CN100497439C - Water dispersible polythiophenes made with polymeric acid colloids - Google Patents

Abstract

Compositions are provided comprising aqueous dispersions of polythiophenes and colloid-forming polymeric acids. Films from invention compositions are useful as buffer layers in organic electronic devices, including electroluminescent devices, such as, for example, organic light emitting diodes (OLED) displays in combination with metal nanowires or carbon nanotubes in applications such as drain, source, or gate electrodes in thin film field effect transistors.

Description

Water dispersible polythiophenes with the polymeric acid colloids preparation

Invention field

The present invention relates to the aqueous dispersions of thiophene conductive polymers, wherein conductive polymers is synthetic in the presence of polymeric acid colloids.

Background technology

Conductive polymers had been used for various organic based devices already, was included in electroluminescent (EL) equipment that uses in the luminous demonstration.For the EL equipment that contains the conductor polymkeric substance, as Organic Light Emitting Diode (OLEDs), this kind equipment generally has following configuration:

Anode/buffer layer/EL polymkeric substance/negative electrode

Typical anode is can be to semi-conductivity EL polymkeric substance, as any material of injected hole in the full π-band (band) of Indium sesquioxide/stannic oxide (ITO).Randomly support negative electrode with glass or plastic-substrates.Typical EL polymkeric substance is the semiconductive polymkeric substance of conjugated, as poly-(to the phenylene vinylene) or poly-fluorenes.Typical negative electrode is the empty π that electronics can be injected semiconductive EL polymkeric substance ^*Any material (as Ca or Ba) of-band.

Buffer layer is typically the polymkeric substance of conduction, can inject the EL polymer layer to the hole from anode.Buffer layer also can be described as hole-injecting layer, hole-transporting layer, or it is characterized by the part of bilayer anode.Typical conductive polymer as buffer layer comprises polyaniline and poly-dioxy base thiophene, as poly-(3,4-ethylidene dioxy base thiophene) (PEDT).These materials can be by making aniline or dioxy base thiophene monomer aqueous solution in water-soluble polymers acid, prepare as carrying out polymerization under poly-(styrene sulfonic acid) existence (PSS), this, as United States Patent (USP) 5,300,575, denomination of invention was described in " Polythiophene disperses thing, their preparation method and its application ".Known PEDT/PSS material is

, available from Starck, and GmbH (Germany, Leverkusen).

PH level with the polymer dispersion liquid of water-soluble polymeric sulfonic acid synthetic waterborne conductive is too low.Low pH can reduce the stress life of the EL equipment that contains this class buffer layer, and causes corrosion in equipment.Therefore, need have composition and the buffer layer prepared therefrom that improves character.

Conductive polymers also can be used as electronics, as electrodes for thin film field.In this transistorlike, organic semiconductor film is between source electrode and drain electrode.For as electrode, the liquid that conductor polymkeric substance and being used to disperses or dissolves the conductor polymkeric substance must dissolve to avoid conductor polymkeric substance or semi-conducting polymer with semi-conducting polymer with as the solvent coupling of semi-conducting polymer again.Should be from the electric conductivity of the electrode of conductor polymer manufacture greater than 10S/cm (wherein S is the inverse of ohm).But, be about 10 with the typical electric conductivity of the conductive polythiophene of polymeric acid preparation ^-3S/cm or be lower than 10 ^-3S/cm.In order to increase electric conductivity, can in polymkeric substance, add conductive additive.But the existence of this class additive can damage the workability of the Polythiophene of conduction.Therefore, need have the higher improved conductor Polythiophene of good workability and electric conductivity.

Summary of the invention

The composition that is provided comprises the water dispersion of Polythiophene and at least a formation colloidal polymeric acid.The present composition can be used as buffer layer, be used for various organic based devices, as Organic Light Emitting Diode (0LEDs) and with the filler of conduction, as the combination of metal nano electric wire or carbon nanotube, in the middle of such as leakage, source or the gate electrode etc. of Thin Film Transistor (TFT), use.

According to another embodiment of the invention, the invention provides organic based device, comprise comprising the electroluminescence device that makes the buffer layer that present composition casting obtains.

According to another embodiment of the invention, it provides the method for the aqueous liquid dispersion that is used for synthetic Polythiophene and at least a formation colloidal polymeric acid.The method of the aqueous liquid dispersion of preparation Polythiophene and at least a formation colloidal polymeric acid comprises:

(a) provide the even aqueous mixture of a kind of water and thiophene;

(b) provide the aqueous liquid dispersion that forms the colloidal polymeric acid;

(c) make thiophene mixture and the aqueous liquid dispersion combination that forms the colloidal polymeric acid;

(d) before or after the combination of step (c), make oxygenant and catalyzer and formation colloidal polymeric acid with any sequential combination.

Below detailed description other embodiment of the present invention.

The accompanying drawing summary

Fig. 1 has shown the sectional view of the electronics that comprises buffer layer of the present invention.

Fig. 2 has shown the sectional view of the Thin Film Transistor (TFT) that comprises electrode of the present invention.

Fig. 3 has shown

The change that the electric conductivity of film takes place along with oxygenant in the polyreaction and monomeric ratio.

Fig. 4 has shown The film electric conductivity is along with in the polyreaction

Change with monomeric ratio generation.

Fig. 5 has shown the operation lifetime of OLED equipment of the polymkeric substance of green light.

Fig. 6 has shown the operation lifetime of the OLED equipment of the polymkeric substance that glows.

Fig. 7 has shown the operation lifetime of OLED equipment of the polymkeric substance of blue light-emitting.

Fig. 8 (a) has shown the influence of the pH of PEDT/PSSA buffer layer to the OLED equipment performance to Fig. 8 (d).

Fig. 9 (a) has shown PEDT to Fig. 9 (c)

The pH of buffer layer is to the effect of OLED equipment performance.

Figure 10 has shown and has been immersed in PEDT

Or the change of ITO thickness among the PEDT/PSSA time.

Detailed Description Of The Invention

In one embodiment of the invention, it provides the composition of the aqueous liquid dispersion that comprises polythiophene, and said composition comprises poly-dioxy base thiophene and forms the polymeric acid of colloid. Term used herein " dispersion or dispersion liquid " refers to contain the continuous liquid medium of the suspension of molecule. According to the present invention, " continuous media " be waterborne liquid normally, such as water. " water-based " used herein refers to that major part is the liquid of water (in one embodiment, it is at least about the water of 40% weight). Term used herein " colloid " refers to be suspended in the molecule in the continuous media, and described particle has the particle diameter of Nano grade. Term used herein " formation colloid " forms the material of molecule when referring in being scattered in aqueous solution, that is, the polymeric acid of " formation colloid " is not water miscible.

Term used herein " comprises ", " comprising ", " having ", " with " or their other variant be intended to cover the situation of nonuniqueness. For example, a kind of method, goods or equipment of series of elements of comprising not necessarily is confined to these elements, can comprise that also other does not list in wherein other element or the intrinsic element of this class methods, goods or equipment. In addition, unless opposite statement is arranged, "or" refer to a kind of that comprise or, do not refer to get rid of or. For example, it is that genuine (or existence) and B are false (or non-existent) that condition A or B satisfy following arbitrary situation: A, A is that false (or non-existent) and B are genuine (existence), and A and B are genuine (or existence).

Employed " a kind of " is used for describing element of the present invention and component. This is that what provide is general sense of the present invention for convenience. This description can be regarded as and comprises a kind ofly or at least a, singlely also comprises a plurality ofly, and it is not meaned that unless expressly stated otherwise,.

Have found that, when the thiophene monomer that comprises dioxy base thiophene monomer carries out chemical polymerization in the presence of the acid of formation colloid, can prepare the polythiophene of conduction, the particularly aqueous dispersions of poly-(dioxy base thiophene). In addition, have found that the aqueous liquid dispersion that uses non-water-soluble polymeric acid to prepare polythiophene or poly-(dioxy base thiophene) can obtain the composition with superior electrical properties. An advantage of these aqueous liquid dispersions is that the conduction molecule is stable in aqueous medium, can not form the separation phase in the long period before use, in addition, in case they generally can not disperse again when dry in film.

Composition according to one embodiment of the invention contains continuous water, the polymeric acid of wherein be scattered here and there poly-dioxy base thiophene and formation colloid. Can be used for poly-dioxy base thiophene of the present invention in the expection practice and have lower array structure:

Wherein:

R ₁And R₁' be selected from independently of one another hydrogen and the alkyl of 1-4 carbon atom is arranged,

Or R ₁And R ₁' the alkylidene chain that is joined together to form 1-4 carbon atom, can be randomly had the alkyl or aryl of 1-12 carbon atom to replace, or 1, the 2-cyclohexylidene,

N is approximately greater than 6.

Thiophene of the present invention has the structure identical with above-mentioned general formula, wherein R ₁And R ₁' be " OR ₁O " and " OR ₁' substituting group.

In a specific embodiment, R ₁And R ₁' be joined together to form the alkylidene chain of 1-4 carbon atom.In another embodiment, poly-dioxy base thiophene is poly-(3,4-ethylidene dioxy base thiophene).

It is insoluble in water to can be used for formation colloidal polymeric acid of the present invention, can form colloid when being dispersed in the aqueous medium.The typical molecular weight ranges of polymeric acid is about 10,000 to 4,000,000.In one embodiment, the molecular weight of polymeric acid is about 100,000 to about 2,000,000.The colloidal typical particle diameter is that 2 nanometers (nm) are to about 140 nanometers.In a such scheme, the colloidal particle diameter is that 2 nanometers are to about 30 nanometers.In the time of in being dispersed in water, forming any polymeric acid of colloidal and be applicable to the present invention.In one embodiment, forming the colloidal polymeric acid is polymerization sulfonic acid.Other acceptable polymeric acid comprises polymer phosphate, polymerization of carboxylic acid and polymeric acrylic acid, and their mixture, comprises the mixture that contains polymerization sulfonic acid.In another embodiment, polymerization sulfonic acid is fluoro sulfonic acid.In a further embodiment, forming colloidal polymkeric substance sulfonic acid is perfluoro.In another embodiment, forming colloidal polymerization sulfonic acid is perfluoro alkylidene group sulfonic acid.

In another embodiment, forming the colloidal polymeric acid is height fluoric sulfonic acid polymer (" FSA polymkeric substance ").In " height fluoro " expression polymkeric substance the total amount of halogen and hydrogen atom at least about 50% being fluorine atom, be at least about 75% in one embodiment, be at least about 90% in another embodiment.In one embodiment, polymkeric substance is a perfluoro.Term " sulfonate functional groups " refers to the salt of sulfonic acid group or sulfonic acid group, in one embodiment, is alkali metal salts or ammonium salt.This functional group is by formula-SO ₃X represents that wherein X is a positively charged ion, is also referred to as " companion ion ".X can be H, Li, Na, K or N (R ₁) (R ₂) (R ₃) (R ₄), R ₁, R ₂, R ₃, R ₄Be identical or different, in one embodiment, be H, CH ₃Or C ₂H ₅In another embodiment, X is H, and the polymkeric substance of this moment is called as " sour form ".X also can be polyvalent, and representational example is Ca ⁺⁺And Al ⁺⁺⁺The person of ordinary skill in the field knows, for by M ^N+The multivalence companion ion of representative, the sulfonate functional groups of each companion ion equals its valence mumber " n ".

In one embodiment, the FSA polymkeric substance comprises polymer backbone, and it repeats side chain and is connected on the skeleton, and side chain has cation exchange group.Polymkeric substance comprises homopolymer or two or more monomeric multipolymers.Multipolymer is typically from non-monomer and have cation group or its precursor, as sulfonic acid fluoride group (SO ₂F) form in second monomer, this group hydrolyzable subsequently forms sulfonate (ester) group, for example can adopt the first fluorinated ethylene monomer and contain fluoro alkylsulfonyl (SO ₂F) the monomeric multipolymer of second fluorinated ethylene.The first possible monomer comprises tetrafluoroethylene (TFE), R 1216, vinyl fluoride, vinylidene fluoride, trifluoro-ethylene, a chlorotrifluoroethylene, perfluor (alkyl vinyl ether) and their combination.TFE is preferred first monomer.

In other embodiment, the second possible monomer comprises and has the fluorinated ethylene base ether that sulfonate functionality maybe can provide the precursor group of required side chain in the polymkeric substance.Other monomer comprises ethene, propylene and R-CH=CH ₂(wherein R is the perfluoroalkyl that 1-10 carbon atom arranged) can incorporate in these polymkeric substance when needing.Polymkeric substance can be the type that this paper is called random copolymers, promptly by the multipolymer of polyreaction preparation, in the described polyreaction, it is constant that the relative concentration of comonomer keeps as much as possible, makes along the monomeric unit of polymer chain distribution consistent with its relative response concentration and relative reactivity.Also can use by changing the less multipolymer of random degree that monomeric relative concentration prepares in the reaction process.Also can use and be called segmented copolymer (disclosing) polymer type as european patent application 1026152A1.

In one embodiment, be used for FSA polymkeric substance of the present invention and comprise height fluoric polymkeric substance, in one embodiment, be the carbon skeleton and the side chain of perfluoro, as follows:

-(O-CF ₂CFR _f) _a-O-CF ₂CFR’ _fSO ₃X

R wherein _fAnd R ' _fBe independently selected from F, Cl or the perfluoroalkyl of 1-10 carbon atom arranged, a=0,1 or 2, X be H, Li, Na, K or N (R1) (R2) (R3) (R4), R1, R2, R3 and R4 identical or different, in one embodiment, be H, CH ₃Or C ₂H ₅In another embodiment, X is H.As mentioned above, X can be multivalence.

In one embodiment, the FSA polymkeric substance comprises, for example, United States Patent (USP) 3,282,875 and United States Patent (USP) 4,358,545 and 4,940,525 in those polymkeric substance of disclosing.The example of preferred FSA polymkeric substance comprises perfluoro carbon skeleton and side chain, is expressed from the next:

-O-CF ₂CF(CF ₃)-O-CF ₂CF ₂SO ₃X

Wherein the definition of X is the same.United States Patent (USP) 3,282,875 have disclosed the FSA polymkeric substance of the type, can prepare like this: make Tetrafluoroethane (TFE) and perfluoro vinyl ether CF ₂=CF-O-CF ₂CF (CF ₃)-O-CF ₂CF ₂SO ₂F, (PDMOF) copolymerization of perfluor (3,6-two oxa-s-4-methyl-7-octene SULPHURYL CHLORIDE) then by making the sulfonic acid fluoride hydrolysis be converted into sulfonate (ester) group, and are translated into required ionic species by ion-exchange.United States Patent (USP) 4,358,545 and 4,940,525 have disclosed the example of this base polymer, and they have side chain :-O-CF ₂CF ₂SO ₃X, wherein the definition of X is the same.Can prepare this polymkeric substance like this: make Tetrafluoroethane (TFE) and perfluoro vinyl ether CF ₂=CF-O-CF ₂CF ₂SO ₂F, (POPF) copolymerization of perfluor (3-oxa--4-five sulfonic acid fluoride), ion-exchange is carried out in hydrolysis then more as required.

In one embodiment, be used for the typical ion exchange ratio of FSA polymkeric substance of the present invention and be lower than about 33.In this application, " ion exchange ratio " or " IXR " is defined as in the polymer backbone with respect to carbonatoms in the polymer backbone of cation exchange group.Be lower than in about 33 the scope, can changing IXR by the needs of specific use.In one embodiment, IXR is about 3-33, in another embodiment, is about 8-23.

The cation exchange capacity (CEC) of polymkeric substance usually is expressed as equivalent (EW).For the application, during equivalent (EW) is defined as and the weight of the polymkeric substance of the needed sour form of monovalent sodium hydroxide.For having perfluoro carbon skeleton and side chain be-O-CF ₂-CF (CF ₃)-O-CF ₂-CF ₂-SO ₃The sulfonate polymer of H (or its salt) for about 750EW arrives about 1500EW for about 8-23 when weight range corresponding to IXR.The IXR of this polymkeric substance can calculate with following equation: 50 IXR+344=EW.Though United States Patent (USP) 4,358,545 and 4,940,525 have disclosed the identical IXR scope that is used for sulfonate polymer, for example have side chain-O-Cf ₂CF ₂So ₃The polymkeric substance of H (or its salt), but owing to the monomeric molecular weight that contains cation exchange group is lower, so equivalent is also lower.For preferred IXR scope is about 8-23, works as weight range accordingly and arrives about 1325EW for about 575EW.Can be with following equation association for the IXR of this polymkeric substance: 50 IXR+178=EW.

The FSA polymkeric substance can be prepared into the colloid aqueous dispersions.They also can be the dispersion thing in other medium, and the example of medium includes, but is not limited to alcohol, water-soluble ethers, and as tetrahydrofuran (THF), the mixture of water-soluble ethers and their combination.When preparation disperses thing, can use the polymkeric substance of sour form.United States Patent (USP) 4,433,082,6,150,426 and WO 03/006537 disclosed the method for preparing the aqueous alcoholic dispersion liquid.After preparing the dispersion thing, regulate concentration and dispersion liquid composition by the known method of prior art.

The typical particle diameter of aqueous liquid dispersion that forms colloidal polymeric acid (comprising the FSA polymkeric substance) is as much as possible little, and EW is also as much as possible little, as long as can form stable colloid.

The aqueous dispersion of FSA polymkeric substance can commercially availablely be buied, and commodity are by name

Dispersion liquid, (Wilmington's E.I.duPont de Nemours and Company DE) produces.

In one embodiment, thiophene or dioxy base thiophene monomer are containing the water oxygen polymerization of polymeric acid colloids.Be typically, thiophene or dioxy base thiophene monomer with contain polymerisation catalysts, oxygenant and colloidal polymer granulates and be scattered in aqueous dispersions combination wherein or be added to and contain polymerisation catalysts, oxygenant and colloidal polymer granulates and be scattered in wherein the aqueous dispersions.In this embodiment, can change combination or reinforced order, condition is that oxygenant and catalyzer are mixed with monomer.

The catalyzer of polyreaction comprises, but is not limited to ferric sulfate, iron(ic) chloride etc. and their mixture.

Oxygenant comprises, but is not limited to, and Sodium Persulfate, Potassium Persulphate, ammonium persulphate etc. also comprise their combination.Oxidative polymerization has obtained stable water dispersion, it contains positively charged conducting polymer thiophene and/or dioxy base thiophene, electronegative side chain by polymeric acid in the colloid, as sulfonate anionic, carboxylate anion, acetate negatively charged ion, phosphate anion, its combination etc., and make charge balance.

In the embodiment of the aqueous dispersions method of a poly-dioxy base thiophene of preparation and at least a formation colloidal polymeric acid, this method comprises that (a) provides the aqueous dispersions of polymeric acid; (b) in the dispersion liquid of step (a), add oxygenant; (c) in the dispersion liquid of step (b), add catalyzer; (d) dioxy base thiophene monomer is added in the dispersion liquid of step (c).A replacement embodiment of aforesaid method is added to dioxy base thiophene monomer in the aqueous liquid dispersion of polymkeric substance before being included in and adding oxygenant.Another embodiment is the even aqueous mixture of preparation water and poly-dioxy base thiophene, wherein the concentration range of polyoxy thiophene in water is typically about 0.5-2.0% weight, before adding oxygenant and catalyzer, this poly-dioxy base thiophene mixture is added in the aqueous liquid dispersion of polymeric acid.

Polyreaction can with water miscible be divided into the liquid that looses in the presence of carry out.The suitable example that is divided into the liquid that looses includes, but not limited to ether, alcohol, alcohol ether (al ethers), cyclic ethers, ketone, nitrile, sulfoxide and their combination.In one embodiment, the amount that is divided into the liquid that looses should be lower than 30% volume.In one embodiment, the amount that is divided into the liquid that looses is lower than 60% volume.In one embodiment, the amount that is divided into the liquid that looses is the 5-50% volume.In one embodiment, be divided into the liquid that looses and be alcohol.In one embodiment, be divided into the liquid that looses and be selected from n-propyl alcohol, Virahol, the trimethyl carbinol, methyl alcohol N,N-DIMETHYLACETAMIDE, dimethyl formamide, N-Methyl pyrrolidone.Acid can be mineral acid, as HCl, sulfuric acid etc., or is organic acid, as right-toluenesulphonic acids, Witco 1298 Soft Acid, methylsulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, acetate etc.Perhaps, this acid can be water miscible polymeric acid, as poly-(styrene sulfonic acid), poly-(2-acrylamido-2-methyl isophthalic acid-propanesulfonic acid) etc., or the aforesaid second formation colloidal acid.Can use the combination of acid.

Any moment before adding oxygenant or thiophene monomer can be added in the reaction mixture being total to acid, and any one in oxygenant or the thiophene monomer in the end adds.In one embodiment, add before adding thiophene monomer and forming the colloidal polymeric acid altogether-acid, oxygenant adds at last.In one embodiment, before adding thiophene monomer, add altogether-acid, add formation colloidal polymeric acid then, add oxygenant at last.

Add oxygenant, catalyzer or monomer altogether-preceding any moment of dispersion liquid (any one in them in the end adds) can add common-dispersion liquid in reaction mixture.

Optional is that after finishing above-mentioned any method and finishing polyreaction, the synthetic aqueous liquid dispersion contacts under the condition that is fit to generation stabilized aqueous dispersion liquid with at least a ion exchange resin.In one embodiment, the synthetic aqueous liquid dispersion contacts with second ion exchange resin with first ion exchange resin.

In another embodiment, first ion exchange resin is the tart Zeo-karb, and as above-mentioned sulfonic acid cation exchange resin, second ion exchange resin is the anionite-exchange resin of alkalescence, as tertiary amine or quaternary ammonium ion exchange resin.

Ion-exchange is a reversible chemical reaction, wherein the ion in liquid medium (as aqueous liquid dispersion) to be connected the fixed solid particulate on, insoluble in liquid medium, ion-exchange that similar electric charge is arranged.Term used herein " ion exchange resin " refers to this all class materials.Because ion-exchange group connects the crosslinked character of the polymer support on it, makes resin insoluble.It is electronegative basic anion exchanger that ion exchange resin is divided into the acidity, cationite and the tradable ion that have for the positive charge moving iron that exchanges.

Acidic cation-exchange resin and basic anion exchange resin all can be used for the present invention.In one embodiment, acidic cation-exchange resin is organic acid, Zeo-karb, as sulfonic acid cation exchange resin.Can be used for sulfonic acid cation exchange resin of the present invention and comprise, for example, sulfonated phenylethylene-divinyl benzene copolymer, sulfonation crosslinked styrene polymers, phenolic aldehyde sulfonate resin, benzene-formaldehyde-sulfonate resin and their mixture.In another embodiment, acidic cation-exchange resin is organic acid, Zeo-karb, as carboxylic acid, vinylformic acid or phosphoric acid Zeo-karb.In addition, can use the mixture of different Zeo-karbs.In many occasions, can use deacidite that pH regulator is arrived required level.In some cases, can further use alkaline aqueous solution, further regulate pH as the alkaline aqueous solution of sodium hydroxide, ammonium hydroxide, Tetramethylammonium hydroxide etc.

In another embodiment, basic anion exchange resin is a tertiary amine anion exchange.Can be used for tertiary amine anion exchange of the present invention and comprise, for example, the aminating styrene diethylene benzene copoly mer of uncle, the aminating crosslinked styrene polymers of uncle, the aminating phenol-formaldehyde resin of uncle, the aminating benzene-formaldehyde resin of uncle and their mixture.In another embodiment, basic anion exchange resin is the tertiary amine anion exchange or the mixture of these and other exchange resin.

First and second ion exchange resin can or contact successively with the synthetic aqueous liquid dispersion while.For example, in one embodiment, two kinds of resins are added in the aqueous liquid dispersion of synthetic conductive polymers simultaneously, and it was contacted with dispersion liquid at least about 1 hour, for example about 2 hours to about 20 hours.Then can be by filtering deionizing exchange resin from dispersion liquid.Select the size of strainer like this, big relatively ion-exchange resin particles is removed, and less dispersion composition granule can pass through.Do not wish to be fettered, but it is believed that ion exchange resin ended polyreaction by theoretical, and deionizing and nonionic impurities and from the most of unreacted monomer in the synthetic aqueous dispersions effectively.In addition, basic anion exchange resin and/or acidic cation-exchange resin make more alkalify of acidic site, and the pH of dispersion liquid is risen.In general, for the formation colloidal polymer acid of every about 1 gram, use at least 1 gramion exchanger.In other embodiment, with respect to Polythiophene/polymeric acid colloids, and according to the pH of gained, the rate of utilization of ion exchange resin is for being up to 5 gramion exchange resins.In one embodiment, for the composition of poly-dioxy base thiophene of every gram and at least a formation colloidal polymeric acid, use about 1 gram

MP62WS (available from the weak base anion-exchange resin of Bayer GmbH) and about 1 gram

MonoPlus S100 (available from Bayer, the strongly-acid sodium cation exchange resin of GmbH).

In one embodiment, the aqueous liquid dispersion from dioxy base thiophene and fluoro polymerization sulfonic acid colloidal polyreaction is added in the reaction vessel of the aqueous dispersions that has fluorinated polymer.Inwardly add oxygenant, catalyzer and dioxy base thiophene monomer successively, or add dioxy base thiophene monomer, oxygenant and catalyzer successively.Stir the mixture, allow then and carry out under the temperature that is reflected at control.When polyreaction was finished, reaction was stirred and is filtered with strong acid cation resin and basic anion exchange resin cancellation.Perhaps, dioxy base thiophene is added in the water, is adding

Mixture is stirred, then add oxygenant and catalyzer.Oxygenant: the monomer ratio is generally 0.5-2.0.Fluorinated polymer: dioxy base thiophene monomer ratio is generally 1-4.Total solids content scope is 1.5% to 6%; Be 2-4.5% in one embodiment.Temperature of reaction is generally 5 ℃ to 50 ℃; Be 20 ℃ to 35 ℃ in one embodiment.Reaction times was generally 1 to 30 hour.

The synthetic aqueous liquid dispersion that comprises poly-dioxy base thiophene and fluorinated polymer sulfonic acid colloidal polythiophene polymers acid colloids can have the pH scope of broad, typically can be adjusted to about 1-8, and general pH is about 3-4.Usually need higher pH, because acidity is mordant.Have found that available known technology, regulate pH as ion-exchange or with the alkaline aqueous solution titration.Form pH already and be up to poly-dioxy base thiophene of 7-8 and the stable dispersion liquid of fluoro polymerization sulfonic acid colloidal.Can do similar processing to regulate pH to Polythiophene and other aqueous dispersions that forms the colloidal polymeric acid.

In another embodiment, form the higher dispersion liquid of electroconductibility by in the aqueous liquid dispersion of poly-dioxy base thiophene and formation colloidal polymeric acid, adding the high conductivity additive.Owing to can form the higher dispersion liquid of pH, conductive additive, particularly metal additive are not corroded by the acid in the dispersion liquid.In addition, because polymeric acid has colloidal property, acid groups is mainly contained on its surface, and therefore the Polythiophene of conduction forms on colloid surface.Because this unique texture has only the high conductivity additive of less weight percentage need reach percolation limit.Suitable conductive additive includes, but not limited to metallic particles and nano particle, nanometer electric wire, carbon nanotube, graphite fibre or particle, carbon granule and their combination.

In another embodiment of the invention, it provides buffer layer, and it comes self-contained Polythiophene and forms the aqueous liquid dispersion of colloidal polymeric acid, in one embodiment, comprises poly-dioxy base thiophene and forms the colloidal polymeric acid.In one embodiment, buffer layer obtains by comprising the aqueous liquid dispersion casting that forms colloidal polymkeric substance sulfonic acid.In one embodiment, cast in the aqueous liquid dispersion of buffer layer poly-by containing (alkylenedioxy group thiophene) and fluorinated polymer acid colloids and obtain.In another embodiment, the fluorinated polymer acid colloids is a fluorinated polymer sulfonic acid colloid.In another embodiment, cast in buffer layer poly-by containing (3,4-ethylidene dioxy base thiophene) and the perfluor ethylidene sulfonic acid colloidal aqueous liquid dispersion and obtain.

Polythiophene, comprising can redispersion in water the exsiccant film of poly-dioxy base thiophene and polymeric acid colloids (as fluorinated polymer sulfonic acid colloid).Like this, buffer layer can be used as a plurality of thin layers uses.In addition, buffer layer can cover and can damage do not arranged to it with the different water-soluble or water dispersible material of one deck.

In another embodiment, it provides the self-contained aqueous dispersions that comprises the Polythiophene of polymerization dioxy base thiophene and be mixed with the formation colloidal polymer acid of other water-soluble or water dispersible material.According to the final service condition of material, water-soluble or the water dispersible property of the gas that can add examples of material comprises, but be not limited to polymkeric substance, dyestuff, coating auxiliary agent, carbon nanotube, nanometer electric wire, organic and inorganic conductive is black and paste, electric charge transport material, linking agent and their combination.Material can be simple molecule or polymkeric substance.Other suitable example water-soluble or dispersible polymers includes, but not limited to conductive polymers, as Polythiophene, polyaniline, polyamine, polypyrrole, polyacetylene and their combination.

In another embodiment of the invention, it provides electronics, comprises at least a electroactive layer (normally semiconductive conjugated polymer), and it is between two electronics contact layers, and wherein Zhuan Zhi one deck at least comprises buffer layer of the present invention.One embodiment of the invention are a kind of OLED type of device, and as shown in Figure 1, this device has anode layer 110, buffer layer 120, electroluminescence layer 130 and cathode layer 150.Adjacent with cathode layer 150 is electronics-injection/transhipment layer 140 of choosing wantonly.Between buffer layer 120 and cathode layer 150 (or optional electronics injection/transhipment layer 140) is electroluminescence layer 130.

This device can comprise carrier or the substrate (not shown) adjacent with anode layer 110 or cathode layer 150.Under the common situation, carrier is adjacent with anode layer 110.Carrier can be flexible or inflexible, organic or inorganic.In general, glass or elasticity organic membrane can be used as carrier.Anode layer 110 is electrodes, compares with cathode layer 150, and it can more effectively inject the hole.Negative electrode can comprise the material that contains metal, hybrid metal, alloy, metal oxide or mixed oxide.Suitable material comprises the 2nd family's element (being Be, Mg, Ca, Sr, Ba, Ra), the 11st family's element, the blended oxide compound of the 4th, 5 and 6 family's elements and 8-10 family transition element.If anode layer 110 is luminous, can use the blended oxide compound of the 12nd, 13 and 14 family's elements, as indium-tin-oxide.Phrase used herein " blended oxide compound " refers to have two or more different cationic, oxidized things that are selected from the 2nd family's element or the 12nd, 13 or 14 family's elements.The specific examples that is used as some indefinitenesses of anode layer 110 includes, but not limited to indium-tin-oxide (" ITO "), aluminium-tin-oxide, gold and silver, copper and mickel.Negative electrode also can comprise organic materials such as polyaniline or polypyrrole.Be to use the IUPAC numbering system in the whole text at this, from left to right be numbered 1-18 (the CRC handbook of chemistry and physics, the 81st edition, 2000) from the family of the periodic table of elements.

Can form anode layer 110 by chemistry or physical gas-phase deposition or rotational molding technology.Chemical vapour deposition can be carried out with the chemical vapour deposition (" PECVD ") or the metal organic chemical vapor deposition (" MOCVD ") that increase plasma body.Physical deposition comprises the sputter of form of ownership, comprises the ionic fluid sputter, and electron beam evaporation plating and resistance evaporation (resistance evaporation).The physical deposition of particular form comprises Rf magnetic field sputter and induction-coupled plasma physical deposition (" IMP-PVD ").These deposition techniques are known in field of semiconductor manufacture.

Anion layer 110 can form pattern in lithography.This pattern can change as required.By, for example before applying the first electric contacting layer material, on the first elastic composite barrier structure, place pattern mask or etching reagent and in pattern, form each layer.Perhaps, each layer can be used as one total layer (being also referred to as the bed course deposition) and uses, then, and for example with pattern etching layer and wet-chemical or dry etching technology formation pattern.Also can use known other method of this technical field to form pattern.When electronics was in the array, anode layer 110 typically formed the substantially parallel band that length is extended to equidirectional basically.

Usually cast buffer layer 120 with the known various technology of this technical field at the substrate top-pour.Typical casting technique comprises.For example, solution-cast, dropping casting, curtain casting, rotation coating, silk screen printing, ink jet printing etc.Perhaps, buffer layer can be used many deposition methods, forms pattern as ink jet printing.

Electroluminescent (EL) layer 130 typically can be conjugated polymers, as poly-(to phenylene 1, the inferior ethene of 2-), is abbreviated as PPV or poly-fluorenes.Selected concrete material can be decided according to current potential or other factors that specific application, operating period use.Can pass through any routine techniques, comprise that rotation applies, casts and printing obtains containing on the EL layer 130 of electroluminescent organic materials with the solution coating.The EL organic materials can directly apply by CVD (Chemical Vapor Deposition) method according to the character of material.In another embodiment, can apply the EL polymer precursor, then, typically, be converted into polymkeric substance by heating or other outside resources (as visible light or UV radiation).

Optional layer 140 can work to be convenient to electron emission/transhipment, also can be used as sealing ply and prevents that the place, bed interface from the cancellation reaction taking place.More particularly, layer 140 can promote to take place when electron motion also reduces layer 130 and 150 directly contact the possibility of cancellation reaction.The examples of material that is used for optional layer 140 includes, but not limited to metal-chelate and closes hydroxyquinoline class (oxinoid) compound (as Alq ₃Deng); The phenanthroline based compound (as, 2,9-dimethyl-4,7-phenylbenzene-1,10-phenanthroline (" DDPA "), 4,7-phenylbenzene-1,10-phenanthroline (" DPA ") etc.); Pyrazole compound (as, 2-(4-xenyl)-5-(4-tert-butyl-phenyl)-1,3,4-oxadiazole (" PBD " etc.), 3-(4-xenyl)-4-phenyl-5-(4-tert-butyl-phenyl)-1,2,4-triazole (" TAZ " etc.); The compound that other is similar; Or their any or multiple combination.Perhaps, optional layer 140 can be inorganic, comprises BaO, Lif, LI ₂O etc.

Cathode layer 150 is the electrodes of emitting electrons or negative charge carrier very effectively.Cathode layer 150 can be any metal or work content lower (being lower than the first electronics contact layer (in the case for anode layer 110)) nonmetal." work content is lower " used herein means the material that work content is not more than about 4.4eV." work content is higher " used herein means the material that work content is at least about 4.4eV.

As the material of cathode layer can be selected from the 1st family's basic metal (as, Li, Na, K, Rb, Cs), group II metal (as, Mg, Ca, Ba etc.), the 12nd family's metal, lanthanon (as Ce, Sm, Eu etc.) and actinide elements (as Th, U etc.).Also can use material such as aluminium, indium, yttrium and their combination.Specific indefiniteness example as cathode layer includes, but not limited to barium, lithium, cerium, caesium, europium, rubidium, yttrium, magnesium, samarium and alloy and their combination.

Cathode layer 150 forms by chemistry or physical deposition method usually.In general, the method that can use when as above anode layer 110 being discussed of cathode layer becomes pattern.If device lines up array (array), cathode layer 150 can become the pattern of substantially parallel band, and wherein the length of cathode layer band is with substantially the same direction extension, and is substantially perpendicular to the length direction of anode layer band.(wherein from the plane or top when seeing array, the cathode layer band intersects with the anode layer band) forms the electronic component that is called pixel in the point of crossing.

In other embodiment, layer in addition can exist in organic electronic device.For example, one deck (not shown) between buffer layer 120 and EL layer 130 can be convenient to that positive charge transports, interlayer band-crack coupling and can be as protective layer etc.Similar is, other layer (not shown) between EL layer 130 and cathode layer 150 can be convenient to that negative charge transports, the band of interlayer-crack coupling, and can be as protective layer etc.Can use layer well known in the prior art.In addition, above-mentioned any layer can be by two-layer or more multi-layered manufacturing.Perhaps, in inorganic anode layer 110, buffer layer 120, EL layer 130 and the cathode layer 150 some or all are carried out surface treatment and transport usefulness to increase the electric charge load.Provide the purpose of high performance devices and manufacturing cost, manufacturing complicacy or other latency to decide selection by balance to each layer material.

Different layers can have any suitable thickness.Inorganic anode layer 110 is not more than about 500 nanometers usually, for example about 10-200 nanometer; Buffer layer 120 is not more than about 250 nanometers usually, for example about 50-200 nanometer; EL layer 130 is not more than about 1000 nanometers usually, for example about 50-80 nanometer; Optional layer 140 is not more than about 100 nanometers usually, for example about 20-80 nanometer; Cathode layer 150 is not more than about 100 nanometers usually, for example about 1-50 nanometer.If anode layer 110 or cathode layer 150 need at least some light of transmission, the thickness of this class layer is no more than about 100 nanometers.

Application according to electronics, EL layer 130 can be for by signal (as the signal in the photodiode) activated luminescent layer, or by quantity of radiant energy being had response and produce the layer that the material of signal constitutes, and no matter whether impressed voltage (as detector or voltaic cell) is arranged.After having read this specification sheets, the person of ordinary skill in the field can select to be suitable for the special material of using.Luminescent material can be dispersed in the matrix of another kind of material, can be with or without additive, can become one deck separately.EL layer 130 general thickness range are about 50-500 nanometer.

From comprise example with other organic based device that obtains an advantage one or more layers of the aqueous dispersions Polythiophene of polymeric acid colloids preparation comprise (1) with electric energy be converted into radiating equipment (as, photodiode, light emitting diode indicator or diode laser), (2) equipment by electronics technology detection signal (as, photodetector is (as photocell, photo-resistor, photoswitch, phototransistor, phototube), the IR detector), (3) comprise one or more equipment (as triode transistor or diode) that contain the electronic package of one or more organic semiconductor layers with equipment (as photovoltaic equipment or solar cell) and (4) that radiation is converted into electric energy.

In Organic Light Emitting Diode (OLEDs), emission enters EL layer 130 separately from the electronics and the hole of cathode layer 150 and anode layer 110, forms negative charge polarity ion and positive charge polarity ion in polymkeric substance.These polarity ions act on migration under the electric field that adds, form polarity ion excitation that has the opposite charges kind, then carry out the radiation reorganization.Competent potential difference generally is lower than about 12 volts between anode and negative electrode, is not more than about 5 volts in many cases.Real potential difference can be decided according to the equipment that uses in the big electronic package.In many embodiments, during operating electronic equipment, at anode layer 110 deflection positive voltages, cathode layer 150 is essentially basic current potential or zero volt.Battery or other energy source can be electrically connected on the electronics part as the loop, but Fig. 1 does not show.

Have found that to have and have the longer life-span by comprising the OLEDs of polymkeric substance dioxy base thiophene with the buffer layer of the aqueous dispersions casting that forms the colloidal polymeric acid.Buffer layer can be obtained by poly-dioxy base thiophene and the casting of fluorinated polymer sulfonic acid colloidal aqueous liquid dispersion, and in one embodiment, the pH of aqueous liquid dispersion is adjusted to about more than 3.5.

Use acid lower or pH to be the etching that the neutral material causes adding ITO layer in man-hour and obviously reduce, therefore the In of more low concentrations and the polymer layer that the Sn ion diffusion enters OLED.Because In and Sn ion may reduce operation lifetime, this is a tangible advantage.

When making and long storage, lower acidity also can reduce the corrosion of indicating meter (as the electronics contact mat) metal component.PEDT/PSSA residue and residual moisture interaction allow acid enter and cause in the indicating meter slowly corroding.

Be used for disperseing the equipment claimed of acid PEDT/PSSA to design especially, make it can handle highly acid PEDT/PSSA.For example, because PEDT/PSSA is acid, we find that being used for that PEDT/PSSA is coated to the suprabasil chromium plating slot die of ITO application head can be corroded.Because the film that applies can not be used described head by the chromium particle contamination.Some ink jet printing heads can be used to make the OLED indicating meter.The position distributing buffer layer and the light-emitting polymer layer of their precisions on indicating meter.These print heads contain the trapped inside device of nickel sieve strainer as ink particle.These nickel strainers are decomposed by tart PEDT/PSSA and become useless.These etching problems can not take place in water-based PEDT dispersion liquid of the present invention, because acidity wherein decreased already.

In addition, some luminescence polymer is found the acidic conditions sensitivity, if they contact with the acidic buffer layer, their luminous power reduces.Advantageously use water-based PEDT dispersion liquid of the present invention to form buffer layer, very low or be neutrality because of its acidity.

If each luminescent material all needs different anode materials to make its best performanceization, it is very complicated making indicating meter panchromatic or regional color with two or more different luminescent materials.Display equipment is made up of luminous a plurality of pixels.In multicolour equipment, need the light of at least two kinds of dissimilar pixels (being sometimes referred to as sub-pix) emission different colours.Sub-pix is made up of different luminescent materials.Be sought after single anode material, it can give all luminescent devices good performance.This can make the complicacy of equipment making minimize.Have found that common negative electrode can be used for the multicolour device of buffer layer by water-based PEDT dispersion liquid preparation of the present invention, can keep the functional of every kind of color simultaneously.This negative electrode utmost point can be made by any material of above-mentioned discussion; Can be barium, the outside applies the more inert metal such as aluminium.

The organic based device of other that from one or more layers of the aqueous liquid dispersion of the Polythiophene that comprises poly-dioxy base thiophene and at least a formation colloidal polymeric acid, obtains an advantage comprise (1) with electric energy be converted into radiating equipment (as, photodiode, light emitting diode indicator, or diode laser), (2) equipment by electronics technology detection signal (as, photodetector is (as photoconductive cell, photo-resistor, photoswitch, phototransistor, phototube), the IR detector), (3) comprise one or more equipment (as triode transistor or diode) that contain the electronic package of one or more organic semiconductor layers with equipment (as photovoltaic equipment or solar cell) and (4) that radiation is converted into electric energy.

Buffer layer also can further be applied by one deck conductive polymers by applying aqueous solution or solvent.Conductive polymers helps transporting electric charge, but also can propose coating.The example of suitable conductive polymers comprises, but be not limited to, polyaniline-polymkeric substance-acid-colloid, polypyrrole, polyacetylene and their combination of polyaniline, Polythiophene, poly-dioxy base thiophene/polystyrolsulfon acid, announcement in the application DuPont numbering UC 0223 that awaits the reply jointly.

In another embodiment of the invention, it provides Thin Film Transistor (TFT), comprises the electrode that comprises poly-dioxy base thiophene and form colloidal polymkeric substance sulfonic acid.For as the electrode in the thin film field-effect triode transistor, conductive polymers and being used to disperse or dissolve conductive polymers liquid must with the solvent coupling of semi-conducting polymer and semi-conducting polymer, dissolve again to avoid semi-conducting polymer.The electroconductibility of the thin film field effect transistor electrodes of being made by the conductor polymkeric substance is greater than 10S/cm.But the polymkeric substance of making the conduction of each with water-soluble polymers acid only provides about 10 ^-3S/cm or be lower than 10 ^-3Electric conductivity in the S/cm scope.Like this, in one embodiment, electrode comprises poly-(alkylenedioxy group thiophene) and form colloidal fluorinated polymer sulfonic acid and the combination of conduction toughener (as nanometer electric wire, carbon nanotube etc.).In another embodiment, electrode comprises poly-(3,4-ethylidene dioxy base thiophene) and form colloidal perfluoro ethylidene sulfonic acid and such as the composition of the conduction dose of nano wire, carbon nanotube etc.The present composition can be used for Thin Film Transistor (TFT) as gate electrode, drain electrode or source electrode.

The present invention has disclosed Thin Film Transistor (TFT) on the other hand, as shown in Figure 2.In the scheme of this demonstration, dielectric polymer or dielectric oxide film 210 have gate electrode 220 at the one mask, have drain electrode 230 and source electrode 240 on other face.Between drain electrode and source electrode, depositing organic semiconductor film 250.The present invention contains the aqueous liquid dispersion of nanometer electric wire or carbon nanotube because can be compatible with the dielectric polymer and the semi-conducting polymer of organic radical in the solution film deposition, so be ideal for being applied on gate electrode, drain electrode and the source electrode.Because electrically conductive composition of the present invention (is PEDT and colloidal perfluoro ethylidene sulfonic acid as an example) exists with the colloidal dispersion form, (with respect to containing water-soluble polymers sulfonic acid) needs still less conductive filler material of percentage ratio can obtain the seepage threshold values of high conductivity.

In another embodiment of the invention, it provides the method for preparing the aqueous dispersions of the poly-dioxy base thiophene that comprises polymeric dioxy base thiophene monomer in the presence of polymkeric substance sulfonic acid colloid.In the method for one embodiment of the invention, poly-dioxy base thiophene is a polyalkylene dioxy base thiophene, and forming colloidal polymer sulfonic acid is fluoric.In another embodiment of the inventive method, poly-dioxy base thiophene is poly-(3,4-ethylidene dioxy base thiophene), and forming colloidal polymkeric substance sulfonic acid is perfluoro.In another embodiment, forming colloidal polymkeric substance sulfonic acid is perfluoro ethylidene sulfonic acid.Polyreaction is carried out in the presence of water.The reaction mixture of gained can be used ion exchange resin treatment, to remove byproduct of reaction.

The present invention does more detailed elaboration referring now to following indefiniteness embodiment.

Embodiment

The comparative example 1

This comparative example has shown that ethylidene dioxy base thiophene is at water-soluble polymers sulfonic acid, carry out oxidative polymerization under promptly poly-(styrene sulfonic acid) existence (PSSA), obtain (PEDT/PSSA) complex compound of non-colloidal poly-(ethylidene dioxy base thiophene)/poly-(styrene sulfonic acid).

By with 0.3246 the gram ferric sulfate hydrate (Sigma-Aldrich Corp., U.S. MO) be dissolved in deionized water obtain total amount be 39.4566 the gram solution prepare ferrum sulfuricum oxydatum solutum.In Plastic Bottle, make 2.28 these ferrum sulfuricum oxydatum solutums of gram and 300 gram deionized waters, 10.00 gram PSSA (30% weight PSSA, 70,000 molecular weight, PolySciences, Inc., pennsylvania, USA) and 1.72 gram Sodium Persulfates (Fluka, Sigma-Aldrich Crop, U.S. MO) mix.Ferric sulfate is as the catalyzer of polyreaction, and Sodium Persulfate is the oxygenant of the oxidative polymerization of ethylidene dioxy base thiophene.Stir the mixture, be placed on then in 500 milliliters of three-necked flasks that are equipped with for the hot well of placing thermopair.Using by the air operated overhead stirrer provides the agitating vane of power that mixture is stirred, and adds 0.63 milliliter 3 simultaneously in the mixture that contains PSSA, 4-ethylidene dioxy base thiophene (Baytron-M

, available from Bayer, pennsylvania, USA).Make 3,4-ethylidene dioxy base thiophene is in room temperature, promptly about 22 ℃ of following polymerizations 24 hours.Polymerization result is to make clarifying liquid become adopting dark liquid, for the PEDT/PSSA complex compound is dispersed in color in the water.Use 5.0 microns available from Millipore Corp. (Maryland, US)

Injection filter is measured the filterability of PEDT/PSSA complex compound dispersion liquid, when syringe piston is applied manual high pressure, has only the colourless liquid of clarification by strainer, thereby shows that PEDT/PSSA complex compound particle is too big, can not pass through strainer.

The aqueous liquid dispersion of half PEDT/PSSA complex compound (for about 158 grams) is for further processing with two kinds of ion exchange resin.A kind of is cationite, crosslinked sodium polystyrene sulfonate ( S100WS, available from Bayer, pennsylvania, USA).Another kind is an anionite, the free base/chloride of the tertiary amine/quaternary ammonium of crosslinked polystyrene (

MP62 WS, available from Bayer, pennsylvania, USA).53 grams

S100WS and 51 grams

MP62WS separately with deionized water wash in the water colourless till.Two kinds of washed resins filter then, and the aqueous liquid dispersion with 158 gram PEDT/PSSA complex compounds mixes again.Mixture stirred 8 hours with magnetic stirrer.By removing by filter resin.The aqueous liquid dispersion of finding resin processed PEDT/PSSA complex compound by gravimetric analysis contains 1.2wt%.Use 5.0 microns then available from Millipore Corp. (Maryland, US)

-SV injection filter and measure the filterability of the aqueous liquid dispersion of resin processed PEDT/PSSA available from 1.2 microns GF/C syringe filter of Whatman Inc. (New Jersey).Dispersion liquid can be by 5.0 microns

-SV syringe filter, but when syringe piston is added manual high pressure, have only the colourless liquid of clarification by 1.2 microns GF/C syringe filter.By the resin processed PEDR/PSSA complex compound particulate median size of aforesaid light scattering measurement, be found to be 1.12 microns (mean number of 5 measuring results, 0.04 micron of standard deviation), polymolecularity is 0.40.

Measure electroconductibility and luminosity then through resin processed PEDT/PSSA complex compound.With the ITO layer thickness is that commercially available tin indium oxide (the ITO)/sheet glass of 100-150 nanometer cuts into 30 millimeters * 30 millimeters size.The ITO layer is then used oxygen plasma etch.The ITO that is used for measuring specific conductivity on the substrate of glass is etched into series of parallel ITO line, as electrode.Being used for being prepared into LEDs in the substrate supplies the ITO of luminous measurement to be etched into the ITO layer of 15mm * 20mm as anode.The speed rotation with 1200 rev/mins of the aqueous liquid dispersion of resin processed PEDT/PSSA complex compound is coated on the ITO/ glass substrate.About 140 nanometers of PEDT/PSSA complex compound bed thickness of gained.The quality of layer is inhomogeneous.The ITO/ substrate of glass that has applied the PEDT/PSSA complex compound under 90 ℃ of nitrogen dry 30 minutes.

Measure the electric conductivity of PEDT/PSSA complex layer by measuring resistance between two electrodes, according to the thickness of resistance, conductive layer be used for the distance of two electrodes of measuring resistance, calculating electric conductivity is 6.1 * 10 ^-3S/cm.

For luminous measurement, the PEDT/PSSA complex layer then by super yellow casting charge poly-(replacement-phenylene vinylidene) (available from Covion Company, the PDY 131 of Frankfurt, Germany) top coating as reactive electro photoluminescence (EL) layer.About 70 nanometers of the thickness of EL layer.Use TENCOR500 SuR _fAce Profiler measures film thickness.For negative electrode, 1.3 * 10 ^-4Under the vacuum of pa, with Ba and the vapour deposition of Al layer top to the EL layer.The final thickness of Ba layer is 3 nanometers; The thickness of the Al layer on Ba layer top is 300 nanometers.In order to following method test LED equipment performance.Measure electric current one impressed voltage, luminous intensity is to impressed voltage, and use (Cleveland from Keithley Instrument Inc., OH) Keithley 236 sources-measuring unit and have S 370Optometer (UDT Sensor, Inc. California, United States) the measurement luminous efficiency of proofreading and correct silicon photo diode (international candle/ampere-c/A).Obtaining optical density(OD) by the raising impressed voltage is 200cd/m ²To 5 LED testing equipments.The average impressed voltage that obtains this density is 5.0 volts, and average light efficient is 5.4cd/A.The stress half-life of these equipment under 80 ℃ is lower than 1 hour.

Embodiment 1

This embodiment has shown

Existence under the oxidative polymerization of ethylidene dioxy base thiophene, this embodiment has also described the character of poly-(the ethylidene dioxy base thiophene) of gained.

With 142.68 gram (16.03 mmoles

Monomeric unit) SE-10072 and 173.45 gram deionized waters are poured 500 milliliters into In the Plastic Bottle.By being dissolved in deionized water, 0.0667 gram ferric sulfate hydrate (97%, Sigma-Aldrich Corp., U.S. MO) obtains the ferric sulfate stock solution that total amount is 12.2775 grams.1.40 gram ferrum sulfuricum oxydatum solutums and 1.72 gram (7.224 mmole) Sodium Persulfates (Fluka, Sigma-Aldrich Crop., U.S. MO) are placed in the Plastic Bottle.Close

Plastic bottle closure is with the fierce jolting bottle of hand.The bottle content is poured into 500 milliliters of three-necked flasks of above-mentioned band cover.Mixture was stirred in reaction vessel 30 minutes.Stir and add 0.63ml (5.911 mmole) Baytron-M (3, the trade(brand)name of 4-ethylidene dioxy base thiophene, Bayer product, pittsburgh,U.S.A) in the downhill reaction mixture.Polyreaction is carried out under about 23 ℃ then.After 1 hour 7 minutes, polyreaction liquid becomes mazarine, then it is assigned in two 250 milliliters the Plastic Bottle.Take reaction vessel apart, on the glass wall of stir shaft or reaction vessel, do not have gel particle.The total amount of liquid of polyreaction is 297.10 grams.Liquid contains 5.303% (w/w) solid, supposes not loss, and all transforms.Solid contains primary poly-(3,4-ethylidene dioxy base thiophene), PEDT by inference

To the gram of 148.75 in one of two Plastic Bottles water-based PEDT

Be for further processing with two kinds of ion exchange resin.One of two kinds of resins are

S100WS, the trade(brand)name of crosslinked polystyrene sodium sulfate (available from Bayer, the pennsylvania, USA Pittsburgh).Another kind is

MP62 WS, the trade(brand)name of the free base/chloride of the tertiary amine/quaternary ammonium of crosslinked polystyrene (available from Bayer, the pennsylvania, USA Pittsburgh).Before the use, two kinds of resins respectively with deionized water wash in the water colourless till.Make 7.75 grams S100 and 7.8 grams

In WS and the Plastic Bottle 148.75 gram water-based PEDT

Dispersion liquid mixes.Then bottle was placed on the roller stir about 23 hours.The soup compound of gained is then by coarse sintered glass funnel suction filtration.Obtain 110.2 grams.According to the ultimate analysis of the sample that disperses fluid drying to obtain from 2.6% (w/w), sample contains 21.75% carbon, 0.23% hydrogen, and 1.06% nitrogen and 2.45% sulphur are not analyzed other element such as oxygen and fluorine.In order to eliminate the interference that fluorine is analysed sulphur content, added CeCl ₃And anionite-exchange resin.

Make 10 gram PEDT

Dispersion liquid mixes with 10.01 gram deionized waters, and it has constituted based on anhydrous solid being carried out gravimetric 2.6% (w/w) solid.Measure water-based PEDT then

The electroconductibility of dispersion liquid and luminosity.To be that 100-150 nanometer, ito surface are long-pending clean for the glass of 15mm * 20mm/ITO substrate (30 millimeters * 30 millimeters) the ITO layer thickness, follows as comparative example 2, uses oxygen plasma treatment.With 700 rev/mins speed of rotation with water-based PEDT

The dispersion liquid rotation is coated on the ITO/ substrate of glass, obtains 96nm thickness.Use PEDT

The ITO/ substrate of glass that applies in 90 ℃ vacuum drying oven dry 30 minutes.Record PEDT

The electric conductivity of film is 2.4 * 10 ^-3S/cm and 5.7 * 10 ^-4S/cm.

PEDT

Layer is used super yellow casting charge (PDY131) then: poly-(replacement-phenylene vinylidene),, carry out top coating available from Covion Company Frankfurt, Germany.About 70 nanometers of the thickness of EL layer.With TENCOR 500 SuR _fAce Profiler measures film thickness.For negative electrode, 1 * 10 ^-6Under the vacuum of holder, with Ba and the vapour deposition of Al layer top to the EL layer.The final thickness of Ba layer is

The thickness of Al layer is

In order to following method metering equipment performance.Measure the voltage of electric current to adding, the voltage of luminous intensity to applying, and use (Cleveland from Keithley Instrument Inc., OH) Keithley 236 sources-unit of measure and the S370 Optometer (UDT Sensor, Inc. California, United States) that has a gauged silicon photo diode measure luminous efficiency (international candle/ampere-c/A).5 luminaires are tested, and the display operation voltage range is 3.2 to 3.3 volts, is 200Cd/m in brightness ²Under luminous efficiency be that 8.3Cd/A is to 9.8Cd/A.The stress half-life scope of these equipment under 80 ℃ is 243-303 hour.

The comparative example 2

This comparative example has shown the character with exsiccant solid film in the commercially available water-based PEDT dispersion liquid of water-soluble poly-(styrene sulfonic acid) preparation.

Under nitrogen gas stream, room temperature, (Lot#06Y76982, available from H.C.Starck, GmbH (Leverkusen, Germany)) is dried to solid film to Baytron-P VP Al 4083 that will about 30mL in glass beaker.Exsiccant solid film thin slice is mixed, by manual jolting mixture with about 10 ml deionized water.When most thin slice redispersion was in water, water became blueness, and very dark.The acid height of water is used (Gibbson, NJ, USA available from EM Science; Cat #9590) The pH that color indicator (pH0-14 scope) shows is 0.

The comparative example 3

This comparative example has shown by the absorption of the solid film that obtains with the water-soluble another kind of commercially available water-based PEDT dispersion liquid drying of gathering (styrene sulfonic acid) preparation to moisture.

Under nitrogen gas stream, room temperature, (Lot#CHN0004, available from H.C.Starck, GmbH (Leverkusen, Germany)) is dried to solid film to Baytron-P CH8000 that will about 30mL in glass beaker.Most desciccator diaphragm is carried out dispersibility test and acid test again in about 10 ml deionized water, find as comparative example 2 described results.To take in situation (carrying out in 20 ℃/minute nitrogen) preceding analyze moisture with thermogravimeter, allows small portion desciccator diaphragm thin slice balance under the atmosphere condition.The film thin slice absorbs 29.4% water under the atmosphere condition.This result clearly illustrates, the very moisture absorption of PEDT film, and the moisture of Xi Shouing makes the acidity of water very high as comparative example 2 like this.VP Al 4083 and CH8000 PEDT are the buffer layers of commercially available OLED.

Embodiment 2

This embodiment has shown by water-based PEDT of the present invention

The character of the solid film that drying obtains.

Water-based that will about 30mL embodiment 1 under nitrogen gas stream, room temperature

(2.6%) is dried to solid film.Most desciccator diaphragm mixes with deionized water, by manual jolting mixture.Thin slice is still glossy, shows that film does not have swelling.Surprisingly, water is colourless, this means PEDT

There is not redispersion in water.In addition, use (Gibbson, NJ, USA available from EM Science; Cat#9590)

Color indicator (pH0-14 scope) shows that the pH of water is 7.This result clearly illustrates that polymeric acid does not move.In addition, the result shows PEDT

The surface mainly be conductive layer with sulfonic acid anion electric charge (by PEDT balance).

To take in situation (carrying out in 20 ℃/minute nitrogen) preceding analyze moisture with thermogravimeter, allows small portion desciccator diaphragm thin slice balance under the atmosphere condition.This film thin slice has only absorbed 5.6% water, and the water that this commercially available PEDT that shows more than comparative example 3 absorbs is low.Low moisture is taken in two and is also shown PEDT

The surface mainly be conductive layer with sulfonic acid anion electric charge (by PEDT balance).This makes its water absorbability ratio use the low of comparative example 2 and 3 desciccator diaphragms that prepare.

Embodiment 3

This embodiment has shown makes use PEDT In Thin Film Transistor (TFT) as the application of electrode.

Embodiment 2 described part desciccator diaphragms mix with toluene, chloroform or methylene dichloride (being used for dissolving organic solvent commonly used in the semiconducting organic polymer in Thin Film Transistor (TFT)).Organic solvent can not make film thin slice swelling, and thin slice can not make the organic solvent decolouring.The result clearly illustrates PEDT

Film is compatible with the organic solvent that is used for semi-conducting polymer.Because conductive polymers is obtained by the aqueous liquid dispersion casting, water can not influence only at organic aromatic solvent (as toluene) or chlorinated solvent (as chloroform or methylene dichloride) dissolved semi-conducting polymer.

Water-based PEDT to embodiment 2 preparations

Dispersion liquid (2.6%w/w) is measured its electric conductivity.With the ITO layer thickness is that the glass/ITO substrate (30 millimeters * 30 millimeters) of 100-150 nanometer is cleaned, and then uses oxygen plasma treatment.With water-based

The dispersion liquid rotation is coated on the ITO/ substrate of glass.With The ITO/ substrate of glass that applies in 90 ℃ vacuum drying oven dry 30 minutes.Record

The electric conductivity of film is 2.4 * 10 ^-3S/cm and 5.7 * 10 ^-4S/cm.This specific conductivity is lower than the required electric conductivity of thin film field effect transistor electrodes.But, use conductive polymers wherein to be present in conduction in the dispersion liquid with colloidal form

The time, allow to mix the nano particle or the carbon nanotube of nanometer electric wire, metal.For example, can obtain as Zach etc. at Science, the diameter of the 2120th page of description of the 290th volume is that 15nm, electric conductivity are 1.7 * 10 ⁴The metal molybdenum electric wire of S/cm.As Niu etc., Appl.Phys.Lett., the 70th volume, the 1480th page is described, also can obtain diameter and is 8nm, length and be 20 microns, electric conductivity and be the carbon nanotube of 60S/cm, and can be used to increase electric conductivity.Because

Colloidal property and particle surface mainly be conductive layer, need be than the high conductive filler material of low weight percentage ratio, in case

Assemble and just can reach the seepage threshold values that high conductivity needs.

Embodiment 4

This embodiment has shown under various conditions and has existed

The time, the polyreaction of ethylidene dioxy base thiophene.Used three kinds dissimilar

SE-10072, DE-1021 and DE-1020.

In the flask of band cover, add aqueous liquid dispersion and water.Make mixture be warming to specified temperature, stirred 45 minutes.In this mixture, add oxygenant, catalyzer and dioxy base thiophene monomer successively.After reinforced the finishing, allow mixture under specified temperature, stir the specified time.Use then

Strong acidic ion resin (sodium type) and

Weak anion resin makes the reaction cancellation by the batch processing reaction mixture or by the post of having filled these two kinds of ion exchange resin.The paste mixture of gained at room temperature stirred 16 hours then, filtered by filter paper (aperture〉6 micron) again.At last, the filtrate of gained is by 0.45 micron filter.By the adding deionized water, and the jolting thorough mixing, the finished product that filtrate being mixed with of gained had target solids content.Polymerization parameter is listed in the table below 1.

Table 1

Synthetic

Sample	Nafion criticizes	Oxygenant/monomer	The Nafion/ monomer	Temperature (℃)	Reaction times (hour, minute)	Ion-exchange	Existing P EDT-Nafion (%)	The PEDT-Nafion of preparation
									A	SE-10072	1.221	2.756	20.2	20，49	Batch	2.81	2.8
B	DE-1021	1.221	2.756	20.2	20，47	Batch	2.81	2.8
									C	DE-1021	1.221	2.756	20.2	21，00	Post	2.81	2.8
D	DE-1020	1.221	2.756	20.2	21，00	Batch	2.81	2.8
									E	DE-1020	1.221	2.756	20.1	21，00	Post	2.81	2.8
F	DE-1020	1.221	5.513	20.2	23，15	Post	2.80	5.5
									G	DE-1021	1.221	5.513	20.2	44，08	Post	2.80	5.9
H	DE-1020	1.221	5.513	20.2	24，56	Batch	5.48	5.4
									I	DE-1020	0.50	3.00	20.2	23，43	Batch	2.89	2.8
J	DE-1020	1.50	3.00	20.1	24，00	Post	2.69	2.6
									K	DE-1020	2.00	1.00	20.1	14，52	Batch	3.04	3.0
L	DE-1020	1.25	3.00	35.0	16.34	Batch	6.04	3.4
									M	DE-1020	2.00	3.00	35.0	24，05	Post	3.01	3.0
N	DE-1020	1.25	3.00	35.0	14，54	Batch	4.52	3.4
									O	DE-1020	1.5	3.00	35.0	14，55	Batch	4.52	4.5
P	DE-1020	0.75	3.00	35.0	24，00	Batch	4.51	4.5
									Q	DE-1020	1.00	3.00	35.0	16，36	Batch	4.52	3.8
R	DE-1020	1.00	2.00	35.0	16，31	Batch	4.52	4.5
									S	DE-1020	1.00	2.50	35.0	16，28	Batch	4.52	3.0

T	DE-1020	1.00	3.00	35.0	41，17	Batch	3.51	3.5
									U	DE-1020	1.25	3.00	35.0	41，19	Batch	3.51	3.5
V	DE-1020	1.50	3.00	35.0	41，22	Batch	3.51	3.5
									W	DE-1020	1.25	3.00	35.0	14，02	Post	4.52	3.0
X	DE-1020	1.00	2.75	35.0	14，27	Batch	4.52	3.6
									Y	DE-1020	1.00	2.25	35.0	13，20	Batch	4.52	3.6
Z	DE-1020	1.25	2.75	35.0	14，28	Batch	4.52	3.6
									AA	DE-1020	1.25	2.50	35.0	13，47	Batch	4.52	3.5
BB	DE-1020	1.25	2.25	35.0	13，39	Batch	4.53	3.5
									CC	DE-1020	1.25	2.00	35.0	13，42	Batch	4.53	3.5
DD	DE-1020	1.50	2.75	35.0	13，16	Batch	4.53	3.5
									EE	DE-1020	1.50	2.50	35.0	13，17	Batch	4.53	3.5
FF	DE-1020	1.50	2.25	35.0	13，18	Batch	4.53	2.8
									GG	DE-1020	1.50	2.00	35.0	12，58	Batch	4.54	3.0
HH	DE-1020	1.75	3.00	35.0	13，10	Batch	4.53	3.5
									II	DE-1020	1.75	2.75	35.0	13，05	Batch	4.53	3.0
JJ	DE-1020	0.75	2.75	35.0	13，27	Batch	4.51	3.5
									KK	DE-1020	0.75	2.50	35.0	13，25	Batch	4.51	3.5
LL	DE-1020	0.75	2.25	35.0	5，55	Batch	4.52	3.5
									MM	DE-1020	0.75	2.00	35.0	5，52	Batch	4.52	3.0
NN	DE-1020	0.50	3.00	35.0	23，38	Batch	4.51	3.5
									OO	DE-1020	0.50	2.75	35.0	23，38	Batch	4.51	3.5
PP	DE-1020	0.50	2.50	35.0	22，53	Batch	4.51	3.5
									QQ	DE-1020	0.50	2.25	35.0	22，54	Batch	4.51	3.5

Embodiment 5

This embodiment has shown from embodiment 4 preparation The electric conductivity difference of the film for preparing in the dispersion liquid.The ITO electrode preparation of substrate of glass into pattern.Buffer layer forms film by the dispersion liquid rotated mold filing on the top of one-tenth figure substrate, after this cured in 90 ℃ vacuum drying oven 0.5 hour.Be used in the resistance between the high resistance electroscope measurement ITO electrode in the dry box.By using Dec-Tac surface profile determinator (Alpha-Step 500 SuR _fAceProfiler, Tencor Instruments) the measurement film thickness.From resistance and thickness, calculate the electric conductivity of buffer layer.

The result is shown in Fig. 3 and 4.As seen electric conductivity can be controlled at 10 well by changing composition ^-2Scm ^-1To 10 ^-9Scm ^-1Between.

Embodiment 6

This embodiment has shown the difference as buffer layer among the OLED The performance of composition.

With soluble poly-(1, the 4-phenylene vinylidene) multipolymer (C-PPV) (H.Becker, H.Spreitzer, W.Kreduer, E.Kluge, H.Schenk, I.D.Parker and Y.Cao, Adv.Mater.12,42 (2000)) make photodiode as active semiconductor, luminescence polymer; The thickness of C-PPV film is

C-PPV launches Huang-green light, and emission peak is about 560nm place.Indium/tin-oxide is as negative electrode. Film, after this cured in 90 ℃ vacuum drying oven 0.5 hour in figuratum substrate from the solution rotated mold filing.The structure of equipment is ITO/PEDT-

/ C-PPV/ metal.Use comes producing apparatus at ITO on glass as substrate (the ITO/ glass that applies).During preparation equipment with Ca or Ba layer as anode.Metallic cathode film vacuum vapor deposition is being lower than 1 * 10 ^-6In the preparation of the top of C-PPV layer, the area that obtains active coating is 3cm under the pressure of holder ²(Sycon Instruments Inc.) detects deposition conditions with STM-100 thickness/ratio gauge.2,000-

Al deposition exist

Ba or the top of Ca layer.For each equipment, measure electric current to voltage curve, light to voltage curve and quantum effect.

Use accompanies the cover glass sealing equipment of UV-curable epoxy thing.Sealed equipment is in 80 ℃ of baking ovens, move under the constant electric current.Total current by equipment is about 10mA, and brightness is about 200cd/m ²Or 600cd/m ²The brightness of recording unit and voltage are to determine transformation period and the voltage increment rate under 80 ℃.

Following table 2 has provided the result.

Table 2 equipment performance

The initial brightness of I.L.=

(1) at 200cd/m ²The following measurement

(2) at 600cd/m ²The following measurement

Embodiment 7

This embodiment has shown preparation

Aqueous dispersions.

Be 12.5% (w/w) aqueous colloidal dispersion liquid, its EW is 900, uses and United States Patent (USP) 6,150, and the similar process of 426 embodiment 8 prepares.

With 63.87 gram (8.06 mmoles

Monomeric unit)

Aqueous colloidal dispersion liquid and 234.47 gram deionized waters are poured in the three neck round-bottomed flasks of 500 milliliters of band overcoats.Mixture was stirred 45 minutes.By with deionized water dissolving 0.0141 gram ferric sulfate hydrate (97%, Aldrich cat.#30,771-8) ad pond om 3.6363 grams at first prepare the stock solution of ferric sulfate.(Fluka cat.#71899) is placed in the reaction flask, stirs the mixture simultaneously then 0.96 gram (0.0072 mmole) ferric sulfate and 0.85 to be restrained (3.57 mmole) Sodium Persulfate.Adding preceding mixture stirring 3 minutes that make of 0.312 milliliter of (2.928 mmole) Baytron-M (3, the trade(brand)name of 4-ethylidene dioxy base thiophene, Bayer product, pittsburgh,U.S.A).Carry out polyreaction controlling to by circulating liquid under about 20 ℃, the initial change after 13 minutes of the liquid of polyreaction is blue.By adding 8.91 grams

S100 (pittsburgh,U.S.A is produced for trade(brand)name, Bayer) replaces crosslinked sodium polystyrene sulfonate and 7.70 grams MP62WS (pittsburgh,U.S.A is produced for trade(brand)name, Bayer) replaces the free alkali/tertiary amine muriate/quaternary ammonium of crosslinked polystyrene.At first use two kinds of resins of deionized water wash before the use, in water colourless till.Plastic resin treatment has been carried out 5 hours.The soup compound of gained is then by Whatman #54 filter paper suction filtration.It can pass through filter paper soon.Yield is 244 grams.According to the polymeric component that adds, solid % is about 3.1% (w/w).Use 315pH/ ionometer measuring device to record water-based from Corning Company (Corning, USA New York)

PH be 3.8.

Embodiment 8

This embodiment has shown

The non-dispersive of desciccator diaphragm.

About 10 milliliters of water-baseds of embodiment 7 preparations

Dispersion liquid is at room temperature dry with nitrogen gas stream.Exsiccant

Mix with 10 ml deionized water.After many months, water still keeps colourless and clarification.

Embodiment 9

This embodiment has shown water-based

Dispersion liquid is to the non-aggressive of ITO.

Water-based with embodiment 7 preparations

Rotation is coated on the ITO substrate.Check with X-ray photoelectric spectroscope (XPS) Top surface.Do not detect indium or tin element, show that ITO is not 3.8 water-based by pH Dispersion liquid corrodes,

The comparative example 4

This comparative example has shown the redispersion ability and its corrodibility to ITO of exsiccant Baytron-P.

CH8000, (available from H.C.Starck, GmbH (German Leverkusen) is a kind of poly-(3,4-dioxy base ethylidene thiophene) of water-based to a kind of OLED level Baytron-P, and PEDT is with polystyrolsulfon acid (PSSA) preparation.The ratio of PEDT and PSSA and poly styrene sulfonate (PSS) is 1:20 (w/w).The pH scope of PEDT/PSS/PSSA is 1.

Exsiccant PEDT/PSS/PSSA is very easy to redispersion in water from aqueous liquid dispersion at ambient temperature.PEDT/PSS/PSSA is coated on the ITO as embodiment 9.Check that with X-photoelectricity spectroscope (XPS) top shows.Detect the result of indium and tin element, show that ITO is attacked by about 1 water-based PEDT/PSSA/PSS dispersion liquid by pH.

Embodiment 10-12

These embodiment have shown in multiple coating and have used

Embodiment 10

This embodiment has shown by making use

Laminated coating form thicker layer.

Prepare with the method identical with embodiment 7

Aqueous liquid dispersion is 800 rev/mins in speed of rotation and rotates coating three times down.Each rotation applies, and the film of casting all cures under 90 ℃ vacuum.Measure thickness with Tencor surface profile determinator, adopt the mean value of twice measurement.

Cure the 1st layer=99 nanometers in back.

Cure the 2nd layer of (total thickness)=203 nanometer in back.

Cure the 3rd layer of (total thickness)=322 nanometer in back.

Thickness data clearly illustrates each sedimentary thickness 100 nanometers of all having an appointment.In addition, data also show exsiccant Film is not redispersible in water.

Embodiment 11

This embodiment has shown in the OLED that has two buffer layers and has used

Wherein Contact with ito anode.

Using two water-based PEDT dispersion liquids to make up double-buffering layer uses for luminous test.One is the CH8000 (lot# KIM4952) that comparative example 4 describes, and another is that embodiment 7 introduces Cleaning is that 100-150 nano-ITO area is glass/ITO substrate (30mm * 30mm), then use oxygen plasma treatment of 15mm * 20mm for the ITO thickness of illuminating.Earlier will

Aqueous liquid dispersion rotation is coated on the ITO/ glass substrate, then cures 30 minutes under vacuum, 90 ℃.Double-deck total thickness is 86 nanometers.The double-layer bumper layer is then used xylene solution (1.2%w/w) top coating of BP-79 (DowChemica1, polymkeric substance turns blue).The thickness of BP-79 layer is 70nm.The BP-79 layer then with LiF, Ca, uses aluminium 1 * 10 at last ^-6Holder vacuum deposit, deposit thickness separately is followed successively by 2 nanometers, 20 nanometers and 500 nanometers.The initial efficient of the equipment for preparing from bilayer structure is 2.9-3.5Cd/A, and initial operating voltage is the 3.8-3.9 volt.The transformation period of equipment is 307 hours under the room temperature.

This shows and can use

Passivation layer as ITO.

Embodiment 12

This embodiment has shown in the OLED that has two buffer layers and has used

Wherein

Contact with the EL layer.

CH8000 (Lot#KIM4952) rotation is coated on the embodiment 11 described ITO/ glass substrate, follows on the aerial hot plate and under 200 ℃, cured 3 minutes.Layer thickness is 85 nanometers.The CH8000 layer is use then

Top coating was then cured under 90 ℃ vacuum 30 minutes.

The thickness of layer is 21nm.Double-buffering layer uses xylene solution (1.2%w/w) (Dow Chemical, the blue light-emitting polymkeric substance) top of BP-79 to be coated with then.The thickness of BP-79 layer is 70nm.The BP-79 layer is used LiF then, and Ca uses aluminium 1 * 10 at last ^-6Vapour deposition under the holder vacuum, its that obtains thickness separately is 2nm, 20nm and 500nm.By the initial efficient of the equipment of bilayer structure thing preparation is 2.5 to 3.1Cd/A, and initial operating voltage is 4.1 to 4.2 volts.The equipment transformation period at room temperature is 54 hours.This is to similar with the life-span of CH8000 preparation separately, and is more much lower than the 11 described equipment transformation period of embodiment.Relatively show

The deactivation function that contacts with the ITO substrate.

Embodiment 13

This embodiment has shown usefulness

Buffer layer and green light polymkeric substance can improve the operation lifetime of OLED equipment.

Be prepared as follows OLED equipment: the 30mm * 30mm substrate of glass with 15mm * 20mmITO area cleans with solvent and oxygen plasma.The thickness of ITO layer is 100-150nm.Water-based

Dispersion liquid is rotated in air and is coated on the ITO/ substrate of glass, cures 30 minutes under vacuum, 90 ℃.The exsiccant film thickness is the 50-100 nanometer.These substrates are transferred in the dry box that is full of nitrogen then, and wherein the concentration of oxygen G﹠W is about 1ppm.With luminescence polymer, DOWGreen K2 (Dow Chemical Co., U.S. Miami) rotation is coated to

The top of layer.DOW K2 solution is about 1% solid in xylene solvent.Film was cured under 130 ℃ 5 minutes.The thickness of K2 layer is about 75 nanometers.These substrates are transferred in the hot vaporizer then, about 1 * 10 ^-6The vacuum deposit negative electrode of holder (torr).Negative electrode is made of the Ba of about 5nm and about 0.5 micron Al following closely.Take out these equipment at last from the exsiccant box, test operation sealed before the life-span in environmental chamber.Operation lifetime test condition to these indicating meters is: initial brightness is 200cd/m ², stablize direct current, probe temperature is 80 ℃ (in order to accelerate process of the test).

Test-results as shown in Figure 5.Have

The predicted life of indicating meter approximately be more than 10 times of indicating meter that have PEDT/PSSA.Initial operating voltage ratio

Low～10%.Voltage advances the speed low about 25% in addition.

Embodiment 14

This embodiment shows use

The buffer layer and the polymkeric substance that glows improve the operation lifetime of OLED equipment.

Be prepared as follows OLED equipment: the 30mm * 30mm substrate of glass with 15mm * 20mmITO area cleans with solvent and oxygen plasma.The thickness of ITO layer is 100-150nm.With water-based

Dispersion liquid rotates in air and is coated on the ITO/ substrate of glass, cures 30 minutes under vacuum, 90 ℃.The exsiccant film thickness is the 50-100 nanometer.Then these substrates are transferred in the dry box that is full of nitrogen, wherein the concentration of oxygen G﹠W is about 1ppm.With luminescence polymer, AEF2157 (Covion GmbH, Frankfurt, Germany) rotation is coated to

The top of layer.AEF2157 solution is about 1% solid in xylene solvent.Film was cured under 130 ℃ 5 minutes.The thickness that AEF is 2157 layers is about 75 nanometers.Then these substrates are transferred in the hot vaporizer, about 1 * 10 ^-6The vacuum deposit anode of holder.Anode by the Ba of about 5nm, be that about 0.5 micron Al constitutes then.Take out these equipment at last from the exsiccant box, test operation sealed before the life-span in environmental chamber.Operation lifetime test condition to these indicating meters is: initial brightness is 170cd/m ², stablize direct current, test temperature is 80 ℃ (in order to accelerate process of the test).

Test-results as shown in Figure 6.Have

The predicted life of indicating meter for approximately being more than 4 times of indicating meter that have PEDT/PSSA.Initial operating voltage ratio

Low～20%.Voltage is advanced the speed and is reduced more than 3 times in addition.

Embodiment 15

This embodiment shows use Buffer layer and blue light-emitting polymkeric substance improve the operation lifetime of OLED equipment.

Be prepared as follows OLED equipment: the 30mm * 30mm substrate of glass with 15mm * 20mmITO area cleans with solvent and oxygen plasma.The thickness of ITO layer is 100-150nm.Water-based

Dispersion liquid is rotated in air and is coated on the ITO/ substrate of glass, cures 30 minutes under vacuum, 90 ℃.The exsiccant film thickness is the 50-100 nanometer.These substrates are transferred in the dry box of filling nitrogen then, and the level of its oxygen G﹠W is about 1ppm.With luminescence polymer, SCB-11 (Dow Chemical Co., U.S. Miami), rotation is coated to

The top of layer.SCB-11 solution is about 1% solid in xylene solvent.Film was cured under 130 ℃ 5 minutes.The thickness of SCB-11 layer is about 75 nanometers.These substrates are transferred in the hot vaporizer then, about 1 * 10 ^-6The vacuum deposit anode of holder.Anode by the LiF of about 2nm, then be the Ca of 20nm, be that about 0.5 micron Al constitutes then.Take out these equipment at last from the exsiccant box, test operation sealed before the life-span in environmental chamber.Operation lifetime test condition to these indicating meters is: initial brightness is 170cd/m ², stablize direct current, test temperature is 80 ℃ (in order to accelerate process of the test).

Test-results as shown in Figure 7.For having

The predicted life of indicating meter is to be more than 10 times of indicating meter that have PEDT/PSSA approximately.Initial operating voltage ratio

Low～20%.Voltage is advanced the speed and is reduced greater than 6 times in addition.

Embodiment 16-21

These embodiment have shown the effect of pH to various PEDT buffer layers.

Embodiment 16

This embodiment has shown Preparation.

Be the aqueous colloidal dispersion liquid of 12.5% (w/w), its EW is 1050, uses the similarity method of embodiment 9 in the United States Patent (USP) 6,150,426 to prepare.

With 150.90 gram (17.25 mmoles

Monomeric unit) the hydro-colloid dispersion liquid of (1050 EW) (12.%, w/w) and 235.11 the gram deionized waters pour 500 milliliters into

In the Plastic Bottle, it was rolled about 2 hours.Then the colloidal dispersion of dilution is transferred in 500 milliliters of three neck round-bottomed flasks that have an overcoat.Because loss paucidisperse liquid has only 146.18 grams in shifting

Be transferred, the phase group has 16.71 mmoles in reaction flask Elder generation's deionized water dissolving 0.0339 gram ferric sulfate hydrate (97%, Aldrich cat.#30,771-8) ad pond om 3.285 grams prepare stock solution.(Fluka cat.#71899) puts into reaction flask, stirs the mixture simultaneously then 1.50 gram (0.0315 mmole) ferrum sulfuricum oxydatum solutums and 1.76 to be restrained (7.392 mmole) Sodium Persulfates.Mixture is put into stirred 5 minutes, add 0.647 milliliter of (6.071 mmole) Baytron-M again, stir simultaneously.Polyreaction is carried out temperature being controlled under about 20 ℃ by circulating liquid.The liquid of 5 minutes post-polymerizations becomes blueness.As embodiment 7, by adding 20.99 grams S100 and 20.44 grams

MP62WS is termination reaction after 3.2 hours.Before use, two kinds of resins are used deionized water wash respectively earlier, do not have color in water.Plastic resin treatment 21 hours.The soup compound of gained is then by the suction of Whatman# 54 filter paper.It is quite easy to filter.Percent solids based on the polymeric component that adds is about 4.89% (w/w).

At 255.6 gram PEDT/ The middle deionized water ad pond om that adds is 480.8 grams, obtains 2.6% solid (w/w).Use that (315pH/ ionometer measuring device USA) records the water-based PEDT/ of dilution for Corning, New York from Corning Company

PH be 3.9.

Embodiment 17

This embodiment shows that preparation pH is 2.2 PEDT/

The preparation of dispersion liquid.

Rare PEDT/ with embodiment 16 preparations

Make parent material.(Aldrich Cat.#43,660-7), a kind of strongly basic anion exchange resin allows it stir 1.2 hours to add 3.07 gram Dowex550A resins.

At first wash Dowex 550A with deionized water before use and to water, do not have color.Filtering mixt adds 3.0 gram Amberlyst 15 (Aldrich Cat#21,639,9, proton Zeo-karb) in filtrate, allow it stir 45 minutes, and filter.Add the fresh Amberlyst of 3.0 grams in the filtrate and allow it stir 15 hours, and filtration is used for the OLED test.Before the use, Amberlyst15 spends sub-water washing earlier for several times.Record use

The pH of the Amberlyst 15 that handles is.

Embodiment 18

This embodiment has shown that preparation pH is 4.3

Dispersion liquid.

Prepare a collection of with the method identical with embodiment 16

With 45.05 gram deionizations the prepared dispersion liquid of 61.02 grams is diluted to 2.8% (w/w).The pH of the dispersion liquid of dilution is

Embodiment 19

This embodiment shows that preparation pH is 7.0

Dispersion liquid.

As described belowly neutralize with lithium ion

Dispersion liquid.This is the method for two steps: at first remove the metal remained ion with proton by ion-exchange; Use second ion-exchanger to exchange these protons then with lithium ion.This makes the purity of dispersion liquid very high.

(Aldrich Cat.#43,660-7), a kind of strongly basic anion exchange resin Processing Example 16 is described rare at first to use 5.13g Dowex 550A resin

Stirred then 2 hours.Use deionized water wash Dowex 550A colourless to the water before use.Filtering mixt, filtrate is handled with 4.13 gram Amberlyst 15 (Aldrich Cat#21,639,9, proton Zeo-karb), stirs 10 hours, and filters.Add the fresh Amberlyst 15 of 3.14 grams then, stirred 1.5 hours.Filter dispersion liquid at last.

With 1.99 grams, 2.33 grams, 2.06 grams, 2.08 grams and 2.00 restrain the lithium salts of Amberlyst 15 and handle 37.82 gram tart then At the gap filtering mixt of changing each new Amberlyst 15 lithium salts.Between each the filtration, also to stir the mixture, to total time of plastic resin treatment be 7 hours.Processed

PH be 7.0.

Embodiment 20

This embodiment shows that using sodium salt to prepare pH is 7.2

Dispersion liquid.

Now describe and use the sodium ion neutral

Dispersion liquid.Parent material is the lithium ion dispersion liquid that embodiment 16 discloses.It is as described below with sodium ion exchange lithium ion further handling.This has obtained highly purified dispersion liquid.

Embodiment 16 is described rare At first with 2.76 grams, 3.57 restrain, 3.55 grams and 3.25 grams

S100 handles..Filtering mixt between the lithium salts that substitutes each fresh Amberlyst 15.Between each filters, also stir the mixture, to total time of plastic resin treatment be 7 hours.Processed

PH be 7.2.

The comparative example 5

This comparative example has described the PEDT/PSSA dispersion liquid of preparation pH value through overregulating.

Comparative sample 5-A

The pH of PEDT/PSSA (A14083, a kind of Baytron-P of OLED level, from H.C.Starck GmbH, German Leverkusen) is 1.8.

Comparative sample 5-B

In 24 hours, in the 58.9 deionized A14083 of gram (available from H.C.Starck, as deionized AI4083), add the lithium salts that total amount is the Amberlyst 15 of 10 grams.Stir the mixture in the whole period.Filtering mixt, the pH that collects the filtrate that obtains is 3.2.

Comparative sample 5-C

In about 18 hours, in the deionized AI4083 of 58.18 grams, add the barium salt that total amount is the Amberlyst 15 of 14 grams.Stir the mixture in the whole period, filtering mixt, the pH that collects the filtrate that obtains is 3.4.

Comparative sample 5-D

Making does not have the deionization of sodium A14083, is converted into tertiary butyl ammonium salt available from H.C.Starck GmbH.In 20 hours, in 50.96 gram deionization A14083, add the tertiary butyl ammonium salt that total amount is the Amberlyst15 of about 9 grams.In the whole period mixture is stirred, filtering mixt, the pH that collects the filtrate that obtains is 4.3.

Similarly, sample A14083 handles with lithium and cesium ion exchange resin, obtains two kinds of samples of series in addition, and its pH value is greater than 1.8.

Embodiment 21

This embodiment has shown the performance of the OLED that uses the buffer layer preparation that the dispersion liquid by embodiment 16-21 and comparative example 5 prepares.

Prepare equipment with similarity method with embodiment 6 descriptions.

Use following EL polymkeric substance:

Title polymer type manufacturers

Super Yellow PPV Covion

Blue BP79 gathers fluorenes Dow

Green K2 gathers fluorenes Dow

AEF 2198 poly-spiral shell Covion

Wherein " poly-spiral shell " refers to polymerization spiral shell-two fluorenes.

Fig. 8 (a) has shown the original device performance of the OLED that contains the PEDT/PSSA buffer layer that pH regulated already to Fig. 8 (c).Be clear that, the pH of Baytron-P be increased to the performance of OLED equipment is obviously degenerated.Fig. 8 (a) and 8 (b) with two kinds of similar products but different Baytron-P A1 4071 and the Baytron-P 4083 of electric conductivity compare.They all use the sodium exchange resin to carry out pH regulator.Fig. 8 (c) has shown respectively that with 8 (d) lithium with the cesium ion exchange resin identical phenomenon can take place.

Fig. 9 (a) has shown to 9 (c) and has contained that pH regulated already

The original device performance of the OLED of buffer layer.Unlike the equipment that contains PEDT/PSSA, these equipment can be not that the neutral buffer layer is degraded by pH.

For the evaluation operation life-span, obtaining initial brightness with the galvanic current operating equipment is 200cd/m ², in 80 ℃ baking oven, place to accelerate their degraded.The change of monitoring equipment on its light output and operating voltage constantly.Operation lifetime is defined as brightness and drops to its initial value half (promptly drops to 100cd/m ²) time time.The result is as shown in table 3 below.

The operation lifetime of table 3 equipment

^*Indication equipment does not have luminous.

Be clear that, PEDT/PSSA equipment only in very narrow pH scope (pH＜about 2.5) the good life-span is arranged, and

Equipment (pH is 1.8-7.0 at least) in very wide pH scope can be operated.

Embodiment 22

This embodiment shows

Not etching ITO contactant.

Be prepared as follows ITO test substrate: with about

The substrate of glass that ITO applies derives from AppliedFilms Inc..The ITO layer is etched into banding pattern, and width is 300 microns.These bands extend to whole degree of depth of ITO layer, and the substrate glasses between the band can be able to come out as a result.These bands have clearly edge.Use vertical repeatability for about

Tencor surface profile determinator measure the height of ITO band.At room temperature, sample is immersed in reaches among CH8000 or the PEDOT:NAFION for several times.Before measuring ITO thickness, sample is immersed in deionized water and ashing 15 minutes in plasma body, to remove any organic residue.Under each situation, measure ITO thickness like this: independently measure 4 bands in the substrate at two, measure 8 data altogether at every turn.As preparation as described in the embodiment 7

Solution, its pH are 3.8.PEDT/PSSA solution is Baytron CH 8000, and pH is approximately 1.The result as shown in figure 10.After 24 hours, ITO thickness reduces about 1% at the PEDT/PSSA dipping in attention.This can be clear that in the optical interference color of ITO film.In device fabrication, ITO is exposed among the liquid PEDT/PSSA, generally continue the only several seconds.But moisture residual in the PEDT/PSSA film can for good and all corrode ITO from start to finish in the life-span of equipment.ITO layer dissolving 1% can produce the indium and the tin ion of high density in the PEDT/PSSA layer.

Embodiment 23

This embodiment has shown water-based

The consistency of dispersion liquid and PEDT/PSSA.

Select PEDT/PSSA (Baytron-P, rank Al4083) test and water-based from embodiment 16

Consistency.Preparation is from 95:5's AI4083 to 5:

All aqueous mixtures of A14083.All aqueous mixtures are found to be uniformly, are not separated.These mixtures can be used to prepare OLED and other electronically active equipment.

Embodiment 24

This embodiment shows and uses common cathodic metal and the common panchromatic OLED indicating meter of buffer layer polymer manufacture, and increases its performance.

Be prepared as follows OLED equipment: have the 30mm * 30mm substrate of glass of 15mm * 20mmITO area with solvent and oxygen plasma cleaning.The thickness of ITO layer is the 100-150 nanometer.(embodiment 16 prepares with aqueous buffer in air

Or Baytron-P CH8000) dispersion liquid rotation is coated on the ITO/ substrate of glass, and cures 30 minutes under vacuum, 90 ℃.The exsiccant film thickness is the 50-100 nanometer.These substrates are transferred in the dry box that fills nitrogen then, and the concentration of its oxygen G﹠W is about 1ppm.(redness: COVION AEF 2198, or green: DOW K2, or blueness: COVION HS 670) rotation is coated to the top of buffer layer with light generation polymkeric substance.Light generation polymers soln is in ordinary organic solvents, as about 1% solid in toluene or the dimethylbenzene.In the exsiccant box, dry by the fire the 2nd time then: film was cured 5 minutes.The thickness of light genetic horizon is about 75 nanometers.Then these substrates are transferred in the hot vaporizer, about 1 * 10 ^-6The vacuum deposit negative electrode of holder.Negative electrode is one of following composition: (i) about 5nm Ba is about 0.5 micron Al then, or the (ii) Ca of about 5nm, is about 0.5 micron Al then, or the (iii) LiF of about 5nm, is the Ca of about 20nm then, is about 0.5 micron Al then.At last, these equipment are taken out from the exsiccant box, and test operation sealed before the life-span in environmental chamber.The operation lifetime test condition of these indicating meters is: initial brightness 200cd/m ², stablize direct current, test temperature is 80 ℃ (in order to accelerate process of the test).The result is as shown in table 4 below:

Table 4

Though the present invention is described in detail with reference to its specific embodiment already, should be understood that to modify and change to fall within the spirit and scope of claims.

Embodiment 25

This embodiment has shown with being total to the preparation of dispersive liquid in middle preparation

Dispersion liquid.

Be 12% (w/w) aqueous colloidal dispersion liquid, its EW is 1050, uses and United States Patent (USP) 6,150, and the similar process of 426 embodiment 9 prepares.

With 95.41 gram (10.89 mmoles

Monomeric unit)

(1050EW) (12.0%, w/w), (Aldrichcat#49 619-7) pours in the three neck round-bottomed flasks of 500 milliliters of band overcoats the aqueous colloidal dispersion liquid for 185.12 gram deionized waters and 14.49 gram 1-propyl alcohol.Mixture was stirred 10 minutes.Stir about is 1 hour before adding ferric sulfate and ammonium persulphate.By with deionized water dissolving 0.0722 gram ferric sulfate hydrate (97%, Aldrich cat.#30,771-8) ad pond om 21.44 grams at first prepare the stock solution of ferric sulfate.Then 4.47 gram (0.0452 mmole) ferric sulfate and 1.65 gram (7.23 mmole) ammonium persulphates are placed in the reaction flask, stir the mixture simultaneously.In final polyreaction liquid, the ratio of water and 1-propyl alcohol is 9 to 5.Carry out polyreaction controlling to by circulating liquid under about 20 ℃, at once initial the changes indigo plant of the liquid of polyreaction.After 17 hours, by adding 13.89 grams S100 and 13.89 grams

MP62W comes termination reaction.At first use two kinds of resins of deionized water wash before the use, in water colourless till.Plastic resin treatment has been carried out 5 hours.The soup compound of gained is then by Whatman #54 filter paper suction filtration.It can pass through filter paper soon.According to the polymeric component that adds, solid % is about 4.5% (w/w).

Use 315pH/ ionometer measuring device to record water-based from Corning Company (Corning, USA New York)

PH be 5.3.20.6 ℃ of surface tension that record with FAT10TensiometerModel1000IUD (KSV Instruments LTD, Finland) down is 41.9 milli Newton/meter.Surface tension is than the water-based PEDOT/Nafion that not being divided into diffusing liquid preparation shown in the embodiment 7 ^*Much lower (about 73mN/m).The filterability of test dispersion liquid.(MilliporeMillex-HV 25mm Cat.#SLHVR25KS) and does not change strainer with the HV strainer of 40 milliliters of dispersion liquids by 0.45 micron.From the outward appearance of liquid-flow also notice its viscosity be lower than significantly same solid %'s but be not divided into the liquid that looses viscosity.

Claims (11)

1. a composition comprises poly-dioxy base thiophene and at least a aqueous liquid dispersion that forms the colloidal polymeric acid in the aqueous medium that is dispersed in, and the molecular weight ranges of described polymeric acid is 10,000 to 4,000,000.

2. composition according to claim 1, wherein said poly-dioxy base thiophene has the following formula structure:

Wherein:

R ₁And R ₁' be selected from hydrogen independently of one another and the alkyl of 1-4 carbon atom is arranged,

Or R ₁And R ₁' the alkylidene chain that is joined together to form 1-4 carbon atom, can be randomly had the alkyl or aryl of 1-12 carbon atom to replace, or 1, the 2-cyclohexylidene,

N is greater than 6.

3. composition according to claim 1 and 2 wherein forms the colloidal polymeric acid and is selected from polymerization sulfonic acid, polymerization of carboxylic acid or polymer phosphate, or their combination.

4. composition according to claim 3, wherein said polymerization of carboxylic acid is a polymeric acrylic acid.

5. composition according to claim 1 and 2, wherein forming the colloidal polymeric acid is the perfluorosulfonic acid polymkeric substance, poly-dioxy base thiophene is poly-(3,4-ethylidene dioxy base thiophene).

6. one kind prepares poly-dioxy base thiophene and at least a method that forms the aqueous liquid dispersion of colloidal polymeric acid in the aqueous medium that is dispersed in of comprising as claimed in claim 1, comprising:

(a) provide the uniform aqueous mixture of water and dioxy base thiophene;

(b) provide the aqueous liquid dispersion of polymeric acid;

(c) described dioxy base thiophene mixture is mixed with the aqueous liquid dispersion that forms the colloidal polymeric acid;

(d) oxygenant and catalyzer are mixed with any reinforced order with dispersion liquid in the step (c).

7. method according to claim 6, wherein this method further comprises the poly-dioxy base thiophene dispersion liquid of described water-based is contacted for the ion exchange resin of Zeo-karb, anionite-exchange resin or its combination with at least a.

8. method according to claim 6, wherein said oxygenant are selected from Sodium Persulfate, Potassium Persulphate, ammonium persulphate or its combination;

Described catalyzer is selected from ferric sulfate, iron(ic) chloride or its mixture;

Described step (c) is carried out in the presence of the dispersion aids that is selected from ether, alcohol, alcohol ether, cyclic ethers, ketone, nitrile, sulfoxide and their combination;

This method further comprises makes described dispersion liquid contact with ion exchange resin, described ion exchange resin is selected from the styrene diethylene benzene copoly mer of sulfonic acid salinization, sulfonic acid, the crosslinked styrene polymer of sulfonic acid salinization, benzene-formaldehyde sulfonic acid, carboxylic acid, phosphoric acid, tertiary amine, quaternary ammonium anion resin and its mixture.

9. method according to claim 8, wherein said carboxylic acid is a vinylformic acid.

10. organic based device comprises the organic layer that one deck is at least made by the arbitrary described composition of claim 1-5.

11. equipment according to claim 10, wherein equipment is optical flame detector, photoswitch, photovaristor, phototransistor, phototube, IR detector, barrier-layer cell, solar cell, photodiode, biosensor, light emitting diode indicator or diode laser.

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