CN1910261A - Organic electroluminescent polymer having 9,9-di(fluorenyl)-2,7-fluorenyl unit and organic electroluminescent device manufactured using the same - Google Patents
Organic electroluminescent polymer having 9,9-di(fluorenyl)-2,7-fluorenyl unit and organic electroluminescent device manufactured using the same Download PDFInfo
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Abstract
Disclosed herein is an organic electroluminescent polymer having 9,9-di(fluorenyl)-2,7-fluorenyl unit and an electroluminescent device using the same. Specifically, the current invention provides an organic electroluminescent polymer having 9,9-di(fluorenyl)-2,7-fluorenyl unit, which can be used as a blue electroluminescent polymer and host material by introducing the substituted fluorenyl group at the 9-position of fluorene, and an electroluminescent device using the electroluminescent polymer. The electroluminescent polymer is applicable as a host material for highly pure blue, green and red, having high solubility, high heat stability and high quantum efficiency.
Description
Technical field
The invention relates to and a kind ofly have 9,9-two (fluorenyl)-2, the organic field luminescence polymkeric substance of 7-fluorenyl unit and use the organic electroluminescence device of this polymer.More specifically, what the invention relates to a kind of performance high thermal stability, high light stability, high resolution, excellent film-forming properties and high-quantum efficiency (quantumefficiency) has 9,9-two (fluorenyl)-2, the organic field luminescence polymkeric substance of 7-fluorenyl unit and use the organic electroluminescence device of this organic field luminescence polymer.
Background technology
Along with the huge advance made in recent optical communication and multi-media field, quicken to the development of information highly dense type society.Therefore, utilizing photon to change into the optoelectronic device that electronics or electronics change into photon comes into one's own in the present information electronic industry.
Semiconductor optoelectronic device is divided into electroluminescence device, optical pickup apparatus and their combination.
Therefore most of indicating meter of up-to-date manufacturing is the light-receiving type, yet electroluminescent display has the luminous characteristic, does not need backlightly can show quick response and high brightness.Therefore, electroluminescent display is considered to indicating meter of future generation.
According to the luminescent layer type of material, electroluminescence device is divided into inorganic light-emitting device and organic light-emitting device.
Organic field luminescence (electroluminescence, EL) be meant when the electronics that comes from the migration of negative electrode and anode respectively and hole organic materials by be applied on this organic materials electric field and in conjunction with the time energy that produces send with the form of light.People such as Pope have reported this electroluminescence of organic materials in 1963.Quantum yield is 1% when the people such as Tang of Eastmann Kodak used the tinting material with aluminum oxide-quinone p conjugated structure to produce 10 volts in 1987 or when being lower than 10 volts, brightness is 1000 international candles/square metre (cd/m
2) the multilayer light-emitting device, big quantity research carries out.Because can synthesize various materials and toning easily at an easy rate according to simple synthetic route, therefore this device has advantage.But processibility or stability are low, and when applying voltage, the joule heating that is produced by luminescent layer causes molecular transposition and to the luminous efficiency of this device or disadvantageous effect is arranged work-ing life.Therefore propose to have the organic electroluminescence device that can alleviate the problems referred to above of polymer architecture.
Based on this, Fig. 1 represents the conventional organic electroluminescence device that comprises base material/anode/hole transporting layer/luminescent layer/electron supplying layer/negative electrode.
As shown in Figure 1, anode 12 is formed on the base material 11.On anode 12, form hole transporting layer 13, luminescent layer 14, electron supplying layer 15 and negative electrode 16 successively.Similarly, hole transporting layer 13, luminescent layer 14 and the organic film of electron supplying layer 15 for making by organic compound.The following operation of organic electroluminescence device with said structure:
When voltage is applied to anode 12 and negative electrode 16, move to luminescent layer 14 by hole transporting layer 13 from anode 12 injected holes.Simultaneously, electronics is injected into the luminescent layer 14 from negative electrode 16 by electron supplying layer 15, and current carrier (carrier) is recombine in the zone of luminescent layer 14, produces exciton.Exciton becomes ground state from excited state, thereby the fluorescence molecule in the luminescent layer is luminous, therefore forms image.
The organic materials that is used to form the organic membrane of EL device can be lower molecular weight or high molecular weight organic materials.
When using the lower molecular weight organic materials, easily with described materials purification to the inclusion-free state, so good luminous performance.Yet low molecular weight material does not allow spray ink Printing or rotary coating (spin coating), and poor heat resistance, therefore can be by pyrolytic damage that produces in the device operational process or recrystallization.
On the other hand, when using macromolecular material (being polymkeric substance), energy level is divided into conduction band and valence band, and the wave function of the p electronics that exists in its skeleton (backbone) is overlapped.Band gap between conduction band and the valence band is determined the semiconductor property of polymkeric substance, and therefore controlling band gap can realize full-colorization demonstration.This polymkeric substance is called the p conjugated polymers.
(the Cambridge University of research group by professor R.H.Friend leader, England) nineteen ninety carry out based on conjugated polymers poly-(to the inferior ethene of phenylene) (poly (p-phenylenevinylene), below be called " PPV ") the exploitation first of EL device, excited the active research of going deep into to organic polymer with semiconductor property.Except thermotolerance is better than low molecular weight material, polymeric material owing to can ink jet printing or rotary coating be applied to big surperficial indicating meter.It is reported that (polythiopene, Pth) derivative has higher processibility, and shows shades of colour to introduce PPV that various functional moieties are arranged and Polythiophene.Yet,, be difficult to launch efficiently blue light although these PPV and Pth derivative can be applied to red-emitting and green glow efficiently.It is reported that polyphenylene derivative and poly-fluorene derivatives are blue light emitting material.Polyphenylene has high oxidation stability and high thermal stability, but luminous efficiency and poorly soluble.
About poly-fluorene derivatives, relevant prior art is as follows:
US 6255449 discloses the luminescent layer that is suitable as in luminescent material such as the photodiode or the 9-substituting group-2 of carrier transport layer, 7-dihalo fluorenes (9-substituted-2,7-dihalofluorene) compound and oligopolymer thereof and polymkeric substance.
US 6309763 and US 6605373 disclose and have contained fluorine-based in repeating unit and electroluminescence multipolymer amido.According to US 6309763, this multipolymer can be used for luminescent layer or the hole transporting layer in the electroluminescence device.
WO 02/77060 discloses and has contained the unitary conjugated polymers of spiro-bisfluorene (spirobifluorene).According to the document, wherein disclosed this polymkeric substance demonstrates as electronic component such as polymer LED (Polymer Light-emitting Diode, PLED) performance profile of the improvement of the electroluminescent material in (property profile).
Summary of the invention
As mentioned above, carry out all sidedly as the research of blue luminescent polymer although will gather fluorene derivatives, the exciton that produces between adjacent molecule interactional minimizes and the raising in efficient and work-ing life remains task to be achieved.
The problem that runs into for fear of prior art, the present inventor has carried out deeply research completely to the organic field luminescence polymkeric substance, found that to contain in the electroluminescent polymer and on its 9, be substituted the disubstituted fluorenes of fluorenyl unit, thereby this electroluminescent polymer can be used as and is used for blueness, the novel material of main part of green and emitting red light, when making interaction between the molecule minimize and solve the shortcoming of conventional poly-fluorenes (PFs), has excellent thermostability, high-luminous-efficiency and high resolution, and can make the electroluminescence device that uses this electroluminescent polymer, thereby finish the present invention.
Therefore, an object of the present invention is the organic field luminescence polymkeric substance for the material of main part that, green blue as need realizing and emitting red light are provided, this organic field luminescence polymkeric substance is because inhibition electronic vibration pattern (vibronic mode) shows thermostability and oxidative stability height, interaction of molecules is low, transmission ofenergy is easy and luminous efficiency is high advantage.
Another object of the present invention is the organic electroluminescence device that uses this organic field luminescence polymkeric substance in order to provide.
To achieve these goals, the invention provides and a kind ofly have 9,9-two (fluorenyl)-2, the organic field luminescence polymkeric substance of 7-fluorenyl unit, this organic field luminescence polymkeric substance is as shown in the formula shown in 1:
Wherein, R
1, R
2, R
3And R
4Identical or different, the straight or branched alkyl of 1-20 the carbon atom of respectively doing for oneself; Unsubstituted or by the aryl that at least a substituting group replaced that is selected from the group of forming by the straight or branched alkyl and the alkoxyl group of 1-20 carbon atom; Straight or branched alkyl or alkoxyl group with at least a heteroatomic 1-20 carbon atom that is selected from the group of forming by F, S, N, O, P and Si; By the aryl that at least a substituting group that is selected from the group of being made up of straight or branched alkyl that contains at least one heteroatomic 1-20 carbon atom and alkoxyl group replaces, described heteroatoms is selected from the group of being made up of F, S, N, O, P and Si; Have 2-24 carbon atom heterocyclic moiety, do not replace or by the aryl that is selected from least a substituting group replacement in the group of forming by the straight or branched alkyl and the alkoxyl group of 1-20 carbon atom; Have 2-24 carbon atom heterocyclic moiety, by being selected from the aryl that at least a substituting group replaces in the group of being made up of straight or branched alkyl that contains at least one heteroatomic 1-20 carbon atom and alkoxyl group, described heteroatoms is selected from the group of being made up of F, S, N, O, P and Si; Replace or trialkylsilkl (trialkylsilylgroup) replacement of a unsubstituted 3-40 carbon atom or the aryl silyl of a unsubstituted 3-40 carbon atom; The carbazyl of a replacement or a unsubstituted 12-60 carbon atom; The phenothiazinyl of a replacement or a unsubstituted 6-60 carbon atom; Perhaps replace or the aryl amine of a unsubstituted 6-60 carbon atom;
R
5, R
6, R
7And R
8Identical or different, the straight or branched alkyl or the alkoxyl group of the hydrogen 1-20 carbon atom of respectively doing for oneself; Unsubstituted or by the aryl that at least a substituting group replaced that is selected from the group of forming by the straight or branched alkyl and the alkoxyl group of 1-20 carbon atom; Straight or branched alkyl or alkoxyl group with at least a heteroatomic 1-20 carbon atom that is selected from the group of forming by F, S, N, O, P and Si; By the aryl that at least a substituting group that is selected from the group of being made up of straight or branched alkyl that contains at least one heteroatomic 1-20 carbon atom and alkoxyl group replaces, described heteroatoms is selected from the group of being made up of F, S, N, O, P and Si; Have 2-24 carbon atom heterocyclic moiety, do not replace or by the aryl that is selected from least a substituting group replacement in the group of forming by the straight or branched alkyl and the alkoxyl group of 1-20 carbon atom; Have 2-24 carbon atom heterocyclic moiety, by being selected from the aryl that at least a substituting group replaces in the group of being made up of straight or branched alkyl that contains at least one heteroatomic 1-20 carbon atom and alkoxyl group, described heteroatoms is selected from the group of being made up of F, S, N, O, P and Si; The trialkylsilkl of a replacement or a unsubstituted 3-40 carbon atom; The aryl silyl of a replacement or a unsubstituted 3-40 carbon atom; The carbazyl of a replacement or a unsubstituted 12-60 carbon atom; The phenothiazinyl of a replacement or a unsubstituted 6-60 carbon atom; Perhaps replace or the aryl amine of a unsubstituted 6-60 carbon atom;
A, b, c and d are identical or different, 1 to 3 the integer of respectively doing for oneself;
Ar be selected from by replace or the aromatics of a unsubstituted 6-60 carbon atom partly, in the heteroaromatic moiety of replacement or a unsubstituted 2-60 carbon atom and the group that their combination is formed;
L is 1 to 100000 integer, and m is 0 to 100000 integer, and n is 1 to 100000 integer.
The present invention also provides a kind of organic electroluminescence device, and this device has one deck at least and contains the layer of polymkeric substance as mentioned above between anode and negative electrode, and wherein, described layer is hole transporting layer, luminescent layer, electron supplying layer or hole barrier layer.
The invention provides and have 9,9-two (fluorenyl)-2, the organic field luminescence polymkeric substance of 7-fluorenyl unit and use the organic electroluminescence device of this polymer.Electroluminescent polymer of the present invention has higher thermostability, high-luminous-efficiency and high resolution, and the interaction of molecule is minimized.In addition, above-mentioned polymkeric substance can reduce the shortcoming of conventional poly-fluorenyl polymkeric substance, and can be used as the material of main part of blueness, green and the emitting red light of electroluminescence device, therefore shows the characteristics of luminescence preferably.
Description of drawings
In conjunction with the accompanying drawings, above and other objects of the present invention, feature and other advantage will more be expressly understood by the following detailed description.
Fig. 1 is the schematic cross-section of the conventional organic electroluminescence device structure that comprises base material/anode/hole transporting layer/luminescent layer/electron supplying layer/negative electrode of expression;
Fig. 2 is the synoptic diagram of expression according to the monomer building-up reactions by the electroluminescent polymer shown in the formula 2 of the present invention;
Fig. 3 is the synoptic diagram of expression according to the monomer building-up reactions by the electroluminescent polymer shown in the formula 4 of the present invention;
Fig. 4 is according to monomeric by shown in the compound (2) of the present invention
1The H-NMR spectrum;
Fig. 5 is by the electroluminescent polymer shown in the formula 2 according to of the present invention
1The H-NMR spectrum;
Fig. 6 is by (photoluminescence, PL) spectrum of the photoluminescence in chloroformic solution and film respectively of the electroluminescent polymer shown in the formula 2 according to of the present invention;
Fig. 7 is according to electroluminescence (electroluminescence, EL) spectrum of use of the present invention by the electroluminescence device of the preparation of the electroluminescent polymer shown in the formula 2;
Fig. 8 is by the photoluminescence in chloroformic solution and film (PL) spectrum respectively of the electroluminescent polymer shown in the formula 4 according to of the present invention;
Fig. 9 is according to electroluminescence (EL) spectrum of use of the present invention by the electroluminescence device of the preparation of the electroluminescent polymer shown in the formula 4.
Embodiment
Describe the present invention in detail below in conjunction with accompanying drawing.
The invention provides and have 9,9-two (fluorenyl)-2, the organic field luminescence polymkeric substance of 7-fluorenyl unit and use the organic electroluminescence device of this polymer, this electroluminescent polymer can be used as high pure blue, green and emitting red light material of main part, has high resolution, high thermal stability and high-quantum efficiency simultaneously.
Organic field luminescence polymkeric substance provided by the invention is the material with high thermal stability, high light stability, high resolution, high-quantum efficiency and fabulous film-forming properties, it is characterized in that, be introduced on as the fluorenes of main chain 9 as the fluorenyl of main body substituting group (bulky substituent), therefore this substituent structure is identical with main chain.Therefore, the arrangement between main chain and the substituting group becomes at random, has also suppressed to form intermolecular excite state atom by substituting group, thereby has avoided the problem of the maximum that runs in poly-fluorenyl polymkeric substance promptly to assemble and/or the formation of excite state atom.And can realize intramolecularly or intermolecular energy are transferred to main chain from the short substituting group of wavelength.
In addition, be used as 9 effects that utilize main body fluorenyl substituting group to play controls revolution or electronic vibration pattern of the fluorenes of main chain, with thorough reduction on-radiation decay.Therefore, organic field luminescence polymkeric substance of the present invention shows high color purity, high luminous and high-level efficiency.
According to the present invention, this organic field luminescence polymkeric substance has 9,9-two (fluorenyl)-2, and the 7-fluorenyl unit, shown in 1:
Wherein, R
1, R
2, R
3And R
4Identical or different, the straight or branched alkyl of 1-20 the carbon atom of respectively doing for oneself; Unsubstituted or by the aryl that at least a substituting group replaced that is selected from the group of forming by the straight or branched alkyl and the alkoxyl group of 1-20 carbon atom; Straight or branched alkyl or alkoxyl group with at least a heteroatomic 1-20 carbon atom that is selected from the group of forming by F, S, N, O, P and Si; By the aryl that at least a substituting group that is selected from the group of being made up of straight or branched alkyl that contains at least one heteroatomic 1-20 carbon atom and alkoxyl group replaces, described heteroatoms is selected from the group of being made up of F, S, N, O, P and Si; Have 2-24 carbon atom heterocyclic moiety, do not replace or by the aryl that is selected from least a substituting group replacement in the group of forming by the straight or branched alkyl and the alkoxyl group of 1-20 carbon atom; Have 2-24 carbon atom heterocyclic moiety, by being selected from the aryl that at least a substituting group replaces in the group of being made up of straight or branched alkyl that contains at least one heteroatomic 1-20 carbon atom and alkoxyl group, described heteroatoms is selected from the group of being made up of F, S, N, O, P and Si; The trialkylsilkl of a replacement or a unsubstituted 3-40 carbon atom; The aryl silyl of a replacement or a unsubstituted 3-40 carbon atom; The carbazyl of a replacement or a unsubstituted 12-60 carbon atom; The phenothiazinyl of a replacement or a unsubstituted 6-60 carbon atom; Perhaps replace or the aryl amine of a unsubstituted 6-60 carbon atom;
R
5, R
6, R
7And R
8Identical or different, the straight or branched alkyl or the alkoxyl group of the hydrogen 1-20 carbon atom of respectively doing for oneself; Unsubstituted or by the aryl that at least a substituting group replaced that is selected from the group of forming by the straight or branched alkyl and the alkoxyl group of 1-20 carbon atom; Straight or branched alkyl or alkoxyl group with at least a heteroatomic 1-20 carbon atom that is selected from the group of forming by F, S, N, O, P and Si; By the aryl that at least a substituting group that is selected from the group of being made up of straight or branched alkyl that contains at least one heteroatomic 1-20 carbon atom and alkoxyl group replaces, described heteroatoms is selected from the group of being made up of F, S, N, O, P and Si; Have 2-24 carbon atom heterocyclic moiety, do not replace or by the aryl that is selected from least a substituting group replacement in the group of forming by the straight or branched alkyl and the alkoxyl group of 1-20 carbon atom; Have 2-24 carbon atom heterocyclic moiety, by being selected from the aryl that at least a substituting group replaces in the group of being made up of straight or branched alkyl that contains at least one heteroatomic 1-20 carbon atom and alkoxyl group, described heteroatoms is selected from the group of being made up of F, S, N, O, P and Si; The trialkylsilkl of a replacement or a unsubstituted 3-40 carbon atom; The aryl silyl of a replacement or a unsubstituted 3-40 carbon atom; The carbazyl of a replacement or a unsubstituted 12-60 carbon atom; The phenothiazinyl of a replacement or a unsubstituted 6-60 carbon atom; Perhaps replace or the aryl amine of a unsubstituted 6-60 carbon atom;
A, b, c and d are identical or different, 1 to 3 the integer of respectively doing for oneself;
Ar be selected from by replace or the aromatics of a unsubstituted 6-60 carbon atom partly, in the heteroaromatic moiety of replacement or a unsubstituted 2-60 carbon atom and the group that their combination is formed;
L is 1 to 100000 integer, and m is 0 to 100000 integer, and n is 1 to 100000 integer.Preferably, the ratio of l and m is 5: 95 to 95: 5.
According to the present invention, preferred described R
1, R
2, R
3And R
4Be selected from respectively in the following group:
In addition, preferred described R
5And R
6Be selected from respectively in the following group:
Wherein,
(i) described R
9And R
10Identical or different, be respectively the straight or branched alkyl of 1-20 carbon atom.
Above-mentioned fluorenyl is selected from the following group typically:
(ii) R
11Be hydrogen, perhaps straight or branched alkyl, alkoxyl group or the trialkylsilkl of 1-20 carbon atom;
R
12And R
13Identical or different, be respectively the straight or branched alkyl of 1-20 carbon atom;
X is O or S;
Y and Z are N; And
A is 1 to 3 integer.
Above-mentioned aryl with heterocyclic moiety is selected from the following group typically:
(iii) R
14, R
15And R
16Identical or different, be respectively the straight or branched alkyl or the alkoxyl group of 1-20 carbon atom, perhaps unsubstituted or by the aryl that at least a substituting group replaced that is selected from the group of forming by the straight or branched alkyl and the alkoxyl group of 1-20 carbon atom;
R
17, R
18, R
19, R
20, R
21And R
22Identical or different, be respectively hydrogen, the straight or branched alkyl or the alkoxyl group of 1-20 carbon atom, perhaps unsubstituted or by the aryl that at least a substituting group replaced that is selected from the group of forming by straight or branched alkyl and alkoxyl group.
Above-mentioned silyl, carbazole, thiodiphenylamine and arylamine can be selected from the following group typically:
In addition, preferred described R
7And R
8Be selected from respectively in the following group:
According to the present invention, preferred described Ar is selected from the following group: (i) arylidene of a replacement or a unsubstituted 6-60 carbon atom; (ii) the heterocycle arylidene of a replacement or a unsubstituted 2-60 carbon atom wherein contains at least a heteroatoms that is selected from the group of being made up of N, S, O, P and Si in the aromatic ring; (iii) replace or the arylidene vinylidene (arylenevinylene) of a unsubstituted 6-60 carbon atom; (iv) replace or the aryl amine of a unsubstituted 6-60 carbon atom; (v) replace or the carbazyl of a unsubstituted 12-60 carbon atom; And (vi) their combination,
Wherein Ar can comprise substituting group for example the straight or branched alkyl or the alkoxyl group of 1-20 carbon atom; Do not replace or by the aryl that is selected from least a substituting group replacement in the group of forming by straight or branched alkyl that contains at least one heteroatomic 1-20 carbon atom and alkoxyl group; Cyano group (CN) or silyl.
More specifically,
(i) in the arylidene of a replacement or a unsubstituted 6-60 carbon atom, when Ar was phenylene or fluorenylidene, Ar can be selected from the following group typically:
(ii) when Ar was the heterocycle arylidene of a replacement or a unsubstituted 2-60 carbon atom, Ar can be selected from the following group typically:
(iii) when Ar was the arylidene vinylidene of a replacement or a unsubstituted 6-60 carbon atom, Ar can be selected from the following group typically:
(iv) when Ar was the aryl amine of a replacement or a unsubstituted 6-60 carbon atom, Ar can be selected from the following group typically:
R wherein
23, R
24And R
25Identical or different, be the straight or branched alkyl or the alkoxyl group of hydrogen, a 1-20 carbon atom, perhaps unsubstituted or by the aryl that at least a substituting group replaced that is selected from the group of forming by the straight or branched alkyl and the alkoxyl group of 1-20 carbon atom.More preferably, Ar is selected from the following group:
(v) when Ar was the carbazyl of a replacement or a unsubstituted 12-60 carbon atom, Ar can be selected from the following group typically:
R wherein
26Be the straight or branched alkyl or the alkoxyl group of 1-20 carbon atom, perhaps unsubstituted or by the aryl that at least a substituting group replaced that is selected from the group of forming by the straight or branched alkyl and the alkoxyl group of 1-20 carbon atom.
In addition, when described Ar was the aryl amine of a (iv) replacement or a unsubstituted 6-60 carbon atom, the content of Ar in described electroluminescent polymer was preferably about 5-15 mole %.
The preparation of organic field luminescence polymkeric substance of the present invention for example comprises waiting by alkanisation, bromination, Grignard reaction (Grignard reaction), witig reaction (Wittig reaction) and prepares monomers, prepares the organic field luminescence polymkeric substance by carbon-to-carbon linked reaction such as Yamamoto linked reaction or Suzuki linked reaction then.The number-average molecular weight of the polymkeric substance that obtains is 1500-10000000, and molecular weight distribution is 1-50.
Organic field luminescence polymkeric substance of the present invention can be used as blueness, green and emitting red light main body, have fabulous thermostability, oxidative stability and solvability, and show the advantage that interaction of molecules is low, transmission ofenergy is easy and luminous efficiency is high owing to suppressing the electronic vibration pattern.
According to the present invention, described organic field luminescence polymkeric substance can be used as the formation material of luminescent layer, hole transporting layer, electron supplying layer or hole barrier layer between the pair of electrodes of electroluminescence device.
Described organic electroluminescence device comprises basic structure: anode/luminescent layer/negative electrode also optionally has hole transporting layer and electron supplying layer.
With reference to Fig. 1, Fig. 1 is the typical structure schematic cross-section that expression comprises the organic electroluminescence device of base material/anode/hole transporting layer/luminescent layer/electron supplying layer/negative electrode, for example uses organic field luminescence polymkeric substance of the present invention to be prepared as follows this organic electroluminescence device.
The electrode materials of anode 12 is applied on the base material 11.
Can use any base material that is used for conventional organic electroluminescence device as described base material 11.The preferred use has excellent transparency, surface, handles and the glass baseplate or the transparent plastic substrate of water-repellancy easily.
In addition, the electrode materials of anode 12 comprises transparent and tin indium oxide that conductivity is high (indium tinoxide, ITO), stannic oxide (SnO
2), zinc oxide (ZnO).
Can or sputter at by vacuum moulding machine subsequently and form hole transporting layer 13 on the anode 12, then by solution coat method such as rotary coating or ink jet printing formation luminescent layer 14.On luminescent layer 14, also form electron supplying layer 15, form negative electrode 16 then.Therefore, the thickness of luminescent layer 14 is extremely about 1 millimeter of about 5 nanometer, is preferably about 500 nanometers of about 10-.The about 10-10000 dust of hole transporting layer and electron transport bed thickness ().
Electron supplying layer 15 is by using conventional electron supplying layer formation material or will being obtained by compound vacuum moulding machine, sputter, rotary coating or the ink jet printing shown in the formula 1.
Hole transporting layer 13 and electron supplying layer 15 play thereby current carrier are delivered to the effect that luminescence polymer improves the luminous efficiency of luminescence polymer effectively.In addition, there is no particular limitation to the formation material of hole transporting layer 13 and electron supplying layer 15.For example, the cavity conveying layer material comprise as be doped with (poly-(styrene sulfonic acid) (PSS) poly-(3,4-enedioxy thiophene) (PEDOT) layer PEDOT:PSS, and N, N '-two (3-aminomethyl phenyl)-N, N-phenylbenzene-[1,1 '-xenyl]-4,4 '-diamines (TPD), and the electron transport layer material comprises trihydroxy-quinoline aluminum (aluminum trihydroxyquinoline, Alq3), 1,3,4-oxadiazole derivative PBD (2-(4-xenyl)-5-phenyl-1,3, the 4-oxadiazole), quinoxaline derivatives TPQ (1,3,4-three [(3-phenyl-6-trifluoromethyl) quinoxaline-2-yl] benzene) and triazole derivative.
When the organic field luminescence polymkeric substance being carried out solution coat to form described when layer, can be with organic field luminescence polymkeric substance and the polymkeric substance with conjugated double bond such as the inferior ethene of polyphenylene and polyparaphenylene (polyparaphenylene) and other fluorenyl mixed with polymers.As required, can use by the mixed adhesive resin.The example of described adhesive resin comprises Polyvinyl carbazole, polycarbonate, polyester, polyarylate (polyarylate), polystyrene, acrylic polymers (acryl polymer), methylacrylic acid base polymer (methacryl polymer), poly-butyral, polyvinyl acetal, diallyl phthalate polymkeric substance, resol (phenol resin), Resins, epoxy, silicone resin, polysulfone resin or urea resin.Described resin can use separately or be used in combination.
Can also optionally form the hole barrier layer of making by lithium fluoride (LiF) by for example vacuum moulding machine, to play the transfer rate of control hole in luminescent layer 14 and the effect that improves the joint efficiency between electronics and hole.
Electrode materials with negative electrode 16 is coated on the electron supplying layer 15 at last.
The metal that is used to form low work function cathode for example comprises lithium (Li), magnesium (Mg), calcium (Ca), aluminium (Al) and Al:Li.
Organic electroluminescence device of the present invention manufactures order for anode/hole transporting layer/luminescent layer/electron supplying layer/negative electrode, or conversely, i.e. negative electrode/electron supplying layer/luminescent layer/hole transporting layer/anode.
In addition, organic field luminescence polymkeric substance of the present invention not only can be used as high molecular organic electroluminescence device material, can also (ThinFilm Transistor TFT) uses semiconductor material with light conversion material or polymer thin film transistors as optical diode.
According to the present invention, described organic field luminescence polymkeric substance position has the fluorenyl on 9 that are introduced in as main body substituting group (bulkysubstituent) as the fluorenes of main chain.Thereby this substituting group has the structure identical with main chain, and therefore the random alignment between main chain and the substituting group takes place.Can also suppress to form intermolecular excite state atom, thereby avoid greatest problem in poly-fluorenyl field promptly to assemble or form the excite state atom by substituting group.And can realize intramolecularly or intermolecular energy are transferred to main chain from the short substituting group of wavelength.By replacing fluorenyls introducing as 9 of the fluorenyl of main chain, controls revolution or electronic vibration pattern, thus significantly reduce the on-radiation decay, to show high thermal stability, light stability, solvability, film-forming properties and quantum yield.Therefore, the organic electroluminescence device of organic field luminescence polymkeric substance of the present invention and this polymer of use can show high color purity, high luminous and high-level efficiency.
The present invention may be better understood by the following examples, and the following examples are used for purpose of description and can not be understood that limitation of the present invention.
Carry out the following examples 1-4 according to reaction shown in Figure 2.
5.64 gram magnesium are put into 1000 milliliters there-necked flask, and slowly dropping is dissolved in the gram of 80 in 300 milliliters of tetrahydrofuran (THF)s (THF) 9,9-dihexyl-2-bromine fluorenes is with the preparation Grignard reagent.The temperature of reaction chamber is reduced to-40 ℃ or when lower, with 52 grams 2, the 7-dibromo fluorenone joins in the reactive bath technique under nitrogen atmosphere.Slowly be warming up to room temperature, then stirred 10 hours.The reaction soln that obtains is poured in the water, uses diethyl ether to extract then.Use rotatory evaporator that solvent evaporation is fallen.Carry out column chromatography and separate, obtain 60 gram (58%) 9-(9,9-dihexyl fluorenes-2-yl)-2,7-dibromo fluorenes-9-alcohol (1).
Embodiment 29, two (9,9-dihexyl fluorenes-2-yl)-2 of 9-, 7-dibromo fluorenes (2) synthetic
In 2 liters of round-bottomed flasks, digest compound (1) and 200 with 50 and restrain 9,9-dihexyl fluorenes is dissolved in 1000 milliliters of methylene dichloride, is cooled to 0 ℃ then.Under agitation condition, will slowly join in the described reaction soln, continue then to stir 2 hours by the solution that 10 milliliters of methylsulfonic acids are dissolved in 100 milliliters of methylene dichloride.The reaction soln that obtains is poured in the water, uses diethyl ether to extract then.Use rotatory evaporator that solvent evaporation is fallen.Carry out column chromatography and separate, obtain two (9,9-dihexyl fluorenes-2-yl)-2 of 60 grams (58%) 9,9-, 7-dibromo fluorenes (2).
Embodiment 39, two (9, the 9-dihexyl fluorenes-2-yl) fluorenes-2 of 9-, 7-hypoboric acid (3) synthetic
In 250 milliliters round-bottomed flask, digest compound (2) with 10 and be dissolved in 60 milliliters of tetrahydrofuran (THF)s, be cooled to-70 ℃ then.2 normal 2.5 mol n-Butyl Lithiums are slowly joined in the above-mentioned reaction soln, and (70 ℃ to-40 ℃) reaction is 2 hours at low temperatures.Under same temperature, also add 4 normal triethyl borates, the reaction soln that obtains was left standstill 12 hours.The reaction soln that obtains is joined in the 3 mol aqueous hydrochloric acids, stirred then 4 hours, extract with diethyl ether.Use rotatory evaporator to remove solvent, obtain curing material, with this curing material for several times, obtain two (9, the 9-dihexyl fluorenes-2-yl) fluorenes-2 of 3.6 grams (39%) 9,9-, 7-hypoboric acid (3) with toluene wash.
Embodiment 49, two (9, the 9-dihexyl fluorenes-2-yl) fluorenes-2 of 9-, 7-hypoboric acid glycol ester (4) synthetic
Digesting compound (3), 3 equivalent ethylene glycol and 50 milliliters of dry toluenes with 2 joins in 100 milliliters of round-bottomed flasks that Dean and Stark apparatus is housed.Then, carry out refluxing in 24 hours to remove water.With the material recrystallization in toluene that obtains, obtain 1.8 grams 9, two (9, the 9-dihexyl fluorenes-2-yl) fluorenes-2 of 9-, 7-hypoboric acid glycol ester (4).
Carry out the following examples 5-8 according to reaction scheme shown in Figure 3.
10 gram 2-bromine fluorenes, 2 equivalent methylsulfonic acids and 100 gram phenol are put into 500 milliliters of round-bottomed flasks, stirred 24 hours down at 150 ℃ then.Mix to cross filter solid with the reaction soln cooling and with water.With this solid recrystallization in toluene, obtain 12 gram 2-bromo-9,9-two (4-hydroxyphenyl) fluorenes (5) then.
In 250 milliliters round-bottomed flask, digest compound (5) and 2.2 equivalent 2-methyl butyl p-toluenesulfonic esters are dissolved in 100 milliliters of dimethyl sulfoxide (DMSO) (Dimethyl Sulphoxide with 10, DMSO) in,, 2.3 equivalent potassium tert.-butoxides (t-BuOK) are slowly added wherein to obtain reaction soln.Reacted 12 hours down at 70 ℃, the reaction soln that obtains is poured in 500 ml waters, then uses dichloromethane extraction, and uses rotatory evaporator to remove and desolvate.The mixed solvent of use hexane and ethyl acetate carries out column chromatography to be separated, and obtains 14 gram 2-bromo-9,9-two (4-(2-methyl) butyl oxygen) phenyl) fluorenes (6).
Embodiment 74, and 4-'-dibromobiphenyl-2-base-two [9, two (4-(2-methyl) butyl oxygen) phenyl of 9-) fluorenes-2-base-methyl alcohol (7) synthetic
In 250 milliliters there-necked flask, digest compound (6) with 18 and be dissolved in 300 milliliters of tetrahydrofuran (THF)s, with extremely-40 ℃ of reactor cooling,, stirred then 2 hours then toward wherein dropwise slowly adding 2.5 mol n-Butyl Lithiums.The temperature of reactive bath technique is reduced to-40 ℃ or lower, under nitrogen atmosphere 0.4 equivalent methyl-(2-bromo-4-bromophenyl) benzoic ether is joined in the reactive bath technique, is warming up to room temperature gradually, stirs then 10 hours.Reaction solution is poured in the water, extracted with diethyl ether then.Using rotatory evaporator to remove desolvates.Separate by column chromatography, obtain 17 grams 4,4-'-dibromobiphenyl-2-base-two [9, two (4-(2-methyl) butyl oxygen) phenyl of 9-] fluorenes-2-base-methyl alcohol (7).
Embodiment 82,7-two bromo-[9,9-two [9, two (4-(2-methyl) the butyl oxygen phenyl) fluorenes-2-base of 9--] fluorenes] (8) synthetic
Digest compound (7) and 100 milliliters of acetate join in 250 milliliters of round-bottomed flasks with 10, the hydrochloric acid toward wherein adding 5 35 weight % refluxed 12 hours then.Reaction soln is cooled to room temperature to cross filter solid.Then with the washing of filtering solid water and methanol mixture, and in monochloro methane and alcoholic acid mixing solutions recrystallization, obtain 2,7-two bromo-[9,9-two [9, two (4-(2-methyl) the butyl oxygen phenyl) fluorenes-2-base of 9--] fluorenes] (8) white solid.
Embodiment's 9 poly-(9,9-two (9,9-dihexyl fluorenes-2-yl)-2,7-fluorenyl) (formula 2) is synthetic
Wherein, n
1It is 1 to 100000 integer.
In 500 milliliters of Schrenk flasks, 6 grams (607 millis rub) compound (2) is dissolved in 66 milliliters of toluene that outgased by nitrogen, preserves in nitrogen atmosphere then.Under condition of nitrogen gas, will be as 3.576 grams (12.74 millis the rub 2.1 equivalents) Ni (COD) of catalyzer
2, 1.392 the gram (12.74 the milli rub, 2.1 equivalent) 1, (12.74 millis rub for 4-cyclooctadiene (COD), 2.010 grams, 2.1 equivalent) dipyridyl joins in the Schrenk flask, add 33 milliliters of toluene and 33 milliliters of N, dinethylformamide (N, N-Dimethylformamide by the nitrogen degassing, DMF), stirred 30 minutes down at 80 ℃ then.The monomer solution of preparation is joined in the reaction vessel, reacted 24 hours.The reaction soln that obtains is mixed with 2 milliliters of bromobenzenes, react termination reaction after 24 hours.Then, reaction soln is joined hydrochloric acid (35 weight %): acetone: in 1500 ml solns of ethanol=1: 1: 1, to remove unreacted catalyzer and to make polymer precipitation.With polymer filtration and be dissolved in the chloroform, use celite (celite) to filter then to remove remaining catalyzer.Concentrate, in methyl alcohol, precipitate again, and washed 24 hours with Soxhlet (Soxlet).Yield is 69%, weight-average molecular weight Mw=180000, and number-average molecular weight Mn=58000, polymolecularity (polydispersity, PDI)=3.1.
Fig. 4 and Fig. 5 represent monomer shown in compound (2) and electroluminescent polymer as shown in Equation 2 respectively
1The H-NMR spectrum.From these accompanying drawings as can be seen, the structure of above-mentioned monomer and polymkeric substance conforms to each other.Fig. 6 represents the electroluminescent polymer photoluminescence in chloroformic solution and film (PL) spectrum respectively as shown in Equation 2, wherein the photoluminescence in chloroformic solution (PL) spectrographic climax is in 418 nanometers, corresponding to the blue-light-emitting zone, acromion (shoulder peak) is in 442 nanometers.Photoluminescence on film (PL) spectrographic climax is in 427 nanometers, and corresponding to the blue-light-emitting zone, acromion (shoulder peak) is in 448 nanometers.In addition, do not observe excite state atom peak in the present invention, described excite state atom peak is generally observed near 530 nanometers in the poly-epilamellar photoluminescence of fluorenes (PL) spectrum.Therefore, can confirm that compound of the present invention can be as the material with high-luminous-efficiency.
Embodiment 10
Polymkeric substance (l shown in the formula 3
1: m
1=95: 5) synthetic
Wherein, l
1Be 1 to 100000 integer, m
1It is 1 to 100000 integer.
Use the method identical with embodiment 3 to prepare this polymkeric substance, different is, the compound (2) of use 95% and 5% 4,4-dibromo triphenylamine is as monomer.Weight-average molecular weight Mw=165000, number-average molecular weight Mn=61000, polymolecularity=2.7.
Polymkeric substance (l shown in the formula 3
1: m
1=90: 10) synthetic
Use the method identical with embodiment 3 to prepare this polymkeric substance, different is, the compound (2) of use 90% and 10% 4,4-dibromo triphenylamine is as monomer.Weight-average molecular weight Mw=162000, number-average molecular weight Mn=56000, polymolecularity=2.9.
Embodiment 12
Polymkeric substance (l shown in the formula 3
1: m
1=85: 15) synthetic
Use the method identical with embodiment 3 to prepare this polymkeric substance, different is, the compound (2) of use 85% and 15% 4,4-dibromo triphenylamine is as monomer.Weight-average molecular weight Mw=157000, number-average molecular weight Mn=60,000, polymolecularity=2.6.
Embodiment 13
Synthesizing of polymkeric substance shown in the formula 4
Wherein, l
2Be 1 to 100000 integer, m
2It is 1 to 100000 integer.
Digest compound (8), 0.38 gram 9 with 0.55, two (4-octyl phenyl) fluorenes-2 of 9-, 7-hypoboric acid glycol ester and 0.075 gram N, N-two (4-bromophenyl)-N, two (the 4-methoxyphenyls)-[1 of N-, the 1-xenyl]-4, the 4-diamines is dissolved in 10 milliliters of toluene, toward wherein adding 2.5 ml waters, 0.55 gram K
3PO
4, 0.02 the gram three decanoyl chloromethane ammoniums, used nitrogen bubble then 30 minutes.In reaction mixture, add 0.01 gram tetrakis triphenylphosphine palladium (0), reacted 24 hours down at 89 ℃ then.The reaction soln that obtains is cooled to room temperature, and precipitates in 200 ml methanol to filter polymkeric substance.Then filtering polymkeric substance is dissolved in the chloroform and and filter, to remove remaining catalyzer with celite.Concentrate, in methyl alcohol, precipitate again, and washed 24 hours with Soxhlet.Yield is 72%, weight-average molecular weight Mw=150000, number-average molecular weight Mn=63000, polymolecularity=2.4.
Fig. 8 represents the electroluminescent polymer photoluminescence in chloroformic solution and film (PL) spectrum respectively as shown in Equation 4.As shown in the drawing, observe respectively near 556 nanometers corresponding to the blue-light-emitting zone in solution and film on photoluminescence (PL) spectrographic climax.
Comparative Examples 1
According to synthetic electroluminescent polymer (the weight-average molecular weight M of disclosed method among the WO 02/077060 with following repeating unit
w=180000).
Embodiment 14-18 and Comparative Examples 2
The making of electroluminescence device
On glass baseplate, form tin indium oxide (ITO) electrode.The polymkeric substance that is used for electroluminescence device that following table 1 is provided is spun onto the ITO electrode then, forms the luminescent layer of thick 600-1500 dust ().The Al:Li vacuum moulding machine to luminescent layer, is formed the aluminium lithium electrode of thick 100-1200 dust (), thereby makes organic electroluminescence device, measure the characteristics of luminescence then, the result is as shown in table 1 below.
Table 1
| The embodiment numbering | Luminescent layer | Driving voltage (volt) | ELλ Maximum(nanometer) | High-high brightness (international candle/square metre) | Maximum efficiency (international candle/peace) | Hue coordinate (x, y) | External quantum efficiency (%) |
| 14 | Embodiment 9 | 7.1 | 426，447 | 467 | 0.716 | 0.160， 0.080 | 1.18 |
| 15 | Embodiment 10 | 7.0 | 443 | 693 | 1.45 | 0.160， 0.090 | 1.94 |
| 16 | | 6.5 | 439 | 740 | 1.08 | 0.159， 0.093 | 1.44 |
| 17 | Embodiment 12 | 6.5 | 439 | 864 | 0.88 | 0.159， 0.096 | 1.16 |
| 18 | Embodiment 13 | 6.0 | 455 | 720 | 0.64 | 0.160， 0.150 | 0.58 |
| Comparative Examples 2 | Comparative Examples 1 | 7.0 | 427，450 | 206 | 0.03 | 0.165， 0.097 | 0.04 |
Fig. 7 represents the electroluminescence spectrum that obtained by the electroluminescence device (embodiment 14) that uses electroluminescent polymer as shown in Equation 2, has corresponding to the climax of 426 nanometers in blue-light-emitting zone and the acromion of 447 nanometers.So narrow wavelength band (wavelength band) makes the purity of color height, does not observe generally near the peak of observed excite state atom 530 nanometers of the electroluminescence spectrum of poly-fluorenyl polymkeric substance in the present invention.Therefore, can find that employed polymer compound is the high material of luminous efficiency.The electroluminescence spectrum that Fig. 9 represents to use the electroluminescence device (embodiment 18) of electroluminescent polymer as shown in Equation 4 to be obtained, the climax with 455 nanometers, and owing to narrow wavelength band shows high purity of color.
In last table, the result of embodiment 14 represents to use the luminescent layer of being made by the compound of embodiment 9 and the characteristic of the electroluminescence device that makes is compared with the characteristic of other poly-fluorenyl polymkeric substance, and the characteristic of described electroluminescence device is unexpectedly excellent.X=0.160 in hue coordinate system particularly, the said apparatus of y=0.080 have and meet U.S.'s national television standards committee (National TelevisionStandards Committee, NTSC) hue coordinate of standard blueness system substantially.In addition, the maximum in the homopolymerization fluorenes (homopolyfluorene) known to 1.18% external quantum efficiency is considered to so far.Amido Ar embodiment 15, embodiment 16, embodiment 17 and embodiment 18 partly for use formula 1 drives initial voltage and shown reduction.Especially in embodiment 15 as can be seen quantum yield significantly improved.This is because because the introducing fluorenyl makes substituent structure and main chain similar as the main body substituting group, and the result makes random alignment between main chain and the substituting group.In addition, the gathering and the forming of intermolecular excite state atom that are caused by substituting group have obtained inhibition, thereby have avoided being regarded as the gathering of the greatest problem in poly-fluorenyl polymer arts and/or the formation of excite state atom.Can also realize intramolecularly or intermolecular energy are transferred to main chain from the substituting group with short wavelength.By as the replacement fluorenyl on 9 of the fluorenes of main chain, rotation and electronic vibration pattern have been suppressed, with thorough reduction on-radiation decay.Therefore, organic field luminescence polymkeric substance of the present invention has high-luminous-efficiency, uses the organic electroluminescence device of this polymkeric substance to have high color purity, high radiance and high-level efficiency.Therefore, electroluminescent polymer of the present invention is suitable for the commerce use of electroluminescence device.
Industrial applicibility
As mentioned above, the invention provides and a kind ofly have 9,9-two (fluorenyl)-2, the organic field luminescence polymkeric substance of 7-fluorenyl unit and use the organic electroluminescence device of this polymer.Electroluminescent polymer of the present invention has fabulous thermostability, high-luminous-efficiency and high resolution, and plays the minimized effect of interaction of molecules that makes.And above-mentioned polymkeric substance can avoid the shortcoming of conventional poly-fluorenyl polymkeric substance, can be used as the material of main part of blueness, green and the emitting red light of electroluminescence device, thereby shows the fabulous characteristics of luminescence.
Although for purpose of description has provided preferred implementation of the present invention, it will be recognized by those of skill in the art that under not departing from and to carry out various modifications, interpolation and replacement as the prerequisite of the disclosed scope and spirit of the present invention of claim of enclosing.
Claims (12)
1, a kind of have 9,9-two (fluorenyl)-2, and the organic field luminescence polymkeric substance of 7-fluorenyl unit, this organic field luminescence polymkeric substance is as shown in the formula shown in 1:
Formula 1
Wherein, R
1, R
2, R
3And R
4Identical or different, the straight or branched alkyl of 1-20 the carbon atom of respectively doing for oneself; Unsubstituted or by the aryl that at least a substituting group replaced that is selected from the group of forming by the straight or branched alkyl and the alkoxyl group of 1-20 carbon atom; Straight or branched alkyl with at least a heteroatomic 1-20 carbon atom that is selected from the group of forming by F, S, N, O, P and Si; By the aryl that at least a substituting group that is selected from the group of being made up of straight or branched alkyl that contains at least one heteroatomic 1-20 carbon atom and alkoxyl group replaces, described heteroatoms is selected from the group of being made up of F, S, N, O, P and Si; Have 2-24 carbon atom heterocyclic moiety, do not replace or by the aryl that is selected from least a substituting group replacement in the group of forming by the straight or branched alkyl and the alkoxyl group of 1-20 carbon atom; Have 2-24 carbon atom heterocyclic moiety, by the aryl that at least a substituting group that is selected from the group of being made up of straight or branched alkyl that contains at least one heteroatomic 1-20 carbon atom and alkoxyl group replaces, described heteroatoms is selected from the group of being made up of F, S, N, O, P and Si; The trialkylsilkl of a replacement or a unsubstituted 3-40 carbon atom; The aryl silyl of a replacement or a unsubstituted 3-40 carbon atom; The carbazyl of a replacement or a unsubstituted 12-60 carbon atom; The phenothiazinyl of a replacement or a unsubstituted 6-60 carbon atom; Perhaps replace or the aryl amine of a unsubstituted 6-60 carbon atom;
R
5, R
6, R
7And R
8Identical or different, the straight or branched alkyl or the alkoxyl group of the hydrogen 1-20 carbon atom of respectively doing for oneself; Unsubstituted or by the aryl that at least a substituting group replaced that is selected from the group of forming by the straight or branched alkyl and the alkoxyl group of 1-20 carbon atom; Straight or branched alkyl or alkoxyl group with at least a heteroatomic 1-20 carbon atom that is selected from the group of forming by F, S, N, O, P and Si; By the aryl that at least a substituting group that is selected from the group of being made up of straight or branched alkyl that contains at least one heteroatomic 1-20 carbon atom and alkoxyl group replaces, described heteroatoms is selected from the group of being made up of F, S, N, O, P and Si; Have 2-24 carbon atom heterocyclic moiety, do not replace or by the aryl that is selected from least a substituting group replacement in the group of forming by the straight or branched alkyl and the alkoxyl group of 1-20 carbon atom; Have 2-24 carbon atom heterocyclic moiety, by the aryl that at least a substituting group that is selected from the group of being made up of straight or branched alkyl that contains at least one heteroatomic 1-20 carbon atom and alkoxyl group replaces, described heteroatoms is selected from the group of being made up of F, S, N, O, P and Si; The trialkylsilkl of a replacement or a unsubstituted 3-40 carbon atom; The aryl silyl of a replacement or a unsubstituted 3-40 carbon atom; The carbazyl of a replacement or a unsubstituted 12-60 carbon atom; The phenothiazinyl of a replacement or a unsubstituted 6-60 carbon atom; Perhaps replace or the aryl amine of a unsubstituted 6-60 carbon atom;
A, b, c and d are identical or different, 1 to 3 the integer of respectively doing for oneself;
Ar be selected from by replace or the aromatics of a unsubstituted 6-60 carbon atom partly, in the heteroaromatic moiety of replacement or a unsubstituted 2-60 carbon atom and the group that their combination is formed;
L is 1 to 100000 integer, and m is 0 to 100000 integer, and n is 1 to 100000 integer.
2, organic field luminescence polymkeric substance according to claim 1, wherein, described R
1, R
2, R
3And R
4Be selected from respectively in the following group:
3, organic field luminescence polymkeric substance according to claim 1, wherein, described R
5And R
6Be selected from respectively in the following group:
Wherein said R
9And R
10Identical or different, be respectively the straight or branched alkyl of 1-20 carbon atom;
R
11Be hydrogen, perhaps straight or branched alkyl, alkoxyl group or the trialkylsilkl of 1-20 carbon atom;
R
12And R
13Identical or different, be respectively the straight or branched alkyl of 1-20 carbon atom;
R
14, R
15And R
16Identical or different, be respectively the straight or branched alkyl or the alkoxyl group of 1-20 carbon atom, perhaps unsubstituted or by the aryl that at least a substituting group replaced that is selected from the group of forming by the straight or branched alkyl and the alkoxyl group of 1-20 carbon atom;
R
17, R
18, R
19, R
20, R
21And R
22Identical or different, be respectively hydrogen, the straight or branched alkyl or the alkoxyl group of 1-20 carbon atom, perhaps unsubstituted or by the aryl that at least a substituting group replaced that is selected from the group of forming by the straight or branched alkyl and the alkoxyl group of 1-20 carbon atom;
X is O or S;
Y and Z are N; And
A is 1 to 3 integer.
4, organic field luminescence polymkeric substance according to claim 1, wherein, described R
7And R
8Be selected from respectively in the following group:
5, organic field luminescence polymkeric substance according to claim 1, wherein, described Ar is selected from the following group:
(i) arylidene of a replacement or a unsubstituted 6-60 carbon atom;
(ii) the heterocycle arylidene of a replacement or a unsubstituted 2-60 carbon atom wherein contains at least a heteroatoms that is selected from the group of being made up of N, S, P, O and Si in the aromatic ring;
(iii) replace or the arylidene vinylidene of a unsubstituted 6-60 carbon atom;
(iv) replace or the aryl amine of a unsubstituted 6-60 carbon atom;
(v) replace or the carbazyl of a unsubstituted 12-60 carbon atom; And
(vi) their combination,
Wherein Ar can comprise straight or branched alkyl or the alkoxyl group that is selected from by 1-20 carbon atom; Do not replace or by the aryl that is selected from least a substituting group replacement in the group of forming by the straight or branched alkyl and the alkoxyl group of 1-20 carbon atom; Substituting group in the group that cyano group and silyl are formed.
6, organic field luminescence polymkeric substance according to claim 1, wherein, the ratio of l and m is 5: 95 to 95: 5.
7, organic field luminescence polymkeric substance according to claim 5, wherein, when described Ar was the aryl amine of a replacement or a unsubstituted 6-60 carbon atom, the content of Ar in described electroluminescent polymer was 5-15 mole %.
8, organic field luminescence polymkeric substance according to claim 1, wherein, described organic field luminescence polymkeric substance is as shown in the formula shown in 2:
Formula 2
Wherein n is 1 to 100000 integer.
9, organic field luminescence polymkeric substance according to claim 1, wherein, described organic field luminescence polymkeric substance is as shown in the formula shown in 3:
Formula 3
L wherein
1Be 1 to 100000 integer, m
1It is 1 to 100000 integer.
10, organic field luminescence polymkeric substance according to claim 1, wherein, described organic field luminescence polymkeric substance is as shown in the formula shown in 4:
Formula 4
L wherein
2Be 1 to 100000 integer, m
2It is 1 to 100000 integer.
11, a kind of organic electroluminescence device, this device have at least one layer that contains the described polymkeric substance of claim 1 between anode and negative electrode, wherein, described layer is hole transporting layer, luminescent layer, electron supplying layer or hole barrier layer.
12, organic electroluminescence device according to claim 11, wherein, described organic electroluminescence device comprises following structure: anode/luminescent layer/negative electrode, anode/hole transporting layer/luminescent layer/negative electrode or anode/hole transporting layer/luminescent layer/electron supplying layer/negative electrode.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106537634A (en) * | 2014-07-22 | 2017-03-22 | 罗门哈斯电子材料韩国有限公司 | Organic electroluminescent device |
| CN108137444A (en) * | 2015-12-04 | 2018-06-08 | 广州华睿光电材料有限公司 | Terphenyl pentalene class compound, high polymer, mixture, composition and organic electronic device |
| CN108137445A (en) * | 2015-12-04 | 2018-06-08 | 广州华睿光电材料有限公司 | Spirocyclic derivatives, high polymer, mixture, composition and organic electronic device |
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| KR101412887B1 (en) * | 2007-05-25 | 2014-06-26 | 에스케이이노베이션 주식회사 | Organic electroluminescent polymer with triphenyl amine group and organic electroluminescent device manufactured using the same |
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| WO2011093392A1 (en) * | 2010-01-29 | 2011-08-04 | 住友化学株式会社 | Luminescent composition and light-emitting element using said composition |
| JP5862086B2 (en) * | 2010-07-21 | 2016-02-16 | 住友化学株式会社 | Manufacturing method of organic EL element |
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| KR101476231B1 (en) * | 2013-10-02 | 2014-12-24 | 롬엔드하스전자재료코리아유한회사 | An Organic Electroluminescent Compound and an Organic Electroluminescent Device Comprising the Same |
| JP2016000773A (en) * | 2014-06-11 | 2016-01-07 | 東ソー株式会社 | Arylamine polymer, and electronic element using the same |
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| JP2023134362A (en) * | 2022-03-14 | 2023-09-27 | 住友化学株式会社 | Polymer compound and light-emitting element using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69943334D1 (en) | 1998-12-28 | 2011-05-19 | Idemitsu Kosan Co | METHOD FOR SELECTION OF ORGANIC COMPOUNDS FOR ORGANIC ELECTROLUMINESCENT PLANT |
| JP2004500463A (en) * | 2000-02-25 | 2004-01-08 | ケンブリッジ ディスプレイ テクノロジー リミテッド | Electroluminescent polymers, methods for their preparation and use |
| JP2002326965A (en) * | 2001-05-02 | 2002-11-15 | Sony Corp | Spirofluorene compound, method for producing the same, intermediate for synthesizing the same, and organic electroluminescent element using the spirofluorene compound |
| GB0111549D0 (en) * | 2001-05-11 | 2001-07-04 | Cambridge Display Tech Ltd | Polymers, their preparation and uses |
| JP2006056821A (en) * | 2004-08-19 | 2006-03-02 | Jsr Corp | Fluorene compound, method for producing the same, fluorene polymer, method for producing the same and organic electroluminescent element |
-
2005
- 2005-01-27 KR KR1020050007522A patent/KR101170168B1/en not_active IP Right Cessation
- 2005-01-28 CN CNB2005800028379A patent/CN100523122C/en not_active Expired - Fee Related
- 2005-01-28 JP JP2006550950A patent/JP4754501B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106537634A (en) * | 2014-07-22 | 2017-03-22 | 罗门哈斯电子材料韩国有限公司 | Organic electroluminescent device |
| CN106537634B (en) * | 2014-07-22 | 2020-08-07 | 罗门哈斯电子材料韩国有限公司 | Organic electroluminescent device |
| CN108137444A (en) * | 2015-12-04 | 2018-06-08 | 广州华睿光电材料有限公司 | Terphenyl pentalene class compound, high polymer, mixture, composition and organic electronic device |
| CN108137445A (en) * | 2015-12-04 | 2018-06-08 | 广州华睿光电材料有限公司 | Spirocyclic derivatives, high polymer, mixture, composition and organic electronic device |
| CN108137445B (en) * | 2015-12-04 | 2021-03-19 | 广州华睿光电材料有限公司 | Spirocyclic derivatives, polymers, mixtures, compositions and organic electronic devices |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4754501B2 (en) | 2011-08-24 |
| KR101170168B1 (en) | 2012-07-31 |
| KR20050078211A (en) | 2005-08-04 |
| JP2007519800A (en) | 2007-07-19 |
| CN100523122C (en) | 2009-08-05 |
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