tolyl, H, , H, , , the tert-butyl group, H, HIIe-4, , between tolyl, H, , H, , , H, , H, MeIIe-5, , between tolyl, H, , the tert-butyl group, H, , H, MeIIe-6, , between tolyl, H, , H, , , the tert-butyl group, H, MeIIe-7, ,-Et, , , H, , H, , , H, , H, HIIe-8, ,-Et, , , H, , the tert-butyl group, H, , H, HIIe-9, ,-Et, , , H, , H, , , the tert-butyl group, H, HIIe-10, ,-Et, , , H, , H, , , H, , H, MeIIe-11, ,-Et, , , H, , the tert-butyl group, H, , H, MeIIe-12, ,-Et, , , H, , H, , , the tert-butyl group, H, MeIIe-13, , Ph, , , H, , H, , , H, , H, NPh2IIe-14, , Ph, , , H, , the tert-butyl group, H, , H, NPh2IIe-15, , Ph, , , H, , H, , , the tert-butyl group, H, NPh2IIe-16, , Ph, , , H, , H, , , H, , H, HIIe-17, , Ph, , , H, , the tert-butyl group, H, , H, HIIe-18, , Ph, , , H, , H, , , the tert-butyl group, H, HIIe-19, , 1- naphthyls, , H, , H, , , H, , H, HIIe-20, , 1- naphthyls, , H, , the tert-butyl group, H, , H, HIIe-21, , 1- naphthyls, , H, , H, , , the tert-butyl group, H, HIIe-22, , 1- naphthyls, , H, , H, , , H, , H, MeIIe-23, , 1- naphthyls, , H, , the tert-butyl group, H, , H, MeIIe-24, , 1- naphthyls, , H, , H, , , the tert-butyl group, H, MeIIe-25, , to xenyl, H, , H, , , H, , H, HIIe-26, to xenyl, H, , the tert-butyl group, , H, , , , H, , , HIIe-27, to xenyl, H, , H, , , the tert-butyl group, , H, , , HIIe-28, to xenyl, H, , H, , , H, , , , H, , , MeIIe-29, to xenyl, H, , the tert-butyl group, , H, , , , H, , , Me, IIe-30, to xenyl, H, , H, , , the tert-butyl group, , H, , , MeIIe-31,-butyl, , H, , H, , , H, , , , H, , , HIIe-32,-butyl, , H,-the tert-butyl group, , H, , , , H, , , HIIe-33,-butyl, , H, , H, , ,-the tert-butyl group, , H, , , HIIe-34,-butyl, , H, , H, , , H, , , , H, , , MeIIe-35,-butyl, , H, ,-the tert-butyl group, H, , , , H, , , MeIIe-36,-butyl, , H, , H, , ,-the tert-butyl group, , H, , , MeIIe-37, p-methylphenyl, H, , H, , , H, , , , H, , , HIIe-38, p-methylphenyl, H, ,-the tert-butyl group, H, , , , H, , , HIIe-39, p-methylphenyl, H, , H, , ,-the tert-butyl group, , H, , , HIIe-40, p-methylphenyl, H, , H, , , H, , , , H, , , MeIIe-41, p-methylphenyl, H, ,-the tert-butyl group, H, , , , H, , , MeIIe-42, p-methylphenyl, H, , H, , ,-the tert-butyl group, , H, , , Me
In the present invention, another kind of preferred dopant material is a class anthracene derivant.This anthracene derivant is represented by having structure formula III：
Wherein：
R1And R2It is respectively the alkyl or aryl of hydrogen, 1-20 carbon atom；R is alkyl, the aryl or heteroaryl containing 5-24 carbon atom of hydrogen or 1-24 carbon atom.Preferred example is (but not limited to) as described below：Compound R R1 R2III-1 H H HIII-2 H H HIII-3 H t-Bu HIII-4 Me H HIII-5 Me H HIII-6 Me t-Bu HIII-7 Ph H HIII-8 Ph H HIII-9 Ph t-Bu HIII-10 1- naphthyl H HIII-11 1- naphthyl H HIII-12 1- naphthyl t-Bu HIII-13 2- naphthyl H HIII-14 2- naphthyl H HIII-15 2- naphthyl t-Bu HIII-16 PhIII-17 Ph
III-18 Ph
Following fluorescent dye also is used as the dopant material of the present invention：
Perylene III-19III-20Tetraphenyl pyrene III-21III-22III-23III-24
Coumarin-6 III-25Cumarin -545TIII-26
DMQAIII-27
DCJTB
III-28
The preferred material of electron transfer layer for forming organic EL media is included in U.S 4,539,507；The metal-chelator of 8-hydroxyquinoline disclosed in 5,151,629 and 5,150,006.The example of this metal chelate includes three (8-hydroxyquinoline acid) aluminium (AIQ3), three (8-hydroxyquinoline acid) galliums, two (8-hydroxyquinoline acid) magnesium, two (8-hydroxyquinoline acid) zinc, three (5- methyl -8-hydroxyquinoline acid) aluminium, three (7- propyl group -8- quinolinols) aluminium, double benzo -8- quinolinic acid zinc, double (10- hydroxy benzos quinolinic acid) berylliums, double (2- methylquinolines alcohol) aluminium (III), double (2- methyl -8- quinolinols) aluminium (III), double (2- methyl -8- quinolinols) (phenol) aluminium, double (2- methyl -8- quinolinols) (p-phenyl phenol) aluminium, double (2- methyl -8- quinolinols) (beta naphthal) aluminium etc..
All the elements disclosed in each patent are hereby incorporated by reference above.Another kind of preferred electron injection and transport compound are the metal thioxinoid compounds disclosed in United States Patent (USP) 5648542.The example of the compound includes double (8- quinoline thiols) aluminium, double (8- quinoline thiols) cadmiums, three (8- quinoline thiols) galliums, three (8- quinoline thiols) indiums, double (5- methylquinolines mercaptan) zinc, three (5- methylquinolines mercaptan) galliums, three (5- methylquinolines mercaptan) indiums, three (5- methylquinolines mercaptan) cadmiums, two (3- methylquinolines mercaptan) cadmiums, two (5- methylquinolines mercaptan) zinc, double benzo -8- quinoline thiol zinc, two-methyl benzo -8- quinoline thiol zinc, double 7- dimethylbiphenyls -8- quinoline thiol zinc etc..
The particularly preferred electron transport material of electron transfer layer for forming EL media includes the anthracene derivant represented by structural formula IV：
Wherein：
R1, R2, R3, R4And R5It is respectively hydrogen, alkyl or alkoxy containing 1-16 carbon atom, aryl or substituted aryl containing 6-24 carbon atom, heteroaryl or substituted heteroaryl containing 5-24 carbon atom；
X is methylene, dialkyl methylene radical and Diarylmethylidene, S, and O or NR, wherein R are hydrogen, alkyl or alkoxy containing 1-16 carbon atom, aryl or substituted aryl containing 6-24 carbon atom.
According to the present invention, these anthracene derivants IV representative example includes those as follows.Following instance is to be used to further illustrate the present invention, rather than limitation the scope of the present invention：Compound R1, R3 R2, R4 X R5IV-1 H H O HIV-2 H H O t-BuIV-3 H t-Bu O HIV-4 H t-Bu O t-BuIV-5 t-Bu H O HIV-6 t-Bu H O t-BuIV-7 t-Bu t-Bu O HIV-8 t-Bu t-Bu O t-BuIV-9 H H S HIV-10 H H S t-BuIV-11 H t-Bu S HIV-12 H t-Bu S t-BuIV-13 t-Bu H S HIV-14 t-Bu H S t-BuIV-15 t-Bu t-Bu S HIV-16 t-Bu t-Bu S t-BuIV-17 H H -NMe HIV-18 H H -NMe t-BuIV-19 H t-Bu -NMe HIV-20 H t-Bu -NMe t-BuIV-21 t-Bu H -NMe HIV-22 t-Bu H -NMe t-BuIV-23 t-Bu t-Bu -NMe HIV-24 t-Bu t-Bu -NMe t-BuIV-25 H H -NPh HIV-26 H H -NPh t-BuIV-27 H t-Bu -NPh HIV-28 H t-Bu -NPh t-BuIV-29 t-Bu H -NPh HIV-30 t-Bu H -NPh t-BuIV-31 t-Bu t-Bu -NPh HIV-32 t-Bu t-Bu -NPh t-BuIV-33 H H -CMe2 HIV-34 H H -CMe2 t-BuIV-35 H t-Bu -CMe2 HIV-36 H t-Bu -CMe2 t-BuIV-37 t-Bu H -CMe2 HIV-38 t-Bu H -CMe2 t-BuIV-39 t-Bu t-Bu -CMe2 HIV-40 t-Bu t-Bu -CMe2 t-Bu
Shorthand notation Me used above represents methyl；Et represents ethyl；Bu represents butyl；Ph represents phenyl.
The benzene derivative of electron transport material as the electric transmission area for forming organic EL device of the present invention has several advantages.They have high electron mobility and with good film-forming quality.After vacuum evaporation, the benzene derivative shows the amorphous thin film with good thermal stability.
In the present embodiment, the gross thickness of organic light emitting medium layer, including hole injection and transmission range 4 and electron injection and transmission range 5, it is preferred that for example, less than about 1 micron, for example, about 0.05-1 microns, to keep the current density matched with enough brightness emissions under the relative low voltage that applies between electrode.Hole is injected and the suitable depth of transport layer can be about 50-2000 angstroms, preferably from about 400-1000 angstroms.Similarly, the thickness of electron injection and transport layer can be about 50-2000 angstroms, preferably from about 400-1000 angstroms.
The thickness of negative electrode 6 is, for example, about 10-5000 angstroms, more specifically, being about 50-250 angstroms.Mg: Ag negative electrode disclosed in United States Patent (USP) 4,885,211 constitutes preferred cathode construction.Another preferred cathode construction is described in United States Patent (USP) 5,429,884, and wherein negative electrode is to be formed by lithium alloy with other high work function metals such as aluminium and indium.The disclosure of which is all hereby incorporated by reference.
The negative electrode 6 and anode 3 of organic EL device of the present invention can be any convenient form.About 200 angstroms of a thin conductive anode can be for example coated on light-transmissive substrate (such as transparent or substantial transparent glass plate or plastic foil).The device may include the light transmissive anode 3 formed by the zinc oxide or indium coated on a glass.In addition, very thin, such as less than 200 angstroms, such as about 50-200 angstroms of light-transparent metal anode may be selected from gold, palladium etc..In addition, it is transparent or semitransparent thin, it is selectable as anode such as 200 angstroms of conjugated polymers such as polyanilines, polypyrrole.In addition, the suitable form of anode 3 illustrates that the entire disclosure is hereby incorporated by reference by United States Patent (USP) 4885211.
Hereinbefore structural formula I-IV is luminescent material known in the art.The following is the general synthetic route of the various materials used in the present invention.It should be noted that these synthetic routes are known in the art, it is only intended to explanation, is not intended to limit the present invention, and various materials of the invention can also be synthesized with other method known in the art.General synthesis The anthracene derivant I of synthetic route 1. general synthesis
The coumarin derivative II of synthetic route 2. general synthesis
R1Equal to R3, and R2Equal to R4.
The benzene derivative IV of synthetic route 3. general synthesis
The following is the specific synthetic example of material therefor of the present invention, it is only intended to explanation, is not intended to limit the present invention.Embodiment 1. 9, the synthesis of 9- diethyl fluorenes
In 1.5 hours, to the fluorine (83.2g that 15-20 DEG C is cooled to through mechanical agitation, 0.5mol), powdered potassium hydroxide (140g, 2.5mol), KI (4.0g, 0.024mol) and in DMSO (225ml) mixture add bromoethane (104ml, 151.84g, 1.39mol), and be stirred at room temperature overnight.The mixture is diluted with water (1200ml), is extracted with toluene (2 × 400ml).The extract of the toluene is washed with water, is dried and concentrated, 116.66g red oils are obtained.Distilled at 1.2mmHg pressure, b.p.125 DEG C, obtain colorless oil, it is cured, obtain 104.32g subject compounds (94% yield).The synthesis of bromo- 9, the 9- diethyl fluorenes of embodiment 2.2-
At 57 DEG C, into the solution in the diethyl fluorenes (22.2g, 0.1mol) of propylene carbonate (100ml), N- bromines succinimide (17.8g, 0.1mol) is added portionwise.The mixture is diluted with 1200ml water and is extracted with 500ml toluene.With the 300ml water washings toluene extract three times, dry, concentration, total obtains crude product 117g, is oily body.Distilled under 2mmHg pressure, it is found that Part I distillation is propylene carbonate, b.p.90-93 DEG C, 22.33g.Part II distillation is subject compound, b.p.155-165 DEG C, 81.0g (89.7% yield).Embodiment 3. 9, the synthesis of 9- diethyl fluorenyl -2- boric acid
By adding n-BuLi solution (1.6M, in 100ml hexanes, 0.16mol) in bromo- 9, the 9- diethyl fluorenes (42.0g, 0.14mol) of 2- prepared through embodiment 2 of the charging hopper into the anhydrous THF of 200ml at -78 DEG C.The suspension half an hour of the black is stirred at this temperature, in the case where temperature is maintained at less than -60 DEG C, is added dropwise to the B (OMe) in the anhydrous THF of 150ml3(26.6ml, 29,1g, 0.28mol) solution.Obtained colourless solution is incubated at room temperature 2 hours, then adds 300ml 5M HCl, and is stirred for the mixture under nitrogen atmosphere 1 hour.Water and ether are added, with ether aqueous layer extracted several times.Merge the organic extract, through MgSO4Dry and evaporate under reduced pressure, obtain white solid (34.0g, 95%), it need not be further purified, so that it may in coupling reaction.Embodiment 49, the synthesis of 10- bis- [2- (9,9- diethyl fluorenyl)] anthracene (compound Ib-2)
By Pd (PPh3)4(1.0g, 0.8mmol) and 300ml 2.0MNa2CO3The aqueous solution is added in the solution of 9, the 10- dibromoanthracenes (34.0g, 0.1mol) in 600ml toluene and 100ml ethanol and 9,9- diethyl fluorenyl -2- boric acid (40.0g, 0.232mol).The reactant mixture is purged with nitrogen 10 minutes.After refluxed overnight, separation organic suspension layer, while heating and adding 300ml 2.0NHCl, flows back 1 hour with vigorous stirring.Separate aqueous layer, heats, is then washed with water three times, until pH is about 7 simultaneously again.Sediment is filtered out from organic layer, through chromatogram purification, pure 9, the 10- bis- of 47.5g [2- (9,9- diethyl fluorenyl)] anthracene (compound Ib-2), yield 80.0% is obtained.The synthesis of embodiment 5. 2- tert-butyl groups -9,10- bis- [2- (9,9- diethyl fluorenyl)] anthracene (compound Ib-4)
By Pd (PPh3)4(0.50g, 0.4mmol) and 150ml 2.0M Na2CO3The aqueous solution is added in the solution of 2- tert-butyl groups -9,10- dibromoanthracene (19.8g, 0.05mol) in 300ml toluene and 50ml ethanol and 9,9- diethyl fluorenyl -2- boric acid (20.0g, 0.12mol).The reactant mixture is purged with nitrogen 10 minutes.After refluxed overnight, separation organic suspension layer, while heating and adding 150ml 2.0N HCl, flows back 1 hour with vigorous stirring.Separate aqueous layer, heats, is then washed with water three times, until pH is about 7 simultaneously again.Sediment is filtered out from organic layer, through chromatogram purification, the pure 2- tert-butyl groups -9,10- bis- of 27.4g [2- (9,9- diethyl fluorenyl)] anthracene (compound Ib-4), yield 80.0% is obtained.The synthesis of embodiment 6.2,7,9,10- tetra- [2- (9,9- diethyl fluorenyl)] anthracene (compound III-22)
By Pd (PPh3)4(0.20g) and 50ml2.0M Na2CO3The aqueous solution is added in the solution of 2,7,9, the 10- tetrabromo anthracenes (4.94g, 0.01mol) in 100ml toluene and 20ml ethanol and 9,9- diethyl fluorenyl -2- boric acid (13.2g, 0.05mol).The reactant mixture is purged with nitrogen 10 minutes.After refluxed overnight, separation organic suspension layer, while heating and adding 50ml 2.0N HCl, flows back 24 hours with vigorous stirring.Separate aqueous layer, heats, is then washed with water three times, until pH is about 7 simultaneously again.Organic solvent is removed with vacuum rotary evaporator, then sediment is filtered out from organic layer, through chromatogram purification, obtains 7.4g pure 2,7,9,10- tetra- [2- (9,9- diethyl fluorenyl)] anthracene (compound III-22), yield 74.0%.The embodiment 7.9- phenyl -10- [synthesis of 2- (9,9- diethyl fluorenyl) anthracene (compound Ia-2)
By Pd (PPh3)4(0.20g) and 30ml2.0M Na2CO3The aqueous solution is added in the solution of the 9- phenyl -10- bromines anthracenes (6.62g, 0.02mol) in 50ml toluene and 10ml ethanol and 9,9- diethyl fluorenyl -2- boric acid (5.4g, 0.02mol).The reactant mixture is purged with nitrogen 10 minutes.After refluxed overnight, separation organic suspension layer, while heating and adding 50ml 2.0N HCl, flows back 2 hours with vigorous stirring.Separate aqueous layer, heats, is then washed with water three times, until pH is about 7 simultaneously again.Organic solvent is removed with vacuum rotary evaporator, then sediment is filtered out from organic layer, through chromatogram purification, obtains the pure 9- phenyl -10- of 8.7g [2- (9,9- diethyl fluorenyl) anthracenes (compound Ia-2), yield 91.0%.The synthesis of the 2- cyano-phenyl benzimidazoles of embodiment 8.
In 250ml round-bottomed flasks, merge cyan-acetic ester (14.2g, 0.12mol), N- phenyl -1,2- phenylenediamine (15.5g, 0.084mol) and 15ml bis- (2- methoxy ethyls) ether.Under agitation, the reactant mixture is heated, is heated three hours at 150-160 DEG C, while distilling water outlet and ethanol byproducts.Cool down after reactant mixture, add 10ml isopropanols.It is settled out the crude product and filters.Obtain the pure 2- cyano-phenyl benzimidazoles of 12.5g, yield 65.0%.The N- benzimidazolyl-2 radicals of embodiment 9., the synthesis of 3,6,7- tetrahydrochysene-N, N- diethyl -11H, 5H, 11H- (1) chromene (6,7,8-ij) quinolizine -11- ketone (compound IIb-14)
In 250ml round-bottomed flasks, merge 4- diethylaminos-Benzaldehyde,2-hydroxy (6.2g, 3.2mmol), 2- cyano-phenyls benzimidazole (7.4g, 3.2mmol) and 30mlN, dinethylformamide.Under agitation, the reactant mixture is heated to 50 DEG C, then adds 3mlHCl into the reactant mixture.Continue to heat half an hour at 90 DEG C, add other 6mlHCl, the red-orange mixture 30 minutes is heated at 90 DEG C.Cool down after the reactant mixture, 120ml distilled water is added under cooling and stirring.The sediment that is filtrated to get and with distillation water washing.Sediment obtained above is added in 100ml distilled water, suspension is made, saturated sodium carbonate is added dropwise under agitation, until pH is about 7-8.Then filtering precipitate, is washed with distilled water, alcohol, obtains the pure N- benzimidazolyl-2 radicals of 9.1g, 3,6,7- tetrahydrochysene-N, N- diethyl -11H, 5H, 11H- (1) chromene (6,7,8-ij) quinolizine -11- ketone (compound IIb-14), yield 70.0%.The preparation of organic EL device：
Embodiment 10-36 is prepared as follows：
1. the glass for about 1 mm of thickness for scribbling 500 angstroms of thickness oxidation indium tin is cleaned with detergent commercially, then dried 1 hour with deionized water rinsing and in 60 DEG C of vacuum drying ovens.The glass is handled 0.5 hour with UV ozone immediately before.
2. ITO substrates made above are put into vacuum evaporation room.The speed of evaporation and the thickness of layer are controlled by Inficon Model IC/5 controllers.Slightly below about 5 × 10-6Under Torr pressure, copper phycynin CuPc are evaporated in electrically heated tantalum ware, deposits on ito glass layer, forms 20 nanometers of (200 angstroms) hole injection layers.The evaporation rate for controlling CuPc is 0.4nm/ seconds.
3. evaporating arylamine NPB or arylamine isomer mixture NPBX from electrically heated tantalum ware, 80 nanometers (800 angstroms) the thick hole transmission layers on ito glass layer are deposited into.The deposition velocity of the amines is controlled in 0.6 nm/sec.
4. with the evaporation rate of 0.6 nm/sec to the anthracene derivant that Formulas I is deposited on hole transmission layer, form 30 nanometers of luminescent layer.The luminescent layer also can be by the way that the luminescent material of the anthracene derivant of Formulas I and Formula II or another dopant material Zhu such as perylene, tetraphenyl pyrene, Coumarin-6, cumarin-C545T, DMQA or DCJTB co-evaporation be formed.The concentration of the dopant material is controlled in the 0.1-5 moles of % for material of main part.
5. benzene derivative IV or commonly used metallo-chelate 8-hydroxyquinoline aluminium (Alq) is deposited with the evaporation rate of 0.6 nm/sec on to luminescent layer, the electron injection and electron transfer layer of 30 nano thickness are formed.
6. evaporated from two independent controlled tantalum wares containing Mg and Ag simultaneously, 100 nanometer thickness magnesium silver alloy are deposited into electron injection and electron transfer layer with total nm/sec of evaporation rate 0.5.General composition is that Mg and Ag atomic ratio is 9: 1.Finally, 200 nano-silver layers are covered on Mg: Ag negative electrode, main purpose is that the moisture content for protecting magnesium not with environment reacts.
Device made above is stored in the drying box constantly purged with nitrogen.The performance of the device is evaluated by determining its electric current-voltage characteristic and light output at a dc voltage.Electric current-voltage characteristic is determined with the high current source measurement apparatus of Keithley types 238.ITO electrode is always connected with the positive pole of power supply.Meanwhile, the light output of the device is monitored with silicon photoelectric diode.
In constant current intensity 40mA/cm2The lower performance for evaluating general structure for ITO/CuPc (20nm)/NPB (80nm)/EML (30nm)/ETL (30nm)/9: 1 Mg-Ag (100nm) device.The initial light intensity and colourity of these devices are outlined in table 1 below, 2,3 and 4.
Table 1.
ITO/CuPc(20nm)/NPB(80nm)/EML(30nm)/Alq(30nm)/9∶1 Mg-Ag(100nm)
| Embodiment | Luminescent layer (EML) | cd/A | Voltage (V) | Maximum EL peaks (nm) | |
| Material of main part | Dopant material (%) | ||||
| 10 | Ib-2 | 0 | 1.9 | 11.5 | 448 |
| 11 | Ib-2 | Perylene (0.1%) | 3.2 | 12.3 | 464 |
| 12 | Ib-2 | Perylene (0.5%) | 2.9 | 12.3 | 464 |
| 13 | Ib-2 | Perylene (0.8%) | 3 | 12.1 | 464 |
These results illustrate, comprising anthracene material of main part Ib-2 He the organic EL device of perylene blueness dopant material can obtain the blue output light of continual high levels.
Table 2.
ITO/CuPc(20nm)/NPB(80nm)/EML(30nm)/IV-25(30nm)/9∶1 Mg-Ag(100nm)
| Embodiment | Luminescent layer | cd/A | Voltage (V) | Maximum EL peaks (nm) | |
| Material of main part | Dopant material (%) | ||||
| 14 | Ib-2 | 0 | 1.7 | 12.4 | 448 |
| 15 | Ib-2 | Perylene (0.1%) | 4.65 | 12.2 | 464 |
| 16 | Ib-2 | Perylene (0.5%) | 4.2 | 11.9 | 464 |
| 17 | Ib-2 | Perylene (0.8%) | 3.8 | 11.5 | 464 |
| 18 | Ib-2 | Perylene (1.0%) | 3.1 | 12 | 464 |
| 19 | Ib-2 | Perylene (2.0%) | 2.7 | 11.8 | 464 |
These results illustrate comprising anthracene material of main part Ib-2 He perylene blueness dopant material and replacing Alq (referring to embodiment 6) organic EL device to obtain more effective indigo plant output light with anthracene derivant IV-25.
Table 3.
ITO/CuPc(20nm)/NPB(80nm)/EML(30nm)/Alq(30nm)/9∶1 Mg-Ag(100nm)
| Embodiment | Emitting Layer | cd/A | Voltage (V) | Maximum EL peaks (nm) | |
| Material of main part | Dopant material (%) | ||||
| 22 | Alq | 0 | 2.5 | 10.0 | 524 |
| 23 | Alq | IId-16 (0.5%) | 2.5 | 10.1 | 524 |
| 24 | Alq | IId-16 (1.0%) | 2.8 | 9.8 | 516 |
| 25 | Alq | IId-16 (1.5%) | 2.9 | 9.6 | 508 |
| 26 | Ib-2 | 0 | 1.7 | 12.4 | 448 |
| 27 | Ib-2 | IId-16 (0.5%) | 3.2 | 10.5 | 476 |
| 28 | Ib-2 | IId-16 (1.0%) | 3.8 | 10.1 | 476 |
| 29 | Ib-2 | IId-16 (1.5%) | 4.4 | 10.2 | 476 |
| 30 | Ib-2 | Cumarin -545T III-26 (0.5%) | 5.5 | 10.1 | 500 |
| 31 | Ib-2 | Cumarin -545T III-26 (1.0%) | 5.6 | 10.1 | 500 |
| 32 | Ib-2 | Cumarin -545T III-26 (1.5%) | 5.5 | 9.3 | 500 |
These results illustrate that the organic EL device comprising anthracene material of main part Ib-2 and cumarin IId-16 and III-26 can obtain the blue-green output light of continual high levels.However, enough energy transfers can not be obtained as dopant material using Alq as material of main part and cumarin IId-16.
Table 4.
ITO/CuPc(20nm)/NPB(80nm)/EML(30nm)/Alq(30nm)/9∶1 Mg-Ag(100nm)
| Embodiment | Luminescent layer | cd/ A | Voltage (V) | Maximum EL peaks (nm) | |
| Material of main part | Dopant material (%) | ||||
| 33 | Ib-2 | 0 | 1.8 | 12.0 | 448 |
| 34 | Ib-2 | DCJTB (III- 28) (0.1%) | 4.7 | 11.3 | 576 |
| 35 | Ib-2 | DCJTB (III- 28) (0.5%) | 3.0 | 12.3 | 592 |
| 36 | Ib-2 | DCJTB (III- 28) (1.0%) | 2.7 | 12.5 | 604 |
These results illustrate that the organic EL device comprising anthracene material of main part (Ib-2) and the red dopant materials (III-28) of DCJTB can be held
Continue high-caliber red output light.
Claims (6)
1. a kind of organic electroluminescence device, it includes anode, the organic dielectric layer of negative electrode and folder between the anode and cathode, the organic dielectric layer includes hole injection and transport layer, luminescent layer and electron injection and transport layer, and the anthracene derivant that wherein luminescent layer in the organic dielectric layer includes one or more Formulas I is used as material of main part：
Wherein R1, R2, R3And R4It is respectively hydrogen, alkyl or alkoxy containing 1-16 carbon atom, the alkenyl containing at least one carbon-carbon double bond, aryl or substituted aryl containing 6-24 carbon atom, heteroaryl or substituted heteroaryl, amino, N- alkyl aminos, N- arylaminos, N containing 5-24 carbon atom, N- dialkyl amidos, N, N- diaryl, cyano group, the perfluoroalkyl containing 1-8 carbon atom, chlorine, bromine and fluorine；
R5It is alkyl or perfluoroalkyl containing 1-16 carbon atom；Aryl or substituted aryl containing 6-24 carbon atom；Heteroaryl or substituted heteroaryl containing 5-24 carbon atom, cyano group, chlorine, bromine and fluorine；
X is methylene, dialkyl methylene radical and Diarylmethylidene, the amino selected from the substitution of oxygen, the hetero atom of sulphur or alkyl or aryl or dialkyl group or the silicyl of diaryl substitution.
2. organic electroluminescence device according to claim 1, its luminescent layer also includes dopant material, its concentration is 0.1-5 moles of % of material of main part, and the dopant material is selected from the luminous coumarin derivative of the one or more with below general formula II, the luminous anthracene derivant of one or more or their mixture of general formula III：
Wherein R is hydrogen, the alkyl containing 1-24 carbon atom, aryl, heteroaryl or carbocyclic ring system；R1, R2, R3, R4, R5, R6, R7, R8And R9It is respectively alkyl, aryl or the carbocyclic ring system of 1-20 carbon atom；EDG is the aryl or electron donating group of hydrogen, the alkyl of 1-24 carbon atom, 5-24 carbon atom, more specifically：
-OR10
Wherein：R10, R11And R12It is respectively the alkyl, aryl or carbocyclic ring system of 1-20 carbon atom；R11And R1, R11And R12, and R12And R2It may then bond together to form member ring systems, it is selected from piperidines, julolidine or tetramethyl julolidine,
Wherein R1It is the alkyl containing 1-20 carbon atom；R and R2It is respectively hydrogen, the alkyl containing 1-24 carbon atom, aryl or heteroaryl containing 5-24 carbon atom.
3. organic electroluminescence device according to claim 1, wherein the electron injection and transport layer in the organic dielectric layer include the anthracene derivant of formula IV：
Wherein：
R1, R2, R3, R4And R5It is respectively hydrogen, alkyl or alkoxy containing 1-16 carbon atom, aryl or substituted aryl containing 6-24 carbon atom, heteroaryl or substituted heteroaryl containing 5-24 carbon atom；
X is methylene, dialkyl methylene radical and Diarylmethylidene, S, and O or NR, wherein R are hydrogen, alkyl or alkoxy containing 1-16 carbon atom, aryl or substituted aryl containing 6-24 carbon atom.
4. organic electroluminescence device according to claim 2, wherein one or more luminous coumarin derivative of the dopant material for the formula II.
5. organic electroluminescence device according to claim 2, wherein one or more luminous anthracene derivant of the dopant material for the general formula III.
6. according to any claim 1-5 organic electroluminescence device, it is used to prepare display device.
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