TWI327152B - Water dispersible polythiophenes made with polymeric acid colloids - Google Patents

Description

1327152 发明Inventive Description: TECHNICAL FIELD The present invention relates to an aqueous dispersion of a thiophene conductive polymer obtained by synthesizing a conductive polymer in the presence of a polyacid colloid. [Prior Art] Conductive polymers have been used in many organic electronic devices' including the development of electroluminescent (EL) devices t for luminescent displays. With regard to EL devices, such as organic light-emitting diodes (OLEDs) containing conductive polymers, such devices generally have the following configurations: Anode/buffer layer/EL polymer/cathode anodes are generally capable of injecting holes into semiconducting. E] L polymer such as, for example, indium oxide/tin (ITO) other materials that have been filled with π-energy bands. The anode is loaded on a glass or plastic substrate as appropriate. The polymer is generally a conjugated semiconductive polymer such as poly(p-phenylacetylene) or polyfluorene. The cathode is typically any material (e.g., Ca or Ba) that is capable of injecting electrons into other empty π*-bands of the semiconductive EL polymer. The buffer layer is typically a conductive polymer and can help the hole be injected into the layer by the anode. This buffer layer is also referred to as a hole injection layer, a hole transfer layer, or a portion that can be depicted as a double layer anode. Typical conductive polymers used as the buffer layer include polyaniline and polydioxy p-cephene such as poly(3,4-ethylenedioxythiophene) (PEDT). For example, as described in U.S. Patent No. 5,3,575, entitled "Poly 11 Semen Dispersion, Methods of Making and Uses", these materials may be exemplified by aniline or dioxin. The preparation is obtained by polymerizing a water-soluble polyacid in an aqueous solution, such as poly(styrenesulfonic acid) (PSS). The well-known PEDT/PSS material OA8S\8843S 00C -6- 1327152 is spoken by H.C. Starck, GmbH VIII, A Division (Leverkusen, Germany)

Bayt〇n®-P. The aqueous conductive polymer dispersion obtained by synthesizing the water-soluble polyacrylic acid has a low pH and a low pH, which may cause the stress of the rainbow device containing the buffer layer to decrease and cause corrosion in the device. Therefore, there is a need for a composition and a buffer layer which are preferably produced therefrom. Conductive polymers also have utility as electrodes for use as electronic devices, such as thin film field effect transistors. In such a transistor, an electric day-to-day basket is present between the source and the drain. For use in lightning applications, the conductive polymer and the liquid dispersing or dissolving the conductive polymer must be compatible with the semiconductive polymer and the solvent of the semiconductive polymer to avoid redissolution of the conductive polymer or semiconductive polymer. . The conductivity of the electrode made of conductive polymer should be greater than (10) centistokes is ohmic). However, conductive materials made of polyacids generally provide a range of ~10·3 S/cm or lower. Low conductivity. A conductive additive is added to the polymer for improved conductivity. However, the sub-agents of this type of additive have an adverse effect on the conductivity of the conductive poly(1). Therefore, there is a need for a preferred conductive poly-doping having good processability and high electrical conductivity. SUMMARY OF THE INVENTION The present invention provides a composition comprising an aqueous dispersion of a polyphenol and at least a colloid to form a polyacid. The composition of the present invention can be used in many organic devices such as organic light-emitting diodes (OLEDs) as a buffer layer and in applications such as thin film field effect transistors, sources or gates, such as metals. The nanowire or carbon nanotubes are combined. Package, according to another embodiment of the invention, providing a composition containing a komin

O:\88\88435 DOC 1327152 The organic electronic device of the cast buffer layer 'includes an electroluminescent device. According to another embodiment of the invention, there is provided a method of synthesizing polysulfimide with at least one colloid to form an aqueous dispersion of a polyacid. A method for producing a polydisperse and an aqueous dispersion of a colloid to form a polyacid comprises: U) providing a uniform aqueous mixture of water and p-cephen; (b) providing a colloid to form an aqueous dispersion of a polyacid; (c) combining the porphin mixture with the colloid-forming aqueous dispersion of the polyacid; and (d) the oxidizing agent and the catalyst and the colloid forming an aqueous dispersion of the polyacid in any order before or after the combining step (c) merge. Other specific embodiments are described in the embodiments of the invention. [Embodiment] In a specific embodiment of the invention, a composition comprising polysulfimide, comprising a polydioxythiophene and a colloid to form an aqueous dispersion of a polyacid, is provided. As used herein, the dispersion "-word is equivalent to a continuous liquid medium containing fine particle suspension. According to the invention, "continuous medium, generally an aqueous liquid, such as water. As used herein, the term "aqueous" corresponds to a liquid which is mostly water, and in one embodiment, at least about 40% by weight is water. liquid. As used herein, the "glue word is equivalent to a fine particle suspended in a continuous medium having a particle size of a micron size. As used herein, the term "colloidal &" is equivalent to a substance that forms fine particles when dispersed in an aqueous solution, that is, a colloidal shape 'ν, and the acid is not water-soluble. ♦ As used herein, "contains" , "contains,"includes","covers","presentation, """ or any other variation of the words it is intended to cover (4) / with '. S.

O:\88\88435.DOC -8 - 1327152 The procedures, methods, objects or equipment of a female 'include-series' are not necessarily limited to these items, but also include other unrepresented or such procedures, methods, objects or equipment. Inherent components. In addition, unless stated to the contrary, " or" is fairly inclusive or not exclusive. For example, any of the following may satisfy condition eight or eight: A is true (or exists) and 8 is not True (or non-existent), A is not true (or non-existent) AB is true (or exists) and both 8 and 8 are true (or both). The use of the components you use to describe the components and components of the present invention. This description is to be construed as a convenience of the invention, and the description of the invention is intended to be construed as a singular or a singular singular and singular. When chemically polymerized in the presence of a polyacid, conductive polybenz, especially an aqueous dispersion of poly(dioxan), can be obtained. Furthermore, the use of polyacids has been found to produce a combination of excellent electrical properties. Where the polyacid is insoluble in the preparation of an aqueous dispersion of polystimulus or poly(dioxane). These aqueous dispersions have the advantage that the electrically conductive fine particles are stable in the aqueous medium, Forming points . They phase ... - Once dry film according to a wooden cup BH pi, eleven: Examples of specific embodiments compositions comprise - polydioxanone having

1327152 wherein: an alkyl group R having from 1 to 4 carbon atoms, and R, 'series are each independently selected from hydrogen and have or MR, forming a chain of four (four) chains having a carbon atom, which may optionally be 1 to 12 carbon atoms are substituted with an alkyl or an aromatic group, or n is a cyclohexyl group, and the η system is greater than about 6. The thiophene of the present invention has the same general structure as that provided above, and its center and size are replaced by "OR丨0" and "OR丨•, substituents. In a particular embodiment, R, together with R!, form an alkyl chain having from i to 4 carbon atoms. In another embodiment, the polydioxonole is poly(3,4-exoethylenedioxysulfonyl). The colloid-forming polyacid to be used in the examples of the present invention is insoluble in water and forms a colloid when dispersed in an aqueous medium. The molecular weight of the polyacid is generally

It is in the range of about 10,000 to about 4,000,000. In one embodiment, the molecular weight of the polyacid is from about 100,000 to about 2,000,000. The particle size of the colloid is generally in the range of from 2 house microns (nm) to about 1403. In a specific embodiment, the colloid has a particle size of from 2 nanometers to about 30 nanometers. Any polyacid which forms a colloid when dispersed in water is suitable for use in the examples of the present invention. In a particular embodiment, the colloid forming polyacid is a polysulfonic acid. Other acceptable polyacids include polyphosphoric acid, polycarboxylic acids, and polyacrylic acids and mixtures thereof, including mixtures containing polysulfonic acids. In another embodiment, the polysulfonic acid is fluorinated. In another embodiment, the colloid-forming polysulfonic acid is perfluorinated. In another embodiment, the colloid-forming polysulfonic acid is a perfluoroalkylalkylsulfonic acid. 0.\88\88435.DOC -10- 1327152 In another embodiment, the 'colloidal polyacid is a highly fluorinated sulfonic acid polymer ("FSA polymer."Highly fluorinated" It is meant that at least about 50% of the total number of halogen and hydrogen atoms in the polymer is a fluorine atom, and in one embodiment is at least about 75%, and in another embodiment at least about 90%. In one embodiment In the example, 'the polymer is perfluorinated. The term acidifying functional group" is equivalent to a salt of a repeating acid group or a reductive acid group, and in one embodiment is a metal or ammonium salt. The formula _s〇3X represents, where X is carbon, and is also known as "counter ion". X can be Η, Li, Na, K or N(Ri)(R2)(R3)(R4), and R 〖, R2, 尺3, and 尺4 may be the same or different, in one embodiment Η, CH3 or C2H5. In another specific embodiment, X疋Η, in this case, the polymer may be " Acid type, % X can also be multi-valent, as expressed by ions such as Ca++ and Al+++. Those skilled in this technology are well aware of the multivalent counter ion, one In the example indicated as Μη+, the number of acid-reducing functional groups per counterion will be equal to the valence "η". In a specific embodiment, the FSA polymer comprises a polymer backbone and a % side chain attached to the backbone, Wherein the side chain carries a cation exchange group. The polymer comprises a homopolymer or copolymer of two or more monomers. The copolymer is generally a non-s-cycle b monomer and a second monomer bearing a cation exchange group or a precursor, such as a sulfonium fluoride group (s〇2F) which can then be hydrolyzed to a sulfonating functional group. For example, a fluorinated vinyl monomer and a fluorinated B group having a fluorinated vinyl group (-(7) can be used. A copolymer formed by a dilute base monomer. The first monomer usable is: tetrafluoroethylene (TFE), hexafluoropropylene, fluorinated ethylene, vinylidene fluoride, - ethylene, I, ethylene dioxide, total gas ( Burning Ethylene Puzzle and its combination. Move is the preferred first monomer.

O:\88\88435.DOC 1327152 2 In other embodiments, the second monomer that is usable includes a fluorinated ethylene group having a reductive acid group or a pendant precursor group that provides a desired side of the polymer. When desired, additional monomers, including ethylene, propidium and r-CH=CH2 #, may be introduced into the polymer 'wherein R is a perfluorinated alkyl group of 1 to 10 carbon atoms. This polymer may be equivalent to the type of the chaotic copolymer herein, that is, the relative concentration of the comonomer is kept as fixed as possible, so that the monomer unit is polymerized along the 7-cutter system of the polymer chain according to its relative concentration and relative reactivity. The resulting copolymer is obtained. Copolymers having a lower degree of clutter can also be obtained by varying the relative concentrations of the monomers during the polymerization. It is also possible to use a so-called block copolymerization class of the sacrificial compound, as disclosed in European Patent Application No. m Ai. In one embodiment, the FSA polymer used in the present invention comprises a high degree of fluorination, in one embodiment a perfluorinated carbon backbone and a side chain as shown below

-(〇-CF2CFRf)a-〇-CF2CFR, fS〇3X wherein Rf and R, f are independently selected from F, C1 or a perfluorinated alkyl group having from 丨 to 1 carbon atom, a =. , 1 or 2, X is Η, Li ' Na, K or 'N〇U)(R2)(R3)(R4), and R1, R2, and think the same or different, in a specific implementation H, CH3 or CA. In another specific implementation. In the example, X is Η. As stated above, χ can also be multivalent. In a specific embodiment, the FSA polymer includes, for example, the polymers disclosed in U.S. Patent No. 3,282,875 and U.S. Patent Nos. 4,358,545 and 4,940,525. Examples of preferred FSA polymers include a full gas carbon backbone and side bonds as shown in the following formula

0 \88\88435 OOC -12- 1327152 -o_cf2cf(cf3)-o-cf2cf2so3x where X is as defined above. This type of FS A polymer is disclosed in U.S. Patent No. 3,282,875 and may be based on tetrafluoroethylene (TFE) and perfluorinated vinyl ether CF2 = CF-0-CF2CF(CF3)-0-CF2CF2S02F, perfluoro( 3,6-dioxin-4-mercapto-7-octenesulfonylfluoro) (PDMOF) copolymerization, followed by hydrolysis of the sulfonyl fluoride group to a sulfonate group, which is converted to the desired ion by ion exchange if necessary State made. Examples of polymer types disclosed in U.S. Patent Nos. 4,358,545 and 4,940,525 have the side chain -0-CF2CF2S03X wherein X is as defined above. The polymer can be copolymerized with tetrafluoroethylene (TFE) and perfluorinated vinyl ether CF2 = CF-0-CF2CF2S02F, perfluoro(3-ox-4-pentenesulfonyl fluoride) (POPF), followed by hydrolysis and Further ion exchange is made if necessary. The ion exchange ratio of the FSA polymer used in the present invention is generally less than about 33. In this application, "ion exchange ratio" or nIXR" is defined as the number of carbon atoms relative to the cation exchange group in the polymer backbone. For a particular application, the IXR may vary within a range of less than about 33, if desired. In particular embodiments, the IXR is from about 3 to about 33, and in another embodiment from about 8 to about 23. The cation exchange capacity of the polymer is often expressed in terms of equivalents (EW). For purposes of this application, Equivalent (EW) is defined as the weight of the acid-type polymer required to neutralize one equivalent of sodium hydroxide. The polymer has a perfluorocarbon backbone and the side chain is -o-cf2cf(cf3)-o-cf2-cf2-so3h In the case of the sulfonated polymer of (or a salt thereof), the equivalent range of from about 8 to about 23 for the IXR is from about 750 EW to about 1 500 EW. The relationship between the IXR and the equivalent of the polymer can be as follows. The sulfonated polymer disclosed in U.S. Patent Nos. 4,358,545 and 4,940,525, such as having a side chain 诏33诏S435 DOC -13 - 1327152 -0-CF2CF2S〇3H ( The polymer of the salt or its salt) uses the same range, but contains a cation exchange group. The molecular weight of the monomer unit is lower, so the equivalent is slightly lower. For a preferred IXR range of from about 8 to about 23, the corresponding equivalent range is from about 575 EW to about 1325 EW. The relationship between the ixr and the equivalent of the polymer can be utilized. The following formula shows: 50 IXR + 178 = EW. FS A polymer can be made into a colloidal aqueous dispersion. They can also be in the form of a dispersion in other media. Examples include, but are not limited to, alcohols, water-soluble ethers, For example, a mixture of a tetrahydrofuran 'water-soluble ether and a composition thereof. An acid-type polymer can be used in the production of a dispersion. A method for producing an aqueous alcohol dispersion is disclosed in U.S. Patent Nos. 4,433, (4), 4,150,426 and WO 03/006537. After the dispersion is prepared, the concentration and dispersion of the liquid composition can be adjusted by methods known in the art. Colloid-forming polyacids The aqueous dispersions including FSA polymers generally have as small a particle size as possible and are as small as possible (4) As long as a stable colloid can be formed. The aqueous dispersion of FSA polymer can be purchased from commercial companies such as by E. h du

Pont de Nem〇UI^ (Dalerville, Wilmington) has a wealth of _8 points. The rubber plug or dioxophene system contains polyacids. In general, P phenophene or dioxythiophene mono I# #:3 has a polymerization catalyst, an oxidizing agent, and a colloidal polyacid raw dispersion, or a water-based or added order of adding a snail ant eight, In the embodiment, the merging may be changed as the reducing agent and the catalyst are not combined with the monomer until the polymerization is carried out. The socket catalyst includes, but does not, bismuth iron and the like and

O:\88\88435.DOC -14- 102/iyz mixture. T ^ includes but is not limited to sodium persulfate, potassium persulfate, persulfate, and the like 'including its * and eight private, , and ' and D. Oxidative polymerization to form a stable aqueous dispersion comprising a positively charged conductive poly; phenanthrene and/or dioxin, wherein the poly, plug: and / or - chylotropes are based on the negative charge side of the polyacid contained in the colloid Chains, such as acidified anions, molybdenum anions, acetylated ions, composition filaments (4) (iv) load balance. The method for producing an aqueous dispersion of polydioxan and at least one colloid to form a small i, includes: (4) providing an aqueous dispersion of a polyacid; and (8) dispersing the oxidizing agent in the step (4). (4) adding the catalyst to the dispersion of the step (8); and (4) adding the dioxane, the phenanthrene monomer to the dispersion of the step (4), and the specific embodiment of the above method includes adding the oxidizing agent to the oxidizing agent. The monomer is added to the aqueous dispersion of the polyacid. Another embodiment is a homogeneous aqueous mixture of water and polydioxythiophene which produces a polyoxygen octaphene concentration value in water, wherein the concentration of polyoxy porphin is generally from about 5% by weight to about 2.% by weight. The polydioxythiophene mixture is added to the aqueous polyacid dispersion in the range of polyoxytetraphenone and in the presence of oxidation d and a catalyst. The polymerization can be carried out in the presence of a water-miscible co-dispersion. Examples of suitable co-dispersion solutions include, but are not limited to, acetonide, lysine, cyclic ketone, ketone, nitrile, sulfoxide, and combinations thereof. In a particular embodiment, the amount of co-dispersion should be less than 30% by volume. In a specific embodiment, the content of the co-dispersion is less than 60% by volume. In a particular embodiment, the co-dispersion is present in an amount between 5 vol% and 50 vol%. In one embodiment, O:\88\88435 DOC -15- 1327152, the co-dispersion is an alcohol. In a particular embodiment, the co-dispersion is selected from the group consisting of n-propanol, isopropanol, tert-butanol, methanol dimercaptoacetamide, dimercaptocaramine, N-methylpyrrolidone. The acid may be an inorganic acid such as HCl, sulfuric acid and the like, or an organic acid such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, decanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, acetic acid and the like. Things. Alternatively, the acid may be a water-soluble polyacid such as poly(styrenesulfonic acid), poly(2-propenylamine-2-mercapto-1-propanesulfonic acid) or the like, or the above second colloid forming acid. Combinations of these acids can be used. The co-acid can be added to the reaction mixture at any point in the procedure, prior to the addition of the oxidizing agent or the thiophene monomer. In one embodiment, the co-acid is added prior to the formation of the polyacid by the thiophene monomer and the colloid and the oxidizing agent is finally added. In a particular embodiment, the co-acid is added prior to the addition of the p-cetin monomer, followed by the addition of a colloid to form a polyacid, and finally the addition of an oxidizing agent. The co-dispersion can be added to the reaction mixture at any point prior to the addition of the oxidizing agent, catalyst or monomer, whatever is added last. Depending on the case, after completion of any of the above methods and polymerization, the aqueous dispersion (4) thus obtained is contacted with at least the ion exchange resin under a material suitable for the production of the aqueous dispersion. In a specific embodiment, the resultant aqueous dispersion (4) is contacted with the first-core (four) fat and the first exchange resin. In another embodiment, the first ion exchange resin is a hydrazine, a heteropoly ion exchange resin, such as an acid cation exchange resin, and the ionic exchange resin is an anionic, anion exchange resin such as: or Four-stage exchange resin. Hard amine 〇 '88\884J5.doc -J6- ion exchange shirt - a reversible chemical reaction, in which the fluid medium (such as the aqueous dispersion of the ionic system and the similar charge attached to the fixed solid particles, 乂 change the solid The solid particles are insoluble in the fluid medium. The term “ion 乂 树 曰 曰 本文 本文 本文 相当于 相当于 相当于 相当于 相当于 相当于 相当于 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一The exchange resin is divided into an alkaline, anion exchanger which is acidic, a cation, and a negative ion which have a positively charged mobile ion. Acidic, cation exchange resin and anion exchange resin It is intended to be used in the embodiments of the present invention. In a specific embodiment, the acidic, cation exchange resin is an organic acid, a cation exchange resin, such as a sulfonic acid cation exchange resin, which is to be used in the embodiment of the present invention. The cation exchange resin system includes, for example, a decanoic acid-divinylbenzene copolymer, a acidified crosslinked f-ethylene polymer, a phenol-formaldehyde-sulfonic acid resin, a benzene-formaldehyde-sulfonic acid. Resin and mixtures thereof. In another embodiment, the acidic, cation exchange resin is an organic acid, a cation exchange resin such as a carboxylic acid, acrylic acid or phosphoric acid cation exchange resin. Moreover, the mixture can be mixed with a cation exchange resin. 5 in the midnight example of the 'Alkaline ion exchange resin can be used to adjust the pH to the desired value. In some cases, 'aqueous alkaline solution such as sodium hydroxide, hydrazine hydroxide tetramethyl or similar The solution is further adjusted in pH. In another embodiment, the basic, anion exchange resin is a secondary amine anion exchange resin. The tertiary amine anion exchange resin to be used in the examples of the present invention includes, for example, tertiary amination. Ethylene-divinylbenzene copolymer, secondary aminated crosslinked styrene polymer, tertiary aminated phenol formaldehyde resin, tertiary aminated benzene-formaldehyde resin, and mixtures thereof. In another embodiment

0\88\8843S.DOC -17- 1327152 'Alkal, anion, sputum + t a 卞 and sapphire, a quaternary amine anion exchange resin or a mixture of these and other exchange resins. The first and second ion exchange resins may be contacted simultaneously or sequentially with the aqueous dispersion thus synthesized. For example, in one embodiment, the two resins may be simultaneously added to the aqueous dispersion of the conductive polymer thus synthesized and kept in contact with the dispersion for at least about several hours, such as from about 2 hours to about 2 seconds. The ion exchange resin is then removed from the dispersion by filtration. The size of the filter is selected such that relatively large ion exchange resin particles are removed and smaller dispersion particles are passed through. Without wishing to be bound by theory, it is believed that the ionic f-exchange resin terminates the polymerization and effectively removes ionic and non-ionic impurities and most of the unreacted monomers from the aqueous dispersion thus synthesized. Further, the basic, anion exchange, and/or acid and cation exchange resins cause the acid I to be more alkaline and increase the pH of the dispersion. Typically, at least one gram of colloid is formed into a polyacid system using at least a gram ion exchanger. In another embodiment, the ion exchange resin used is used in an amount of up to about 5 grams of ion exchange resin per gram of polythiophene/polyacid colloid and is desired to be achieved. 11 depending on. In a specific embodiment, the composition of polyacids per gram of polydioxythiophene and at least one colloid forms about 1 gram of LeWatit® MP62 WS, a weak anion exchange resin available from Bayer GmbH and about 1 gram of Lewatit. ® MonoPlus S 100, a strong acid, sodium cation exchange resin from Bayer GmbH. In a specific embodiment, an aqueous dispersion formed by polymerizing a mixture of dioxane B and fluorinated polysulfonic acid and an aqueous dispersion of a fluorinated polymer are first charged into a reaction vessel. To this, an oxidizing agent, a catalyst, and a dioxin monomer are sequentially added or a mono-oxy-p-thiophene monomer, an oxidizing agent, and a catalyst are sequentially added. Search for a mixture of O:\88\S8435 DOC 18 1327152 and then allow the reaction to proceed at a controlled temperature. When the polymerization is completed, the reaction is terminated by stirring with a strong s-cationic resin and a basic anion exchange resin. Alternatively, prior to the addition of the Naflon 8 dispersion, dioxetane is added: the water is sub-stirred to homogenize the mixture, followed by the addition of the oxidizing agent and the catalyst sandpaper. Oxidizer: The monomer ratio is generally in the range of 〇 5 to 2 (). The fluorinated polymer: the dioxythiophene monomer is generally in the range of 1 to 4. The total solids content is generally in the range of 1.5% to 6%, and in the particular embodiment is 5% in winter. The reaction temperature is generally at 5. (: to 5 〇. (: In the range, in a specific example, it is 20 C to 35 C. The reaction time is generally in the range of ! to 3 hr. The polymorphic polyacid colloid thus synthesized, including Aqueous dispersions of polydioxime and chlorinated polysulfonic acid colloids have a broad pH range and are generally adjustable to between about 1 and about 8, typically having a pH of about 3-4. It is often desirable to have a lower pH, Since acidity may cause corrosion of the button, it has been found that the pH can be adjusted by known techniques such as ion exchange or titration with an aqueous solution. The formation of a polydioxane and a gasified polyacid colloid having a pH of 7-8 has been formed. The dispersion, the poly-P-phene, and the colloid-forming aqueous dispersion of the polyacid can be similarly treated to adjust the pH. In another embodiment, a highly conductive additive is added to the polydioxan and the colloid to form a polyacid. In the aqueous dispersion, a conductive liquid can be formed: because the dispersion can be formed, the conductive additive, especially the metal additive, is not attacked by the acid of the dispersion. Furthermore, since the polyacid is a colloid Nature, and Φ亜4 people are missing and> '' '', Comprising a main surface having an acid group, the poly woven conductive polythiophene so: as formed on the surface of the colloidal this unique structure, thus requiring only a low weight percentage of highly conductive additives, can reach a suitable reference filter Hong limit.

O:\88\8W35 DOC 1327152 Examples of conductive additives include, but are not limited to, metal particles and nanoparticles, nanowires, carbon nanotubes, graphite fibers or particles, carbon particles, and combinations thereof. In another embodiment of the invention, there is provided a buffer layer formed by forming a polyacid comprising a polythiophene and a colloid, including a polydioxy phenanthrene and a colloid forming polyacid as an aqueous dispersion of a specific embodiment. In a specific embodiment, the buffer layer is cast from an aqueous dispersion comprising a colloid to form a polysulfonic acid. In a specific embodiment, the buffer layer is cast from an aqueous dispersion comprising a poly(alkylene dioxymethane) and a fluorinated polyacid colloid. In another embodiment, the fluorinated polyacid colloid is a fluorinated polyacid colloid. In another embodiment, the buffer layer comprises poly(M-ethylenedioxythiophene) and perfluoroethylene. An aqueous dispersion of a sulfonic acid colloid is cast. Polyporphins, including polydioxythiophenes and polyacid colloids, such as dry films of fluorinated polysulfonic acid colloids, are generally not redispersed in water. Therefore, the buffer layer can be coated into a plurality of layers. Moreover, the buffer layer can be covered by a layer of different water-soluble or water-dispersible materials without damage. In another embodiment, a buffer layer is provided that is formed from a polyporide comprising a polydithiolactide and a colloid to form a polyacid and blended with other water soluble or water dispersible materials - = aqueous dispersion. Depending on the final application of the material. 疋, examples of additional types of water-soluble or water-dispersible materials may be added, including but not limited to polymers, dyes, coated auxiliaries, carbon nanotubes, nanowires, organic and inorganic Conductive inks and pastes, charge transport materials, crosslinkers, and combinations thereof. This material can be a simple molecule or a polymer. Examples of suitable other water soluble or water dispersible polymers include, but are not limited to, conductive poly

0, 88\88435 00C -20- Complexes such as polybenzazole, polyaniline, polyamine, poly, ratio, each, & fast and combinations thereof. In another embodiment of the invention, an electronic device, a medium to y device layer, is provided between the two electrical contact layers to provide an electrical layer of the tongue (usually a semiconductive common polymer) comprising a buffer layer of the invention. An embodiment of the present invention is illustrated in a device of the type illustrated in Figure} which is a device having an anode layer 110' buffer layer 120, an electroluminescent layer 130 and a cathode layer 150. Adjacent to the cathode layer 15 is an electron injecting/transporting layer 'mo. Between the buffer layer 120 and the cathode layer 150 (or the scorpion injection/transport layer WO) is the electroluminescent layer 13A. The gaze may comprise a support or substrate (not shown) that may abut the anode layer 110 or the cathode layer 150. Most often the support abuts the anode layer 11〇. The support can be flexible or rigid, organic or inorganic. Generally, a glass or a copper-coated organic film can be used as a support. The anode layer 11A is an electrode which can be injected into the hole more efficiently than the cathode layer 150. The anode may comprise a material comprising a metal, a mixed metal, an alloy, a metal oxide or a mixed oxide. Suitable materials include mixed oxidation of Group 2 elements (ie, Be, Mg, Ca, Sr, Ba, Ra), Group " family elements, elements of Groups 4, 5 and 6 and Group 8_1 Group transition metal elements. Things. If the anode 11 is permeable to light, a mixed oxide of elements of Groups 12, 13 and 14 may be used, such as indium tin oxide. As used herein, "mixed oxide, sheet language is equivalent to an oxide having two or more different cations selected from Group 2 elements or Group 12, 13 or 14 elements. Part of the anode layer 〇 1 〇 material is not limited Specific examples include, but are not limited to, indium tin oxide ("IT〇"), alumina tin gold, silver, copper, and nickel. The anode may also contain organic materials such as polyaniline or polypyrrole. 〇.\88^8435 OOC - 2i * 1327152 Thoroughly use the IUPAC nomenclature system, which groups the population of the periodic table from left to right 1-18 (CRC Handbook of Chemistry and Physics, 81st edition, 2 years). The anode layer 110 can be chemically or physically Formed by a vapor deposition process or a spin casting process. Chemical vapor deposition can be performed by plasma assisted chemical vapor deposition ("PECVD") or metal organic chemical vapor deposition ("M〇CVD"). Physical vapor deposition can include all types of sputtering, including ion beam sputtering and e-beam plating and thermal blocking. Special types of physical vapor deposition including ^ magnetron

Sputtering and inductively coupled plasma physical vapor deposition ("IMp_pvD"). These deposition techniques are well known in the art of semiconducting fabrication.

The anode layer 110 can be patterned during a photolithographic etching operation. This pattern can be changed as needed. These layers may be formed in a patterned form prior to application of the first electrical contact layer material by, for example, placing a pattern "mask or resist" on the first flexural composite barrier structure. Alternatively, the layers are applied as a monolithic layer (so-called full deposition) and then patterned using, for example, a patterned resist layer and a wet chemical or dry etch technique. Patterning programs well known in the art can also be used. When the electronic devices are in an array, the anode layer η〇 generally forms substantially parallel strips, and the length of the strips extends substantially in the same direction. Buffer layer 120 is typically deposited on a substrate using a variety of techniques well known to those skilled in the art. Typical casting techniques include, for example, solution casting, drop casting, flood coating, screen printing, inkjet printing, and the like or 'buffer layers can be used to make many deposition processes, such as inkjet printing. The electroluminescent (EL) layer 130 is typically a co-light polymer such as poly(p-phenylene)' abbreviated as PPV or W. The particular material selected may depend on the particular application, the potential used during the process, or other factors. The EL layer 1 30 comprising the electroluminescent organic material O:\8S\88435 D〇c • 22-1327152 can be applied by solution by any conventional technique including spin coating, casting and printing. Depending on the nature of the material, the EL organic material can be directly coated by a vapor deposition process. In another embodiment, the EL polymer precursor is coated and then typically converted to a polymer by heat or other applied energy source such as visible light or uv radiation. Layer 140 may be selected to aid electron injection/transfer and may also serve as a confinement layer to prevent the layer interface from terminating the reaction. More specifically, if layers 13 and 15 are otherwise in direct contact, layer 140 promotes electron mobility and reduces the likelihood of termination of the reaction. Examples of materials for layer 140 include, but are not limited to, metal chelating oxinoid compounds (such as Alqs or the like); morphine matrix compounds (such as 2,9-dimercapto-4,7-diphenyl-) 1,1 〇 morpholine ("DDPA"), 4,7 diphenyl-no- phenanthroline ("DPA") or the like; azole compound (such as 2_(4_biphenyl)_5 — (4_First Dingben)-1,3,4-° Evil-sigma sitting ("PBD" or the like), 3-(4-linked base)_心笨基-5-(4-third Butylbenzene 4-triazole ("TAZ" or the like); other similar compounds; or any combination of one or more thereof. Alternatively, the layer 14 is an inorganic material and contains ruthenium, LiF, Li20 or the like. Cathode layer 150 is an electrode that is particularly effective for injecting electrons or negatively charge carriers. Cathode layer 15 can be any metal or non-metal having a lower working function than the first electrical contact layer (in the example, anode layer 11A). The term "lower working function" as used herein refers to a material whose working function is not greater than approximately 4.4 eV. As used herein, ''higher working function' is intended to refer to a working function. Less than 4.4 ev of material. The material of the cathode layer may be selected from the alkali metal of Group 1 (such as L!, Na, K, Rb, Cs), the second known metal (such as Mg, Ca, Ba or the like), Group 12 metal,

O:\88\88435.DOC -23 - 1327152 Lanthanide (such as Ce, Sm, Eu or the like) and lanthanide (such as Th, u or the like). Materials such as aluminum, indium, antimony, and combinations thereof can also be used. Specific non-limiting examples of cathode layer materials include, but are not limited to, ruthenium, lithium, osmium, ruthenium, osmium, iridium, magnesium, osmium, and alloys and compositions thereof. The cathode layer 150 is typically formed by a chemical or physical vapor deposition process. At one point, the cathode layer will be patterned as discussed above for the anode layer. If the device is placed in an array, the cathode layer i 5 can be patterned into substantially parallel strips 'where the length of the cathode layer strips is substantially extending in the same direction and substantially perpendicular to the length of the anode layer strips . An electronic component called a pixel is formed at the intersection point (the anode layer strip intersects the cathode layer strip at this point when viewed from a plane or a plan view). In other embodiments, an additional layer may exist. In an organic electronic device, for example, a layer (not shown) between the buffer layer 120 and the rainbow layer 130 can help the positive charge transfer 'band gap fit each layer as a protective layer or the like. Similarly, the EL layer 130 and the cathode Additional layers (not shown) between layers 150 may aid in the transfer of negative charges, with gaps in between, as a protective layer or the like. The layers known in the art may be used. Moreover, any of the above layers may be made of two or more layers. Or 'partial or all inorganic anode layer (10), buffer layer trace (1) and cathode layer thoracic surface treatment to increase the charge carrier transfer efficiency. (4) Selection of each component layer by the purpose of providing high plant efficiency The trade-off between manufacturing cost, manufacturing complexity, or other possible factors may vary. The different layers may have any suitable thickness. The inorganic anode layer (iv) is typically not much near 500 nanometers, such as near 1G_2GG nanometers. Buffer layer 12〇 usually not

0 \88\88435 DOC -24- =: 〇 nanon', for example, near 50_200 nm =. . Nano's, for example, near 5". Nano; layer 14 is selected. Usually not more than nearly 100 亳 half, ', such as nearly 20-80 nm; cathode layer 150 is usually no more than nearly 100 nano-half, Cangjie, ', 1-50 nm. If anode 110 or cathode 150 must penetrate at least -4b ~ the thickness of this layer must not exceed approximately 100 nanometers. Depending on the application of the display electronics, the rainbow layer 13() can be a signal-activated luminescence: (as in a light-emitting diode) or a layer of material that responds to radiant energy with or without an applied voltage (eg, shop) Measurer or voltaic battery). After reading this patent description, the enthusiasm of this technology will be able to choose the material suitable for its (4) system. The luminescent material may be dispersed in a substrate of another material or may be separately formed with or without additives. The anal layer 130 generally has a thickness in the range of approximately 50-500 nanometers. Examples of other organic electronic devices that may benefit from having an aqueous dispersion comprising - or multiple layers comprising (iv) phenone and polyacid colloids include (1) devices that convert electrical energy into radiation (eg, light emitting diodes, light emitting diode displays, or diodes) Laser), (2) devices that detect signals from electronic programs (such as photodetectors (such as photoconductive cells, photoresistors, photoelectric switches, optoelectronic crystals, photocells), and detectors), (3) A device that converts into electrical energy (such as a photovoltaic device or a solar cell) and (4) a device (eg, a transistor or a diode) that includes - or a plurality of electronic components - wherein the electronic component includes one or more organic semiconducting layers. In the organic light-emitting diode (0LED), electrons and holes are injected into the EL layer 130 from the cathode ^50 and the anode 110, respectively, to form negative and positively charged ions in the polymer. These polar ions migrate under the influence of the applied electric field, form polar ionic excitons with opposite charge species, and then undergo radiation recombination. A sufficient potential difference between the anode and the cathode can be applied in the device, typically less than approximately 12 volts. O:\88\88435.DOC -25· In the case of 5 noon, the system is no more than approximately 5 volts. The actual potential difference can be used in a larger electronic component. [In many embodiments, the anode layer 110 is biased to a positive voltage, and the cathode layer 150 is grounded or zeroed on the slab of the electronic device. volt. The battery or other power source can be electrically connected to the electronic device as part of the circuit, but not illustrated in Figure 1. It has been found that a ruthenium LED having a buffer layer has a long life, wherein the buffer layer is formed by an aqueous dispersion containing polydioxan-4 and a colloid to form a polyacid. The buffer layer may be formed by washing an aqueous dispersion of polydioxane and a fluorinated polysulfonic acid colloid; in a specific embodiment, the aqueous dispersion is a dispersion having a pH adjusted to about 3.5 or more. The use of lower acid or pH neutral materials significantly reduces the etching of the IT layer during device fabrication, thus extremely low enthalpy and "ion concentration diffuses into the 聚合物led polymer layer. Because of the suspected enthalpy and Sn ions, the operating life is reduced. It is an important profit. Lower acidity also reduces corrosion of metal components (such as electrical contact pads) on the display during manufacturing and during long-term storage. PEDT/PSSA residues will react with residual moisture, releasing acid to the display causing slowness Corrosion. Equipment used to disperse acidic PEDT/PSSA must be specially designed to handle the strong acidity of PEDT/PSSA. For example, chrome-plated slot die coating heads for coating pEDT/pssA on ιτο substrates were found to be pEDT/ The acidity of pssA is corroded. This makes the head unusable because the coated film is contaminated with chromium particles. Moreover, the manufacture of OLED displays is of interest to certain inkjet printheads. They are used for buffer layers and luminescent polymers. The layers are distributed on the display at the exact position O:\88\88435.DOC -26- ^27152 2. These print heads contain a nickel mesh filter as an internal trap for the ink particles. These nickel filters Acidic PED/PSSA decomposition/, Field 1 and Tanjung method. The use of the aqueous PEDT dispersion of the present invention which has been reduced in acidity will not cause these corrosion problems. Further, it has been found that certain luminescent polymers are sensitive to acidic conditions, and If it is in contact with the acidic buffer layer, its light-emitting ability will be lowered. It is preferred to use the invention of the aqueous PEDT dispersion to form a buffer layer because of its low acidity or 4 Km·^ | right luminescent materials require different cathode materials for optimum It would be complicated to make a full-color or partial-color display with two or fewer different luminescent materials. The display device is composed of multiple illuminating pixels. There are at least two different types of pixels that emit different colors of light. (Sometimes equivalent to - under-pixels.) The sub-pixels are made up of different luminescent materials. It is highly desirable to have a single cathode material that can provide good device performance for all light emitters. 4 Reduce the complexity of device fabrication. Found that common cathodes can be used The buffer layer is made of the aqueous PEDT dispersion of the present invention and has a colorful device f for each color. The cathode can be any of the above. The materials discussed are made and may be covered with a more inert metal such as aluminum. Benefits may be obtained from aqueous dispersions having - or multiple layers comprising polycuts, including polydioxane and at least one colloid to form a polyacid. Other organic electronic devices include (1) devices that convert electricity 15 into conditioned devices (such as light-emitting diodes, hair: diode displays or diode lasers), and (2) devices that detect signals from electronic programs (eg, Photoinverter (such as photoconductive battery, photoresistor, photoelectric switch, photoelectric crystal, photocell), IR detector), (3) device that converts radiation into electrical energy (such as

0.\88\88435 DOC -27- 1327152 t- or solar cells) and (4) semi-conducting layers or diodes containing - or multiple electronic components) where the electronic component contains one or more There is a cover: == The conductive polymer layer coated with the liquid or solvent is coated with the conductive polymer, and the transfer can also improve the coating property. Suitable porphin/3⁄4 phenyl b-bundle but not limited to polyaniline, poly 4 phenanthene

0223 in the blessing _ to ... month of the declaration of the DuPont number UC compound. .... Polyacid-colloid, poly(tetra), polybromide and its combination. In a specific embodiment, a polydioxane and a field effect transistor are provided as electrodes, and the conductivity is two:=. The liquid for use in the film polymer must disperse or dissolve the conductive I1 valley to avoid redissolution of the conductive polymer or semiconductive polymer. Conductivity of a thin film field effect transistor made of conductive hydrate. However, the water-soluble poly:= there is: in... the conductivity is around ~ Μ S / cm or lower. Therefore, in a specific example of j yoke, the electrode comprises poly(ethylene oxide, gamma, ^, and fluorinated colloids to form a polyfluorene-based conductivity enhancer such as a nanowire or a carbon nanotube Or the like. In another embodiment, the electrode comprises a polycolloid to form a perfluoroethylene acid and is in turn introduced to the m) and a nanotube or the like. The present invention can be used as a thin film field effect transistor, and another method for the present invention is another one of the inventions of Fig. 2: Crystal. here

〇 \88\88435 DOC -28· 1327152 In the description, the dielectric polymer or dielectric oxide film 21 has a gate 2 2 0 on one side and a drain 2 3 〇 and a source 2 4 另一 on the other side. The organic semiconductive film 25 is deposited between the drain and the source. The invention includes a nanowire or a carbon nanotube. The invention can be ideally used in applications such as gate, immersion and source, because it is in solution film deposition with an organic matrix dielectric polymer and The phase tropism of semiconducting polyδ. Because the conductive composition of the present invention, such as a specific embodiment of PEDT and colloidal perfluoroethylene sulfonic acid, is present as a colloidal dispersion, the percentage of conductive filler required to achieve a high conductivity percolation limit is relatively low (relative to the inclusion of water soluble) Composition of polysulfonic acid). In another embodiment of the invention, there is provided a method of making an aqueous dispersion of polydioxythiophene comprising polymerizing a dioxyl far olefin monomer in the presence of a polysulfonic acid colloid. In a particular embodiment of the method of the invention, the polydioxane is a polyalkylene dioxy sulfonate and the colloid-forming polysulfonic acid is fluorinated. In another embodiment of the method of the invention, the polydioxophene is poly(3,4-exoethylenedioxy-terminated) and the colloid-forming polysulfonic acid is perfluorinated. In another embodiment of the method of the invention, the colloid-forming polysulfonic acid is peroxyethylene sulfonic acid. The polymerization is carried out in the presence of water. The resulting reaction mixture can be treated with an ion exchange resin to remove reaction by-products. The invention will now be described in more detail by reference to the following non-limiting examples. EXAMPLES Comparative Example 1 This comparative example illustrates the oxidative polymerization of ethylenedioxythiophene in the presence of a water-soluble polysulfonic acid, i.e., poly(p-ethylidene acid) (PSSA), to produce a non-colloidal poly(ethylenedioxy). Thiophene) / poly (stupidyl sulfonic acid) (PEDT / PSSA) complex. O:\88\88435.DOC -29- 1327152 A solution of iron sulfate was prepared by dissolving 0.3246 g of iron sulfate hydrate (Sigma-Aldrich, St. Louis, MO) in deionized water to give a solution having a total weight of 39.4566 g. This 2.28 grams of ferric sulfate solution in a plastic bottle with 300 grams of deionized water, 10.00 grams? 33 eight (30% by weight? 33, molecular weight 70,000, PolySciences, Remington, PA) and 1.72 grams of sodium persulfate (Fluka, Sigma-Aldrich, St. Louis, Missouri, USA). Iron sulfate is used as a catalyst for polymerization, and sodium persulfate is an oxidizing agent for the oxidative polymerization of ethylenedioxy porphin. The mixture was stirred and then placed in a 3-neck 500 ml flask equipped with a hot well for thermocouples. The mixture was stirred using a stirring paddle driven by a pneumatic overhead stirrer, and 0.63 ml of 3,4-extended ethylenedioxythiophene (Baytron®-M available from Bayer, Pittsburgh, PA) was added to the PSS A-containing mixture. The polymerization of 3,4-extended ethylenedioxysulfonate was carried out at room temperature, i.e., at about 22 ° C for 24 hours. As a result of the polymerization, the clarified liquid turned into a dark liquid having a color in which the PEDT/PSSA complex was dispersed in water. The filterability of the PEDT/PSSA complex dispersion was tested with a 5.0 micron Millex®-SV syringe filter available from Millipore Corporation (Bedford, MA). Applying high pressure by hand Only clear, colorless liquid passes through the filter on the syringe plunger, thus indicating that the PEDT/PSSA complex particles are too large to pass through the filter. An aqueous dispersion of about 158 grams of one-half PEDT/PSSA complex is additionally treated with two ion exchange resins. One is a cation exchanger, cross-linked polystyrene sodium sulfonate (Lewatit® S100 WS, available from Bayer Corporation of Pittsburgh, PA). The other is an anion exchanger, a cross-linked polystyrene third/quaternary amine free test/vapor (Lewatit® MP62 WS, by 〇 \88\88435 DOC -30-1327152

Obtained by Bayer of Pittsburgh, PA). Clean 53 grams of Lewatit® S100 WS and 51 grams of Lewatit® MP62 WS ′ with deionized water until the water has no color. The two washed resins were then filtered prior to mixing with 158 grams of the aqueous dispersion of PEDT/PSSA complex. The mixture was stirred with a magnetic stirrer for 8 hours. The resin was removed by filtration. An aqueous dispersion of the resin-treated PEDT/PSSA complex was measured by gravimetric analysis to contain 1.2% by weight solids. The resin was then tested with a 5.0 micron Millex®-SV syringe filter from Millipore Corporation (Bedford, MA) and a 1.2 micron GF/C syringe filter from Whatman Corporation (Clifton, New Jersey, USA). The filterability of the PEDT/PSSA aqueous dispersion. The dispersion passed through a 5.0 micron Millex®-SV syringe filter, but with a high pressure applied to the syringe plunger by hand, only the clear, colorless liquid passed through the 1.2 micron GF/C syringe filter. The average particle diameter of the resin-treated PEDT/PSSA complex particles was measured by light scattering as described above, and found to be 1.12 μm (average of five measurements, standard deviation of 0.04 μm), and the polymerization dispersion was 〇, 40 . The conductivity and f-luminescence properties of the resin treated PEDT/PSSA complex were then tested. A commercially available indium tin oxide (IT0)/glass plate having an ITO layer of 110 to 150 nm thick was cut into a sample having a size of 30 cm x 30 cm. The ITO layer is then etched with oxygen plasma. The 1τ〇 on the glass substrate to be used for conductivity measurement is etched into a series of parallel turns to be used as electrodes. The IT0 on the substrate to be made into an LED for luminescence measurement was etched into a 15 cm X 20 cm ITO layer as an anode. An aqueous dispersion of the resin-treated PEDT/PSSA complex was spin coated onto each ITO/glass substrate at a rotational speed of 1200 rpm. The resulting PEDT/PSSA complex layer was about 140 nm thick. The layer 0:\88«8435.D0C -31 - 1327152 is uneven. The IT0/glass substrate coated with the pedt/pssa complex was dried in nitrogen at 90 ° C for 30 minutes. The conductivity of the PEDT/PSSA complex layer was measured by measuring the resistance between the electrodes and based on the resistance, the thickness of the conductive layer, and the distance between the two resistors used to measure the resistance, the conductivity was calculated to be 61 x 10 -3 s / cm. For luminescence measurement 'The ultra-yellow emitter poly(substituted phenyl b) (obtained from Pov 131 from Covion, Frankfurt, Germany) was applied to the top of the PEDT/PSSA complex layer as active electroluminescence (EL) )Floor. The thickness of the £1^ layer is approximately 70 nm. The thickness of all films was measured by the TENC〇R 5〇〇 surface % profiler. For the cathode, the Ba and A1 layers are vapor deposited on the top of the EL layer at a vacuum of 1·3χ1 〇·4 Pa. The final thickness of the Ba layer is 3 nm;

The thickness of the A1 layer at the top of the Ba layer is 3 〇〇 nanometer. The performance of the LED device is tested as follows. The change in current applied to the applied voltage and the luminous intensity were measured by a Keithley 236 source-measuring unit from Keithley Instruments, Ohio, and a S37 illuminometer with a corrected calender diode (UDt Sensor, Hawthorne, Calif.). The change in voltage applied and the luminous efficiency (candle | female-cd/A). Five LED devices were tested by increasing the applied voltage to obtain a light intensity of 2 〇〇candela/cm 2 . The applied voltage of the intensity is 5.0 volts, and the average light efficiency is 5 4 candelas/ampere. These devices have a stress half-life of less than 〖, and the stress half-life of the time. Example 1 Polymerization in the presence of Nafion® and describes the properties of the poly(epi-ethoxy p-phene) thus obtained. U2.68 g (16.03 mmol of Nafion® monomer unit) SE-10072

0\88\8S435.DOC • 32- and 173.45 grams of deionized water are poured into a 500 ml Nalgenic® plastic bottle. First, deionized water was used to dissolve 0.0667 g of iron sulfate hydrate (97%, Sigma-Aldrich, St. Louis, Missouri, USA) to prepare a total solution of 12 2775 grams of iron sulphate stock solution. Then, 1 _4 gram of ferric sulphate solution and 1.72 g (7.224 mM) of sodium persulfate (Fluka, Sigma-Aldrich, St. Louis, Missouri, USA) were placed in plastic bottles. Place the lid tightly back on the Nalgenic® plastic bottle and shake the bottle vigorously with your hand. The contents of the bottle were poured into the above 5 liter milliliter three-necked flask. The mixture was then stirred in a reaction vessel for 3 minutes. With stirring, 〇_63 ml (5.911 mmol) & ^011_]^ (trade name of 3,4-ethylenedioxy porphin purchased by Bayer, Pittsburgh, USA) was added to the reaction. In the mixture. The polymerization was allowed to stir at about 23. Let's go under your arm. Within 1 hour and 7 minutes, the polymerization liquid turned into a very dark blue color, which was then filled into two 250 ml plastic coatings. When the reaction vessel was opened, it was noted that there were no gel particles on the glass wall of the stirring shaft or the reaction vessel. The total yield of the polymerization liquid was 297.10 g. Assuming that there was no loss and complete conversion, the liquid contained 5.303% (w/w) solids. It is speculated that the solid mainly contains poly(3,4-extension|ethyl-oxy-p-thiophene), PEDT/Naficm®.

P An aqueous PEDT/Nafion® in one of 148 75 g two plastic bottles was treated with two ion exchange resins. One of the two resins is Lewatit® si00, a trade name for sodium sulfonate of crosslinked polystyrene available from Bayer Corporation of Pittsburgh, PA. Another ion exchange resin is Lewatit® MP62WS, a free base/vapor of cross-linked polystyrene tertiary/quaternary amine available from Bayer Corporation of Pittsburgh, PA. Before use, wash the two resins with deionized water and see that the water has no color. Then 7 75 g] ^; ^ price (§) 31 〇〇 and 78 O: \88 \88435.DOC -33- 1327152 gram Lewatit® MP62® WS mixed with 148.75 grams of aqueous PEDT/Nafion® dispersion in a plastic bottle . The bottle was then placed on a roller and stirred for about 23 hours. The resulting slurry was then filtered through a thick semi-molten glass bucket. The yield was 110.2 g. Based on the elemental analysis of a sample dried by a 2.6% (w/w) dispersion, the sample contained 21.75% carbon, 0.23% hydrogen, 1.06% nitrogen, and 2.45% sulfur. No other elements such as oxygen and fluorine were analyzed. To remove the interference of I on the sulfur analysis, CeCl3 and a cation exchange resin were added. Ten grams of PEDT/Nafion® dispersion was mixed with 10.01 grams of deionized water based on a dry solids weight analysis which constituted 2.6% (w/w) solids. The conductivity and luminescent properties of the aqueous PEDT/Nafion® dispersion were then tested. A glass/ITO substrate (30 cm x 30 cm) having an ITO thickness of 100 to 150 nm and an ITO light-emitting area of 15 cm x 20 cm was cleaned as in Comparative Example 2, followed by treatment with oxygen plasma. The aqueous PEDT/Nafion® dispersion was spin coated onto the ITO/glass substrate at a rotational speed of 700 rpm to produce a 96 nm thickness. The ITO/glass substrate coated with PEDT/Nafion® was dried in a vacuum oven at 90 ° C for 30 minutes. The PEDT/Nafion® film was measured to have a conductivity of 2.4 x 1 (T3 and 5.7 x 1 (T4 S/cm.) The ultra-yellow emitter (PDY 131) was then applied to the top of the PEDT/Nafion® layer, where the ultra-yellow emitter was a Poly (substituted phenylacetylene) from Covion (Frankfurt, Germany). The thickness of the EL layer is approximately 70 nm. The thickness of all films is measured by the TENCOR 500 surface profiler. For the cathode, Ba and A1 layers Vapor deposition on the top of the EL layer at a vacuum of T6. The final thickness of the Ba layer was 30 angstroms; the thickness of the A1 layer was 3000 angstroms. The performance of the device was tested as follows. It was purchased from Keithley Instruments (Cleveland, Ohio). ) 0\88\88435.DOC -34- 1327152

Keithley 236 source-measure unit and purchased from udt company (California

Hawthorne) The s37 illuminometer with a calibrated neon diode measures the change in current, the change in luminescence intensity versus the applied voltage, and the efficiency. The five illuminators tested showed an operating voltage range from 32 to 33 volts at a brightness of 200 watts per square meter with luminous efficiencies ranging from 8.3 ray/amperes to 9.8 candelas per amp. These devices are at 8 inches. The stress half-life of the underarm is in the range of 243 to 303 hours. Comparative Example 2' This comparative example illustrates the solid film properties obtained by drying a commercially available % PEDT dispersion made of water-soluble poly(styrenesulfonic acid). About 3 〇 ml in a glass beaker at room temperature in a nitrogen stream was purchased from H c

Starck, GmbH (Leverkusen, Germany) Baytron-P VP A1 4083 (batch number 06Y76982) is dried into a solid film. This dry film sheet is mixed with about 1 ml of deionized water and the mixture is shaken by hand, and the water turns blue. When most of the flakes were redispersed in water, the color became very deep and the water became very acidic. Using color from EM Science (Gibbs〇n, New Jersey, USA, catalogue number 959〇)| 1^1@indicator (卩^10-14 range) obtains 1) 11 as 〇. Comparative Example 3 This comparative example illustrates the moisture absorption of a solid film obtained by drying another commercially available aqueous PEDT dispersion made of another water-soluble poly(styrenesulfonic acid). About 30 ml of glass beaker in a nitrogen stream at room temperature is constructed from h. C.

Starck, GmbH (Leverkusen, Germany) Baytron-P CH8(R) (batch number CHN0004) was dried to form a solid film. Most of the dry film was tested for redispersibility and acidity in about 10 ml of deionized water and found to behave as described in Comparative Example 2 O:\88\884i5 D0C -35-1327152. A small portion of the dry film sheet was then equilibrated under ambient conditions before analyzing the moisture absorbance by a thermogravimetric analyzer (at a rate of 20 ° C / min in nitrogen). This film sheet absorbed 29.4% water under ambient conditions. This result clearly shows that the PEDT film is extremely hygroscopic, and any water that has absorbed water becomes very acidic as described in Example 2. VP AI 4083 and CH8000 PEDT are sold as buffer layers for OLEDs. Example 2 This example illustrates the properties of a solid film formed by drying the aqueous PEDT/Nafion® of the present invention. Approximately 30 ml of the aqueous PEDT/Nafion® (2.6%) of Example 1 was dried into a solid film in a glass beaker at room temperature under a stream of nitrogen. Most of the dry film flakes were mixed with deionized water and the mixture was shaken with water. The continued illumination of the sheet indicates that the film is not inflated. Surprisingly, the water is colorless, indicating that PEDT/Nafion® is no longer dispersible in water. Moreover, the pH of the water was obtained using a color 卩1^51@ indicator (range 卩11 0-14 range) purchased from EM Science (New Jersey, USA 0丨1^3〇11; catalog number 95 90) 7. This result clearly shows that the acid is not moving. Again, this result shows that the PEDT/Nafion® surface is primarily a conductive layer with a sulfonic acid anion charge balanced by PEDT. A small portion of the dry film sheet was equilibrated under ambient conditions by a thermogravimetric analyzer (analyze the moisture absorbance at 2 (TC/min speed) in nitrogen. This film sheet only absorbed 5.6% water, which is much lower. The commercially available PEDT as described in Comparative Example 3. The low moisture absorbance also indicates that the PEDT/Nafion® surface is primarily a conductive layer having a sulfonic acid anion charge balanced by PEDT. This makes it more hygroscopic than Comparative Examples 2 and 3. The dry film was made low. O:\88\88435.DOC -36- 1327152 Example 3 In a thin film field effect transistor This example illustrates the use of an aqueous PEDT/Nafi〇n8 as an electrode. The dry film described in Part 2 It is mixed with toluene, chloroform or bismuth (the common, organic solvent used to dissolve the organic semiconductive polymer used in the thin film field effect transistor). The film is not bubbled by the organic solvent or the film is discolored by the solvent. This result clearly shows that the PEDT/Nafi〇n8 film is compatible with the organic solvent of the semiconductive polymer. Because the conductive polymer is bound by the aqueous dispersion, the water will not attack and dissolve only in the organic aromatic solvent, such as Benzene or chlorinated A semi-conductive polymer such as a gas-like or di-methane.

The conductivity of the aqueous PEDT/Nafi〇n@dispersion (2.6% w/w) prepared in Example 2 was tested. The glass/germanium substrate (3 cm cm 3 cm) with an IT0 thickness of 1 〇〇 to 15 〇 nm was cleaned and then treated with oxygen. The IT. A parallel etched tantalum wire is provided on the substrate for resistance measurement. The aqueous PEDT/Nafion® dispersion was spin coated onto a ruthenium/glass substrate. The PEDT/Nafion® coated glass/glass substrate is 9 inches in a vacuum supply. Dry under the arm for 30 minutes. The conductivity of the PEDT/Nafion® film was measured to be 2.4 x 10 〇 3 and 5.7 x 10 S/cm. This conductivity is lower than that required for thin film field effect transistor electrodes. However, the use of conductive PEDT/Nafion® in which the conductive polymer is present in the dispersion as a colloid allows the incorporation of a conductive filler such as a nanowire, a metal nanoparticle or a nanotube. For example, a metal molybdenum wire having a diameter of 15 nm and a conductivity of 1.7 x 10 4 S/cm is available and as Zach et al.

It can be used to improve conductivity as described in Science, Vol. 290, page 2120. Carbon 0\88\88435.DOC -37- 1327152 nanotubes with a diameter of 8 nm, a length of 20 μm and a conductivity of 60 S/cm are also available and are available as Niu et al. at corpse/zys. Ze/ ί., as described in Volume 70, page 1480, can be used to increase conductivity. Because of the colloidal nature of PEDT/Nafion® and the predominantly conductive surface of the particles, once PEDT/Nafion® is bonded, the high percentage of conductive filler required for high conductivity percolation limits is low. EXAMPLE 4 This example 5 shows the polymerization of B. ethoxyphene 11 in different conditions and in the presence of Nafion®. Three different types of Nafi on® resins are used: SE-10072, DE-1021 and DE-1020. Aqueous Nafion® dispersion and water were added to the jacketed flask. The mixture was warmed to the indicated temperature and allowed to mix for 45 minutes. An oxidizing agent, a catalyst, and a dioxoprene monomer are sequentially added to the mixture. After the addition is complete, the mixture is allowed to stir at the indicated temperature for a indicated period of time. The reaction mixture is then batch treated with Lewatit® strong acid cation tree ruthenium (sodium form) and Lewatit® weakly anion resin or passed through a column containing the two ion exchange resins to terminate the reaction. The resulting slurry mixture was then stirred at room temperature for 6 hours and then filtered through a filter paper (pore size > 20-25 microns). The filtrate was then filtered through filter paper (pore size > 6 microns). The resulting filtrate was filtered through a 0.45 micron filter. The resulting filtrate was formulated into the final product having the desired solid content by addition and shaking with sufficient shaking. The polymerization parameters are summarized in Table 1 below.

O:\88\88435.DOC -38- 1327152 Table 1. Summary of the synthesis of PEDT/Nafion® Nafion oxidant / Nafion / temperature reaction ion obtained sample batch monomer monomer (°C) time (hours, minutes) Exchange PEDT· Nafion (%) PEDT· Nafion (%) A SE-10072 1.221 2.756 20.2 20,49 Lot 2.81 2.8 B DE-1021 1.221 2.756 20.2 20,47 Lot 2.81 2.8 C DE-1021 1.221 2.756 20.2 21, 00 Column 2.81 2.8 D DE-1020 1.221 2.756 20.2 21,00 Lot 2.81 2.8 E DE-1020 1.221 2.756 20.1 21,00 Column 2.81 2.8 F DE-1020 1.221 5.513 20.2 23,15 Column 2.80 5.5 G DE- 1021 1.221 5.513 20.2 44,08 Column 2.80 5.9 H DE-1020 1.221 5.513 20.2 24,56 Lot 5.48 5.4 I DE-1020 0.50 3.00 20.2 23,43 Lot 2.89 2.8 J DE-1020 1.50 3.00 20.1 24,00 Tube Column 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 Column 3.01 3.0 N DE-1020 1.25 3.00 35.0 14,54 Batch 4.52 3.4 0 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 Lot 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 Column 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 3.5 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 batches 4.53 3.5 II DE-1020 1.75 2.75 35.0 13,05 batch 4.53 3.0 KK DE-1020 0.75 2.75 35.0 13,27 lot 4.51 3.5 KK DE-1020 0 .75 2.50 35.0 13,25 Lot 4.51 3.5 LL DE-1020 0.75 2.25 35.0 5,55 Batch 4.52 3.5 O:\88\88435 DOC -39- 1327152 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 00 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 batches 4.51 3.5 example 5

This example illustrates the difference in conductivity of each film made from the PEDT/Nafion® dispersion of Example 4. The glass substrate was prepared using a patterned ITO electrode. The buffer layer was spin-cast from the indicated dispersion to form a film on top of the pattern substrate, followed by baking at 90 ° C for 0.5 hour in a vacuum oven. The resistance between the ITO electrodes was measured using a high resistance static electricity meter in a dry box. The film thickness was measured using a Dec-Tac surface profiler (Alpha-Step 500 surface profiler, Tencor instrument). The conductivity of the buffer layer is calculated from the resistance and the thickness. The results are graphically represented in Figures 3 and 4. It can be seen that the conductivity can be excellently controlled in the range of 1 (T2 S/cm to 10_9 S/cm by the change of composition. Example 6

This example illustrates the performance of different PEDT/Nafion® compositions for use as a buffer layer in OLEDs. Using soluble poly(1,4-phenylacetylene) copolymer (C-PPV) (H. Becker, H. Spreitzer, W. Kreduer, E. Kluge, H. Schenk, ID Parker AY. Cao, Ji/v. Ma /er. 12, 42 (2000)) A light-emitting diode is produced as an active semiconductive light-emitting polymer; the thickness of the C-PPV film is 700-900 angstroms. C-PPV emits yellow-green light at ~5 60 nm with a radiation peak. Indium oxide/tin is used as the anode. The PEDT/Nafion® film was spin-dried from the solution on the top surface of the pattern substrate and then baked in a vacuum oven at 90 ° C for 0.5 hours. The device structure is ITO/PEDT- Nafion®/C-PPV/metal. A device was fabricated using ITO on glass as a base 88 \88\88435 DOC -40-1327152 plate (coated ITO/glass). The apparatus was prepared using a Ca or Ba layer as a cathode. A metal cathode film was fabricated on the top surface of the C-PPV layer by vacuum vapor deposition at a pressure of less than 1 X 1 (Γ6 Torr, resulting in an active layer having an area of 3 cm 2 . STM-100 thickness/rate meter (Sycon Instruments) monitors the deposition. 2,000-5,000 angstroms of aluminum is deposited on the top surface of the 30 angstrom or calcium layer. The current versus voltage curve, the light versus voltage curve, and the quantum efficiency of each device are measured. UV hardened epoxy resin cover glass encapsulation. It is operated in an oven at 80 ° C and a fixed current. The total current through the device is ~10 mA, and the brightness is nearly 200 turbid / square meter or 600 candelas. / square meter. Record the brightness and voltage of each device to determine the half-life and voltage increase rate at 80 ° C. The results are provided in Table 2. Table 2. Device performance sample ED Rotation 〆 M 〇 ° C Rate thickness conductivity Voltage efficiency IL tl/2 IL* t,/2 [rpm] [Angstrom] [S/cm] [Volt] [Cloudy/Amp] [Candle/m2] [Hour] 4-N 3000 1114 1.2x10'° 3.8-3.9 (1) 7.8-8.8 (1) 141 252 35532 4-Q 2000 2096 6.9x10° 3.0-3.1 (1) 8.8-9.7 (1) 162 317 51354 4-X 2300 1390 1.0x1 O'4 3-5(2) 10.6(2) 468 140 65520 4-Z 2000 840 5.9x10'° 4.6(2) 9.3(2) 471 102 48042 4-AA 800 1227 2.4x10° 4(2) 10(2) 449 112 50288 Control 1 1200 1400 6.1xl0'J 5(1) 5-4(1) <1 IL = initial brightness (1) at 200 candelas per square meter The amount of (2) is measured at 600 candelas per square meter.

0\88\88435.DOC -41 - rI327152 This example illustrates the preparation of a PEDT/Nafion® aqueous dispersion. Nafi〇n®® A 12.5% (w/w) aqueous colloidal dispersion having an EW of 990 was prepared using a procedure similar to that of U.S. Patent No. 6,150,426, Example 9. 63.87 g (8.06 mmol) ^心〇11@单单位)1^£][〇11@aqueous colloidal dispersion and 234_47g deionized water concentrated in 5〇〇 ml set of three-necked round bottom flask in. Mix the mixture for 45 minutes before adding ferric sulfate and sodium persulfate. First, deionized water was used to dissolve 〇 〇 141 g of ferric sulfate hydrate (97%,

Aldrich model number 30,771-8) obtained a total weight of 3.6363 grams of iron sulfate stock solution, then G.96 grams (G.GG72 millimoles) sulfur g "iron solution and · 0.85 grams (3,57 millimol The ear sodium persulfate (Fluka, catalog number 71899) was placed in the reaction flask and the mixture was stirred. Then, before adding 12 ml (2·928 mmol) Baytron-M (trade name of 3,4_ethylenedioxy 4 phene from Bayer, Pittsburgh, USA), the mixture was stirred for 3 minutes, then Baytron-M was added to the reaction mixture with stirring. The polymerization was allowed to proceed by stirring at about 20 ° C controlled by the circulating fluid. The polymerization liquid began to change color within 13 minutes. The reaction was terminated by the addition of 8.91 g of Lewatit® S100 and 7.70 g of Lewatit® MP62 WS, which was sold under the trade name of sodium sulfonate of cross-linked polystyrene from Bayer, Pittsburgh, Pennsylvania.

Lewatit® MP62 WS is the trade name for the free base/vapor of crosslinked polystyrene tertiary/quaternary amines obtained from Bayer Corporation of Pittsburgh, PA. Wash the two resins separately with deionized water before use until the water has no color. This resin treatment was carried out for 5 hours. The resulting slurry was then suction filtered through Whatman, No. 54 filter paper. It passes the filter paper very quickly. The yield was 244 grams. The % solids was about 31% (w/w) based on the added polymer component. Purchased from

OA88\S8435.DOC -42- 1327152

The pH of the aqueous PEDT/Nafion® was 3.8 measured by a 3 1 5 pH/ion meter from Corning (Corning, NY). Example 8 This example illustrates the non-dispersibility of PEDT/Nafion 8 dry film. Approximately 10 ml of the aqueous PEDT/Nafion® dispersion prepared in Example 7 was dried under a nitrogen stream at ambient temperature and mixed with 10 ml of deionized water. The water remains colorless and clarifies for several months. Example 9

This example demonstrates that the aqueous PEDT/Nafion® dispersion is non-corrosive to ITO. The aqueous PEDT/Nafion 8 prepared in Example 7 was spin-coated on an ITO substrate. The top surface of the PEDT/Nafion® was tested using an X-ray photoelectron spectroscopy (XPS). No indium or tin was detected, indicating that the ITO was not attacked by an aqueous PEDT/Nafion® dispersion having a pH of 3.8. Comparative Example 4 This comparative example illustrates the redispersibility of dry Baytron-P and its effect on ITO

Rotten money. CH8000, one from H. C. Starck GmbH (Leverkusen, Germany)

The OLED grade Baytron-P is an aqueous poly(3,4-ethylenedioxythiophene) made from polystyrenesulfonic acid (pss A). Has been selected 1'. ? £01' right? The ratio of 33 and polystyrene sulfonate (PSS) is 1:20 (weight/weight). The pH of PEDT/PSS/PSSA is in the range 1. PEDT/PSS/PSSA, which is dried from an aqueous dispersion under ambient conditions, is easily redispersed in water. PEDT/PSS/PSSA was coated on ITO as in Example 9. Indium and tin were measured by X-ray photoelectron spectroscopy (XPS) on top surface, indicating that ITO 〇\88\88435 DOC -43-1327152 was attacked by aqueous PEDT/PSS/PSSA dispersion with pH ~1 . Examples 10-12 These examples illustrate the use of PEDT/Nafion® in multilayer coatings. Example 10 This example illustrates the formation of a thicker layer using a multilayer coating of aqueous PEDT/Nafion®. The aqueous PEDT/Nafion® dispersion prepared in the same manner as in Example 7 was continuously spin-coated three times at a rotation speed of 800 rpm. The cast film was baked at 90 ° C in a vacuum between each spin coating. The thickness was measured with a Tencor profiler and the average of the two measurements was taken. After baking, the first layer = 99 nm. After baking, the second layer (total thickness) = 203 nm. After baking, the third layer (total thickness) = 322 nm. The thickness data clearly indicates that each deposition thickness is about 1 〇〇 nanometer. In addition, the data also shows that dry PEDT/Nafion® membranes are no longer dispersible in water. Example 11 This example illustrates the use of PEDT/NaHon® in an OLED with two buffer layers, where the PEDT/Nafion® system is in contact with the ITO anode. Two aqueous PEDT dispersions were used to construct a double buffer layer for luminescence testing. One is the CH8000 (batch number KIM4952) described in Comparative Example 4. The other is the aqueous PEDT/Nafion® described in Example 7. A glass/ITO substrate (30 cm x 30 cm) having an ITO thickness of 100 to 150 nm and an ITO light-emitting area of 15 cm x 20 cm was cleaned and then treated with oxygen plasma. The aqueous PEDT/Nafion® dispersion was first spin coated onto an ITO/glass OA88\88435.DOC-44- 1327152 substrate and then baked at 90 ° C for 30 minutes in vacuum. The CH8000 was then coated on the top surface of the PEDT/Nafion® layer and then baked at 90 ° C for 30 minutes in a vacuum. The total thickness of the double layer is 86 nm. A solution of BP-79 (Dow Chemical Co., Blue Luminescent Polymer) in diphenylbenzene (1_2% w/w) was then applied to the top surface of the double buffer layer. The thickness of the BP-79 layer is 70 nm. Then, under the vacuum of lxlO·6 Torr, LiF, Ca and finally aluminum were respectively 2 nm.

A thickness of 20 nm and 500 nm was vapor deposited on the BP-79 layer. The device made from the two-layer structure has an initial efficiency of 2.9 to 3.5 candelas per amp and an initial operating voltage of 3.8 to 3.9 volts. At room temperature, the device has a half-life of 307 hours. This illustrates the practicality of PEDT/Nafion® as a passivation layer for ITO. Example 12 This example illustrates the use of PEDT/Nafion® in an OLED having two buffer layers, wherein the PEDT/Nafion® is in contact with the EL layer. CH8000 (batch number KIM4952) was spin coated onto an ITO/glass substrate as described in Example 11, followed by baking at 200 ° C for 3 f minutes on a hot plate in air. This layer has a thickness of 85 nm. The aqueous PEDT/Nafion® was then applied to the top surface of the CH8000 layer and then baked at 90 ° C for 30 minutes in a vacuum. The thickness of the PEDT/Nafion® layer is 21 nm. A solution of BP-79 (Dow Chemical Co., Blue Luminescent Polymer) in diphenylbenzene (1.2% w/w) was then applied to the top surface of the double buffer layer. The thickness of the BP-79 layer is 70 nm. Then, LiF, Ca, and finally aluminum were vapor-deposited on the BP-79 layer at a thickness of 2 nm, 20 nm, and 500 nm, respectively, under a vacuum of T6 Torr. The initial efficiency of the resulting device is 2.5 to 3.1 candelas / ampere 0 \88 \88435 DOC -45 - 1327152 ps, the initial operating voltage is 4.1 to 4.2 volts. At room temperature, the half-life of the device is 54 hours. This is similar to CH8000 alone. The lifetime of the device produced was much lower than the half-life described in Example 11. This comparison illustrates the passivation function of PEDT/Nafion® in contact with the ITO substrate. Example 13 This example illustrates the use of a PEDT/Nafion® buffer layer and green light. A preferred operational life of a polymer OLED device. The OLED device is fabricated as follows: a 30 cm x 30 cm glass substrate having an ITO area of 15 cm x 20 cm is cleaned with a solvent and oxygen plasma. The ITO layer is 100-150 nm thick. The aqueous PEDT/Nafion® dispersion was spin coated onto the ITO/glass substrate in air and baked in vacuum for 30 minutes at 90° C. The thickness of the dry film was in the range of 50-100 nm. The substrate is filled with nitrogen and the amount of oxygen and water is ~1 pp In a dry box of m. The luminescent polymer, DOW Green K2 (Dow Chemical Company, Midland, Michigan) was spin coated onto the top surface of the PEDT/Nafion® layer. The D〇W K2 solution was ~1% solids in the second layer. The benzene solvent was then baked again in a dry box at 130 ° C for 5 minutes. The thickness of the K 2 layer was ~ 75 nm. These substrates were then transferred into a thermal evaporator at approximately 1×1 (T6 Torr vacuum) The cathode is deposited. The cathode consists of ~5 nm Ba, then ~0.5 μm A1. Finally, these devices are removed from the oven and sealed before operating life testing in the environmental chamber. The operating life test conditions for these displays are : Initial brightness of 200 candelas per square meter, DC fixed current, test temperature of 80 ° C (to speed up the test procedure). The results are graphically represented in Figure 5. Estimated life ratios for displays with PEDT/Nafion® The display of PEDT/PSSA is nearly 10 times longer. a\SS诏8435 DOC -46- 1327152 The initial operating voltage of PEDT/Nafion® is about ~10% lower. Moreover, the voltage increase rate is about ~25% lower. Example illustrates the use of PEDT/Nafion® buffer layer and red Preferred Operating Life of OLED Devices for Luminescent Polymers OLED devices are fabricated as follows: a 30 cm x 30 cm glass substrate having an ITO area of 15 cm x 20 cm is cleaned with solvent and oxygen plasma. The ITO layer is 100-150 nm thick. The aqueous PEDT/NaHon® dispersion was spin coated onto the ITO/glass substrate in air and baked in vacuum at 90 ° C for 30 minutes. The thickness of this dry film is in the range of 50-1 000 nm. The substrates were then transferred to a dry box filled with nitrogen and having an oxygen and water content of ~1 ppm. The luminescent polymer, AEF 2 1 57 (Covion GmbH, Frankfurt, Germany), was spin coated onto the top surface of the PEDT/Nafion® layer. The AEF 2157 solution was ~1% solids in toluene solvent. The films were then baked again in a dry box at 1 30 ° C for 5 minutes. AEF 2 15 7 layers have a thickness of ~75 nm. The substrates were then transferred into a thermal evaporator and the cathode was deposited at approximately 1 x 1 (T6 Torr vacuum. The cathode consisted of ~5 nm Ba, then ~0.5 micron Α1. Finally, these devices were removed from the dry box and Sealed before the operational life test in the environmental chamber. The operating life test conditions of these displays are: initial brightness of 170 candelas per square meter, DC fixed current, and test temperature of 80 ° C (in order to speed up the test procedure). Shown in Figure 6. The life expectancy of a display with PEDT/Nafion® is nearly four times longer than that of a display with PEDT/PSSA. The initial operating voltage of PEDT/Nafion® is about ~20% lower. The σ rate is about > 3 times. 〇\88\88435 DOC -47- 1327152 Example 15 This example illustrates the preferred operational lifetime of an OLED device utilizing a PEDT/Nafion® buffer layer and a blue light emitting polymer. The manufacture is as follows: a 30 cm χ 3 cm glass substrate having an ITO area of 15 cm X 20 mils is cleaned with a solvent and an oxygen plasma. The IT 〇 layer is 100-150 nm thick. The water is 1 gt; £] 〇 171 ^^!1〇11@Dispersion spray coating Bake on a 1 〇/glass substrate and vacuum for 9 〇t for 3 〇t. The dry film thickness is in the range of 50-1 〇〇 nanometer. The substrates are then filled with nitrogen and the amount of oxygen and water is ~i ppm in a dry box. The luminescent polymer, SCB-11 (Midland 2D〇wK, Michigan), was spin coated onto the top surface of the PEDT/Nafi0n® layer. The SCB_n solution was ~1% solids in xylene solvent. Then, the films were again baked in a dry box at 13 (5 minutes under rc. The thickness of the SCB-11 layer was ~75 nm. These substrates were then transferred to the thermal evaporation and near 1x1 〇6 Torr. The cathode was deposited under vacuum. The cathode consisted of ~2 nm LiF followed by 20 nm Ca and then ~5 μm A1. Finally, these devices were removed from the dry box and sealed before operating life testing in the environmental chamber. The operational life test conditions of these displays are: initial brightness of 170 candelas per square meter, DC fixed current, and test temperature of 8 〇 °c (in order to speed up the test procedure). The results are graphically represented in Figure 7. With pEDT/Nafi 〇n8 display estimated life ratio is P The display of EDT/psSA is nearly 1 times longer. The initial operating voltage of PEDT/Nafi〇n® is about ~2〇% lower, and the voltage increase rate is more than 6 times lower. Example 16-21

0\88\88435.DOC -48· 1327152 These examples illustrate the effect of pH on different PEDT buffer layers. Example 16 This example illustrates the preparation of PEDT/Nafion®. Nafi〇n® is a 12.5% (w/w) aqueous colloidal dispersion having an ew of 1050, which is similar to the procedure of Example 9 of U.S. Patent No. 6,150,42. 150.90 g (17.25 mmol of Nafion® monomer unit) Nafion® (1050 EW) aqueous colloidal dispersion (12%, weight/weight) and 235.1 1 gram of deionized water were concentrated in 500 ml Nalgene® plastic bottles. Then roll for about 2 hours. The dilute colloidal dispersion was then transferred to a 500 ml jacketed three-necked round bottom flask. Due to the loss of a small amount of dispersion in the transfer, only 146 18 grams of ^ 〇 〇 118 transferred to the reaction flask was approximately 16.71 millimoles Nafion®. An iron sulfate stock solution having a total weight of 3.285 grams was prepared by deionized water > glutamine 0.0339 g of iron sulfate hydrate (97%, Aldrich model number 30,771-8). Then 1.50 g (0.03 15 mmol) of ferric sulfate solution and 1 76 g (7.392 mmol) of sulfur per fluent (F1U k a, catalog number 718 9 9) were placed in the reaction flask and mixed

Compound. The mixture was then stirred for 5 minutes before the addition of 0.647 ml (6.071 mmol) of 837 to 1 - 1 ^ with stirring. "The polymerization was carried out at about 20 ° C controlled by the circulating fluid with stirring. The polymerization liquid began to turn blue in 5 minutes. As in Example 7, the reaction was terminated by adding 20.99 g of 1^\\^@3100 and 20.44 g of Lewatit® MP62 WS at 3.2 hours. Before use, wash the two resins separately with deionized water until the water has no color. This resin treatment was carried out for 21 hours. The resulting mud was then collected by Whatman, No. 54 paper, and filtered. Filtration is extremely easy. The solid % was about 4.89% (w/w) based on the added polymer component. 0\88\88435.DOC -49- 1327152 Add 255.6 grams with deionized water? £〇1' Chuan & Negative 11@ makes a total weight of 480.8 grams to make 2.6% solids (weight/weight). The pH of the dilute aqueous PEDT/Nafion® was determined to be 3.9 using a 315 pH/ion meter purchased from Corning Corporation (Corning, NY). Example 17 This example illustrates the preparation of a PEDT/Nafion® dispersion having a pH of 2.2.

The dilute PEDT/Nafion® prepared in Example 16 was used as a starting material. 3.07 g of Dowex 5 50A resin (Aldrich model number 43,660-7) was added as a strong base anion exchange resin and stirring was continued for 1.2 hours. Wash Dowex 550A with deionized water before use until the water has no color. The mixture was filtered and 3.0 g of Amberlyst 15 (Aldrich model number 21,639,9 'proton cation exchange resin) was added to the liquid, stirring was continued for 45 minutes and filtered. 3.0 grams of fresh Amberlyst 15 was added to the effluent and the mixing was continued for 15 hours and transitioned for OLED testing. Amberlyst 1 5 is washed several times with deionized water before use. Measured water treated by Amberlyst 15

The pH of PEDT/Nafion® is 2.2. Example 18 This example illustrates the preparation of a PEDT/Nafion® dispersion having a pH of 4.3. A PEDT/Nafion® batch was prepared in the same manner as in Example 16. 61. 2 g of the thus obtained dispersion was diluted to 2.8% by weight (by weight & weight) with 45.05 g of deionized. The pH of this dilute dispersion was 4.3. EXAMPLE 19 This example illustrates the preparation of a PEDT/Nafion® dispersion having a pH of 7.0 using a lithium salt. 0 O:\88\SS435 DOC • 50· 1327152 The PEDT/NaHon® dispersion neutralized by ionic ions is described in a wide range. . This is a two-step procedure: first removing the residual metal ions left by the synthesis by proton exchange; then using a second ion exchange to exchange the ions with lithium ions. This gives a southern purity dispersion.

The dilute PEDT/Nafion® as described in Example 16 was first treated with 5.13 grams of Dowex 550A resin (Aldrich Model No. 43,660-7), a strong base anion exchange resin and stirring was continued for 2 hours. Wash Dowex 550A with deionized water until any color is present in the water before use. The mixture was filtered and treated with 4.13 g of 八1^61^3115 (8, 1 〇11 type number 21, 63 9,9, proton cation exchange resin), and the mixture was continuously mixed for 1 hr and filtered. Then 3.14 grams of fresh Amberlyst 15 was added and stirring was continued for 1.5 hours. Finally, the data was separated. 37.82 grams of acidified PEDT/Nafion® was then treated with 1.99 grams, 2.33 grams, 2.06 grams, 2.08 grams, and 20.00 grams of Amberlyst 15 lithium salt. Replace each fresh Amberlyst 1 5 lithium salt and filter the mixture. Moreover, in each filter

The mixture was stirred and the total resin treatment time was 7 hours. The pH of the treated Nafion® was determined to be 7.0. Example 20 This example illustrates the preparation of a PEDT/Nafion® dispersion having a pH of 7.2 using a sodium salt. The PEDT/Nafion® dispersion neutralized by Nanoparticles. The starting material was the lithium ion dispersion described in Example 16. Additional treatment of the ions is replaced by sodium ions as described below. This gives a high purity dispersion. Treatment of 2.76 g, 3.57 g '3.55 g and 3.25 g Lewatit® S100 O:\88\88435.DOC -51 · 1327152 The dilute PEDT/Nafion® described in Example 16. The mixture was filtered between each fresh resin. Further, the mixture was stirred between each filtration, and the total resin treatment time was 7 hours. The pH of the treated Nafion® was measured to be 7.2. Comparative Example 5 This comparative example illustrates the preparation of a PEDT/PSSA dispersion having an improved pH.

Sample Control 5-A

PEDT/PSSA (AI4083 > an OLED grade Baytron-P from C. Starck GmbH, Leverkusen, Germany) has a pH of 1.8.

Sample Control 5-B

58.9 grams of deionized AI4083 (purchased from H. C. Starck, such as deionized AI4083) was added via salt to a total of 10 grams of Amberly St 15 over 24 hours. The mixture was stirred during the entire time. The mixture was filtered and the pH of the collected filtrate was measured to be 3.2. Sample Control 5-C

58.18 grams of deionized AI4083 was added over a period of about 18 hours with a total of 14 grams of Amberly st 15 钡 salt. The mixture was stirred during the entire time. The mixture was filtered and the pH of the collected filtrate was measured to be 3.4.

The sample control 5-D was purchased from H. C. Starck GmbH and should be free of sodium deionized AI4083 for conversion to the tetrabutylammonium salt. 50.96 grams of deionized AI4083 was added over 20 hours with a total of about 9 grams of Amberlyst 1 5 tetrabutylammonium salt. The mixture was stirred throughout the time. The mixture was filtered and the pH of the collected filtrate was determined to be 4.3. Similarly, AI4083 samples were treated with lithium and planer ion exchange resins, and another 0\88\88435.DOC -52· 1327152 produced two series of samples with ρ Η values greater than 1,8. Example 21 This example illustrates the performance of an OLED produced by using the dispersion of Example 16-2 1 and Comparative Example 5 to prepare a buffer layer. These devices were prepared in a manner similar to that described in Example 6. The following EL polymers were used: Name Polymer Type Manufacturer Super Yellow PPV Covion Blue BP79 Poly 芴 Dow Green K2 Poly 芴 Dow AEF 2198 Poly Helox Covion where π snail is equivalent to poly snail - bismuth. Figure 8 (a) to 8(c) shows the initial device performance of a PLED containing a PEDT/PSS buffer layer and pH adjusted. Clearly, increasing the pH of Baytron-P to much higher than 2_5 significantly reduces the performance of the OLED device. Figure 8(a) And 8(b) compare Baytron-P AI4071 with Baytron-P AI4083, two similar products but with different conductivity. Their pH has been adjusted with sodium ion exchange resin. Figures 8(c) and 8(d) show lithium And the planer ion exchange resin caused some phenomena, respectively. Figures 9(a) to 9(c) show the initial device performance of a pH-adjusted OLED containing a PEDT/Nafion® buffer layer. Unlike devices containing PEDT/PSSA, These devices are not degraded by the pH neutral buffer layer. To evaluate the operating life, a fixed DC current operating device is used to obtain an initial brightness of 200 candelas per square meter and placed in an oven at 80 ° C to accelerate its O:\ 88\88435.DOC -53- 1327152 Degradation. Continuous monitoring device in light output and operation The change in pressure is defined as the time when the brightness falls to half of its original value (ie, to 100 candelas per square meter). The results are provided in Table 3. Table 3. Operating life of the device, hour buffer layer EL polymer buffer layer pH 1.8-2.0 3.2 3.4 3.8-4.3 6.8-7.0 PEDT/Nafion Ultra-yellow 200-250 200-240 PEDT/Nafion Green K2 900-1100 900-1100 900-1100 PEDT/Nafion AEF2198 300-400 400 PEDT/PSSA Super Yellow 200-250 46 4 氺氺PEDT/PSSA Green Κ 2 400 ** 氺氺 ** The indicator does not illuminate clearly, the PEDT/PSSA unit only has a narrow pH range (ρΗ<~2·5) Good life, whereas PEDT/Nafion® units operate over a wide pH range (at least pH 1.8-7.0). Example 22 This example shows that PEDT/Nafion® does not etch ITO contacts. The ITO test substrate is prepared as follows: The 1300 ITO glass substrate was obtained from Applied Films Inc. The ITO layer was etched into a strip pattern having 300 micron wide ITO strips. These strips extended to the depth of the entire ITO layer, thus exposing the substrate glass between the strips. These strips have a well-defined edge. The Tencor profiler with a vertical repeatability of ~10 angstroms is used to measure the height of the ITO strip. Immerse the sample in CH8000 or PEDOT: NAFION at room temperature for different times. Prior to measuring the ITO thickness, the sample was rinsed with DI water and plasma etched for 15 minutes to remove any organic residue. In each of the examples, the thickness of four ITOs was measured on two different substrates, and a total of eight data points were obtained for each measurement. The PEDT/Nafion® solution was prepared as described in Example 7, and its pH was O:\88\88435.DOC • 54-1327152 3_8. The PEDT/PSSA solution is a Baytron CH 8000 having a pH of about 1. The results are shown in Figure 10. Note that after immersion in PEDT/PSSA for 24 hours, the thickness of ITO is reduced by ~1%. This is clearly visible in the optical interface color of the ITO film. In the manufacture of devices, ITO is typically exposed to liquid PEDT/PSSA for only a few seconds. However, residual moisture in the PEDT/PSSA film will permanently corrode ITO throughout the life of the unit. Dissolution of the 1% ruthenium layer will produce high concentrations of indium and tin ions in the PEDT/PSSA. Example 23

This example illustrates the compatibility of aqueous PEDT/Nafion® dispersions with PEDT/PSSA. PEDT/PSSA (Baytron-P, grade AI4083) was selected for compatibility with the aqueous PEDT/Nafion® of Example 16. An aqueous blend was prepared from 95 : 5 PEDT/Nafion® : AI4083 up to 5 : 95 PEDT/Nafion® : AI4083. All dispersion blends were found to be homogeneous and phase free. These blends are useful in the fabrication of OLEDs and other electrically activated devices.

Example 24 This example illustrates the fabrication and performance enhancement of a color OLED display using conventional cathode metal and common buffer layer polymers of all colors. The OLED device was fabricated as follows: a 30 cm x 30 cm glass substrate having an ITO area of 15 cm x 20 cm was cleaned with a solvent and oxygen plasma. The ITO layer is 100-150 nm thick. An aqueous buffer (such as PEDOT/Nafion® or Baytron-P CH8000 prepared in Example 16) was spin coated onto the ITO/glass substrate in air and baked in vacuum at 90 ° C for 30 minutes. This dry film thickness is in the range of 50-100 nm. The substrates were then transferred to a dry box filled with nitrogen 〇\SS^&43S.DOC -55-1327152 and having an oxygen and water content of ~1 ppm. A luminescent polymer (red: COVION AEF 2198, or green: DOW K2 or blue: COVION HS 670) was spin coated onto the top surface of the buffer layer. The luminescent polymer solution is ~1% solids in a common organic solvent such as toluene or xylene. The films were then baked a second time in a dry box at 130 ° C for about 5 minutes. The thickness of the luminescent layer is ~75 nm. The substrates are then moved into a thermal evaporator and placed in a vacuum

The cathode is deposited under the degree. The cathode system consists of one of the following: (1) ~ 5 nm Ba, then ~ 0.5 μm A1, or (ii) ~ 5 nm Ca, then ~ 0.5 μm A1, or (iii) ~ 5 nm LiF, then ~ 20 nm Ca, then ~0.5 micron A1. These devices are finally removed from the dry box and sealed prior to operational life testing in the environmental chamber. The operational life test conditions for these displays are: initial brightness of 200 candelas per square meter, DC fixed current, and test temperature of 80 °C (for accelerated test procedures). The results are provided in Table 4 below. Table 4 Polymer Buffer Layer Cathode Voltage (Volts) Efficiency (Candle/Amp) Life (hours) Red (AEF2198) CH8000 Ba 4.5 1.4 120 PEDOT/Nafion® Ba 4.0 1.5 500 Green (Κ2) CH8000 Ca 3.4 3.2-6.8 400 4 PEDOT/Nafion® Ca 3.0 4.0-6.0 700 ^ PEDOT/Nafion® Ba 2.8 6.0-10.0 > 2,000 Blue (HS670) CH8000 Ba 4.3 4.0-4.5 50 PEDOT/Nafion® LiF/Ca 4.7 4.0-4.5 40 PEDOT/Nafion ® Ba 4.0-4.4 4.0-4.5 150 Although the invention has been described in detail with reference to the specific embodiments thereof, it is understood that modifications and variations are within the spirit and scope of the invention. Example 25 This example illustrates the preparation of a PEDOT/Nafion® dispersion in water and a co-dispersion. Nafion® is a 12% (w/w) aqueous colloidal dispersion having an EW of 1050 prepared by a procedure similar to that of U.S. Patent No. 6,150,426, Example 9, 〇Λ88\88435 DOC-56-1327152. 95.41 g (10.89 mM Nafion® monomer unit) Nafi〇n (g) (1〇5〇EW) aqueous colloidal dispersion (12.0%, weight/weight), 18512 g deionized water and 14.49 Kebpropanol (Aldrich Model No. 49, 619-7) was concentrated in a 5 inch ml three-necked round bottom flask. The mixture was stirred for 10 minutes before adding 0.421 ml of Baytron_M dioxythiophene monomer. Stir for about 1 hour before adding ferric sulfate and ammonium persulfate. First, deionized water was used to dissolve 〇 722 g of iron sulfate hydrate (97% 'Aldrich model number 30, 771-8) to prepare a total weight of 21.44 g of iron sulfate stock solution. Then, 4.47 g (0.0452 mmol) of the iron sulfate stock solution and 1.65 g (7.23 mmol) of persulfuric acid were placed in the reaction flask and the mixture was stirred. In the final polymerization liquid, the ratio of water to 丨-propanol is 9 to 5 » and then the polymerization is carried out with stirring at about 20 ° C controlled by the circulating fluid. The polymerization liquid immediately began to turn blue. After 17 hours, the reaction was terminated by the addition of 13.89 grams of Lewatit® S100 and 13.89 grams of Lewatit® MP62 WS. Before use, wash the two resins separately with deionized water until the water has no color. This resin treatment was carried out for 5 hours. The resulting mud was then filtered through a Whatman's No. 54 filter paper. It easily passes through the filter paper. The pH of the PEDOT/Nafion® dispersion measured at 5% pH/wt by a 315 pH/ion meter available from Corning, Inc. (Corning, NY, USA) was 5.3 at 20.6 percent by weight of the polymerized component. The surface tension was measured to be 41_9 mN/m with a 1000 IUD type FTA T10 Tensiometer (Finnish KSV Instrument Co., Ltd.) at ° C. This surface tension was much lower than that of Example 7 without the use of a co-dispersion. Surface tension of aqueous PEDOT/Nafion* (~73 mN/m). Test the filterability of this dispersion. 4 〇 ml dispersion O:\88\88435.DOC -57 - 1327152 The solution passes through a 0.45 μm HV filter ( Millipore Millex-HV 25 cm, catalog number SLHVR25KS) without changing the filter. It is also noted that the viscosity of the fluid flow is judged to be significantly lower than the viscosity of the same solid % produced without the use of the co-dispersion. [Simplified illustration] BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates a cross-sectional view of an electronic device comprising a buffer layer in accordance with the present invention. Figure 2 illustrates a cross-sectional view of a thin film field effect transistor comprising an electrode in accordance with the present invention. Figure 3 illustrates the conductivity of a PEDT/Nafion 8 film with an oxidant in a polymerization reaction. Pair The ratio of the body changes. Figure 4 illustrates the conductivity of the PEDT/Nafion® film as a function of the ratio of Nafion® to monomer in the polymerization. Figure 5 illustrates the operational lifetime of an OLED device with a green light-emitting polymer. Figure 6 illustrates red light emission Operating Life of Polymeric OLED Devices Figure 7 illustrates the operational lifetime of an OLED device with a blue light emitting polymer.

Figures 8(a) through 8(d) illustrate the effect of the pH of the PEDT/PSSA buffer layer on the performance of the OLED device. Figures 9(a) through 9(c) illustrate the effect of the pH of the PEDT/Nafion® buffer layer on the performance of the OLED device. Figure 10 illustrates the change in ITO thickness when immersed in a PEDT/Nafion® or PEDT/PSSA dispersion. [Description of Symbols] 110 Anode Layer 120 Buffer Layer O:\88\88435 DOC -58- 1327152 130 Electroluminescent layer 140 Electron injection/transport layer 150 Cathode layer 210 Dielectric polymer; Dielectric oxide film 220 Gate 230 Bungee 240 Source 250 Organic Semi Conductive Film O:\88\88435 DOC -59·

Claims (1)

1327152 Patent application No. 092127470: η 1 ί--f.: Chinese patent application scope replacement (99 years f pickup, patent application scope:----11:-------[:- - A composition comprising: an aqueous dispersion of a polyfluorinated phenanthrene and at least one colloid to form a fluorinated polyacid, wherein the colloid forms a fluorinated polyacid comprising perfluoroethylene sulfonic acid, and the polydipyrimidine The phenotype is a poly(3,4-exoethylenedioxy porphin). The composition according to claim 1, wherein the polydioxythiophene has a structure: Wherein: the core and the 1^' are each independently selected from hydrogen and an alkyl group having 1 to 4 carbon atoms, or the core and 1^' together form an alkyl chain having 1 to 4 carbon atoms, as the case may be. It is substituted with a tocolyl group or an aromatic group having 1 to 12 carbon atoms, or a 1,2-cyclohexylene group, and the η system is more than 6. 3. The composition according to claim ii or 2 wherein the colloid-forming polyacid is selected from the group consisting of polyacids, polycarboxylic acids, and polyphosphoric acid or polyacrylic acid or mixtures thereof. 4. A method of making a polydioxane and at least one of the steroids to form an aqueous dispersion of a polyacid comprising: (a) providing a homogeneous aqueous mixture of monohydrate and thiophene; 88435-990127.doc 1327152 (b) providing an aqueous dispersion of the polyacid; (C) combining the thiophene mixture with the colloid to form an aqueous dispersion of the fluorinated polyacid; and (d) incorporating the oxidizing agent and the catalyst in any order of addition In the dispersion, the polydioxythiophene is poly(3,4-extended ethylenedioxy porphin). 5. The method according to claim 4, wherein the method further comprises contacting the aqueous poly P plug dispersion with at least one ion exchange resin, wherein the ion exchange resin is a cation exchange resin, an anion exchange resin Or a mixture thereof. According to the method of claim 4, wherein the method further comprises an oxidizing agent, a catalyst, a co-dispersing agent, a co-acid or all of these additional processing aids. The method of claim 4, wherein the method further comprises: an oxidizing agent selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate or a combination thereof; and a catalyst selected from the group consisting of sulfuric acid Iron, gasified iron or a mixture thereof; a co-dispersant' selected from the group consisting of a mystery, an alcohol, an alcohol ether, a cyclic acid, a ketone, a nitrile, a sub-minus, and combinations thereof; and further comprising contacting the dispersion with an ion exchange resin Wherein the ion exchange resin is selected from the group consisting of sulfonated styrene-divinylbenzene copolymers, carboxylic acid, sulfonated crosslinked stupid ethylene polymers, stupid-furfural sulfonic acid, carboxylic acid, acrylic acid, phosphoric acid, tertiary amine A quaternary amine anion exchange resin and mixtures thereof.零88435-990l27.doc drawer: an organic electronic device comprising at least one organic layer, and the organic: cerium is composed of a combination of a polyoxygen phenanthrene and at least one colloidal polyacid. The composition is prepared wherein the colloid forms a fluorinated acid A-containing perfluoroethylene sulfide, and the polydioxime is poly(3,4-ethylenedioxy-4). • The device according to claim 8 of the patent application, wherein the device is a photo sensor, a photoelectric switch, a photoresistor, a photoelectric crystal, a photocell, a claw detector, a photovoltaic cell, a solar cell, a light emitting diode, a living being Sensor, LED display or diode laser. 88435-990127.doc