KR20100065302A - 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 composition comprises an aqueous dispersion of at least one electrically conductive polymer doped with at least one highly fluorinated acid polymer, and inorganic nanoparticles.

Description

Aqueous dispersion of electrically conductive polymer comprising inorganic nanoparticles {AQUEOUS DISPERSIONS OF ELECTRICALLY CONDUCTING POLYMERS CONTAINING INORGANIC NANOPARTICLES}

The present invention relates generally to electrically conductive polymer compositions comprising inorganic nanoparticles, and to use in electronic devices.

Electronic devices define a category of products that include an active layer. The organic electronic device has 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, or include one or more organic semiconductor layers.

An organic light emitting diode (OLED) is an organic electronic device including an organic layer capable of electroluminescence. OLEDs comprising a conductive polymer can have the following configuration with additional layers between the electrodes:

Anode / buffer layer / EL material / cathode

Typically the anode is any material having the ability to inject holes into an EL material, for example indium / tin oxide (ITO). The anode is optionally supported on a glass or plastic substrate. EL materials include fluorescent compounds, fluorescent and phosphorescent metal complexes, conjugated polymers, and mixtures thereof. The cathode is typically any material (such as Ca or Ba) that has the ability to inject electrons into the EL material. Electrically conductive polymers having low conductivity in the range of 10 ⁻³ to 10 ⁻⁷ S / cm are commonly used as buffer layers in direct contact with electrically conductive inorganic oxide anodes such as ITO.

There is a continuing need for improved buffer layer materials.

A composition is provided that comprises an aqueous dispersion of at least one electrically conductive polymer doped with at least one highly fluorinated acid polymer and in which inorganic nanoparticles are dispersed.

In another embodiment, a film formed from the composition is provided.

In another embodiment, an electronic device comprising at least one layer comprising the film is provided.

The invention is shown by way of example and not by way of limitation in the figures of the accompanying drawings.
<Figure 1>
1 is a schematic diagram of an organic electronic device.
The skilled person will understand that the objects in the figures are shown simply and clearly and not necessarily to scale. For example, the dimensions of some of the objects in the figures may be exaggerated relative to other objects to help enhance understanding of the embodiments.

Many aspects and embodiments are described herein and these 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 effects of any one or more of the embodiments will be apparent from the following detailed description, and from the claims. The detailed description first reviews the definition and description of terms followed by the preparation of electrically conductive polymers, highly fluorinated acid polymers, inorganic nanoparticles, doped electrically conductive polymer compositions, buffer layers, electronic devices, and finally examples. .

1. Definition and explanation of terms used in the specification and claims

Before discussing the details of the embodiments described below, some terms will be defined or clarified.

The term " conductor " and variations thereof are intended to refer to such layer materials, members or structures having electrical properties that allow current to flow through the layer material, member or structure without a substantial drop in potential. The term is intended to include semiconductors. In some embodiments, the conductor will form a layer having a conductivity of at least 10 ⁻⁷ S / cm.

The term “electrically conductive” when referring to a material is intended to mean a material that is inherently or essentially electrically 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 monomeric unit. The term includes copolymers having two or more different monomer units, including homopolymers having only one type, or one species of monomer unit, and copolymers formed from monomer units of different species.

The term "acid polymer" refers to a polymer having acidic groups.

The term “acidic group” refers to a group that is ionized to contribute hydrogen ions to the Bronsted base.

The term "highly fluorinated" refers to compounds in which at least 90% of the available hydrogens bonded to carbon are substituted with fluorine.

The terms "fully fluorinated" and "perfluorinated" are used interchangeably and refer to compounds in which all of the available hydrogens bonded to carbon are substituted with 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 an electrically conductive polymer, is intended to mean that the electrically 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 conductive 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. The area can be as large as the entire device, as small as a specific functional area such as a real visual display, or as small as a single subpixel. The layers and films may be formed by any conventional deposition technique, including deposition, liquid deposition (continuous and discontinuous techniques), and thermal transfer.

The term "nanoparticle" refers to 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 mostly water, in one embodiment at least about 40 weight percent water, and in some embodiments at least about 60 weight percent water.

When referring to a layer, material, member, or structure, the term "hole transport" refers to the transfer of positive charge through the thickness of such layer, material, member, or structure. To promote relatively efficient and low charge losses.

When referring to a layer, material, member, or structure, the term "electron transport" means that such layer, material, member, or structure is another layer, material, member, or other layer through the layer, material, member, or structure. Or to promote or promote the transfer of negative charges into the structure.

The term "organic electronic device" is intended to mean a device comprising one or more semiconductor layers or materials. Organic electronic devices include (1) devices that convert electrical energy into radiation (e.g., light emitting diodes, light emitting diode displays, diode lasers, or lighting panels), and (2) devices that detect signals through electronic processes (e.g., For example, photodetectors, photoconductive cells, photoresistors, optical switches, phototransistors, phototubes, infrared ("IR") detectors, or biosensors, (3) devices that convert radiation into electrical energy (e.g., Photovoltaic devices or solar cells), and (4) devices (eg, transistors or diodes) comprising one or more electronic elements, including one or more organic semiconductor layers.

As used herein, the terms “comprises”, “comprising”, “comprises”, “comprising”, “haves”, “having” or any other variation thereof include non-exclusive inclusions. It is to be covered. For example, a process, method, article, or apparatus that includes a list of elements is not necessarily limited to such elements, and may not be explicitly listed or include other elements inherent to such process, method, article, or apparatus. It may be. Also, unless expressly stated to the contrary, "or" refers to an inclusive 'or' and not an exclusive 'or'. For example, condition A or B is satisfied by any of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B Is true (or present), both A and B are true (or present).

In addition, the use of the indefinite article "a" or "an" is used to describe the elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be understood 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" convention as shown in the CRC Handbook of Chemistry and Physics, 81 ^st Edition (2000-2001). do.

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 formula, the letters Q, R, T, W, X, Y and Z are used to indicate the atoms or groups defined. All other letters are used to indicate conventional atomic signs. Group numbers corresponding to columns in the periodic table of elements use the "new notation" convention as shown in the CRC Handbook of Chemistry and Physics, 81 ^st Edition (2000).

To the extent not described herein, many details regarding specific materials, processing behaviors, and circuits are common, and textbooks and other sources in the art of organic light emitting diode displays, light sources, photodetectors, photovoltaic cells, and semiconducting members. Can be found in

2. electrically conductive polymer

Any electrically conductive polymer can be used in the new composition. In some embodiments, the electrically conductive polymer will form a film with conductivity greater than 10 ⁻⁷ S / cm.

Conductive polymers suitable for the new composition are prepared from at least one monomer which, when polymerized alone, forms an electrically conductive homopolymer. Such monomers are referred to herein as "conductive precursor monomers". Monomers that, when polymerized alone, form homopolymers that are not electrically conductive are referred to as "non-conductive precursor monomers". The conductive polymer may be a homopolymer or a copolymer. Suitable conductive copolymers for the new compositions can be prepared from two or more conductive precursor monomers or from a combination of one or more conductive precursor monomers and one or more nonconductive precursor monomers.

In some embodiments, the conductive polymer is made from at least one conductive precursor monomer selected from thiophene, pyrrole, aniline, and polycyclic aromatic materials. The term "polycyclic aromatic" refers to a compound having more than one aromatic ring. Rings may be linked by one or more bonds, or they may be fused together. The term "aromatic ring" is intended to include heteroaromatic rings. A "polycyclic heteroaromatic" compound has at least one heteroaromatic ring.

In some embodiments, the conductive polymer is prepared from at least one precursor monomer selected from thiophene, selenophene, tellurophene, pyrrole, aniline and polycyclic aromatics. Polymers made from such monomers are referred to herein as polythiophenes, poly (selenophenes), poly (tellurophenes), polypyrroles, polyanilines, and polycyclic aromatic polymers, respectively. The term "polycyclic aromatic" refers to a compound having more than one aromatic ring. Rings may be linked by one or more bonds, or they may be fused together. The term "aromatic ring" is intended to include heteroaromatic rings. A "polycyclic heteroaromatic" compound has at least one heteroaromatic ring. In some embodiments, the polycyclic aromatic polymer is poly (thienothiophene).

In some embodiments, the monomers contemplated for use to form the electrically conductive polymer of the new composition include formula (I):

[Formula I]

here,

Q is selected from the group consisting of S, Se and Te;

R ¹ are each independently selected to be the same or different when appearing, hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkyl Amino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane , Siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate, ester sulfonate, and urethane; Or both R ¹ groups can together form an alkylene or alkenylene chain to complete a 3, 4, 5, 6, or 7-membered aromatic or cycloaliphatic ring, which ring is optionally one or more divalent nitrogens , Selenium, tellurium, sulfur or oxygen atoms.

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

As used herein, the term "alkenyl" refers to a group derived from an aliphatic hydrocarbon having at least one carbon-carbon double bond, and includes linear, branched and cyclic groups which may be unsubstituted or substituted. The term "heteroalkenyl" is intended to mean an alkenyl group in which one or more of the carbon atoms in the alkenyl group is substituted with other atoms 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 given below:

Wherein all "R" groups are the same or different when appearing respectively,

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 from 1 to 20,

Z is H, an alkali metal, an alkaline earth metal, N (R ⁵ ) ₄ or R ⁵ .

Any of the above groups may also be unsubstituted or substituted, and any group may have F substituted for one or more hydrogen, including perfluorinated groups. In some embodiments, alkyl and alkylene groups have 1-20 carbon atoms.

In some embodiments, in the monomer, both R ¹ together form -W- (CY ¹ Y ² ) _m -W-, wherein m is 2 or 3 and W is O, S, Se, PO, NR ⁶ , Y ¹ is the same or different at each occurrence and is hydrogen or fluorine, Y ² is the same or different at each occurrence of hydrogen, halogen, alkyl, alcohol, amidosulfonate, benzyl, carboxylate, ether, Selected from ether carboxylates, ether sulfonates, ester sulfonates, and urethanes, the Y group may be partially or fully fluorinated. In some embodiments, all Y is hydrogen. In some embodiments, the polymer is poly (3,4-ethylenedioxythiophene). In some embodiments, at least one Y group is not hydrogen. In some embodiments, at least one Y group is a substituent having F substituted for at least one hydrogen. In some embodiments, at least one Y group is perfluorinated.

 In some embodiments, the monomer has formula Ia:

Formula Ia

here,

Q is selected from the group consisting of S, Se and Te;

R ⁷ is the same or different when present, respectively, hydrogen, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alcohol, amidosulfonate, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester Sulfonate, and urethane, provided that at least one R ⁷ is not hydrogen,

m is 2 or 3.

In some embodiments of Formula Ia, m is 2, one R ⁷ is an alkyl group having more than 5 carbon atoms and all other R ⁷ are hydrogen.

In some embodiments of Formula Ia, at least one R ⁷ group is fluorinated. In some embodiments, at least one R ⁷ group has at least one fluorine substituent. In some embodiments, the R ⁷ groups are fully fluorinated.

In some embodiments of Formula Ia, the R ⁷ substituent on the fused alicyclic ring on the monomer provides improved solubility of the monomer in water and promotes polymerization in the presence of the fluorinated acid polymer.

In some embodiments of Formula Ia, m is 2, one R ⁷ is sulfonic acid-propylene-ether-methylene and all other R ⁷ are hydrogen. In some embodiments, m is 2, one R ⁷ is propyl-ether-ethylene and all other R ⁷ are hydrogen. In some embodiments, m is 2, one R ⁷ is methoxy and all other R ⁷ are hydrogen. In some embodiments, one R ⁷ is sulfonic acid difluoromethylene ester methylene (-CH2-OC (O) -CF ₂ -SO ₃ H) and all other R ⁷ are hydrogen.

In some embodiments, pyrrole monomers contemplated for use to form the electrically conductive polymer of the new composition include Formula II:

[Formula II]

In formula (II),

R ¹ are each independently selected to be the same or different when appearing, hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkyl Amino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane , Siloxane, alcohol, benzyl, carboxylate, ether, amidosulfonate, ether carboxylate, ether sulfonate, ester sulfonate, and urethane; Or both R ¹ groups can together form an alkylene or alkenylene chain to complete a 3, 4, 5, 6, or 7-membered aromatic or cycloaliphatic ring, which ring is optionally one or more divalent nitrogens May contain sulfur, selenium, tellurium or oxygen atoms,

R ² are each independently selected to be the same or different when appearing, hydrogen, alkyl, alkenyl, aryl, alkanoyl, alkylthioalkyl, alkylaryl, arylalkyl, amino, epoxy, silane, siloxane, alcohol, benzyl, carbox Selected from the group consisting of carboxylates, ethers, ether carboxylates, ether sulfonates, ester sulfonates, and urethanes.

In one embodiment, R ¹ is the same or different when appearing, respectively, hydrogen, alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alcohol, benzyl, carboxylate, ether, amidosulfonate, ether carboxyl Among the late, ether sulfonate, ester sulfonate, urethane, epoxy, silane, siloxane, and sulfonic acid, carboxylic acid, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane or siloxane moiety Independently from one or more substituted alkyl.

In some embodiments, R ² is selected from hydrogen, alkyl, and alkyl substituted with one or more of sulfonic acid, carboxylic acid, acrylic acid, phosphoric acid, phosphonic acid, halogen, cyano, hydroxyl, epoxy, silane, or siloxane moiety do.

In some embodiments, the pyrrole monomer is unsubstituted and both R ¹ and R ² are hydrogen.

In some embodiments, both R ¹ together form a 6- or 7-membered alicyclic ring, which ring is also alkyl, heteroalkyl, alcohol, benzyl, carboxylate, ether, ether carboxylate, ether Substituted with a group selected from sulfonates, ester sulfonates, and urethanes. These groups can improve the solubility of the monomers and the resulting polymers. In some embodiments, both R ¹ together form a 6- or 7-membered alicyclic ring, which ring is also substituted with an alkyl group. In some embodiments, both R ¹ together form a 6- or 7-membered cycloaliphatic ring, which ring is also substituted with an alkyl group having at least one carbon atom.

In some embodiments, both R ¹ both are together _{^{- O - m (CHY) -}} O - to form wherein m is 2 or 3, Y is the same or different when they appear and represents 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 having F substituted for at least one hydrogen. In some embodiments, at least one Y group is perfluorinated.

In some embodiments, aniline monomers contemplated for use in forming the electrically conductive polymer of the new composition include Formula III below.

[Formula III]

here,

a is 0 or an integer from 1 to 4;

b is an integer from 1 to 5, provided that a + b = 5;

R ¹ are each independently selected to be the same or different when appearing and are hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, 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, carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate, ester sulfonate, and urethane; Or both R ¹ groups can together form an alkylene or alkenylene chain to complete a 3, 4, 5, 6, or 7-membered aromatic or cycloaliphatic ring, which ring is optionally one or more divalent nitrogens , Sulfur or oxygen atoms.

When polymerized, the aniline monomer units may have a combination of formulas IVa or IVb, or both shown below.

[Formula IVa]

[Formula IVb]

Where a, b and R ¹ are as defined above.

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

In some embodiments, a is not zero 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 monomers contemplated for use to form the electrically conductive polymer of the new composition have two or more fused aromatic rings, at least one of which is heteroaromatic. In some embodiments, the fused polycyclic heteroaromatic monomer has the formula (V):

[Formula V]

here,

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 when appearing, hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, aryl Alkyl, 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, amidosulfonate, ether sulfonate, ester sulfonate, and urethane;

At least one of R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , and R ¹⁰ and R ¹¹ together form an alkenylene chain to complete a five or six-membered aromatic ring, which ring optionally contains one or more divalent nitrogens; , Sulfur, selenium, tellurium, or oxygen atoms.

In some embodiments, the fused polycyclic heteroaromatic monomer is from the group consisting of Formula Va, Formula Vb, Formula Vc, Formula Vd, Formula Ve, Formula Vf, Formula Vg, Formula Vh, Formula Vi, Formula Vj, and Formula Vk. Has the formula selected:

here,

Q is S, Se, Te or NH;

T is the same or different at each occurrence 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.

Fused polycyclic heteroaromatic monomers may also be substituted with groups selected from alkyl, heteroalkyl, alcohols, benzyl, carboxylates, ethers, ether carboxylates, ether sulfonates, ester sulfonates, and urethanes. In some embodiments, the substituents are fluorinated. In some embodiments, the 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, 7281-7286 (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 do. In some embodiments, the thieno (thiophene) monomer is also in at least one group selected from alkyl, heteroalkyl, alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane Is substituted. In some embodiments, the substituents are fluorinated. In some embodiments, the substituents are fully fluorinated.

In some embodiments, the polycyclic heteroaromatic monomers contemplated for use to form the polymer of the new composition include Formula VI:

[Formula VI]

here,

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;

R ⁶ is hydrogen or alkyl;

R ¹² is the same or different at each occurrence and is hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkyl Sulfinyl, 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, amidosulfonate, ether sulfonate, ester sulfonate, and urethane; Or both R ¹² groups can together form an alkylene or alkenylene chain to complete a 3, 4, 5, 6, or 7-membered aromatic or cycloaliphatic ring, which ring is optionally one or more divalent nitrogens , Sulfur, selenium, tellurium or oxygen atoms.

In some embodiments, the electrically conductive polymer is a copolymer of precursor monomers and at least one second monomer. Any type of second monomer can be used so long as the second monomer does not adversely affect the desired properties of the copolymer. In some embodiments, the second monomer comprises up to 50% of the polymer, based on the total number of monomer units. In some embodiments, the second monomer comprises up to 30% of the polymer, based on the total number of monomer units. In some embodiments, the second monomer comprises up to 10% of the polymer, based on the total number of monomer units.

Exemplary types of second monomers include, but are not limited to, alkenyl, alkynyl, arylene, and heteroarylene. Examples of second monomers include, but are not limited to, fluorene, oxadiazole, thiadiazole, benzothiadiazole, phenylenevinylene, phenyleneethynylene, pyridine, diazine, and triazine. All may also be substituted.

In some embodiments, the copolymer is prepared by first forming an intermediate precursor monomer having structures A-B-C, where A and C represent precursor monomers, which may be the same or different, and B represents a second monomer. A-B-C intermediate precursor monomers can be prepared using standard synthetic organic techniques such as Yamamoto, Sille, Grignard metathesis, Suzuki and Negishi coupling. The copolymer is then formed either alone, or by oxidative polymerization of one or more additional precursor monomers.

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

In some embodiments, the electrically 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”) can be any polymer having acid groups that are highly fluorinated and have acidic protons. Acidic groups provide ionizable protons. 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 can be attached directly to the polymer backbone, or it can be attached to the side chain on the polymer backbone. 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 more than one type of acidic group. In some embodiments, the acidic group is selected from the group consisting of sulfonic acid groups, sulfonamide groups, and combinations thereof.

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

In some embodiments, HFAP is water soluble. In some embodiments, HFAP is dispersible in water. In some embodiments, HFAP is organic solvent wettable. The term "organic solvent wettability" refers to a material having a contact angle of 60 ° or less with respect to an organic solvent when formed into a film. In some embodiments, the wettable material forms a film wettable by phenylhexane with a contact angle of 55 ° or less. Methods of measuring contact angles are well known. In some embodiments, wettable materials can be prepared from polymeric acids that can themselves be wettable using non-wetting or optional additives.

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

In one embodiment, the acidic group is a sulfonic acid group or sulfonimide group. Sulfonimide groups have the general formula:

-SO ₂ -NH-SO ₂ -R

Here, R is an alkyl group.

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

In one embodiment, the HFAP is a highly fluorinated olefin backbone with highly fluorinated pendant alkyl sulfonates, highly fluorinated ether sulfonates, highly fluorinated ester sulfonates, or highly fluorinated ether sulfonimide groups. . In one embodiment, the HFAP is a perfluoroolefin with perfluoro-ether-sulfonic acid side chains. In one embodiment, the polymer is 1,1-difluoroethylene and 2- (1,1-difluoro-2- (trifluoromethyl) allyloxy) -1,1,2,2-tetrafluoro It is a copolymer of ethanesulfonic acid. In one embodiment, the polymer is ethylene and 2- (2- (1,2,2-trifluorovinyloxy) -1,1,2,3,3,3-hexafluoropropoxy) -1,1 Copolymer of 2,2-tetrafluoroethanesulfonic acid. These copolymers can be prepared as the corresponding sulfonyl fluoride polymers, which can then be converted to the sulfonic acid form.

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

In one embodiment, HFAP is a sulfonimide polymer having Formula IX:

(IX)

here,

R _f is selected from highly fluorinated alkylene, highly fluorinated heteroalkylene, highly fluorinated arylene, and highly fluorinated heteroarylene, which 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 comprises a highly fluorinated polymer backbone and side chains having Formula X:

[Formula X]

here,

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 to 4;

In one embodiment, the HFAP has the formula XI:

(XI)

here,

R ¹⁶ is a highly fluorinated alkyl group or a highly fluorinated aryl group;

c is independently 0 or an integer from 1 to 3;

n is at least 4.

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; A. J. Appleby et al., J. Electrochem. Soc. 1993, 140 (1), 109-111; And US Pat. No. 5,463,005 to Desmarteau.

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. Representative perfluoroolefins are tetrafluoroethylene, hexafluoropropylene, perfluoro- (2,2-dimethyl-1,3-diosol), perfluoro- (2-methylene-4-methyl-1 , 3-dioxolane), CF ₂ = CFO (CF ₂ ) _t CF = CF ₂ , wherein t is 1 or 2, and R _f '' OCF = CF ₂ , wherein R _f '' is 1 to A saturated perfluoroalkyl group of about 10 carbon atoms). In one embodiment, the comonomer is tetrafluoroethylene.

In one embodiment, HFAP is a colloid-forming polymeric acid. As used herein, the term "colloid-forming" refers to a material that is insoluble in water and forms a colloid when dispersed in an aqueous medium. Colloid-forming polymeric acids typically range in molecular weight from 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. Colloidal particle sizes typically range from 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 with acidic protons can be used.

Some of the polymers disclosed above may be formed in non-acid form, for example as salts, esters, or sulfonyl fluorides. These will be converted to the acid form for the preparation of the conductive composition, as described below.

In some embodiments, the HFAP comprises a highly fluorinated carbon backbone and side chains represented by the formula below.

-(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 is 0, 1 or 2, and E ⁵ . In some cases, E ⁵ can be a cation such as Li, Na or K and can be converted to the acid form.

In some embodiments, the HFAP can be a polymer disclosed in US Pat. No. 3,282,875 and US Pat. No. 4,358,545 and US Pat. No. 4,940,525. In some embodiments, the HFAP comprises a perfluorocarbon backbone and side chains represented by the formula below.

-O-CF ₂ CF (CF ₃ ) -O-CF ₂ CF ₂ SO ₃ E ⁵

Wherein E ⁵ is as defined above. This type of HFAP is disclosed in US Pat. No. 3,282,875, which discloses tetrafluoroethylene (TFE) and perfluorinated vinyl ethers CF ₂ = CF-O-CF ₂ CF (CF ₃ ) -O-CF ₂ CF ₂ SO ₂ F, perfluoro (3,6-dioxa-4-methyl-7-octensulfonyl fluoride) (PDMOF) is copolymerized, and then the sulfonyl fluoride group is hydrolyzed to convert to a sulfonate group, and necessary It can be prepared by converting into a desired ion form by time ion exchange. Examples of polymers of the type disclosed in US Pat. No. 4,358,545 and US Pat. No. 4,940,525 have side chain —O—CF ₂ CF ₂ SO ₃ E ⁵ , wherein E ⁵ is as defined above. This polymer is composed of tetrafluoroethylene (TFE) and perfluorinated vinyl ether CF ₂ = CF-O-CF ₂ CF ₂ SO ₂ F, perfluoro (3-oxa-4-pentenesulfonylfluoride) (POPF ) May be copolymerized, then hydrolyzed and further ion exchanged as necessary.

One type of HFAP is this. children. Commercially available as an aqueous Nafion® dispersion from E. I. du Pont de Nemours and Company (Wilmington, Delaware, USA).

4. Inorganic Nanoparticles

The inorganic nanoparticles can be insulating or semiconducting.

In some embodiments, the inorganic nanoparticles are metal sulfides or metal oxides. Examples of semiconducting metal oxides include mixed valence metal oxides such as zinc antimonite, and non-stoichiometric metal oxides such as oxygen deficient molybdenum trioxide, vanadium pentoxide, and the like. It is not limited to this. Examples of insulating metal oxides include, but are not limited to, titanium dioxide, zirconium oxide, molybdenum trioxide, vanadium oxide, and aluminum oxide.

In some embodiments, nanoparticles are surface treated with a coupling agent to make them compatible with aqueous electrically conductive polymers. Classes of surface modifiers include, but are not limited to, silanes, titanates, zirconates, aluminates and polymeric dispersants. Surface modifiers include chemical functional groups, such as nitrile, amino, cyano, alkyl amino, alkyl, aryl, alkenyl, alkoxy, aryloxy, sulfonic acid, acrylic acid, phosphoric acid, and alkali salts of these acids, acrylates , Sulfonates, amidosulfonates, ethers, ether sulfonates, estersulfonates, alkylthios, and arylthios. In one embodiment, the chemical functional groups may include crosslinkers such as epoxy groups, alkylvinyl groups and arylvinyl groups that react with the conductive polymer in the nanocomposite or hole transport material of the adjacent top layer. In one embodiment, the surface modifiers include tetrafluoro-ethyltrifluoro-vinyl-ether triethoxysilane, perfluorobutane-triethoxysilane, perfluorooctyltriethoxysilane, bis (trifluoro Fluorinated or perfluorinated, such as propyl) -tetramethyldisilazane, and bis (3-triethoxysilyl) propyl tetrasulfide.

5. Preparation of Doped Electrically Conductive Polymer Composition

In the discussion that follows, conductive polymers, HFAPs, and inorganic nanoparticles will be referred to as singular forms. However, it is understood that any or all of the one or more may be used.

The new electrically conductive polymer composition is prepared by first forming the doped conductive polymer and then adding the inorganic nanoparticles.

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

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

In some embodiments, the pH is increased before or after the addition of the inorganic particles. Dispersions of the doped conductive polymer and inorganic nanoparticles remain stable at about 2 to about pH formed to neutral pH. The pH can be adjusted by treatment with cation exchange resin prior to nanoparticle addition. In some embodiments, the pH is adjusted by adding an aqueous base solution. The cations of the base can be, but are 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 below as "new films described herein". The film can be made using any liquid deposition technique, including continuous and discontinuous techniques. Continuous deposition techniques include, but are not limited to, spin coating, gravure coating, curtain coating, dip coating, slot-die coating, spray coating, and continuous nozzle coating. Discontinuous deposition techniques include, but are not limited to, inkjet printing, gravure printing, and screen printing.

The film thus formed is smooth, relatively transparent, has a refractive index greater than 1.4 (at a wavelength of 460 nm), and conductivity may range from 10 ⁻⁷ to 10 ⁻³ S / cm.

6. Buffer layer

In another embodiment of the present invention, there is provided a buffer layer deposited from an aqueous dispersion comprising a new conductive polymer composition. The term " buffer layer " or " buffer material " is intended to mean an electrically conductive or semiconducting material, which is to planarize the underlying layer, charge transport and / or charge injection properties, impurities of oxygen or metal ions in organic electronic devices. It may have one or more functions, including but not limited to removal, and other aspects of enhancing or improving the performance of organic electronic devices. 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. The area can be as large as the entire device, as small as a specific functional area such as a real visual display, or as small as a single subpixel. The layers and films may be formed by any conventional deposition technique, including 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, inkjet printing, gravure printing, and screen printing.

Dry films of new conductive polymer compositions are generally not redispersible in water. Thus, the buffer layer can be applied as a plurality of thin layers. In addition, the buffer layer can be overcoated with layers of different water soluble or water dispersible materials without damage. Buffer layers comprising the new conductive polymer composition have been surprisingly found to have improved wettability.

In another embodiment, a buffer layer deposited from an aqueous dispersion comprising a new conductive polymer composition blended with other water soluble or water dispersible materials is provided. 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. Other water soluble or water dispersible materials may be simple molecules or polymers. Examples of suitable polymers include, but are not limited to, conductive polymers such as polythiophene, polyaniline, polypyrrole, polyacetylene, poly (thienothiophene), and combinations thereof.

7. Electronic device

In another embodiment of the present invention, there is provided an electronic device comprising at least one electroactive layer positioned between two electrical contact layers, the device further comprising a new buffer layer. The term "electroactive" when referring to a 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 exhibit a change in concentration of the electron-hole pair when receiving radiation.

As shown in FIG. 1, a typical 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 an optional electron-injection / transport layer 140.

The device may include a support or substrate (not shown) that may be adjacent to the anode layer 110 or the cathode layer 150. Most often, the support is adjacent to the anode layer 110. The support can be flexible or rigid, 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 for hole injection than the cathode layer 150. The anode may comprise a material containing a metal, mixed metal, alloy, metal oxide or mixed oxide. Suitable materials include mixed oxides of Group 2 elements (ie Be, Mg, Ca, Sr, Ba, Ra), Group 11 elements, Group 4, Group 5 and Group 6 elements, and Group 8-10 transition elements. . If the anode layer 110 is to be light transmissive, a mixed oxide of Group 12, Group 13 and Group 14 elements such as indium tin oxide may be used. As used herein, the phrase "mixed oxide" refers to an oxide having at least two different cations selected from Group 2 elements or Group 12, 13, or 14 elements. Some non-limiting specific examples of materials for anode layer 110 include, but are not limited to, indium tin oxide (“ITO”), indium zinc oxide, aluminum tin oxide, gold, silver, copper, and nickel. The anode is also described in "Flexible light-emitting diodes made from soluble conducting polymer," Nature vol. 357, pp 477 479 (11 June 1992), including organic materials, in particular conductive polymers such as polyaniline. At least one of the anode and the cathode must be at least partially transparent to allow observation of the generated light.

The anode layer 110 may be formed by a chemical or physical vapor deposition process or a spin-cast process. Chemical vapor deposition can be performed as plasma chemical vapor deposition ("PECVD") or organic metal chemical vapor deposition ("MOCVD"). Physical vapor deposition can include e-beam evaporation and resistive evaporation as well as all forms of sputtering, including ion beam sputtering. Certain forms of physical vapor deposition include rf magnetron sputtering and inductively coupled plasma physical vapor deposition ("IMP-PVD"). Such deposition techniques are well known within the semiconductor fabrication arts.

In one embodiment, anode layer 110 is patterned during a lithography operation. The pattern can change as desired. The layers may be patterned, for example, by placing a patterned mask or resist on the first flexible composite barrier structure prior to applying the first electrical contact layer material. Alternatively, the layers can be applied as an entire layer (also called a blanket deposit) and then patterned using, for example, a patterned resist layer and wet chemical or dry etching techniques. Other patterning processes that are well known in the art can also be used.

Buffer layer 120 includes the new conductive composition described herein. Buffer layers made from conductive polymers doped with HFAP are generally not wettable by organic solvents and have a refractive index of less than 1.4 (at 460 nm wavelength). The buffer layer described herein can be more wettable and is therefore more easily coated using the next layer from a nonpolar organic solvent. The buffer layer described herein may also have a refractive index greater than 1.4 (at 460 nm). The buffer layer is usually deposited on the substrate using various techniques well known to those skilled in the art. Typical deposition techniques include deposition, liquid deposition (continuous and discontinuous techniques) and thermal transfer, as discussed above.

An optional layer, not shown, may be present between the buffer layer 120 and the electroactive layer 130. This layer may comprise a hole transport material. Examples of hole transport materials are described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol. 18, p. 837-860, 1996, by Y. Wang. Both hole transport molecules and polymers can be used. Commonly used hole transport molecules are 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-ethylphenyl)-[1,1 '-(3,3'-dimethyl) biphenyl] -4,4'-dia Min (ETPD); Tetrakis- (3-methylphenyl) -N, N, N ', N'-2,5-phenylenediamine (PDA); 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) benzidine (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), polyaniline, and polypyrrole. Hole transport polymers can also be obtained by doping hole transport molecules such as those described above into polymers such as polystyrene and polycarbonate.

Depending on the use of the device, the electroactive layer 130 may be applied (as in a photodetector) in response to a light emitting layer that is activated by an applied voltage (such as in a light emitting diode or a light emitting electrochemical cell), i. It can be a layer of material that generates a signal with or without a bias voltage. In one embodiment, the electroactive material is an organic electroluminescent (“EL”) material. Any EL material can be used in the device, including but not limited to small molecule organic fluorescent compounds, fluorescent and phosphorescent metal complexes, conjugated polymers, and mixtures thereof. 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), and US Pat. No. 6,670,645 to Petrov et al. And WO 03. Cyclometalated iridium and platinum electroluminescent compounds such as phenylpyridine, phenylquinoline, or a complex of iridium with phenylpyrimidine ligands as disclosed in / 063555 and WO 2004/016710; Organometallic complexes described in WO 03/008424, WO 03/091688 and WO 03/040257, and mixtures thereof, include, but are not limited to. An electroluminescent emissive layer comprising a charge carrying host material and a metal complex is disclosed by Thompson et al in US Pat. No. 6,303,238 and in Burroughs in WO 00/70655 and WO 01/41512. (Burrows) and Thompson. Examples of conjugated polymers include but are not limited to poly (phenylenevinylene), polyfluorene, poly (spirobifluorene), polythiophene, poly (p-phenylene), copolymers thereof, and mixtures thereof. It is not limited.

The optional layer 140 can function to facilitate both electron injection / transport and can also serve as a limiting layer to prevent quenching reactions at the layer interface. More specifically, layer 140 increases electron mobility and may reduce the likelihood of a quench reaction if layers 130 and 150 are in direct contact. Examples of materials for the optional layer 140 include metal chelate oxanoid compounds such as bis (2-methyl-8-quinolinolato) (para-phenyl-phenololato) aluminum (III) (BAlQ) And tris (8-hydroxyquinolato) aluminum (Alq ₃ ); Tetrakis (8-hydroxyquinolinato) zirconium; Azole compounds such as 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole (PBD), 3- (4-biphenylyl) 4-phenyl-5- (4-t-butylphenyl) -1,2,4-triazole (TAZ), and 1,3,5-tri (phenyl-2-benzimidazole) benzene (TPBI); Quinoxaline derivatives such as 2,3-bis (4-fluorophenyl) quinoxaline; Phenanthroline derivatives such as 9,10-diphenylphenanthroline (DPA) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA); And any one or more combinations thereof. Alternatively, optional layer 140 may be inorganic and include BaO, LiF, Li ₂ O, or the like.

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

Materials for the cathode layer include alkali metals of Group 1 (eg Li, Na, K, Rb, Cs), Group 2 metals (eg Mg, Ca, Ba, etc.), Group 12 metals, lanthanide elements. (Eg, Ce, Sm, Eu, etc.), and actinium group elements (eg, Th, U, etc.). Materials such as aluminum, indium, yttrium, and combinations thereof may also be used. Specific non-limiting examples of materials for the cathode layer 150 include, but are not limited to, barium, lithium, cerium, cesium, europium, rubidium, yttrium, magnesium, samarium, and alloys and combinations thereof.

The cathode layer 150 is usually formed by a chemical or physical vapor deposition process. In some embodiments, the cathode layer will be patterned as described above with respect to the anode layer 110.

The other layers in the device may be made of any material known to be useful for such layers given the functionality to be provided by such layers.

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

Although not shown, it is understood that device 100 may include additional layers. Other layers known or not in the art may be used. In addition, any of the foregoing layers may include two or more sub-layers or form a laminar structure. Alternatively, some or all of the anode layer 110, hole transport layer 120, electron transport layer 140, cathode layer 150, and other layers may be treated, in particular surface treated, to provide charge carrier transport efficiency or other Physical properties can be increased. The choice of material for each component layer is preferably determined by comparing and evaluating the goals of providing devices with high device efficiency, device operating life considerations, fabrication time and complexity factors, and other considerations as understood by those skilled in the art. do. Determination of optimal components, composition of components, and compositional identity will be understood by those skilled in the art.

In one embodiment, the different layers have a thickness in the following range: anode 110 is 500-5000 mm 3, in one embodiment 1000-2000 mm 3; Buffer layer 120, 50-2000 mm 3, in one embodiment 200-1000 mm 3; Photoactive layer 130, 10-2000 kPa, in one embodiment 100-1000 kPa; The optional electron transport layer 140 is 50-2000 mm 3, in one embodiment 100-1000 mm 3; The cathode 150 is 200-10000 mm 3, in one embodiment 300-5000 mm 3. The positioning of the electron-hole recombination zones in the device, and thus the emission spectrum of the device, can be influenced by the relative thickness of each layer. Therefore, the thickness of the electron transport layer should be selected so that the electron-hole recombination zone is in the light emitting layer. The desired ratio of layer thicknesses will depend on the exact nature of the materials used.

In operation, a voltage from a suitable power source (not shown) is applied to element 100. Thus, current passes across the layers of device 100. The electrons enter the organic polymer layer and emit photons. In some OLEDs, called active matrix OLED displays, the individual deposits of the photoactive organic film can be excited independently by the passage of current, resulting in individual light emitting pixels. In some OLEDs called passive matrix OLED displays, deposits of photoactive organic films 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 in the practice or testing of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. 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 certain features of the invention described above and below in connection with separate embodiments may also be provided in a single embodiment in combination. Conversely, various features of the invention described in connection with a single embodiment for the sake of simplicity may also be provided separately or in any subcombination. Also, reference to values stated in ranges includes each and every value within that range.

EXAMPLE

Comparative Example A

This comparative example illustrates the low electrical conductivity and non-wetting of PAni / Nafion®, poly (tetrafluoroethylene) / perfluoroethersulfonic acid film without addition of inorganic nanoparticles.

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

In a 500 mL reaction vessel was charged 96.4 g of 12% solids content aqueous Nafion® dispersion (11.57 mmol SO ₃ H group), 103 g of water. The diluted Nafion® was stirred at 300 RPM using an overhead stirrer fitted with a two stage propeller blade. Dilute Nafion® In the dispersion, 1.21 g (5.09 mmol) sodium persulfate (Na ₂ S ₂ O ₈ ) dissolved in 15 mL water, and 422 microliters (4.63 mmol) aniline dissolved in 266 microliters (9.28 mmol) HCl, and 20 ML of water was added quickly. The polymerization liquid turned opaque and very viscous but no visible color change within 5 minutes. About 20 mg of ferric sulfate was added but there was no visible change. However, after 30 minutes the polymerization liquid began to turn bluish and then turn green. After about 8 hours, 25 g of Doex M31 and Dox M43 ion exchange resin, and 100 g of deionized water, respectively, 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 equal parts.

One portion was left without adding a base. This part was measured to have a pH of 2 and contained 2.88% (w / w) of PAni / Nafion®. Thin films were prepared from PAni / Nafion® and then baked in air at 130 ° C. The room temperature electrical conductivity of the thin film was measured to be 1.2 × 10 ⁻⁸ S / cm, which is also shown in Table 1. A small drop of toluene was placed on a piece of thin film but toluene quickly rolled off the film, indicating that the film surface is not wettable for nonpolar organic solvents. Nonpolar solvents are commonly used for light emitting polymers and light emitting small molecules.

pH 2 was made by adding 0.1 M aqueous NaOH solution to the second portion of pH 2 PAni / Nafion®. This portion of the Na ⁺ containing dispersion was measured to contain 2.89% (w / w) PAni / Nafion®. pH 5.0 PAni / Nafion® The electrical conductivity of the thin film prepared from was measured to be 3.8 × 10 ⁻⁸ S / cm, which is also shown in Table 1. PAni / Nafion® thin films were tested and non-wetting to toluene.

Example  One

This example illustrates the effect of semiconducting nanoparticles on the enhancement of electrical conductivity and wettability of PAni / Nafion®, poly (tetrafluoroethylene) / perfluoroethersulfonic acid films.

Embodiments of the invention are illustrated using the pH 2 and pH 5.0 PAni / Nafion® dispersions prepared in Comparative Example 1. 1.1313 g of Celnax CX-Z300H-F2® (5.0166 g of pH2 PAni / Nafion® dispersion) (Nissan Chemical Industries, Nissan Chemical Industries, Houston, TX, USA) Aqueous zinc antimonite dispersion from Co. Ltd.) was added. CX-Z300H-F2 contains 26.47% (w / w) zinc antimonite particles having a pH of about 7 and a size of less than 20 nm. The weight ratio of PAni / Nafion® polymer to zinc antimonite in the formulation is about 0.47. The mixture forms a stable dispersion with no signs of precipitation of the particles over a period of at least 5 months. It also forms a smooth and transparent film upon drying of water. The data clearly shows that certain tin antimonite particles from Selnax CX-Z300H-F2® are compatible with PAni / Nafion®. However, the process should be improved by a more energy intensive process besides simply adding the two components together to improve surface smoothness with roughness less than at least 5 nm. The thin film conductivity of the dispersion comprising PAni / Nafion® and zinc antimonite was measured to be 6.6 × 10 ⁻⁴ S / cm (average of two film samples) at room temperature, which is also shown in Table 1 have. Conductivity increased by orders of magnitude more than four times. The thin film piece was contacted with 1 drop of toluene. Toluene spreads easily on the film surface, indicating that the film is wettable to common nonpolar organic solvents.

CX-Z300H-F2 was also added to pH5.0 PAni / Nafion® to determine the effect on conductivity and wettability. To 5.0666 g of pH5.0 PAni / Nafion® dispersion was added 1.1450 g of Celnax CX-Z300H-F2®. The weight ratio of PAni / Nafion® polymer to zinc antimonite in the formulation is about 0.47. The mixture forms a stable dispersion with no signs of precipitation of the particles. It also forms a smooth and transparent film upon drying of water. The data clearly shows that certain tin antimonite particles from Selnax CX-Z300H-F2® are compatible with PAni / Nafion®. However, the process should be improved by a more energy intensive process besides simply adding two components together to improve surface smoothness with roughness at least less than 5 nm. The thin film conductivity of the dispersion comprising PAni / Nafion® and zinc antimonite was measured to be 9.3 × 10 ⁻⁴ S / cm (average of two film samples) at room temperature, which is also shown in Table 1 have. Conductivity increased by orders of magnitude more than four times. The thin film piece was contacted with 1 drop of toluene. Toluene spreads easily on the film surface, indicating that the film is wettable to common nonpolar organic solvents.

It should be understood that not all of the actions described above in the general description or the embodiments may be required, that some portions of the specific actions may not be required, and that one or more additional actions may be performed in addition to those described. Also, the order in which the actions are listed is not necessarily the order in which they are performed.

In the foregoing specification, the concepts 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 present invention.

Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, any benefit, advantage, solution to a problem, and any feature (s) that can generate or become clearer of any benefit, advantage, or solution are critical to any or all claims. It should not be construed as required or essential.

It is to be understood that certain features described herein in connection with separate embodiments can also be provided in combination in a single embodiment for clarity. Conversely, various features that are described in connection with a single embodiment for the sake of simplicity may also be provided separately or in any subcombination.

The use of numerical values in the various ranges specified herein is described as an approximation, as preceded by the term "about" in both the minimum and maximum values within the stated range. In this way, slight variations above and below the stated range can be used to achieve results that are substantially the same as values within that range. In addition, the disclosure of this range includes a continuous range that includes all values between the minimum and maximum average values, including fractional values that can be generated when some components of one value are mixed with components of different values. It is intended as. Moreover, when wider and narrower ranges are disclosed, matching the minimum value from one range to the maximum value from another range and vice versa is within the contemplation of the present invention.

Claims (15)

An aqueous dispersion of at least one electrically conductive polymer doped with at least one highly fluorinated acid polymer, and
A composition comprising inorganic nanoparticles that are either semiconducting or insulating. The method of claim 1, wherein the electrically conductive polymer is selected from the group consisting of polythiophene, poly (selenophene), poly (telurofen), polypyrrole, polyaniline, polycyclic aromatic polymers, copolymers thereof, and combinations thereof. Composition. The non-substituted polyaniline, poly (3,4-ethylenedioxythiophene), unsubstituted polypyrrole, poly (thieno (2,3-b) thiophene), poly (thier) No (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 acids and sulfonamides. The composition of claim 1 wherein the highly fluorinated acid polymer is a perfluoroolefin having a perfluoro-ether-sulfonic acid side chain. The polymer of claim 1 wherein the highly fluorinated acid polymer is 1,1-difluoroethylene and 2- (1,1-difluoro-2- (trifluoromethyl) allyloxy) -1,1,2 Copolymer of, 2-tetrafluoroethanesulfonic acid, and 2- (2- (1,2,2-trifluorovinyloxy) -1,1,2,3,3,3-hexafluoro with ethylene Propoxy) -1,1,2,2-tetrafluoroethanesulfonic acid copolymer. The polymer of claim 1 wherein the highly fluorinated acid polymer is a copolymer of tetrafluoroethylene and perfluoro (3,6-dioxa-4-methyl-7-octensulfonic acid), and tetrafluoroethylene and purple Composition selected from copolymers of luoro (3-oxa-4-pentenesulfonic acid). The composition of claim 1, wherein the nanoparticles are selected from the group consisting of metal sulfides, metal oxides, and combinations thereof. The composition of claim 9, wherein the metal oxide is selected from the group consisting of zinc antimonite, oxygen deficient molybdenum trioxide, vanadium pentoxide, and combinations thereof. The composition of claim 1 wherein the nanoparticles are selected from the group consisting of titanium dioxide, zirconium oxide, molybdenum trioxide, vanadium oxide, aluminum oxide, and combinations thereof. The composition of claim 1, wherein the weight ratio of nanoparticles to electrically conductive polymer is in the range of 0.1 to 10.0. A film made from the composition of claim 1. The film of claim 13, wherein the refractive index is greater than 1.4 at 460 nm. An electronic device comprising at least one layer prepared from the composition of claim 1.

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