CN1194428C - High resistance polyaniline useful in high efficiency pixellated polymer electronic displays - Google Patents
High resistance polyaniline useful in high efficiency pixellated polymer electronic displays Download PDFInfo
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- CN1194428C CN1194428C CNB008166463A CN00816646A CN1194428C CN 1194428 C CN1194428 C CN 1194428C CN B008166463 A CNB008166463 A CN B008166463A CN 00816646 A CN00816646 A CN 00816646A CN 1194428 C CN1194428 C CN 1194428C
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/17—Passive-matrix OLED displays
Abstract
A film including polyaniline in the emeraldine salt form (PANI) and poly(2-acrylamido-2 -methyl-1-propanesulfonic acid) (PAAMPSA) as a counterion and optionally a water-soluble host polymer, the film is useful in an electronic device such as pixellated displays.
Description
FIELD OF THE INVENTION
The present invention relates to be used for the emerald green imonium salt of the high specific resistance type polyaniline preparation of efficient picture point polymer electronics (as emission display).The high specific resistance layer provides good hole to inject, and prevents short circuit current, improves device lifetime, avoids electric current leakage between picture point.
The background of invention
The light-emitting diode made from the conjugation organic polymer layers (LEDs) is owing to the potentiality that are applied in the Display Technique receive publicity.
In organic polymer-based LEDs field, reported and used higher work function metal as anode; Described high work content anode is used for the π that the semiconductor light emitting polymer fills with other method-can be with is injected in the hole.Low work function metal is suitable as cathode material; Described low work function cathode is used for electronics is injected the π * that the semiconductor light emitting polymer vacates with other method-can be with.Anode injected holes and negative electrode injected electrons in active layer emissivity in conjunction with and launch light.For the criterion of electrode adaptability by I.D.ParKer, J.Appl.Phys, 75,1656 (1994) describe in detail.
As the suitable higher work function metal of anode is indium/tin-oxide transparent conductive film (H.Burroughs, D.D.C.Boadley, A.R.Brown, R.N.Marks, K.Mackay, R.H.Friend, P.L.Burns and A.B.Holmer, Natnre 347,539 (1990); Braun and A.J.Heeger Appl Phys.Lett, 58,1982 (1991)).
On the other hand, as in (G.Gustafsson, Y.Cao, G.M.Treacy, F.Klavetter, N.Colaneri and A.J.Heeger, Nature, 357,477 (992); Y.Yang and A.J.Heeger, Appl.Phys.Lett 64,1245 (1994) and United States Patent (USP) 5,723,873; Y.Yang, E.westerweele, C.Zhang, P.Smith and H.J.Heeger, J.Appl.Phys.77,694 (1995); J.Gao, A.J.Heeger, J.Y.Lee and C.Y Kim, Synth.met., 82,221 (1996) and Y.cao, G.Yu, C.Zhang, R.Menon and A.J.Heeger, Appl.Phys.Lett, 70, confirmed in 3191 (1997), can be used conducting polymer thin film, (seen P.Snuth as polyaniline film, A.J.Heeger, Y.Cao, J.Chiang and A.Andreatta, United States Patent (USP) 5,470,505).Indium/tin oxide film is preferably with the emerald green imonium salt type polyaniline film (PANI (ES)) with suitable gegenion, because as transparency electrode, the two can both make light of LED emission be penetrated by device with the level that is suitable for.C.Zhang, G.Yu and Y.Cao (United States Patent (USP) 5,798,170) directly use one deck PANI (ES) or contain the blend of PANI (ES) between ITO and light-emitting polymer layer, prove that the polymer LED s with two-layer electrode has long working life.
Although use PANI (ES) that superiority (referring to United States Patent (USP) 5,798,170) is arranged in polymer LED s two-layer electrode, typical PANI (ES) low resistivity hinders the application of PANI (ES) in the picture point display.In order to be used in the picture point display, PANI (ES) layer should be that high sheet resistor is arranged, otherwise transverse conductance can cause between the adjacent picture point cross interference takes place that electric current leaks and obviously reduces electric energy efficiency between the picture point that is produced, and has limited exploration on display resolution ratio and definition.
Improve with the minimizing film thickness that the PANI sheet is worthless than resistance in the two-layer electrode, because thin film is because the generation short circuit reduces the rate of finished products of its making.This point confirms clearly that in Fig. 1 this figure is depicted as the relation between " leakage " ratio of picture point in 96 * 64 dot matrix and the poly-blended thing layer thickness of PANI (ES).Therefore, for fear of short circuit, must used thickness be about thicker PANI (ES) layer of 200nm.
Used thickness 200nm or thicker film, the ratio resistance of PANI (ES) layer should be more than or equal to 10
4Ohm-cm, electric current leaks between cross interference and image point to avoid.Than resistance value greater than 10
5Best.Even 10
5Under the ohm-cm, still have residual electric current leakage and cause unit efficiency to decrease.Therefore be approximately 10 than resistance value
6Ohm-cm is then better.Than resistance value greater than 10
7Ohm-cm will cause injection/resilient coating to produce tangible voltage drop, and this point should be avoided.In order to obtain than resistance, must change the prescription of PANI (ES) at the high specific resistance PANI of desired scope (ES) material.
Therefore, need high specific resistance PANI (ES) preparation that is applicable to high efficiency picture point formula polymer emission display.
Summary of the invention
The present invention relates to a kind of PANI-PAAMPSA film, it comprises that (2-acrylamido-2-methyl isophthalic acid-propyl sulfonic acid (PAAMPSA) is as the emerald green imonium salt type polyaniline (PANI) of gegenion, and the method for casting film-forming to gather.In a suitable instantiation, the PANI-PAAMPSA film is the blend of PANI-PAAMPSA and at least a water-soluble base polymer.The invention still further relates to a kind of electronic installation, it comprises the PANI-PAAMPSA film.The invention still further relates to a kind of light-emitting diode of the PANI-PAAMPSA of including film in addition.In a suitable instantiation, film of the present invention is positioned in the position adjacent to high work function electrode.In another suitable instantiation, in the light emitting polymer device, the PANI-PAAMPSA layer is positioned between luminescent layer and the high work function electrode.
Terminology used here " adjacent " be meant than with the distance of low work function electrode, the more close high work function electrode of PANI-PAAMPSA layer, and between PANI-PAMPSA layer and high work function electrode, have and maybe may not have other thin layers to exist.Used here term " between " also do not get rid of except that the PANI-PAAMPSA layer, other component layer are present in the possibility between high work function electrode and the light emitting polymer in addition.
Use can be replaced in term used herein " conductivity " " bulk conductivity ", and the unit of its numerical value is Siemens/cm (s/cm).In addition, term " surface ratio resistance " and " sheet resistor " replace mutually again, refer to resistance value.For specified material, it is the function of sheet thickness, and the unit of the numerical value that provides is per 100 square feet of ohms (ohms/100 square feet).The also replaceable use of term " body is than resistance " and " than resistance " refers to than resistance, and it is the fundamental characteristics of specifying material (promptly not changing with the size of material), and the unit of the numerical value that is provided is ohm-cm (ohm-cm).Than resistance value is the inverse of conductivity.
The accompanying drawing summary
Fig. 1 is the graph of a relation of " leakage image point " (in 96 * 64 dot matrix) ratio and known PANI (ES) layer thickness.
Fig. 2 is a component layer schematic diagram passive addressed, picture point formula polymer LED display.
Fig. 3 shows the conductivity of the poly-blended thing of PANI-PAAMPSA and the graph of a relation of PSNI-PAAMPSA content.
Fig. 4 shows luminous efficiency and the external quantum efficiency with the made device of PANI-PAAMPSA layer.
Fig. 5 shows that the device of band PANI-PAAMPSA layer is at 85 ℃ of quality decline figure that work and induce down.
Fig. 6 shows the quality decline figure that at room temperature induces with the device work of PANI-PAAMPSA layer.
The quality decline figure that Fig. 7 induces for the device work that shows band PANI-PAAMPSA blend (embodiment 9) layer; Data are obtained down at 70 ℃ by this device.
Fig. 8 is the photo of three passive addressed displays (96 * 64).These display everyways are the same, just Fig. 8 a display has low resistance PEDT layer (being about 200 ohm-cms than resistance), Fig. 8 b display has the poly-blended thing layer of PANI-PAAMPSA (than about 4000 ohm-cms of resistance), and Fig. 8 c display has the poly-blended thing layer of high electrical resistance PANI-PAAMPSA (being about 50,000 ohm-cms than resistance).
The detailed description of better example
The present invention is the prescription with the emerald green imonium salt of polyaniline [PANI (ES)], and particularly the PANI-PAAMPSA prescription is developed as the basis.This prescription obtains being used for high specific resistance PANI (ES) film of high efficiency electronic installation (as image point polymer emission display).In addition, having developed a kind of method is used for being deposited on the substrate (for example form the ITO-glass substrate of pattern in advance, or form the ITO-plastic substrate of pattern in advance) from the transparent membrane of aqueous dispersions with high specific resistance PANI (ES).The application of the invention high specific resistance PANI (ES) layer can not need the pattern of registration PANI (ES) layer just can be arranged the long life-span in the high information quantity display.
Though prescription of the present invention can be applicable to non-picture point formula electronic installation and picture point formula electronic installation, is applied in picture point formula device especially, as the most superior in the electroluminescent display.
Unit configuration
The polymer emitter 10 of Fig. 2 for having 156 (12 * 13) picture point.As shown in Figure 2, each picture point of device 10 comprises 1 electronics and injects (electrode) contact 20, and this contact is made by low work function metal, as an electrode on the emission film 30 that is deposited on glass or the polymer thin film substrate 40.Transparent conductive material layer 50 parts that substrate 40 usefulness have high work content (high ionization gesture) apply, as second (transparent) extraction electronics electrode (anode). Component layer 20,30,40,50th, common assembly (D.Braunand A.J.Heeger, Appl.Phys.Lett, 58,1982 (1991)) among the known polymer LEDs.According to the present invention, the layer 60 that contains high specific resistance PANI (ES) is inserted between emission layer 30 and the high work function electrode 50, and electrode 20 is electrically connected with contact mat 80, and electrode 50 is electrically connected with contact mat 82. Layer 20,30,40,50 and 60 usefulness one sealant 70 is isolated with environment.By applying electric current to the contact mat 80,82 that exposes sealant 70, light penetrates from device with the direction shown in the arrow 90.
PANI-PAAMPSA layer (60)
According to the present invention, layer 60 comprises and containing with poly-(2-acrylamido-2-methyl isophthalic acid-propyl sulfonic acid) the PANI-PAAMPSA film as the emerald green imonium salt type polyaniline of gegenion.
PANI-PAAMPSA complex compound of the present invention can be with the method preparation of any known formation PANI (ES) complex compound, the method described in for example following document: Y.Cao etc., Polymer, 30 (1989) 2305; With Steven P.Armes and Mahmoud Aldissi, J.Chem, Soc, Chem.Comman, 1989,88.In an instantiation that suits, aniline is dissolved in the suitable aniline solvent, then PAAMPSA is joined in the aniline that is dissolved in solvent, obtain being dissolved in the aniline-PAAMPSA salt of water.In case aniline is dissolved in the water fully, reactor can be positioned in the constant temperature bath with the conditioned reaction temperature.Though can adopt lower temperature, typical polymerization temperature can remain between 0 ℃-25 ℃, and lower temperature obtains the polyaniline of HMW, but the reaction time is longer.In solution, add strong oxidizer then with initiated polymerization.After the polymerization fully, the PANI-PAAMPSA emulsion is separated from reactant mixture by adding acetone.The PANI-PAAMPSA that obtains purifies with acetone precipitation by being scattered in the water again, and the secondary of purifying is at least removed unreacted benzene amine monomers and oxidant, and polymeric by-products, makes it to disappear from PANI-PAAMPSA.
Suitable aniline solvent is a water-soluble solvent, and desired response is not had adverse effect, and it comprises as water; The mixture of water and at least a water-soluble alcohol; The mixture of water and oxolane (THF); The mixture of water and dimethyl sulfoxide (DMSO) (DMSO); Water and N, the mixture of the mixture of N '-dimethyl formamide (DMF) or water and other solvents that can mix with water.
The oxidant that is suitable for being used for making the PANI-PAAMPSA complex compound comprises ammonium persulfate, potassium bichromate, iron chloride and hydrogen peroxide.
In a suitable instantiation, the aniline that is used to make the PANI-PAAMPSA complex compound is 2: 1 to 0.5: 1 to the weight ratio of PAAMPSA, and preferably aniline is about 1: 1 to the weight ratio of PAAMPSA.We find that along with the minimizing of aniline to the PAAMPSA weight ratio, the conductivity of PANI (ES) and dispersiveness also descend thereupon.
According to the amount and the type of other composition in the layer 60, layer 60 typical thickness range are from about 100 to about 2500 .
In a suitable instantiation, by the PANI-PAAMPSA blend is come the ratio resistance of key-course 60 in one or more water dispersibles and/or water miscible matrix polymer.Suitable matrix polymer is including, but not limited to following several: polyacrylamide (PAM), PAAMPSA, polyacrylic acid (PAA), poly-(styryl sulfonic acid) gathers (vinyl pyrrolidone) (PVPd), acrylamide copolymer, cellulose derivative, carboxy vinyl polymer, poly-(ethylene glycol), gather (oxirane) (PEO), polyvinyl alcohol (PVA), poly-(methoxy ethylene), polyamine, polynary imines, polyvinylpyridine, polysaccharide and dispersions of polyurethanes and their composition.
The amount of these matrix polymers formation blends or poly-blended thing depends on that final film is desirable than resistance value and processing Consideration in layer 60, comprises matrix polymer molecular weight and blend or the desirable viscosity of poly-blended thing.In a suitable instantiation, PANI in layer 60 (ES)-PAAMPSA complex compound is 1: 0.1 to 1: 9 to the weight ratio of matrix polymer.
When PANI-PAAMPSA and one or more matrix polymers formation blend, below method can be used to prepare blend or poly-blended thing: PANI (ES)-PAAMPSA and be dissolved in and become first solution in the suitable water-soluble solvent, matrix polymer is dissolved in becomes second solution in the suitable water-soluble solvent, in desirable ratio first, second solution is mixed into blend solution.
In the blend preparation technique, being used for the suitable water-soluble solvent of first and second solution can be identical with the aniline solvent or different, can be water for example, the mixture of water and at least a water-soluble alcohol, the mixture of water and tetrachloro furans (THF), the mixture of water and dimethyl sulfoxide (DMSO) (DMSO), water and N, the mixture of the mixture of N '-dimethyl formamide (DMF) or water and other solvents that can mix with water.In a suitable instantiation, PANI-PAAMPSA layer 60 is used in the non-picture point electronic installation, than resistance greater than 10
2Ohm-cm.In another suitable instantiation, layer 60 comprises the blend of PANI-PAAMPSA and at least a water-soluble or water dispersible matrix polymer, than resistance greater than 10
4Ohm-cm, more preferably 10
5Ohm-cm is better greater than 10
6Ohm-cm.The blend of this PANI-PAAMPSA or poly-blended thing are useful in the picture point electronic installation.
Although be not with pattern, can think that PANI-PAAMPSA film of the present invention also can have pattern in illustrated device 10 middle levels 60.
High work function electrode (50)
Other organic substance or inorganic material with the electric work letter that is similar to ITO can be used in the assembly 50, comprise for example IIA family (Be, Mg, Ca, Sr, Ba, Ra), other metals of IIIA family (B, Al, Ga, Tl) and the metal (C of IVA family, Si, Ge, Sn, hopcalite Pb).Replace the example of the suitable organic material of ITO to comprise polyaniline and poly-(3,4-ethylidene dioxy thiophene) (PEDT).
In the picture point el light emitting device, the sheet resistance of layer 50 is preferably lower than about 100 ohm/100 square feet, and layer 50 typical thickness scope are that 100 are to 2500 like this.
In illustrative instantiation, component layer 50 and 60 and substrate 40 (when existing) can be " transparent " or " translucent ", can allow these component layer of light transmission of sending like this." transparent " or " translucent " material is so a kind of material, can see through at least a portion and shine light on it, for example can see through at least 10%, preferably emitted light under the emission wavelength of at least 20% luminescent layer 30.In other instantiation (not shown), low work function electrode 20 is transparent or translucent, and assembly 40,50 and/or 60 is opaque.
Luminescent layer (30)
Layer 30 can comprise any luminous organic material, comprises polymer and/or mulecular luminescence material.
The material of making active layer in polymer LED has poly-(phenylethylene), PPV and PPV soluble derivative, for example poly-(2-methoxyl group-5-(2 '-ethyl-own oxygen base)-1,4-phenylethylene); MEH-PPV (a kind of bandwidth Eg is about the semi-conducting polymer of 2.1eV).This material is at United States Patent (USP) 5,189, more detailed description arranged in 136.Other polymer that are fit to comprise for example D.Braun, G.Gustatsson, D.McBranch and A.J.Heeger, J.Appl.Phys.72,564 (1992) described poly-(3-alkylthrophenes) and by M.Berggren, O.Inganas, G.Gustalsson, J.Rasmusson, M.R.Anderson, the described related derivatives of T.Hjertberg and O.Wennetrom; By G.Grem, G.Leditzlcy, B.Ullrich and G.Leising, described poly-(to phenylene) (Poly (para-phenylene)) of Adv.Mater 4,36 (1992) and by Z.Yang, I.Sokolik, F.E.Karas, Macromolecules, 26,1188 (1993) described its soluble derivatives; By I.D.Parker, Q.Pe and M.Marrocco, Appl.Phys, Lett, 65,1272 (1994) described poly quinolines.The blend of conjugation semi-conducting polymer in non-conjugated matrix polymer also can be used as the active layer among the polymer LED s, this point at C.Zhang, H.vonSeggern, K Pakbaz, B.Krsabel, H.W.Schmidt and A.J.Heeger, Synth.Met has in 62,35 (1994) illustrated.Also can use H.Nishino, G.Yu, T-A Chen, R.D.Rieke and H.J.Heeger, Synth, Met, 48,243 (1995) the described blends that comprise two kinds or multiple conjugated polymer.Conjugated copolymer is used for the electroluminescence purposes at A.Holmes, D.D.Bradley, and R.H.Friend, A.Kraft has illustrated in the United States Patent (USP) 5,401,827 of P.Burn and A.Brown.The general material that is used as active layer in polymer LED s has semiconductive conjugated polymer, particularly presents the conjugated polymer of luminescence generated by light, especially presents luminescence generated by light and is conjugated polymer solubility and that can be processed into homogeneous film by solution.
In another instantiation, luminescent layer 30 can comprise organic molecule, as anthracene, thiadiazoles derivative, and coumarin derivative, they all present electroluminescence.In addition, of the United States Patent (USP) 5,552,678 of Tang etc., oxine (8-hydroxyquinolate) and trivalent metal ion especially are widely used as the electroluminescence component with the formed complex compound of aluminium.Specifically, face-three (2-phenylpyridine) iridium can be used as active component (Burroughes and Thompson, Appl, Phys, Lett, 1999,75,4) in organic light emitting apparatus.When iridic compound is present in the matrix electric conducting material, performance the best.In the device that Thompson further reports, active layer is doping face-three [2-(4 ', 5 '-two fluorine-based benzene) pyridine-C '
2, N] and poly-(N-vinylcarbazole) (Polymer Preprints 2000,41 (1), 770) of iridium (III).
Low work function electrode (20)
The low work function metal that is suitable for as cathode material is alkaline-earth metal (as calcium, barium, strontium) and rare earth metal (as yttrium).In prior art (United States Patent (USP) 5,047,687; 5,059,862 and 5,408,109) alloy of known low work function metal also in is as alloy and lithium the alloy in aluminium of magnesium in silver.As confirm in the prior art (United States Patent (USP) 5,151,629,5,247,190,5,317,169 and J.Kido, H.Shionoya, K.Nagai, Appl PhysLett., 67 (1995) 2281) like that, the thickness range that electronics injects cathode layer is 200-5000 .As cathode layer thickness (United States Patent (USP) 5,512,654 of lower 200-500 are arranged preferably in order to obtain continuous (fully covering) film; J.C.Scott, J.H.KauLman, P.J.Brock, R.Di Pietro, J.Salem and J.A.Goitia, J.Appl.Phys, 79 (1996) 2745; I.D.Parker, H.H.Kim, Appl, Phys, Lett., 64 (1994) 1774).
Proposed to comprise that the electronics injection negative electrode of alkaline-earth metal (calcium, strontium, barium) superthin layer is used for high brightness, high efficiency polymer LED.The conventional cathode of being made greater than same metal (perhaps other the low work function metal) film of 200 by thickness that compares, the negative electrode of being made up of less than the ultra-thin alkaline-earth metal layer of 100 thickness has significant improvement the (Y.Cao and G.Yu PCT WO98/57381) to the stability and the working life of polymer LED.Y.Cao describes the electronics injection negative electrode that will comprise the metal oxide thin layer and is used for polymer LED in PCT WO 00/22683.
The application of the invention high specific resistance PANI (ES) layer can not need the pattern of registration PANI (ES) layer just can obtain long working life in the high information quantity display.
Although illustrative device 10 is described as suitable active display, but can think that PANI-PAAMPSA material of the present invention can also be applied to other electronic installations, comprise, optical sensor for example, photo-detector, microdischarge cavities, electric pumping polymer and organic laser instrument and organic and polymer FETs (field-effect transistor).
Contact mat (80,82)
Can use any electrode to be connected to the contact mat 80,82 of power supply (not showing), comprise for example gold (Au), silver (Ag), nickel (Ni), copper (Cn) or aluminium conducting metals such as (Al) display 10.
Preferably contact mat 80,82 has a summit (not shown), its outstanding thickness that is lower than the high work function electrode line 50 of layer gross thickness.
Manufacture method
Except that the PANI-PAAMPSA layer, each element of apparatus of the present invention can be made of methods known in the art, as solution casting, steam deposition, silk screen printing, contact print, dash coat, gasification, polymer precursor processing, melt etc., perhaps any combination of these methods.
PANI-PAAMPSA layer of the present invention can be made of any known casting technique, as flow of solution casting and drop curtain coating, and silk screen printing, contact print etc., the perhaps combination of any of these method, the aqueous solution or the aqueous liquid dispersion that contain the blend/poly-blended thing of PANI-PAAMPSA complex compound or at least a matrix polymer and PANI-PAAMPSA complex compound can be made with suitable solvent, the PANI-PAAMPSA solvent that is suitable for curtain coating processing is water miscible, comprise for example water, the mixture of water and water-soluble alcohol, the mixture of water and THF, the mixture of water and DMSO, the mixture of the solvent that the mixture of water and DMF or water and other can mix with water.Although be not necessary, can use the same aniline solvent that is used for making the PANI-PAAMPSA complex compound to come curtain coating processing PANI-PAAMPSA film.
As known in the art, film thickness is subjected to comprising the influence of viscosity, solids content and the chemical composition of the aqueous solution or aqueous dispersions.The typical viscosities scope be from 50 centipoises (cps) to 200cps, therefore, polymeric material (be PANI-PAAMPSA and as use at least a matrix polymer) is that 0.5% (w/w) is to 5% (w/w) with the weight ratio of solvent.Processing aid (as viscosity modifier) can be made an addition to and be used for carrying out in the aqueous dispersions/solution of curtain coating processing.
Curtain coating is preferably at room temperature carried out, though can use lower or higher temperature known in the art.
Subsequently can be from the aqueous solution or aqueous dispersions with film casting to a carrier (anode material thin layer for example, it randomly carrier band on glass, plastics, pottery or silicon chip, perhaps on the flexible carrier) on.
The present invention is by using the method that the anode that contains the PANI-PAAMPSA preparation provides the acquisition long service live that applies.
Unless otherwise indicated, all percentages are percetage by weight.
Embodiment
Use is similar to .Polymer such as Y.Cao., and the described method of 30 (1989) 2305 lists of references prepares PANI-PAAMPSA.More accurately as described below, promptly with poly-(2-acrylamido-2-methyl isophthalic acid-propyl sulfonic acid) (PAAMPSA) (W1 53201 provides for Aldrich, Milwaukee) replace the HCl in the list of references.
Emerald green imonium salt (ES) type can be verified by typical green.At first add 170ml water 30.5g (0.022mole) the 15%PAAMPSA aqueous solution (Aldrich system) is diluted to 2.3%.Under agitation 2.2g (0.022M) aniline is added in the PAAMPSA solution, under forcing stirring, slowly the solution of 2.01g (0.0088M) ammonium persulfate in 10ml water is added in aniline/PAAMPSA solution then.Stirred reaction mixture is 24 hours under the room temperature.In reactant mixture, add 1000ml acetone so that product P ANI-PAAMPSA precipitation.Most of acetone decant is come out, and then with the PANI-PAAMPSA sedimentation and filtration, the gumminess product that obtains is with acetone washing several, 40 ℃ of following vacuumizes 24 hours.
Present embodiment explanation PANI-PAAMPSA can directly synthesize.
In plastic bottle, 1 gram (1.0g) embodiment, 1 prepared PANI-PAAMPSA powder is mixed with the 100g deionized water.At room temperature mixture is rotated and stirred 48 hours.Then solution is filtered by 0.45 μ m polypropylene filter.Be mixed in the quantity of the PANI-PAAMPSA in the water by change, prepare the PANI-PAAMPSA aqueous solution/dispersion liquid of variable concentrations set by step.
Present embodiment explanation PANI-PAAMPSA can dissolution also filter by 0.45 μ m filter in water subsequently.
Become the PANI-PAAMPSA film by 1% (w/w) aqueous solution/dispersion droplets (drop) curtain coating.Recording film thickness with surface profile analyzer (Alpha-step 500, KLA-Tencor, San Jose CA95134 system) is 650nm.Obtain PANI-PAAMPSA film wide-angle X-ray diffraction figure (WAXD) with standard x light instrument.Can find out that by this diffraction pattern no characteristic diffraction peak exists, and shows that film is amorphous.
The present embodiment explanation is unbodied (degree of crystallinity is less than 10%) from the PANI-PAAMPSA film of aqueous solution curtain coating
In plastic bottle, 4 gram (4.0g) polyacrylamides (PAM) (M.W. is 5,000,000-6,000,000, Polysciences (Warrinton, PA 18976) system) are mixed with the 400ml deionized water.Mixture rotates under room temperature and stirred at least 48 hours.Filter this solution by 1 μ m polypropylene filter then.By changing the PAM amount of being dissolved, make the solution of different PAM concentration set by step.
Present embodiment explanation PAM can dissolution in water, filter with 1 μ m filter again
The PANI-PAAMPSA solution that 10 gram (10g) embodiment 2 are prepared and 20g embodiment 4 prepared 1% (w/w) PAM solution mix (mixing is 24 hours under the room temperature).Then solution is filtered by 0.45 μ m polypropylene filter.In blend solution, PANI-PAAMPSA is 1: 2 to the ratio of PAM.Concentration by PANI-PAAMPSA and PAM in the change starting soln prepares the solution of different PANI-PAAMPSA to PAM blend ratio, comprises following ratio: PANI-PAAMPSA/PAM (w/w) 2/1 and 1/1.
Present embodiment explanation can prepare the PANI-PAAMPSA/PAM blend under various PAM concentration, and illustrate this blend can dissolution in water, and they can filter with 0.45 μ m filter.
Present embodiment explanation can be with various PAAMPSA prepared at concentrations PANI-PAAMPSA/PAAMPSA blends, and illustrate this blend can dissolution in water, and available 0.45 μ m filter filtration.
Embodiment 8
With patterned ITO electrode preparation glass substrate.With prepared blend solution in embodiment 5,6 and 7, at patterned substrate surface rotational casting polyaniline blend layer, in 90 ℃ vacuum drying oven, dried by the fire 0.5 hour then, resistance between the ITO electrode is measured with the high resistance Keithley 487 type micromicroampere instrument of Keithley instrument company (Cleveland, Ohio 44139) system.Table 1 is the conductivity of PANI (ES) blend thin films of various blend compositions, and as can be seen from Table 1, conductivity can be controlled in very wide scope.
Present embodiment explanation PANI-PAAMPSA blend can be made bulk conductivity less than 10
-4S/cm, even less than 10
-5S/cm promptly must not form pattern with the PANI-PAAMPSA blend thin films, just electric current between picture point can be leaked the enough low level that controls to.
Table 1
The surface ratio resistance of PANI-PAAMPSA blend and body conductance
Blend | Matrix polymer (B) (if existence) | Thickness () | The A/B ratio * (w/w) | Sheet resistance (ohm/100 square feet) | Conductance (s/cm) | Than resistance (ohm-cm) ** |
100 | Do not have | 350 | 1.2×10 8 | 2.3×10 -3 | 4.3×10 2 | |
101 | Do not have | 200 | 2.2×10 8 | 2.2×10 -3 | 4.5×10 2 | |
102 | PAM | 300 | 2/1 | 2.3×10 9 | 1.5×10 -4 | 6.7×10 3 |
103 | PAM | 230 | 2/1 | 5.3×10 9 | 8.2×10 -5 | 1.2×10 4 |
104 | PAM | 510 | 1/1 | 8.2×10 9 | 2.3×10 -5 | 4.3×10 4 |
105 | PAM | 264 | 1/1 | 2.0×10 10 | 1.9×10 -5 | 5.3×10 4 |
106 | PAM | 220 | 1/1 | 2.2×10 10 | 2.1×10 -5 | 4.8×10 4 |
107 | PAM | 285 | 1/2 | 1.4×10 11 | 2.5×10 -6 | 4×10 5 |
108 | PAAMPSA | 260 | 1/0.1 | 2.4×10 9 | 1.6×10 -4 | 6.3×10 3 |
109 | PAAMPSA | 350 | 1/0.3 | 9.2×10 9 | 4.6×10 -4 | 2.2×10 3 |
110 | PAAMPSA | 230 | 1/0.5 | 4.5×10 8 | 9.5×10 -4 | 1.1×10 3 |
111 | PAAMPSA | 630 | 1/0.5 | 3.7×10 8 | 4.3×10 -4 | 2.3×10 3 |
112 | PAAMPSA | 920 | 1/0.5 | 6.8×10 7 | 1.6×10 -4 | 6.3×10 3 |
113 | PAAMPSA | 950 | 1/1 | 2.8×10 8 | 3.8×10 -4 | 2.6×10 3 |
114 | PAAMPSA | 1280 | 1/1 | 6.7×10 7 | 1.2×10 -3 | 8.3×10 2 |
115 | PAAMPSA | 1740 | 1/2 | 2.5×10 8 | 2.3×10 -4 | 4.3×10 3 |
116 | PAAMPSA | 3060 | 1/2 | 8.4×10 7 | 3.9×10 -4 | 2.6×10 3 |
117 | PEO | 250 | 1/1 | 3.0×10 9 | 1.3×10 -4 | 7.7×10 3 |
* A is PANI-PAAMPSA
* is than resistance (being the inverse of conductance)
Embodiment 9
The PANI-PAAMPSA solution of preparation among the 20g embodiment 2 is mixed with 1 weight %PAM solution and the 2.0g 15%PAAMPSA solution (Aldrich system) that 10g embodiment 4 makes (in following 12 days of room temperature).Then the polypropylene filter of solution by 0.45 μ m filtered.The content of PANI-PAAMPSA in blend solution is 33 weight %.Prepare the PANI-PAAMPSA of different mixture ratio by changing the solution initial concentration: PAAMPSA: PAM blend solution.
Embodiment 10
Repeat embodiment 9, PANI-PAAMPSA content remains 33 weight %, but the ratio of matrix polymer PAAMPSA/PAM (w/w) changes into 2/0,0.5/1,1/1 and 0/2 respectively.
Embodiment 11
Embodiment 12
Repeat the resistance measurement among the embodiment 8, but PANI (ES) layer is used to be executed by embodiment 11 prepared blend solution and is changeed casting.Figure 3 shows that the conductance of PANI (ES)-blend thin films under the different mixture thing is formed.By data as can be known, can be in wide region inner control conductance to satisfy in the display requirement.Conductivity values can be less than 10
-5S/cm is (than resistance greater than 10
-5Ohm/cm).During higher PAM concentration, conductance is reduced to and is lower than 10 in the blend
-6S/cm is (than resistance greater than 10
-6Ohm/cm).
Present embodiment shows can make conductance less than 10
-5S/cm, even less than 10
-6The PANI of s/cm (ES)-blend thin films.
Embodiment 13
Repeat the resistance measurement of embodiment 8, but PANI (ES) layer is obtained by blend solution rotating casting prepared among embodiment 9 and the embodiment 10.Table 2 is the conductivity of poly-blended thing film under different mixture is formed; Conductivity can be controlled in the wide number range.
Present embodiment shows can make the PANI-PAAMPSA blend of making matrix polymer with PAAMPSA/PAM, and its bulk conductivity is lower than 10
-5S/cm, even less than 10
-6S/cm, and also can be lower than 10 with special formulation
-7S/cm.The conductivity of PANI (ES) blend is low just to limit electric current leakage between picture point to being enough to not need that blend thin films is formed pattern.
Table 2
The volume resistance and the sheet resistance of PANI (ES) blend of different compositions and thickness
The matrix polymer ratio
*Thickness R (ohm)
*Ohm/100 ordinary telegram conductances compare resistance
PAAMPSA/PAM () super superficial (s/cm) (ohm-cm)
1.5/0.5 2100 9.8×10
6 5.2×10
8 9.0×10
-5 1.1×10
4
1000 1.0×10
8 5.3×10
9 1.9×10
-5 5.3×10
4
2/0 2080 1.6×10
7 8.5×10
8 5.6×10
-5 1.8×10
4
1300 3.9×10
7 2.1×10
9 3.7×10
-5 2.7×10
4
0.5/1 1850 1.2×10
9 6.4×10
10 9.3×10
-7 1.1×10
6
1000 6.8×10
9 3.6×10
11 2.8×10
-7 3.6×10
6
1/1 1620 1.1×10
9 5.9×10
10 1.0×10
-6 1.6×10
6
1100 2.6×10
10 1.4×10
12 6.5×10
-8 1.5×10
7
0/2 1200 2×10
10 1.0×10
12 8.3×10
-8 1.2×10
7
750 3.4×10
11 1.8×10
13 7.4×10
-9 1.4×10
8
* polyaniline is 1/2 (w/w) to total matrix polymer ratio
* is the resistance between the two adjacent ITO wiring in 10 * 10 configurations
Embodiment 14
(DMO-PPV) make light-emitting diode with poly-(2-(3,7-dimethyl octyloxy)-5-methoxyl group-1,4-phenylene vinylidene) as the active semiconductor light emitting polymer; The thickness of DMO-PPV film is 500-1000 .Indium/tin-oxide is used as the ground floor of bilayer anode.With PANI-PAAMPSA (embodiment 2 makes) by its 1% aqueous solution/dispersion liquid rotational casting on ITO, thickness is 100 to 800 , then under 90 ℃ in vacuum drying oven the baking 0.5 hour.Apparatus structure is ITO/PANI (ES)-PAAMPSA/DMO-PPV/ metal.Make substrate (the ITO/ glass that applies) and make substrate (Courtauld ' s ITO/PET) with ITO on glass during manufacturing installation with the ITO on the plastics (PETG (PET)), under these two kinds of situations, the ITO/PANI-PAAMPSA bilayer is that contact is injected in anode and hole.Make device with a Ba layer as negative electrode.Be lower than 1 * 10 with vaccum gas phase sedimentation method
-6Under the pressure of torr the metallic cathode film is placed on the surface of DMO-PPV layer, obtaining area is 3cm
2Active layer.Deposition process is monitored with Sycon instrument company (East Syracuse, NY 13057) system STM-100 type thickness/speedometer, make thickness 2000 to the al deposition of 5000 at the calcium laminar surface.Two kinds of devices are carried out the curve of electric current to voltage, and light is to the curve of voltage and the mensuration of quantum efficiency.Figure 4 shows that the luminous efficiency (curve 400) and the external quantum efficiency (curve 410) of ITO/PANI (ES)-PAAMPSA/DMO-PPV/Ba device.With the external efficiencies of the device of double-deck PANI (ES)-PSSPMSA/ITO anode device apparently higher than the band ito anode.
Present embodiment shows with PANI-PAAMPSA can produce high-performance polymer LEDs as the second layer of bilayer anode.
Embodiment 15
(PEDT) (Pitt sburgh, PA15205) the poly-blended thing solution of system repeats the resistance measurement of embodiment 8 with Bayer AG to use commercially available poly-(ethylidene dioxy thiophene).Table 3 shows that the thin layer of (seeing embodiment 9) PANI (ES) blend that the present invention is prepared is more much lower than the conductivity of the thin layer of being made by PEDT.Present embodiment shows that the conductivity of PEDT is too high can not to be used for passive addressed picture point formula display; Leakage current will cause cross interference and efficient to reduce between picture point.
Table 3
Compare thickness and the conductivity of new PEDT-PSS with PANI (ES) blend
Type rotation thickness R
*The Rs conductivity compares resistance
Speed () (megohm) (megohm/100 (S/cm) (ohm-li
(RPM) rice square feet))
PEDT-PSS 600 2800 0.22 11.7 3.0×10
-3 3.3×10
2
800 2500 0.31 16.5 2.4×10
-3 4.2×10
2
1000 2000 0.33 17.0 2.9×10
-3 3.4×10
2
1400 1700 0.38 19.4 3.0×10
-3 3.3×10
2
2000 1330 0.57 30.4 2.5×10
-3 4.0×10
2
4000 1000 0.77 41.0 2.4×10
-3 4.2×10
2
PEDT-TSS 600 1000 0.16 8.5 1.2×10
-2 8.3×10
1
1000 760 0.19 10.1 1.3×10
-2 7.7×10
1
PANI(ES) 1000 2100 9.8 522 9.0×10
-5 1.1×10
4
Blend
2000 1500 29.0 1550 4.3×10
-5 2.3×10
4
3000 1200 84.0 4480 1.9×10
-5 5.3×10
4
4000 1000 100.0 5300 1.9×10
-5 5.3×10
4
R* is configured as the resistance (unit: megohm) between 10 * 10 the two adjacent ITO
Rs: surface ratio resistance (unit: megohm/100 square feet)
Embodiment 16
Embodiment 17
The device that repeats to be summarized among the embodiment 14 is measured.But PANI (ES) blend layer is to form with blend solution rotating casting prepared among embodiment 5 and the embodiment 16.Table 4 is depicted as the device performance by the LEDs of the poly-blended thing film preparation of band different substrates polymer.
Present embodiment explanation PANI-PAAMPSA blend can be used for making has remarkable high efficiency polymer LED s; This high efficiency acquisition is because by using high resistance PANI (ES)-blend significantly to reduce electric current leakage between picture point as hole injection layer.
Table 4
The performance of the device of making of different PANI (ES) blend
Matrix polymer 8.3mA/cm
2*Under characteristic
V QE(%) cd/A Lm/W
PAM(300) 4.9 3.5 6.3 4.1
PAM(2000)
** 4.3 3.1 4.5 3.3
Poly-(acrylic acid) (300 ) 4.4 3.7 7.0 5.0
PAM-carboxylic acid---0.04
PVP 6.3 1.0 1.3 0.6
Polystyrene (aqueous emulsion) 6.1 0.6 0.8 0.4
* the 5-10 device is an optimum device
(promptly after making blend solution, remove some solvents and make solution more viscous, thereby and make thicker film) of * enrichment.
Embodiment 18
Repeat the device mensuration that embodiment 14 is summarized.But PANI (ES) layer is made with the blend solution rotating casting of different PANI (ES) PAAMPSA/PAM ratio (seeing embodiment 11).Table 5 is depicted as the LEDs device performance of the poly-blended thing film making of different PANI-PAAMPSA/PAM ratios.
Higher efficient and PANI (ES) (ES) high electrical resistance of blend layer are relevant well.By PANI (ES) (ES)-the higher resistance of blend layer can obtain higher efficient because not since between picture point electric current leak caused reactive current.
Table 5
The performance of the device that different PANI (ES) blends are made
PANI (ES) PAAMPSA/PAM 8.3mA/cm
2*Under characteristic
(w/w) V QE(%) cd/A Lm/W
1/9 9.1 5.0 10.7 3.7
1/3 5.6 5.0 12.6 7.1
1/2 5.2 4.9 13.0 7.8
1/1.5 5.2 4.8 12.1 7.3
1/0 4.6 4.4 11.6 8.0
Embodiment 19
The device that repeats to be summarized among the embodiment 14 is measured, but with poly-[5-(4-(3,7-dimethyl octyloxy)-phenyl)-phenylene-1,4-ethenylidene] (DMOP-PPV) and it and the random copolymer replacement DMO-PPV of DMO-PPV.The equipment energy characteristic data are listed in table 6.
Present embodiment proof uses PANI-PAAMPSA can make different color (as red, green, orange etc.) as hole injection layer.
Table 6
The device performance of different light emitting polymers on PANT (ES)-PAAMPSA electrode
Polymer is formed EL peak device performance
*Color
(DMOP-PPV) n-(DMO-PPV) m (nm) V luminance efficiency
n m (V) (cd/m
2) (%)
100 0 510 5.3 47 1.2 greens
98 2 530 4.8 130 3.2 yellow greens
50 50 580 6.6 198 4.9 is orange
0 100 610 3.3 160 3.9 redness
* current density 8.3mA/cm
2Down
The device of embodiment 14 is sealed with being clipped in the interbedded cladding glass of ultraviolet solidifiable epoxy resin.Sealing device is with 8.3mA/cm
2Constant current moves in oven temperature is 25,50,70 and 85 ℃ atmospheric pressure environment.Total current by device is 25mA, the about 100cd/cm of brightness
2Figure 5 shows that luminous efficiency (curve 510) and voltage rising (curve 512) in 85 ℃ of following runnings.With ITO that 10-20 hour quality of 85 ℃ of work descends is that the device of anode is compared, and the half-life of the device of band ITO/PAAMPSA bilayer surpasses 450 hours, and voltage raise very little (5mV/ hour).Scheme as can be known from the Arrhenius (Ahrennius) of 50,70 and 85 ℃ of following resulting brightness decays and voltage rising data, the temperature accelerated factor is estimated to be about 100.The working life that is extrapolated to thus under the room temperature is about 40,000 hours.
Figure 6 shows that room temperature running time data in 25 ℃ of luminous efficiencies (curve 600) of working down and voltage rising (curve 610).As seen from Figure 6, after 10000 hours operating times, it is only about 10% that luminous efficiency reduces, and voltage increased less than 0.15mV/ hour.
The present embodiment explanation, the polymer LED s that makes of high resistance PANI (ES) layer can obtain long service live.
Embodiment 21
Present embodiment shows that use PANI-PAAMPSA/PAM blend can make Performance Monitor as hole injection layer.
Embodiment 22
Present embodiment illustrates that desirable high resistance PANI (ES)-PAAMPSA/PAM blend can directly synthesize with simple technology.
Embodiment 23
Prepare three passive addressed displays, 96 row and 64 row are respectively arranged, the gap is 50 μ m between the ITO row.The addressing in each display of single picture point.Resulting emission photo as shown in Figure 8.Except as the material of hole injection layer than the resistance difference, three kinds of displays all are the same in all fields.Display among Fig. 8 a has low resistance PEDT layer (than about 200 ohm-cms of resistance), thereby resistance is about 20,000 ohm between its row.Display among Fig. 8 b has-the poly-blended thing layer of PANI (ES) (being about 4000 ohm-cms than resistance), thereby resistance is about 400,000 ohm between its row.Display among Fig. 8 c has the poly-blended thing layer of a high electrical resistance PANI (ES) (being about 50,000 ohm-cms than resistance), thereby resistance is about 5,000,000 ohm between its row.
Shown in Fig. 8 a, significant cross interference is arranged when resistance is 20,000 ohm between row.This cross interference comprises two layers of meaning:
(i) display (Fig. 8 resolution and definition restriction of being subjected to cross interference a).Notice that the display among Fig. 8 b makes moderate progress than Fig. 8 a, and the problem of cross interference does not appear in the display of Fig. 8 c.
(ii) the efficient of display (Fig. 8 a and Fig. 8 b) reduces because of the influence that electric current between picture point leaks.
Lower efficient means that this display is than the negligible display of cross interference (Fig. 8 c) power that needs are higher.Because electric current leaks between picture point, the efficient that display had shown in Fig. 8 a is about half of the display shown in Fig. 8 c.According to spacing between picture point and picture point size, the 3-5 factor doubly can be arranged because of electric current between picture point leaks caused efficient reduction.Utilize these data estimation to go out to use than resistance as 10
4Ohm-cm to 10
5Reducing because of electric current between picture point leaks the efficient that is caused will can not appear in the prepared display of the poly-blended thing layer of PANI (ES) in the ohm-cm scope.
The present embodiment explanation is used the importance of high resistance PANI (ES) multiple copolymer as hole injection layer in passive addressed polymer LED display.
Claims (7)
1. the preparation method of a PANI-PAAMPSA film comprises following steps:
A kind of substrate is provided:
A kind of aqueous dispersions or solution are provided, and it contains with poly-(2-acrylamido-2-methyl isophthalic acid-propyl sulfonic acid) the emerald green imonium salt type polyaniline as gegenion; With
This aqueous solution or dispersion liquid are deposited on the substrate to form film.
2. the method for claim 1, the ratio resistance that it is characterized in that described film is greater than 10
2Ohm/cm.
3. method as claimed in claim 1 or 2 is characterized in that in that it also comprises the step at least a water-soluble base polymer with described aqueous dispersions or solution blending before on the substrate with described aqueous dispersions or solution deposition.
4. method as claimed in claim 3 is characterized in that described water-soluble base polymer is a polyacrylamide, poly-(2-acrylamido-2-methyl isophthalic acid-propyl sulfonic acid), polyacrylic acid, polystyrolsulfon acid, PVP, acrylamide copolymer, cellulose derivative, carboxy vinyl polymer, polyethylene glycol, poly(ethylene oxide), polyvinyl alcohol, polymethyl vinyl ether, polyamine, polynary imines, polyvinylpyridine, polysaccharide, or dispersions of polyurethanes.
5. method as claimed in claim 4, the ratio resistance that it is characterized in that described film is greater than 10
4Ohm/cm.
6. method as claimed in claim 5, the ratio resistance that it is characterized in that described film is greater than 10
5Ohm/cm.
7. method as claimed in claim 5, the ratio resistance that it is characterized in that described film is greater than 10
6Ohm/cm.
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US20020031602A1 (en) * | 2000-06-20 | 2002-03-14 | Chi Zhang | Thermal treatment of solution-processed organic electroactive layer in organic electronic device |
US20020036291A1 (en) | 2000-06-20 | 2002-03-28 | Parker Ian D. | Multilayer structures as stable hole-injecting electrodes for use in high efficiency organic electronic devices |
US7033646B2 (en) * | 2002-08-29 | 2006-04-25 | E. I. Du Pont De Nemours And Company | High resistance polyaniline blend for use in high efficiency pixellated polymer electroluminescent devices |
EP1546283B1 (en) | 2002-09-24 | 2012-06-20 | E.I. Du Pont De Nemours And Company | Electrically conducting organic polymer/nanoparticle composites and methods for use thereof |
US7317047B2 (en) | 2002-09-24 | 2008-01-08 | E.I. Du Pont De Nemours And Company | Electrically conducting organic polymer/nanoparticle composites and methods for use thereof |
AU2003275203A1 (en) | 2002-09-24 | 2004-04-19 | E.I. Du Pont De Nemours And Company | Water dispersible polythiophenes made with polymeric acid colloids |
JP2006500461A (en) | 2002-09-24 | 2006-01-05 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Water-dispersible polyaniline produced using polymer acid colloids for electronics applications |
US7351358B2 (en) | 2004-03-17 | 2008-04-01 | E.I. Du Pont De Nemours And Company | Water dispersible polypyrroles made with polymeric acid colloids for electronics applications |
JP2006241339A (en) * | 2005-03-04 | 2006-09-14 | Nippon Shokubai Co Ltd | Polyaniline-containing composition and method for producing the same |
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US20080191172A1 (en) | 2006-12-29 | 2008-08-14 | Che-Hsiung Hsu | High work-function and high conductivity compositions of electrically conducting polymers |
US8241526B2 (en) | 2007-05-18 | 2012-08-14 | E I Du Pont De Nemours And Company | Aqueous dispersions of electrically conducting polymers containing high boiling solvent and additives |
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