KR20090009871A - High energy-potential bilayer compositions - Google Patents

Abstract

There is provided a bilayer composition. The first layer is a hole injection layer having a work function greater than 5.2 eV. The second layer is a hole transport layer. There are also provided electronic devices having the bilayer composition.

Description

High Energy-Potential Bilayer Composition {HIGH ENERGY-POTENTIAL BILAYER COMPOSITIONS}

The present invention generally relates to high energy-potential bilayer compositions, and their use in organic electronic devices.

 Organic electronic devices define a category of products that include an active layer. Such devices convert electrical energy into radiation, detect signals through electronic processes, convert radiation into electrical energy, or include one or more organic semiconductor layers.

Organic light emitting diodes (OLEDs) are organic electronic devices that include an organic layer capable of electroluminescence. The OLED can have the following configuration.

Anode / buffer layer / EL material / cathode

The anode is typically any material that is transparent and has the ability to inject holes into the EL material, such as indium oxide / tin (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. The buffer layer is typically an electrically conductive polymer, which facilitates the injection of holes from the anode into the EL material layer. The buffer layer may also have other properties that facilitate device performance.

There is a continuing need for buffer materials with improved properties.

Summary of the Invention

Bilayer compositions are provided. The first layer is a hole injection layer having a work function of greater than 5.2 eV. The second layer is a hole transport layer.

In another embodiment, a bilayer composition is provided. The first layer is a hole injection layer made from a composition having a work function of greater than 5.0 eV and having a pH of greater than 2.0. The second layer is a hole transport layer.

In another embodiment, an electronic device is provided. The device has an anode. The anode is in contact with the hole injection layer having a work function of greater than 5.2 eV. The hole injection layer is in contact with the hole transport layer.

The foregoing general description and the following detailed description are exemplary and explanatory only and do not limit the invention as defined in the appended claims.

Embodiments are shown in the accompanying drawings to facilitate understanding of the concepts described herein.

1 is a view showing a contact angle.

2 includes an example of an electronic device having a high energy-potential bilayer composition.

Those skilled in the art recognize that the objects in the figures are illustrated for simplicity and clarity, and are not necessarily drawn to scale. For example, the dimensions of some objects in the figures may be exaggerated relative to other objects to facilitate understanding of the embodiments.

Many aspects and embodiments have been described above, which are merely illustrative and not restrictive. Those skilled in the art, after reading this specification, recognize that other aspects and embodiments are possible without departing from the scope of the invention.

Other features and advantages of any one or more of the embodiments will be apparent from the following detailed description, and from the claims. In the detailed description, first of all, definitions and explanations of terms are provided, followed by a hole injection layer, a hole transport layer, a method for producing a bilayer composition, an electronic device, and finally an embodiment.

1. Definitions and explanations of terms used in the specification and claims

Before providing a detailed description of the following embodiments, some terms are defined or explained.

The term "conductor" and variations thereof, as used herein, is intended to refer to such layer material, member or structure having electrical properties such that current flows through the layer material, member or structure without a substantial potential drop. The term is intended to include semiconductors. In one embodiment, the conductor forms a layer having a conductivity of at least 10 ⁻⁶ S / cm.

The term “electrically conductive material” refers to a material that can be inherently or essentially electrically conductive without the addition of carbon black or conductive metal particles.

The term "work function" is intended to mean the minimum energy required to remove electrons from a conductor or semiconductor material to a point of infinite distance away from the surface. The work function is typically obtained by UPS (Ultraviolet Photoemission Spectroscopy) or Kelvin-probe contact potential difference measurements.

The term “energy potential” is intended to mean the potential of the sandwiched nonconductive material between the conductive test piece and the tip of the vibrating Kelvin probe. The conductive test piece may be gold, indium tin oxide or an electrically conductive polymer, but is not limited thereto. In the present invention, the nonconductive material is a hole transport material.

When referring to a layer, material, member or structure, the term “hole injection” refers to such layer, material which facilitates the injection and transfer of positive charges through the thickness of such layer, material, member or structure relatively efficiently and with little charge loss. It is intended to mean a member or structure.

When referring to a layer, material, member or structure, the term “hole transport” refers to such layer, material, member that facilitates the transfer of positive charges through the thickness of such layer, material, member or structure relatively efficiently and with little charge loss. Or structure. The term "hole transport layer" as used herein does not include a light emitting layer even though the light emitting layer may have some hole transport properties.

In some embodiments, the electrically conductive material is a polymer. The term "polymer" is intended to mean a material having one or more repeating monomer units. The term includes copolymers having two or more different monomer units, including homopolymers having only one monomer unit, and copolymers formed from different kinds of monomer units. The term "organic solvent wettability" refers to a material that is wettable by an organic solvent when formed into a film. The term also encompasses polymeric acids that do not form a film alone, but form electrically conductive polymer compositions that are wettable. In one embodiment, the organic solvent wettable material forms a wettable film with phenylhexane at a contact angle of 40 ° or less. The term “fluorinated acid polymer” refers to a polymer having an acidic group, at least in which some hydrogen is replaced with fluorine. The term “acidic group” refers to a group that can be ionized to donate hydrogen ions to the Broensted base. The composition may comprise at least one different electrically conductive polymer and at least one different organic solvent wettable fluorinated acid polymer.

As used herein, the terms “comprise, include”, “comprising, including”, “have”, “having” or any other variation thereof are intended to encompass non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a series of elements is not necessarily limited to these elements, and may include elements that are not explicitly listed or inherent to such process, method, article, or apparatus. . Also, unless expressly stated otherwise, “or” refers to an inclusive “or” and does not represent an exclusive “or”. For example, condition A or B is satisfied by any of the following: A is true (or present) B is false (or not present) and A is false (or not present) B is true (or present), both A and B are true (or present).

In addition, "a" or "an" is used in the English language to describe the elements and components described herein. This is for convenience only and gives a general meaning of the scope of the invention. Unless it is obvious to have a different meaning, such description includes one or more than one, and the singular should be understood to include the plural as well.

Family numbers corresponding to columns in the Periodic Table of Elements utilize the "New Notation" convention as shown in the CRC Handbook of Chemistry and Physics, 81 ^st 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. 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 unless specific passages are cited. In case of inconsistency, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

To the extent not described herein, many details of specific materials, processing behaviors, and circuits are common, and these can be found in textbooks and other materials within the field of organic light emitting diode displays, light sources, photodetectors, photovoltaics and semiconductor components. have.

2. Hole injection layer

The first layer of the bilayer composition is a hole injection layer. In one embodiment, the hole injection layer has a work function of greater than 5.2 eV. In one embodiment, the hole injection layer has a work function of greater than 5.3 eV. In one embodiment, the hole injection layer has a work function of greater than 5.5 eV. In one embodiment, the hole injection layer has a work function of greater than 5.0 eV and is formed from a liquid composition having a pH of greater than 2. The term "liquid composition" is intended to mean a liquid medium in which the substance is dissolved to form a solution, a liquid medium in which the substance is dispersed to form a dispersion, or a liquid medium in which the substance is suspended to form a suspension or emulsion. The term "liquid medium" is intended to mean a liquid material, including pure liquids, combinations of liquids, solutions, dispersions, suspensions, and emulsions. Liquid media are used regardless of whether one or more solvents are present. In one embodiment, the liquid medium is one solvent or a combination of two or more solvents. Any solvent or combination of solvents can be used as long as a layer of conductive polymer can be formed. The liquid medium may comprise other materials, such as coating aids.

In one embodiment, the hole injection layer comprises an electrically conductive material. Any conductive material can be used as long as the hole injection layer has the desired work function. In one embodiment, the electrically conductive material comprises one or more charge transfer complexes. Examples of such complexes include, but are not limited to, complexes of tetrathiafulvalene or tetramethyltetraselenafulvalene and tetracyanoquinomimethane (“TCNQ”). Metal-TCNQ complexes such as Ag-TCNQ, Cu-TCNQ, and K-TCNQ can also be used. In one embodiment, the electrically conductive material comprises a semiconductor oxide deposited from a liquid medium. In another embodiment, the fluorinated acid polymer is added to the semiconductor oxide dispersion to increase the work function of the semiconductor oxide.

 In one embodiment, the electrically conductive material comprises one or more conductive polymers. The term “polymer” is intended to refer to a compound having three or more repeat units, which includes homopolymers and copolymers. In some embodiments, the electrically conductive polymer is conductive in protonated form and not conductive in nonprotonated form. Any conductive polymer can be used as long as the hole injection layer has the desired work function.

In one embodiment, the conductive material comprises one or more conductive polymers doped with one or more fluorinated acid polymers. The term “doped” is intended to mean that the electrically conductive polymer has a polymer counterion derived from the polymer acid to balance the charge on the conductive polymer. The term “fluorinated acid polymer” refers to a polymer having an acidic group, at least in which some hydrogen is replaced with fluorine. The term “acidic group” refers to a group that can be ionized to donate hydrogen ions to the Bronsted base.

a. Electrically conductive polymer

In one embodiment, the electrically conductive polymer forms a film having a conductivity of at least 10 ⁻⁷ S / cm. Monomers that form conductive polymers are referred to as “precursor monomers”. The copolymer has more than one precursor monomer.

In one embodiment, the conductive polymer is prepared from one or more precursor monomers selected from thiophenes, selenophenes, tellurophenes, pyrroles, anilines, and polycyclic aromatic compounds. Polymers made from these 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 joined together. The term "aromatic ring" is intended to include heteroaromatic rings. A "polycyclic heteroaromatic" compound has one or more heteroaromatic rings. In one embodiment, the polycyclic aromatic polymer is poly (thienothiophene).

In one embodiment, the monomers contemplated for use in forming the electrically conductive polymer in the novel composition include formula (I).

In the formula,

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

R ¹ is independently selected at each occurrence to be the same or different and is selected from 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 two R ¹ groups together form an alkylene which together completes a 3, 4, 5, 6 or 7 membered aromatic or cycloaliphatic ring, which may optionally contain one or more divalent nitrogen, selenium, tellurium, sulfur or oxygen atoms Or alkenylene chains.

The term "alkyl" as used herein 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 in which one or more carbon atoms in the alkyl group are 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" refers to a group derived from an aliphatic hydrocarbon having one or more carbon-carbon double bonds and includes linear, branched, and cyclic groups that may be unsubstituted or substituted. The term "heteroalkenyl" is intended to mean an alkenyl group in which one or more carbon atoms in the alkenyl group are replaced with another atom, such as nitrogen, oxygen, sulfur, or 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.

"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 -OC (O) -Z

"Ether" -R ^3- (OR ⁵ ) _p -OR ⁵

"Ether carboxylate" -R ³ -OR ⁴ -C (O) OZ or -R ³ -OR ⁴ -OC (O) -Z

"Ether sulfonate" -R ³ -OR ⁴ -SO ₃ Z

"Ester sulfonate" -R ³ -OC (O) -R ⁴ -SO ₃ Z

"Sulfonimide" -R ³ -SO ₂ -NH-SO ₂ -R ⁵

"Urethane" -R ³ -OC (O) -N (R ⁶ ) ₂

Wherein all “R” groups are the same or different at each occurrence,

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 these groups may be further unsubstituted or substituted, and any group may have F substituted for one or more hydrogens, which includes perfluorinated groups. In one embodiment, the alkyl and alkylene groups have 1 to 20 carbon atoms.

In one embodiment, in the monomer, two R ¹ together are —O— (CHY) _m —O—, wherein m is 2 or 3, Y is the same or different at each occurrence and is hydrogen, halogen, alkyl , Alcohol, amidosulfonate, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate and urethane, wherein the Y group can be partially or fully fluorinated). . In one embodiment, all Y is hydrogen. In one embodiment, the polymer is poly (3,4-ethylenedioxythiophene). In one embodiment, at least one Y group is not hydrogen. In one embodiment, at least one Y group is a substituent having F substituted for at least one hydrogen. In one embodiment, at least one Y group is perfluorinated.

In one embodiment, the monomer has the general formula (la).

In the formula,

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

R ⁷ is the same or different at each occurrence and is hydrogen, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alcohol, amidosulfonate, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester Selected from sulfonates and urethanes, provided that at least one R ⁷ is not hydrogen,

m is 2 or 3.

In one embodiment of Formula (la), m is 2, one R ⁷ is an alkyl group having more than 5 carbon atoms and all other R ⁷ are hydrogen. In one embodiment of Formula Ia, at least one R ⁷ group is fluorinated. In one embodiment, at least one R ⁷ group has at least one fluorine substituent. In one embodiment, the R ⁷ groups are fully fluorinated.

In one embodiment of Formula (la), the R ⁷ substituent on the conjugated cycloaliphatic ring provides improved water solubility of the monomer and facilitates polymerization in the presence of the fluorinated acid polymer.

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

In one embodiment, the pyrrole monomers contemplated for use in forming the electrically conductive polymer in the novel composition include Formula II below.

In the formula,

R ¹ is independently selected at each occurrence to be the same or different and is selected from 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 two R ¹ groups together form an alkylene which optionally completes a 3, 4, 5, 6 or 7 membered aromatic or cycloaliphatic ring which may comprise one or more divalent nitrogen, sulfur, selenium, tellurium or oxygen atoms Or may form an alkenylene chain;

R ² is independently selected to be the same or different at each occurrence and is selected from hydrogen, alkyl, alkenyl, aryl, alkanoyl, alkylthioalkyl, alkylaryl, arylalkyl, amino, epoxy, silane, siloxane, alcohol, benzyl, carbo Selected from carboxylates, ethers, ether carboxylates, ether sulfonates, ester sulfonates and urethanes.

In one embodiment, R ¹ is the same or different at each occurrence and is hydrogen, alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alcohol, benzyl, carboxylate, ether, amidosulfonate, ether carboxyl Latex, 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 residue Independently selected from substituted alkyl.

In one embodiment, 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 residues. .

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

In one embodiment, two R ¹ together are 6 or 7 further substituted with a group selected from alkyl, heteroalkyl, alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate and urethane To form a cycloaliphatic ring. These groups can improve the solubility of the monomers and the resulting polymers. In one embodiment, two R ¹ together form a 6 or 7 membered alicyclic ring further substituted with an alkyl group. In one embodiment, two R ¹ together form a 6 or 7 membered alicyclic ring further substituted with an alkyl group having at least one carbon atom.

In one embodiment, two R ¹ together are —O— (CHY) _m —O—, wherein m is 2 or 3, Y is the same or different at each occurrence, and hydrogen, alkyl, alcohol, benzyl, Carboxylate, amidosulfonate, ether, ether carboxylate, ether sulfonate, ester sulfonate and urethane). In one embodiment, at least one Y group is not hydrogen. In one embodiment, at least one Y group is a substituent having F substituted for at least one hydrogen. In one embodiment, at least one Y group is perfluorinated.

In one embodiment, the aniline monomers contemplated for use in forming the electrically conductive polymer in the novel composition include Formula III.

In the formula,

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 is independently selected at each occurrence to be the same or different and is selected from 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 two R ¹ groups together form an alkylene or alkenylene chain which together form a 3, 4, 5, 6 or 7 membered aromatic or cycloaliphatic ring which may optionally comprise one or more divalent nitrogen, sulfur or oxygen atoms Can be formed.

In the polymerization, the aniline monomer unit may have formula IVa or formula IVb shown below, or a combination of these two formulas.

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

In one embodiment, the aniline monomer is unsubstituted and a = 0.

In one embodiment, a is not zero and at least one R ¹ is fluorinated. In one embodiment, at least one R ¹ is perfluorinated.

In one embodiment, the conjugated polycyclic heteroaromatic monomers contemplated for use to form the electrically conductive polymer in the novel composition have two or more conjugated aromatic rings where at least one is heteroaromatic. In one embodiment, the conjugated polycyclic heteroaromatic monomer has the formula (V):

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 independently selected at each occurrence to be the same or different and are selected from 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 may optionally contain 5 or 6 members, which may optionally include one or more divalent nitrogen, sulfur, selenium, tellurium or oxygen atoms; To form an alkenylene chain that completes the aromatic ring.

In one embodiment, the conjugated polycyclic heteroaromatic monomers have the formulas Va, Vb, Vc, Vd, Ve, Vf and Vg.

In the formula,

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 ;

R ⁶ is hydrogen or alkyl.

The conjugated polycyclic heteroaromatic monomers may be further substituted with groups selected from alkyl, heteroalkyl, alcohols, benzyl, carboxylates, ethers, ether carboxylates, ether sulfonates, ester sulfonates and urethanes. In one embodiment, the substituent is fluorinated. In one embodiment, the substituents are fully fluorinated.

In one embodiment, the conjugated polycyclic heteroaromatic monomer is thieno (thiophene). Such monomers are described, for example, in Macromolecules, 34, 5746-5747 (2001); And Macromolecules, 35, 7281-7286 (2002). In one embodiment, the thieno (thiophene) is selected from thieno (2,3-b) thiophene, thieno (3,2-b) thiophene and thieno (3,4-b) thiophene. . In one embodiment, the thieno (thiophene) monomer is added with at least one group selected from alkyl, heteroalkyl, alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate and urethane. Is replaced by. In one embodiment, the substituent is fluorinated. In one embodiment, the substituents are fully fluorinated.

In one embodiment, the polycyclic heteroaromatic monomers contemplated for use to form the polymers in the novel composition include Formula VI below.

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;

R ⁶ is hydrogen or alkyl;

R ¹² in each case is the same or different and is 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, nitrile, cyano, hydroxyl, epoxy, silane, siloxane , Alcohol, benzyl, carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate, ester sulfonate and urethane; Or two R ¹² groups together form an alkylene which together completes a 3, 4, 5, 6 or 7 membered aromatic or cycloaliphatic ring, which may optionally comprise one or more divalent nitrogen, sulfur, selenium, tellurium or oxygen atoms Or alkenylene chains.

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

Examples of the second monomer type include, but are not limited to, alkenyl, alkynyl, arylene and heteroarylene. Examples of second monomers include fluorene, oxadiazole, thiadiazole, benzothiadiazole, phenylenevinylene, phenyleneethynylene, pyridine, diazine and triazine, all of which may be further substituted ), But is not limited to such.

In one embodiment, the copolymer is prepared by first forming an intermediate precursor monomer having a structure of A-B-C, wherein 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, Stille, Grignard metathesis, Suzuki and Negishi coupling. The copolymer is then formed by oxidative polymerization of the intermediate precursor monomers alone or with one or more additional precursor monomers.

In one embodiment, the electrically conductive polymer is a copolymer of two or more precursor monomers. In one embodiment, the precursor monomer is selected from thiophene, selenophene, tellurophene, pyrrole, aniline and polycyclic aromatic compounds.

b. Fluorinated Acid Polymer

The fluorinated acid polymer may be any polymer that is fluorinated and has acidic groups with acidic protons. The term includes partially and fully fluorinated materials. In one embodiment, the fluorinated acid polymer is highly fluorinated. The term "highly fluorinated" means that at least 50% of the available hydrogens bonded to carbon are substituted with fluorine. Acidic groups supply ionizable protons. In one embodiment, the pKa of the acidic protons is less than 3. In one embodiment, the pKa of the acidic protons is less than zero. In one embodiment, the pKa of the acidic protons is less than -5. The acidic groups can be bonded directly to the polymer backbone or can be linked to side chains 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 acidic group.

In one embodiment, the fluorinated acid polymer is water soluble. In one embodiment, the fluorinated acid polymer is dispersible in water.

In one embodiment, the fluorinated acid polymer is organic solvent wettable. The term "organic solvent wettability" refers to a material that is wettable by an organic solvent when formed into a film. In one embodiment, the wettable material forms a wettable film with phenylhexane at a contact angle of 40 ° or less. The term "contact angle" as used herein is intended to mean the angle Φ shown in FIG. 1. In the case of droplets of liquid medium, the angle Φ is formed by the intersection of the line from the plane of the surface and the outer edge of the droplet to the surface. In addition, the angle Φ is measured after the droplet reaches the equilibrium position on the surface (ie, the "static contact angle"). The film of organic solvent wettable fluorinated polymer acid serves as a surface. In one embodiment, the contact angle is 35 degrees or less. In one embodiment, the contact angle is no greater than 30 °. Methods of measuring contact angles are known.

In one embodiment, the polymer backbone is fluorinated. Examples of suitable polymer backbones include, but are not limited to, polyolefins, polyacrylates, polymethacrylates, polyimides, polyamides, polyaramids, polyacrylamides, polystyrenes, and copolymers thereof. In one embodiment, the polymer backbone is highly fluorinated. In one embodiment, the polymer backbone is 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 present on the fluorinated side chain. In one embodiment, the fluorinated side chain is selected from alkyl groups, alkoxy groups, amido groups, ether groups, and combinations thereof.

In one embodiment, the fluorinated acid polymer has a fluorinated olefin backbone with pendant fluorinated ether sulfonate, fluorinated ester sulfonate, or fluorinated ether sulfonimide groups. 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 And a 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, the fluorinated acid polymer is a homopolymer or copolymer of fluorinated and partially sulfonated poly (arylene ether sulfone). The copolymer may be a block copolymer. Examples of comonomers include, but are not limited to, butadiene, butylene, isobutylene, styrene, and combinations thereof.

In one embodiment, the fluorinated acid polymer is a homopolymer or copolymer of monomers having the general formula (VII):

In the formula,

b is an integer from 1 to 5,

R ¹³ is OH or NHR ¹⁴ ,

R ¹⁴ is alkyl, fluoroalkyl, sulfonylalkyl, or sulfonylfluoroalkyl.

In one embodiment, the monomer is "SFS" or "SFSI" shown below.

After polymerization, the polymer can be converted to the acid form.

In one embodiment, the fluorinated acid polymer is a homopolymer or copolymer of trifluorostyrene having acidic groups. In one embodiment, the trifluorostyrene monomer has the formula VIII.

In the formula,

W is selected from (CF ₂ ) _b , O (CF ₂ ) _b , S (CF ₂ ) _b , (CF ₂ ) _b O (CF ₂ ) _b ,

b is independently an integer of 1 to 5,

R ¹³ is OH or NHR ¹⁴ ,

R ¹⁴ is alkyl, fluoroalkyl, sulfonylalkyl, or sulfonylfluoroalkyl.

In one embodiment, the fluorinated acid polymer is a sulfonimide polymer having Formula (IX)

In the formula,

R _f is selected from fluorinated alkylene, fluorinated heteroalkylene, fluorinated arylene and fluorinated heteroarylene;

n is 4 or more.

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 fluorinated acid polymer comprises a fluorinated polymer backbone and a side chain having Formula X:

In the formula,

R ¹⁵ is a fluorinated alkylene group or a fluorinated heteroalkylene group;

R ¹⁶ is a fluorinated alkyl or fluorinated aryl group;

a is 0 or an integer of 1 to 4;

In one embodiment, the fluorinated acid polymer has the formula (XI):

In the formula,

R ¹⁶ is a fluorinated alkyl or fluorinated aryl group;

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

n is 4 or more.

Synthesis of fluorinated acid polymers 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 fluorinated acid polymer comprises one or more repeat units derived from ethylenically unsaturated compounds having the formula XII:

In the formula,

d is 0, 1, or 2;

R ¹⁷ to R ²⁰ are independently H, halogen, alkyl or alkoxy having 1 to 10 carbon atoms, Y, C (R _f ') (R _f ') OR ²¹ , R ⁴ Y or OR ⁴ Y;

Y is COE ² , SO ₂ E ² , or sulfonimide;

R ²¹ is hydrogen or an acid labile protecting group;

R _f ′ is the same or different at each occurrence and is a fluoroalkyl group having 1 to 10 carbon atoms, or together is (CF ₂ ) _e , wherein e is 2 to 10;

R ⁴ is an alkylene group;

E ² is OH, halogen, or OR ⁵ ;

R ⁵ is an alkyl group;

Provided that at least one of R ¹⁷ to R ²⁰ is Y, R ⁴ Y or OR ⁴ Y.

R ⁴ , R ⁵ , and R ¹⁷ to R ²⁰ may be optionally substituted with halogen or ether oxygen.

Some non-limiting examples of representative monomers of formula (XII) within the scope of the present invention are shown below.

Wherein R ²¹ is a group capable of forming or rearranged to a tertiary cation, more typically an alkyl group having from 1 to 20 carbon atoms, most typically t-butyl.

Compound of formula (XII) wherein d is 0 (Formula XII-a) is a cyclo of tetracyclane (tetracyclo [2.2.1.0 ^2,6 0 ^3,5 ] heptane) and an unsaturated compound of formula XIII as shown in the following scheme It can manufacture by addition reaction.

The reaction can be carried out in the absence or presence of an inert solvent such as diethyl ether at temperatures ranging from about 0 ° C. to about 200 ° C., more typically from about 30 ° C. to about 150 ° C. For reactions carried out above the boiling point of one or more reagents or solvents, a closed reactor is typically used to avoid loss of volatile components. Compounds of formula (XII), wherein d is a higher value (ie, d = 1 or 2), can be prepared by reaction of cyclopentadiene and compounds of formula (XII) in which d is 0, as is known in the art.

In one embodiment, the fluorinated acid polymer also includes repeating units derived from one or more ethylenically unsaturated compounds containing one or more fluorine atoms bonded to ethylenically unsaturated carbons. Fluoroolefins contain 2 to 20 carbon atoms. Representative fluoroolefins include tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, 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 a saturated fluoroalkyl group having from 1 to about 10 carbon atoms. In one embodiment, the comonomer is tetrafluoroethylene.

In one embodiment, the fluorinated acid polymer comprises a polymer backbone having pendant groups comprising siloxane sulfonic acid. In one embodiment, the siloxane pendant group has the formula:

In the formula,

a is 1 to b;

b is 1 to 3;

R ²² is a non-hydrolyzable group independently selected from the group consisting of alkyl, aryl, and arylalkyl;

R ²³ is a bidentate alkylene radical which may be substituted with one or more ether oxygen atoms, provided that R ²³ has two or more carbon atoms linearly disposed between Si and R _f ;

R _f is a perfluoroalkylene radical which may be substituted with one or more ether oxygen atoms.

In one embodiment, the fluorinated acid polymer having pendant siloxane groups has a fluorinated backbone. In one embodiment, the backbone is perfluorinated.

In one embodiment, the fluorinated acid polymer has a fluorinated backbone and pendant groups represented by the general formula (XIV) below.

Wherein R _f ² is F, or a perfluoroalkyl radical having 1 to 10 carbon atoms unsubstituted or substituted with one or more ether oxygen atoms, h = 0 or 1, i = 0-3 , g = 0 or 1.

In one embodiment, the fluorinated acid polymer has the general formula (XV).

Wherein j ≥ 0, k ≥ 0 and 4 ≤ (j + k) ≤ 199, Q ¹ and Q ² are F or H, and R _f ² is unsubstituted or substituted with F, or one or more ether oxygen atoms Perfluoroalkyl radical having 1 to 10 carbon atoms, h = 0 or 1, i = 0-3, and g = 0 or 1.

In one embodiment, R _f ² is -CF ₃ , g = 1, h = 1, i = 1. In one embodiment, the pendant group is present at a concentration of 3 to 10 mol%.

In one embodiment, Q ¹ is H, k ≧ 0, Q ² is F, which may be synthesized according to the teachings of US Pat. No. 3,282,875 (Connolly et al.). In another embodiment, Q ¹ is H, Q ² is H, g = 0, R _f ² is F, h = 1, i = 1, which is co-pending US Patent Application 60 / Synthesis in accordance with the teachings of 105,662. Another embodiment is synthesized according to various teachings in WO 9831716 (A1) (Drysdale et al.) And co-pending US patent application WO 99/52954 (A1), and 60 / 176,881 (Choi et al.). can do.

In one embodiment, the fluorinated acid polymer is a colloid forming polymer acid. As used herein, the term “colloid formation” refers to a substance that is insoluble in water and forms a colloid when dispersed in an aqueous medium. The molecular weight of the colloid forming polymer acid typically ranges from about 10,000 to about 4,000,000. In one embodiment, the molecular weight of the polymeric acid is about 100,000 to about 2,000,000. Colloidal particle size typically ranges 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 colloid forming polymeric material with acidic protons can be used. In one embodiment, the colloid forming fluorinated polymer acid has an acidic group selected from carboxyl groups, sulfonic acid groups, and sulfonimide groups. In one embodiment, the colloid forming fluorinated polymeric acid is polymeric sulfonic acid. In one embodiment, the colloid forming polymer sulfonic acid is perfluorinated. In one embodiment, the colloid forming polymer sulfonic acid is perfluoroalkylenesulfonic acid.

In one embodiment, the colloid forming polymer acid is a highly fluorinated sulfonic acid polymer ("FSA polymer"). "Highly fluorinated" means that at least about 50% of the total number of halogen and hydrogen atoms in the polymer, at least about 75% in one embodiment, and at least about 90% in another embodiment are fluorine atoms. In one embodiment, the polymer is perfluorinated. The term “sulfonate functional group” refers to a sulfonic acid group or a salt of a sulfonic acid group, in one embodiment an alkali metal or ammonium salt. The functional group is represented by the formula -SO ₃ E ⁵ , wherein E ⁵ is also a cation known as "counter ion". E ⁵ can be H, Li, Na, K or N (R ₁ ) (R ₂ ) (R ₃ ) (R ₄ ), and R ₁ , R ₂ , R ₃ and R ₄ are the same or different, and In an embodiment, H, CH ₃ or C ₂ H ₅ . In another embodiment, E ⁵ is H, in which case the polymer is said to be in "acid form". E ⁵ may also be multivalent, as represented by ions such as Ca ⁺⁺ , and Al ⁺⁺⁺ . In the case of polyvalent counterions, generally represented by M ^{x +} , it is apparent to those skilled in the art that the number of sulfonate functional groups per counterion is equivalent to the valence “x”.

In one embodiment, the FSA polymer comprises a polymer backbone having a repeating side chain bonded to the backbone, having a cation exchange group. Polymers include homopolymers or copolymers of two or more monomers. Copolymers are typically formed from nonfunctional monomers and second monomers having cation exchange groups or precursors thereof, such as sulfonyl fluoride groups (-SO ₂ F), which can then be hydrolyzed to sulfonate functional groups . For example, a copolymer having both a first vinyl fluoride monomer and a second vinyl fluoride monomer having a sulfonyl fluoride group (-SO ₂ F) can be used. Possible first monomers are tetrafluoroethylene (TFE), hexafluoropropylene, vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, perfluoro (alkyl vinyl ether), and their Combinations. TFE is the preferred first monomer.

In other embodiments, possible second monomers include vinyl fluoride ethers having sulfonate functional groups or precursor groups that can provide the desired side chains to the polymer. If desired, additional monomers may be incorporated into these polymers, including ethylene, propylene and R—CH═CH ₂ , where R is a perfluorinated alkyl group having 1 to 10 carbon atoms. Polymers are polymers of the type referred to herein as random copolymers, i.e. by polymerization in which the relative concentration of comonomers is kept as constant as possible so that the distribution of monomer units along the polymer chain depends on the relative concentration and relative reactivity of the comonomers. It may be a copolymer prepared. It is also possible to use less random copolymers prepared by varying the relative concentrations of monomers during the polymerization. As disclosed in EP 1 026 152 A1, polymers of the type called block copolymers can also be used.

In one embodiment, the FSA polymer for use in the present invention comprises a highly fluorinated, in one embodiment perfluorinated carbon backbone and a side chain represented by the formula:

Wherein R _f ³ and R _f ⁴ are independently selected from F, Cl or a perfluorinated alkyl group having 1 to 10 carbon atoms, a = 0, 1 or 2, and E ⁵ is H, Li, Na, K or N (R1) (R2) (R3) (R4), R1, R2, R3 and R4 are the same or different and in one embodiment are H, CH ₃ or C ₂ H ₅ . In another embodiment E ⁵ is H. As mentioned above, E ⁵ may be multivalent.

In one embodiment, FSA polymers include the polymers disclosed, for example, in US Pat. Nos. 3,282,875, 4,358,545, and 4,940,525. Examples of preferred FSA polymers include perfluorocarbon backbones and side chains represented by the formula:

In the formula, X is as defined above.

FSA polymers of this type are disclosed in US Pat. No. 3,282,875, which discloses tetrafluoroethylene (TFE) and perfluorinated vinyl ether CF ₂ = CF-O-CF ₂ CF (CF ₃ ) -O-CF ₂ CF Copolymerize ₂ SO ₂ F, perfluoro (3,6-dioxa-4-methyl-7-octensulfonyl fluoride) (PDMOF), and then convert to sulfonate groups by hydrolysis of sulfonyl fluoride groups And ion exchange as needed to convert them to the desired ionic form. One example of a polymer of the type disclosed in US Pat. Nos. 4,358,545 and 4,940,525 has side chain —0-CF ₂ CF ₂ SO ₃ E ⁵ , wherein E ⁵ is as defined above. The polymer is tetrafluoroethylene (TFE) and perfluorinated vinyl ether CF ₂ = CF-O-CF ₂ CF ₂ SO ₂ F, perfluoro (3-oxa-4-pentenesulfonyl fluoride) (POPF) After copolymerizing, it can be manufactured by hydrolyzing and further ion-exchanging as needed.

In one embodiment, the ion exchange rate of the FSA polymer for use in the present invention is typically less than about 33. In this use, "ion exchange rate" or "IXR" is defined as the number of carbon atoms in the polymer backbone for the cation exchange group. Within the range of less than about 33, the IXR can be modified as desired for the particular use. In one embodiment, the IXR is about 3 to about 33, and in another embodiment about 8 to about 23.

The cation exchange capacity of a polymer is often expressed in equivalent weight (EW). For this use, the equivalent weight (EW) is defined as the weight of the polymer in acid form required to neutralize one equivalent of sodium hydroxide. From about 8 to about a sulfonate polymer wherein the polymer has a perfluorocarbon backbone and the side chain is -O-CF ₂ -CF (CF ₃ ) -O-CF ₂ -CF ₂ -SO ₃ H (or salts thereof) The equivalent weight range corresponding to IXR of about 23 is from about 750 EW to about 1500 EW. The IXR for this polymer can be associated with the equivalent weight using the formula: 50 IXR + 344 = EW. The same IXR range is used for the sulfonate polymers disclosed in US Pat. Nos. 4,358,545 and 4,940,525, for example polymers having side chain —0-CF ₂ CF ₂ SO ₃ H (or salts thereof), but cations The equivalent weight is somewhat lower due to the lower molecular weight of monomer units containing exchange groups. For the preferred IXR range of about 8 to about 23, the corresponding equivalent weight range is about 575 EW to about 1325 EW. The IXR for this polymer can be associated with the equivalent weight using the formula: 50 IXR + 178 = EW.

FSA polymers can be prepared as colloidal water dispersions. They may also be in the form of dispersions in other media, including but not limited to, for example, water soluble ethers such as alcohols, tetrahydrofuran, mixtures of water soluble ethers, and combinations thereof. In the preparation of the dispersions, the polymers can be used in acid form. U.S. Patent Nos. 4,433,082, 6,150,426 and WO 03/006537 disclose methods for the preparation of aqueous alcoholic dispersions. After preparing the dispersion, the concentration and the dispersion liquid composition can be adjusted by methods known in the art.

Aqueous dispersions of colloid-forming polymer acids, including FSA polymers, typically have as small a particle size and possible EW as possible, as long as stable colloids are formed.

The water dispersion of the FSA polymer is children. Commercially available as Nafion® dispersion from E. I. du Pont de Nemours and Company (Wilmington, Delaware, USA).

Some of the polymers described above herein may be formed in non-acid form, for example as salts, esters, or sulfonyl fluorides. These are converted to the acid form for the preparation of the following conductive compositions.

c. Preparation of Conductive Composition

The novel electrically conductive polymer composition can be prepared by (i) polymerizing the precursor monomer in the presence of a fluorinated acid polymer; Or (ii) first forming an intrinsically conductive polymer and combining it with a fluorinated acid polymer.

(i) Polymerization of Precursor Monomer in the Presence of Fluorinated Acid Polymers

In one embodiment, the electrically conductive polymer composition is formed by oxidative polymerization of precursor monomers in the presence of a fluorinated acid polymer. In one embodiment, the precursor monomers comprise two or more conductive precursor monomers. In one embodiment, the monomers comprise intermediate precursor monomers having the structure of A-B-C, wherein A and C represent conductive precursor monomers, which may be the same or different and B represents a non-conductive precursor monomer. In one embodiment, the intermediate precursor monomer is polymerized with at least one conductive precursor monomer.

In one embodiment, the oxidative polymerization is carried out in a homogeneous aqueous solution. In another embodiment, the oxidative polymerization is carried out in an emulsion of water and an organic solvent. Generally, some water is present to obtain the proper solubility of the oxidant and / or catalyst. Oxidizing agents such as ammonium persulfate, sodium persulfate, potassium persulfate and the like can be used. Catalysts such as ferric chloride or ferric sulfate may also be present. The resulting polymerization product is a solution, dispersion or emulsion of a conductive polymer associated with a fluorinated acid polymer. In one embodiment, the intrinsically conductive polymer is positively charged and the charge is balanced by the fluorinated acid polymer anion.

In one embodiment, a method of preparing a water dispersion of a novel conductive polymer composition comprises forming the reaction mixture by combining water, precursor monomers, one or more fluorinated acid polymers, and an oxidant in any order, provided that At least a portion of the fluorinated acid polymer is present upon addition of at least one of the conductive monomer and the oxidant.

In one embodiment, a method of making a novel conductive polymer composition is

(a) providing an aqueous solution or an aqueous dispersion of a fluorinated acid polymer;

(b) adding an oxidizing agent to the solution or dispersion of step (a); And

(c) adding the precursor monomer to the mixture of step (b)

It includes.

In another embodiment, the precursor monomer is added to an aqueous solution or aqueous dispersion of the fluorinated acid polymer before adding the oxidant. Subsequently, step (b) is performed to add an oxidizing agent.

In another embodiment, a mixture of water and precursor monomer is typically formed at a concentration ranging from about 0.5% to about 4.0% by weight of the total precursor monomer. This precursor monomer mixture is added to an aqueous solution or aqueous dispersion of the fluorinated acid polymer and the step (b) above is carried out to add an oxidizing agent.

In another embodiment, the aqueous polymerization mixture may include a polymerization catalyst such as ferric sulfate, ferric chloride, and the like. The catalyst is added before the last step. In another embodiment, the catalyst is added with the oxidant.

In one embodiment, the polymerization is carried out in the presence of a co-dispersing liquid that is miscible with water. Examples of suitable codispersions include, but are not limited to, ethers, alcohols, alcohol ethers, cyclic ethers, ketones, nitriles, sulfoxides, amides, and combinations thereof. In one embodiment, the co-dispersion is an alcohol. In one embodiment, the co-dispersion is an organic solvent selected from n-propanol, isopropanol, t-butanol, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, and mixtures thereof. In general, the amount of co-dispersion should be less than about 60% by volume. In one embodiment, the amount of co-dispersion is less than about 30 volume percent. In one embodiment, the amount of co-dispersion is 5-50 vol%. The use of co-dispersions in the polymerization significantly reduces the particle size and improves the filterability of the dispersion. In addition, the buffer material obtained by the process exhibits increased viscosity and the films made from these dispersions are high quality films.

The co-dispersion may be added to the reaction mixture at any point in the process.

In one embodiment, the polymerization is carried out in the presence of a co-acid which is Bronsted acid. The acid may be an inorganic acid such as HCl, sulfuric acid, or the like, or an organic acid such as acetic acid or p-toluenesulfonic acid. Alternatively, the acid may be a water soluble polymer acid such as poly (styrenesulfonic acid), poly (2-acrylamido-2-methyl-1-propanesulfonic acid), or a second fluorinated acid polymer as described above. Combinations of acids can be used.

Whichever is added last, the auxiliary acid can be added to the reaction mixture at any point in the process prior to the addition of the oxidizing agent or precursor monomer. In one embodiment, the auxiliary acid is added before both the precursor monomer and the fluorinated acid polymer and the oxidant is added last. In one embodiment, the auxiliary acid is added prior to the addition of the precursor monomer, followed by the fluorinated acid polymer and the oxidant added last.

In one embodiment, the polymerization is carried out in the presence of both co-dispersions and co-acids.

In one embodiment, the reaction vessel is first filled with a mixture of water, alcohol, co-dispersant and inorganic co-acid. To this are added precursor monomers, aqueous solutions or aqueous dispersions of fluorinated acid polymers and oxidants in order. The oxidizing agent is added slowly and added dropwise to prevent the formation of ubiquitous regions of high ion concentration which may destabilize the mixture. The mixture is stirred and then the reaction proceeds at controlled temperature. Upon completion of the polymerization, the reaction mixture was treated with a strong acid cation resin, stirred and filtered; Then treated with base anion exchange resin, stirred and filtered. As discussed above, alternative order of addition may be used.

In the process for preparing novel conductive polymer compositions, the molar ratio of oxidant to total precursor monomer is generally in the range of 0.1 to 2.0, and in one embodiment in the range of 0.4 to 1.5. The molar ratio of fluorinated acid polymer to total precursor monomer is generally in the range of 0.2-5. In one embodiment, the ratio is in the range of 1-4. Total solids generally range from about 1.0% to 10% by weight, and in one embodiment range from about 2% to 4.5%. The reaction temperature generally ranges from about 4 ° C. to 50 ° C., and in one embodiment ranges from about 20 ° C. to 35 ° C. The molar ratio of any auxiliary acid to precursor monomer is about 0.05-4. The addition time of the oxidant affects the particle size and viscosity. Therefore, the particle size can be reduced by lowering the addition rate. At the same time, the viscosity is increased by lowering the rate of addition. The reaction time is generally in the range of about 1 to about 30 hours.

(ii) a combination of an intrinsically conductive polymer and a fluorinated acid polymer

In one embodiment, the intrinsically conductive polymer is prepared separately from the fluorinated acid polymer. In one embodiment, the polymer is prepared by oxidative polymerization of the corresponding monomer in aqueous solution. In one embodiment, the oxidative polymerization is carried out in the presence of a water soluble acid. In one embodiment, the acid is a water soluble non-fluorinated polymer acid. In one embodiment, the acid is a non-fluorinated polymer sulfonic acid. Some non-limiting examples of acids are poly (styrenesulfonic acid) (“PSSA”), poly (2-acrylamido-2-methyl-1-propanesulfonic acid) (“PAAMPSA”) and mixtures thereof. When a polymer with a positive charge is produced in an oxidative polymerization, the acid anion is the counterion for the conductive polymer. Oxidative polymerization is carried out using oxidizing agents such as ammonium persulfate, sodium persulfate and mixtures thereof.

The novel electrically conductive polymer composition is prepared by blending an intrinsically conductive polymer with a fluorinated acid polymer. This can be achieved by adding a water dispersion of the intrinsically conductive polymer to a dispersion or solution of the polymer acid. In one embodiment, the composition is further processed using sonication or microfluidization to ensure mixing of the components.

In one embodiment, one or both of the essentially conductive polymer and the fluorinated acid polymer are isolated in solid form. Solid materials may be redispersed in water or in aqueous solutions or aqueous dispersions of other components. For example, the intrinsically conductive polymer solid can be dispersed in an aqueous solution or an aqueous dispersion of the fluorinated acid polymer.

(iii) pH adjustment

The water dispersion of the novel conductive polymer composition as synthesized generally has a very low pH. In one embodiment, the pH is adjusted to a higher value without adversely affecting device characteristics. In one embodiment, the pH of the dispersion is adjusted to about 1.5 to about 4. In one embodiment, the pH is adjusted to 3-4. It has been found that pH can be adjusted using known techniques, for example ion exchange, or by titration with a basic aqueous solution.

In one embodiment, after completion of the polymerization reaction, the as-synthesized aqueous dispersion is contacted with one or more ion exchange resins under conditions suitable to remove decomposed species, reaction by-products and unreacted monomers and adjust the pH. Thus, a stable water dispersion with the desired pH is formed. In one embodiment, the as-synthesized water dispersion is contacted with the first ion exchange resin and the second ion exchange resin in any order. The as-synthesized aqueous dispersion may be treated simultaneously with both the first and second ion exchange resins, or sequentially with one, and then with the other.

Ion exchange is a reversible chemical reaction in which ions in a fluid medium (such as an aqueous dispersion) are exchanged with similarly charged ions attached to fixed solid particles that are insoluble in the fluid medium. The term "ion exchange resin" is used herein to refer to all such materials. The resin becomes insoluble due to the crosslinking properties of the polymer support with ion exchange groups attached. Ion exchange resins are classified as cation exchangers or anion exchangers. Cation exchangers have metal ions, such as mobile ions, typically protons or sodium ions, charged in an amount available for exchange. Anion exchangers have negatively charged ion exchange ions, typically hydroxide ions.

In one embodiment, the first ion exchange resin is a cation acid exchange resin that may be present in the form of protic or metal ions, typically sodium ions. The second ion exchange resin is a basic anion exchange resin. Both acidic cations and basic anion exchange resins, including proton exchange resins, are contemplated for use in the practice of the present invention. In one embodiment, the acidic cation exchange resin is an inorganic acid cation exchange resin, such as sulfonic acid cation exchange resin. Sulfonate cation exchange resins contemplated for use in the practice of the present invention are, for example, sulfonated styrene-divinylbenzene copolymers, sulfonated crosslinked styrene polymers, phenol-formaldehyde-sulfonic acid resins, benzene-formaldehyde-sulfonic acid resins , And mixtures thereof. In another embodiment, the acidic cation exchange resin is an organic acid cation exchange resin, such as a carboxylic acid, acrylic or phosphorous cation exchange resin. It is also possible to use mixtures of different cation exchange resins.

In another embodiment, the basic anion exchange resin is a tertiary amine anion exchange resin. Tertiary amine anion exchange resins contemplated for use in the practice of the present invention include, for example, tertiary-aminoated styrene-divinylbenzene copolymers, tertiary-aminoated crosslinked styrene polymers, tertiary-aminoated phenols -Formaldehyde resins, tertiary-aminoated benzene-formaldehyde resins, and mixtures thereof. In further embodiments, the basic anion exchange resin is a quaternary amine anion exchange resin, or a mixture of these and other exchange resins.

The first and second ion exchange resins can be contacted simultaneously or continuously with the aqueous dispersion as synthesized. For example, in one embodiment, both resins are simultaneously added to the aqueous dispersion of the as-synthesized electrically conductive polymer and left in contact with the dispersion for at least about 1 hour, for example, from about 2 hours to about 20 hours. Keep it. The ion exchange resin can then be removed from the dispersion by filtration. The size of the filter is chosen so that smaller dispersion particles are passed while relatively large ion exchange resin particles are removed. Without wishing to be bound by theory, it is believed that ion exchange resins quench polymerization and effectively remove most of the ionic and nonionic impurities and the unreacted monomer from the as-synthesized aqueous dispersion. In addition, basic anion exchange and / or acidic cation exchange resins make the acidic sites more basic, thereby increasing the pH of the dispersion. Generally, about 1-5 grams of ion exchange resin is used per gram of novel conductive polymer composition.

In many cases, basic ion exchange resins can be used to adjust the pH to the desired level. In some cases, the pH may be further adjusted with basic aqueous solutions such as sodium hydroxide, ammonium hydroxide, tetra-methylammonium hydroxide, and the like.

In another embodiment, a more conductive dispersion is formed by adding highly conductive additives to the water dispersion of the novel conductive polymer composition. Since dispersions having a relatively high pH can be formed, conductive additives, in particular metal additives, are not attacked by acids in the dispersion. Examples of suitable conductive additives include, but are not limited to, metal particles and nanoparticles, nanowires, carbon nanotubes, graphite fibers or particles, carbon particles, and combinations thereof.

3. Hole transport layer

Any hole transport material can be used in the hole transport layer. In one embodiment, the hole transport material has an optical band gap of 4.2 eV or less and a HOMO level of 6.2 eV or less for vacuum levels.

In one embodiment, the hole transport material comprises one or more polymers. Examples of hole transporting polymers include those having hole transporting groups. Such hole transport groups include, but are not limited to, carbazole, triarylamine, triarylmethane, fluorene, and combinations thereof.

In one embodiment, the hole transport layer comprises a non-polymeric hole transport material. Examples of 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-ethylphenyl)-[1,1 '-(3,3'-dimethyl) biphenyl] -4,4'-diamine ( 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-based compounds such as copper phthalocyanine.

In one embodiment, the hole transport layer comprises a material having Formula XVI:

In the formula,

Ar is an arylene group;

Ar 'and Ar "are independently selected from aryl groups;

R ²⁴ to R ²⁷ are hydrogen, alkyl, aryl, halogen, hydroxyl, aryloxy, alkoxy, alkenyl, alkynyl, amino, alkylthio, phosphino, silyl, -COR, -COOR, -PO ₃ R ₂ , -OPO ₃ R ₂ is independently selected from the group consisting of CN;

R is selected from the group consisting of hydrogen, alkyl, aryl, alkenyl, alkynyl and amino;

m and n are each independently integers having a value of 0 to 5, where m + n ≠ 0.

In one embodiment of Formula (XVI), Ar is an arylene group containing two or more ortho-conjugated benzene rings in a linear arrangement.

4. Method of Making Bilayer Composition

The hole injection and hole transport layer of the bilayer composition can be prepared using any layer forming technique. In one embodiment, the hole injection layer is first formed and the hole transport layer is directly formed on at least a portion of the hole injection layer. In one embodiment, a hole transport layer is formed to cover it over the entire hole injection layer.

In one embodiment, the hole injection layer is formed on the substrate by liquid deposition from the liquid composition. The term “substrate” is intended to mean a base material that can be rigid or flexible, which can include one or more layers of one or more materials. Substrate materials may include, but are not limited to, glass, polymer, metal or ceramic materials or combinations thereof. The substrate may or may not include layers of electronic components, circuits, conductive members, or other materials.

Any known liquid deposition technique (including continuous and discontinuous techniques) can be used. Continuous liquid 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, flexographic printing, and screen printing.

In one embodiment, the hole injection layer is formed by liquid deposition from a liquid composition having a pH greater than 2. In one embodiment, the pH is greater than 4. In one embodiment, the pH is greater than 6.

In one embodiment, the hole transport layer is formed directly on at least a portion of the hole injection layer by liquid deposition from the liquid composition.

In one embodiment, the hole transport layer is formed by deposition on at least a portion of the hole injection layer. Any deposition technique can be used, including sputtering, thermal evaporation, chemical vapor deposition, and the like. 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 (including e-beam evaporation and resistive evaporation as well as beam sputtering). Certain forms of physical deposition include rf magnetron sputtering and inductively coupled plasma physical deposition ("IMP-PVD"). These deposition techniques are known in the semiconductor fabrication industry.

The thickness of the hole injection layer can be large as desired for the intended use. In one embodiment, the thickness of the hole injection layer is in the range of 100 nm to 200 μm. In one embodiment, the thickness of the hole injection layer is in the range of 50 to 500 nm. In one embodiment, the hole injection layer is less than 50 nm thick. In one embodiment, the hole injection layer is less than 10 nm thick. In one embodiment, the hole injection layer has a thickness greater than the thickness of the hole transport layer.

The thickness of the hole transport layer can be as small as a single monolayer. In one embodiment, the thickness is in the range of 100 nm to 200 μm. In one embodiment, the thickness is less than 100 nm. In one embodiment, the thickness is less than 10 nm. In one embodiment, the thickness is less than 1 nm.

5. Electronic device

In another embodiment of the present invention, an electronic device comprising a bilayer composition is braked. The term "electronic device" is intended to mean a device comprising one or more organic semiconductor layers or materials. Examples of 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 using 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. Whole devices or solar cells), (4) devices (eg transistors or diodes) comprising at least one electronic component comprising at least one organic semiconductor layer, or any of the devices of items (1) to (4) Combinations include, but are not limited to.

In one embodiment, the electronic device includes one or more electroactive layers disposed between two electrical contact layers further comprising a bilayer. The term "electroactive" when referring to a layer or material is intended to mean a layer or material that exhibits electron or electro-radiative properties. The electroactive layer material may emit radiation or exhibit a change in concentration of the electron-hole pair upon receiving radiation.

One type of device is an organic light emitting diode (“OLED”). One such device is shown in FIG. 2. 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 buffer layer is a bilayer as defined herein comprising a hole injection layer 122 and a hole transport layer 124.

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 may 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 a more efficient electrode for injecting holes 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, 5 and 6 elements and Group 8 to 10 transition elements. When the anode layer 110 should be light transmissive, a mixed oxide of Group 12, 13 and 14 elements such as indium tin oxide can 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 the material of anode layer 110 include, but are not limited to, indium tin oxide (“ITO”), indium zinc oxide, aluminum tin oxide, gold, silver, copper, and nickel. Anodes are organic materials, in particular conductive polymers such as polyaniline, such as "Flexible light-emitting diodes made from soluble conducting polymer", Nature vol. 357, pp 477-479 (June 11, 1992). At least one of the anode and the cathode must be at least partially transparent so that the generated light can be observed.

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

In one embodiment, anode layer 110 is patterned during lithographic operations. The pattern can vary as desired. The layer may be formed in a pattern by, for example, disposing a patterned mask or resist on the first flexible composite barrier structure and then applying the first electrical contact layer material. Alternatively, the layers can be applied as a whole layer (also called blanket deposition) and subsequently patterned using, for example, a patterned resist layer and wet chemistry or dry etching techniques. Other patterning methods known in the art can also be used.

Depending on the device application, the electroactive layer 130 may emit a signal according to an applied bias voltage or without an applied bias voltage in response to a light emitting layer (e.g., in a light emitting diode or light emitting electrochemical cell) activated by an applied voltage, radiant energy. May be a layer of material (eg, within a photodetector). In one embodiment, the electroactive material is an organic electroluminescent (“EL”) material. Any EL material may 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 chelate oxynoid compounds such as tris (8-hydroxyquinolato) aluminum (Alq3); Cyclometalated iridium and platinum electroluminescent compounds such as iridium and phenylpyridine as disclosed in US Pat. No. 6,670,645 and PCT Patent Application Publication Nos. WO 03/063555 and WO 2004/016710 (Petrov et al.), Phenylquinoline, or a complex with a phenylpyrimidine ligand, and the organometallic complexes described in, for example, PCT Patent Application Publication Nos. WO 03/008424, WO 03/091688, and WO 03/040257, And mixtures thereof, but is not limited thereto. Electroluminescent emitting layers comprising charge transport host materials and metal complexes are described in US Pat. No. 6,303,238 (Thompson et al.), And PCT Patent Application Publications WO 00/70655 and WO 01/41512 (Burrows and Thompson). ). Examples of conjugated polymers include poly (phenylenevinylene), polyfluorene, poly (spirobifluorene), polythiophene, poly (p-phenylene), copolymers thereof, and mixtures thereof However, the present invention is not limited thereto.

Optional layer 140 may function to facilitate both electron injection / transport and may also act as a limiting layer to prevent quenching reactions at the layer interface. More specifically, layer 140 may enhance electron mobility and reduce the likelihood of quenching reaction when layers 130 and 150 are in direct contact in other ways. Examples of the material of optional layer 140 include bis (2-methyl-8-quinolinolato) (para-phenyl-phenolyrato) aluminum (III) (BAIQ), and tris (8-hydroxyquinolato). ) Metal chelate oxynoid compounds such as aluminum (Alq ₃ ); 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole (PBD), 3- (4-biphenylyl) -4-phenyl-5- Azole compounds such as (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 combinations of one or more of these. Alternatively, optional layer 140 may be inorganic and include BaO, LiF, Li ₂ O, and the like.

The cathode layer 150 is an electrode that is particularly efficient for the injection of 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, the term “higher 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 may be 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 For example, Ce, Sm, Eu, etc.), and actinides (eg, Th, U, etc.). Materials such as aluminum, indium, yttrium, and combinations thereof may 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.

The cathode layer 150 is typically formed by chemical or physical vapor deposition methods. In some embodiments, the cathode layer is patterned as discussed above with respect to the anode layer 110.

Other layers in the device may be made of any material known to be useful in such layers, given the functionality provided by such layers.

In some embodiments, an encapsulation layer (not shown) is deposited over the contact layer 150 to prevent the introduction of undesirable components such as water and oxygen into the device 100. Such components may have a detrimental effect on 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 in the art or otherwise may be used. In addition, any of the above layers may include two or more sub-layers or may form a layered structure. Alternatively, some or all of the anode layer 110, the hole injection layer 122, the hole transport layer 124, the electron transport layer 140, the cathode layer 150, and other layers may be treated, in particular surface treated, to charge carriers. It can improve transport efficiency or other physical properties of the device. The choice of material of each component layer is preferably determined in view of the purpose of providing a device with high device efficiency, taking into account the device operating life and taking into account the manufacturing time and complexity factors and others recognized by those skilled in the art. It will be appreciated by those skilled in the art that determining the optimal components, component composition, and nature of the composition is common.

In one embodiment, the different layers have a thickness in the range of: anode 110, 500-5000 mm 3, in one embodiment 1000-2000 mm 3; Buffer bilayer 120, 100-4000 mm 3, where hole injection layer 122, 50-2000 mm 3, in one embodiment 200-1000 mm 3, and hole transport layer 124, 50-2000 mm 3, in one embodiment 200 To 1000 kPa; Photoactive layer 130, 10-2000 kPa, in one embodiment 100-1000 kPa; Optional electron transport layer 140, 50-2000 mm 3, in one embodiment 100-1000 mm 3; Cathode 150, 200-10000 mm 3, in one embodiment 300-5000 mm 3. The location of the electron-hole recombination zone in the device, and thus the emission spectrum of the device, can be affected 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 depends on the exact nature of the material used.

In operation, a voltage from a suitable power source (not shown) is applied to the device 100. The current thus passes across the layers of device 100. Electrons are introduced into the organic polymer layer to emit photons. In some OLEDs, called active matrix OLED displays, individual deposits of photoactive organic films can be excited independently by passage of current, providing individual pixels of light emission. In some OLEDs called passive matrix OLED displays, deposits of photoactive organic films may be excited by rows and columns of electrical contact layers.

The concepts described herein are further illustrated in the following examples, which do not limit the scope of the invention described in the claims.

General Procedure for Film Sample Preparation and Kelvin Probe Measurement

Film samples of Kelvin probe measurements were prepared on 30 mm × 30 mm glass / ITO substrates by spin-coating a water dispersion, or polymer solution as shown in the Examples and Comparative Examples. For bilayer film samples, the water dispersion was first spin-coated onto an ITO substrate and then top-coated with a hole transport polymer solution. The ITO / glass substrate had an ITO thickness of 100 to 150 nm and had an ITO region of 15 mm x 20 mm in the center. At one corner of the 15 mm x 20 mm ITO region, the ITO film surface extending to the edge of the glass / ITO served as an electrical contact with the Kelvin probe electrode. Prior to spin coating, the ITO / glass substrates were cleaned and then treated with 300 Watts of oxygen / plasma for 15 minutes at 0.3 Torr or with UV-ozone for 10 minutes. Once spin-coated, the material deposited on the edges of the elongated ITO film was removed with a Q-tip wetted with water or toluene. The exposed ITO pad was for contact with the Kelvin probe electrode. The deposited film was then baked as shown in the Examples and Comparative Examples. The baked film sample was then placed on a glass jug flooded with nitrogen before capping with a lid prior to measurement.

For work function, or energy potential measurement, an ambient-aged gold film was first measured as a reference and then the sample was measured. Gold films of the same size glass pieces were placed in the cutout cavity at the bottom of the square steel container. On the cavities there were four retaining clips to hold the sample pieces firmly in place. One of the retaining clips was attached with wires to make contact with the Kelvin probe. With the gold film facing upwards, the Kelvin probe tip protruding from the center of the steel lid was lowered above the center of the gold film surface. The lid was then tightened firmly onto a square steel container at four corners. The side port of the square steel vessel was contacted with a tube allowing nitrogen to continuously sweep the Kelvin probe cell, and the nitrogen outlet was capped with a septum inserted with a steel needle to maintain ambient pressure. The probe settings were then optimized for the probe and only the height of the tip was changed during the entire measurement. Kelvin probes were connected to McAllister KP6500 Kelvin Probe meter with the following parameters: 1) Frequency: 230; 2) amplitude: 20; 3) DC offset: varies from sample to sample; 4) upper backing potential: 2 volts; 5) lower backing potential: -2 volts; 6) scan speed: 1; 7) trigger delay: 0; 8) Acquisition (A) / Data (D) points: 1024; 9) A / D ratio: 12405 @ 19.0 cycles; 10) D / A: delay: 200; 11) set point slope: 0.2; 12) step size: 0.001; 13) Maximum slope deviation: 0.001. As soon as the tracking slope stabilized, the contact potential difference (“CPD”) (volts) between the gold films was recorded. The (4.7-CPD) eV was then obtained for the probe tip based on the CPD of gold. 4.7 eV (electron volts) is the work function of the peri-aged gold film surface (Surface Science, 316, (1994), P380). The CPD of the sample was measured while periodically measuring the CPD of gold. Each sample was loaded into the cavity in the same manner as the gold film sample using four retaining clips. On the retaining clip in electrical contact with the sample, care was taken to ensure good electrical contact with the exposed ITO pad at one corner. During CPD measurements, a small amount of nitrogen was continuously flowed through the cell without disturbing the probe tip. Once the CPD of the sample was recorded, the sample energy potential was then calculated by adding the difference of 4.7 eV and CPD of gold to the CPD of the sample.

Example 1

This example illustrates the preparation of a high work function hole injection material. The hole injection material is a low pH water dispersion of electrically conductive polypyrrole / Nafion®, where Nafion® is poly (tetrafluoroethylene) / perfluoroethersulfonic acid).

A 25% (w / w) aqueous colloidal dispersion of Nafion® having an EW of 1050 was prepared using a procedure similar to the procedure in Example 1, Part 2 of US Pat. No. 6,150,426, except that the temperature was approximately 270 ° C. Prepared. The dispersion was diluted with water to form a 12% (w / w) dispersion for the polymerization.

In a 500 mL reaction kettle was placed 243.5 g of a 12% solid aqueous Nafion® dispersion (29.22 mmol SO ₃ H group) and 685 g of water. The mixture cooled to 5 ° C. was stirred at 200 RPM using an overhead stirrer equipped with two stage propeller blades. Then to the mixture was added a solution of 604.3 mg (1,168.6 μmol) of iron (III) sulfate (Fe ₂ (SO ₄ ) ₃ ) in 10 mL of deionized water. The reaction mixture was stirred at 200 RPM for 15 minutes, then added both 2.5 g (10.5 mmol) of sodium persulfate Na ₂ S ₂ O _{8 in} 20 mL of water and 809 μL (11.69 mmol) of distilled pyrrole diluted in 20 mL of water. It was. The reaction mixture was first all degassed with nitrogen and kept under nitrogen until addition of the ion exchange resin. After 3 hours of adding both sodium persulfate and pyrrole, 50 g of Doex M31 and Dox M43 ion exchange resin and 50 g of deionized water, respectively, were added to the reaction mixture and this was further added at 120 RPM for 5 hours. Stirred. Finally the ion exchange resin was filtered out of the suspension with VWR 417 filter paper. The pH of the dispersion was 2.18 and the film baked for 10 minutes at 130 ° C. in air had a conductivity of 1.7 × 10 ⁻² S / cm at room temperature.

A sufficient amount of the water dispersion prepared above was filtered through a 0.45 μm HV filter and spin-coated for 60 minutes at 1,800 RPM on an ozone-treated ITO / glass surface. Ozone treatment of ITO / glass was achieved using UVO-Cleaner Model # 256 (92718 Irvine Mason, CA, USA). The film was baked for 10 minutes at 130 ° C. in air and then loaded into Kelvin probe cells. The contact potential difference (CPD) between the sample and the probe tip was measured at 1.76 volts. The work function (Wf) of Polypyrrole / Nafion® was then calculated to 5.87 eV based on the CPD (0.69 volts) of the pre-measured air-aging gold film. Aqueous polypyrrole / Nafion® at pH 2.18 has been shown to form films of high Wf.

Example 2

This example shows a high energy potential double layer composition. The bilayer comprises a high work function hole injection layer of a polypyrrole / Nafion® layer deposited from a dispersion of pH 2.18, and a hole transport layer (“HT-1”) of a crosslinkable polymer of fluorene-triarylamine.

A sufficient amount of polypyrrole / Nafion® water dispersion prepared in Example 1 was filtered through a 0.45 μm HV filter and spin-coated onto the ITO / glass surface. ITO / Glass was first plasma-separated for 15 minutes at 0.3 Torr at 300 Watts using an O ₂ -Plasma-25 chamber (Mercator Control Systems, Inc., LF-5 Plasma System). Treatment with oxygen. The spin-coated film was then baked for 10 minutes at 130 ° C. in air, which was a P-15 model profilometer from KLA-Tencor Corporation (San Jos, CA). Measured at about 20 nm (nanometer). The surface profiler was also used in the following examples and comparative examples. Polypyrrole / Nafion® on ITO was then top-coated with 0.4% (w / v) of HT-1. ITO / (Polypyrrole / Nafion®) / HT-1 was baked at 200 ° C. in nitrogen for 30 minutes to react the crosslinker. The crosslinked film was measured at about 20 nm. Glass / ITO / (Polypyrrole / Nafion®) / bridged HT-1 was then loaded into Kelvin probe cells. The contact potential difference (CPD) between the sample and the probe tip was measured at 0.95 volts. The energy potential of HT-1 was then calculated to 4.96 eV based on the CPD (0.69 volts) of the pre-measured air-aging gold film. The energy potential was lower than the work function of the polypyrrole / Nafion® of Example 1, but it was higher than that of the crosslinked HT-1 without polypyrrole / Nafion® at the bottom as shown in Comparative Example A.

Comparative Example A

This comparative example shows the low energy potential HT-1 when used as a single layer without the underlying high work function hole injection material.

A sufficient amount of 0.4% (w / v) of HT-1 in toluene was filtered through a 0.45 μm HV filter and spin-coated onto the ITO / glass surface. ITO / glass was first treated with plasma / oxygen for 15 minutes at 0.3 Torr at 300 Watts. The HT-1 film on ITO / glass was baked at 200 ° C. in air for 30 minutes to react the crosslinker, which was measured at about 18 nm. HT-1 / ITO / glass was then loaded into Kelvin probe cells. The contact potential difference (CPD) between the sample and the probe tip was measured at 0.26 volts. The energy potential of the HT-1 film on ITO was then calculated to be 4.27 eV based on the CPD (0.69 volts) of the pre-measured air-aging gold film. The energy potential (4.27 eV) was lower than (4.96 eV) for HT-1 / polypyrrole-Nafion® / ITO as shown in Example 2.

Example 3

This example shows a high pH water dispersion of electrically conductive polypyrrole / Nafion®, and its high work function.

The polypyrrole / Nafion® dispersion used in this example was prepared using an aqueous Nafion® colloidal dispersion having an EW (acid equivalent weight) of 1000. A 25% (w / w) Nafion® dispersion was prepared using a procedure similar to the procedure in Example 1, Part 2 of US Pat. No. 6,150,426, except that the temperature was approximately 270 ° C., followed by dilution with water. To form a 12.0% (w / w) dispersion for polymerization.

In a 4 L reaction pot was placed 1704.3 g of a 12% solid aqueous Nafion® dispersion (204.51 mmol SO ₃ H group) and 1,790 g of water. The mixture was stirred with a 3-blade overhead stirrer set at 300 rpm. To the mixture was then added a solution of 4,230.0 mg (8.18 mmol) of iron (III) sulfate (Fe ₂ (SO ₄ ) ₃ ) and sodium persulfate Na ₂ S ₂ O ₈ dissolved in 150 mL of water (73.62 mmol). It was. After degassing the mixture in the pot, 5.66 mL (81.8 mmol) of distilled pyrrole diluted in 150 mL of water was added. Pyrrole addition was achieved using four 60 mL syringes. Each of the four syringes was fed with a portion of an equal amount of pyrrole stirring at 300 rpm at the bottom of the pot, one at the center and two at the top. 3.5 hours after the addition of the pyrrole solution, 350 g of Dow's M31 and Dow's M43 ion exchange resin each were added to the reaction mixture, which was further stirred at 120 RPM for 3 hours. Finally the ion exchange resin was filtered out of the suspension with VWR 417 filter paper. The pH of the dispersion was 2.32 and the film baked for 10 minutes at 130 ° C. in air had a conductivity of 1.1 × 10 ⁻² S / cm at room temperature.

Some of the polypyrrole / Nafion® prepared above was adjusted to pH 7 with Lewatit Monoplus S100. A sufficient pH 7 water dispersion was filtered through a 0.45 μm HV filter and first spin-coated onto a plasma / oxygen treated ITO / glass substrate at 0.3 Torr for 15 minutes at 300 Watts. The film was baked at 130 ° C. for 10 minutes in air, which was measured at 20 nm. Polypyrrole / Nafion® was then loaded into Kelvin probe cells. The contact potential difference (CPD) between the sample and the probe tip was measured at 1.27 volts. The work function (Wf) of Polypyrrole / Nafion® was then calculated to 5.28 eV based on the CPD of the pre-measured air-aging gold film (0.69 volts). An aqueous dispersion of pH 7 of Polypyrrole / Nafion® was shown to form a film with a lower Wf than the dispersion of pH 2.18 as shown in Example 1. However, this work function was still high enough to improve the energy potential of HT-1 as shown in Example 4.

Example 4

This example shows HT-1 on a high energy-potential polypyrrole / Nafion® layer formed from an aqueous dispersion of pH 7.

Sufficient amount of polypyrrole / Nafion® pH 7 water dispersion prepared in Example 3 was filtered through a 0.45 μm HV filter and spin-coated onto the ITO / glass surface. ITO / glass was first treated with plasma / oxygen for 15 minutes at 0.3 Torr at 300 Watts. The spin-coated film was then baked for 10 minutes at 130 ° C. in air, which was measured at about 20 nm (nanometer). Polypyrrole / Nafion® on ITO was then top-coated with 0.4% (w / v) HT-1 in toluene. The hole transport polymer, HT-1, on polypyrrole / Nafion® / ITO was baked at 200 ° C. in nitrogen for 30 minutes to react the crosslinker. The crosslinked film was measured at about 20 nm. Free / ITO / Polypyrrole-Nafion® / bridged HT-1 was loaded into a Kelvin probe cell. The contact potential difference (CPD) between the sample and the probe tip was measured at 0.63 volts. The energy potential of HT-1 was calculated to be 4.64 eV based on the CPD (0.69 volts) of the pre-measured air-aging gold film. This energy potential (4.64 eV) was lower than the work function (5.28 eV) of polypyrrole / Nafion® in Example 3, but this was a crosslinked HT- without the polypyrrole / Nafion® layer at the bottom as shown in Comparative Example B. It is higher than the energy potential of 1.

Comparative Example B

This comparative example was carried out simultaneously with Example 4 to show the low energy potential of HT-1 as a single layer without a high work function hole injection material at the bottom.

Sufficient 0.4% (w / v) of HT-1 in toluene was filtered through a 0.45 μm HV filter and spin-coated onto the ITO / glass surface. ITO / glass was first treated with plasma / oxygen for 15 minutes at 0.3 Torr at 300 Watts. The HT-1 film on ITO / glass was baked at 200 ° C. in air for 30 minutes to crosslink the crosslinker, which was measured at about 18 nm. HT-1 / ITO / glass was then loaded into Kelvin probe cells. The contact potential difference (CPD) between the sample and the probe tip was measured at 0.12 volts. The work function (Wf) or energy potential of the HT-1 film on ITO was then calculated to be 4.13 eV based on the CPD (0.69 volts) of the pre-measured air-aging gold film. This energy potential (4.13 eV) was lower than (4.64 eV) for the HT-1 / polypyrrole / Nafion® / ITO shown in Example 4. This comparison shows that the insertion of polypyrrole / Nafion® between HT-1 and ITO raises the energy potential to facilitate hole injection into the subsequent light emitting layer.

Example 5

This example shows a hole transport polymer on a high energy-potential polypyrrole / Nafion® layer prepared from an aqueous dispersion of pH 2.0.

A new batch of polypyrrole / Nafion® at pH 2.0 was prepared using the method described in Example 3, but without the addition of NaOH. This polypyrrole / Nafion® dispersion formed a film with a work function of 5.87 eV. A sufficient amount of polypyrrole / Nafion® water dispersion was filtered through a 0.45 μm HV filter and spin-coated for 60 seconds at 1,000 RPM on an ITO / glass surface. ITO / glass was first treated with plasma / oxygen for 15 minutes at 0.3 Torr at 300 Watts. The spin-coated film was then baked for 10 minutes at 120 ° C. in air. Polypyrrole-Nafion® on ITO was then top-coated with 0.5% (w / v) hole transport polymer ("HT-2") in toluene.

HT-2 was prepared according to the procedure in PCT Patent Application Publication No. WO 2005/080525, Example 1. The glass / ITO / Polypyrrole-Nafion® / HT-2 was then baked for 30 minutes at 195 ° C. in an inert box and then loaded into Kelvin probe cells. The contact potential difference (CPD) between the sample and the probe tip was measured at 0.58 volts. The energy-potential of HT-2 was calculated to be 4.59 eV based on the CPD of the pre-measured air-aging gold film (0.69 volts). This energy-potential (4.59 eV) was lower than the work function (5.87 eV) of polypyrrole-Nafion®, but higher than that of crosslinked HT-2 without polypyrrole / Nafion® at the bottom as shown in Comparative Example C. Appeared.

Comparative Example C

This comparative example was implemented simultaneously with Example 5 in order to show the low energy potential of HT-2 as a single layer which does not have a high work function hole injection layer at the bottom.

Sufficient 0.5% (w / v) of HT-2 in toluene was filtered through a 0.45 μm HV filter and spin-coated for 60 seconds at 1,000 RPM on an ITO / glass surface. ITO / glass was first treated with plasma / oxygen for 15 minutes at 0.3 Torr at 300 Watts. The glass / ITO / HT-2 was then baked for 30 minutes at 195 ° C. in an inert box. The thickness of HT-2 was measured at 19 nm, which was loaded into Kelvin probe cells. The contact potential difference (CPD) between the sample and the probe tip was measured at 0.25 volts. The energy potential of the HT-2 film on ITO was then calculated to be 4.26 eV based on the CPD (0.69 volts) of the pre-measured air-aging gold film. This energy potential (4.26 eV) was lower than (4.59 eV) for HT-2 / polypyrrole / Nafion® / ITO, as shown in Example 5. This comparison shows that the insertion of a polypyrrole / Nafion® layer between HT-2 and ITO raises the energy potential, facilitating hole injection into subsequent light emitting layers.

Example 6

This example shows the work function of an electrically conductive poly (3,4-dioxy-ethylenethiophene) / Nafion®, where Nafion® is poly (tetrafluoroethylene) / perfluoroethersulfonic acid) PH effect on.

The PEDOT-Nafion® dispersion used in this example was prepared using an aqueous Nafion® colloidal dispersion having an EW (acid equivalent weight) of 1050. A 25% (w / w) Nafion® dispersion was prepared using a procedure similar to the procedure in Example 1, Part 2 of US Pat. No. 6,150,426, except that the temperature was approximately 270 ° C., followed by dilution with water. To form a 12.0% (w / w) dispersion for polymerization.

63.5 g of an aqueous Nafion® dispersion (7.26 mmol SO ₃ H group) of 12% solids, 156 g of water, iron (III) sulfate (Fe ₂ (SO ₄ ) ₃ ) 13.7 mg (25.4 μm) in a 500 mL reaction kettle ol) and 130 μl (1.58 mmol) of 37% HCl were added. The reaction mixture was stirred for 15 minutes at 175 RPM using an overhead stirrer equipped with a two-stage propeller type blade, followed by 0.79 g (3.30 mmol) of sodium persulfate (Na ₂ S ₂ O ₈ ) in 10 mL of water and 281 μl of ethylenedioxythiophene (EDT) was added. The addition was initiated from a separate syringe using an addition rate of 0.8 mL / hour for Na ₂ S ₂ O ₈ / water and 20 μl / hour for EDT with continued stirring at 200 RPM. EDT addition was achieved by placing the monomers in a syringe connected to a Teflon® tube that leads directly to the reaction mixture. The ends of the Teflon® tubes connecting the Na ₂ S ₂ O ₈ / water solution were placed on top of the reaction mixture so that the injections were gradually injected, including the individual loads dropping from the ends of the tubes. 2 hours after the addition of the monomers is complete, 15 g of Rewatite MP62WS and 20 Rewatite MonoPlus S100 ion exchange resin and 20 g of n-propanol are added to the reaction mixture, which is further stirred at 120 RPM for 7 hours. Thereby stopping the reaction. Finally, Whatman No. The ion exchange resin was filtered out of solution using 54 filter paper. The pH of the dispersion was 4 and the dry film derived from the dispersion had a conductivity of 1.4 × 10 ⁻³ S / cm at room temperature.

200 g of the PEDOT-Nafion® obtained above were run through a glass column first charged with 15 g of MP62WS and then 15 g of Amberlyst 15 (proton exchange resin). The pH of the collected PEDOT-Nafion® was 1.9, which is shown as Example 6a. To 48 g of PEDOT-Nafion® at pH 1.9, an aqueous solution of NaOH diluted until pH 4.2 was added. This sample is shown as Example 6b. To 46 g of PEDOT-Nafion® at pH 1.9, an aqueous solution of NaOH diluted until pH 6.1 was added. This sample is shown as Example 6c. Three dispersion samples with pH of 1.9, 4.2 and 6.1 were spin-coated onto an ITO / glass substrate and first dried to remove water. The work function (Wf) of the dry film was measured by ultraviolet photoelectron emission spectroscopy (UPS), which is a known technique. Wf energy levels were measured from the second electron cut-off relative to the position of the vacuum level using He I (21.22 eV) radiation. Table 1 below shows that the work function (Wf) of PEDOT-Nafion® at pH 1.9 is higher than that of Baytron-P at pH 1.8 shown in Comparative Example C (5.9 eV vs. 5.1 eV). Wf decreased to 5.5 eV and 5.3 eV, respectively, at pH 4.2 and 6.1, but Wf was much higher than that of Baitron-P at three pH levels. This comparison clearly shows that PEDOT-Nafion® is much less sensitive to pH than Baitron-P and still maintains high Wf at high pH.

Comparative Example D

This comparative example is a water dispersion of electrically conductive poly (3,4-dioxyethylenethiophene) / polystyrenesulfonic acid, not fluoropolymeric acid, Baittron-P® Al4083 (Lot # CHDSPS0006; Solids: 1.48%, pH = 1.8 ) Shows the effect of pH on the work function.

Ha. sieve. Baitron-P Al4083 from H. C. Starck, GmbH, Leverkusen, Germany is PEDOT-PSSA, poly (3,4-dioxy-ethylenethiophene) -poly (styrenesulfonic acid). To 80 g of Baitron-P Al4083, 4 g of Rewatit S100 and MP 62 WS each were added for 20 minutes. Rewart® S100 is a trade name from Bayer, Pittsburgh, Pa., For sodium sulfate of crosslinked polystyrene. ReWattite® MP62 WS is a trade name from Bayer (Pittsburgh, Pa.) For the free base / chloride of tertiary / quaternary amines of crosslinked polystyrene. The resin in Baitron-P was filtered off through VWR # 417 filter paper (40 μm). The pH was measured at 2.2 and adjusted to 3.95 by addition of 1.0 M aqueous NaOH solution. Half of the samples are shown as Comparative Example D-a (see Table 2 below). The other half was further adjusted to pH 7 with 1.0 M NaOH solution. This sample is shown as Comparative Example D-b.

Comparative Examples D-a and D-b and Al4083 were spin-coated on an ITO / glass substrate and first dried to remove water. The work function (Wf) of the dry film was measured by ultraviolet photoelectron emission spectroscopy (UPS). Wf energy levels were measured from the second electron cut-off relative to the position of the vacuum level using He I (21.22 eV) radiation. The data show that Baitron-P as purchased has a low work function of 5.1 eV (electron volts), which decreases to 4.7 eV as the pH increases to 4 and 7. This comparative example shows that Baitron-P is not a high work function conductive polymer at low pH, and its function is lowered to lower levels with increasing pH.

Example 7

This example shows that the addition of Nafion®, poly (tetrafluoroethylene / perfluoroethersulfonic acid) increases the work function of Baitron-P® Al4083.

Baitron-P® Al4083 (Lot # CHDSPS0006; Solid: 1.48%, pH = 1.77) was used to form a blend with Nafion®. Al4083 galaxy. sieve. PEDOT / PSSA from Stark, Geembeha (Leverkusen, Germany). The w / w ratio between PEDOT / PSSA is 1: 6. Nafion® used for blending is an aqueous colloidal dispersion with an EW of 1050, which was prepared as follows. 25% (w / w) of Nafion® was prepared using a procedure similar to the procedure in Example 1, Part 2 of US Pat. No. 6,150,426, except that the temperature was approximately 270 ° C. The Nafion® dispersion was then diluted with water to form a 12.0% (w / w) dispersion for use in the present invention.

330.94 g of Nafion® was added dropwise and stirred with a magnetic stirrer and mixed with 1269.59 g of Baitron-P® in the flask. It took about 5 hours to complete the addition. The resulting dispersion contained 3.66% solids with an equivalent ratio of Nafion® / PEDT / PSSA of 2.0 / 1.0 / 4.6. The mixture was further treated with Microfluidizer Processor M-110EH (Microfluidics, Massachusetts, USA) using a pressure of 8,000 psi. The diameters of the first chamber and the second chamber were 200 μm (H30Z model) and 87 μm (G10Z), respectively. In one pass, the PSC decreased from 693,000 to about 240,000. The microfluidization mixture had a film (baked at 90 ° C. for 40 minutes) of 7.7 × 10 ⁻⁶ S / cm.

A small amount of microfluidized dispersion was run on a 100 mL column packed at the bottom with MonoPlus S100 and at the top with MP 62 WS. The two resins were first washed before use separately with deionized water until no color appeared in the water. The pH of the resin-treated dispersion was 1.98, which had a film (baked at 90 ° C. for 40 minutes) of 1.4 × 10 ⁻⁵ S / cm. Two drops of the dispersion were spin-coated onto an ITO / glass substrate and first dried to remove water. The work function (Wf) of the dry film was measured by ultraviolet photoelectron emission spectroscopy (UPS), which measured 5.8 eV. This work function was much higher than Baitron-P used in the blending of blends.

Example 8

In this example, 1,1-difluoroethylene ("VF2") and 2- (1,1-difluoro-2- (trifluoromethyl) allyloxy) -1,1,2,2- A composition of high work function polyaniline prepared in the presence of sulfonic acid converted from tetrafluoroethanesulfonyl fluoride (“VF ₂ -PSEBVE”). VF ₂ -PSEBVE sulfonic acid forms an organic solvent wettable surface.

Ingredient structure and terminology:

400 mL of Hastelloy C276 reaction vessel was charged with 160 mL of Bertrel® XF, 4 mL of a 20% by weight solution of HFPO dimer peroxide in Bertrel® XF, and 143 g (0.42 mol) PSEBVE. The vessel was cooled to -35 ° C, vented to -3 PSIG, and purged with nitrogen. The exhaust / purging cycle was repeated two more times. Then 29 g (0.45 mol) of VF ₂ were added to the vessel. The vessel was heated to 28 ° C. and the pressure increased to 92 PSIG. The reaction temperature was maintained at 28 ° C. for 18 hours at which time the pressure was lowered to 32 PSIG. The vessel was evacuated and the crude liquid material recovered. Bertrel® XF was removed in vacuo to yield 110 g of the desired copolymer.

The conversion to sulfonic acid in the sulfonyl fluoride copolymer prepared above was carried out in the following manner. 20 g of dry polymer and 5.0 g of lithium carbonate were refluxed in 100 mL of anhydrous methanol for 12 hours. The mixture was brought to room temperature and filtered to remove any residual solids. Methanol was removed in vacuo to isolate the lithium salt of the polymer. The lithium salt of the polymer was then dissolved in water and proton acid exchange resin, Amberlyst 15, thoroughly washed with water until no color appeared in water. The mixture was stirred and filtered. The filtrate was added again with Amberlyst 15 resin and filtered again. The step was repeated two more times. The water was then removed from the final filtrate and then the solid was dried in a vacuum oven. The VF2 / PSEBVE acid polymer was then dissolved in water to prepare a 4.39% (w / w) solution for polymerization with the aniline shown below.

78.61 g of deionized water and 45.38 g of 99.7% n-propanol were added directly to a 1000 mL reaction vessel at room temperature. Then 0.0952 mL (1.2 mmol) of 37 wt.% HCl and 0.6333 mL (7.0 mmol) of aniline (distilled) were added to the reactor by pipette. The mixture was stirred overhead with a U-shaped stir bar set at 100 RPM. After 5 minutes, 53.60 g (5.80 mmol) of a 4.39% aqueous solution of VF2 / PSEBVE sulfonic acid polymer were added slowly with a glass funnel. The mixture was homogenized at 200 rpm for an additional 10 minutes. 1.65 g (7.2 mmol) of ammonium persulfate (99.99 +%) dissolved in 20 g of deionized water was added dropwise to the reaction with a syringe infusion pump within 6 hours. After 8 minutes, the solution turned bright cyan. The solution ran dark blue before it turned very dark green. After APS addition, the mixture was stirred for 60 minutes and Amberley-15 (Rohm and Haas Co., Philadelphia, PA) cation exchange resin (32% n-propanol / deionized water mixture) Rinsed several times and dried under nitrogen) 4.68 g were added and stirring was started at 200 RPM overnight. The next morning, the mixture was filtered through a steel mesh. The pH of the Amberlyst 15 treated dispersion was 1.2. Some dispersions were added to the Amberjet 4400 (OH) (Rom and Haas Company, Philadelphia, PA) anion exchange resin (32% n-propanol / deionized water mixture) until the pH changed from 1.2 to 5.7. Rinsed several times and dried under nitrogen). The resin was filtered again and the filtrate was a stable dispersion.

Two drops of Pani dispersion were spin-coated onto an ITO / glass substrate. The work function of the dry film on ITO was measured by ultraviolet photoelectron emission spectroscopy, which was determined to be 5.5 eV. Work function was high at pH 5.7.

Example 9

This example shows a polymer light emitting diode using a high energy-potential bilayer. The bilayer consisted of a first layer of polypyrrole / nafion spin-coated with a second layer of HT-1.

As shown in Example 4, HT-1 top-coated on high pH Polypyrrole / Nafion® had a high energy-potential. This bilayer surface was used to produce a polymer light emitting diode using a red light-emitting material. A sufficient amount of polypyrrole / Nafion® water dispersion was filtered through a 0.45 μm HV filter and spin-coated onto a glass / ITO backlight substrate (30 mm × 30 mm) to make a light emitting diode. Each ITO substrate having an ITO thickness of 100 to 150 nm consisted of 1 part 2 mm x 2 mm pixels and 3 parts 5 mm x 5 mm pixels for light emission. Once spin-coated on an ITO substrate, the film was first baked for 10 minutes at 120 ° C. in air. The baked film had a thickness of 12 nm and the work function was 5.3 eV as shown in Example 3. The polypyrrole / ITO substrate was spin-coated at 2,000 RPM for 60 seconds with a crosslinkable polymer solution of HT-1 (0.4% w / v in toluene). The crosslinkable polymer was then baked at 198 ° C. in nitrogen for 30 minutes to form a hole transport layer (HTL). Film thickness was measured at approximately 20 nm. The HTL was then top-coated with a 1% (w / v) solution (in toluene) with a red electroluminescent polymer and then baked at 130 ° C. in nitrogen for 30 minutes to form a film thickness of 70 nm. After baking, the cathode with 3 nm of Ba and 250 nm of Al was thermally evaporated at a pressure of less than 4 × 10 ⁻⁶ Torr. Encapsulation of the device was achieved by bonding a glass slide to the back of the device using a UV-curable epoxy resin.

Table 2 summarizes the light emitting device efficiency and voltage at 200, 500, 1,000 nits (Cd / m ² ), and the lifetime of 1,200 nits to 1,000 nitros. The data show that the high surface energy-potential bilayer has better device efficiency, lower voltage and much longer lifetime than the hole transport layer without the high work function hole injection layer at the bottom as shown in Comparative Example E. Shows.

Comparative Example E:

This comparative example shows a polymer light emitting diode made of a hole transport layer having a low energy-potential.

As shown in Comparative Example B, HT-1 had a low surface-energy potential without a high work function hole injection layer at the bottom. Polymeric light emitting diodes were prepared by spin-coating the ITO substrate with only HT-1. The device fabrication procedure described in Example 9 (including each layer order, baking temperature and layer thickness) was followed. Device efficiency and lifetime are summarized in Table 2 below. This clearly shows that ITO without the polypyrrole / nafion layer under the HT-1 layer has lower device efficiency, higher voltage and much shorter lifetime than the bilayer as shown in Example 9.

TABLE 2

Comparative Example F

This comparative example shows the work function of ITO. The ITO substrates used in the examples of Examples and Comparative Examples were treated with UV-ozone for 10 minutes or with oxygen / plasma for 15 minutes at 0.3 Torr at 300 Watts. Treated ITO samples were loaded into Kelvin probe cells with ITO facing the Kelvin prop tip. The contact potential difference (CPD) between the UV / ozone treated ITO and the probe tip was measured at 0.805 volts. The work function of the surface was then calculated to 4.9 eV based on the CPD (0.69 volts) of the premeasured gold film. The CPD between the oxygen-plasma treated ITO and the probe tip was measured as high as 1.17 volts. The work function of the ITO surface was then calculated to be 5.2 eV based on the CPD (0.69 volts) of the premeasured gold film. The work function was not stable and decreased by 0.2 eV or more upon exposure to air or solvents such as toluene. This comparative example shows that ITO alone is not sufficient to form a high energy-potential in the hole transport layer.

It is appreciated that not all of the acts described in the general description or examples above are required, that some of the specific acts may not be required, and that one or more additional acts may be performed in addition to those described. In addition, 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. Accordingly, the specification and figures are 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 respect to specific embodiments. However, any benefit, advantage, solution to a problem, and any feature (s) that can generate or make any benefit, advantage, or solution more prominent are significant, necessary, or essential features of any or all of the claims. It should not be intended as.

It should be appreciated that certain features described herein in separate embodiments may be provided in combination in a single embodiment for clarity. Conversely, various features that are described in a single embodiment for the sake of simplicity may be provided individually or in any subcombination. In addition, reference to values stated in ranges includes each and every value within that range.

Claims (17)

A hole injection layer having a work function of greater than 5.2 eV, and Hole transport layer Bilayer composition comprising a. The bilayer composition of claim 1, wherein the hole injection layer comprises at least one electrically conductive material selected from the group consisting of a charge transfer complex and a conductive polymer. 3. The charge transfer complex of claim 2 wherein the charge transfer complex is a tetracyanoquinomimethane complex with tetrathiafulvalene or tetramethyltetraselenafulvalene, a metal-tetracyanoquinomethanemethane complex, and a semiconductor oxide deposited from a liquid medium. A bilayer composition selected from the group consisting of. The bilayer composition of claim 2, wherein the conductive polymer is formed from at least one monomer selected from the group consisting of thiophene, selenophene, tellurophene, pyrrole, aniline, and polycyclic aromatic compounds. The bilayer composition of claim 3, wherein the semiconductor oxide is deposited with at least one fluorinated acid polymer. The bilayer composition of claim 4, wherein the conductive polymer is doped with at least one fluorinated acid polymer. 6. The bilayer composition of claim 5, wherein the fluorinated acid polymer has a perfluorinated carbon backbone and a side chain represented by 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 the group consisting of F, Cl, and perfluorinated alkyl groups having 1 to 10 carbon atoms; a = 0, 1 or 2; E ⁵ is H. The bilayer composition of claim 6, wherein the fluorinated acid polymer has a perfluorinated carbon main chain and a side chain represented by the following 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 the group consisting of F, Cl, and perfluorinated alkyl groups having 1 to 10 carbon atoms; a = 0, 1 or 2; E ⁵ is H. The bilayer composition of claim 1, wherein the hole transport layer is crosslinkable. The bilayer composition of claim 1, wherein the hole injection layer has a work function of greater than 5.3 eV. The bilayer composition of claim 1, wherein the hole injection layer has a work function of greater than 5.5 eV. A hole injection layer prepared from a composition having a work function of greater than 5.0 eV and having a pH greater than 2.0, and Hole transport layer Bilayer composition comprising a. Anode, A hole injection layer having a work function of greater than 5.2 eV in contact with the anode, and Hole transport layer in contact with the hole injection layer Electronic device comprising a. 4. The bilayer composition of claim 3, wherein the hole transport layer comprises at least one polymer having a hole transport group selected from the group consisting of carbazole, triarylamine, triarylmethane, fluorene, and combinations thereof. The bilayer composition of claim 4, wherein the hole transport layer comprises at least one polymer having a hole transport group selected from the group consisting of carbazole, triarylamine, triarylmethane, fluorene, and combinations thereof. 4. The hole transport layer of claim 3, wherein the hole transport layer comprises 4,4 ', 4 "-tris (N, N-diphenyl-amino) -triphenylamine; 4,4', 4" -tris (N-3-methylphenyl-). N-phenyl-amino) -triphenylamine; N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine; 1,1-bis [(di-4-tolylamino) phenyl] cyclohexane; N, N'-bis (4-methylphenyl) -N, N'-bis (4-ethylphenyl)-[1,1 '-(3,3'-dimethyl) biphenyl] -4,4'-diamine; Tetrakis- (3-methylphenyl) -N, N, N ', N'-2,5-phenylenediamine; α-phenyl-4-N, N-diphenylaminostyrene; p- (diethylamino) benzaldehyde diphenylhydrazone; Triphenylamine; Bis [4- (N, N-diethylamino) -2-methylphenyl] (4-methylphenyl) methane; 1-phenyl-3- [p- (diethylamino) styryl] -5- [p- (diethylamino) phenyl] pyrazoline; 1,2-trans-bis (9H-carbazol-9-yl) cyclobutane; N, N, N ', N'-tetrakis (4-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine; N, N'-bis (naphthalen-1-yl) -N, N'-bis- (phenyl) benzidine; A bilayer composition comprising a porphyrin-based compound and a non-polymeric material selected from the group consisting of compounds represented by formula (XVI) below. <Formula XVI> In the formula, Ar is an arylene group; Ar 'and Ar "are independently selected from aryl groups; R ²⁴ to R ²⁷ are hydrogen, alkyl, aryl, halogen, hydroxyl, aryloxy, alkoxy, alkenyl, alkynyl, amino, alkylthio, phosphino, silyl, -COR, -COOR, -PO ₃ R ₂ , -OPO ₃ R ₂ is independently selected from the group consisting of CN; R is selected from the group consisting of hydrogen, alkyl, aryl, alkenyl, alkynyl and amino; m and n are each independently integers having a value of 0 to 5, where m + n ≠ 0. 5. The hole transport layer of claim 4, wherein the hole transport layer comprises 4,4 ′, 4 ″ -tris (N, N-diphenyl-amino) -triphenylamine; 4,4 ′, 4 ″ -tris (N-3-methylphenyl-). N-phenyl-amino) -triphenylamine; N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine; 1,1-bis [(di-4-tolylamino) phenyl] cyclohexane; N, N'-bis (4-methylphenyl) -N, N'-bis (4-ethylphenyl)-[1,1 '-(3,3'-dimethyl) biphenyl] -4,4'-diamine; Tetrakis- (3-methylphenyl) -N, N, N ', N'-2,5-phenylenediamine; α-phenyl-4-N, N-diphenylaminostyrene; p- (diethylamino) benzaldehyde diphenylhydrazone; Triphenylamine; Bis [4- (N, N-diethylamino) -2-methylphenyl] (4-methylphenyl) methane; 1-phenyl-3- [p- (diethylamino) styryl] -5- [p- (diethylamino) phenyl] pyrazoline; 1,2-trans-bis (9H-carbazol-9-yl) cyclobutane; N, N, N ', N'-tetrakis (4-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine; N, N'-bis (naphthalen-1-yl) -N, N'-bis- (phenyl) benzidine; A bilayer composition comprising a porphyrin-based compound and a non-polymeric material selected from the group consisting of compounds represented by formula (XVI) below. <Formula XVI> In the formula, Ar is an arylene group; Ar 'and Ar "are independently selected from aryl groups; R ²⁴ to R ²⁷ are hydrogen, alkyl, aryl, halogen, hydroxyl, aryloxy, alkoxy, alkenyl, alkynyl, amino, alkylthio, phosphino, silyl, -COR, -COOR, -PO ₃ R ₂ , -OPO ₃ R ₂ is independently selected from the group consisting of CN; R is selected from the group consisting of hydrogen, alkyl, aryl, alkenyl, alkynyl and amino; m and n are each independently integers having a value of 0 to 5, where m + n ≠ 0.