TW201005020A - Aqueous dispersions of electrically conducting polymers containing inorganic nanoparticles - Google Patents

Abstract

The present invention relates to electrically conductive polymer compositions, and their use in electronic devices. The compositions contain an aqueous dispersion of at least one electrically conductive polymer doped with at least one highly-fluorinated acid polymer, and inorganic nanoparticles.

Description

201005020 VI. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a conductive polymer composition containing inorganic nanoparticles and its use in an electronic device. The present invention is a part of a continuation application of the patent application No. 12/177,359 filed on July 22, 2008, which claims priority over the provisional patent application filed on July 27, 2007. No. 952,372, both of which are incorporated herein in their entirety by reference. φ [Prior Art] Electronic devices define a class of products that include an active layer. The organic electronic device has at least one organic active layer. The devices convert electrical energy into radiation (e. g., a light-emitting diode), detect the signal via an electronic process, convert the radiation into electrical energy (e.g., photovoltaic cells), or include one or more layers of organic semiconductor. An organic light emitting diode (OLED) is an organic electronic device comprising an organic layer capable of electroluminescence. A germanium LED containing a conductive polymer can have the following configuration: anode/buffer layer/EL material/cathode and an additional layer between the electrodes. The anode is typically capable of injecting holes into any of the materials, such as indium/tin oxide (IT〇). The anode is supported on a glass or plastic substrate as needed. EL materials include fluorescent compounds, fluorescent and scalar metal complexes, conjugated polymers and mixtures thereof. Cathodes are generally any material that can inject electrons into EL materials. (eg Ca4Ba). A conductive polymer having a low electrical conductivity in the range of 10 -3 to 1 Torr-7 S/cm is generally used as a buffer layer in direct contact with a conductive inorganic oxide anode such as ITO. There is still a need for improved buffer layer materials in the industry. SUMMARY OF THE INVENTION 139092.doc 201005020 The present invention provides a composition comprising at least one aqueous dispersion of a conductive polymer doped with at least one highly fluorinated acid polymer, and in which inorganic nanoparticles are dispersed. In another embodiment, a film formed from the above composition is provided. In another embodiment, an electronic device comprising at least one layer comprising the above film is provided. [Embodiment] It should be understood by those skilled in the art that the drawings in the drawings are for the purpose of clarity and clarity and are not necessarily drawn to scale. For example, to facilitate an understanding of the embodiments, the dimensions of certain workpieces in the drawings may be exaggerated relative to other workpieces. The various aspects and embodiments are set forth herein and are merely illustrative and not limiting. After reading this specification, those skilled in the art will understand that other aspects and embodiments may be present without departing from the scope of the invention. Other features and advantages of any one or more of the embodiments will be apparent from the following description and the appended claims. The embodiment first describes the definition and interpretation of the term, and then describes the conductive polymer, highly fluorinated acid polymer, inorganic nanoparticle, preparation of the doped conductive polymer composition, buffer layer, electronic device, and finally elaborated. Example. 1 . Definitions and Interpretation of Terms Used in the Specification and Patent Application Scope Certain terms are defined or explained before the embodiments described below are elaborated. The term "conductor" and variations thereof are intended to mean a layer, component or structure having electronic properties such that the potential does not decrease significantly as current flows through the layer of material, component or structure. The term is intended to include semiconductors. In some embodiments the 'conductor can form a layer having an electrical conductivity of at least 10 Å to 7 S/cm. 139092.doc 201005020 The term "conductivity" means when referring to a material. Intrinsic or essential in the case of metal particles: capable of conducting:: black or conductive The term "polymer" is intended to mean. ^ ^ Kind of repeat single gift strict. The term includes a material having only two or more different monomer units, and eight monomer units. -Polymers, including from various classes The term "acid polymer" refers to a polymer having an acidic group.

The term "four" group refers to a group capable of ionization to supply hydrogen ions to a Bronsted base. The term "highly fluorinated" means that at least (four) of the compounds and carbon-bonded available hydrogen are replaced by fluorine. The terms "fully gasified" and "all perfluorinated carbon-bondables in the product" are used interchangeably and mean that the hydrogen is replaced by fluorine. The composition may comprise a bite chain, a plurality of electrically conductive polymers and one or more different highly fluorinated acid polymers. In the case of the conductive polymer, it is intended to direct the electropolymer to have a polymeric counterion to balance the charge on the conductive polymer. Technology, noisy V-electropolymer" is intended to guide the electropolymer and its associated polymeric counterion. The term "layer" is used interchangeably with the term "media" and refers to a coating that covers a desired area. This term is not limited by size. The area can be as large as the entire device, or as small as a specific functional area such as an actual visual display, or as small as a single sub-pixel. The layers and films can be formed by any conventional deposition technique including vapor deposition, liquid deposition (continuous and discontinuous techniques) and heat transfer. 139092.doc 201005020 The term "nanoparticles" means a particle size of less than 1〇. Material of 〇 nm. In some embodiments, the particle size is less than 10 nm. In some embodiments, the particle size is less than 5 nm 〇, the term "aqueous" means that the liquid is mostly water, and in the embodiment - to v About 40% by weight of water; in some embodiments, at least about (10)% by weight of water. t.. Hole transport" when expressing layers, materials, components or structures, "deliberation", layer, material, A component or structure facilitates the relatively efficient transfer of a positive charge through the thickness of the layer, material, component or structure with less charge loss. "Electron transfer" when expressing a layer, material, component or structure, the layer material, The element or structure may facilitate or facilitate the migration of negative charges through the layer of material, component or structure into another layer, material, component or structure. π Organic electronic device is intended to include one or more layers of semiconductor or material. Device Organic electronic devices include, but are not limited to, (1) devices that convert electrical energy into radiation (eg, light-emitting diodes, light-emitting diode displays, - polar lasers or light-emitting panels), and (7) devices that detect signals via electronic processes. (eg photodetectors, photoconductive cells, photoresistors, photoswitches, optoelectronic transistors, photocells, infrared ("IR") detectors, or biosensors)' (3) devices that convert radiation into electrical energy (eg a photovoltaic device or a solar cell, and (4) a device (eg, a transistor or a diode) comprising one or more electronic components including one or more layers of an organic semiconductor layer. The term r includes, "includes" as used herein. , "有有", or any other variation thereof, is intended to cover non-exclusive content. For example, 139092.doc 201005020, the processes, methods, objects or devices containing the elements of the series are not necessarily limited to the elements and may include List or other elements of such processes, methods, objects or installations. In addition, unless otherwise stated to the contrary, otherwise "or" means Inclusive "or" and not exclusive "or". For example, 'conditions can be satisfied by any - following proposition: A is true (or exists) and B is false (or non-existent), A is false (or Does not exist) and B is true (or exists), and both A and B are true (or exist).

Called silver, using |-" for the elements or components described in this document. This is for convenience only and is intended to provide a general understanding of the invention. This description is to be construed as inclusive, unless otherwise Corresponding to the use of the number of each of the blocks in the 7G prime periodic table, it is found in the "new symbol" convention in the 10th edition of the moxibustion, the 81st edition (2〇〇〇 2〇〇1). Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. In the chemical formula, the letters Q, R, T, W, χ, γ & ζ are used to indicate the atom or group as defined herein. All other letters are used to indicate the customary atomic symbols. Corresponding to the use of the family number of each block in the periodic table of elements, see if (10) do 00 free • less price p do ... friend, the 81st version (2 〇〇〇) in the "new symbol" convention. For the scope not described herein, many details about specific materials, processing methods, and circuits are known and can be found in textbooks on organic light-emitting diode displays, light sources, photodetectors, photovoltaic devices, and semiconductor component technologies. 201005020 and other sources. 2. Conductive Polymers Any conductive polymer can be used in the new complex. In certain embodiments, the conductive polymer can form a film having a conductivity greater than 1 〇 -7 s/cm. Conductive polymers suitable for use in the novel compositions are prepared from at least one monomer which forms a conductive homopolymer upon polymerization alone. These monomers are referred to herein as conductive precursor monomers. A monomer which forms a non-conductive homopolymer when polymerized alone is referred to as a "non-conductive precursor monomer". The conductive polymer can be a homopolymer or a copolymer. The conductive copolymer suitable for use in the new composition can be prepared from two or more conductive rigid body monomers or from a combination of one or more conductive precursor single precursor monomers. L or eve species are non-conductive: In some embodiments, the 'conductive polymer is prepared from at least one selected electrically conductive precursor monomer: phenoxy, aniline, and more. The term "polycyclic aromatic" means having: a family rr ring may be bonded by - or a plurality of bonds, or a combination: ring ^ "aromatic ring" is intended to include a heteroaryl ring. The "polycyclic hetero compound" compound has at least one heteroaromatic ring. "Fangxiang In some embodiments, the conductive polymer is prepared from a precursor monomer: thiophene, porphin, porphin". The ring-aromatic compound is derived from the following amines. Poly-phenoline, poly-polymerization (anthracene-ring aromatic polymer. The term "polyamine, and the compound of the upper aromatic ring. The ring can be," means that there is one to be able to knead to. The term "aromatic: π: a bond to be joined, or a mixture thereof" includes a heteroaromatic ring. A broad 139092.doc -8-201005020 cycloheteroarene compound has at least one heteroaromatic ring. In certain embodiments Medium polycyclic aromatic polymer poly("septene η phenophene). In certain embodiments, the new composition t is intended to form a conductive polymer monomer comprising Formula I:

Wherein: Q is selected from the group consisting of S, Se, and Te; R is independently selected to be the same or different at each occurrence and is selected from the group consisting of hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, Alkylthio, aryloxy, alkylsulfanyl, alkylaryl, arylalkyl, amine 'institutional amine group, monoalkylamino group, aryl group, alkyl group, burning oxygen Base, base, arylthio, aryl sulphate, alkoxy, aryl thiol, acrylate, phosphate, phosphonic acid, halogen, nitro , cyano, hydroxy, epoxy, decyl, decyl, alcohol, benzyl, carboxylic acid ketone, ether, ether carboxylate, decyl sulfonate, ether acid And an ester sulfonate group and an amino phthalate group; or two R1 groups may together form a stretching group or a stretching group constituting a 3, 4, 5, 6 or 7-membered aromatic ring or a cycloaliphatic ring. A base chain in which one or more divalent nitrogen, selenium, tellurium, sulfur or oxygen atoms may be included as desired. The term "alkyl" as used herein, refers to a group derived from an aliphatic hydrocarbon and includes unsubstituted or substituted straight chain, branched chain and cyclic groups. Terminology 139092.doc -9· 201005020 "Hybrid" refers to a sleek group in which one or more carbon atoms in a yard has been replaced by another atom (eg, nitrogen, oxygen, sulfur, and the like). The term "alkylene" refers to an alkyl group having two points of attachment. The term "alkenyl" as used herein, refers to a radical derived from an aliphatic hydrocarbon and having at least one carbon-carbon double bond, and includes unsubstituted or substituted linear, branched and cyclic groups. The term "heteroalkenyl" is intended to mean an alkenyl group in which one or more carbon atoms in the alkenyl group have been replaced by other atoms (e.g., nitrogen, oxygen, sulfur, and the like). The term "alkenyl" refers to an alkenyl group having two points of attachment. The term "substituent" as used herein refers to the formula listed below: "Alcohol" -R3-OH guanylamino" -R3-C(0)N(R6)R6 decyl sulfonate" -R3-C ( 0) N(R6)R4-S03z benzyl"-ch2-c6h5 carboxylate" -r3-c(o)〇-z or -r3-〇-c(o)-z ether" -R3-(0 -R5)p-0-R5 ether carboxylate" -r3-o-r4-c(o)oz or -R3-aR4-〇c(o)-z ethersulfonate" -R3-0- R4-S03Z ester sulfonate group" -R3-OC(O)-R4-S03Z sulfonimide group "-R3-S〇2-NH-S〇2-R5 urethane group" -R3- 0-C(0)-N(R6)2 wherein all "R" groups may be the same or different at each occurrence and: R3 is a single bond or an alkyl group R4 is an alkylene group 139092.doc 201005020 R5 is The alkyl group R6 is hydrogen or the alkyl group p is ruthenium or an integer between 1 and 2 ζ is ruthenium, metal, soil test metal, n(r5)4 or r5. Any of the above groups may be additionally unsubstituted or substituted, and any of the - or a plurality of hydrogens may be substituted by F, including perfluorinated groups. In certain embodiments, the alkyl and alkylene groups have from - 20 carbon atoms. In some embodiments, in the monomer, two Ris together form _w_(CYlY2)m_w_ 'where m is 2 or 3' W is 0, S, Se, P〇, nr6, Y1 is present at each occurrence Are the same or different and are hydrogen or fluorine, and Υ2 is the same or different at each occurrence and is selected from the group consisting of hydrogen, _, alkyl, alcohol, sulfonate, benzyl, carboxylate, An ether group, an ether carboxylate group, an ether sulfonate group, an ester sulfonate group, and an amino phthalate group, wherein the γ group may be partially or completely fluorinated. In certain embodiments, all Y are hydrogen. In certain embodiments, the polymer is poly(3,4-extended ethyldioxythiophene). In certain embodiments, at least one Y group is not wind. In certain embodiments, at least one Y-based oxime is a substituent substituted with at least one hydrogen via F. In certain embodiments, at least one Y group is perfluorinated. In certain embodiments, the monomer has the formula I(a): (C(R7)2),

139092.doc -11- 201005020 wherein: Q is selected from the group consisting of S, Se and Te; R7 is the same or different at each occurrence and is selected from the group consisting of argon, alkyl, miscible, dilute, heterogeneous Base, alcohol group, decyl sulfonate, sulfhydryl group, sulfhydryl group, ruthenium group, (iv) acid group, bond acid vine group, ester sulfonate group and urethane group, the premise The condition is that at least one R7 is not hydrogen and m is 2 or 3. In certain embodiments of Formula 1 (&), m is 2, one R7 is an alkyl group having 5 or more carbon atoms, and all other R7 are hydrogen. In certain embodiments of Formula 1 (a), at least one r7 group is vaporized. In certain embodiments, at least one Rule 7 group has at least one gas substituent. In certain embodiments the 'R7 group is fully fluorinated. In certain embodiments of Formula 1 (a), the r7 substituent on the fused cycloaliphatic ring of the monomer provides the monomer with improved solubility in water and is advantageous in the presence of a gasified acid polymer. polymerization. In certain embodiments of Formula I(a), m is 2, one R7 is a sulfonic acid·propionic ether methylene group and all other R7 are hydrogen. In certain embodiments, Hungry 2, one R7 is propyl-ether-extended ethyl and all other R7 are hydrogen. In some embodiments, m is 2, one R7 is methoxy and all other r7 are ammonia. In certain embodiments, one is 7 and the other is R. All of R7 are hydrogen. In certain embodiments t, the pyrrole monomer to be used to form the conductive polymer in the new composition comprises Formula II below, i39092.doc 12 (II) 201005020

Wherein in Formula II: R1 is independently selected to be the same or different at each occurrence and is selected from the group consisting of hydrogen, alkyl, alkenyl, alkoxy, alkyl fluorenyl, alkylthio, aryloxy, alkyl Sulfhydryl, alkylaryl, arylalkyl, amine, alkylamino, dialkylamino, aryl, fluorenyl, alkoxyalkyl, alkylsulfonyl, Arylthio, arylsulfinyl, oxycarbonyl, arylsulfonyl, acryl, acid-phosphonate, nitro, cyano, hydroxy, epoxy, decyl , oxoalkyl, alcohol, benzyl, phthalate, ether, decyl sulfonate, ether carboxylate, ether sulfonate, ester sulfonate and urethane Or two R1 groups may together form an alkyl or alkenyl chain constituting a 3, 4, 5, 6 or 7-membered aromatic or cycloaliphatic ring. The ring may include - or more a divalent nitrogen, sulfur, code, hydrazine or oxygen atom; and the R stages are independently selected to be the same or different at each occurrence and are selected from the group consisting of gas, alkyl, alkenyl, aryl, alkyl sulfonyl, alkyl sulphur Alkyl, alkylaryl, aryl Base, amine group, epoxy group, decyl group, decyloxy group, alcohol group, benzyl group, carboxylate group, ether group, ether carboxylate group, ether sulfonate group, ester sulfonate group and A urethane group. 139092.doc -13- 201005020 In certain embodiments, R1 is the same or different at each occurrence and is independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, Alcohol group, benzyl group, carboxylate group, ether group, decyl sulfonate group, ether carboxylate group, sulfonate group, ester sulfonate group, urethane group, epoxy group, Anthraquinone, anthracycline, and one or more sulfonic acids, carboxylic acids, acrylic acid, phosphoric acid, phosphonic acid, dentate, nitro, cyano, hydroxy, epoxy, decane or decane Partially substituted alkyl.

In a second embodiment, 'R is selected from the group consisting of hydrogen, alkyl and one or more of a repeating acid, a carboxylic acid, an acrylic acid, a phosphoric acid, a phosphonic acid, a dentate, a cyano group, a hydroxyl group, an epoxy group, a decane or a hydrazine. An alkyl group substituted with an alkane moiety. In certain embodiments, the oxime monomer is unsubstituted and Rl & R2 are both chlorine. In certain embodiments, two R1 together form a 6- or 7-membered cycloaliphatic ring, and 2 is further substituted with a group selected from the group consisting of alkyl, heteroalkyl, alcohol, thiol, carboxylic acid Ester group, ether group, ether carboxylate group, ether sulfonate group, ester sulfonate group and urethane group. These groups improve the solubility of the monomer and the polymer produced. In some embodiments, two r1s are formed into a plant or a plant

The ring is an aliphatic ring which is further substituted with an alkyl group. In certain embodiments, the two R1s together form a 6- or 7-membered cycloaliphatic ring with at least a step! Substituted by an alkyl group of carbon atoms. In some embodiments, two: 2 or 3 ' and γ are the same or different at each occurrence and are oxime, alkyl, alcohol, benzyl, decanoic acid, decyl sulfonic acid Ester group, lysine group, acidified vinegar group, vinegar acid vinegar group and aminomethyl group. In certain embodiments, at least one gamma group is not gas. In a 139092.doc.14-201005020 example to a J/-Y group is a radical in which at least one chlorine is replaced by F. In certain embodiments, at least one of the ¥ groups is perfluorinated. In certain embodiments, the aniline monomer to be used to form the conductive polymer in the new composition comprises Formula III, (R1)a

(H) bl where: a is 0 or an integer from 1 to 4; b is an integer from 1 to 5 where the condition is a + b = 5; and R1 is independently selected to be the same or different at each occurrence and Selected from hydrogen, alkyl, alkenyl, alkoxy, alkyl fluorenyl, alkylthio, aryloxy, alkylsulfanyl, alkylaryl, arylalkyl, amine, alkylamino, Dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylsulfonyl, arylsulfinyl, alkoxycarbonyl, arylsulfonyl , acrylate, phosphate, phosphonic acid, dentate, nitro, cyano, hydroxy, epoxy, alkyl, oxime, alcohol, benzyl, carboxylate, ether, ether Carboxyl ester group, decyl sulfonate group, ether sulfonate group, ester sulfonate group and urethane group; or two R1 groups may be formed together to form 3, 4, 5, 6 or 7 An alkyl or an extended alkenyl chain of an aromatic or cycloaliphatic ring which may include one or more divalent nitrogen, sulfur or oxygen atoms as desired. The aniline monomer unit may have the following formula IV(a) or formula 139092.doc -15-201005020 IV(b), or a combination of two formulas, (R1)a during polymerization.

IV(a)

Where a, b and R are as defined above. In certain embodiments, the strepamine monomer is unsubstituted and a == 〇〇 In certain embodiments, a is not deuterium and at least one R1 is vaporized. In certain embodiments, at least one R1 is perfluorinated. In certain embodiments, the fused polycyclic heteroaromatic monomer to be used in the formation of a conductive polymer in the novel composition has two or more fused aromatic rings' wherein at least one is heteroaromatic. In certain embodiments, the fused polycyclic heteroaromatic monomer has the formula V:

Wherein: Q is S, Se, Te or NR6; 139092.doc 16- 201005020 R6 is hydrogen or alkyl; R8, R9, R10 and R11 are independently selected to be the same or different at each occurrence and are selected from Hydrogen, alkyl, dilute, alkoxy, aryl, thiol, aryloxy, alkylthio, aryl, aryl, amine, alkylamine, dioxane Amino group, aryl group, alkyl group, calcined base, calcined base, arylthio group, aryl sulfhydryl group, alkoxy group, aryl group, propyl group Glycolic acid group, dish acid group, phosphonic acid group, i element, nitro group, nitrile group, cyano group, hydroxyl group, epoxy group, sulphur group, oxyalkyl group, alcohol group, benzyl group, decanoic acid group , brewing base, shouting acid vinegar, brewing amine acid s, base acid, purine group and urethane group; and R8 and R9, R9 and R10, and R10 Together with at least one of R11, a dilute base bond constituting a 5 or 6-membered aromatic ring is formed which may optionally include one or more divalent nitrogen, sulfur, selenium, tellurium or oxygen atoms. In certain embodiments, the fused polycyclic heteroaromatic ring monomer has a formula selected from the group consisting of V(a), V(b), V(c), V(4), V(f) , V(g), V(h), V(i), V(j), and v(k):

139092.doc -17- 201005020

Wherein: Q is S, Se, Te or NH; and T is the same or different at each occurrence and is selected from the group consisting of S, NR6, yttrium, SiR62, Se, Te and PR6; Y is N; and R6 is hydrogen or alkyl. The fused polycyclic heteroaromatic monomer may be additionally substituted with a group selected from the group consisting of alkyl, heteroalkyl, alcohol, benzyl, carboxylate, ether, ether carboxylate 139092.doc -18 · 201005020 base, ether sulfonate group, ester sulfonate group and urethane group. In certain embodiments, the substituents are fluorinated. In certain embodiments, the substituents are fully described. In certain embodiments, the "fused polycyclic heteroaromatic mono system thieno (thiophene). Such compounds are discussed, for example, in Macromolecules, 34, 5746-5747 (2001) and Macromolecules, 35, 7281-7286 (2002). In certain embodiments, the 'thieno (thiophene) is selected from the group consisting of thieno (2,3_b) thiophene, ° pheno[3,2-b) thiophene, and sinter (3,4-b) Thiophene. In certain embodiments, the thieno (thiophene) monomer is additionally substituted with at least one group selected from the group consisting of an alkyl group, a heteroalkyl group, a yeast group, a sulfhydryl group, a carboxylic acid aryl group, an ether group, an ether group. A carboxylate group, an ether sulfonate group, an ester sulfonate group, and a urethane group. In certain embodiments, the substituent is fluorinated. In some embodiments, the substitution base is fully described. In certain embodiments, the polycyclic heteroaromatic monomer to be used to form a polymer in a new composition comprises Formula VI:

R12

R12 (VI) wherein: Q is S, Se, Te or NR6; T is selected from the group consisting of S, NR6, yttrium, SiR6, yttrium; 2k, Te and PR6; and E is selected from the group consisting of an alkenyl group and an aryl group. 139092.doc -19. 201005020 R is nitrogen or leuco; R12 is the same or different at each occurrence and is selected from the group consisting of hydrogen, alkyl, dilute, alkoxy, sputum, burn Thio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl 'amine, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxy Alkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, aryl fluorenyl, acryl, linonic, phosphonic, dentate, exact, nitrile , cyano, thiol, epoxy, decyl, decyloxy, alcohol, benzyl, carboxylic acid, ether, ether carboxylate, decyl sulfonate, ether acid S a base, a vinegar, a vinegar group, and a urethane group; or two r12 groups may together form an alkylene group constituting a 3, 4, 5, fluorene or 7-membered-aromatic ring or a cycloaliphatic ring or An alkenyl chain, wherein the ring may include - or a plurality of divalent nitrogen, sulfur, selenium as needed , hydrazine or oxygen atom 0 In certain embodiments, a copolymer of a conductive polymer-based precursor monomer and at least one second monomer. A second monomer of any type may be used as long as it does not adversely affect the desired properties of the copolymer. In some embodiments, the second monomer accounts for less than 50% of the polymer, based on the total of the monomer units. In some embodiments, the amount of monomer units is less than 3 Å/0 of the polymer. In certain embodiments, the second unit accounts for less than 10% based on the total amount of monomer i. ^ 千的第一单的例型包包 γ m ★ includes, but is not limited to, alkenyl, alkynyl, aryl and heteroaryl. Examples of the second monomer include: (but not limited to) 苐 ... evil 139092.doc • 20- 201005020 Two β sitting, σ sedation, ethynyl, pyridine, and substituted. Benzothiadiazole

And triazines, all of which may further be in some embodiments, #', the polymer is formed by first forming an intermediate precursor having the structure Α-Β·C. Α and C represent the same or different and 5 represents the second monomer. A-B-C intermediate precursor monomers can be prepared using standard synthetic organic techniques, such as 丫_She, Stille,

Grenard complex knife solution, Suzuki, and Negishi coupling reactions. The copolymer is then formed by oxidative polymerization of the meso-body 4 monomer alone or with - or a plurality of additional precursor monomers. In a second embodiment, the electrically conductive polymer is selected from the group consisting of polyphthyl, polymeric, polymeric fused polycyclic heteroaromatic compounds, copolymers thereof, and combinations thereof. In certain embodiments, the conductive polymer is selected from the group consisting of poly(3,4-extended ethyldioxythiophene), unsubstituted polypyrrole, poly(thieno(2,3-b) Thiophene), poly(thieno(3,2-b)thiophene), and poly(thieno(3,4-b)thiophene). 3. Highly Fluorinated Acid Polymers Highly fluorinated acid polymers ("HFAP") can be any polymer that is highly fluorinated and contains acidic groups having acidic protons. The acidic group supplies ionizable protons. In certain embodiments, the acidic proton has a pKa of less than 3. In certain embodiments, the acidic proton has a pKa less than 〇. In certain embodiments, the acidic proton has a pKa of less than -5. The acidic group may be directly attached to the polymer backbone, or it may be attached to a side chain on the polymer backbone. I39092.doc • 21- 201005020 Examples of T-groups include (but are not limited to, m-acid groups, continued An acid group, a (iv) imine group, a decanoic acid group, a phosphonic acid group, and combinations thereof. The acidic group may be in the same phase @, or the polymer may have more than one type of acidic group. In some implementations In the example, the 'acid group' is selected from the group consisting of: a sulfonic acid group, a sulfonamide group, and combinations thereof. In certain embodiments, the HFAP is at least 95% fluorinated; in certain embodiments 'It is fully fluorinated. In some embodiments, ship!> is water soluble. In certain embodiments, HFAP can be dispersed in water. In certain embodiments, Η· can be wetted by an organic solvent The term "organic solvent turbidity wet" means that the contact angle of the material with the organic solvent is not more than 6 generations when the film is formed. In some embodiments, the wettable material can form a film which can be wetted by phenylhexidone. A method in which the contact angle is not greater than 55 and the contact angle is measured is well known. In some embodiments: a wettable material The material can be prepared by polymerizing an acid which is not wettable by itself but which can be made wettable by selective additives. ~ Examples of suitable polymer backbones include, but are not limited to, polyolefins, polyacrylates, Polyf-based acrylates, polyimines, polyamines, linalylamines, polyacrylamides, polystyrenes, and copolymers thereof, all of which are highly fluorinated; in certain embodiments, In one embodiment, the acid-based sulfonic acid group or the sulfonimide group has the following formula: -S〇2-NH-S〇2-R R is an alkyl group. In one embodiment, the acidic group is located on the fluorinated side chain. In an embodiment 139092.doc -22· 201005020 the 'fluorinated side chain is selected from the group consisting of alkyl, alkoxy, decylamine Bases, ether groups, and combinations thereof, all of which are fully fluorinated. In the case of real fines, HFAP has a southern fluorinated dilute primary bond, and a pendant fluorinated alkyl sulfonate, highly fluorinated. An ether sulfonate, a highly fluorinated ester sulfonic acid vinegar, or a highly fluorinated ether sulfonimide group. In one embodiment, the HFAP system has a perfluoro-ether-acid side Perfluoroolefin. In one embodiment, the polymer is vinylidene fluoride and 2-0'-difluoro-2-(trifluoromethyl) allyloxy)-1,1,2, a copolymer of 2-tetrafluoroethyl acid. In one embodiment, the polymer is ethylene and 2-(2-(1,2,2-trifluoroethyleneoxydip, ^, 3,3,3-hexafluoropropoxy)-1,1, a copolymer of 2,2-tetrafluoroethanesulfonic acid which can be converted to a hydrogenated form after preparation of the corresponding fluoropolymer. In one embodiment, the HFAP is fluorinated and partially a homopolymer or copolymer of a sulfonated poly(aryl ether sulfone). The copolymer may be a block copolymer. In one embodiment 'HFAP is a sulfonimide polymer of formula IX: S〇2 -Rf-S〇2-N Η

among them:

Rf is selected from the group consisting of a two-degree fluorinated alkyl group, a highly heterozygous alkyl group, a highly derivatized aryl group, and a highly fluorinated heteroaryl group, which may be substituted with one or more ether oxygens; and η is at least Is 4. 139092.doc -23- 201005020 In one embodiment of Formula IX, Rf is a perfluoroalkyl group. In one embodiment, Rf is perfluorobutyl. In one embodiment, Rf contains ether oxygen. In an embodiment, η is greater than 10. In one embodiment, the HFAP comprises a highly fluorinated polymer backbone and a side chain having the formula X: -OR15-S02-NH-(S〇2-NS〇2-N)a-S02R16 (X) Η Η R15 is a highly fluorinated alkyl or highly fluorinated alkyl; R16 is a highly fluorinated alkyl or highly fluorinated aryl; and a is 0 or an integer from 1 to 4. In one embodiment, the HFAP has the formula XI: (CF2-CF2)c-(CF2-CF> π(XI) Ο" I 16 (CF2-CF-0)c-(CF2)c-S02-N-( S02-(CF2)c-S02-N)c-S02R16 Η Η R16 wherein: R16 is a highly fluorinated alkyl group or a highly fluorinated aryl group; c is independently 0 or an integer from 1 to 3; and η is at least 4. The synthesis of HFAP is described, for example, in A. Feiring et al. A 5 J. Fluorine Chemistry 2000, 105, 129-135; A. Feiring 139092.doc -24- 201005020 et al., Macromolecules 2000, 33, 9262-9271 ; DD

Desmarteau, J. Fluorine Chem. 1995, 72, 203-208; A. J. Appleby et al., J. Electrochem. Soc. 1993, 140(1), 109-111; and Desmarteau, U.S. Patent No. 5,463,005. In one embodiment, the HFAP also comprises repeating units derived from at least one highly fluorinated ethylenically unsaturated compound. Perfluoroolefins contain from 2 to 20 carbon atoms. Representative perfluoroolefins include, but are not limited to, tetrafluoroethylene, hexafluoropropylene, perfluoro-(2,2-dimercapto-1,3-dioxole), perfluoro-(2-Asia Methyl-4-methyl-1,3-dioxolane), CF2=CFO(CF2)tCF=CF2 (where t is 1 or 2), and Rf"OCF=CF2 (wherein the RfM system has from 1 to about A saturated perfluoroalkyl group of 10 carbon atoms). In one embodiment, the system is a single system of tetrafluoroethylene. In one embodiment, the HFAP colloid forms a polymeric acid. As used herein, the term "colloidal formation" means a material that is insoluble in water and forms a colloid when dispersed in an aqueous medium. The colloid-forming polymeric acid typically has a molecular weight of between about 1 Torr and about 4,000,000. In one embodiment, the polymeric acid has a molecular weight of from about φ 100,000 to about 2,000,000. The colloidal particle size is usually from 2 nanometers (nm) to about 140 nm. In one embodiment, the colloid has a particle size of from 2 nm to about 30 nm. Any highly fluorinated colloid having an acidic proton can be used to form the polymeric material. Certain polymers described above may be formed in a non-acid form, such as a salt, an ester, or a sulfonium fluoride. It can be converted to an acid shape as described below for the preparation of a conductive composition. In certain embodiments, the HFAP comprises a highly fluorinated carbon backbone and a side chain designated as 139092.doc • 25· 201005020 -(0-CF2CFRf3)a-0-CF2CFRf4S03E5 wherein Rf3 and Rf4 are independently selected from F , Cl or a highly fluorinated alkyl group having from 1 to 10 carbon atoms, a = 0 '1 or 2, and E5. In some cases, E5 may be a cation such as Li, Na, or K, and may be converted to an acid form. In certain embodiments, the HFAP can be a polymer disclosed in U.S. Patent No. 3,282,875 and U.S. Patent Nos. 4,358,545 and 4,940,525. In certain embodiments, the HFAP comprises a perfluorocarbon backbone and a side chain of the formula -o-cf2cf(cf3)-o-cf2cf2so3e5 wherein E5 is as defined above. Such HFAPs are disclosed in U.S. Patent No. 3,282,875 and may be prepared by the following methods: tetrafluoroethylene (TFE) and perfluorinated vinyl ether cf2 = cf-o-cf2cf (cf3)-o-cf2cf2so2f (ie full Fluorine (3,6-dioxa-4-indolyl-7-octenesulfonylfluorene) (??)^0?)) is copolymerized and then converted to a solvent by hydrolysis of a sulfonium fluoride group The sulfonate group is ion exchanged as needed to convert it to the desired ionic form. An example of a polymer of the type disclosed in U.S. Patent Nos. 4,358,545 and 4,940,525 has a side chain - 〇-CF2CF2S03E5, wherein E5 is as defined above. This polymer can be prepared by subjecting tetrafluoroethylene (TFE) to perfluorinated vinyl ether CF2 = CF-0-CF2CF2S02F (ie, perfluoro(3-oxa-4-pentenesulfonate) (POPF) copolymerization followed by hydrolysis and further ion exchange as needed. One type of HFAP is available as an aqueous Nafion® dispersion from EI du Pont de Nemours and Company (Wilmington, DE). 4. Inorganic Nanoparticles 139092.doc -26- 201005020 The inorganic nanoparticle may be an insulator or a semiconductor. In certain embodiments, the inorganic nanoparticle is a metal sulfide or a metal oxide. Examples of the semiconductor metal oxide include, but are not limited to, a mixed valence metal oxide. (eg zinc citrate), and non-stoichiometric metal oxides (eg, oxygen-deficient molybdenum dioxide, vanadium pentoxide, and the like). Zinc citrate Zn〇/Sb2〇5 is sold under the trade name “Celnax” and various ratios. It is commercially available from Nissan Chemical Co., Ltd. (see, for example, U.S. Patent No. 5,7,7,552). Examples of insulating metal oxides include, but are not limited to, cerium oxide, titanium oxide, cerium oxide, molybdenum trioxide, vanadium oxide, oxygen. Aluminum, zinc oxide, antimony oxide, antimony oxide, antimony oxide, copper oxide, tin oxide, antimony oxide, and the like. Examples of metal sulfides include cadmium sulfide, copper sulfide, lead sulfide, mercury sulfide, indium sulfide, silver sulfide. , cobalt sulfide, nickel sulfide, and molybdenum sulfide. Mixed metal sulfides such as Ni/Cd sulfide, C〇/Cd sulfide, Cd/In sulfide, and Pd_c〇_pd sulfide may be used. In one embodiment, the metal nanoparticle may contain sulfur and oxygen. In certain embodiments, a combination of metal nanoparticles is used. The metal oxide nanoparticle can be prepared by reacting a metal in the presence of oxygen. Sputtering, evaporating selected oxides and multi-component oxides; or performing vapor phase hydrolysis on inorganic compounds such as tetragas hydride. It can also be used to hydrolyze metal oxides by sol-gel chemistry, especially Alkoxides are manufactured to form multicomponent and multidimensional network oxides by hydrolysis and polycondensation. Metal sulfide nanoparticles can be obtained by various chemical and physical methods. Some examples are gas sulfides such as sulfide ore (CdS), sulphurization 139092.doc -27· 201005020 (PbS), sulphide (ZnS), silver sulfide (Agj), and molybdenum sulfide (M〇S2). Phase deposition, lithography process, and molecular beam epitaxy The chemical process for preparing metal sulfide nanoparticles is based on the reaction of metal ions in solution with H2S gas or Na2Si in an aqueous medium. In certain embodiments, 'nanoparticles The surface is treated with a coupling agent to make it compatible with the aqueous conductive polymer. Types of surface modifiers include, but are not limited to, decane, titanate, citrate, aluminate, and polymeric dispersion oximes. Surface modifiers contain chemical functional groups' examples of which include, but are not limited to, nitriles, amine groups, cyano groups, alkyl amine groups, alkyl groups, aryl groups, alkenyl groups, alkoxy groups, aryloxy groups, sulfonic acids, acrylic acid , phosphoric acid, and alkali metal salts, acrylate groups, sulfonate groups, decyl sulfonate groups, ether groups, ether sulfonate groups, ester sulfonate groups, alkylthio groups, and arylthio groups of the above acids . In one embodiment, the chemical functional group may include a crosslinking agent such as an epoxy group, an alkyl vinyl group, and an aryl vinyl group to react with the conductive polymer in the nanocomposite or the hole transporting material on the adjacent upper layer. . In one embodiment, the surface modifier is fluorinated or perfluorinated, such as tetrafluoro-ethyltrifluoro-vinyl-ether triethoxydecane, perfluorobutane-ethoxylated decane, perfluoro Octyltriethoxydecane, bis(trifluoropropyl)tetramethylglyoxime, and bis(3-triethoxymethylglycosyl)propyltetrasulfide. 5. Preparation of doped conductive polymer composition In the following discussion, 'conductive polymer, HFAp, and inorganic nanoparticle are used in the singular form. However, it should be understood that any or all of these materials may be used. The new conductive polymer composition is prepared by first forming a doped conductive polymer 139092.doc -28-201005020 and then adding inorganic nanoparticles. The doped conductive polymer is formed by oxidative polymerization of a precursor monomer in an aqueous medium in the presence of HFAP. The polymerization is described in U.S. Patent Application No. 2004/0102577, No. 2/4, 127, 637, and No. 2005/205,860. The inorganic nanoparticles can be added directly to the doped conductive polymer dispersion as a solid. In certain embodiments, the inorganic nanoparticles are dispersed in an aqueous solution and the dispersion is mixed with the doped conductive polymer dispersion. The weight ratio of the nanoparticle to the conductive polymer is in the range of 0.1 to 10.0. In certain embodiments, the pH is raised before or after the addition of the inorganic particles. The dispersion of the doped conductive polymer and the inorganic nanoparticle remains stable at a pH ranging from about 2 to a neutral pH. The pH can be adjusted by treatment with a cation exchange resin prior to the addition of the nanoparticles. In certain embodiments, the cation of the ρΗβ base can be adjusted by adding an aqueous alkaline solution to be, but not limited to, an alkali metal, an alkaline earth metal, an ammonium, and an alkyl ammonium. In some embodiments, the metal cation is preferred to the alkaline earth metal cation. Films prepared from the novel conductive compositions described herein are referred to as "new mash as described herein." Films can be prepared using liquid deposition techniques, including continuous and discontinuous techniques. Continuous deposition techniques include, but are not limited to, spin coating, gravure coating, curtain coating, dip coating, slot die coating, spray coating, and continuous nozzle coating. Discontinuous deposition techniques include, but are not limited to, ink jet printing, gravure printing, and screen printing. The film thus formed is smooth and relatively transparent, has a refractive index greater than 14 (at a wavelength of 46 〇 ηπι), and has an electrical conductivity in the range of from 1 〇 -7 to 1 〇 - 33 Å. 139092.doc • 29- 201005020 6. Buffer Layer A buffer layer deposited from an aqueous dispersion comprising a novel conductive polymer composition is provided in another embodiment of the present invention. The term "buffer layer" or "buffer material" is intended to mean a conductive or semiconductive material that may have one or more functions in an organic electronic device, including but not limited to planarization underlayer, charge transport and/or charge injection characteristics. Removing impurities such as oxygen or metal ions, and other aspects that may or may improve the performance of the organic electronic device. The term "layer" is used interchangeably with the term "film" and refers to a coating that covers a desired area. This term is not limited by size. The area can be as large as the entire device, or as small as a specific functional area such as an actual visual display, or as small as a single sub-pixel. The layers and films can be formed by any conventional deposition technique including gas phase deposition, liquid phase deposition (continuous and discontinuous techniques), and heat transfer. Continuous deposition techniques include, but are not limited to, spin coating, gravure coating, curtain coating, dip coating, slot die coating, and continuous nozzle coating. Discontinuous deposition techniques include, but are not limited to, ink jet printing, gravure printing, and screen printing. The dried film of the new conductive polymer composition is generally not redispersible in water. It is therefore possible to use a buffer layer in the form of a plurality of thin layers. In addition, the buffer layer can be coated with a different layer of water soluble or water dispersible material without damage. Surprisingly, it has been found that buffer layers comprising new conductive polymer compositions have improved wettability. In certain embodiments, the film prepared from the new conductive polymer composition exhibits less than 5 Å of organic solvent. Contact angle. In certain embodiments, the film may be less than 50 via dimethyl benzene. The contact angle is 139092.doc 30· 201005020 Wet, in some embodiments, the contact angle is less than 4 〇. In some embodiments, less than 30. .

In another embodiment, a buffer layer is provided for the deposition of an aqueous dispersion comprising an electropolymer conjugate of a material incorporating other water soluble or water dispersible materials. Examples of types of materials that may be added include, but are not limited to, polymers, materials, coating aids, organic and inorganic conductive inks and pastes, charge transfer materials, crosslinkers, and combinations thereof. Other water soluble or water dispersible materials can be simple molecules or polymers. Examples of suitable polymers include, but are not limited to, conductive polymers such as polythiophenes, polyanilines, polypyrroles, polyacetylenes, poly(°enophenethiophenes), and combinations thereof. 7. Electronic Devices In another embodiment of the present invention, an electronic device comprising at least one electrically active layer located between two electrical contacts H is provided, the device additionally comprising a new buffer layer. "Electrical activity" when referring to a layer or material is intended to mean a layer or material that exhibits electronic or electro-optical properties. When receiving radiation, the electroactive layer material can emit radiation or exhibit a change in concentration of electron-hole pairs. As shown in FIG. 1, a typical device 1 has an anode layer, a buffer layer 12, an electroconductive layer 130, and a cathode layer 15A. Adjacent to cathode layer 15 () is an optional electron injection/transport layer 14". The thief may include a support or (not shown) that may be adjacent to the anode layer 11 or the cathode layer 15A. In most cases, the support is adjacent to the anode layer 110. The pieces can be flexible or rigid, organic or inorganic. Support members 歹J include, but are not limited to, glass, ceramic, metal, and plastic films. The pole layer 110 is a 139 〇 92, doc • 31· 201005020 pole which is more efficiently injected into the cavity than the cathode layer 15 。. 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 oxides of Group 2 elements (i.e., Be, Mg, Ca, Sr, Ba, Ra), Group 11 elements, Group 4, 5 and 6 elements, and Group 8-10 transition elements. If the anode layer 11 is permeable to light, a mixed oxide of elements of Groups 12, 13 and 14 such as indium-tin oxide can be used. The phrase "mixed oxide" as used herein refers to an oxide having two or more different cations selected from Group 2 elements or Group 12, 13 or 14 elements. Some non-limiting specific examples of the anode layer 110 material include, but are not limited to, indium-tin oxide (ΓIT〇), indium-de-oxide, aluminum-tin-oxide, gold, silver, copper. And nickel. The anode may also comprise an organic material, especially a conductive polymer such as polyaniline, including, for example, "Flexible light-emitting diodes made from s〇iuble c〇nducting p〇lymer".

Exemplary materials described in Nature's Vol. 357, pp. 477_479, June 992, 992. At least one of the anode and the cathode should be at least partially transparent to allow observation of the generated light. The anode layer 110 can be formed by a chemical or physical vapor deposition process or a spin casting process. Chemical vapor deposition can be carried out by plasma enhanced chemical vapor deposition ("PECVD") or metal organic chemical vapor deposition ("M〇CVD"). Physical vapor deposition can include all forms of sputtering, including ion beam sputtering as well as electron beam evaporation and resistance evaporation. Specific forms of physical vapor deposition include rf magnetron sputtering and inductively coupled plasma physical vapor deposition ("iMp_PVD"). Such deposition techniques are well known in the semiconductor manufacturing industry. In one embodiment, the anode layer i1 is patterned during lithography operations. 139092.doc •32- 201005020 The file can be changed as needed. The patterned layer can be formed by, for example, placing a patterned mask or photoresist on the first flexible composite barrier structure prior to applying the first electrical contact layer material. Alternatively, the layer can also be applied in a monolithic form (also known as blanket deposition) and subsequently patterned using, for example, a patterned photoresist layer and wet chemical or dry etching techniques. Other patterning processes well known in the art can also be used. Buffer layer 120 comprises the novel conductive composition described herein. The buffer layer prepared from a conductive polymer doped with HFAp is generally not wettable by an organic solvent and has a refractive index lower than K4 (at a wavelength of 46 Å). The buffer layer described herein is more wettable and thus more readily coated by a layer from a non-polar organic solvent. The refractive index of the buffer layer described herein may also be greater than ^4 (at 46 〇 nmT). The buffer layer is typically deposited onto the substrate using a variety of techniques well known to those skilled in the art. Typical deposition techniques described above include vapor deposition, liquid deposition (continuous and discontinuous techniques), and thermal transfer. The optional layer is not shown to be present between the buffer layer 12A and the electroactive layer ι3. This layer of germanium may contain hole transport material. Examples of hole transport materials are outlined by Y. Wang in, for example, Kirk-Othmer Encyclopedia 〇f Chemical Technology (4th Edition, Vol. 18, pp. 837-860, 1996). Holes can be used to transport both molecules and polymers. Common hole transport molecules include, but are not limited to: 4,4',4"-tris(N,N-diphenyl-amino)-triphenylamine (TDATA); 4,4',4', -Tris(N-3-methylphenyl-N-phenyl-amino)-triphenylamine (MTDATA); N,N,-diphenyl-N,N,-bis(3-methylbenzene Base)-[1,1,_biphenyl]_4,4'-diamine (TPD); 1,1-bis[(di-4-methylphenylamino)phenyl]cyclohexane (TAPC); N,N,-bis(4-methylphenyl)-N,N'-bis(4-ethylphenyl)- 139092.doc -33· 201005020 [1,1'-(3,3'_ 2 Mercapto)biphenyl]-4,4,-diamine (ETPD); tetra-(3-methylphenyl)->1,>},>4',:^-2,5- Phenyldiamine 0〇8);〇1-phenyl-4->^-diphenylaminostyrene (TPS); p-(diethylamino)benzaldehyde diphenylhydrazine (DEH) Triphenylamine (TPA); bis[4·(ν,Ν-diethylamino)-2-hydrylphenyl](4-methylphenyl)decane (MPMP); 1-phenyl· 3_[p-(diethylamino)phenethyl]-5-[p-(diethylamino)phenyl]indole (ppR or DEASP); 1,2-trans-double (9Η -carbazole _9_yl)cyclobutane (DCZB); Ν,Ν,Ν',Ν'-four (4-methylphenyl)-(ι,ι,_biphenyl)_4,4,-diamine (ΤΤΒ); Ν,Ν'-bis(naphthalen-1-yl)-Ν,Ν'-double - (phenyl) phenylamine (α_ΝρΒ); and phthalocyanine compounds such as copper phthalocyanine. Common hole transport polymers include, but are not limited to, polyvinyl carbazole, (phenylmethyl) polydecane, poly(dioxy porphin), polyaniline, and polypyrrole. The hole transporting polymer can also be obtained by doping a hole transporting molecule (e.g., the above) into a polymer such as polystyrene and polycarbonate. Application of the end-view device 'Electroactive layer 130 can be an emissive layer that is excited by application of electricity (for example in a light-emitting diode or a light-emitting electrochemical cell), or in response to radiant energy with or without biasing The layer of material that produces the signal (eg, in a photodetector). In one embodiment, the electroactive material is an organic electroluminescent ("EL") material. Any of the el materials can be used in devices including, but not limited to, small molecule organic fluorescent compounds, fluorescent and disc metal complexes, conjugated polymers, and mixtures thereof. Examples of fluorescent compounds include, but are not limited to, inlaid naphthalene, anthracene, erythroprene, coumarin, derivatives thereof, and mixtures thereof. Examples of metal complexes include, but are not limited to, metal-clamped oxinoid compounds such as, for example, tris(8_by carbaryl- 139092.doc-34-201005020 ke)aluminum (Alq3); Metallated ruthenium and platinum electroluminescent compounds, such as ruthenium and phenyl phthalate, phenyl phthalocyanine, or phenyl occluded ligand complexes (eg, Petrov et al, US Patent No. 6,670,645 and published PCT) And the organic metal complexes as described in the PCT application WO 03/008424, WO 03/091688 and WO 03/040257, the disclosures of which are incorporated herein by reference. ; and mixtures thereof. An electroluminescent emissive layer comprising a charged © host material and a metal complex has been described in U.S. Patent No. 6,303,238, the disclosure of which is incorporated herein by reference. Examples of conjugated polymers include, but are not limited to, poly(phenylene vinyl), polyfluorene, poly(spirobi), polythiophene, poly(p-phenylene), copolymers thereof, and mixtures thereof . The optional layer 140 can be used to promote both electron injection/transportation and can also be used as a sealing layer to prevent the reaction from ending at the layer interface. More specifically, layer 140 promotes electron migration and reduces the likelihood of reaction discontinuation where layers 130 and 150 are otherwise in direct contact. Examples of optional layer 140 materials include, but are not limited to, metal-clamped, etc., such as bis(2-fluorenyl quinquirin) (p-phenyl-phenolate) aluminum (III) (BA1Q) And tris(8-hydroxyquinolinyl group 0# (Alq3); tetrakis(8-hydroxyquinolinyl)zirconium; azole compounds, such as 2-(4-diphenyl)5 (4_t-butylphenyl) Oxadiazole (Pbd), 3_(4_ phenyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ), and ^3, 5. Tris(phenyl-2-benzimidazole)benzene (TPBI); quinoxaline derivatives such as 2,3, bis(4-fluorophenyl)quinoxaline; phenanthroline derivatives, for example 9, 10-monophenylphenanthroline (DPA) and 2,9-dimercapto-4,7-diphenyl-1,10-phenanthroline (DDPA); and any one or more combinations thereof. The layer 14 can be 139092.doc -35- 201005020 inorganic and contains BaO, LiF, Li20 or the like. The cathode layer 150 is particularly effective for injecting electrons or negative charge carriers. The cathode layer 150 can be a work function. Any metal or non-metal that is lower than the first electrical contact layer (in this case, the anode layer 110). The term "compare" is used herein. "Work function" means that the work function of the material is not more than about 4 4 eV. The term "higher work function" as used herein means that the work function of the material is at least about 44 eV. The material of the cathode layer may be selected from the first group. An alkali metal (eg, Li, Na, κ, Rb, Cs), a Group 2 metal (eg, Mg, Ca, or the like), a Group 12 metal, a systemic element (eg, Ce, Sm, Eu, or the like), And the milk system 7L (such as Th, U, or the like). Materials such as aluminum indium, kiln, and the like may also be used. Non-limiting specific examples of the material of the cathode layer 150 include (but are not limited to): lock, clock , enamel, pin, face, tantalum, magnesium, niobium, alloys and combinations thereof. Cathode layer 15〇 is usually formed by chemical or physical vapor deposition process. In some cases, the cathode layer can be Patterned, as described in pole layer 110. 夂爹",,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Materials are prepared. In some embodiments, the seal is deposited on the layer (not shown). The contact layer is 150 parts of the second barrier layer or film. In a consistent embodiment of the application of the two θ 4 , the encapsulation layer is not painted, and the encapsulation layer is a glass cover. It should be understood that the device 100 may include additional layers. 139092.doc -36 - 201005020 Other layers known in the art are used. Further, any of the above layers may comprise two or more sub-layers or may form a laminate structure. Alternatively, the anode layer 11 and the electro-transport layer 120 Some or all of the electron transport layer 14 阴极, cathode layer 5 〇, and other layers may be processed (particularly surface treated) to increase the carrier transport efficiency or other physical properties of the device. Preferably, the choice of material for each component layer is determined by balancing the following objectives: the binder working life factor provides a device with two device efficiencies, manufacturing time and complexity factors, and other factors well known to those skilled in the art. . It should be understood that the best components, ® (4) configuration and compositional properties should be routinely determined by those skilled in the art. In one embodiment, the different layers have the following thickness ranges: anode u〇, 500-5000 A, in one embodiment 1〇〇〇·2〇〇() A; buffer layer 12〇, 50-2000 A, In one embodiment is 2〇〇_1〇〇〇A; photoactive layer 13〇, 10-2000 a, in one embodiment 100_1000 A; optional electron transport layer 140, 50-2000 A, in one In the examples, it is 100·1000 A; the cathode is 15 〇, ❿ 200-10000 A, and in one embodiment is 3〇〇5〇〇〇A. The relative thickness of each layer can affect the position of the electron-hole recombination region in the device and thereby affect the emission spectrum of the device. Therefore, the thickness of the electron transport layer should be selected such that the electron-hole recombination region is located in the light-emitting layer. The desired layer thickness ratio may depend on the exact nature of the materials used. In operation, device 100 is applied with a suitable power source (not shown) so that current passes through the layers in device 100. Electrons enter the organic polymer layer' to release photons. In some 〇LEDs (referred to as active matrix OLED displays), the deposition of each photoactive organic film 139092.doc • 37· 201005020 can be independently excited by a current, which produces individual luminescent pixels. In some germanium LEDs (referred to as passive matrix OLED displays), the deposition of the photoactive organic film can be excited by multiple columns and multiple rows of electrical contact layers. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are set forth below. All publications, patent applications, patents, and other references mentioned herein are hereby incorporated by reference. In the event of a conflict, the specification (including definitions) will prevail. In addition, the materials, methods, and examples are illustrative only and are not intended to limit the invention. It will be appreciated that, for clarity, certain features of the invention described in the context of separate embodiments may also be provided in combination in a single embodiment. Rather, the various features of the invention described in the context of the singular embodiments may be provided or provided in a sub-combination. In addition, when a numerical value is referred to in a range, it includes each and every value in the range. Instance

Comparative Example A This comparative example illustrates the low electrical conductivity and non-wetability of pAni/Nafi(10) (poly(tetrafluoroethylene)/perfluoroether acid) membranes to which inorganic nanoparticles are not added. The PAni/Nafion® dispersion used in this example was prepared using an aqueous Nafion® colloidal dispersion having an EW (acid equivalent) of 1000. 2S% (w/w) of the Nafion® dispersion is prepared using a procedure similar to that of the procedure of Section 2 of the summer example of U.S. Patent No. 6, 丨 5, 426, but at a temperature of about 27 且 and thereafter The water was diluted to form a 12.0% (w/w) dispersion for polymerization. In a 500 mL autoclave, 96.4 g of 12% solids Nafi〇n@139092.doc •38-201005020 dispersion (11.57 mmol S03H group), 103 g of water were added. The diluted Nafion® was stirred at 300 RPM using an overhead stirrer with two stage propeller blades. Quickly add 1.21 g (5.09 mmol) of sodium persulfate (Na2S208) dissolved in 15 mL of water, and 422 pL (4.63 mmol) dissolved in 266 μM (9.28 mmol) of HC1 and 20 mL of water to the diluted Nafion® dispersion. aniline. The polymerization solution became opaque and extremely viscous, but the color did not change visually within 5 minutes. About 20 mg of ferric sulfate was added, but no visible change occurred. However, after 30 minutes the polymerization reaction began to turn pale blue and then © turned green. After about 8 hours, 25 g of each of Dowex M3 1 and Dowex M43 ion exchange resin and 100 g of deionized water were added to the polymerization mixture. The mixture was stirred overnight and then filtered through a filter paper. 100 g of deionized water was added to the filtrate to reduce the viscosity. Divide it into 5 equal parts. One remains as it is, without adding alkali. The fraction was determined to have a pH of 2 and contained 2.88% (w/w) PAni/Nafion®. Films were prepared from PAni/Nafion® and subsequently baked in air at 130 °C. The room temperature conductivity of the film was determined to be 1·2 χ1 (Γ8 S/cm, which is also shown in Table 1. A small drop of f Benzene® was placed on a piece of film, but toluene quickly rolled off the film, indicating that Polar organic solvents do not wet the surface of the film. Non-polar solvents are commonly used for luminescent polymers and luminescent small molecules. Add 0.1 M NaOH aqueous solution to the second pH 2 PAni/Nafion® until the pH is 5.0. This part contains Na+ dispersion. The solution was determined to contain 2.89% (w/w) PAni/Nafion®. The conductivity of the film prepared from pH 5_0 PAni/Nafion® was determined to be 3.8 <1 (Γ8 S/cm, which is also shown in Table 1). Toluene does not wet PAni/Nafion® film. 139092.doc •39· 201005020 Example 1 This example illustrates the modification of PAni/Nafion® (poly(tetrafluoroethylene)/perfluoroether sulfonate by semiconductor nanoparticle pairs) The effect of the conductivity and wettability of the film. The pH 2 and pH 5.0 PAni/Nafion® dispersions prepared in Comparative Example 1 were used to illustrate the examples of the present invention. To 5.0166 g of pH 2 PAni/Nafion® dispersion Add 1.1313 g Celnax CX-Z300H-F2® (from Nissan Che.mical Industries, Houston, T Exas, USA's aqueous zinc phthalate dispersion. CX-Z300H-F2 has a pH of about 7 and contains 26.47% (w/w) of yttrium sulphate particles, which are less than 20 nm in size. PAni/ in the formulation. The weight ratio of Nafion® polymer to zinc citrate is about 0.47. The mixture forms a stable dispersion with no signs of particle precipitation for at least five months. After water drying, it also forms a smooth transparent film. The data clearly indicates that The specific tin bismuth silicate particles of Celnax CX-Z300H-F2® are compatible with PAni/ Nafion®. However, to improve the surface smoothness of roughness less than at least 5 nm, it is desirable to use a higher energy density rather than simply The two components were added together to improve the method. At room temperature, the film conductivity of the dispersion containing PAni/Nafion® and sulfite was determined to be 6.6 x 10·4 S/cm (two film samples) The average value), which is also shown in Table 1. The conductivity is enhanced by more than four orders of magnitude. A piece of film is contacted with a drop of toluene. The benzene is rapidly spread on the surface of the film, and the film becomes wettable by a common non-polar organic solvent. Also added CX-Z300H to pH 5.0 PAni/Nafion® -F2 to determine its effect on conductivity and wettability. Add 1.1450 g of Celnax CX-Z300H-F2® to 5.0666 g of pH 5.0 PAni/NaHon® dispersion. The weight ratio of PAni/Nafion® polymer to zinc citrate in the formulation of 139092.doc -40- 201005020 is about 0.47. The mixture formed a stable dispersion with no signs of particle precipitation. It also forms a smooth transparent film after the water is dried. The data clearly indicates that the specific tin bismuth silicate particles from Celnax CX_ Z300H-F2® are compatible with PAni/ Nafion®. However, in order to improve the surface smoothness of roughness less than at least 5 nm, the method is to be improved by a method of higher energy density rather than simply adding the two components together. At room temperature, the film conductivity of the dispersion containing PAni/Nafion® and zinc tellurite was determined to be 9·3 ΧΙΟ·4 S/cm (average y value of two film samples), which is also shown in Table 1. in. The conductivity is enhanced by more than four orders of magnitude. A piece of film was brought into contact with a drop of toluene. Toluene spreads rapidly on the surface of the film, and the display film becomes wettable by a common non-polar organic solvent. Table 1 Effect of CX-Z300H-F2 on Conductivity pH and cation conductivity (S/cm) of dispersion before adding CX-Z300H-F2 No CX-Z300H-F2 with CX-Z300H-F2 2.0/ΕΓ 1.2χ10' 8 6.6X10·4 5.0/Na+ 3.8χ10·8 9.3X10·4 Example 2 This example illustrates the preparation of a polypyrrole (PPy) aqueous dispersion, which is in D? £(tetrafluoroethylene) with? 5 An aqueous dispersion of a copolymer of ugly ¥£(perfluorinated 3,6-dioxa-4-methyl-7-octenesulfonic acid) (perfluorinated polyacid) is prepared. The aqueous dispersion of PPy/poly(TFE-PSEPVE) is used to express the effect of cerium oxide nanoparticle on the wettability of organic solvent of PPY/poly(TFE-PSEPVE) solid film 139092.doc -41 · 201005020 . The aqueous dispersion of poly(TFE-PSEPVE) was prepared by heating poly(TFE_PSEPVE) having an EW of 1000 to about 270 ° C in water. This aqueous poly(TFE-PSEPVE) dispersion had 25% (w/w) poly(TFE-PSEPVE) in water and was diluted to 10.8% with deionized water, which was then used for polymerization with pyrrole. The pyrrole monomer is polymerized in the presence of a poly(TFE-PSEPVE) dispersion as described in U.S. Patent Application Serial No. 2005-0205860. The polymerization component had the following molar ratio: poly(TFE-PSEPVE): pyrrole = 3.4; Na2S208: pyridene = 1.0; Fe2(S〇4)3: ° pirox = 〇.1. The reaction was allowed to proceed for 15 minutes. The aqueous PPy/poly(TFE-PSEPVE) dispersion was then pumped through three columns connected in series. The three columns contain Dowex M-3 1, Dowex M-43 and Dowex M-31 Na+, respectively. Three Dowex ion exchange resins were obtained from Dow Chemicals, Midland, Michigan, USA. The ionized resin treated dispersion was then microfluidized by treatment at 5,000 psi using a microfluidization processor M-110Y (Microfluidics, Massachusetts, USA). The microfluidized dispersion is then filtered and degassed to remove oxygen. The pH of the dispersion was 4.0 using a standard pH measurement, and the % solids was determined by gravimetry to be 6.4%. The film which was baked in the air at 130 ° C for 10 minutes after spin coating by the dispersion had a conductivity of 7.5 x 〇 -4 S/cm at room temperature. The aqueous PPy/poly(TFE-PSEPVE) dispersion was first diluted from 6.4% to 3.12%, after which cerium oxide nanoparticles were added thereto. The cerium oxide nanoparticle dispersion used in this example was obtained from IPA (isopropyl alcohol)-ST-S of Nissan Chemical Co., Ltd. IPA-ST-S contains 26 w·% cerium oxide nanoparticle 139092.doc •42· 201005020 granules. The particle size of the cerium oxide was measured by Microtrac "nano-super" dynamic light scattering. It has been found that 50% by volume of cerium oxide has a particle diameter of 7.1 nm (nano) or less. The cerium oxide dispersion is then mixed with the corresponding amount of PPy/poly(TFE-PSEPVE) dispersion to have the desired values listed in Table 2 relative to the total solids (PPy/poly(TFE-PSEPVE) and dioxide dioxide). Oxide eve w. %. The data clearly shows that the contact angle of the PPy/poly(TFE-PSEPVE) solid film formed by spin coating with p-diphenyl or anisole is significantly reduced due to the inclusion of cerium oxide. Ο Table 2 Effect of cerium oxide on the wettability of polypyrrole (PPy)/poly(TFE-PSEPVE) (based on total solids of cerium oxide W.%) Contact angle (degrees) p-benzophenone Ether PPy/poly(TFE-PSEPVE) (0% cerium oxide) 50 55 PPy/poly(TFE-PSEPVE) (5.6% cerium oxide) 40 51 PPy/poly(TFE-PSEPVE) (10.5°/.矽) 29 42 PPy/poly(TFE-PSEPVE) (15.0% cerium oxide) 22 38 PPy/poly(TFE-PSEPVE) (20.0% cerium oxide) 19 31 PPy/poly (TFE-PSEPVE) (25_0°/ 〇O2) 18 31 Example 3 This example illustrates the solution of a blue-emitting emitter solution for organic light-emitting diodes. 139092.doc •43- 201005020 Performance [with or without: oxygen-cutting ρρ#(τρΕ_ PSEPVE ) as a buffer layer. The buffer layer was formed by spin coating on a patterned IT(R) substrate (device active area = 224 mm X 2 · 5 mm) using the poly PSEPVE dispersion with or without dioxide 7 in Example 2. The ruthenium substrate was cleaned before use and treated in a UV zone oven for 10 minutes. Spin coating of each of the ppy/poly(TFE_PSEP VE) dispersions with or without oxidized ginseng was set under various conditions to provide a thickness of 5 〇 nm after baking in air for 7 minutes at 14 Torr. It is then transferred to a dry box where all other toppings are carried out in an inert chamber. The buffer layer was then top coated at 275 with a 0.38% (w/v) toluene solution of HT-2, which is an arylamine-containing copolymer having a hole transporting property. The thickness of 2 〇 nm was achieved after baking in argon for 30 minutes. After cooling, the substrate was spin-coated with an emissive layer solution containing 13.1 fluorescent host: blue fluorescent dopant, and then heated at 135 ° C for 15 minutes to remove the solvent. The layer thickness is about 40 nm. The substrate is then masked and placed in a vacuum chamber. A 10 nm thick metal quinolinate derivative layer was deposited by thermal evaporation as an electron transport layer, followed by a 0.8 nm fluorinated planing layer and a 100 nm2 aluminum cathode layer. The devices are packaged using a glass cover, a getter package, and a υν curable epoxy. It is characterized by measuring the following characteristics of the light-emitting diode sample: (1) current-voltage (I_V) curve, (2) electroluminescence radiance as a function of voltage', and (3) change with voltage Electroluminescence spectrum. All three measurements are performed simultaneously and controlled by a computer. The current efficiency of the device at a certain voltage is determined by dividing the electroluminescence radiance of the LED by the current density required by the operating device (cd/A: ^ power efficiency (Lm/W) current efficiency J39092.doc - 44- 201005020 Divided by the value of the operating voltage. The results are shown in Table 3, which shows that the dioxide has no negative impact on device performance. Table 3. PPy/poly (TFE-PSEPVE) with or without cerium oxide Solution as a buffer layer for blue emitters' Device buffer material f flow efficiency (cd/A) quantum efficiency (%) CIEY V (volts) at a certain display brightness 〇50〇ι> PPy/poly(TFE-PSEPVE ® (〇%2 oxidation unit 5.1 5.3 0.1145 4.84 under 513 nits 17217h PPy/poly (TFE-PSEPVE) (0% cerium oxide) 2 device 4.8 5.1 0.1100 4.44 under 4% nit 18782h PPy/poly (TFE-PSEPVE) (10.5% cerium oxide) No. 1 device 5.2 5.3 0.1163 4.51 23160h under 523 nits PPy/poly (TFE-PSEPVE) (10.5% cerium oxide) No. 2 device 5.2 5.3 0.1138 4.52 at 510 nits is 22255 h PPy / poly (TFE-PSEPVE) (20.0 ° / ◦ ◦ 1) No. 1 device 4.8 5.0 0.1094 4 .56 under 487 nits is 21536h ❹ PPy/poly(TFE-PSEPVE) (20.0% cerium oxide) No. 2 device 4.7 5.0 0.1098 4.46 Under 489 nits is 20465 h a-PPy/poly (TFE-PSEPVE) - (25.0% cerium oxide) No. 1 device 4.8 5.0 0.1123 4.68 20606 h under 502 nits ------- PPy/poly (TFE-PSEPVE) (25.0% cerium oxide) No. 2 device 5.0 5.2 0.1138 4.66 Under the 510 nits, 22208 h ~ -1 Unless otherwise specified, all data correspond to the 7-color standard of the Nite ' ciey cie color table (Commision Internationale de L'Eclairage, 1931); T50 (h) = in hours, at half time at 24 ° C, 139092.doc -45· 201005020. It should be agreed that it is not necessary to elaborate on all activities in the above overview or examples. In addition to; and in addition to the above activities, may implement - or a number of other activities. In addition, the order in which the activities are listed is not necessarily the order in which they are implemented. In the above specification, several concepts have been set forth with reference to the specific embodiments. However, I, S, and the technical personnel of the present invention should be able to implement various modifications and changes without departing from the scope of the invention as set forth in the following patent application. It is intended to be inclusive, and not restrictive. The benefits, other advantages, and solutions of the present invention have been described in terms of specific embodiments. However, benefits, advantages, and solutions to problems, and any benefits, advantages, or solutions that may be more prominent. Features S should not be construed as being a critical, essential, or essential feature of any or all of the scope of the claims. It is to be understood that certain features that are described herein in the context of separate embodiments may also be provided in combination in a single embodiment. The features described in the context of the single-embodiment may be provided individually or in any sub-combination. The use of values within the ranges specified herein should be described as approximations, such as = the minimum and maximum values within the range are (4) "about" precedence limits. In this way, the range can be changed slightly up and down to achieve results that are substantially the same as the values in the range. Similarly, when some elements of the #_ value are mixed with the elements of the different values, the disclosure of the ranges is intended to be 139092.doc -46- 201005020 〃 expressed as including between the minimum and maximum Each value is inclusive and includes a continuous range of fractional values that can be generated. Moreover, when a broader or broader range is disclosed, the maximum J value from a range should be matched to the maximum value from the other range, and vice versa, within the scope of the present invention. [Simple Description of the Drawings] I is explained by way of example and not by the drawings. Figure 1 is a schematic illustration of an organic electronic device. [Main component symbol description] Reference 100 110 120 130 140 150 Typical device Anode layer Buffer layer Electroactive layer Optional electron injection/transport layer Cathode layer 139092.doc -47·

Claims (1)

201005020 VII. Patent Application Range: 1 _ A composition comprising: at least one aqueous dispersion of a conductive polymer doped with at least one highly fluorinated acid polymer, and inorganic nanoparticles. 2. The composition of claim 1, wherein the conductive polymer is selected from the group consisting of polythiophene, poly(porphin) poly (hoof pheno), polypyramidine, polyaniline, and more Acyclic aromatic polymers, copolymers thereof, and combinations thereof. ❹3. The composition of claim 2, wherein the conductive polymer is selected from the group consisting of polyaniline, poly(ephedophene), poly D-bilol, polymeric fused polycyclic heteroaromatic compound, copolymer thereof And their combinations. 4. The composition of claim 3, wherein the conductive polymer is selected from the group consisting of unsubstituted polyaniline, poly(3,4-extended ethyldioxythiophene), unsubstituted poly Pyrrole, poly(thieno(2,3-b)thiophene), poly(thieno(3,2-b) sold), and poly(thieno(3,4-b)thiophene). 5. The composition of claim 1 wherein the highly fluorinated acid polymer is to beta 95% iU 匕. 6. The composition of claim 1 wherein the highly fluorinated acid polymer is selected from the group consisting of sulfonic acid and sulfonimide. 7. The composition of claim 1 wherein the highly fluorinated acid polymer is a perfluoroolefin having a perfluoro-ether-sulfonic acid side bond. 8. The composition of claim 1, wherein the highly fluorinated acid polymer is selected from the group consisting of: 1,1-difluoroethylene and 2-(1,1-difluoro-2-((three gas) Copolymer of methyl)allyloxy)-1,1,2,2-tetrafluoroethanesulfonic acid, and bismuth and 139092.doc 201005020 2-(2-(12,2-trifluoroethyleneoxy) _ base) ^ Μ - copolymer of four gas and ethyl acid. ,,",3. Fluorine-oxygen 9 mrr: compound, wherein the highly fluorinated acid polymer is selected as follows: with perfluoro(3,6d methyl-7-octene acid): and tetraethylene and ethylene. Copolymerization of oxa-anthracene acid) composition of the first item, m, and other inorganic nano-particles are semi-conductive by metal from the following, five oxygen η. The composition of claim 10, wherein the nanoparticles are selected from the group consisting of sulfides, metal oxides, and combinations thereof. 12. The composition of claim i wherein the metal oxide is selected from the group consisting of zinc phthalate, indium tin oxide, anoxic molybdenum trioxide, and combinations thereof. Wherein the inorganic nanoparticles are insulated, such as the composition of claim 1. 14. The composition of claim 13 wherein the nanoparticles are selected from the group consisting of oxidized hard, oxidized, oxidized, trioxide, oxidized Q vanadium, alumina, zinc oxide, cerium oxide, Cerium oxide, cerium oxide, copper oxide, tin oxide, cerium oxide, and combinations thereof. The composition of claim 1, wherein the inorganic nanoparticles are selected from the group consisting of sulfide ore, copper sulfide, thinning, mercury sulfide, sulfurized, silver sulfide, cobalt sulfide, nickel sulfide, Molybdenum sulfide 'Ni/Cd sulfide, Co/Cd sulfide, cd/In sulfide, Pd-Co-Pd sulfide, and combinations thereof. 139092.doc -2- 201005020 16 'A composition according to claim 6, wherein the weight ratio of the nanoparticle to the conductive polymer is in the range of from 0.1 to 10.0. 17. A film prepared from the composition of claim 1. 18. The film of claim 17, which has a contact angle with para-xylene of less than 5 Å. . 19. The film of claim n, which has a refractive index greater than 14 at 46 〇 nm. 20. An electronic device 'which comprises at least one freely available composition of the composition. 21. The device of claim 20, wherein the layer is a buffer layer. 22. The device of claim 21, which comprises an anode, a buffer beta, an electroactive layer 139092.doc