CN1689173A - Optical device - Google Patents
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- CN1689173A CN1689173A CNA038235528A CN03823552A CN1689173A CN 1689173 A CN1689173 A CN 1689173A CN A038235528 A CNA038235528 A CN A038235528A CN 03823552 A CN03823552 A CN 03823552A CN 1689173 A CN1689173 A CN 1689173A
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Abstract
A method of forming an optical device comprising the steps of: - providing a substrate comprising a first electrode capable of injecting or accepting charge carriers of a first type; - forming over the first electrode a first layer that is at least partially insoluble in a solvent by depositing a first semiconducting material that is free of cross-linkable vinyl or ethynyl groups and is, at the time of deposition, soluble in the solvent; forming a second layer in contact with the first layer and comprising a second semiconducting material by depositing a second semiconducting material from a solution in the solvent; and - forming over the second layer a second electrode capable of injecting or accepting charge carriers of a second type wherein the first layer is rendered at least partially insoluble by one or more of heat, vacuum and ambient drying treatment following deposition of the first semiconducting material.
Description
Technical field
The present invention relates to comprise organic optical devices and its production method of insoluble organic material layer.
Background technology
It is disclosed as WO 90/13148 that electroactive polymer frequently is used for a lot of optics such as polymer LED (" PLED ") now, disclosed among disclosed and photodetector such as the US 5523555 among photovoltaic device such as the WO 96/16449.
Typical PLED is included in the basic unit of its upper support anode and negative electrode, and is in the organic field luminescence layer that comprises at least a polymer electroluminescent material between anode and the negative electrode.When operation, the space is by in the anode injection device, and electronics is by in the negative electrode injection device.Radiative decay in conjunction with forming exciton, takes place and luminous in space and electronics then in the organic field luminescence layer.Other layer can be present among the PLED, as for example poly-(ethylene dioxythiophene)/poly styrene sulfonate (PEDT/PSS) layer of organic hole-injecting material layer can be set between anode and organic field luminescence layer, to promote that the hole is injected with in the electroluminescent layer of airport from anode.
In typical PLED, the electroluminescent material individual layer is set, as describing among the WO 99/48160, this individual layer comprises the blend of hole transport polymer, electric transmission polymer and emitted polymer.In addition, a kind of single polymers can provide two or more in hole transport, electric transmission and the emission function.One or more electroluminescent polymer preferably dissolve in the conventional organic solvent to help its deposition.The such soluble polymer of one class is poly-fluorenes, and it has good filming performance and can form by Suzuki or Yamamoto polymerization easily, and this polymerization can be carried out height control to local structured's property of resulting polymers.
Yet, preferably can be on single substrate surface the multilayer of the different polymer of curtain coating, promptly lamination can be realized the preferable separate function like this, as electronics or hole charge transmission, luminous, the photoinduction electric charge generates and electric charge sealing or store.In addition, it is believed that PEDT/PSS can have adverse effect to electroluminescent layer, for example enter (promptly wherein the hole combines the layer that forms exciton with electronics) in the electroluminescent layer, cause luminous cancellation by proton or sulfonate groups from PSS.Therefore, need between PEDT/PSS and electroluminescent layer, protective layer be set.Yet because initial curtain coating or the solubility of sedimentary deposit in the solvent that successive layer is used, the polymer stack goods of preparation can have problems.
The electroluminescent polymer layer can be by deposition soluble polymer precursor, it is chemically converted to insoluble electroluminescent form then and forms.For example, WO 94/03030 discloses a kind of method, and wherein insoluble electroluminescent poly-(phenylene vinylidene) is formed by the solubility precursor, then other layer is deposited to from solution on this insoluble layer.Yet chemical conversion process relates to the active byproduct of the performance of extreme processing conditions and harm resulting devices.Correspondingly, the electroluminescent polymer that dissolves in the conventional organic solvent is preferred.These examples of material for example are disclosed among Adv.Mater.2000 12 (23) 1737-1750, comprise and have polymer whole or partly conjugated at least main chain, as the polymer that has the poly-fluorenes, polyphenylene of solubility group and poly-(arlydene ethenylidene) and have a non-conjugated main chain is as poly-(vinylcarbazole).
WO98/05187 discloses the method that forms multilayer device, comprises the steps: poly-(vinylpyridine) is deposited to PEDT/PSS and the PPV precursor deposition is arrived poly-(vinylpyridine) layer.As mentioned above, for being converted into semi-conducting material, this precursor needs harsh processing conditions.
US 6107452 discloses a kind of method that forms multilayer device, will comprise that wherein the fluorenes oligomer that contains of terminal ethylenyl groups deposits and be cross-linked to form insoluble polymer in solution, can deposit other layer on this polymer.Similarly, people such as Kim, Synthetic Metals 122 (2001), and 363-368 discloses and has comprised can be behind the polymer deposition crosslinked triarylamine and the polymer of acetenyl.Choosing of polymer is subjected to requiring to exist a plurality of vinyl or acetenyl partly to limit under these two kinds of situations.
IEEE Transactions on Electron Devices, 44 (8), 1263-1268,1997 disclose the bilayer that forms poly-(vinylcarbazole) PVK and contain the pyridine conjugated polymer.This is possible, does not dissolve PVK lower floor because be used to deposit the solvent that contains the pyridine conjugated polymer.
J.Liu, Z.F.Guo and Y.Yang, J.Appl Phys.91,1595-1600,2002 disclose by deposition with the heating semi-conducting polymer, deposit the method that the identical polymer of another layer forms multilayer device then.
WO 99/48160 discloses PLED, wherein between PEDT/PSS layer and electroluminescent material layer the hole mobile material layer is set.
Although for processing multiple layer polymer optics (comprising PLED) has carried out a lot of trials, still need to provide to have the method for improving performance multi-layer polymer optics and preparing these devices.
Summary of the invention
First aspect present invention provides a kind of method that forms optics, comprises the steps:
-basic unit of first electrode that comprises the charge carrier that can inject or accept the first kind is provided;
-by deposition no crosslinkable vinyl or acetenyl and when depositing, dissolve in first semi-conducting material in the solvent, on first electrode, be formed up to the ground floor that small part is insoluble to solvent;
-form the second layer that contacts and comprise second semi-conducting material with ground floor by deposition second semi-conducting material from the solution of solvent; With
-second electrode of the second type of electrical charge carrier can be injected or accept to formation on the second layer
Wherein behind deposition first semi-conducting material, make this ground floor soluble to small part by one or more modes in heat, vacuum and the environmental drying processing.
At least a polymer that is preferably in first and second semi-conducting materials.More preferably first and second semi-conducting materials all are polymer.
This method is preferably included in and forms the step that the second layer heats ground floor before.More preferably ground floor heats under the glass transition temperature that is higher than first semi-conducting material.
" environmental drying processing " used herein is meant and makes the solvent irrelevant processing that is evaporated by heating or vacuum from ground floor.Particularly, environmental drying handle need be under environmental condition optionally in inert gas flow from ground floor evaporating solvent.
Before this method is preferably included in and forms the second layer, use the wherein step of the cleaning solvent washing ground floor of solubilized first semi-conducting material.
Preferably from the solution of solvent, deposit ground floor.
Solvent is preferably aromatic hydrocarbons, more preferably alkylated benzenes, most preferably toluene or dimethylbenzene.
First semi-conducting material is preferred no crosslinkable groups except that vinyl or acetenyl.
When in first and second semi-conducting materials one or both were polymer, the repetitive of preferred first and second semi-conducting polymers and adjacent repetitive conjugation were formed up to the main polymer chain of small part conjugation thus.
These polymer preferably include 9-replacement or 9,9-two substituted fluorenes-2, and the multiple unit of 7-two basic weights, the unit of the inessential replacement of most preferably following general formula (I):
Wherein R and R ' are independently selected from alkyl, alkoxyl, aryl, aralkyl, heteroaryl and the heteroarylalkyl of hydrogen or inessential replacement, and among R and the R ' at least one is not hydrogen.More preferably, at least one among R and the R ' comprises the C of inessential replacement
4-C
20Alkyl.
In first preferred embodiment by the device of the inventive method preparation, first electrode can inject or accept the hole, and second electrode can inject or accept electronics.In the present embodiment, the conduction organic material layer is set between first electrode and ground floor preferably.The conduction organic material generally includes charged material, particularly charged polymer and charge balance dopant.The example of conducting polymer is to have the PEDT of the poly-acid of charge balance or the polyaniline of conduction form.The conduction organic material layer is preferably PEDT/PSS.
In the present embodiment, first semi-conducting material preferably includes hole mobile material, more preferably comprises the polymer of triarylamine repetitive.Particularly preferred triarylamine repetitive is selected from the repetitive of the inessential replacement of following general formula 1-6:
Wherein X, Y, A, B, C and D are independently selected from H or substituted radical.More preferably one or more alkyl, aryl, perfluoroalkyl, sulfane base, cyano group, alkoxyl, heteroaryl, alkaryl and aralkyl of being independently selected among X, Y, A, B, C and the D.
In addition, the particularly preferred triarylamine repetitive repetitive that is the inessential replacement of following general formula 7:
Wherein Het is a heteroaryl, and Het most preferably is the 4-pyridine radicals.
First semi-conducting material preferably includes 1: 1 regular alternate copolymer of fluorenes repetitive and triarylamine repetitive.
In second preferred embodiment by the device of the inventive method preparation, first electrode can inject or accept electronics, and second electrode can inject or accept the hole.In the present embodiment, first semi-conducting material preferably includes electron transport material, 9 of preferred inessential replacement, 9-dialkyl group fluorenes-2, the homopolymers of 7-two bases.
Ground floor preferably have thickness be lower than 20nm, more preferably less than 10nm, 3-10nm most preferably.
Second semi-conducting polymer preferably includes a plurality of districts, preferably includes at least two in hole transport district, electric transmission district and the emitting area, more preferably comprises all these three zones.
In second aspect, the invention provides a kind of optics that can be prepared according to the methods of the invention.This optics is preferably electroluminescent device, more preferably the electroluminescent device of blue light-emitting.The available method of phosphor by described blue light is changed downwards that can produce red and green glow changed the radiating portion of blue light-emitting device downwards, obtains the electroluminescent device of emission white light thus.
The inventive method can form the wherein thin especially polymer stack goods of ground floor.Therefore,, the invention provides a kind of optics, comprise successively in the third aspect:
-basic unit
-can inject or accept first electrode of first kind charge carrier
-having the ground floor that thickness is lower than 20nm, it comprises first semi-conducting polymer that is insoluble to solvent
-the second layer that contacts with ground floor, it comprises second semi-conducting polymer that dissolves in solvent
-can inject or accept second electrode of the second class charge carrier.
Fourth aspect present invention provides a kind of method that forms optics, comprises the steps:
-provide load can inject or accept the hole and can give the basic unit of the conduction organic material of proton;
-be formed on this conduction organic material and the ground floor that is in contact with it by depositing first semi-conducting polymer that can accept proton, wherein this semi-conducting polymer dissolves in the solvent when deposition;
-this ground floor is carried out one or more processing in handling of heat, vacuum or environmental drying;
-by on ground floor and be in contact with it from the solution of described solvent deposition second semi-conducting polymer and form the second layer; With
-second electrode of electronics can be injected or accept to formation on the second layer.
First semi-conducting polymer preferably includes the triarylamine repetitive.This triarylamine repetitive more preferably is selected from above-mentioned repetitive 1-7.
First semi-conducting polymer preferably includes 1: 1 regular alternate copolymer of fluorenes repetitive and triarylamine repetitive.
Preferably between substrate and conduction organic material, the inorganic material layer that can inject or accept the hole is set.The inorganic material that can inject or accept the hole most preferably is indium tin oxide.。
The conduction organic material is preferably PEDT/PSS.
Fifth aspect present invention provides a kind of method that forms optics, comprises the steps:
-basic unit of first electrode that comprises the charge carrier that can inject or accept the first kind is provided;
-by first semi-conducting material of no crosslinkable vinyl of deposition or acetenyl, on first electrode, be formed up to the ground floor that small part is insoluble to solvent;
-this ground floor is heat-treated;
-form the second layer that contacts and comprise second semi-conducting material with ground floor by deposition second semi-conducting material from the solution of described solvent; With
On the second layer, form second electrode that can inject or accept the second type of electrical charge carrier.
According to first and second semi-conducting materials of fifth aspect present invention preferably at least a, more preferably two kinds be polymer.
Dissolve in maybe according to first semi-conducting material of fifth aspect present invention and can be insoluble to the solvent that is used for depositing second semi-conducting polymer.
The 6th aspect the invention provides the method that forms optics, comprises the steps:
-basic unit of first electrode that comprises the charge carrier that can inject or accept the first kind is provided;
-comprising that by deposition first semi-conducting polymer of fluorenes repetitive forms ground floor on first electrode, this first semi-conducting polymer does not have crosslinkable vinyl or acetenyl and dissolves in the solvent when deposition;
-this ground floor is carried out one or more processing in handling of heat, vacuum or environmental drying;
-form the second layer that contacts and comprise second semi-conducting polymer with ground floor by deposition second semi-conducting polymer from the solution of described solvent; With
-second electrode of the second type of electrical charge carrier can be injected or accept to formation on the second layer.
First and second semi-conducting polymers of either side are different according to the present invention.For example, first and second polymer can be two kinds of polymer of different molecular weight.Or the specific regularity difference of the repetitive of first and second polymer in its polymer.Most preferably, the difference of first and second polymer is, one of first and second polymer comprise at least a in another polymer non-existent repeat unit.Therefore, for example, can form hole transmission layer during first polymer deposition, and can form electroluminescent layer during second polymer deposition, reason is the feature regularity and/or the chemical characteristic difference of first and second its repetitive of polymer.The blend that comprises second semi-conducting polymer can only is made of or can be to the second layer second semi-conducting polymer.
Term " ruddiness " be meant have wave-length coverage 600-750nm, preferred 600-700nm, the more preferably radiation of 610-650nm, most preferably have the about 650-660nm in radiation peak.
Term " green glow " be meant have wave-length coverage 510-580nm, the radiation of preferred 510-570nm.
Term " blue organic light " be meant have wave-length coverage 400-500nm, the more preferably radiation of 430-500nm.
The implication of " hole transport " used herein, " electric transmission " and " emission " is explained in for example WO 00/55927 and WO 00/46321, is that those skilled in the art are conspicuous therefore.
Description of drawings
To only explain the present invention in detail by embodiment with reference to the accompanying drawings below, wherein
Fig. 1 shows PLED or the photovoltaic device according to the inventive method preparation.
Fig. 2 shows the efficient and the bias voltage comparison diagram of the first blue electroluminescent device and two comparative device.
Fig. 3 shows the efficient and the bias voltage figure of Red Square electroluminescence device.
Fig. 4 shows that the first blue electroluminescent device is carrying out or be not rotated efficient and bias voltage figure under the rinsing.
Fig. 5 shows the efficient and the bias voltage figure of the second blue field electroluminescence device and comparative device.
Embodiment
With reference to figure 1, the layer 4 of the layer 3 that comprises substrate 1, indium tin oxide anode 2, organic hole transferring material according to the PLED or the photovoltaic device of the inventive method preparation, the insoluble material that forms by the deposition first soluble semiconductor polymer, the layer 5 and the negative electrode 6 that form by deposition second semi-conducting polymer.
Optical device is tending towards moisture and oxygen sensitivity.Therefore, substrate preferably has and prevents that moisture and oxygen from entering the good barrier performance of device.Substrate is generally glass, yet, can use other substrate, particularly when requiring device soft.For example, substrate can comprise plastics, and is disclosed as US 6268695, and this patent comprises the plastics alternately and the substrate on barrier layer, or the laminate of thin glass and plastics, as disclosed among the EP 0949850.
Although not necessarily, exist organic hole-injecting material layer 3 to suit, because help one or more layers semi-conducting polymer layer is injected from anode in the hole.The example of organic hole injection material comprises PEDT/PSS, as disclosed among EP 0901176 and the EP 0947123, or polyaniline, as disclosed among US 5723873 and the US 5798170.
The negative electrode of choosing 6 should make the effective injection device of electronics, therefore this negative electrode can comprise single electric conducting material such as aluminium lamination, in addition, it can comprise multiple metal such as calcium and aluminium bilayer, as disclosed among the WO 98/10621, or thin layer of dielectric material such as lithium fluoride thin layer inject to help electronics, as disclosed among the WO00/48258.
Device preferably enters to prevent moisture and oxygen with encapsulant parcel (not shown).Suitable encapsulant comprises glass sheet, has the film of suitable barrier properties, as the alternative stacked thing of polymer and dielectric material, and as disclosed among the WO 01/81649, or airtight container, as disclosed among the WO01/19142.
In practical devices, at least one electrode is translucent, so that absorb (for the photoinduction device) or emission (for PLED) light.When anode was transparent, it generally comprised indium tin oxide.Transparent cathode for example is disclosed among the GB 2348316.
The present invention is used to form layer 5 second semi-conducting polymer and can be any semi-conducting polymer that dissolves in the same solvent, and the used solvent of described solvent and first semi-conducting polymer that is used to form insoluble layer 4 is identical.The example of the second suitable semi-conducting polymer comprises soluble poly (to phenylene vinylidene), polyphenylene and poly-fluorenes, as disclosed in Adv.Mater.2000 12 (23) 1737-1750 and the reference wherein.Can from solution, deposit one or more polymer cambium layer 5.When the deposition multiple polymers, they preferably include the blend of at least two kinds of hole transport polymers, electric transmission polymer and (when device is PLED) emitted polymer (disclosed in as WO99/48160).Perhaps layer 5 can be formed by single second semi-conducting polymer, and this polymer comprises the district in the two or more districts that are selected from hole transport district, electric transmission district and emitter region, as disclosed among WO 00/55927 and the US 6353083.Each hole transport, electric transmission and emission function can provide by the not same district of different polymer or single polymers.Perhaps can bring into play more than one function by single district or polymer.Especially, single polymers or district can transmit and launch simultaneously.Each district can comprise single repetitive, and for example the triarylamine repetitive can be the hole transport district.Or each district can be chain of repeat units as poly-fluorenes cellular chain, as the electric transmission district.Can not same district be set along main polymer chain (as according to US6353083) or as the side group (as according to WO 01/62869) of auto polymerization owner chain in polymer.When insoluble layer 4 had hole or electronic transmission performance, polymer or polyidal field with this performance can optionally be got rid of from the polymer that layer 5 comprises.
According to first and second polymer of the present invention is semi-conducting polymer simultaneously.The main chain of each polymer can or unlikely small part conjugation.Example with semi-conducting polymer of partly conjugated at least main chain comprises poly (arylene ether) as poly-fluorenes and polyphenylene, and poly-(arlydene ethenylidene), as described above.The present invention also comprises first and second semi-conducting polymers of no conjugated main chain, as poly-(vinylcarbazole).
When the first and second electrode iunjected charge carriers, spectroscopy device prepared according to the methods of the invention is preferably PLED.In the case, layer 5 is a luminescent layer.
When first and second electrodes are accepted charge carrier.Optics is preferably photovoltaic device or photodetector.In the case, preferably include can transporting holes and the polymer of electronics for the second layer.
The inventor finds surprisingly, if by multi-lager semiconductor polymer manufacture polymer optics is set, then can improve its performance.For preventing any obvious mixing of ground floor and the second layer, the inventor finds surprisingly, suitably handles ground floor, particularly heat treatment and can make ground floor insoluble.
The inventor finds surprisingly, and the semi-conducting polymer of fluorenes repetitive that comprises no crosslink part (for example vinyl or acetenyl) is when deposition forms insoluble layer 4, and the part that becomes is insoluble.The inventor finds, (a) no matter whether uses the PEDT/PSS layer and (b) at air or only in nitrogen environment, all can form insoluble layer.Yet, the inventor finds, behind the poly-fluorenes of deposition, must carry out heat, vacuum or environmental drying and handle, bringing into play the performance of device to greatest extent, and reduce to the second layer and mixing of ground floor minimum by improving the insoluble of ground floor especially this insoluble layer.Do not wish to be bound by any theory, it is believed that, possible the mechanism of solubility forfeiture comprises the soluble groups that the 9-position of the fluorenes repetitive in forfeiture and first semi-conducting polymer is connected when forming ground floor, or from polymer, remove desolvate after and its deposit the cohesive force on the surface of first semi-conducting polymer.
The inventor finds that also other semi-conducting polymer (PVK) also can form insoluble layer as poly-(vinylcarbazole) under condition of the present invention.
As mentioned above, under the condition that the polymer deposition that is used for the inventive method and solvent evaporation are used always, layer 4 can be resisted the dissolving in the used solvent of sedimentary deposit 5.In addition, find also that layer 4 can anti-ly dissolve when with described solvent rinsing.Although may be dissolved in the described solvent in mandatory condition lower floor 4, notice that layer 4 is enough insoluble, can form the multilayer electroactive layer according to the inventive method and under the condition that is usually used in deposited semiconductor polymer in described solvent like this.Therefore should correspondingly explain term " insoluble ".
Found that above-mentioned processing improves efficient and the life-span of PLED.Do not wishing to be bound by any theory down, following factor can help these measured values to increase:
-when being between the anode and the second layer, ground floor can play the effect of hole transport, electrons layer.
-when using the PEDT/PSS layer, insoluble layer can prevent that proton from entering the second layer from acid PSS material.Particularly suitable when this comprises the amine of the alkaline unit that can accept proton such as general formula 1-6 or the Het group in general formula 7 scopes such as pyridine radicals etc. at polymer.
The thickness of-special the layer that reaches when using the rotation rinse step can carry out the electric charge sealing, and device performance such as the high driving voltage that brings because of thick-layer had no effect.
Embodiment
General technology
Here use the following describes and in WO 99/54385 disclosed polymer " F8-TFB " be instance interpretation the present invention as first semi-conducting polymer.
F8-TFB
This general technology carries out according to the following steps:
1) by spin coating with PEDT/PSS (Baytron P is available from Bayer ) deposit to the indium tin oxide that is supported on the substrate of glass (available from Applied Films, Colorado, USA) on.
2) deposit the hole transport polymer layer by spin coating from xylene solution with concentration 2%w/v.
3) this hole mobile material layer of heating in inertia (nitrogen) environment.
4) optionally in dimethylbenzene, rotate the rinsing substrate to remove the solvable hole mobile material of any remnants.
5) in xylene solution, deposit second semi-conducting polymer by spin coating.
6) on second semi-conducting polymer, deposit the NaF/Al negative electrode according to the method for describing among the WO 03/012891 and use air-tightness metal shell packaging available from Saes Getters SpA.
Parameter in this general approach can change, and especially: the concentration of F8-TFB can be up to about 3%w/v, but for the film working concentration 0.5%w/v that approaches especially is provided; Non-essential heating steps is sustainable up to about 2 hours any time; Non-essential heating steps can be to up to about 220 ℃ any temperature but preferably be higher than under the glass transition temperature of deposited polymer and carry out.Conspicuous as those skilled in the art, if heating-up temperature is too high, thermal degradation will take place in first and/or second polymer and other device component such as PEDT/PSS etc.Therefore, should the corresponding heating-up temperature of choosing.At last, the inventor finds that the thickness of ground floor can be by the suitable molecular weight change of choosing first semi-conducting polymer.Therefore have Mw50,000 F8-TFB can produce the thickness that reaches low about 2nm, but for Mw 250,000 to 300,000, produces thickness up to about 15nm.
With F8-TFB as first semi-conducting polymer, with comprise 70%9,9-dioctyl fluorene-2,7-two bases, 10%9,9-diphenylfluorene-2, the blue electroluminescent polymer of 7-two bases, 10% " TFB " repetitive and 10% " PFB " repetitive is carried out above-mentioned general technology as second semi-conducting polymer (F8-TFB polymer, TFB and PFB repetitive for example illustrate below and be described in WO99/54385 in).First and second semi-conducting polymers are by disclosed Suzuki polymerization preparation among the WO 00/53656 for example.
F8-TFB first semiconductor layer 180 ℃ of following heat treatments 1 hour, is deposited second semi-conducting polymer then.
″TFB″ ″PFB″
Fig. 2 shows the influence according to thermal effectiveness of the present invention.Three devices are compared: the device of embodiment 1 (wherein the F8-TFB ground floor being heated to 180 ℃); First comparative device (promptly saving step 2-4) of F8-TFB ground floor wherein is not set; With second comparative device with the F8-TFB ground floor that does not carry out heating steps 3.Can regard as by the result of first and second comparative device relatively, comprise that the device of F8-TFB layer brings efficiency improvement (as putting down in writing among the WO99/48160), yet the most tangible improvement is from device of the present invention, promptly wherein with the device of F8-TFB layer heating.
Technology according to embodiment 1, different is to comprise 3%4, two (the 2-thiophene-5-yl)-2 of 7-, 1,3-diazosulfide repetitive (being disclosed among the WO 01/49768), 80%9,9-dioctyl fluorene-2,7-two bases, 30%2,1,3 diazosulfide-4, the red electroluminescent polymer of multiple unit of 7-two basic weights and 17%TFB repetitive is as second semi-conducting polymer (hereinafter referred to as " red polymer ").
Fig. 3 shows the efficient of this device and bias voltage figure and compares with the comparative device that the insoluble layer of F8-TFB (promptly saving step 2-4) wherein is not set that comprises red polymer.
Use poly-(9-vinylcarbazole) (PVK) as first semi-conducting polymer (Aldrich goods catalogue numbering 18260-5; Average Mw about 1,100,000) and blue emission polymer poly (9,9-dihexyl fluorenes-2,7-two bases) (PFO), available from American Dye Source, (goods catalogue is numbered ADS130BE to Inc; Average Mw about 300,000), carry out above-mentioned general technology.The PVK layer was heated 1 hour down at 200 ℃, deposit the PFO layer then.
Fig. 5 explanation is compared with the comparative device that does not have the PVK layer, and when middle PVK layer carried out heat treated or carry out the environmental drying processing, efficient was improved.
From the accompanying drawing of reference as can be seen, comprise the obvious raising that the device of the insoluble layer of the present invention brings device performance.Simultaneously, the life-span of device (promptly device brightness decays to half time of its original brightness under fixed current) and the brightness of device can not take into account at least simultaneously, and by comprising that insoluble layer can obtain to improve in some cases.
Insoluble layer is in heating or do not heat under the F8-TFB layer and form, yet the thickness of insoluble layer is bigger when heating F8-TFB layer.
The second semi-conducting polymer layer can not be rotated rinsing ground floor deposit.So be preferred: wherein first semi-conducting polymer is by forming ground floor from the weak solution spin-on deposition, this layer is enough thin so that it is soluble on the whole, yet the present invention also is included in and makes the ground floor part solvable and do not remove soluble fraction deposit second semi-conducting polymer.In the case, first and second semi-conducting polymers will have some blend in the second layer.Fig. 4 shows with efficient and the bias voltage figure of blue polymer according to two kinds of devices of the inventive method preparation (wherein a kind of device is rotated rinsing and another kind do not carry out).This figure illustrates that the rotation rinse step is very little to the device performance influence.
Top embodiment has described by first and second layers of spin-on deposition, yet the present invention also can pass through other technology for first and second layers, disclosed laser transfer, aniline printing, screen printing and blade coating deposition among disclosed ink jet printing among the technology of particularly suitable preparation full-color display such as the EP0880303, the EP0851714.When second semi-conducting material deposits by ink jet printing, use the rotation rinse step more favourable than corresponding spin-on deposition, reason is to relate to the very solvent and the semi-conducting material of small size in ink jet printing.
Application examples
Adhere to the device substrate outer surface of down-converter particle and embodiment 1 (blue polymer), as Applied Physics Letters 80 (19), 3470-3472 describes in 2002, and the device that can launch white light is provided thus.
Although the present invention is described according to concrete exemplary, but will understand, under the spirit and scope of the invention that does not leave following claim proposition, the various improvement of feature disclosed herein, variation and/or combination are conspicuous to those skilled in the art.
Claims (40)
1. a method that forms optics comprises the steps:
-basic unit of first electrode that comprises the charge carrier that can inject or accept the first kind is provided;
-by deposition no crosslinkable vinyl or acetenyl and when depositing, dissolve in first semi-conducting material in the solvent, on first electrode, be formed up to the ground floor that small part is insoluble to solvent;
-form the second layer that contacts and comprise second semi-conducting material with ground floor by deposition second semi-conducting material from the solution of described solvent; With
-second electrode of the second type of electrical charge carrier can be injected or accept to formation on the second layer
Wherein behind deposition first semi-conducting material, make this ground floor soluble to small part by one or more modes in heat, vacuum and the environmental drying processing.
2. according to the process of claim 1 wherein that at least a in first and second semi-conducting materials is polymer.
3. according to the method for claim 1 or 2, be included in the step that the deposition second layer heats ground floor before.
4. according to any one method of claim 1 to 3, be included in and form before the second layer with the step of the cleaning solvent washing ground floor of solubilized first semi-conducting material wherein.
5. according to the method for arbitrary aforementioned claim, the solution deposition of ground floor from solvent wherein.
6. according to the method for arbitrary aforementioned claim, wherein solvent is an aromatic hydrocarbons.
7. according to the method for claim 6, wherein solvent is an alkylated benzenes.
8. according to the method for claim 7, wherein solvent is toluene or dimethylbenzene.
9. according to the method for arbitrary claim 2, wherein polymer is the poly-fluorenes of repetitive that comprises the inessential replacement of following general formula (I):
Wherein R and R ' are independently selected from alkyl, alkoxyl, aryl, aralkyl, heteroaryl and the heteroarylalkyl of hydrogen or inessential replacement, and among R and the R ' at least one is not hydrogen.
10. according to the method for claim 9, wherein at least one among R and the R ' comprises the C of inessential replacement
4-C
20Alkyl.
11. according to the method for arbitrary aforementioned claim, wherein first electrode can injected hole, second electrode can inject electronics.
12. according to the method for claim 11, wherein first semi-conducting polymer comprises the triarylamine repetitive.
13. according to the method for claim 12, wherein the triarylamine repetitive is selected from the repetitive of the inessential replacement of following general formula 1-6:
Wherein X, Y, A, B, C and D are independently selected from H or substituted radical.
14. according to the method for claim 13, one or more alkyl, aryl, perfluoroalkyl, sulfane base, cyano group, alkoxyl, heteroaryl, alkaryl and aralkyl of being independently selected among X, Y, A, B, C and the D wherein.
15. according to the method for claim 12, wherein the triarylamine repetitive is the repetitive of the inessential replacement of following general formula 7:
Wherein Het is a heteroaryl.
16. according to the method for claim 15, wherein Het is the 4-pyridine radicals.
17. according to the method for arbitrary aforementioned claim, wherein first semi-conducting polymer comprises as the fluorenes repetitives of claim 9 or 10 definition and 1: 1 regular alternate copolymer as the triarylamine repetitive of any one definition of claim 12-16.
18., the conduction organic material layer is set between first electrode and ground floor wherein according to any one method of claim 11-17.
19. according to the method for claim 18, the organic material layer that wherein conducts electricity is PEDT/PSS.
20. according to the method for arbitrary aforementioned claim, wherein ground floor has thickness and is lower than 20nm.
21. according to the method for claim 20, wherein ground floor has thickness and is lower than 10nm, preferred 3-10nm.
22. according to the method for arbitrary aforementioned claim, wherein second semi-conducting polymer comprises a plurality of districts, and comprises in hole transport district, electric transmission district and the emitter region at least two.
23. according to the method for claim 22, wherein second semi-conducting polymer comprises hole transport district, electric transmission district and emitter region.
24. method that is described with reference to the drawings basically.
25. one kind can be according to any one the optics of method preparation of claim 1-23.
26. one kind can be according to any one the organic electroluminescence display of method preparation of claim 1-23.
27. one kind can cause the blue light-emitting display according to any one the field of method preparation of claim 1-23.
28. one kind can cause the display that emits white light according to any one the organic field of method preparation of claim 1-23.
29. an optics comprises successively:
-basic unit
-can inject or accept first electrode of first kind charge carrier
-having the ground floor that thickness is lower than 20nm, it comprises first semi-conducting polymer that is insoluble to solvent
-the second layer that contacts with ground floor, it comprises second semi-conducting polymer that dissolves in solvent
-can inject or accept second electrode of the second class charge carrier.
30. a method that forms optics comprises the steps:
-provide load can inject or accept the hole and can give the basic unit of the conduction organic material of proton;
-can accept first semi-conducting polymer of proton and on described conduction organic material, form ground floor by deposition, wherein this semi-conducting polymer dissolves in the solvent when deposition;
-this ground floor is carried out one or more processing in handling of heat, vacuum or environmental drying;
-by on ground floor and be in contact with it from the solution of solvent deposition second semi-conducting polymer and form the second layer; With
-second electrode of electronics can be injected or accept to formation on the second layer.
31. according to the method for claim 30, wherein first semi-conducting polymer comprises the triarylamine repetitive.
32. according to the method for claim 31, wherein the triarylamine repetitive is selected from the repetitive of following general formula 1-6:
Wherein X, Y, A, B, C and D are independently selected from H or substituted radical.
33. according to the method for claim 32, one or more alkyl, aryl, perfluoroalkyl, sulfane base, cyano group, alkoxyl, heteroaryl, alkaryl and aralkyl of being independently selected among X, Y, A, B, C and the D wherein.
34. according to the method for claim 31, wherein the triarylamine repetitive is the repetitive of the inessential replacement of following general formula 7:
Wherein Het is a heteroaryl.
35. according to the method for claim 34, wherein Het is the 4-pyridine radicals.
36. according to the method for claim 30, wherein first semi-conducting polymer comprises 1: 1 regular alternate copolymer of fluorenes repetitive and triarylamine repetitive.
37., wherein between substrate and conduction organic material, the inorganic material layer that can inject or accept the hole is set according to the method for claim 30.
38. according to the method for claim 30, the organic material that wherein conducts electricity is PEDT/PSS.
39. a method that forms optics comprises the steps:
-basic unit of first electrode that comprises the charge carrier that can inject or accept the first kind is provided;
-by first semi-conducting material of no crosslinkable vinyl of deposition or acetenyl, on first electrode, be formed up to the ground floor that small part is insoluble to solvent;
-this ground floor is heat-treated;
-form the second layer that contacts and comprise second semi-conducting polymer with ground floor by deposition second semi-conducting material from the solution of solvent; With
-second electrode of the second type of electrical charge carrier can be injected or accept to formation on the second layer.
40. a method that forms optics comprises the steps:
-basic unit of first electrode that comprises the charge carrier that can inject or accept the first kind is provided;
-comprising that by deposition first semi-conducting polymer of fluorenes repetitive forms ground floor on first electrode, this first semi-conducting polymer does not have crosslinkable vinyl or acetenyl and dissolves in the solvent when deposition;
-this ground floor is carried out one or more processing in handling of heat, vacuum or environmental drying;
-form the second layer that contacts and comprise second semi-conducting polymer with ground floor by deposition second semi-conducting polymer from the solution of solvent; With
-second electrode of the second type of electrical charge carrier can be injected or accept to formation on the second layer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0220404.8 | 2002-09-03 | ||
| GBGB0220404.8A GB0220404D0 (en) | 2002-09-03 | 2002-09-03 | Optical device |
| US60/480,502 | 2003-06-20 |
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| Publication Number | Publication Date |
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| CN1689173A true CN1689173A (en) | 2005-10-26 |
| CN100583486C CN100583486C (en) | 2010-01-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN03823552A Expired - Fee Related CN100583486C (en) | 2002-09-03 | 2003-09-03 | Optical device |
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| Country | Link |
|---|---|
| CN (1) | CN100583486C (en) |
| GB (1) | GB0220404D0 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102105507A (en) * | 2008-08-07 | 2011-06-22 | 三菱化学株式会社 | Polymer, material for luminescent layer, material for organic electroluminescent element, composition for organic electroluminescent element, and organic electroluminescent element, solar cell element, organic EL display device, and organic EL lighting |
| CN102473855A (en) * | 2009-07-31 | 2012-05-23 | 住友化学株式会社 | Polymer light-emitting element |
| CN103339168A (en) * | 2011-01-31 | 2013-10-02 | 剑桥显示技术有限公司 | Polymer |
| CN110785409A (en) * | 2017-07-28 | 2020-02-11 | 株式会社Lg化学 | Fluorene derivative and organic light emitting device comprising the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016148184A1 (en) * | 2015-03-17 | 2016-09-22 | 日産化学工業株式会社 | Composition for forming hole collecting layer of photosensor element, and photosensor element |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9215928D0 (en) * | 1992-07-27 | 1992-09-09 | Cambridge Display Tech Ltd | Manufacture of electroluminescent devices |
| US6309763B1 (en) * | 1997-05-21 | 2001-10-30 | The Dow Chemical Company | Fluorene-containing polymers and electroluminescent devices therefrom |
| KR100697861B1 (en) * | 1998-03-13 | 2007-03-22 | 캠브리지 디스플레이 테크놀로지 리미티드 | Electroluminescent devices |
-
2002
- 2002-09-03 GB GBGB0220404.8A patent/GB0220404D0/en not_active Ceased
-
2003
- 2003-09-03 CN CN03823552A patent/CN100583486C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102105507A (en) * | 2008-08-07 | 2011-06-22 | 三菱化学株式会社 | Polymer, material for luminescent layer, material for organic electroluminescent element, composition for organic electroluminescent element, and organic electroluminescent element, solar cell element, organic EL display device, and organic EL lighting |
| US8795849B2 (en) | 2008-08-07 | 2014-08-05 | Mitsubishi Chemical Corporation | Polymers containing thermally dissociable and soluble groups and the use of such polymers as organic electroluminescent materials |
| CN102473855A (en) * | 2009-07-31 | 2012-05-23 | 住友化学株式会社 | Polymer light-emitting element |
| CN103339168A (en) * | 2011-01-31 | 2013-10-02 | 剑桥显示技术有限公司 | Polymer |
| CN103339168B (en) * | 2011-01-31 | 2016-08-10 | 剑桥显示技术有限公司 | Polymer |
| CN110785409A (en) * | 2017-07-28 | 2020-02-11 | 株式会社Lg化学 | Fluorene derivative and organic light emitting device comprising the same |
| US11542237B2 (en) | 2017-07-28 | 2023-01-03 | Lg Chem, Ltd. | Fluorene derivative and organic light emitting device comprising same |
| CN110785409B (en) * | 2017-07-28 | 2023-04-04 | 株式会社Lg化学 | Fluorene derivative and organic light emitting device comprising the same |
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| Publication number | Publication date |
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| GB0220404D0 (en) | 2002-10-09 |
| CN100583486C (en) | 2010-01-20 |
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