CN1846320A - Electroluminescent device - Google Patents
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- CN1846320A CN1846320A CN 200480025238 CN200480025238A CN1846320A CN 1846320 A CN1846320 A CN 1846320A CN 200480025238 CN200480025238 CN 200480025238 CN 200480025238 A CN200480025238 A CN 200480025238A CN 1846320 A CN1846320 A CN 1846320A
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Abstract
An electroluminescent device comprising: - a first electrode for injection of positive charge carriers; - a second electrode for injection of negative charge carriers; and - an electroluminescent layer located between the first and second electrodes comprising a host material and a metal complex, wherein the host material comprises a polymer having a first repeat unit of formula (I): wherein each Ar is the same or different and independently represents an optionally substituted aryl or heteroaryl and any two Ar groups may be directly linked by a single bond.
Description
Technical field
The present invention relates to electroluminescent device and the electroluminescent polymer that is used for it.
Background technology
A class photoelectric device that is causing concern is the Semiconductor Organic material to be used for luminous (electroluminescent device) or as a class device of the active component of photocell or photodetector (" photovoltaic " device).The basic structure of these devices is the Semiconductor Organic layers that inject in organic layer or accept the negative electrode and the injection of negative charge carriers (electronics) or accept to insert between the positive charge carriers (hole).
In organic luminescent device (OLED), electronics and hole to be injected in the Semiconductor Organic layer, in conjunction with producing exciton thus, radiative decay can take place in these excitons therein for they.Various luminous organic materials are known, and particularly: polymer is as poly-(to phenylene vinylidene) (as disclosed among the WO90/13148); Poly-fluorenes and polyphenylene; The material type that is called small molecule material is as three-(8-oxyquinoline) aluminium (" Alq
3"), as US 4,539,507 is disclosed; With the material type that is called dendrimer (dendrimers), as disclosed among the WO 99/21935.These materials are by singlet exciton radiative decay electroluminescence (promptly fluorescing), yet the spin statistics shows that 75% exciton is for the triplet excitons of non-radiative decay takes place at the most, be that quantum efficiency can be hanged down for fluorescence OLED and for example reached 25%-, referring to Chem.Phys.Lett., 1993,210,61, Nature (London), 2001,409,494, Synth.Met., 2002,125,55 and list of references wherein.
Therefore, sizable effort relates to by utilizing spin-track coupling effect that triplet excitons is carried out in the metal complex of radiative decay by triplet excitons luminous (phosphorescent).The example of Yan Jiu complex comprises lanthanide chelates [Adv.Mater., 1999,11,1349], platinum (II) porphyrin [Nature (London), 1998,395,151] and iridium three (phenylpyridine) [Appl.Phys.Lett., 1999,75,4 for this purpose; Appl.Phys.Lett., 2000,77,904.The more detailed summary of this type of complex can be at Pure Appl.Chem., and 1999,71,2095, Materials Science ﹠amp; Engineering, R:Reports (2002), R39 (5-6), 143-222 and Polymeric Materials Science andBngineering (2000), 83, find among the 202-203.
The light-emitting zone of phosphorescent OLED by form with phosphorescent metal complex doped host material (phosphorescent metal complex can according to J.Appl.Phys.65, the similar fashion of describing in 3610,1989 is doped in the matrix).In operation, be transferred in the metal complex in conjunction with the singlet and the triplet excitons that form again, radiative decay takes place then by hole and electronics.The triplet energy state of the efficient requirement on devices main body by the operation of this mechanism is higher than the triplet energy state (referring to Appl.Phys.Lett.82 (7), 1006,2003) of phosphorescent dopant.This matrix also can be by taking place in metal complex but not in the matrix again in conjunction with (or as another selection) hole and/or electric transmission are gone in the metal complex.In the case, matrix must have the HOMO energy level (with effective transporting holes) between the HOMO energy level that is in anode working function and metal complex, or the lumo energy of matrix is between the lumo energy of the working function of negative electrode and metal complex (with effective injection electronics).
Obviously, select suitable host material most important for given phosphorescent OLED for the performance of bringing into play device to greatest extent, and will depend on multiple factor: comprise the working function and the triplet state (T1) of electrode (particularly negative electrode), the HOMO of metal complex and lumo energy.
Multiple matrix is described in the prior art, comprise " micromolecule " matrix as 4,4 '-two (carbazole-9-yl) biphenyl), be called CBP, (4,4 ', 4 " three (carbazole-9-yl) triphenylamine), be called TCTA; be disclosed among the Ikai et al. (Appl.Phys.Lett., 79 no.2,2001,156); With triarylamine as three-4-(N-3-aminomethyl phenyl-N-phenyl) aniline, be called MTDATA.Known homopolymers is also as matrix, and particularly poly-(vinylcarbazole) is disclosed in for example Appl.Phys.Lett.2000,77 (15), 2280; Poly-fluorenes is disclosed in Synth.Met.2001, and 116,379, Phys.Rev.B 2001,63,235206 and Appl.Phys.Lett.2003,82 (7), 1006; Poly-[4-(N-4-vinyl benzyloxy base ethyl, N-methylamino)-N-(2,5-di-tert-butyl-phenyl naphthalimide], be disclosed in Adv.Mater.1999,11 (4), 285; With poly-(to phenylene), be disclosed in J.Mater.Chem.2003,13, among the 50-55.
Except above-mentioned homopolymers matrix, copolymer matrix is disclosed in J.Chem.Phys. (2003), 118 (6), 2853-2864, the document discloses poly-[9,9 '-two-n-hexyl-2,7-fluorenes-alt-1,4-(2,5-two-just own oxygen base) phenylene] as fac-three (2-phenylpyridine) iridium (III) and 2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphyrin platinum (II).For these two kinds of complexs, observe bad performance.Mat.Res.Symp.SpringMeeting 2003 Book of Abstracts, p.214 Heeger discloses from the emitting red light of the complex of iridium of the random copolymer that uses dioctyl fluorene and dicyano-benzene.At last, the AB copolymer of fluorenes repetitive and phenylene repetitive is disclosed in Mat.Res.soc.Symp.Proc.708, in 2002,131.Be not that this fact of copolymer interrelates with importance and matrix; In fact, this open source literature points out that when using with iridium and platinum complex, this copolymer matrix does not produce singlet-singlet or triplet state-triplet energy state shifts.
Polymer body is generally the material of solution processable, and this is an important advantage, because it allows material by cheap technology such as spin coating or dip-coating deposition.Also allow ink-jet printing materials, this is particularly useful for making full-color display.
If matrix is " micromolecule ", then generally by hydatogenesis.Use micromolecule to allow a plurality of molecular layers on its top, to deposit mutually.Therefore, illuminating OLED described in the prior uses hole transporting layer and electron supplying layer (for example referring to J.Appl.Phys.75 (1), 4,1999) usually except matrix/phosphorescent metal complex layer.
On the contrary, when polymeric material deposits to when the layer of solution deposition is gone up from solution, a plurality of polymeric layers of formation are complicated because of the possible mutual mixing of interlayer.
A kind of method that cavity conveying and/or electron transport function are provided on the polymer device that is provided by host material is that the material that will have required function mixes mutually with matrix.Yet the component quantity in the blend need be reduced to minimum potential challenges to avoid being separated and bringing because of blend.
Using conjugated polymer such as homopolymerization fluorenes is that conjugation between the repetitive will reduce the HOMO-LUMO band gap and reduce the energy level (comparing with non-conjugated monomer) of triplet state excited state as another difficulty of matrix.The HOMO-LUMO band gap of host material must be greater than this band gap of emissivity metal complex.In addition, the triplet of matrix must be greater than the triplet (or can compare with it at least) of emission metal complex.Although this is not a problem for very little band gap complex such as burn red complex, this has difficulties as green and blue emission body for those metal complexs that have than broad-band gap and higher triplet energy state.
Therefore, an object of the present invention is to provide the polymer substrate of the phosphorescent OLED that is used for suitable wide metal complex scope.Another object of the present invention provides the polymer substrate with good hole and/or electric transmission function.
Summary of the invention
The inventor finds unexpectedly, comprises that the polymer of some triarylamine repetitive is effective especially as the matrix of phosphorescent metal complex, and this efficient can be optimized by choosing the common-repetitive that is used for the triarylamine repetitive suitably.
Therefore, first aspect present invention provides a kind of electroluminescent device, comprising:
-be used to inject first electrode of positive charge carriers;
-be used to inject second electrode of negative charge carriers; With
-be in the luminescent layer that comprises host material and metal complex between first and second electrodes, wherein host material comprises the polymer of first repetitive with following general formula (I):
Wherein each Ar is identical or different, and represents the aryl or the heteroaryl of inessential replacement independently, and any two Ar groups can directly connect by singly-bound.
" metal complex " used herein is meant a kind of like this metal complex, when itself and host material one are used from electroluminescent device, can accept from host material exciton and luminous by the exciton radiative decay.This metal complex can fluoresce and/or phosphorescence when being used from the electroluminescent device with matrix one.Preferably, basically derived from metal complex all the emission light be phosphorescence.
Host material can be homopolymers or copolymer.This polymer is preferably the copolymer that comprises second kind of repetitive.
Compare with the triplet of non-conjugated units, the repetitive of conjugation reduces the triplet of conjugate unit.Therefore, in one embodiment, second repetitive is unconjugated to small part, with along providing interruption in the conjugation of main polymer chain, and reduces or prevent the energy level adjustment of first repetitive thus by conjugation.When the repetitive of formula (I) has the required energy level that uses with given metal complex and/or when metal complex had high triplet (as green or blue phosphorescent material), this was particularly preferred.
In conjugation, provide preferred repeat units at interval to comprise following formula (II) and repetitive (III):
-(CR
4R
5)
n- -Ar
1-(CR
4R
5)
n-Ar
2-
(II) (III)
R wherein
4And R
5Be independently selected from hydrogen or substituting group; N is 1-10; Ar
1And Ar
2Be independently selected from the aryl or the heteroaryl of inessential replacement.Preferred each R
4And R
5Be independently selected from hydrogen or C
1-10Alkyl; N is 1 or 2 and each Ar
1And Ar
2Be phenyl.
In second embodiment, second repetitive is along the Ar-conjugation of its main chain conjugation and direct and first repetitive.Therefore suitable choose second repetitive can be used for telomerized polymer band gap so that its mate with required triplet state, HOMO or the lumo energy of metal complex.Second repetitive can be for the plane so that its along the main polymer chain total conjugated maybe can introduce distortion with restriction along the main polymer chain conjugation, and can not make along the conjugation of main chain (as first embodiment) fully at interval.Must be higher than in the triplet energy state of polymer substrate under the condition of triplet energy state of phosphorescent metal complex, when the repetitive total conjugated, the present embodiment is more suitable in complex, particularly red phosphorescent material with low triplet.
As the repetitive of total conjugated, the fluorenes of preferred inessential replacement, spiral shell fluorenes, indenofluorene, phenylene and low polyphenylene repetitive.
Copolymer according to first or second embodiment of first aspect present invention is preferably the AB copolymer.
This first repetitive can not have the key of two Ar groups of direct connection.In the case, the repetitive of formula (I) is preferably selected from the repetitive of following formula 1-6:
Wherein X, Y, A, B, C and D are independently selected from H or substituting group.One or more branching or straight chained alkyl, aryl, perfluoroalkyl, alkylthio, cyano group, alkoxyl, heteroaryl, alkaryl and aralkyl that more preferably are independently selected from inessential replacement among X, Y, A, B, C and the D.X, Y, A and B most preferably are C
1-10Alkyl.The repetitive of formula 1 is most preferred.
In addition, the repetitive of formula (I) can have singly-bound between two Ar groups.In the case, the repetitive of preferred following formula (IV):
Wherein R is hydrogen or substituting group, and among x and the y one exists as singly-bound.
When having key x, particularly preferred repetitive is the repetitive of the inessential replacement of following formula (IVa):
When having key y, particularly preferred repetitive is the repetitive of the inessential replacement of following formula (IVb):
Wherein n is 1 or 2, each Ar
3Aryl or the heteroaryl of representing inessential replacement independently, and two Ar wherein
3Group can condense together.(for n=1 and n=2) in a preferred embodiment, the Ar among unit IVa and the IVb
3Be phenyl, each phenyl is 1 under each situation, and 4-connects phenylene.In another embodiment preferred, n=2 and two Ar
3Group condenses and forms 2 together, and 7-connects the fluorenes unit.
In a preferred embodiment, polymer and metal complex can the combinations of physical blending thing form.In another embodiment preferred, metal complex is as the substituting group and the polymer chemistry bonding that combine with main polymer chain or is introduced in the main polymer chain.
The preferable alloy complex is as the repetitive in the polymer or as the end group setting of polymer.
In second aspect, the invention provides a kind of composition, comprise metal complex and the polymer described in the first aspect present invention.
Third aspect present invention provides a kind of electroluminescent polymer, comprises the repetitive of following formula (I) and as the metal complex in the substituting group that is connected to main polymer chain and polymer-bound or the introducing main polymer chain:
Wherein each Ar is identical or different, and the aryl or the heteroaryl of the nonessential replacement of independent separately expression can directly be connected by singly-bound with any two Ar bases.
Electroluminescent polymer can be the homopolymers that has with the metal complex of at least one repetitive Direct Bonding of formula (I).Alternately, this electroluminescent polymer can be copolymer, and in the case, metal complex (a) can form the common repetitive or (b) directly and the repetitive bonding of general formula (I) in the main polymer chain.
Consider the above-mentioned advantage that the repetitive of formula (I) combines with metal complex, the repetitive bonding of preferable alloy complex and formula (I).More preferably this metal complex exists as the part of the repetitive of formula (XII):
Wherein M is a metal; Each L
1, L
2And L
3Be coordinating group; Q is an integer; R and s are 0 or integer independently of one another; (aq)+(br)+(cs) sum equals available coordination positional number on M, and wherein a is L
1On the coordination positional number, b is L
2On the coordination positional number, c is L
3On the coordination positional number.
Ar and L
1Can be connected to form the bidentate ligand that is bonded on the metal M.
L
1, L
2And L
3Independently can be list or multidentate ligand separately.L
1, L
2And L
3In the two or all can be connected to form multidentate ligand.
This metal complex is phosphor preferably.
Aspect the 5th, the invention provides the monomer of formula (XIII):
Wherein each Ar is identical or different, represents the aryl or the heteroaryl of nonessential replacement independently; Any two Ar bases can directly be connected by singly-bound; M is a metal; L
1, L
2And L
3Each is coordinating group naturally; Q is an integer; R and s are 0 or integer independently of one another; (a.q)+(b.r)+(c.s) sum equals available coordination positional number on M, and wherein a is L
1On the coordination positional number, b is L
2On the coordination positional number, c is L
3On the coordination positional number; Identical or different with each P, and be polymerisable group.
In a preferred embodiment, metal complex ML
1 qL
2 rL
3 sBy key by L
1, L
2And L
3The side chain aryl bonding of one or more and triarylamine.In another embodiment, Ar and L
1Be connected to form bidentate ligand with the metal M bonding.L
1, L
2And L
3Can be list or multidentate ligand independently of one another, L
1, L
2And L
3In two or all can be connected to form multidentate ligand.
Preferred each P is independently selected from boric acid, borate, borine or halogen.
Description of drawings
The present invention only further describes by embodiment now with reference to the accompanying drawings, wherein:
Fig. 1 shows according to organic electroluminescence device of the present invention.
Embodiment
With reference to the accompanying drawings 1, comprise clear glass or plastic base thing 1, indium tin oxide anode 2 and negative electrode 4 according to the normal structure of electroluminescent device of the present invention.According to electroluminescence layer of the present invention be between anode 2 and the negative electrode 4 the layer 3.
Except layer 3, the hole transporting layer and/or the electron supplying layer of separation can be set.
Although not necessarily, the organic hole injection material layer (not shown) between anode 2 and polymeric layer 3 is suitable, because it helps the hole to inject the semi-conducting polymer layer by anode.The example of organic hole injection material comprises poly-(ethylene dioxythiophene) (PEDT/PSS), as disclosed among EP 0901176 and the EP 0947123, or polyaniline, as disclosed among US 5723873 and the US 5798170.
Negative electrode 4 is selected from the material with the work content that allows electronics injection electroluminescence layer.Other factors influences the selection of negative electrode, as the unfavorable interactional possibility between negative electrode and the electroluminescent material.Negative electrode can be made up of homogenous material such as aluminium lamination.In addition, it can comprise multiple metal, and for example calcium and aluminium bilayer are as disclosed among the WO 98/10621; Elements Barium, as WO 98/57381, Appl.Phys.Lett.2002,81 (4), 634 and WO 02/84759 in disclosed, or thin layer of dielectric material is injected to help electronics, the example of described dielectric material is as lithium fluoride, as disclosed among the WO 00/48258, or barium fluoride, as Appl.Phys.Lett.2001, disclosed in 79 (5), 2001.
Typical electroluminescent device comprises the anode with work content 4.8eV.Therefore, the HOMO energy level in cavity conveying district preferably has about 4.8-5.5eV.Similarly, the negative electrode of typical device will have the about 3eV of work content.Therefore, the lumo energy in electron transport district is preferred about 3-3.5eV.
Electroluminescent device can be monochrome devices or panchromatic device (promptly being formed by redness, green and blue electroluminescent material).
1) electroluminescence layer 3
Electroluminescence layer 3 can comprise matrix polymer and only according to metal complex of the present invention or one or more other materials.Especially, layer 3 can comprise with one or more cavity conveying polymer with as the matrix polymer of disclosed electron transport polyblend among the WO99/48160 with according to metal complex of the present invention.
2) matrix polymer
This matrix polymer can be homopolymers or copolymer.When it was copolymer, first and second repetitives of this copolymer can be arranged and obtain any type of copolymer such as AB is random or block copolymer.This copolymer can comprise other repetitive except first and second repetitives.For example, can provide the 3rd to repeat the unit, form block or random copolymer thus with first and second repetitives.
This copolymer can comprise cavity conveying district and electron transport district, as disclosed among WO 00/55927 and the US6353083.For example, the district that comprises the unit of general formula (I) generally will provide the hole transport function.Similarly, the electric transmission district can comprise poly-fluorenes cellular chain or the sub-heterocycle repetitive of short of electricity, as Polym.Adv.Technol.1998, and 9,429-42 and J.Mater.Chem.200,10, disclosed among the 1-25.Not same district in this polymer can be along the main polymer chain setting, as according to US 6353083, or as the side group setting of auto polymerization owner chain, as according to WO01/62869.
The substituting group that metal complex can be used as on the homopolymers main chain is introduced in the matrix polymer, or introduces in the copolymer chain, as disclosed among EP 1245659, WO 02/31896, WO 03/18653 and the WO 03/22908.In the case, this copolymer can provide emission function and cavity conveying and electron transport one of at least.
The method for optimizing for preparing these polymer is the Suzuki polymerization, as describing among the WO 00/53656, with the Yamamoto polymerization, as T.Yamamoto, " ElectricallyConducting And Thermally Stable π-Conjugated Poly (arylene) sPrepared by Organometallic Processes ", Progress in PolymerScience 1993,17 describes among the 1153-1205.By " metal insertion " operation, wherein the metallic atom of metal complex catalysts inserts between the aryl and leaving group of monomer these polymerization techniques simultaneously.For the Yamamoto polymerization, use the nickel complex as catalyst agent; For the Suzuki polymerization, use palladium complex catalyst.
For example, by in the Yamamoto polymerization synthesizing linear polymer, use monomer with two active halogen groups.Similarly, according to Suzuki polymerisation method, at least one active group is boron deriveding group such as boric acid or borate, and another active group is a halogen.Preferred halogen is chlorine, bromine and iodine, most preferably bromine.
Therefore, should be understood that as illustrating among whole the application repetitive and comprise that the end group of aryl can be derived from the monomer that has suitable leaving group.
The Suzuki polymerization can be used for preparing regio-regular, block and random copolymer.Especially, when an active group is halogen and another active group when being the boron deriveding group, can prepare homopolymers or random copolymer.Or alternately,, can prepare block or regio-regular, particularly the AB copolymer when two active groups of first monomer all are two active groups of the boron and second monomer when all being halogen.
Other leaving group that can participate in the metal insertion comprises for example such groups such as toluene fulfonate, mesylate and fluoroform sulphonate.
3) metal complex
Preferred metal complex comprises the complex of the inessential replacement of following formula (V):
ML
1 qL
2 rL
3 s
(V)
Wherein M is a metal; Each L
1, L
2And L
3Be coordinating group; Q is an integer; R and s are 0 or integer independently of one another; (a.q)+(b.r)+(c.s) sum equals available coordination positional number on M, and wherein a is L
1On the coordination positional number, b is L
2On the coordination positional number, c is L
3On the coordination positional number.
Heavy element M induces strong spin-track coupling crosslinked and from triplet state luminous (phosphorescent) to allow between rapid system.Suitable heavy metal M comprises:
-lanthanide series metal such as cerium, samarium, europium, terbium, dysprosium, thulium, erbium and neodymium; With
In-d-district the metal, particularly 2 and 3 rows those, i.e. element 39 to 48 and 72 to 80, particularly ruthenium, rhodium, palladium, rhenium, osmium, iridium, platinum and gold.
The suitable coordinating group that is used for f-district metal comprises oxygen or nitrogen to body system such as carboxylic acid, 1,3-diketone hydrochlorate, hydroxycarboxylic acid, and Schiff alkali comprises Acylphenol and imino group.Just as is known, luminous lanthanide complex need have the photosensitive group of the triplet state excitation level that is higher than the metal ion first excited state.Emission is from the f-f transition of metal, and therefore luminous color can be by selecting the metal decision.This launches usually very narrow rapidly, causes can be used for the pure color emission of display application.
Metal formation of d-district and carbon or nitrogen are given the organometallic complex of the bidentate ligand of body such as porphyrin or following formula (VI) etc.:
Ar wherein
4And Ar
5Can be identical or different and be independently selected from the aryl and the heteroaryl of inessential replacement; X
1And Y
1Can be identical or different, and be independently selected from carbon or nitrogen; Ar
4And Ar
5Can condense together.X wherein
1Be carbon and Y
1For the part of nitrogen is particularly preferred.
The example of bidentate ligand provides below:
Each Ar
4And Ar
5Can have one or more substituting groups.Particularly preferred substituting group comprises fluorine or the trifluoromethyl that can be used for the emission of blue shift complex, as disclosed among WO 02/45466, WO 02/44189, US 2002-117662 and the US 2002-182441, alkyl or alkoxyl, as disclosed among the JP2002-324679, at the carbazole that can be used for when the emissive material promoting to the complex transporting holes, as disclosed among the WO02/81448; Can play functionalized bromine, chlorine or the iodine that is used to connect the part of further group, as disclosed among WO 02/68435 and the EP 1245659; With the dendron (dendrons) that can be used for obtaining strengthening the solution processing characteristics of metal complex, as disclosed among the WO 02/66552.
Other part that is fit to use with the d-p-block element p comprises two keto esters, particularly acetoacetic ester (acac); Triaryl phosphine and pyridine can be substituted separately.
The main group metal complex show based on part or the charge transfer emission.For these complexs, the emission color is determined by selecting part and metal.The fluorescence low-molecular-weight metal complex of wide region be known and in organic luminescent device proof [for example referring to Macromol.Sym.125 (1997) 1-48, US-A5,150,006, US-A6,083,634 and US-A5,432,014], three-(8-oxyquinoline) aluminium particularly.Be used for two or the suitable ligand of trivalent metal comprise: oxinoids, for example have oxygen-nitrogen or oxygen-oxygen donor atom, be generally and have the theheterocyclic nitrogen atom that replaces oxygen atom or substituted nitrogen atom or have the oxygen atom that replaces oxygen atom, as oxine hydrochlorate and hydroxy quinoxaline alcohol (quinoxalinol)-10-hydroxy benzo (h) quinoline acid group close (II), indoles (III) (benzazole1s), schiff bases, azo indoles, chromone derivative, 3-flavonol and carboxylic acid such as salicyloyl aminocarboxylate and ester carboxylate.Non-essential substituting group comprises halogen, alkyl, alkoxyl, alkylhalide group, cyano group, amino, acylamino-, sulfonyl, carbonyl, aryl or the heteroaryl on (mixing) aromatic ring that can improve the emission color.
As mentioned above, metal complex can be used as side chain with matrix polymer blending or its or as repetitive in the polymer and polymer chemistry bonding.As follows with the example of the metal complex of formula (I) repetitive bonding:
This arrangement is particularly advantageous, because the ligands for metal complexes copline of side aryl of triarylamine unit (phenyl in the explanation in the above) and side aryl bonding (to phenylpyridine described above) makes the conjugation maximization of metal complex and repetitive like this.On the contrary, with the metal complex (as disclosed among the WO 03/22908) of the arylene repeat units bonding of main polymer chain not with the arylene repeat units copline.
Polymerizable forms the monomer with metal complex side group of corresponding repetitive can be by following formation:
Wherein Hal represents that halogen and LG represent aryl or heteroaryl linking group, particularly 1, and the 4-phenylene.
Metal complex alternately forms repetitive in main polymer chain.In the case, a class suitable monomers that is used to produce this type of repetitive is for having those of following general formula (VII):
P-L
1-M(L
1 q·2L
2 rL
3 8)-L
1-P
(VII)
Be included in two ligand L in the main polymer chain derived from the repetitive of general formula (VII) monomer
1And metal M.An example of this monomer is as follows, as disclosed among the WO 02/068435:
To notice that for the monomer of general formula (VIII), q is at least 2.
4) copolymer second repetitive
Comprise that second repetitive of copolymer of the repetitive of general formula (I) can be selected from the repetitive of wide region according to the desired properties of end polymer, particularly following repetitive:
A) second repetitive on the plane basically of conjugation
One class, second repetitive is an arylene repeat units, particularly: 1,4-phenylene repetitive, as J.Appl.Phys.1996, disclosed in 79,934; The fluorenes repetitive, as disclosed among the EP 0842208, the indenofluorene repetitive, as Macromolecules 2000,33 (6), disclosed and spiral shell fluorenes repetitive among the 2016-2020 is as disclosed among the EP 0707020.In these repetitives every kind is inessential replacement.Substituent example comprises solvation group such as C
1-20Alkyl or alkoxyl; Scold electron group such as fluorine, nitro or cyano group; With the substituting group that is used to improve polymer glass conversion temperature (Tg).
Therefore the fluorine repetitive is the plane, is particularly suitable when need be along the main polymer chain conjugation.Particularly preferably be 2 of inessential replacement, 7-connects fluorenes, the most preferably repetitive of following formula VIII:
R wherein
1And R
2Be independently selected from alkyl, alkoxyl, aryl, aralkyl, heteroaryl and the heteroarylalkyl of hydrogen or inessential replacement, and R
1And R
2In at least one be not hydrogen.More preferably R
1And R
2In at least one comprise the C of inessential replacement
4-C
20-alkyl or aryl.
The present invention contains the suitable spatia zonularis emitter of polymer conduct of this type of repetitive such as the matrix of red emitters is favourable.
B) conjugation on-plane surface second repetitive
The on-plane surface repetitive comprises the unit that contains a distortion, this distortion by the on-plane surface repetitive substituting group and have and can cause in the cubic phase mutual effect between the substituent ring of inducing distortion between the adjacent ring system by steric interaction.
The one class repetitive that can produce distortion between main polymer chain is the repetitive that comprises the inessential replacement of following formula (IX):
Wherein m is 1 or 2, R
3Be substituting group, the alkyl of preferred inessential replacement, alkoxyl, aryl, aryloxy group, heteroaryl or heteroaryloxy, more preferably C
1-10Alkyl.
Radicals R
3By inducing a distortion with the steric interaction of the phenyl of the repetitive of formula (IX), the phenyl of this repetitive be connected R
3Phenyl adjacent.In the case, preferably repetitive comprises following formula (X) or repetitive (XI):
Alternately, radicals R
3Can be by inducing a distortion with interaction adjacent to the repetitive of the repetitive of formula (IX).In the case, R
3Be connected to the carbon atom adjacent with the carbon atom of repetitive, the carbon atom of this repetitive is connected with described adjacent repetitive.
The polymer that the present invention contains this type of on-plane surface conjugation repetitive is suitable as the matrix with band-gap emission body wideer than the corresponding polymer that contains the planar conjugate repetitive.
C) partially or completely non-conjugated repetitive
Partially or completely the object lesson of non-conjugated repetitive has following formula 7-10 (dotted line show to be used for the key that is connected with other repetitive).The repetitive that has aryl at a certain end is particularly advantageous, because they are formed by Suzuki or Yamamoto polymerization by suitable monomers easily.
These second repetitives are particularly suitable for using with first repetitive (IVa) with (IVb), and reason is the high triplet energy state of these unit.In addition, unit (IVa) and (IVb) can provide hole and electric transmission function simultaneously.
Interval in conjugation also can provide by the silicon atom that is arranged in main polymer chain, for example-and Si (Ak)
2-, wherein Ak is an alkyl; Provide by 5 family's elements, as-P (Ak)-; Provide by 6 family's elements such as oxygen and sulphur atom.
The polymer that the present invention contains this type of repetitive is particularly suitable for suitable wide bandgap material.
Embodiment
General technology
With the complex 11 of transmitting green light or the complex 12 of red-emitting (as disclosed among the WO 02/66552) and matrix polymer by by the xylene solution spin-on deposition on the substrate of glass that comprises indium tin oxide layer, this substrate of glass can optionally be provided with hole-injecting material such as PEDT/PSS or hole transporting material layer.Electric transmission/hole confining bed can optionally be set between luminescent layer and negative electrode.Calcium/aluminium two-layer cathode may is deposited on the electroluminescence layer, and use available from the airtight metal shell of Saes Getters SpA and seal this device.
2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphyrin platinum (II) can be used as a kind of selection for red emission complex 12.
The two-layer cathode may of lithium fluoride/aluminium can be used as a kind of selection for calcium/aluminium.
Ak0=2 ethyl oxygen in heptan base
This device prepares with following matrix
Matrix A
Matrix B
Matrix C
m＝1，2?or?3
Matrix D
m＝1，2?or?3
Matrix E
With the matrix of matrix A-E as red emission complex 12, yet, the matrix that the matrix C-E that provides second repetitive that reduces the interval in conjugation or the conjugation is used as green emitted complex 11 only had.
Although the present invention's embodiment of reference example is described, to understand under the spirit and scope of the present invention of listing in the claim below not leaving, various improvement, replacement and/or the combination of feature disclosed herein is that those skilled in the art are conspicuous.
Claims (21)
1. electroluminescent device comprises:
-be used to inject first electrode of positive charge carriers;
-be used to inject second electrode of negative charge carriers; With
-be in the electroluminescence layer that comprises host material and metal complex between first and second electrodes, wherein host material comprises the polymer of first repetitive with following general formula (I):
Wherein each Ar is identical or different, and represents the aryl or the heteroaryl of inessential replacement independently, and any two Ar groups can directly connect by singly-bound.
2. according to the electroluminescent device of claim 1, wherein polymer is the copolymer that comprises second repetitive.
3. according to the electroluminescent device of claim 2, wherein second repetitive is unconjugated to small part.
4. according to the electroluminescent device of claim 3, wherein second repetitive is selected from following formula (II) and repetitive (III)
-(CR
4R
5)
n- -Ar
1-(CR
4R
5)
n-Ar
2-
(II) (III)
R wherein
4And R
5Be independently selected from hydrogen or substituting group; N is 1-10; Ar
1And Ar
2Be independently selected from the aryl or the heteroaryl of inessential replacement.
5. according to the electroluminescent device of claim 4, R wherein
4And R
5Respectively be independently selected from hydrogen or C
1-10Alkyl; N is 1 or 2, and Ar
1And Ar
2It respectively is phenyl.
6. according to the electroluminescent device of claim 2, wherein second repetitive is along the Ar-conjugation of its main chain total conjugated and direct and first repetitive.
7. according to the electroluminescent device of claim 6, wherein second repetitive is selected from fluorenes, spiral shell fluorenes, indenofluorene, phenylene and the low polyphenylene of inessential replacement.
8. according to any one electroluminescent device of claim 2 to 7, wherein copolymer is the AB copolymer.
9. according to the electroluminescent device of arbitrary aforementioned claim, wherein the Ar base of first repetitive does not directly connect by singly-bound.
10. according to any one described electroluminescent device of claim 1-8, wherein first repetitive comprises the repetitive of the inessential replacement of following formula (IV):
Wherein R is hydrogen or substituting group, and among x and the y one exists with singly-bound.
11. according to the electroluminescent device of arbitrary aforementioned claim, wherein metal complex is as the substituting group and the polymer chemistry bonding that are connected with main polymer chain or be introduced in the main polymer chain.
12., wherein metal complex is provided as the repetitive in the polymer according to the electroluminescent device of claim 11.
13. the electroluminescent device according to claim 12 wherein provides metal complex as polymer end groups.
14. according to the electroluminescent device of arbitrary aforementioned claim, wherein to be that electricity causes phosphorescent for metal complex.
15. a composition comprises metal complex and the polymer that limits in any one as claim 1-10.
16. an electroluminescent polymer, the repetitive that comprises following formula (I) with as the metal complex in the substituting group that is connected with main polymer chain and this polymer chemistry bonding or the introducing main polymer chain:
Wherein each Ar is identical or different, and represents the aryl or the heteroaryl of inessential replacement independently, and any two Ar groups can directly connect by singly-bound.
17. according to the electroluminescent polymer of claim 16, the repetitive Direct Bonding of metal complex and formula (I) wherein.
18., comprise the repetitive of following formula (XII) according to the electroluminescent polymer of claim 17:
Wherein M is a metal; L
1, L
2And L
3It respectively is coordinating group; Q is an integer; R and s are 0 or integer independently of one another; (a.q)+(b.r)+(c.s) sum equals available coordination positional number on M, and wherein a is L
1On the coordination positional number, b is L
2On the coordination positional number, c is L
3On the coordination positional number.
19. according to the electroluminescent polymer of claim 16, wherein metal complex is phosphorescent.
20. the monomer of following formula (XIII):
Wherein each Ar is identical or different, and represents the aryl or the heteroaryl of inessential replacement independently, and any two Ar groups can directly connect by singly-bound; M is a metal; L
1, L
2And L
3It respectively is coordinating group; Q is an integer; R and s are 0 or integer independently of one another; (a.q)+(b.r)+(c.s) sum equals available coordination positional number on M, and wherein a is L
1On the coordination positional number, b is L
2On the coordination positional number, c is L
3On the coordination positional number; Identical or different and be polymerizable groups with each P.
21. according to the monomer of claim 20, wherein each P is independently selected from boric acid, borate, borine or halogen.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0318018A GB0318018D0 (en) | 2003-08-01 | 2003-08-01 | Electroluminescent device |
| GB0318018.9 | 2003-08-01 | ||
| GB0318756.4 | 2003-08-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1846320A true CN1846320A (en) | 2006-10-11 |
Family
ID=27799606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200480025238 Pending CN1846320A (en) | 2003-08-01 | 2004-08-02 | Electroluminescent device |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1846320A (en) |
| GB (1) | GB0318018D0 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102947962A (en) * | 2010-05-14 | 2013-02-27 | 剑桥显示技术有限公司 | Organic light-emitting polymer and device |
| CN103038905A (en) * | 2010-05-14 | 2013-04-10 | 剑桥显示技术有限公司 | Polymer, polymer composition and organic light-emitting device |
| CN103154191A (en) * | 2010-10-15 | 2013-06-12 | 剑桥显示技术有限公司 | Polymer and organic light-emitting device |
| WO2023024118A1 (en) * | 2021-08-27 | 2023-03-02 | 京东方科技集团股份有限公司 | Light-emitting device and manufacturing method therefor, and display panel and display apparatus |
-
2003
- 2003-08-01 GB GB0318018A patent/GB0318018D0/en not_active Ceased
-
2004
- 2004-08-02 CN CN 200480025238 patent/CN1846320A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102947962A (en) * | 2010-05-14 | 2013-02-27 | 剑桥显示技术有限公司 | Organic light-emitting polymer and device |
| CN103038905A (en) * | 2010-05-14 | 2013-04-10 | 剑桥显示技术有限公司 | Polymer, polymer composition and organic light-emitting device |
| CN102947962B (en) * | 2010-05-14 | 2015-09-30 | 剑桥显示技术有限公司 | Organic luminescence polymer and device |
| CN103038905B (en) * | 2010-05-14 | 2015-11-25 | 剑桥显示技术有限公司 | polymer, polymer composition and organic luminescent device |
| CN103154191A (en) * | 2010-10-15 | 2013-06-12 | 剑桥显示技术有限公司 | Polymer and organic light-emitting device |
| CN103154191B (en) * | 2010-10-15 | 2016-07-06 | 剑桥显示技术有限公司 | Polymer and organic luminescent device |
| WO2023024118A1 (en) * | 2021-08-27 | 2023-03-02 | 京东方科技集团股份有限公司 | Light-emitting device and manufacturing method therefor, and display panel and display apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| GB0318018D0 (en) | 2003-09-03 |
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