JP2011529115A - Aqueous dispersion of conductive polymer containing inorganic nanoparticles - Google Patents

Abstract

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

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application is a U.S. patent filed on July 22, 2008 which claims priority to US Provisional Patent Application No. 60 / 952,372, filed July 27, 2007. No. 12 / 177,359, which is a continuation-in-part application, both of which are hereby incorporated by reference in their entirety.

  The present disclosure relates generally to conductive polymer compositions containing inorganic nanoparticles and their use in electronic devices.

  Electronic devices are one class of products that include an active layer. Organic electronic devices have at least one organic active layer. Such devices convert electrical energy into radiation, such as light emitting diodes, detect signals through electronic processes, convert radiation into electrical energy, such as photovoltaic cells, One or more organic semiconductor layers.

An organic light emitting diode (OLED) is an organic electronic device that includes an organic layer capable of electroluminescence. An OLED containing a conductive polymer can have the following configuration:
There is an additional layer between the anode / buffer layer / EL material / cathode electrode. Typically, the anode is any material that has the ability to inject holes into the EL material, such as, for example, indium / tin oxide (ITO). In some cases, the anode is supported on a glass or plastic substrate. EL materials include fluorescent compounds, fluorescent and phosphorescent metal complexes, conjugated polymers, and mixtures thereof. Typically, the cathode is any material (such as Ca or Ba) that has the ability to inject electrons into the EL material. As the buffer layer in direct contact with the conductive inorganic oxide anode such as ITO, a conductive polymer having a low conductivity in the range of 10 ⁻³ to 10 ⁻⁷ S / cm is generally used.

  There is a continuing need for improved buffer layer materials.

  A composition comprising an aqueous dispersion of at least one conductive polymer doped with at least one highly fluorinated acid polymer and having inorganic nanoparticles dispersed therein.

  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 film is provided.

  The invention is illustrated by way of example in the accompanying drawings, but is not limited thereto.

It is the schematic of an organic electronic device.

  As will be appreciated by those skilled in the art, the objects in the drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, in order to facilitate understanding of the embodiments, the dimensions of some objects in the drawings may be exaggerated more than other objects.

  Numerous aspects and embodiments are described herein and are merely exemplary and not limiting. After reading this specification, skilled artisans will appreciate that other aspects and embodiments are possible without departing from the scope of the invention.

  Other features and advantages of any one or more embodiments of the invention will be apparent from the following detailed description and from the claims. This detailed description first deals with definitions and explanations of terms, followed by conductive polymers, highly fluorinated acid polymers, inorganic nanoparticles, preparation of doped conductive polymer compositions, buffer layers, electronic devices, And finally, an example is dealt with.

1. Definitions and Explanations of Terms Used in the Specification and the Claims Before addressing details of the embodiments described below, some terms are defined or explained.

The term “conductor” and variations thereof are intended to mean a layer material, member, or structure that has electrical properties such that current flows through the layer material, member, or structure without a substantial drop in potential. ing. This term is intended to include semiconductors. In some embodiments, the conductor forms a layer having a conductivity of at least 10 ⁻⁷ S / cm.

  The term “conductive” when referring to a material is intended to mean a material that can be inherently or essentially conductive without the addition of carbon black or conductive metal particles.

  The term “polymer” is intended to mean a material having at least one repeating monomer unit. The term includes homopolymers having only one type or species of monomer units, and copolymers having two or more different monomer units, such as copolymers formed from monomer units of different species.

  The term “acid polymer” means a polymer having acidic groups.

  The term “acidic group” means a group that can donate hydrogen ions to a Bronsted base by ionization.

  The term “highly fluorinated” refers to a compound in which at least 90% of the available hydrogen bonded to the carbon is replaced by fluorine.

  The terms “perfluorinated” and “perfluorinated” are used interchangeably and mean a compound in which all available hydrogen bonded to a carbon is replaced by fluorine.

  The compositions of the present invention can include one or more different conductive polymers and one or more different highly fluorinated acid polymers.

  The term “doped” when referring to a conductive polymer is intended to mean that the conductive polymer has a polymer counterion to balance the charge on the conductive polymer.

  The term “doped conductive polymer” is intended to mean a conductive polymer and a polymer counterion associated therewith.

  The term “layer” is used interchangeably with the term “film” and refers to a coating covering a desired area. This term is not limited by size. This area may be the size of the entire device, the area of a special function such as an actual visual display, or the size of one subpixel. Layers and films can be formed by any conventional deposition technique such as vapor deposition, liquid deposition (continuous and discontinuous techniques), and thermal transfer.

  The term “nanoparticle” means a material having a particle size of less than 100 nm. In some embodiments, the particle size is less than 10 nm. In some embodiments, the particle size is less than 5 nm.

  The term “aqueous” refers to a liquid that is a substantial portion of water, in one embodiment at least about 40% by weight water; in some embodiments, at least about 60% by weight water.

  When referred to in reference to a layer, material, member, or structure, the term “hole transport” refers to such a layer, material, member, or structure such that, with relatively efficient and low charge loss, It is intended to mean to facilitate the movement of positive charges through the thickness of a material, member, or structure.

  When referred to in reference to a layer, material, member, or structure, the term “electron transport” refers to such a layer, material, member, or structure being separated from such layer, material, member, or structure, By promoting or facilitating the transfer of negative charges to a material, member or structure.

  The term “organic electronic device” is intended to mean a device comprising one or more semiconductor layers or semiconductor materials. Organic electronic devices include: (1) devices that convert electrical energy into radiation (eg, light emitting diodes, light emitting diode displays, diode lasers, or lighting panels), (2) devices that detect signals via electronic processes ( (E.g., photo detector, photoconductive cell, photoresistor, optical switch, phototransistor, phototube, infrared ("IR") detector, or biosensor), (3) a device that converts radiation into electrical energy (e.g., light Electromotive force devices or solar cells), and (4) devices that include one or more electronic components (eg, transistors or diodes) that include one or more organic semiconductor layers. .

  As used herein, the terms “comprising”, “comprising”, “comprising”, “comprising”, “having”, “having”, or any other variation thereof, Intended to deal with non-exclusive inclusions. For example, a process, method, article, or apparatus that includes a set of elements is not necessarily limited to only those elements, and is not explicitly or inherently related to such a process, method, article, or apparatus. But other elements can be included. Further, unless stated to the contrary, “or” means an inclusive “or” and not an exclusive “or”. For example, the condition A or B is satisfied when A is true (or exists), B is false (or does not exist), A is false (or does not exist) and B is true ( Or both) and both A and B are true (or present).

  “A” or “an” is also used to describe elements and components of the present invention. This is merely for convenience and is done to provide a general sense of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

  Group numbers corresponding to columns in the Periodic Table of Elements use the “New Notation” rules that can be found in CRC Handbook of Chemistry and Physics, 81st Edition (2000-2001). .

  Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the formulas, the letters Q, R, T, W, X, Y, and Z are used to represent atoms or groups as defined therein. All other letters are used to represent conventional atomic symbols. The group number corresponding to the column in the periodic table uses the rules of “New Notation” that can be found in CRC Handbook of Chemistry and Physics, 81st Edition (2000). .

  Many details regarding specific materials, processing actions, and circuits to the extent not described herein are conventional, including organic light emitting diode displays, light sources, photodetectors, photovoltaic cells, and semiconductors. It can be found in textbooks and other information sources in the technical field of the element.

2. Conductive polymers Any conductive polymer can be used in the novel compositions of the present invention. In certain embodiments, the conductive polymer forms a film having a conductivity greater than 10 ⁻⁷ S / cm.

  Conductive polymers suitable for the novel compositions of the present invention are made from at least one monomer that forms a conductive homopolymer when polymerized alone. Such monomers are referred to herein as “conductive precursor monomers”. Monomers that form non-conductive homopolymers when polymerized alone are referred to as “non-conductive precursor monomers”. The conductive polymer may be a homopolymer or a copolymer. Conductive copolymers suitable for the novel compositions of the present invention can be from two or more conductive precursor monomers, or from a combination of one or more conductive precursor monomers and one or more non-conductive precursor monomers. Can be manufactured.

  In some embodiments, the conductive polymer is made from at least one conductive precursor monomer selected from thiophenes, pyrroles, anilines, and polycyclic aromatics. The term “polycyclic aromatic” means a compound having two or more aromatic rings. These rings may be linked by one or more bonds or may be fused together. The term “aromatic ring” is intended to include heterocyclic aromatic rings. “Polycyclic heteroaromatic” compounds have at least one heterocyclic aromatic ring.

  In some embodiments, the conductive polymer is made from at least one precursor monomer selected from thiophenes, selenophenes, tellurophenes, pyrroles, anilines, and polycyclic aromatics. Polymers made from these monomers are referred to herein as polythiophenes, poly (selenophene) s, poly (tellophenes), polypyrroles, polyanilines, and polycyclic aromatic polymers, respectively. The term “polycyclic aromatic” means a compound having two or more aromatic rings. These rings may be linked by one or more bonds or may be fused together. The term “aromatic ring” is intended to include heterocyclic aromatic rings. “Polycyclic heteroaromatic” compounds have at least one heterocyclic aromatic ring. In some embodiments, the polycyclic aromatic polymer is poly (thienothiophene).

  In some embodiments, the monomers contemplated for use to form the conductive polymer in the new composition include the following Formula I:

式中：
Ｑは、Ｓ、Ｓｅ、およびＴｅからなる群から選択され；
Ｒ^１は、それぞれ同じかまたは異なるように独立して選択され、そして、水素、アルキル、アルケニル、アルコキシ、アルカノイル、アルキチオ、アリールオキシ、アルキルチオアルキル、アルキルアリール、アリールアルキル、アミノ、アルキルアミノ、ジアルキルアミノ、アリール、アルキルスルフィニル、アルコキシアルキル、アルキルスルホニル、アリールチオ、アリールスルフィニル、アルコキシカルボニル、アリールスルホニル、アクリル酸、リン酸、ホスホン酸、ハロゲン、ニトロ、シアノ、ヒドロキシル、エポキシ、シラン、シロキサン、アルコール、ベンジル、カルボキシレート、エーテル、エーテルカルボキシレート、アミドスルホネート、エーテルスルホネート、エステルスルホネート、およびウレタンから選択されるか；あるいは両方のＲ^１基が一緒になってアルキレン鎖またはアルケニレン鎖を形成して、３、４、５、６、または７員の芳香環または脂環式環を完成させてもよく、その環は場合により、１つまたは複数の二価の窒素原子、セレン原子、テルル原子、硫黄原子、または酸素原子を含んでもよい。

In the formula:
Q is selected from the group consisting of S, Se, and Te;
Each R ¹ is independently selected to be the same or different and is hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino , Aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, Selected from carboxylate, ether, ether carboxylate, amide sulfonate, ether sulfonate, ester sulfonate, and urethane Or both R ¹ groups together can form an alkylene chain or alkenylene chain to complete a 3, 4, 5, 6, or 7 membered aromatic or alicyclic ring, The ring may optionally contain one or more divalent nitrogen atoms, selenium atoms, tellurium atoms, sulfur atoms, or oxygen atoms.

  As used herein, the term “alkyl” refers to a group derived from an aliphatic hydrocarbon and refers to linear, branched, and cyclic groups that may be unsubstituted or substituted. Contains. The term “heteroalkyl” is intended to mean an alkyl group in which one or more carbon atoms in the alkyl group is replaced with another atom such as nitrogen, oxygen, sulfur, and the like. The term “alkylene” refers to an alkyl group having two points of attachment.

  As used herein, the term “alkenyl” means a group derived from an aliphatic hydrocarbon having at least one carbon-carbon double bond, whether unsubstituted or substituted. Contains certain 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 is replaced with another atom such as nitrogen, oxygen, sulfur, and the like. The term “alkenylene” refers to an alkenyl group having two points of attachment.

As used herein, the following terms for substituents refer to the formulas shown below:
“Alcohol” —R ³ —OH
“Amido” —R ³ —C (O) N (R ⁶ ) R ⁶
“Amidosulfonate” —R ³ —C (O) N (R ⁶ ) R ⁴ —SO ₃ Z
“Benzyl” —CH ₂ —C ₆ H ₅
“Carboxylate” —R ³ —C (O) OZ or —R ³ —O—C (O) —Z
“Ether” —R ³ — (O—R ⁵ ) _p —O—R ⁵
“Ether carboxylate” —R ³ —O—R ⁴ —C (O) OZ or —R ³ —O—R ⁴ —O—C (O) —Z
“Ether sulfonate” —R ³ —O—R ⁴ —SO ₃ Z
“Estersulfonate” —R ³ —O—C (O) —R ⁴ —SO ₃ Z
“Sulfonimide” —R ³ —SO ₂ —NH—SO ₂ —R ⁵
“Urethane” —R ³ —O—C (O) —N (R ⁶ ) ₂
Wherein all “R” groups are the same or different from each other:
R ³ is a single bond or an alkylene group:
R ⁴ is an alkylene group, R ⁵ is an alkyl group, R ⁶ is hydrogen or an alkyl group, p is 0 or an integer of 1 to 20, and Z is H, an alkali metal, an alkaline earth metal, N (R ⁵ ) ₄ or R ⁵
Any of the above groups may be further substituted or unsubstituted, and any group may have one or more hydrogens replaced with F, such as a perfluorinated group. In certain embodiments, the alkyl and alkylene groups have 1 to 20 carbon atoms.

In certain embodiments, a combination of both R ¹ 's in the monomer forms -W- (CY ¹ Y ² ) _m -W-, wherein m is 2 or 3, and W is O 1, S, Se, PO, NR ⁶ , Y ¹ is the same or different each time it appears, hydrogen or fluorine, Y ² is the same or different every time it appears, hydrogen, halogen , Alkyl, alcohol, amidosulfonate, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane, and the Y group may be partially or fully fluorinated. In some embodiments, all Y are hydrogen. In certain embodiments, the polymer is poly (3,4-ethylenedioxythiophene). In some embodiments, at least one Y group is not hydrogen. In certain embodiments, at least one Y group is a substituent having F substituted with at least one hydrogen. In some embodiments, at least one Y group is perfluorinated.

  In certain embodiments, the monomer comprises Formula I (a).

式中：
Ｑは、Ｓ、Ｓｅ、およびＴｅからなる群から選択され；
Ｒ^７は、それぞれ同じかまたは異なるものであり、水素、アルキル、ヘテロアルキル、アルケニル、ヘテロアルケニル、アルコール、アミドスルホネート、ベンジル、カルボキシレート、エーテル、エーテルカルボキシレート、エーテルスルホネート、エステルスルホネート、およびウレタンから選択され、但し、少なくとも１つのＲ^７が水素ではなく、
ｍは２または３である。

In the formula:
Q is selected from the group consisting of S, Se, and Te;
R ⁷ is the same or different and is from hydrogen, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alcohol, amide sulfonate, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane. Selected, provided that at least one R ⁷ is not hydrogen,
m is 2 or 3.

In certain embodiments of Formula I (a), m is 2, one R ⁷ is an alkyl group of greater than 5 carbon atoms, and all other R ⁷ are hydrogen. In some embodiments of Formula I (a), at least one R ⁷ group is fluorinated. In certain embodiments, at least one R ⁷ group has at least one fluorine substituent. In certain embodiments, the R ⁷ group is fully fluorinated.

In certain embodiments of Formula I (a), the R ⁷ substituent on the fused alicyclic ring on the monomer improves the solubility of the monomer in water and promotes polymerization in the presence of a fluorinated acid polymer. Is done.

In certain embodiments of Formula I (a), m is 2, one R ⁷ is sulfonic acid-propylene-ether-methylene, and all other R ⁷ are hydrogen. In certain embodiments, m is 2, one R ⁷ is propyl-ether-ethylene, and all other R ⁷ are hydrogen. In certain embodiments, m is 2, one R ⁷ is methoxy, and all other R ⁷ are hydrogen. In certain embodiments, one R ⁷ is sulfonic acid difluoromethylene ester methylene (—CH ₂ —O—C (O) —CF ₂ —SO ₃ H), and all other R ⁷ are hydrogen. .

  In certain embodiments, the pyrrole monomer contemplated for use to form the conductive polymer in the novel composition comprises the following Formula II:

式ＩＩにおいて：
Ｒ^１は、それぞれ同じかまたは異なるように独立して選択され、そして、水素、アルキル、アルケニル、アルコキシ、アルカノイル、アルキチオ、アリールオキシ、アルキルチオアルキル、アルキルアリール、アリールアルキル、アミノ、アルキルアミノ、ジアルキルアミノ、アリール、アルキルスルフィニル、アルコキシアルキル、アルキルスルホニル、アリールチオ、アリールスルフィニル、アルコキシカルボニル、アリールスルホニル、アクリル酸、リン酸、ホスホン酸、ハロゲン、ニトロ、シアノ、ヒドロキシル、エポキシ、シラン、シロキサン、アルコール、ベンジル、カルボキシレート、エーテル、アミドスルホネート、エーテルカルボキシレート、エーテルスルホネート、エステルスルホネート、およびウレタンから選択されるか；あるいは両方のＲ^１基が一緒になってアルキレン鎖またはアルケニレン鎖を形成して、３、４、５、６、または７員の芳香環または脂環式環を完成させてもよく、その環は場合により、１つまたは複数の二価の窒素原子、硫黄原子、セレン原子、テルル原子、または酸素原子を含んでもよく；
Ｒ^２は、それぞれ同じかまたは異なるように独立して選択され、そして、水素、アルキル、アルケニル、アリール、アルカノイル、アルキルチオアルキル、アルキルアリール、アリールアルキル、アミノ、エポキシ、シラン、シロキサン、アルコール、ベンジル、カルボキシレート、エーテル、エーテルカルボキシレート、エーテルスルホネート、エステルスルホネート、およびウレタンから選択される。

In Formula II:
Each R ¹ is independently selected to be the same or different and is hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino , Aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, Selected from carboxylate, ether, amide sulfonate, ether carboxylate, ether sulfonate, ester sulfonate, and urethane Or both R ¹ groups together can form an alkylene chain or alkenylene chain to complete a 3, 4, 5, 6, or 7 membered aromatic or alicyclic ring, The ring may optionally contain one or more divalent nitrogen, sulfur, selenium, tellurium, or oxygen atoms;
R ² is independently selected to be the same or different and is hydrogen, alkyl, alkenyl, aryl, alkanoyl, alkylthioalkyl, alkylaryl, arylalkyl, amino, epoxy, silane, siloxane, alcohol, benzyl, Selected from carboxylates, ethers, ether carboxylates, ether sulfonates, ester sulfonates, and urethanes.

In certain embodiments, each R ¹ is the same or different and is hydrogen, alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alcohol, benzyl, carboxylate, ether, amide sulfonate, ether carboxylate, ether. Sulfonate, ester sulfonate, urethane, epoxy, silane, siloxane, and one or more sulfonic acid, carboxylic acid, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane, or siloxane moieties Independently selected from alkyl substituted with

In certain embodiments, R ² is hydrogen, alkyl, and one or more sulfonic acid, carboxylic acid, acrylic acid, phosphoric acid, phosphonic acid, halogen, cyano, hydroxyl, epoxy, silane, or siloxane moieties. Selected from substituted alkyl.

In one embodiment, the pyrrole monomer is unsubstituted and both R ¹ and R ² are hydrogen.

In certain embodiments, both R ¹ together are further substituted with a group selected from alkyl, heteroalkyl, alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane. Forming a 6-membered or 7-membered alicyclic ring. These groups can improve the solubility of the monomer and the resulting polymer. In certain embodiments, both R ¹ together form a 6- or 7-membered alicyclic ring, which is further substituted with an alkyl group. In certain embodiments, both R ¹ together form a 6- or 7-membered alicyclic ring, which is further substituted with an alkyl group having at least one carbon atom.

In certain embodiments, both R ¹ together form —O— (CHY) _m —O—, wherein m is 2 or 3, and Y is the same or different, respectively. Yes, selected from hydrogen, alkyl, alcohol, benzyl, carboxylate, amidosulfonate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane. In some embodiments, at least one Y group is not hydrogen. In some embodiments, at least one Y group is a substituent in which at least one hydrogen is replaced with F. In some embodiments, at least one Y group is perfluorinated.

  In certain embodiments, the aniline monomer contemplated for use to form the conductive polymer in the novel composition comprises the following Formula III:

式中：
ａは０または１〜４の整数であり；
ｂは１〜５の整数であり、但しａ＋ｂ＝５であり；
Ｒ^１は、それぞれ同じかまたは異なるように独立して選択され、そして、水素、アルキル、アルケニル、アルコキシ、アルカノイル、アルキチオ、アリールオキシ、アルキルチオアルキル、アルキルアリール、アリールアルキル、アミノ、アルキルアミノ、ジアルキルアミノ、アリール、アルキルスルフィニル、アルコキシアルキル、アルキルスルホニル、アリールチオ、アリールスルフィニル、アルコキシカルボニル、アリールスルホニル、アクリル酸、リン酸、ホスホン酸、ハロゲン、ニトロ、シアノ、ヒドロキシル、エポキシ、シラン、シロキサン、アルコール、ベンジル、カルボキシレート、エーテル、エーテルカルボキシレート、アミドスルホネート、エーテルスルホネート、エステルスルホネート、およびウレタンから選択されるか；あるいは両方のＲ^１基が一緒になってアルキレン鎖またはアルケニレン鎖を形成して、３、４、５、６、または７員の芳香環または脂環式環を完成させてもよく、その環は場合により、１つまたは複数の二価の窒素原子、硫黄原子、または酸素原子を含んでもよい。

In the formula:
a is 0 or an integer of 1 to 4;
b is an integer from 1 to 5, provided that a + b = 5;
Each R ¹ is independently selected to be the same or different and is hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino , Aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, Selected from carboxylate, ether, ether carboxylate, amide sulfonate, ether sulfonate, ester sulfonate, and urethane Or both R ¹ groups together can form an alkylene chain or alkenylene chain to complete a 3, 4, 5, 6, or 7 membered aromatic or alicyclic ring, The ring may optionally contain one or more divalent nitrogen, sulfur, or oxygen atoms.

  Upon polymerization, the aniline monomer unit may have the formula IV (a) or formula IV (b) shown below, or a combination of both formulas.

（上式中、ａ、ｂ、およびＲ^１は前出の定義の通りである）

(Wherein a, b, and R ¹ are as defined above)

  In some embodiments, the aniline monomer is unsubstituted and a = 0.

In some embodiments, a is not 0 and at least one R ¹ is fluorinated. In some embodiments, at least one R ¹ is perfluorinated.

  In some embodiments, the fused polycyclic heteroaromatic monomer contemplated for use to form the conductive polymer in the novel composition has two or more fused aromatic rings, At least one is a heterocyclic aromatic. In some embodiments, the fused polycyclic heteroaromatic monomer has the formula V:

式中：
Ｑは、Ｓ、Ｓｅ、Ｔｅ、またはＮＲ^６であり；
Ｒ^６は、水素またはアルキルであり；
Ｒ^８、Ｒ^９、Ｒ^１０、およびＲ^１１は、それぞれ同じかまたは異なるように独立して選択され、そして、水素、アルキル、アルケニル、アルコキシ、アルカノイル、アルキチオ、アリールオキシ、アルキルチオアルキル、アルキルアリール、アリールアルキル、アミノ、アルキルアミノ、ジアルキルアミノ、アリール、アルキルスルフィニル、アルコキシアルキル、アルキルスルホニル、アリールチオ、アリールスルフィニル、アルコキシカルボニル、アリールスルホニル、アクリル酸、リン酸、ホスホン酸、ハロゲン、ニトロ、ニトリル、シアノ、ヒドロキシル、エポキシ、シラン、シロキサン、アルコール、ベンジル、カルボキシレート、エーテル、エーテルカルボキシレート、アミドスルホネート、エーテルスルホネート、エステルスルホネート、およびウレタンから選択され；
Ｒ^８とＲ^９、Ｒ^９とＲ^１０、およびＲ^１０とＲ^１１、のうち少なくとも１つがアルケニレン鎖を形成して５または６員の芳香環を完成させ、その環は、場合により１つまたは複数の二価の窒素原子、硫黄原子、セレン原子、テルル原子、または酸素原子を含むことができる。

In the formula:
Q is S, Se, Te, or NR ⁶ ;
R ⁶ is hydrogen or alkyl;
R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are each independently selected to be the same or different and are hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkthio, aryloxy, alkylthioalkyl, alkylaryl, Arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, nitrile, cyano, Hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate, amide sulfonate, ether sulfonate, ester Selected from sulfonate and urethane;
At least one of R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , and R ¹⁰ and R ¹¹ forms an alkenylene chain to complete a 5- or 6-membered aromatic ring, optionally one or A plurality of divalent nitrogen atoms, sulfur atoms, selenium atoms, tellurium atoms, or oxygen atoms can be contained.

  In some embodiments, the fused polycyclic heteroaromatic monomer has the formula V (a), V (b), V (c), V (d), V (e), V (f), V (G), V (h), V (i), V (j), and V (k):

からなる群から選択される式を有する。
式中：
Ｑは、Ｓ、Ｓｅ、Ｔｅ、またはＮＨであり；
Ｔは、それぞれ同じかまたは異なるものであり、Ｓ、ＮＲ^６、Ｏ、ＳｉＲ^６ _２、Ｓｅ、Ｔｅ、およびＰＲ^６から選択され；
ＹはＮであり；
Ｒ^６は、水素またはアルキルである。

Having a formula selected from the group consisting of
In the formula:
Q is S, Se, Te, or NH;
Each T is the same or different and is selected from S, NR ⁶ , O, SiR ⁶ ₂ , Se, Te, and PR ⁶ ;
Y is N;
R ⁶ is hydrogen or alkyl.

  The fused polycyclic heteroaromatic monomer is further substituted with a group selected from alkyl, heteroalkyl, alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane. Also good. In some embodiments, these substituents are fluorinated. In some embodiments, these substituents are fully fluorinated.

  In some embodiments, the fused polycyclic heteroaromatic monomer is thieno (thiophene). Such compounds are discussed, for example, in Macromolecules, 34, 5746-5747 (2001); and Macromolecules, 35, 7281-7284 (2002). In some embodiments, the thieno (thiophene) is selected from thieno (2,3-b) thiophene, thieno (3,2-b) thiophene, and thieno (3,4-b) thiophene. In some embodiments, the thieno (thiophene) monomer is further substituted with at least one group selected from alkyl, heteroalkyl, alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane. Has been. In some embodiments, these substituents are fluorinated. In some embodiments, these substituents are fully fluorinated.

  In certain embodiments, the polycyclic heteroaromatic monomer contemplated for use to form the polymer in the novel composition comprises Formula VI:

式中：
Ｑは、Ｓ、Ｓｅ、Ｔｅ、またはＮＲ^６であり；
Ｔは、Ｓ、ＮＲ^６、Ｏ、ＳｉＲ^６ _２、Ｓｅ、Ｔｅ、およびＰＲ^６から選択され；
Ｅは、アルケニレン、アリーレン、およびヘテロアリーレンから選択され；
Ｒ６は、水素またはアルキルであり；
Ｒ^１２は、それぞれ同じかまたは異なるものであり、水素、アルキル、アルケニル、アルコキシ、アルカノイル、アルキチオ、アリールオキシ、アルキルチオアルキル、アルキルアリール、アリールアルキル、アミノ、アルキルアミノ、ジアルキルアミノ、アリール、アルキルスルフィニル、アルコキシアルキル、アルキルスルホニル、アリールチオ、アリールスルフィニル、アルコキシカルボニル、アリールスルホニル、アクリル酸、リン酸、ホスホン酸、ハロゲン、ニトロ、ニトリル、シアノ、ヒドロキシル、エポキシ、シラン、シロキサン、アルコール、ベンジル、カルボキシレート、エーテル、エーテルカルボキシレート、アミドスルホネート、エーテルスルホネート、エステルスルホネート、およびウレタンから選択されるか；あるいは両方のＲ^１２基が一緒になってアルキレン鎖またはアルケニレン鎖を形成して、３、４、５、６、または７員の芳香環または脂環式環を完成させてもよく、その環は場合により１つまたは複数の二価の窒素原子、硫黄原子、セレン原子、テルル原子、または酸素原子を含んでもよい。

In the formula:
Q is S, Se, Te, or NR ⁶ ;
T is selected from S, NR ⁶ , O, SiR ⁶ ₂ , Se, Te, and PR ⁶ ;
E is selected from alkenylene, arylene, and heteroarylene;
R6 is hydrogen or alkyl;
Each R ¹² is the same or different and is hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, Alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, nitrile, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether , Ether carboxylate, amide sulfonate, ether sulfonate, ester sulfonate, and urethane; Alternatively, both R ¹² groups may together form an alkylene chain or alkenylene chain to complete a 3, 4, 5, 6 or 7 membered aromatic or alicyclic ring. May optionally contain one or more divalent nitrogen, sulfur, selenium, tellurium or oxygen atoms.

  In some embodiments, the conductive polymer of the present invention is a copolymer of a precursor monomer and at least one second monomer. Any type of second monomer can be used provided it does not adversely affect the properties desired for the copolymer. In some embodiments, the second monomer comprises 50% or less of the polymer based on the total number of monomer units. In some embodiments, the second monomer comprises no more than 30% based on the total number of monomer units. In some embodiments, the second monomer comprises 10% or less based on the total number of monomer units.

  Representative types of the second monomer include, but are not limited to, alkenyl, alkynyl, arylene, and heteroarylene. Examples of the second monomer include, but are not limited to, fluorene, oxadiazole, thiadiazole, benzothiadiazole, phenylene vinylene, phenylene ethynylene, pyridine, diazines, and triazines, all of which are further May be substituted.

  In some embodiments, the copolymers of the present invention are made by first forming an intermediate precursor monomer having the structure A—B—C, where A and C may be the same or different. Represents a precursor monomer, and B represents a second monomer. This ABC intermediate precursor monomer uses standard synthetic organic techniques such as Yamamoto, Stille, Grignard metathesis, Suzuki, and Negishi couplings. Can be prepared. The copolymer of the present invention is then formed by oxidative polymerization of this intermediate precursor monomer alone or with one or more other precursor monomers.

  In some embodiments, the conductive polymer is selected from the group consisting of polythiophene, polypyrrole, polymer fused polycyclic heteroaromatics, copolymers thereof, and combinations thereof.

  In some embodiments, the conductive polymer is poly (3,4-ethylenedioxythiophene), 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 polymer The highly fluorinated acid polymer ("HFAP") may be any polymer that is highly fluorinated and has acidic groups with acidic protons. The acidic group provides an ionizable proton. In some embodiments, the acidic proton has a pKa of less than 3. In some embodiments, the acidic proton has a pKa of less than zero. In some embodiments, the acidic proton has a pKa of less than −5. The acidic group may be directly bonded to the polymer main chain, or may be bonded to a side chain on the polymer main chain. Examples of acidic groups include, but are not limited to, carboxylic acid groups, sulfonic acid groups, sulfonimide groups, phosphoric acid groups, phosphonic acid groups, and combinations thereof. The acidic groups may all be the same, or the polymer may have two or more types of acidic groups. In some embodiments, the acidic group is selected from the group consisting of a sulfonic acid group, a sulfonamide group, and combinations thereof.

  In some embodiments, HFAP is at least 95% fluorinated; in some embodiments, fully fluorinated.

  In some embodiments, the HFAP is water soluble. In some embodiments, HFAP is dispersible in water. In some embodiments, HFAP is wettable with organic solvents. The term “wetability with respect to an organic solvent” means a material having a contact angle with an organic solvent of 60 ° C. or less when formed into a film. In some embodiments, the wettable material forms a film that becomes wettable with phenylhexane at a contact angle of 55 ° or less. The method for measuring the contact angle is well known. In some embodiments, the wettable material can be made from a polymeric acid that is itself non-wetting and can be made wettable by using a selective additive.

  Examples of suitable polymer backbones include, but are not limited to, polyolefins, polyacrylates, polymethacrylates, polyimides, polyamides, polyaramids, polyacrylamides, polystyrenes, and copolymers thereof. All of these are highly fluorinated; in some embodiments, fully fluorinated.

In one embodiment, the acidic group is a sulfonic acid group or a sulfonimide group. The sulfonimide group has the following formula:
—SO ₂ —NH—SO ₂ —R
In the formula, R is an alkyl group.

  In one embodiment, the acidic group is on the fluorinated side chain. In one embodiment, the fluorinated side chains are selected from alkyl groups, alkoxy groups, amide groups, ether groups, and combinations thereof, all of which are fully fluorinated.

  In one embodiment, the HFAP has a highly fluorinated olefin backbone and is a pendant of a highly fluorinated alkyl sulfonate group, a highly fluorinated ether sulfonate group, a highly fluorinated ester sulfonate group, or a highly fluorinated ether sulfonimide group. Has a group. In one embodiment, HFAP is a perfluoroolefin having a perfluoro-ether-sulfonic acid side chain. In one embodiment, the polymer comprises 1,1-difluoroethylene and 2- (1,1-difluoro-2- (trifluoromethyl) allyloxy) -1,1,2,2-tetrafluoroethanesulfonic acid and Copolymer. In one embodiment, the polymer is ethylene and 2- (2- (1,2,2-trifluorovinyloxy) -1,1,2,3,3,3-hexafluoropropoxy) -1, It is a copolymer with 1,2,2-tetrafluoroethanesulfonic acid. These copolymers can be made as the corresponding sulfonyl fluoride polymers and can be later converted to the sulfonic acid form.

  In one embodiment, the HFAP of the present invention is a homopolymer or copolymer of fluorinated and partially fluorinated poly (arylene ether sulfone). This copolymer may be a block copolymer.

  In one embodiment, the HFAP of the present invention is a sulfonimide polymer having the formula IX:

式中：
Ｒ_ｆは、高フッ素化アルキレン、高フッ素化ヘテロアルキレン、高フッ素化アリーレン、および高フッ素化ヘテロアリーレンから選択され、１つ以上のエーテル酸素で置換されていてもよく；
ｎは少なくとも４である。

In the formula:
R _f is selected from highly fluorinated alkylene, highly fluorinated heteroalkylene, highly fluorinated arylene, and highly fluorinated heteroarylene, and may be substituted with one or more ether oxygens;
n is at least 4.

In one embodiment of Formula IX, R _f is a perfluoroalkyl group. In one embodiment, R _f is a perfluorobutyl group. In one embodiment, R _f contains ether oxygen. In one embodiment, n is greater than 10.

  In one embodiment, the HFAP of the present invention comprises a highly fluorinated polymer backbone and a side chain having the formula X:

式中：
Ｒ^１５は、高フッ素化アルキレン基または高フッ素化ヘテロアルキレン基であり；
Ｒ^１６は、高フッ素化アルキル基または高フッ素化アリール基であり；
ａは０または１〜４の整数である。

In the formula:
R ¹⁵ is a highly fluorinated alkylene group or a highly fluorinated heteroalkylene group;
R ¹⁶ is a highly fluorinated alkyl group or a highly fluorinated aryl group;
a is 0 or an integer of 1-4.

  In one embodiment, the HFAP of the present invention has the formula XI:

式中：
Ｒ^１６は、高フッ素化アルキル基または高フッ素化アリール基であり；
ｃは独立して０または１〜３の整数であり；
ｎは少なくとも４である。

In the formula:
R ¹⁶ is a highly fluorinated alkyl group or a highly fluorinated aryl group;
c is independently an integer of 0 or 1-3;
n is at least 4.

  The synthesis of HFAP is described, for example, in Feiring et al. Fluorine Chemistry 2000, 105, 129-135; Feiring et al., Macromolecules 2000, 33, 9262-9271; Desmarteau, J. et al. Fluorine Chem. 1995, 72, 203-208; Appleby et al., J. Biol. Electrochem. Soc. 1993, 140 (1), 109-111; and Desmarteau US Pat. No. 5,463,005.

In one embodiment, the HFAP also includes repeating units derived from at least one highly fluorinated ethylenically unsaturated compound. Perfluoroolefins contain 2 to 20 carbon atoms. Typical perfluoroolefins include tetrafluoroethylene, hexafluoropropylene, perfluoro- (2,2-dimethyl-1,3-dioxole), perfluoro- (2-methylene-4-methyl-1,3- Dioxolane), CF ₂ ═CFO (CF ₂ ) _t CF═CF ₂ , where t is 1 or 2, and R _f ″ OCF═CF ₂ , wherein R _f ″ is from 1 to about 10 A saturated perfluoroalkyl group of carbon atoms), but is not limited thereto. In one embodiment, the comonomer is tetrafluoroethylene.

  In one embodiment, the HFAP of the present invention is a colloid-forming polymeric acid. As used herein, the term “colloid-forming” means a material that is insoluble in water and forms a colloid when dispersed in an aqueous medium. Colloid-forming polymeric acids typically have a molecular weight in the range of about 10,000 to about 4,000,000. In one embodiment, the polymeric acid has a molecular weight of about 100,000 to about 2,000,000. The particle size of the colloid is usually in the range of 2 nanometers (nm) to about 140 nm. In one embodiment, the colloid has a particle size of 2 nm to about 30 nm. Any highly fluorinated colloid-forming polymeric material having acidic protons can be used. Some of the polymers previously described herein can be formed as non-acid forms, such as salts, esters, or sulfonyl fluorides. As described below, these are converted to the acid form to prepare a conductive composition.

In some embodiments, the HFAP has a highly fluorinated carbon backbone and the formula — (O—CF ₂ CFR _f ³ ) _a —O—CF ₂ CFR _f ⁴ SO ₃ E ^5.
(Wherein R _f ³ and R _f ⁴ are independently selected from F, Cl, or a highly fluorinated alkyl group having 1 to 10 carbon atoms, a = 0, 1 or 2; ⁵ )
And the side chain represented by Optionally, E ⁵ can be a cation such as Li, Na, or K and can be converted to the acid form.

In some embodiments, HFAP is a polymer disclosed in US Pat. Nos. 3,282,875 and 4,358,545 and 4,940,525. It's okay. In some embodiments, the HFAP has a perfluorocarbon backbone and the formula —O—CF ₂ CF (CF ₃ ) —O—CF ₂ CF ₂ SO ₃ E ^5.
(Where E ⁵ is as defined above)
And the side chain represented by This type of HFAP is disclosed in US Pat. No. 3,282,875, where tetrafluoroethylene (TFE) and the perfluorinated vinyl ether CF ₂ ═CF—O—CF ₂ CF (CF ₃ ). By copolymerization with —O—CF ₂ CF ₂ SO ₂ F (perfluoro (3,6-dioxa-4-methyl-7-octenesulfonyl fluoride) (PDMOF)) followed by hydrolysis of the sulfonyl fluoride group They can be produced by converting them to sulfonate groups and converting them to the desired ionic form by ion exchange if necessary. An example of U.S. Patent No. 4,358,545 Pat and of the type disclosed in U.S. Patent No. 4,940,525 polymer, have a side chain _{-O-CF 2 CF 2 SO 3} E 5 E ⁵ in the formula is as defined above. This polymer consists of tetrafluoroethylene (TFE) and the perfluorinated vinyl ether CF ₂ ═CF—O—CF ₂ CF ₂ SO ₂ F (perfluoro (3-oxa-4-pentenesulfonyl fluoride) (POPF)). After the copolymerization, it can be produced by hydrolysis, and if necessary, ion exchange.

  One type of HFAP is E.P. I. It is used as an aqueous Nafion® dispersion by du Pont de Nemours and Company (Wilmington, DE).

4). Inorganic nanoparticles The inorganic nanoparticles of the present invention may be insulators or semiconductors.

  In some embodiments, the inorganic nanoparticles are metal sulfides or metal oxides.

Examples of semiconductor metal oxides include, but are not limited to, mixed valence metal oxides such as zinc antimonates and non-stoichiometric metal oxides such as oxygen deficient molybdenum trioxide and vanadium pentoxide. Is not to be done. Zinc antimonates ZnO / Sb ₂ O ₅ are commercially available from Nissan Chemical Company under the trade name “Celnax” in various ratios (see, for example, US Pat. No. 5,707,552).

  Examples of insulating metal oxides include silicon oxide, titanium oxides, zirconium oxide, molybdenum trioxide, vanadium oxide, aluminum oxide, zinc oxide, samarium oxide, yttrium oxide, cesium oxide, cupric oxide, and second oxide Although tin, antimony oxide, etc. are mentioned, it is not limited to these.

  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 sulfides, Co / Cd sulfides, Cd / In sulfides, and Pd—Co—Pd sulfides can be used.

  In certain embodiments, the metal nanoparticles can contain both sulfur and oxygen. In some embodiments, a combination of multiple metal nanoparticles is used.

  Metal oxide nanoparticles can be obtained by reactive sputtering of metals in the presence of oxygen, by evaporation of selected oxides and multi-component oxides, or by vapor phase hydrolysis of inorganic compounds such as silicon tetrachloride. Can be manufactured. By forming a multi-component and multi-dimensional network oxide by reacting with either hydrolysis or polycondensation by sol-gel chemistry using hydrolyzable metal compounds, especially alkoxides of various elements It can also be manufactured.

Metal sulfide nanoparticles can be obtained by various chemical and physical methods. Some examples of physical methods are metal sulfides such as cadmium sulfide, (CdS), lead sulfide (PbS), zinc sulfide (ZnS), silver sulfide (Ag ₂ S), molybdenum sulfide (MoS ₂ ). Phase deposition, lithography, and molecular beam epitaxy (MBE). The chemical preparation method for metal sulfide nanoparticles is based on the reaction of metal ions in solution with either H ₂ S gas or Na ₂ S in an aqueous medium.

  In some embodiments, the nanoparticles are surface treated with a coupling agent that is compatible with the aqueous conductive polymer. Types of surface modifiers include, but are not limited to, silanes, titanates, zirconates, aluminates, and polymer dispersants. Surface modifiers have chemical functionality such as nitrile, amino, cyano, alkylamino, alkyl, aryl, alkenyl, alkoxy, aryloxy, sulfonic acid, acrylic acid, phosphoric acid, and the above acids. Examples include, but are not limited to, alkali salts, acrylates, sulfonates, amide sulfonates, ethers, ether sulfonates, ester sulfonates, alkylthios, and arylthios. In one embodiment, this chemical functionality is achieved with crosslinkers such as epoxies, alkyl vinyl groups, and aryl vinyl groups that react with the conductive polymer in the nanocomposite or the hole transport material on the next upper layer. There may be. In one embodiment, the surface modifier is tetrafluoro-ethyl trifluoro-vinyl-ether triethoxysilane, perfluorobutane-triethoxysilane, perfluorooctyltriethoxysilane, bis (trifluoropropyl) -tetramethyl. Fluorinated or perfluorinated such as disilazane and bis (3-triethoxysilyl) propyl tetrasulfide.

5). Preparation of doped conductive polymer composition In the following description, the conductive polymer, HFAP, and inorganic nanoparticles are referred to in the singular. However, it should be understood that any or all of these can be used in more than one type.

  The novel conductive polymer composition of the present invention is prepared by first forming a doped conductive polymer and then adding inorganic nanoparticles.

  Doped conductive polymers are formed by oxidative polymerization of precursor monomers in an aqueous medium in the presence of HFAP. This polymerization is described in US Patent Application Publication Nos. 2004/0102577, 2004/0127637, and 2005/205860.

  The inorganic nanoparticles can be added directly as a solid to the doped conducting polymer dispersion. In some embodiments, inorganic nanoparticles are dispersed in an aqueous solution and the dispersion is mixed with a doped conductive polymer dispersion. The weight ratio of nanoparticles to conductive polymer is in the range of 0.1 to 10.0.

  In certain embodiments, the pH is increased either before or after adding the inorganic particles. The dispersion of doped conductive polymer and inorganic nanoparticles is stable from a pH of about 2 to neutral pH when formed. The pH can be adjusted by treating with a cation exchange resin before adding the nanoparticles. In some embodiments, the pH is adjusted by adding an aqueous base. The base cation may be, but is not limited to, alkali metals, alkaline earth metals, ammonium, and alkylammonium. In some embodiments, alkali metals are preferred over alkaline earth metal cations.

  Films made from the novel conductive compositions described herein are referred to hereinafter as “new films described herein”. These films can be made using any liquid deposition technique, such as 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 1.4 (at a wavelength of 460 nm) and has a conductivity in the range of 10 ⁻⁷ to 10 ⁻³ S / cm. Can have.

6). Buffer Layer In another embodiment of the present invention, a buffer layer is provided that is deposited from an aqueous dispersion comprising the novel conductive polymer composition of the present invention. The term “buffer layer” or “buffer material” is intended to mean an electrically conductive material or a semiconductor material, including but not limited to planarization of the underlying layer, charge transport and / or charge. One or more functions can be included in the organic electronic device, such as implantation characteristics, trapping of impurities such as oxygen or metal ions, and other features that facilitate or improve the performance of the organic electronic device. The term “layer” is used interchangeably with the term “film” and refers to a coating covering a desired area. The term is not limited by size. This area may be the size of the entire device, the area of a special function such as an actual visual display, or the size of one subpixel. Layers and films can be formed by any conventional deposition technique such as vapor deposition, liquid 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 novel conductive polymer composition of the present invention generally does not redisperse in water. Therefore, the buffer layer can be applied as a plurality of thin layers. Further, the buffer layer can be overcoated with a layer of a different water soluble or water dispersible material without causing damage.

  It has been surprisingly found that the buffer layer comprising the novel conductive polymer composition of the present invention has improved wettability. In some embodiments, films made from the novel conductive polymer compositions of the present invention exhibit contact angles with organic solvents of less than 50 °. In some embodiments, the film can be wetted with p-xylene at a contact angle of less than 50 °; in some embodiments less than 40 °; in some embodiments less than 30 °.

  In another embodiment, a buffer layer is provided that is deposited from an aqueous dispersion comprising the novel conductive polymer composition of the present invention blended with another water soluble or water dispersible material. Examples of the types of materials that can be added include, but are not limited to, polymers, dyes, coating aids, organic and inorganic conductive inks and pastes, charge transport materials, crosslinkers, and combinations thereof. It is not something. These other water soluble or water dispersible materials may be simple molecules or polymers. Suitable polymers include, but are not limited to, conductive polymers such as polythiophenes, polyanilines, polypyrroles, polyacetylenes, poly (thienothiophenes), and combinations thereof.

7). Electronic Device In another embodiment of the present invention, an electronic device is provided that includes at least one electroactive layer disposed between two electrical contact layers and further includes the novel buffer layer of the present invention. “Electroactive” when referring to the term layer or material is intended to mean a layer or material that exhibits electronic or electro-radiative properties. The electroactive layer material may emit radiation or may exhibit a change in electron-hole pair concentration upon receipt of radiation.

  As shown in FIG. 1, the exemplary device 100 has an anode layer 110, a buffer layer 120, an electroactive layer 130, and a cathode layer 150. Adjacent to the cathode layer 150 is optionally an electron injection / transport layer 140.

  The device can include a support or substrate (not shown) that can be adjacent to the anode layer 110 or the cathode layer 150. In most cases, the support is adjacent to the anode layer 110. The support may be flexible or rigid, and may be organic or inorganic. Examples of support materials include, but are not limited to glass, ceramic, metal, and plastic films.

  The anode layer 110 is an electrode that is more efficient in injecting holes than the cathode layer 150. The anode can include materials containing metals, mixed metals, alloys, metal oxides, or mixed oxides. Suitable materials include mixed oxides of Group 2 elements (ie, Be, Mg, Ca, Sr, Ba, Ra), Group 11 elements, Groups 4, 5, and 6 elements, and Groups 8-10 Transition elements. In order to make the anode layer 110 light transmissive, a mixed oxide of elements of Group 12, 13, and 14 such as indium tin oxide can be used. As used herein, the phrase “mixed oxide” means an oxide having two or more different cations selected from a Group 2 element, or a Group 12, 13, or 14 element. To do. Some non-limiting examples of materials for the anode layer 110 include indium tin oxide (“ITO”), indium zinc oxide, aluminum tin oxide, gold, silver, copper, and nickel. Although it is mentioned, it is not limited to these. The anode can be an organic material, in particular, a conductive polymer such as polyaniline, for example, “Flexible light-emitting diodes from solid conducting polymer”, Nature vol. 357, pp 477 479 (11 June 1992) can also be included. At least one of the anode and cathode should be at least partially transparent so that the generated light can be observed.

  The anode layer 110 can be formed by chemical vapor deposition, physical vapor deposition, or spin casting. Chemical vapor deposition can be performed as plasma enhanced chemical vapor deposition (“PECVD”) or metal organic chemical vapor deposition (“MOCVD”). Physical vapor deposition can include all forms of sputtering, such as ion beam sputtering, as well as e-beam evaporation and resistance evaporation. Specific forms of physical vapor deposition include radio frequency magnetron sputtering and inductively coupled plasma physical vapor deposition (“IMP-PVD”). These deposition techniques are well known in the semiconductor manufacturing field.

  In one embodiment, the anode layer 110 is patterned during a lithographic operation. This pattern can be changed as desired. These layers can be patterned, such as by placing a patterned mask or resist on the first flexible composite barrier structure before applying the first electrical contact layer material. Alternatively, these layers can be applied as a whole layer (also referred to as blanket deposition) and subsequently patterned using, for example, a patterned resist layer and wet chemical etching or dry etching techniques. be able to. Other patterning methods well known in the art can also be used.

  The buffer layer 120 includes the novel conductive composition described herein. A buffer layer made from a conductive polymer doped with HFAP is generally non-wetting with respect to organic solvents and has a refractive index of less than 1.4 (at a wavelength of 460 nm). The buffer layer described herein can be more wettable so that the next layer is more easily coated from a non-polar organic solvent. The buffer layer described herein can also have a refractive index greater than 1.4 (at 460 nm). Typically, the buffer layer is deposited on the substrate using various techniques well known to those skilled in the art. Typical deposition techniques include vapor deposition, liquid deposition (continuous and discontinuous techniques), and thermal transfer, as described above.

  Although not shown, there may optionally be a layer between the buffer layer 120 and the electroactive layer 130. This layer can include a hole transport material. Examples of hole transport materials are described in, for example, Y.M. Wang, Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol. 18, p. 837-860, 1996. Both hole transport molecules and hole transport polymers can be used. Commonly used hole transport molecules include: 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-methylphenyl)-[1,1'-biphenyl] -4,4 '-Diamine (TPD); 1,1-bis [(di-4-tolylamino) phenyl] cyclohexane (TAPC); N, N'-bis (4-methylphenyl) -N, N'-bis (4-ethyl) Phenyl)-[1,1 ′-(3,3′-dimethyl) biphenyl] -4,4′-diamine (ETPD); tetrakis- (3-methylphenyl) -N, N, N ′, N′-2 , 5-phenylenediamine ( DA); α-phenyl-4-N, N-diphenylaminostyrene (TPS); p- (diethylamino) -benzaldehyde diphenylhydrazone (DEH); triphenylamine (TPA); bis [4- (N, N-diethylamino) ) -2-methylphenyl] (4-methylphenyl) methane (MPMP); 1-phenyl-3- [p- (diethylamino) styryl] -5- [p- (diethylamino) phenyl] pyrazoline (PPR or DEASP); 1,2-trans-bis (9H-carbazol-9-yl) cyclobutane (DCZB); N, N, N ′, N′-tetrakis (4-methylphenyl)-(1,1′-biphenyl) -4, 4′-diamine (TTB); N, N′-bis (naphthalen-1-yl) -N, N′-bis- (phenyl) ben Examples include, but are not limited to, dizine (α-NPB); and porphyrin compounds such as copper phthalocyanine. Commonly used hole transporting polymers include, but are not limited to, polyvinylcarbazole, (phenylmethyl) polysilane, poly (dioxythiophene) s, polyanilines, and polypyrroles. A hole transporting polymer can also be obtained by doping hole transporting molecules such as those mentioned above into a polymer such as polystyrene or polycarbonate.

  Depending on the device application, the electroactive layer 130 is a light emitting layer (such as in a light emitting diode or light emitting electrochemical cell) that is activated by an applied voltage, responsive to radiant energy, with or with the application of a bias voltage. Rather, it may be a layer of material that generates a signal (such as in a photodetector). In one embodiment, the electroactive material is an organic electroluminescent (“EL”) material. Any EL material such as, but not limited to, small molecule organic fluorescent compounds, fluorescent and phosphorescent metal complexes, conjugated polymers, and mixtures thereof can be used in the device. Examples of fluorescent compounds include, but are not limited to, pyrene, perylene, rubrene, coumarin, derivatives thereof, and mixtures thereof. Examples of metal complexes include metal chelated oxinoid compounds such as tris (8-hydroxyquinolato) aluminum (Alq3); US Pat. No. 6,670,645 to Petrov et al., And WO 03 Iridium cyclometallates such as complexes of iridium having phenylpyridine ligand, phenylquinoline ligand, or phenylpyrimidine ligand, as disclosed in US Pat. No. 6,635.555 and WO 2004/016710. And platinum electroluminescent compounds, and organometallic complexes such as described in, for example, WO 03/008424, WO 03/091688, and WO 03/040257. , And mixtures thereof, but is not limited thereto. An electroluminescent emissive layer comprising a charge transport host material and a metal complex is described in Thompson et al., US Pat. No. 6,303,238, and Burrows and Thompson, WO 00/70655, and WO 01. / 41512 pamphlet. Examples of conjugated polymers include, but are not limited to, poly (phenylene vinylene), polyfluorene, poly (spirobifluorene), polythiophene, poly (p-phenylene), copolymers thereof, and mixtures thereof. It is not a thing.

The optionally used layer 140 may serve to facilitate both electron injection / transport, or may serve as a confinement layer that prevents quenching reactions at the layer interface. More specifically, layer 140 can facilitate electron transfer and reduce the likelihood of quenching reactions when layers 130 and 150 are in direct contact without this layer. Examples of optional layer 140 materials include bis (2-methyl-8-quinolinolato) (p-phenyl-phenolato) aluminum (III) (BAlQ) and tris (8-hydroxyquinolato) aluminum (Alq). ₃ ) metal chelated oxinoid compounds; tetrakis (8-hydroxyquinolinato) zirconium; 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (PBD) ), 3- (4-biphenylyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2,4-triazole (TAZ), and 1,3,5-tri (phenyl-2-benz) Imidazole) azole compounds such as benzene (TPBI); quino such as 2,3-bis (4-fluorophenyl) quinoxaline Sarin derivatives; phenanthroline derivatives such as 9,10-diphenylphenanthroline (DPA) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA); and any combination of one or more thereof However, it is not limited to these. Optionally used layer 140 may be inorganic and may include BaO, LiF, Li ₂ O, and the like.

  The cathode layer 150 is an electrode that is particularly effective for injecting electrons or negative charge carriers. Cathode layer 150 may be any metal or non-metal having a lower work function than the first electrical contact layer (in this case, anode layer 110). As used herein, the term “low work function” is intended to mean a material having a work function of about 4.4 eV or less. As used herein, “high work function” is intended to mean a material having a work function of at least about 4.4 eV.

  The material of the cathode layer is a group 1 alkali metal (eg, Li, Na, K, Rb, Cs,), a group 2 metal (eg, Mg, Ca, Ba, etc.), a group 12 metal, a lanthanide (eg, Ce, Sm, Eu, etc.), and actinides (eg, Th, U, etc.). Materials such as aluminum, indium, yttrium, and combinations thereof can also be used. Non-limiting specific examples of the material of the cathode layer 150 include, but are not limited to, barium, lithium, cerium, cesium, europium, rubidium, yttrium, magnesium, samarium, and alloys and combinations thereof. is not.

  In general, the cathode layer 150 is formed by chemical vapor deposition or physical vapor deposition. In some embodiments, the cathode layer can be patterned as described above for the anode layer 110.

  The other layers in the device may be made of any material known to be useful for such layers by considering the function that such layers are to perform.

  In certain embodiments, an encapsulation layer (not shown) is deposited over the contact layer 150 to prevent unwanted components such as water and oxygen from entering the device 100. Such components may adversely affect the organic layer 130. In one embodiment, the encapsulation layer is a barrier layer or film. In one embodiment, the encapsulating layer is a glass lid.

  Although not shown, it will be appreciated that the device 100 can include additional layers. Other layers well known in the art, or other other layers can be used. Further, any of the aforementioned layers may include two or more sublayers, or may form a layered structure. Alternatively, part or all of the anode layer 110 hole transport layer 120, electron transport layer 140, cathode layer 150, and another layer may be treated to improve charge carrier transport efficiency or other physical properties of the device. In particular, surface treatment can be performed. The choice of material for each component layer is the goal of obtaining a device with high device efficiency, taking into account the operational lifetime of the device, manufacturing time, and complex factors, as well as other issues recognized by those skilled in the art. This is preferably determined by balancing. It will be appreciated that determining the optimal component, component configuration, and composition is a routine task for those skilled in the art.

  In one embodiment, the various layers have thicknesses in the following ranges: anode 110, 500-5000 mm, in one embodiment 1000-2000 mm; buffer layer 120, 50-2000 mm, in one embodiment 200- Photoactive layer 130, 10-2000cm, in one embodiment 100-1000mm; optional electron transport layer 140, 50-2000mm, in one embodiment 100-1000mm; cathode 150, 200-10000mm, one embodiment Is 300-5000cm. The location of the electron-hole recombination region in the device, and thus the emission spectrum of the device, can be affected by the relative thickness of each layer. For example, the thickness of the electron transport layer should be selected so that an electron-hole recombination region is present in the light emitting layer. The desired ratio of layer thickness depends on the exact nature of the material used.

  In operation, a voltage from an appropriate power source (not shown) is applied to device 100. Thus, current flows through the entire layer of device 100. Electrons enter the organic polymer layer and emit photons. In some OLEDs, called active matrix OLED displays, individual deposits of photoactive organic film can be excited independently by current flow, thereby causing individual pixels to emit light. In some OLEDs, called passive matrix OLED displays, the photoactive organic film deposit can be excited by rows and columns of electrical contact layers.

  Although methods and materials similar or equivalent to those described herein can be used to practice or test embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are hereby incorporated by reference in their entirety unless otherwise specified. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

  For clarity, it should be understood that in the context of separate embodiments, certain features of the invention described above or below may be provided in combination in one embodiment. Conversely, for the sake of brevity, the various features of the invention described in the context of one embodiment may be provided separately or in any sub-combination. Further, where a plurality of values are referred to as being within a plurality of ranges, the respective value is included within those ranges.

Comparative Example A
This comparative example shows the low conductivity and non-wetting properties of a poly (tetrafluoroethylene) / perfluoroether sulfonic acid film, PAni / Nafion® without added inorganic nanoparticles.

  The PAni / Nafion® dispersion used in this example was prepared using an aqueous Nafion® colloidal dispersion with an EW (acid equivalent) of 1000. 25% (w / w) Nafion using a procedure similar to that of US Pat. No. 6,150,426, Example 1, Part 2, except that the temperature is about 270 ° C. A ® dispersion was made and then diluted with water to form a 12.0% (w / w) dispersion for polymerization.

A 500 mL reaction kettle was charged with 96.4 g solid 12% aqueous Nafion® dispersion (11.57 mmol SO ₃ H groups) and 103 g water. Diluted Nafion® was stirred at 300 RPM using an overhead stirrer fitted with a two-stage propeller blade. To this diluted Nafion® dispersion, 1.21 g (5.09 mmol) of sodium persulfate (Na ₂ S ₂ O ₈ ) dissolved in 15 mL of water, 266 μL (9.28 mmol) of HCl and 422 μL (4.63 mmol) of aniline dissolved in 20 mL water was quickly added. The resulting polymerized liquid became opaque and very viscous, but no color change was seen within 5 minutes. About 20 mg of ferric sulfate was added but no color change was seen. However, after 30 minutes, the polymerization liquid began to turn blue and then turned green. After about 8 hours, 25 g of Dowex M31 and Dowex M43 ion exchange resins, respectively, and 100 g of deionized water were added to the polymerization mixture. The mixture was stirred overnight and then filtered through filter paper. 100 g of deionized water was added to the filtrate to reduce the viscosity. This was divided into five parts.

The first part was kept as it was without adding base. This part was measured and found to have a pH of 2 and contain 2.88% (w / w) of PAni / Nafion®. A thin film was prepared from this PAni / Nafion (registered trademark), followed by baking at 130 ° C. in air. The electrical conductivity at room temperature of this thin film was measured and found to be 1.2 × 10 ⁻⁸ S / cm, which is also shown in Table 1. When one small droplet of toluene was placed on the film, the toluene immediately fell from the film, indicating that the film surface was not wettable by nonpolar organic solvents. Nonpolar solvents are commonly used for luminescent polymers and luminescent small molecules.

To the second portion of pH 2 PAni / Nafion® was added 0.1 M NaOH aqueous solution to pH 5.0. Measurement of this portion of the Na ⁺ -containing dispersion revealed that it contained 2.89% (w / w) PAni / Nafion®. The conductivity of the thin film prepared from PAni / Nafion (registered trademark) at pH 5.0 was measured to be 3.8 × 10 ⁻⁸ S / cm, which is also shown in Table 1. When tested on this PAni / Nafion® thin film, it was non-wetting to toluene.

Example 1
This example shows the effect of semiconductor nanoparticles on improving the conductivity and wettability of a film of poly (tetrafluoroethylene) / perfluoroether sulfonic acid, PAni / Nafion®.

To illustrate embodiments of the present disclosure, pH 2 and pH 5.0 PAni / Nafion® dispersions prepared in Comparative Example 1 were used. An aqueous zinc antimonite of 1.1313 g Celnax CX-Z300H-F2® (Nissan Chemical Industries, Ltd., Houston, Texas, USA) to 5.0166 g pH 2 PAni / Nafion® dispersion. Dispersion) was added. CX-Z300H-F2 has a pH of about 7 and contains 26.47% (w / w) zinc antimonite particles with a size of less than 20 nm, PAni / Nafion® polymer pair in the formulation The weight ratio of zinc antimonite is about 0.47. This mixture forms a stable dispersion with no signs of particle settling over a period of at least 5 months. This mixture also forms a smooth and transparent film when water is dried. These data clearly show that tin antimonite, particularly from Celnax CX-Z300H-F2®, is compatible with PAni / Nafion®. However, this process is improved by a higher energy intensity process rather than simply adding the two components together to improve surface smoothness having a thickness of at least less than 5 nm. The thin film conductivity of the dispersion containing PAni / Nafion® and zinc antimonite was measured at room temperature to be 6.6 × 10 ⁻⁴ S / cm (average of two film samples), which is shown in Table 1. Also shown in The conductivity was improved by more than 4 orders of magnitude. A drop of toluene was contacted with the film. Toluene spreads easily on the surface of the thin film, indicating that the thin film becomes wettable with common non-polar organic solvents.

CX-Z300H-F2 was also added to PAni / Nafion (registered trademark) at pH 5.0 to examine its effect on conductivity and wettability. To 450666 g of pH 5.0 PAni / Nafion® dispersion, 1.1450 g of Celnax CX-Z300H-F2® was added. The weight ratio of PAni / Nafion® polymer to zinc antimonite in the formulation is about 0.47. This mixture forms a stable dispersion with no signs of particle settling. This mixture also forms a smooth and transparent film when water is dried. These data clearly show that tin antimonite, particularly from Celnax CX-Z300H-F2®, is compatible with PAni / Nafion®. However, this process is improved by a higher energy intensity process rather than simply adding the two components together to improve surface smoothness having a thickness of at least less than 5 nm. The thin film conductivity of the dispersion containing PAni / Nafion® and zinc antimonite was measured at room temperature to be 9.3 × 10 ⁻⁴ S / cm (average of two film samples), which is shown in Table 1. Also shown in The conductivity was improved by more than 4 orders of magnitude. A drop of toluene was contacted with the film. Toluene spreads easily on the surface of the thin film, indicating that the thin film becomes wettable with common non-polar organic solvents.

Example 2
In this example, in the presence of an aqueous dispersion of a copolymer of TFE (tetrafluoroethylene) and the perfluorinated polymer acid PSEPVE (perfluorinated 3,6-dioxa-4-methyl-7-octenesulfonic acid). Preparation of an aqueous dispersion of polypyrrole (PPy) produced in This aqueous PPy / poly (TFE-PSEPVE) dispersion is used to demonstrate the effect of silica nanoparticles on the wettability of PPY poly (TFE-PSEPVE) solid films with organic solvents. An aqueous dispersion of poly (TFE-PSEPVE) was prepared by heating poly (TFE-PSEPVE) with 1000 EW in water to about 270 ° C. This aqueous poly (TFE-PSEPVE) dispersion is 25% (w / w) poly (TFE-PSEPVE) in water and diluted to 10.8% with deionized water prior to use in polymerization with pyrrole. did.

The pyrrole monomer was polymerized in the presence of poly (TFE-PSEPVE) dispersion as described in US Patent Publication No. 2005-0205860. The polymerization components have the following molar ratios: poly (TFE-PSEPVE): pyrrole = 3.4; Na ₂ S ₂ O ₈ : pyrrole = 1.0; Fe ₂ (SO ₄ ) ₃ : pyrrole = 0.1. This 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-31, Dowex M-43, and Dowex M-31 Na ⁺ , respectively. These three Dowex ion exchange resins are from Dow Chemicals Company, Midland, Michigan, USA. The dispersion treated with this ionic resin was subsequently microfluidized by passing it once at 5,000 psi using a Microfluidizer Processor M-110Y (Microfluidics, Massachusetts, USA). The microfluidizer treated dispersion was then filtered and degassed to remove oxygen. The dispersion pH was measured using a standard pH meter to be 4.0, and the percent solids measured by gravimetry was 6.4%. A film is spin coated from this dispersion and then baked in air at 130 ° C. for 10 minutes and has a conductivity of 7.5 × 10 ⁻⁴ S / cm at room temperature. The aqueous PPy / poly (TFE-PSEPVE) dispersion was first diluted from 6.4% to 3.12% and then used for the addition of silica nanoparticles. The silica nao particle dispersion used in this example is IPA (isopropanol) -ST-S from Nissan Chemical Company. IPA-ST-S contains 26 wt% silica nanoparticles. The silica particle size was measured using Microtrac “nano-ultra” dynamic light scattering. It was found that 50% by volume of silica has a particle size of 7.1 nm (nanometers) or less. This silica dispersion is then mixed with the corresponding amount of PPy / poly (TFE-PSEPVE) dispersion to the total solids listed in Table 2 which are PPy / poly (TFE-PSEPVE) and silica. The desired silica weight percent was obtained. It is clear from the data that the contact angle of PPy / poly (TFE-PSEPVE) solid film formed by spin coating is significantly reduced in the case of p-xylene and anisole when silica is included. Is shown in

Example 3
This example shows the device performance of a solution-processed organic light emitting diode with a blue light emitter using PPy / poly (TFE-PSEPVE) with and without silica as the buffer layer.

  On a patterned ITO substrate (device active area = 2.24 mm × 2.5 mm) using PPy / poly (TFE-PSEPVE) dispersion with and without the silica of Example 2 A buffer layer was formed by spin coating. The ITO substrate was cleaned prior to use and treated in a UV zone oven for 10 minutes. The spin coating of each PPy / poly (TFE-PSEPVE) dispersion with and without silica was set to a condition where a thickness of 50 nm was obtained after baking at 140 ° C. for 7 minutes in air. did. They were then transferred to a dry box and all further overcoating was performed in the inert chamber. Next, the buffer layer is overcoated with a 0.38% (w / v) toluene solution of HT-2, which is an arylamine-containing copolymer having hole transport properties, and baked in argon at 275 ° C. for 30 minutes to 20 nm. Realized the thickness. After cooling, the substrate was spin coated with a light emitting 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 was about 40 nm. The substrate was then masked and placed in a vacuum chamber. A 10 nm thick layer of a metal quinolate derivative as the electron transport layer was deposited by thermal evaporation, followed by a 0.8 nm layer of cesium fluoride and a 100 nm aluminum cathode layer. The device was encapsulated using a glass lid, getter pack, and UV curable epoxy. The resulting light emitting diode samples were characterized by measuring their 1) current-voltage (IV) curves, (2) electroluminescence radiance versus voltage, and (3) electroluminescence spectrum versus voltage. It was. All three measurements were made simultaneously and controlled by a computer. By dividing the electroluminescence radiance of the LED by the current density required to operate the device, the current efficiency (cd / A) of the device at a certain voltage is determined. The output efficiency (Lm / W) is a value obtained by dividing the current efficiency by the operating voltage. The results are shown in Table 3, indicating that silica does not adversely affect device performance.

  Not all acts described above in the summary or example are required and some of the specific acts may not be necessary, and one or more additional actions may be performed in addition to the actions described above. Please note that there may be cases. Further, the order in which actions are listed are not necessarily the order in which they are performed.

  In the foregoing specification, the concepts of the invention have been described with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the present invention as set forth in the claims below. The specification and drawings are, accordingly, to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of the invention.

  Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, any or all of these benefits, advantages, solutions to problems, and any features that may generate or make any benefit, advantage, or solution appear to be any or all of the claims Should not be construed as an important, necessary, or essential feature of.

  It should be understood that in the context of separate embodiments, the specific features described herein for clarity may be provided in combination in one embodiment. Conversely, the various features described in the context of one embodiment for the sake of brevity can also be provided separately or in any sub-combination.

  Where numbers within the various ranges specified herein are used, they are stated as approximations as if the word “about” preceded both the minimum and maximum values within the stated range. Has been. In this way, variations slightly above and slightly below the stated range can be used to achieve substantially the same results as for values within that range. The disclosure of these ranges also includes all values between the minimum and maximum average values, including fractional values that can occur when some components of one value are mixed with some components of different values. It is intended to be a continuous range containing values. Further, when a wider range and a narrower range are disclosed, it is within the spirit of the invention to match the minimum value of one range with the maximum value of another range and vice versa.

Claims (22)

An aqueous dispersion of at least one conductive polymer doped with at least one highly fluorinated acid polymer;
A composition comprising inorganic nanoparticles.   The conductive polymer is selected from the group consisting of polythiophenes, poly (selenophene) s, poly (tellurophenes), polypyrroles, polyanilines, polycyclic aromatic polymers, copolymers thereof, and combinations thereof. The composition of claim 1.   The composition of claim 2, wherein the conductive polymer is selected from the group consisting of polyaniline, polythiophene, polypyrrole, fused polycyclic heteroaromatic polymers, copolymers thereof, and combinations thereof.   The conductive polymer is unsubstituted polyaniline, poly (3,4-ethylenedioxythiophene), unsubstituted polypyrrole, poly (thieno (2,3-b) thiophene), poly (thieno (3,2-b) thiophene. ) And poly (thieno (3,4-b) thiophene).   The composition of claim 1, wherein the highly fluorinated acid polymer is at least 95% fluorinated.   The composition of claim 1, wherein the highly fluorinated acid polymer is selected from sulfonic acid and sulfonimide.   The composition of claim 1, wherein the highly fluorinated acid polymer is a perfluoroolefin having perfluoro-ether-sulfonic acid side chains.   The highly fluorinated acid polymer is a copolymer of 1,1-difluoroethylene and 2- (1,1-difluoro-2- (trifluoromethyl) allyloxy) -1,1,2,2-tetrafluoroethanesulfonic acid And ethylene and 2- (2- (1,2,2-trifluorovinyloxy) -1,1,2,3,3,3-hexafluoropropoxy) -1,1,2,2-tetrafluoroethane The composition of claim 1 selected from the group consisting of copolymers with sulfonic acids.   The highly fluorinated acid polymer is a copolymer of tetrafluoroethylene and perfluoro (3,6-dioxa-4-methyl-7-octenesulfonic acid), and tetrafluoroethylene and perfluoro (3-oxa-4-pentene). 2. A composition according to claim 1 selected from copolymers with sulfonic acids).   The composition of claim 1, wherein the inorganic nanoparticles are semiconductors.   The composition of claim 10, wherein the inorganic nanoparticles are selected from the group consisting of metal sulfides, metal oxides, and combinations thereof.   The composition according to claim 11, wherein the metal oxide is selected from the group consisting of zinc antimonates, indium tin oxide, oxygen-deficient molybdenum trioxide, vanadium pentoxide, and combinations thereof.   The composition of claim 1, wherein the inorganic nanoparticles are insulating.   The nanoparticles are silicon oxide, titanium oxides, zirconium oxide, molybdenum trioxide, vanadium oxide, aluminum oxide, zinc oxide, samarium oxide, yttrium oxide, cesium oxide, cupric oxide, stannic oxide, antimony oxide, 14. The composition of claim 13, selected from the group consisting of: and combinations thereof.   The inorganic nanoparticles are cadmium sulfide, copper sulfide, lead sulfide, mercury sulfide, indium sulfide, silver sulfide, cobalt sulfide, nickel sulfide, molybdenum sulfide, Ni / Cd sulfides, Co / Cd sulfides, Cd / In The composition of claim 1, selected from the group consisting of sulfides, Pd—Co—Pd sulfides, and combinations thereof.   The composition of claim 1 wherein the weight ratio of nanoparticles to conductive polymer is in the range of 0.1 to 10.0.   A film made from the composition of claim 1.   18. A film according to claim 17, having a contact angle of less than 50 [deg.] with p-xylene.   The film of claim 17 having a refractive index greater than 1.4 at 460 nm.   An electronic device comprising at least one layer made from the composition of claim 1.   21. The device of claim 20, wherein the layer is a buffer layer.   The device of claim 21, comprising an anode, a buffer layer, an electroactive layer, and a cathode.

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