TW200915350A - 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

200915350 IX. Description of the invention: [Technical field to which the invention pertains] η. The present invention relates to conductive polymer compositions containing inorganic nanoparticles and their use in electronic devices. [Prior Art] A class of electronic devices that includes an active layer. The organic electronic device has at least one layer of an organic active layer. The devices convert electrical energy into light (e.g., light-emitting diodes)' to detect signals via electronic processes, 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 a hole 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 phosphorescent metal complexes, conjugated polymers, and mixtures thereof. The cathode is typically any material that can inject electrons into the EL material (e.g., Ca*Ba). A conductive polymer having a low electrical conductivity in the range of 1 〇 -3 to 10·7 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 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 wherein the dispersed 133332.doc 200915350 has inorganic nanoparticles. In another embodiment, a film formed from the above composition is provided. In another embodiment, an electronic device comprising at least a layer comprising a layer of the above described film is provided. [Embodiment] A plurality of aspects and embodiments are described herein and are merely illustrative and not limiting. It will be understood by those skilled in the art after reading this disclosure that other aspects and embodiments may be present without departing from the scope of the invention. Other features and advantages of any or a plurality of embodiments may be apparent from the following description and the scope of the claims. Embodiments first broadly describe the definition and interpretation of terms 'after describing conductive polymers, highly vaporized acid polymers, beneficial nano particles, preparation of doped conductive polymer compositions, buffer layers:, electronic devices, and Finally, an example is explained. 1. Definitions and Interpretations of Terms Used in the Specification and Scope of Application The term is defined or interpreted 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 there is no significant drop in potential when current flows through the layer of material, component or structure. The term is intended to include semiconductors. In some real cases, the conductor can form a layer of electrical conductivity. The term "conductivity" when referring to a material means a material that is inherently or substantially electrically conductive without the addition of carbon black or conductive metal particles. The term "polymer" is intended to mean having at least one repeating monomer unit. Material. The term includes homopolymers having only one or a type of monomer unit, and copolymers having two or more different monomer units of 133332.doc 200915350, including copolymers formed from different types of monomer units. The term "acid polymer" refers to a polymer having an acidic group. The term "acid group" refers to a group capable of ionizing to supply hydrogen ions to a Bronsted base. ". "Inter-fluorinated" means that at least 9% by weight of the compound is substituted with carbon for the carbon-bonded available hydrogen. The 'U-60 perfluoro-chemical" and "perfluorinated" are used interchangeably and refer to all of the compounds. The available hydrogen with the carbon bond is replaced by fluorine. The composition may comprise one or more different electrically conductive polymers and one or more different highly fluorinated acid polymers. The term "doped" when referring to a conductive polymer is intended to direct the electrical polymer to have a polymeric counterion to balance the charge on the conductive polymer. The term "doped conductive polymer" is intended to direct an electrically polymer and a polymeric counterion attached thereto. 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. "Technology nanoparticle" refers to a material with a particle size of less than 100 nm. In some such embodiments, the particle size is less than 10 nm. In certain embodiments, the particle size is less than 5 nm ° 'term, 'aqueous', meaning that the liquid is mostly water, and in one embodiment at least 133332.doc 200915350 about 40 weights & In certain embodiments, at least about 6. Weight % knots: 语::Transfer" In the case of a layer, material, component or structure, it is intended to mean that: =, component or structure facilitates the positive charge to be relatively effective, with less electrical loss through the layer, material The thickness of the component or structure migrates. The term "electronic transfer wheel, I a layer, material = Λ; Γ material, component or structure, means 4. a member or structure that promotes or

Transfer of a crucible, component or structure to another layer, material, component or structural term "organic electronic device" is intended to include one or more layers of semiconductor layers or materials. 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, diode lasers, or light-emitting panels)' (2) Devices that detect signals via electronic processes (eg, photodetectors, photoconductive cells, photoresistors) , photoelectric switches, optical...photocells, photocells, infrared (10), detectors, or biosensingTM) (3) devices that convert radiation into electrical energy (eg photovoltaic devices or solar cells)' 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 terms "include", ""," &" or any other variations thereof, as used herein, are intended to cover a non-exclusive. For example, a process, method, article, or device that comprises a plurality of elements is not necessarily limited to the elements and may include other elements that are not explicitly listed or that are present in the process, method, article, or device. In addition, unless the contrary is explicitly stated, either the inclusiveness "or|| and not exclusive" or π. For example, condition A 133332.doc 200915350 or B may be satisfied by any of the following propositions: A True (or exist) and B is false (or non-existent), A is false (or non-existent) and B is true (or exists), and both A and B are true (or exist). "One" is used to describe the elements or components described herein. This is for convenience only and is intended to provide a general understanding of the scope of the invention. Unless otherwise indicated otherwise, this expression should be understood to include At least one and the singular forms also include the plural. The family numbers corresponding to the columns in the periodic table are used in the "new symbols" conventions found in c and c 〇/81 (2000-2001) 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, and z are used to indicate the meaning as defined herein. Atom or group. all of them His letters are used to indicate the customary atomic symbols. Corresponding to the family number of each block in the periodic table of the elements, the CRC Handbook of Chemistry and Physics, the new symbol " convention in the %\ version. A wide range of details regarding 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, and other sources. Any conductive polymer can be used in the novel composition. In certain embodiments, the conductive polymer can form a film having a conductivity greater than 1 〇 -7 s/cm. 133332.doc 200915350 Suitable for conductive polymerization of new compositions The system is prepared from at least one monomer which forms a conductive homopolymer when polymerized separately. These monomers are referred to herein as "conductive precursor monomers". A monomer that forms a non-conductive homopolymer when polymerized separately is called a "non-conductive precursor monomer". The conductive polymer can be a homopolymer or copolymerized f. Conductive copolymers suitable for use in the novel compositions can be prepared from two or more conductors or combinations of self- or multiple conductive precursor monomers with - or a plurality of non-conductive precursor precursors. In some embodiments, the electrically conductive polymer is prepared from at least one electrically conductive monomer, phenophene, rhodium, aniline, and polycyclic aromatic compound. The term "polycyclic aromatic," means having one of: a compound. The ring may be linked by - or a plurality of bonds, or it may be thick:: The character: an aromatic ring " is intended to include a heteroaromatic ring. "Polycyclic heteroaromatic" has at least one heteroaromatic ring. In some embodiments, the electrically conductive polymer is prepared from at least a precursor monomer: an singly, a stalk Acyclic aromatic compound. The present orthoamines, and the plurality of monomers herein are referred to as polybenzazole, poly(phenophene), poly(hoof pheno), poly(relevant), respectively. The term "polycyclic aromatic" means a compound of::: a ring. The ring may be bonded by - or a plurality of bonds, = up to L. The term "aromatic ring" is intended to include, once The Fangxiang" compound has at least one musket. 'Polycycloheteropolycyclic aromatic polymer system. (In some embodiments, in certain embodiments, the new composition/monomer comprises Formula 1 below: : forming a conductive polymer J33332.doc 200915350

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, alkyl sulfonyl, alkylthio, aryl, thiol, alkyl Aryl, aryl-based, amine, alkylamino, dialkylamino, aryl, alkyl, oxime, oxyalkyl, aryl, aryl, aryl Sub-stone, alkoxy, aryl, aryl, phosphate, phosphonic acid, nitro, cyano, hydroxy, epoxy, decyl, decyl Alcohol group, benzyl group, carboxylate group, ether group, ether carboxylate group, decyl sulfonate group, ether acid ester group, ester sulfonate group and amino phthalate group; or two The R1 group may together form an extended or extended base chain constituting a 3, 4, 5, 6 or 7-membered aromatic or cycloaliphatic ring, wherein one or more divalent nitrogens, ruthenium may be included as desired. , hydrazine, sulfur or oxygen atoms. The term "alkyl" as used herein, refers to a radical derived from an aliphatic hydrocarbon and includes unsubstituted or substituted straight chain, branched and cyclic groups. The term "heteroalkyl" is intended to mean an alkyl group wherein one or more carbon atoms in the alkyl group have been replaced by another atom (e.g., 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 hydrocarbon derived from an aliphatic hydrocarbon and having at least one 133,332.doc •12 to 2009,15,350 carbon-carbon double bonds. a group, and includes straight, branched, and cyclic groups which may be unsubstituted or substituted. The term "heteroalkenyl," is intended to mean an alkenyl group wherein 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 "extended alkenyl" refers to an alkenyl group having two points of attachment. The following substituents are used herein to refer to the formulas listed below. Alcohol groups " amidino" decyl sulfonate benzyl &quot ; Carboxyl ester group " Ether " Ether carboxylate group" Ether sulfonate group " Ester sulfonate group " Sulfonimido-'carbamate-r3-oh-R3- C(0)N(R6)R6

-R3-C(〇)N(R6)R4_s〇3Z -CH2-C6H5

-R3-C(〇)〇_z or -R3-〇-c(〇)-Z -R3-(0-R5)p-〇-R5

_r3_o-r4-c(o)oz or -r3_〇_r4_〇_ C(0)-Z -r3-o-r4-so3z -R3-0-C(0)-R4-S03Z -R3-S 〇2-NH-S〇2-R5 -r3-oc(o)-n(r6)2 wherein all "R" groups may be the same or different at each occurrence and: R3 is a single bond or a stretch of alkane The base R4 is an alkylene group R5 is an alkyl group, R6 is hydrogen or the alkyl group P is 0 or an integer between 1 and 20 133332.doc 13 200915350 2 is an anthracene, an alkali metal, an alkaline earth metal, n(R5)4 or R5 . Any of the above groups may be additionally unsubstituted or substituted, and one or more of the hydrogens of any of the groups may be substituted by F, including perfluorinated groups. In certain embodiments, the alkyl and alkylene groups have from -20 carbon atoms. In certain embodiments, 'in a monomer, two Ri together form -w_(CYlY2)mW- ' where m is 2 or 3, w is 〇, s 'Se, P〇, NR6, Y1 is present at each occurrence The same or different and are hydrogen or fluorine, and γ2 is the same or different at each occurrence and is selected from the group consisting of hydrogen, halogen, alkyl, alcohol, sulfonamide, benzyl, tareate, A mystery group, a mystery acid group, a sulfonate group, an ester sulfonate group, and an amino phthalate group, wherein the γ group may be partially or fluorinated. In certain embodiments, all gamma are hydrogen. In certain embodiments the polymer is poly(3,4-extended ethyldioxyseptene). In certain embodiments, at least one gamma group is not hydrogen. In certain embodiments, at least one anthracene group is a substituent in which at least one hydrogen is replaced by F. In certain embodiments, at least one gamma group is perfluorinated. In certain embodiments, the monomer has the formula I(a): (C(R7)2),

Wherein: Q is selected from the group consisting of S, Se and Te; the alkyl group and the hetero group are the same or different at each occurrence and are selected from hydrogen 133332.doc -14· 200915350 alkyl, alkenyl, heteroalkenyl , an alcohol group, a decyl sulfonate group, a benzyl group, a carboxylate group, an ether group 'ether carboxylate group, an ether sulfonate group, an ester sulfonate group and a urethane group, wherein preconditions At least one R7 is not hydrogen and m is 2 or 3. In certain embodiments of Formula 1 (a), m is 2, one R7 is an alkyl group having more than one carbon atom, and all other R7 are hydrogen. In certain embodiments of Formula 1 (a), at least one R7 group is fluorinated. In certain embodiments, at least one R7 group has at least one fluorine 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 fluorinated acid polymer. polymerization. In certain embodiments of Formula 1 (a), the gripper 2, one R7 is a sulfonic acid-extension-propyl ether-anthracene group and all other R7 are hydrogen. In certain embodiments, the quaternary system 2, one R7 is propyl-ether-extended ethyl and all other r7 are hydrogen. In some embodiments, m is 2, one R, methoxy and all other r7 are hydrogen. In certain embodiments, one R? is direxylene methylene sulfoxide (-CH2-0-C(0)-CF2-S03H) and all other R7 are hydrogen. In certain embodiments, the pyrrole monomer to be used to form the conductive polymer in the new composition comprises Formula II below, 133332.doc -15-200915350

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, fluorenyl, thiol, aryloxy, alkyl sulphide Alkyl, alkylaryl, arylalkyl, amine, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, aryl Thio, arylsulfinyl, alkoxycarbonyl, aryl thiol, acrylate, acid, phosphonic acid, halogen, nitro, cyano, hydroxy, epoxy, decyl, hydrazine Oxyalkyl, alcohol, benzyl, carboxylate, ether, decyl sulfonate, ether carboxylate, ether sulfonate, ester sulfonate, and urethane; Or the 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 one or more divalents as desired. Nitrogen, sulfur, lithus, hoof or oxygen atom; and R2 is independently selected to be the same or different at each occurrence and is selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, alkanoyl, alkylsulfanyl , alkyl aryl, aryl Alkyl, amine, epoxy, decyl, decyloxy, alcoholyl 'benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate And a urethane group. In certain embodiments, R1 is the same or different at each occurrence and is 133332.doc 16 200915350 independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alcohol , alkaloid, resorcinic acid, sulphonyl, sulphate, sulphate, sulphate, sulphonate, ether sulfonate, ester sulfonate, urethane, epoxy, A stone base, a stone base, and one or more of acid, acid, acrylic, phosphoric acid, phosphonic acid, nitrocellulose, nitro, cyano, hydroxy, epoxy, decane or hydrazine An alkyl group partially substituted with an oxane. In certain embodiments, R 2 is selected from the group consisting of hydrogen, alkyl, and one or more of a crude acid, a carboxylic acid, an acrylic acid, a phosphoric acid, a phosphonic acid, a halogen, 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 pyrrole monomer is unsubstituted and both R1 and R2 are hydrogen. And R. An ester group, an ether group, an ether carboxylate group, an ether sulfonate group, a domain acid acrylate group, and a urethane group. These groups improve the solubility of the monomer and the polymer produced. In certain embodiments, two R1 together form a 6- or 7-membered cycloaliphatic ring, which is further substituted with an alkyl group. In certain embodiments, two R1 together form a 6- or 7-membered cycloaliphatic ring, which is further substituted with a burn group having at least a carbon atom. In certain embodiments, two Ri are formed together, wherein m is 2 or 3' and γ is the same or different at each occurrence and is selected from the group consisting of hydrogen, alkyl 'alcohol, benzyl, carboxylic acid ester Base, guanamine sulfonate group, ether group, ether carboxylate group, ether sulfonate group, ester sulfonate group and urethane group. In certain embodiments, at least one gamma group is not hydrogen. In certain embodiments, at least one Y group is one in which at least one hydrogen is replaced by F: 133332.doc 17 200915350. In certain embodiments, at least one gamma group is perfluorinated 'electropolymer. In certain embodiments, the aniline monomer to be used to form the aniline monomer in the new composition comprises the following formula, (R1) a

^nh2 (III) (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 occur at each occurrence The same or different and selected from the group consisting of hydrogen, alkoxylate, oxy, sulphur, aryloxy, thiol thiol, alkyl aryl, arylalkyl, amine Amino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonate Sulfhydryl, acrylate, phosphate, phosphonic acid, halogen, nitro, cyano, hydroxy, epoxy, decyl, decyloxy, alcohol, benzyl, carboxylate, ether , an ether carboxylate group, a decyl sulfonate group, an ether sulfonate group, an ester sulfonate group, and an amino decanoic acid group; or two Ri groups may be formed together to form 3, 4, 5, 6 Or a 7-membered aromatic or cycloaliphatic cycloalkyl or alkenyl chain, wherein the ring 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 IV (b), or a combination of the two formulas when polymerized, 133332.doc -18· 200915350

IV(b) In certain embodiments, the aniline monomer is unsubstituted and a=〇. In an embodiment, a is not 〇 and at least one r1 is vaporized. In certain embodiments, at least one R1 is perfluorinated. In certain embodiments, the force is as _ & human, the slightly polycyclic heteroaromatic star that is intended to form a conductive polymer in the new composition has two or more thick % aromatic, at least one of which is heterozygous. In certain embodiments, the fused polycyclic heteroaromatic monomer has the formula 乂.

Wherein Q is S, Se, Te or]vjr6. R6 is hydrogen or alkyl; R8, R9, RlRll or different and selected from independently selected to be hydrogen, alkyl, alkenyl, alkoxy at each occurrence 133332.doc -19- 200915350 alkylthio, aryloxy, alkylsulfanyl, alkylaryl, arylalkyl, amine, alkylamino, dialkyl Amine, aryl, alkyl thiol, oxyalkyl, aryl, arylthio, aryl sulfhydryl, alkoxy, aryl fluorenyl, acrylic , acid-filling group, phosphonic acid group, dentate, nitro, nitrile group, cyano group, hydroxyl group, epoxy group, decyl group, decyloxy group, fermentyl group, benzyl group, carboxylate group, ether group, ether a carboxylate group, a decyl sulfonate group, an ether sulfonate group, an ester sulfonate group, and a urethane group; and at least one of R8 and R9, 119 and 1110, and 1 〇 and Rh Together, an extended alkenyl chain constituting a 5- or 6-membered aromatic ring is formed which may optionally include one or more divalent nitrogen, sulfur, code, hydrazine 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(d), v( e), v(f), v(g), v(h), v(1), v(1), and v(k):

133332.doc -20- 200915350

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, ο, SiR62, Se, Te and PR6; Y is N; and R6 is hydrogen or Burning base. The slightly polycyclic heteroaromatic monomer may be additionally substituted with a group selected from the group consisting of: an alkyl group, a heteroalkyl group, an alcohol group, a sulfhydryl group, a carboxylate group, an ether group, an ether carboxylate group, an ether sulfonate. An acid ester group, an ester sulfonate group, and a urethane group. In some examples, the substitution system was Dunhua. In certain embodiments, the substituents are fully fluorinated. In certain embodiments, the fused polycyclic heteroaromatic mono system thieno (thiophene). Such compounds are discussed, for example, in Macrom〇lecules, 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, thieno(3,2-b)thiophene, and thieno(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 alkyl, heteroalkyl, alcohol, benzyl, carboxylate, ether, ether carboxylic acid Ester group, ether sulfonate group, ester sulfonate group and urethane group. In certain embodiments, the substituent is fluorinated. In certain embodiments, the substituent is fully fluorinated. In certain embodiments, the polycyclic heteroaromatic monomer to be used to form a polymer in a new composition comprises Formula VI:

Wherein: Se, Te, and PR6; Q series S, Se, Te, or NR6; τ is selected from the group consisting of S, NR6, 〇, SiR62, Se, and Tej E are selected from the group consisting of an alkenyl group, an aryl group, and a heteroaryl group. ; R is hydrogen or alkyl; 133332.doc -22· 200915350

R12 is the same or different at each occurrence and is selected from the group consisting of hydrogen, alkyl, alkenyl, alkoxy, alkyl sulfonyl, alkylthio, aryloxy, alkylthioalkyl, alkyl aryl, aromatic Alkyl, amine, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl , alkoxy, aryl, acryl, acid, phosphonic acid, i, nitro, nitrile, cyano, hydroxy, epoxy, decyl, decyl, Alcohol group, benzyl group, carboxylate group, ether group, ether carboxylate group, decyl sulfonate group, ether sulfonate group, ester sulfonate group and amino phthalate group; or two The RU groups may together form a pendant or extended alkenyl chain constituting a 3, 4, 5, 6 or 7 member-aromatic ring or a cycloaliphatic ring, wherein the ring may include one or more divalent nitrogens as desired. Sulfur, Selenium, Tellurium or Oxygen Atom 0 In certain embodiments, a copolymer of a conductive polymer based precursor monomer and at least one second monomer. Any type of second monomer can be used as long as it does not adversely affect the desired properties of the copolymer. In certain embodiments, the first monomer comprises 5 〇 0 of the polymer in the monomer unit. the following. In some embodiments, the second monomer is below the polymer view, based on the total amount of monomer units. In certain embodiments, the second monomer is less than 10% by weight based on the total of the monomer units. Exemplary types of second monomers include, but are not limited to, alkenyl, alkynyl, extended, and heteroaryl. Examples of the second monomer include, but are not limited to, the second oxime, the oxime, the sputum and the sputum, the stilbene, and the phenyl group: 133332.doc • 23- 200915350 ethynyl, ratio Acridine, monoazine, and triazine, all of which may be further substituted. In certain embodiments, the copolymer is made by first forming an intermediate precursor monomer having the structure A-B-: wherein AK represents the same or different somatic body ' and B represents the second monomer. The a_b_c intermediate precursor monomer can be prepared using standard synthetic organic techniques, such as γ__〇, centroid, Grignard metathesis reaction, Suzuki, and ruthenium coupling reaction. The copolymer is then formed by oxidative polymerization of the intermediate precursor monomer alone or with one or more additional precursor monomers. In certain embodiments, the electrically conductive polymer is selected from the group consisting of polythiophenes, polypyrroles, polymeric fused polycyclic heteroaromatic compounds, copolymers thereof, and combinations thereof. In certain embodiments, the electrically 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) porphin). 3. Highly fluorinated acid polymer The highly fluorinated acid polymer ("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 less than 3 ipKa. In certain embodiments, the acidic proton has a pKa less than 〇. In certain embodiments the 'acid proton has a PKa less than ·5. The acidic group can be attached directly to the polymer backbone or it can be attached to a side chain on the polymer backbone. Examples of the mono-functional group include, but are not limited to, a tick-acid group, a sulfonic acid group, an anthracene group 133332.doc-24-200915350 an amine group, a dish acid group, a phosphonic acid group, and combinations thereof. The acidic groups may all be the same, or the polymer may have more than one type of acidic groups. In certain embodiments the 'acid group' is selected from the group consisting of a 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 certain embodiments, the HFAP is water soluble. In certain embodiments, the HFAP can be dispersed in water. In certain embodiments, Η· may be wetted by an organic solvent. The term "organic solvent tunable wet" means that the contact angle of the material with the organic solvent is not greater than that of the thief when forming the film. In some implementations In one embodiment, the wettable material forms a film that can be wetted by phenyl hexane, wherein the contact angle is no greater than 55. Methods for measuring the contact angle are well known. In certain embodiments, the wettable material can be borrowed. Prepared from a polymeric acid which is not wettable by itself but which can be rendered wettable by selective additives. Examples of suitable polymer backbones include, but are not limited to, polyolefins, polypropylene bismuth (tetra), polymethyl Acetate vinegar 'polyimidamine, polyamine, polyarylamine, polyacrylamide, polystyrene, and copolymers thereof, all of which are highly fluorinated; in certain embodiments, In the embodiment, the acidic group is an acid group or a (iv) imine group. The hydrazine imine group has the formula: "S〇2~NH~S〇2" R is an alkyl group. In the injection, the acidic group is purified on the side chain. In the embodiment, the gasification side bond is selected from the group consisting of Alkoxy, guanamine, _, and combinations thereof 133332.doc -25- 200915350, all of which are fully fluorinated. In one embodiment, HFAP has a highly fluorinated olefin backbone and pendant fluorine Alkyl sulfonate, highly fluorinated ether sulfonate, highly fluorinated ester sulfonate, or highly fluorinated ether sulfonimide group. In one embodiment, HFAP has perfluoro-ether-performance a perfluoroolefin of an acid side chain. In one embodiment, the polymer is 1,1-difluoroethylene and 2-(1,1-difluoro-2·(trifluoromethyl)allyloxy)-1 a copolymer of 1,2,2-tetrafluoroethanesulfonic acid. In one embodiment, the polymer is ethylene and 2-(2-(1,2,2-trifluoroethyleneoxy)-^, 2, a copolymer of 3,3,3-hexafluoropropoxy)-1,1,2,2-tetrafluoroethanesulfonic acid. The copolymers can be converted into corresponding fluoropolymers and converted into The acid form is. In one embodiment, the HF AP is a homopolymer or copolymer of a fluorinated and partially deified poly(aryl ether ether). The copolymer can be a block copolymer. In one embodiment ' HFAP is an quinone imine polymer of formula IX:

among them:

Rf is selected from the group consisting of highly fluorinated alkyl, highly fluorinated alkyl, highly fluorinated aryl, and highly fluorinated heteroaryl, which may be substituted by one or more enzymatic oxygen; and η is at least 4. In one embodiment of Formula IX, Rf is a perfluoroalkyl group. In one embodiment, Rf is perfluorobutyl. In the examples, 1 contains ether oxygen. In an embodiment 133332.doc -26- 200915350, η is greater than 1 0. In one embodiment, the HFAP comprises a highly fluorinated polymer backbone and a side chain having the formula X: -OR15-S〇2-NH-(S02-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) 0" (CF2-CF-0)c-(CF2)c-S02-N-(S02 -(CF2)c-S02.N)c-S02R16 Η Η R16 where:

R16 is a gasification aryl group or a face gasification 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, J. Fluorine Chemistry 2000, 105, 129-135; A. Feiring et al, Macromolecules 2000, 33, 9262-9271; D. D.

Desmarteau, J. Fluorine Chem. 1995, 72, 203-208 I AJ Appleby et al., J. Electrochem. Soc. 1993, 140(1), 109-133332.doc -27- 200915350 111; and 〇631^ coffee 311 U.S. Patent No. 5,463,005. In one embodiment, HFAP also comprises repeating units derived from at least one highly denaturated ethylenically unsaturated compound. The perfluoroolefin comprises from 2 to 2 carbon atoms. Representative perfluoroolefins include, but are not limited to, tetrafluoroethylene, hexa-epoxide, perfluoro-(2,2-dimethyl-1,3-dioxole), perfluoro-(2_ Methylene-4-methyl-1,3-dioxolane), CF2=CFO(CF2)tCF = CF2 (where (10) 1 or 2), &Rf''〇CF=CF2 (its tRf'' A saturated perfluoroalkyl group having from i to about 10 carbon atoms). In one embodiment, the single system is tetrafluoroethylene. In one embodiment, the HFAP colloid forms a polymeric acid. The term "colloidal formation" as used herein refers to 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 100,000 to about 2,000,000. The colloidal particle size is usually from 2 nanometers (rim) to about 140 nanometers. 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, vinegar, or sulfonium fluoride. It can be converted to the acid form for preparation of a conductive composition as described below. In certain embodiments, the HFAP comprises a highly fluorinated carbon backbone and a side chain represented by the formula -(0-CF2CFRf3)a-〇_CF2CFRf4S03E5 wherein Rf3 and Rf4 are independently selected from F, Cl or have from 1 to 丨The height of 0 carbon atoms is agglomerated, a = 〇, 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 4,94,525. 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 hfap is disclosed in U.S. Patent No. 3,282,875 and can be prepared by the following methods: tetrafluoroethylene (TFE) and perfluorinated vinyl ether CF2=CF-〇-CF2CF(CF3)-〇-CF2CF2S02F (ie, Perfluoro(3,6-monooxa-4-methyl-7-octenesulfonylfluorene) (?1)]^〇17)) is copolymerized and subsequently hydrolyzed by a sulfonium fluoride group Conversion to a sulfonate group and ion exchange as needed to convert it to the desired ionic form. Examples of polymers of the type disclosed in U.S. Patent Nos. 4,358,545 and 4,940,525 have the side chain -O-CFaCFJOsE5, wherein E5 is as defined above. The polymer can be prepared by reacting tetrafluoroethylene (TFE) with fully-tanned vinyl ether CF2=CF-0-CF2CF2S02F (ie, all 1 (3-oxa-4-pentenesulfonyl fluoride) ( P〇pf) copolymerization, followed by hydrolysis and further ion exchange as needed. - HFAP-like water-based Nafion®* dispersion from Ej such as p〇nt heart

Nemours and Company (Wilmington, DE) purchased. 4. Inorganic Nanoparticles Inorganic nanoparticles can be an insulator or a semiconductor. In certain embodiments, the inorganic nanoparticles are metal sulfides or metal oxides. Examples of semiconducting metal oxides include, but are not limited to, mixed valences 133332.doc 29· 200915350 genus oxides (eg, zinc citrate), and non-stoichiometric metal oxides (eg, anoxic trioxide pentoxide)鈒, and so on). Examples of insulating metal oxides include, but are not limited to, titanium dioxide, oxidized, trioxide, vanadium oxide, and aluminum oxide. In certain embodiments, the surface of the nanoparticles is treated with a coupling agent to be compatible with the aqueous conductive polymer. Types of surface modifiers include, but are not limited to, decane, titanate, citrate, methacrylate, and polymeric dispersants. Surface modifiers contain chemical functional groups' examples of which include, but are not limited to, nitriles, amine groups, cyano groups, alkyl amine groups, pendant groups, aryl groups, alkenyl groups, alkoxy groups, aryloxy groups, continuation, acrylic acid, Phosphoric acid, and an alkali metal salt of the above acid, an acrylate group, a hydroxyacetate group, a decyl decanoate I, a sulfhydryl group, a (tetra) acid group, a carboxylic acid group, a sulfur group, and an aryl group . In one embodiment, the chemical functional group may include a crosslinking agent such as an epoxy group, a vinyl group, and an aryl vinyl group to conduct electricity in the adjacent upper layer with the nano-composite or the hole-transport material. Polymer reaction. In one embodiment, the surface modifying agent is vaporized or fully vaporized, such as tetrafluoro-ethyltrifluoro-vinyl-ether triethoxydecane, perfluorobutane-triethoxydecane, perfluorooctane Triethoxy decane, bis(trifluoropropyl)-tetramethyl oxime and bis(3-diethoxymethyl sulfanyl) propyl tetrasulfide. 5. Preparation of doped conductive polymer composition In the discussion: conductive polymer, HFAP, and inorganic nanoparticle are referred to 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 and then adding inorganic nanoparticles. 133332.doc -30- 200915350 The # heteroconductive 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 Nos. 2004/0102577, 2004/0127637 and 2005/205860. 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 water/column' 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 〇1_1〇〇.

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 pH is adjusted by the addition of an aqueous alkaline solution. The cation of the base can be, but is not limited to, an alkali metal, an alkaline earth metal, an ammonium, and an alkyl ammonium. In certain embodiments, the alkali metal cation is preferred over the alkaline earth metal cation. Films prepared from the novel conductive compositions described hereinafter are referred to as " The new membranes T described herein use liquid deposition techniques to prepare films, 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 continuous deposition techniques including, but not limited to, mouth ink printing. And continuous nozzle coating. The film formed by the non-printing, gravure printing, and silk is smooth and relatively transparent, has a refractive index greater than Μ (at the paste nm wavelength), and has an electrical conductivity of 1 ().7 to 1 (r3s/e_). 6. Warm layer 133332.doc •31 · 200915350

The present invention provides a buffer layer for the deposition of raw dispersion from the water containing the new conductive polymer composition. The term "buffer layer" or "buffering material" is intended to be a conductive or semiconductive material that can have one or more functions in a proprietary electronic device. Its functions include, but are not limited to, a planarized underlayer, a charge transfer wheel, and / or charge 1 person characteristic, remove 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 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 phase deposition (continuous and discontinuous techniques), and thermal transfer. 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 dried film of the new conductive polymer composition is generally not redispersible in water. Therefore, the buffer layer can be used in the form of multiple layers of thin layers. In addition, the buffer layer can be made of different water-soluble or water-dispersible materials. The layer is coated without damage. Surprisingly, it has been found that the buffer layer comprising the new conductive polymer composition has been modified to provide a new self-contained blend of other water-soluble or water-dispersible materials in another embodiment. A layer of an aqueous dispersion of a conductive polymer composition. Examples of types of materials that can be added include, but are not limited to, polymerization: agents, organic and inorganic conductive inks and pastes, charge transport materials, parenting agents, and combinations thereof. Other water soluble or water dispersible materials may be 133332.doc • 32·200915350 s single knife or agglomerate. Examples of suitable polymers include, but are not limited to, conductive polymers such as polythiophenes, Aniline, polypyrrole, acetylene, poly(thienothiophene), and combinations thereof. 7. Electronic device In another embodiment of the invention, an electronic device comprising at least one electroactive layer between two electrical contact layers is provided, Wherein the device additionally includes a new buffer layer, which is intended to mean a layer or material that exhibits electron or sputtering characteristics when representing a layer or material. Upon receipt of radiation, the electroactive layer material 丨 can emit radiation or exhibit a change in concentration of electron-hole pairs. As shown in Fig. 1, a typical device has an anode layer 110, a buffer layer 120, an electrothermal layer 3, and a cathode layer 150. Adjacent to cathode layer 150 is an optional electron injection/transport layer 140. The device can include a support or substrate (not shown) that can 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 support can be flexible or rigid, organic or inorganic. Support members ◎ Examples of materials include, but are not limited to, glass, ceramic, metal and plastic films. The % pole layer 110 is an electrode that can be injected more efficiently into the hole than the cathode layer. The anode may comprise a material comprising a metal, a mixed metal, an alloy 'metal oxide or a mixed oxide. Suitable materials include mixed oxides of Group 2 elements (i.e., Be, Mg, Ca, Sr, Ba, Ra), Group u elements, Group 4, 5 and 6 elements, and Group 8-10 transition elements. If the anode layer 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 a Group 2 element or a Group 12, 13 or 14 element 133332.doc -33- 200915350 . Some non-limiting specific examples of anode layer no materials include, but are not limited to, indium-tin-oxide ("ITO"), indium-zinc-oxide, s-tin-oxide, gold, silver, copper The anode can also contain organic materials, especially conductive polymers such as polyaniline, including, for example, Flexible Hght_emitting diodes made from soluble conducting polymer" » Nature - Vol. 357, pp. 477-479 (June 1992) An exemplary material as described in Japanese. At least one of the anode and the cathode should be at least partially transparent to permit observation of the generated light. The anode layer 110 can be formed by a chemical or physical vapor deposition process or a rotary casting process. Deposition of chemical vapor deposition ("PECVD") or metal organic chemical vapor deposition ("m〇cvd") physical vapor deposition may include all forms of sputtering, including ion beam sputtering. And electron beam evaporation and resistance evaporation. The specific forms of physical vapor deposition include rf magnetron sputtering and inductive-electro-destruction physical vapor deposition (Police_PVD"). These deposition techniques are in semi-conductivity. In the manufacturing industry, it is well known to us. In the embodiment, the anode layer is patterned during the lithography process. The pattern can be changed as needed. Before the application of the first electrical contact layer material, For example, a patterned mask or photoresist is placed on the first flexible composite to form a patterned layer. Alternatively, the layer can be applied in a monolithic form (also known as blanket deposition) and then used, for example, via The patterned photoresist layer and the wet chemical or dry etching technique are used to implement the other patterning process of the drawing. The shaking layer 120 includes the new guiding method described herein.

Conductive composition. The buffer layer prepared from a conductive polymer doped with HFAP 133332.doc -34- 200915350 is generally not wettable by an organic solvent and has a refractive index lower than 14 at a wavelength of 460 nm). The buffer layer described herein is more wettable and thus more readily coated by a layer from a non-polar organic solvent. The buffer layer described herein may also have a refractive index greater than 丨4 (at 46 〇 nm). The buffer layer & is typically deposited on 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. An optional layer is not shown to be present between the buffer layer 12A and the electroactive layer 13A. This layer can contain hole transport materials. Examples of hole transport materials are summarized by γ. Wang, for example, in Kirk-〇thmer Encyclopedia of 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-nonylphenyl) )-[1,1,·biphenyl]-4,4'-diamine (TPD); 1,1_bis[(di-4-indolylphenylamino)phenyl]cyclohexane (TAPC) ; N,N'-bis(4-mercaptophenyl)-N,N,-bis(4-ethylphenyl)-[1,1'-(3,3'-dimethyl) phenyl ]-4,4'-diamine (ETPD); tetra-(3-methylphenyl)-indole, anthracene, Ν', Ν·-2,5-phenylenediamine (PDA); α-benzene 4--4-,N-diphenylaminostyrene (TPS); p-(diethylamino)benzaldehyde diphenylhydrazine (DEH); triphenylamine (TPA); double [4-(N , N-diethylamino)·2_nonylphenyl](4-mercaptophenyl)decane (ΜΡΜΡ); 1-phenyl_3_[p-_(diethylamino) phenethyl ]]-5-[p-(diethylamino)phenyl]D ratio. sitin (PPR or DEASP); 1,2-trans-bis(9Η-ηcarbazol-9-yl)cyclobutane (DCZB); 133332.doc •35· 200915350 ν,ν,ν',ν·,(&quot Phenylphenyl Hu,-linked N,N,-bis (naphthalene small group (TTB), (n-base) conjugated amine (α-ΝΡΒ); and porphyrin-like δ-like substance such as copper. When used, the door and the bone hole transport polymer include, but are not limited to, polyethylene flavor 0 sit, ν Λ ( (local methyl) polydecane, poly (dioxy thiopolyamine) And a polymer material. The hole-passing polymer can also be obtained by doping a hole-transmitting molecule (for example, the above) into a polymer such as polystyrene and polycarbonate. The active layer 13 can be a light-emitting layer that is excited by applying a voltage (for example, in a light-emitting diode or a light-emitting electrochemical cell), or is a main signal in response to radiant energy and with or without a bias voltage. a layer of material (eg, in a photodetector). In an embodiment, the electroactive material is an organic electroluminescent ("EL") material. Any ELM material can be used in the device 'it includes (but; Ϊ; limited Small molecule organic fluorescent compounds, glory and phosphorescent metal complexes, conjugated polymers, and mixtures thereof. Examples of compounds include, but are not limited to, inlaid naphthalene, anthracene, erythroprene, coumarin, organisms thereof, and mixtures thereof. Examples of metal complexes include, but are not limited to, metal tyrosine a compound, for example, tris(8-hydroxyquinolinyl)aluminum (Alqd, a cyclopentadienide and a platinum electroluminescent compound, such as a complex of hydrazine with a phenylpyridine, a phenylquinoline, or a phenylpyrimidine ligand) (e.g., as disclosed in PCT Application Nos. 6, 670, 645 and the PCT Application Nos. WO 03/063 555 and WO 2004/016710) and organometallic complexes (e.g., published PCT application w〇03) /008424, WO 03/091688 and WO 03/040257); and mixtures thereof. The electroacupuncture of a charged host material and a metal complex has been described in U.S. Patent No. 6,303,238, and to Burrows and Thompson, PCT Application Serial No. 133,332, filed to PCT Application Serial No. WO 00/7065 and WO 01/41512. Light-emitting layer. Examples of conjugated polymers include, but are not limited to, poly(phenylene vinyl)' poly(poly(phenyl)), poly (porphyrin), poly(p-phenylene), copolymers thereof, and mixture. 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 cessation if layer 13 〇 and 〇 5 are otherwise in direct contact. Examples of optional layer i4 bismuth materials include, but are not limited to, oxo compounds such as metal mismatches, such as bis(2-methyl-8-quinolinyl)(p-phenyl-phenolate)aluminum(III) (BA1Q) and tris(8-hydroxyquinolinyl)aluminum (Alqs); tetrakis(8-hydroxyquinolinyl)anthracene; azole compounds such as 2-(4-biphenyl)-5-(4-tert-butyl Phenyloxy, 'oxadiazole (pBD), > (4-biphenyl)-4-phenyl-5-(4-t-butylphenyl) 4,2,4-triazole (TAZ) And 1,3,5-tris(phenyl-2-benzimidazole)benzene (1^]31); quinoxaline derivatives such as 2,3-bis(4-fluorophenyl)quinoxaline a phenanthroline derivative such as 9,1 〇diphenylphenanthroline (DPA) and 2,9-dimethyl-47-diphenyl-ul〇-phenanthroline (DDPA), and any One or more combinations. Alternatively, the optional layer may be inorganic and comprise Ba, UF, U2, or the like. Cathode layer 150 may be particularly effective for injecting electrons or negative charge carriers. Cathode layer 150 may be work. The function is lower than any metal or non-metal of the first electrical contact layer (in this case, the private anode layer 110). The term "lower work is used herein. The number " desire means that the work function of the material is not more than about 4 4 eV. The function used in this paper is more than the work function. The material function of the material is at least about 4 4 . The material of the cathode layer can be selected from the first Alkaloid metals (eg Li, Na, K, 133332.doc -37- 200915350

Rb, Cs), a Group 2 metal (eg, Mg, Ca, Ba, or such a Group 12 metal, a lanthanide (eg, Ce, Sm, Eu, or such a lanthanide (eg, Th, U, or Materials such as aluminum, indium, and the like, and combinations thereof may also be used. Non-limiting specific examples of the material of the cathode layer 15 include, but are not limited to: ruthenium, lithium, osmium, iridium, osmium, iridium, B, magnesium, lanthanum, and alloys and combinations thereof. 'Cathode layer 150 is typically formed by gas phase or gas phase s; especially in four steps. In some embodiments, the cathode layer can be patterned, as above Referring to the anode layer 110. In view of the function to be provided by the layers, the other layers of the device + can be prepared from any material known to be useful for the layers. In a second embodiment, the encapsulation layer (not shown) ) is deposited on the contact layer 15 5 to prevent undesired components such as water and oxygen from entering the device. These components have a detrimental effect on the organic layer 130. In the implementation, the encapsulation layer P is an early wall. Layer or film. In the embodiment, the encapsulation layer is a glass cover. Although not shown, it should The device 100 may comprise additional layers. Alternatively, other layers known in the industry may be used. Further, any of the above layers may comprise two or more layer sub-layers or may form a stacked structure. Alternatively, the anode layer 110, the hole transport layer 120, one or all of the electron transport layer 140, the cathode layer 150, and other layers may be processed (particularly surface treated) to improve the device's electrical transfer efficiency or other physical characteristics. The choice of materials for each component layer is determined by balancing the following objectives: combining device lifetime factors to provide devices with n device efficiencies, manufacturing time and complexity factors, and other factors that are known to those skilled in the art of AS. Good component, 133332.doc -38- 200915350 Component configuration and composition properties should be routinely determined by those of ordinary skill in the art. In one embodiment, different layers have the following thickness ranges: anode 丨丨0, 5 00 -5 000 A ' is 1000-2000 A in one embodiment; buffer layer 120, 50-2000 A '200-1 000 A in one embodiment; photoactive layer 13〇, 10-2000 A 'in one In the embodiment, loo-iooo A Optional electronic transmission sound 140, 50-2000 A, in one embodiment 100-1000 A; cathode 15 〇, 200-10000 A, in one embodiment 300-5000 A. Relative thickness of each layer It 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 luminescent layer. Depending on the exact nature of the material used. The deposition 'this produces individual luminescent pixels. · In some OLEDs (called passive moments)

Deposition of an active organic film. In operation, a voltage from a suitable power source (not shown) is applied to device 100. Current therefore passes through the various layers in device 100. Electrons enter the organic polymer layer, releasing photons. In some OLEDs (called active matrix OLED displays), each photoactive organic film can be independently excited by current flow.

. In addition, the materials, methods, and examples are merely illustrative 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 features of the invention described in the context of a single embodiment may be provided separately or in a sub-combination. In addition, when a numerical value is recited in the 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/Nafion® (poly(tetrafluoroethylene)/all I ether sulfonic acid) membranes without the addition of inorganic nanoparticles. The PAni/Nafion® dispersion used in this example was prepared using an aqueous Nafion® colloidal dispersion having an EW (acid equivalent) of 1000. The μ% (w/w) Nafion® dispersion was prepared using a procedure similar to that of Part 2 of Example 1 of U.S. Patent No. 6,15,426, but at a temperature of about 270 ° C and then passed through water. It was diluted to form a 12.0% (w/w) dispersion for polymerization. In a 500 mL·reactor, 96.4 g of 12% solids Nafion® knife dispersion (11.57 mmol SO3H group) and 1〇3 g of water were added. Dilute with 3 〇〇 RPM using an overhead stirrer with two-stage propeller blades ϊ

Nafion®. 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 pL (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. Add about 20 mg of ferric sulfate, but no visible change 133332.doc •40- 200915350. ...: However, after 30 minutes, the polymerization reaction solution began to turn pale blue and then turned green. After about 8 hours, Dowex M31 and D〇wex M43 ions were again added to the polymerization mixture with 25 g of resin and 1 〇〇g of deionized water. The mixture was stirred overnight and then filtered through a filter paper. Add i 〇〇 g deionized water to the filtrate to reduce the viscosity. Divide it into 5 equal parts. The wound remains as it is, without adding alkali. The pH of the fraction was determined to be 2 and contained 2.88. /. (w/w) PAni/Nafion®. Films were prepared from PAni/Nafion® and subsequently baked in air at 13 CTC. The room temperature conductivity of the film was determined to be l_2xl0·8 S/cm, which is also shown in the table. A small drop of toluene was placed on a piece of film, but toluene quickly rolled off the film, indicating that the non-polar organic solvent did not wet the film surface. Non-polar solvents are commonly used in luminescent polymers and luminescent small molecules. A 0.1 M aqueous NaOH solution was added to the second portion of PH 2 PAni/Nafion® until the pH was 5.0. This Na+-containing dispersion was determined to contain 2.89% (w/w) PAni/Nafion®. The conductivity of the film prepared from pH 5.0 PAni/Nafi〇n@ was determined to be 3.8 X1 〇·8 s/cm, which is also shown in Table 1. It has been tested that the § 曱 曱 does not wet the PAni/Nafion® film. Example 1 This example illustrates the effect of semiconductor nanoparticle on the conductivity and wettability of a PAni/Nafion® (poly(tetrafluoroethylene)/perfluoro-sulfonic acid) membrane. 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. Adding mu g Celnax CX-Z300H-F2® to 5.0166 g of pH 2 PAni/Nafion® dispersion (from Nissan Chemical Industries, Houston, Texas, 133332.doc 41 200915350 1; 8 octadecyl phthalate aqueous dispersion) ). €:^_23〇〇1^_172 ^^ is about 7 and contains 26.47% (w/w) yttrium acid granules, the size of which is less than 2〇nn^ in the formulation PAni/Nafion® polymer and Aachen The weight ratio of zinc acid is about 0.47. The mixture forms a stable dispersion with no signs of particle precipitation for at least five months. After the water is dried, it also forms a smooth transparent film. 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, the method is to be modified 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 6·6>1 (Γ4 S/cm (average of two film samples), which also shows In Table i, the conductivity is enhanced by more than four orders of magnitude. A piece of film is contacted with a drop of toluene. Toluene spreads rapidly on the surface of the film, which shows that the film becomes wettable by common non-polar organic solvents. Also to pH 5.0 PAni/Nafion Add CX-Z300H-F2 to the green to determine its effect on conductivity and wettability. Add υβο g Celnax cx_Z3〇〇H_F2@ to 5 〇 666 g pH 5.〇PAni/ Nafion® dispersion. The weight ratio of PAni/Nafion® polymer to zinc tellurite in the formulation was about 0.47. The mixture formed a stable dispersion with no signs of particle precipitation. It also formed a smooth transparent film after water drying. The data clearly indicated from Celnax cX_ Z300H -F2® specific tin bismuth silicate particles are compatible with PAni/ Nafi〇n8. However, in order to improve the surface smoothness of the thick chain less than at least 5 nm, it is desirable to use two methods of higher energy density instead of simply The components are added together to improve the method. The film conductivity of the dispersion containing PAni/Nafion® and zinc tellurite 133332.doc -42· 200915350 was determined to be 9 3xl·4 S/cm (average of two film samples), which also shows In Table 1, the conductivity is enhanced by more than four orders of magnitude. A 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. Table 1 CX-Z300H- Effect of F2 on conductivity Addition of CX-Z300H-F2 before cation and cation conductivity (S/cm) No CX-Z300H-F2 with CX-Z300H-F2 2.0/FT 1.2χ10'8 6.6x10'4 5.0 /Na+ 3.8χ1〇·8 9.3 χΙΟ·4 It should be noted that 'not all activities described in the above overview or examples may be required, and some part of a specific activity may not be required; and one or more other may be implemented in addition to the above activities In addition, the order in which the activities are listed is not necessarily in the order of their implementation. In the foregoing specification, several concepts have been described with reference to the specific embodiments. However, those skilled in the art should understand that the invention can be practiced without departing from the scope of the claims Scope of the invention Various modifications and changes may be made thereto, and thus the description and drawings are to be regarded as illustrative and not restrictive, and all such modifications are intended to be included within the scope of the invention. Benefits of the invention, other advantages, and solutions to problems. However, benefits, advantages, and solutions to problems and any features that achieve any benefit, advantage, or resolution (4) or make them more prominent should not be construed as any or all. The key, necessary or essential features of the patent scope. 133332.doc -43- 200915350 It will be appreciated that certain features that are described herein in the context of separate embodiments may also be provided in combination in a single embodiment. On the contrary, the features described in the context of a single embodiment can be provided individually or in any sub-combination. The use of numerical values in the various ranges specified herein should be construed as an approximation, as the minimum and maximum values within the scope of the invention are defined by the word "about". 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 a value are combined with the elements of the different values, the disclosure of the range is intended to be construed as including each value between the minimum and maximum The sub-values are in the continuous range. Moreover, when a wider or narrower range is disclosed, the minimum value from one range should be matched to the maximum value from another range, and vice versa, within the scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS The present invention is illustrated by way of example and not of limitation. Figure 1 is a schematic illustration of an organic electronic device. Those skilled in the art should understand that the components in the drawings are for clarity and clarity and are not necessarily drawn to scale. For example, in order to facilitate an understanding of the embodiments, one of the drawings may be exaggerated relative to other workpieces. [Major component symbol description] 100 110 Typical device Anode layer Buffer layer 133332.doc -44 - 120 200915350 130 Electroactive layer 140 Optional electron injection/transport layer 150 Cathode layer

133332.doc -45-

Claims (1)

200915350 X. 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(selenophene)' poly(porphin), polypyrrole, polyphenylamine, polycyclic aromatic Polymers, copolymers thereof, and combinations thereof. 3. The composition of claim 2, wherein the electrically conductive polymer is selected from the group consisting of polyaniline, polythiophene, polypyrrole, polymeric fused polycyclic heteroaromatic compounds, copolymers thereof, and combinations thereof. 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(thiazepine (3,2-b) sinter), and poly(α-s-(3,4-b) sinter). 5. The composition of claim 1, wherein the highly fluorinated acid polymer is at least 95% fluorinated. 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 has a perfluoro-ether-sulfonic acid side chain perfluoroolefin. 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, difluoro- 2 〒丞) Copolymer of oxy)-1,1,2,2-tetrafluoroethanesulfonic acid, and B. 133332.doc 200915350 ΓΓ; (;, 2,2-three gas ethoxylated 1,1,2 , a copolymer of tetrafluoroethanesulfonic acid, a composition of claim 1, a fluorescing acid polymer selected from the group consisting of tetrafluoroethylene and a copolymer of fluorine (3 6__ ^ V-milk methyl-7-octenesulfonic acid) and a copolymer of tetrafluoroethylene strontium total vinegar and fluorine (3 oxacyclotetradecanoic acid). Wherein the inorganic nanoparticles are semiconducting 10. The composite of claim 1. The composition of claim 10, the sulfide, the metal oxide 12. The composition of the composition of claim 11: Aachen The acid particles and combinations thereof, wherein the nano particles are selected from the group consisting of metals and combinations thereof, wherein the metal oxide is selected from the group consisting of the following hypoxic molybdenum trioxide, vanadium pentoxide, wherein the inorganic naphthalene Rice Insulating wherein the nanoparticles are selected from the group consisting of oxidatively oxidized, molybdenum trioxide, vanadium oxide, gas, 13. The combination of claim 1. The group consisting of the composition of claim 13: titanium dioxide And a combination thereof. The composition of claim i wherein the ratio of the nanoparticle to the conductive polymer is in the range of 0.1 to 10.0. 16. A film prepared from the composition of claim 1. For example, the refractive index of the item 16 is greater than 14 at 46 〇 nm. 18. An electronic device comprising at least one layer that can be prepared freely. "I33332.doc 200915350 19. The device, wherein the layer is a buffer layer. An electroactive layer, 20. The device of claim 19, comprising an anode, a buffer layer, and a cathode. 133332.doc