JP2006527277A - Water dispersible polythiophene produced by polymeric acid colloid - Google Patents

Abstract

Compositions comprising an aqueous dispersion of polythiophene having a homopolymer or copolymer of formula I (a) or formula I (b) and at least one colloid-forming polymeric acid are provided. Further provided are methods of making such compositions and methods of using such compositions in organic electronic devices.

Description

  The present invention relates to an aqueous dispersion of a conductive polymer of thiophene, wherein the conductive polymer is synthesized in the presence of a polymer acid colloid.

(Cross-reference of related applications)
This application is a continuation-in-part of US patent application Ser. No. 10 / 669,494 filed on Sep. 24, 2003, and from US Provisional Patent Application No. 60/464370 filed on Apr. 22, 2003. Claim priority.

Conductive polymers have been used in a variety of organic electronic devices, such as in the development of electroluminescent (“EL”) devices for use in light emitting displays. With respect to EL devices such as organic light emitting diodes (OLEDs), such devices generally 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 an EL material such as indium / tin oxide (ITO). The anode is optionally supported on a glass or plastic substrate. EL materials include fluorescent dyes, 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 a conductive polymer that facilitates the injection of holes from the anode into the EL material layer. The buffer layer can also be referred to as a hole injection layer, a hole transport layer, or can be characterized as part of a bilayer anode. Typical conductive polymers used as the buffer layer include polyaniline; and polydioxythiophenes such as poly (3,4-ethylenedioxythiophene) (PEDT). These materials are poly (styrene sulfonic acid) (as described, for example, in the US Patent Publication (Patent Document 1), titled “Polythiophene Dispersion, Their Production and Use”). It can be prepared by polymerizing aniline or dioxythiophene monomers in an aqueous solution in the presence of a water-soluble polymeric acid such as PSS). Known PEDT / PSS materials include H.E. C. “Baytron®-P, commercially available from HC Starck, GmbH (Leverkusen, Germany).

  Aqueous conductive polymer dispersions synthesized with water soluble polymeric sulfonic acids have undesirable low pH levels. Low pH can contribute to the low stress life of EL devices that include such buffer layers as well as to corrosion in the device. Accordingly, there is a need for compositions and layers prepared from aqueous conductive polymer dispersions to have improved properties.

Conductive polymers that have the ability to deliver high currents when exposed to low voltages are also useful as electrodes for electronic devices such as thin film field effect transistors. In such a transistor, an organic semiconducting film having high mobility for electron and / or hole charge carriers is present between the source and drain electrodes. The gate electrode is on the opposite side of the semiconductive polymer layer. In order to be useful for electrode applications, the conductive polymer and the liquid in which the conductive polymer is dispersed or dissolved are semiconductive polymer and semiconductive to avoid re-dissolution of either the conductive polymer or the semiconductive polymer. Must be compatible with the solvent for the soluble polymer. The conductivity of the electrode fabricated from the conductive polymer should exceed 10 S / cm (where S is Mo). However, conductive polythiophenes made with polymeric acids typically provide conductivity in the range of about 10 ⁻³ S / cm or less. In order to enhance conductivity, a conductive additive may be added to the polymer. However, the presence of such additives can adversely affect the processability of the conductive polythiophene. Accordingly, there is a need for improved conductive polythiophenes.

US Pat. No. 5,300,575 European Patent Application No. 1 026 152A1 US Pat. No. 3,282,875 U.S. Pat. No. 4,358,545 US Pat. No. 4,940,525 US Pat. No. 4,433,082 US Pat. No. 6,150,426 International Publication No. 03/006537 Pamphlet International Publication No. 02/02714 Pamphlet US Patent Application Publication No. 2001/0019782 EP 1191612 Specification International Publication No. 02/15645 Pamphlet EP 1191614 specification US Pat. No. 6,303,238 International Publication No. 00/70655 Pamphlet International Publication No. 01/41512 Pamphlet Co-pending application No. 10 / 669,777 Co-pending application No. 10/669494 Current Applied Physics, 2002 No. 2, pp. 339-343 Nature, pp. 166-169, vol. 426, 2003 Advanced Materials, pp. 490-491, Vol. 12, No. 7, 2000

  Provided is a novel composition comprising an aqueous dispersion of at least one polythiophene and at least one colloid-forming polymeric acid, wherein the polythiophene comprises formula I (a) or formula I (b) Is done.

Wherein R ″ is the same or different at each occurrence, and R ″ is hydrogen, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alcohol, amide sulfonate, provided that at least one R ″ is not hydrogen. Selected from benzyl, carboxylate, ether, ether carboxylate, ether sulfonate and urethane;
m is 2 or 3,
n is at least about 4)

Wherein R ′ ₁ and R ₁ are independently selected from hydrogen and alkyl, or
R ′ ₁ and R ₁ are combined to form an alkylene chain having 1 to 4 carbon atoms optionally substituted with an alkyl group or aromatic group having 1 to 12 carbon atoms, Or form a 1,2-cyclohexylene group,
n is at least about 4)

In another embodiment, a method is provided for synthesizing an aqueous dispersion of at least one polythiophene comprising at least one of Formula I (a) or Formula I (b) and at least one colloid-forming polymeric acid. The One method for producing an aqueous dispersion of polythiophene and at least one colloid-forming polymeric acid is:
(A) Formula II (a) or Formula II (b)

In which R ″, R ′ ₁ and R ₁ and m are as defined above.
Providing a homogeneous aqueous mixture of at least one thiophene monomer and water having:
(B) providing an aqueous dispersion of colloid-forming polymeric acid;
(C) The step of combining the thiophene mixture with the aqueous dispersion of the colloid-forming polymer acid and (d) The aqueous dispersion of the colloid-forming polymer acid before or after the combination of the step (c). Combining the liquids in any order.

  In another embodiment, a novel composition comprising at least one polythiophene, at least one colloid-forming polymeric acid, and at least one co-dispersing liquid, wherein the polythiophene is of formula I as described above. Novel compositions comprising (a) or I (b) are provided.

  In another embodiment, an electronic device is provided that includes at least one layer that includes the novel composition.

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

  The examples illustrate the invention. The present invention is not limited to the attached drawings.

  In one embodiment, a composition is provided comprising an aqueous dispersion of at least one polythiophene having Formula I (a) or Formula I (b) and at least one colloid-forming polymeric acid.

  A novel aqueous dispersion of at least one polythiophene having formula I (a) or formula I (b) and at least one colloid-forming polymeric acid has at least formula II (a) or formula II (b) It is possible to prepare one thiophene monomer when chemically polymerizing in the presence of a colloid-forming polymeric acid.

  Furthermore, it has been discovered that the use of non-water soluble polymeric acids in the preparation of aqueous dispersions of polythiophene having formula II (a) or formula II (b) results in compositions having superior electrical properties. In one embodiment, the aqueous dispersion of the novel composition comprises conductive microparticles that are stable in an aqueous medium without forming a separate phase for extended periods of time prior to use. In one embodiment, the layer comprising the new composition does not redisperse into the film or layer during secondary processing of the electronic device once dried.

  The composition according to one embodiment of the novel composition comprises a continuous aqueous phase in which at least one polythiophene and at least one colloid-forming polymeric acid are dispersed.

  The polythiophenes contemplated for use in the new composition are made from at least one monomer having the following formula II (a) or formula II (b) to provide either a homopolymer or a copolymer. Here, Formula II (a) or Formula II (b) is as follows.

In which R ″ is the same or different at each occurrence and R ″ is hydrogen, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alcohol, amide sulfonate, provided that at least one R ″ is not hydrogen. Selected from benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, sulfonate and urethane;
R ′ ₁ and R ₁ are independently selected from hydrogen and alkyl, or R ′ ₁ and R ₁ together are optionally selected by an alkyl or aromatic group having 1 to 12 carbon atoms An alkylene chain having 1 to 4 carbon atoms which may be optionally substituted, or a 1,2-cyclohexylene group.

The thiophene of the new composition has the same general structure as shown above, where R ₁ and R ′ ₁ are substituted for the “OR ₁ ” substituent and the “OR ₁ ′” substituent.

  The polythiophene of the novel composition can be a homopolymer or the polythiophene can be a copolymer of two or more thiophene monomers. The aqueous dispersion of polythiophene and colloid-forming polymeric acid can include one or more polythiophene polymers and one or more colloid-forming polymeric acids.

  As used herein, the term “dispersion” means a continuous liquid medium containing a suspension of microparticles. “Continuous medium” includes aqueous liquids. As used herein, the term “aqueous” refers to a liquid having a significant portion of water, and in one embodiment, the liquid is at least about 40% by weight water. As used herein, the term “colloid” refers to microparticles suspended in a continuous medium having a nanometer scale particle size. As used herein, the term “colloid-forming” means a substance that forms microparticles when dispersed in an aqueous solution. That is, “colloid-forming” polymeric acids are not water soluble.

  As used herein, the term “co-dispersing liquid” means a substance that is liquid at room temperature and miscible with water. As used herein, the term “miscible” means that the co-dispersing liquid is water (at the concentration described herein for each particular co-dispersing liquid) to form a substantially homogeneous solution. It can be mixed with.

  The term “layer” or “film” means a coating covering a desired area. The area can be as large as the entire device, as small as a specific functional area such as a real visual display, or as small as a single sub-pixel. The film can be formed by any conventional deposition technique including vapor deposition and liquid deposition. Typical liquid deposition techniques include continuous deposition techniques such as spin coating, gravure coating, curtain coating, dip coating, slot die coating, spray coating and continuous nozzle coating and discontinuous deposition such as inkjet printing, gravure printing and screen printing. Techniques, but not limited to.

  The term “alkyl” as used herein means a group derived from an aliphatic hydrocarbon and includes straight-chain, branched and cyclic groups which may be unsubstituted or substituted. The term “heteroalkyl” is a pile meaning an alkyl group in which one or more of the carbon atoms in the alkyl group is replaced by another atom such as nitrogen, oxygen and sulfur. The term “alkylene” refers to an alkyl group having two points of attachment.

  As used herein, the term “alkenyl” refers to a group derived from an aliphatic hydrocarbon having at least one carbon-carbon double bond, which may be unsubstituted or substituted. Includes branched and cyclic groups. The term “heteroalkenyl” is a pile meaning an alkenyl group in which one or more of the carbon atoms in the alkyl group is replaced by another atom, such as nitrogen, oxygen and sulfur. The term “alkynylene” refers to an alkenyl group having two points of attachment.

As used herein, the following terms for substituents refer to the formulas shown below.
“Alcohol” —R ³ —OH
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
“Ether” —R ³ —O—R ⁵
“Ether carboxylate” —R ³ —O—R ⁴ —C (O) OZ
“Ether sulfonate” —R ³ —O—R ⁴ —SO ₃ Z
“Sulfonate” —R ³ —SO ₃ Z
“Urethane” —R ³ —O—C (O) ON (R ⁶ ) ₂
Here, 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.
Z is H, an alkali metal, an alkaline earth metal, N (R ⁵ ) ₄ or R ⁵ .

  None of the above groups may be further substituted or may be substituted, and any group, including perfluorinated groups, may be substituted with one or more hydrogens for F. .

  As used herein, the terms “comprises”, “comprising”, “includes”, “including”, “has”, “having” or Any other variation of these is a pile dealing with non-limiting inclusion. For example, a process, method, article or device that includes a list of elements is not necessarily limited to only those elements, but other elements that are not explicitly listed or are unique to such processes, methods, articles or devices. May be included. Further, unless expressly stated to the contrary, "or / or" means non-exclusive "or / or" and exclusive "or / or" I don't mean. For example, condition A or B is satisfied by any one of the following: A is true (or exists) and B is false (does not exist). A is false (does not exist) and B is true (or exists). And both A and B are true (or exist).

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

  In one embodiment, the polythiophene has the formula I (a) (m is 2, one R ″ is an alkyl group of more than 5 carbon atoms, and all other R ″ are hydrogen). .

  In one embodiment of Formula I (a), at least one R ″ group has at least one fluorine substituent.

  In one embodiment of Formula I (a), the R ″ substituent on the fused alicyclic ring on thiophene should provide improved solubility of the monomer in water and in the presence of the polymeric acid colloid. In another embodiment, the resulting polythiophene / colloid-forming polymeric acid composition has a small particle size and dispersion stability.

  In one embodiment, the polythiophene is poly [(sulfonic acid-propylene-ether-methylene-3,4-dioxyethylene] thiophene) In one embodiment, the polythiophene is poly [(propyl-ether-ethylene-3, 4-dioxyethylene) thiophene].

In one embodiment, the polythiophene has the formula I (b), wherein R ₁ and R ₁ ′ combine to form an alkyl chain having 1 to 4 carbon atoms. In another embodiment, the polydioxythiophene is poly (3,4-ethylenedioxythiophene).

  Colloid-forming polymeric acids contemplated for use in the novel compositions are insoluble in water and form colloids when dispersed in an aqueous medium. The polymeric acid typically has a molecular weight in the range of about 10,000 to about 4,000,000.

  In one embodiment, the polymeric acid has a molecular weight of about 100,000 to about 2,000,000. The particle size of the polymeric acid colloid is typically in the range of about 2 nanometers (nm) to about 140 nm. In one embodiment, the colloid has a particle size of 2 nm to about 30 nm.

  Any polymeric acid that is colloid-forming when dispersed in water is suitable for use in preparing the new composition. In one embodiment, the colloid-forming polymeric acid is at least one high polymer selected from polymeric sulfonic acid, polymeric phosphoric acid, polymeric phosphonic acid, polymeric carboxylic acid, polymeric acrylic acid and mixtures thereof. Contains molecular acids. In another embodiment, the polymeric sulfonic acid is fluorinated. In yet another embodiment, the colloid-forming polymeric acid is perfluorinated. In yet another embodiment, the colloid-forming polymeric sulfonic acid comprises perfluoroalkylene sulfonic acid.

In yet another embodiment, the colloid-forming polymeric acid comprises a highly fluorinated sulfonic acid polymer (“FSA polymer”). “Highly fluorinated” means at least about 50% of the total number of halogen and hydrogen atoms in the polymer, in one embodiment at least about 75%, and in another embodiment at least about 90% fluorine atoms. It means that. In one embodiment, the polymer is perfluorinated. The term “sulfonate functional group” means either a sulfonic acid group or a salt of a sulfonic acid group, and in one embodiment an alkali metal salt or an ammonium salt. This functional group is represented by the formula —SO ₃ X, where X is a cation, also known as a “counter ion”. X may 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 may be the same or different. , In one embodiment, H, CH ₃ or C ₂ H ₅ . In another embodiment, X is H, in which case the polymer is said to be in the “acid form”. X may be multivalent, as represented by ions such as ^{Ca ++} and ^{Al +++.} In the case of a multivalent counterion, generally expressed as M ^{n +} , it will be apparent to one skilled in the art that the number of sulfonate functional groups per counterion is equal to the valence “n”.

In one embodiment, the FSA polymer comprises a polymer backbone having repeating side chains attached to the polymer backbone. The polymer includes a homopolymer or copolymer of two or more monomers. The copolymer is typically a non-functional monomer and a second monomer that carries a cation exchange group or precursor thereof, eg, a sulfonyl fluoride group (—SO ₂ F) that can be subsequently hydrolyzed to a sulfonate functional group. Formed from. For example, a copolymer of a first fluorinated vinyl monomer combined with a second fluorinated vinyl monomer having a sulfonyl fluoride group (—SO ₂ F) can be used. Possible first monomers include tetrafluoroethylene (TFE), hexafluoropropylene, vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, perfluoro (alkyl vinyl ether) and combinations thereof. . TFE is the preferred first monomer.

In other embodiments, one other monomer comprises a fluorinated vinyl ether having a sulfonate functional group or precursor group that can provide the desired side chain in the polymer. Additional monomers including ethylene, propylene and R—CH═CH _{2 where} R is a perfluorinated alkyl group having 1 to 10 carbon atoms can be introduced into these polymers if desired. is there. The polymer may be a type of polymer referred to herein as a random copolymer. A random copolymer is a copolymer produced by polymerization in which the relative concentration of the comonomer is kept as constant as possible so that the distribution of monomer units along the polymer chain follows the relative concentration and relative reactivity. Copolymers that are less random and are produced by varying the relative concentration of monomers during the polymerization may also be used. A type of polymer called a block copolymer such as the polymer disclosed in Patent Document 2 may also be used.

In one embodiment, the FSA polymer for use in the novel composition has the formula — (O—CF ₂ CFR _f ) _a —O—CF ₂ CFR ′ _f SO ₃ X
The highly fluorinated and perfluorinated carbon backbones and side chains represented by:
Wherein R _f and R ′ _f are independently selected from F, Cl or a perfluorinated alkyl group having 1 to 10 carbon atoms, a is 0, 1 or 2, and X is H, Li, Na , K or N (R ₁ ) (R ₂ ) (R ₃ ) (R ₄ ), wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different, and in one embodiment H, CH ₃ or C it is a ₂ H _5. In another embodiment, X is H. As described above, X may be multivalent.

In one embodiment, the FSA polymer includes, for example, the polymers disclosed in US Patent Publication (Patent Document 3), US Patent Publication (Patent Document 4) and US Patent Publication (Patent Document 5). An example of a preferred FSA polymer is the formula —O—CF ₂ CF (CF ₃ ) —O—CF ₂ CF ₂ SO ₃ X
The perfluorocarbon main chain and side chain represented by
Where X is as defined above. FSA polymers of this type are disclosed in U.S. Patent Publication (Patent Document 3), tetrafluoroethylene (TFE) and the perfluorinated vinyl ether _{CF 2 = CF-O-CF} 2 CF (CF 3) -O-CF 2 Copolymerization of CF ₂ SO ₂ F, perfluoro (3,6-dioxa-4-methyl-7-octenesulfonyl fluoride) (PDMOF), followed by hydrolysis of the sulfonyl fluoride group and ion exchange as necessary Can be prepared by converting them to sulfonate groups and converting them to the desired ionic form. Examples of U.S. Patent Publication (Patent Document 4) and U.S. Patent Publication of the type disclosed in (Patent Document 5) polymers in the side chain _{-O-CF 2 CF 2 SO 3} X ( wherein, X is as defined above Is). This polymer is a copolymer of tetrafluoroethylene (TFE) and perfluorinated vinyl ether CF ₂ ═CF—O—CF ₂ CF ₂ SO ₂ F, perfluoro (3-oxa-4-pentenesulfonyl fluoride) (POPF). It can be produced by subsequent hydrolysis and further ion exchange as required.

  In one embodiment, FSA polymers for use in the new composition typically have an ion exchange ratio of less than about 33. In the present application, “ion exchange ratio” or “IXR” is defined as the number of carbon atoms in the polymer backbone, based on cation exchange groups. Within a range of less than about 33, IXR can be varied as required for a particular application. In one embodiment, the IXR is from about 3 to about 33, and in another embodiment from about 8 to about 23.

The cation exchange capacity of a polymer is often expressed in terms of equivalent weight (EW). For purposes of this application, equivalent weight (EW) is defined as the weight of the polymer in the acid form required to neutralize one equivalent of sodium hydroxide. When the polymer is a sulfonate polymer having a perfluorocarbon backbone and side chains —O—CF ₂ —CF (CF ₃ ) —O—CF ₂ —CF ₂ —SO ₃ H (or a salt thereof), about 8 to about 23 The equivalent range for IXR is from about 750 EW to about 1500 EW. The IXR for this polymer can be related to equivalent weight using the formula 50 IXR + 344 = EW. Sulfonate polymers having the same IXR range disclosed in US Pat. Nos. 4,099,086 and 5,037, for example, polymers having a side chain —O—CF ₂ CF ₂ SO ₃ H (or a salt thereof) While the equivalent weight is somewhat lower due to the lower molecular weight of the monomer unit containing the cation exchange group. For a preferred IXR range of about 8 to about 23, the corresponding equivalent range is about 575 EW to about 1325 EW. The IXR for this polymer can be related to the equivalent weight using the formula 50 IXR + 178 = EW.

  The synthesis of FSA polymers is well known. The FSA polymer can be prepared as a colloidal aqueous dispersion. The FSA polymer may take the form of a dispersion in other media. Examples of other media include, but are not limited to, water soluble ethers such as alcohols, tetrahydrofuran, mixtures of water soluble ethers and combinations thereof. In preparing the dispersion, the polymer can be used in acid form. US Patent Publication (Patent Document 6), US Patent Publication (Patent Document 7) and (Patent Document 8) disclose methods for producing an aqueous dispersion. After producing the dispersion, the concentration and dispersion composition can be adjusted by methods known in the art.

  In one embodiment, an aqueous dispersion of colloid-forming polymeric acid comprising an FSA polymer has the smallest possible particle size and the smallest possible EW as long as a stable colloid is formed.

  Aqueous dispersions of FSA polymers are commercially available from the Applicant as “Nafion” ® dispersions.

  In one embodiment, the thiophene monomer having formula II (a) or formula II (b) is oxidatively polymerized in water containing at least one polymeric acid colloid. Typically, the thiophene monomer is combined with or added to the aqueous dispersion containing the polymerization catalyst, oxidant and colloidal polymeric acid particles dispersed therein. In this embodiment, the order of combination or addition may be varied as long as at least one part of the colloid-forming polymeric acid is present when the oxidant and catalyst are combined with the monomer. In one embodiment, the reaction mixture may further comprise a co-dispersant, a co-acid or a mixture thereof.

  In one embodiment, the colloid-forming polymeric acid is FSA and the co-dispersing liquid of the aqueous FSA dispersion is optionally removed before or after polymerization of the thiophene monomer.

  In one embodiment, the thiophene monomer continuously mixes the reaction mixture with an aqueous reaction mixture comprising colloid-forming polymeric acid particles, an oxidizing agent and a catalyst by dispersing the thiophene monomer at a controlled rate of addition. To form a monomer meniscus in the reaction mixture.

  In one embodiment, the oxidant pre-dissolved in water is dispersed in an aqueous reaction mixture containing colloid-forming polymeric acid particles, thiophene monomer and catalyst therein by dispersing the oxidant solution at a controlled rate of addition. , Combined with continuous mixing of the reaction mixture.

  In one embodiment, the oxidant and thiophene monomer are added separately and simultaneously to the reaction mixture at the same or different controlled addition rates to achieve the final desired amount of oxidant to effect the oxidative polymerization reaction. Consumes the monomer at a controlled rate.

  In one embodiment, the controlled thiophene monomer addition rate is determined taking into account the amount of material used. The goal of controlling the rate of monomer addition from the distribution mechanism is to ensure rapid dissolution in the reaction mixture. With controlled addition, the polymerization and oxidation chemistries are performed in a uniform and homogeneous manner. Examples of dispensing mechanisms include, but are not limited to, the use of tubes, syringes, pipettes, nozzle guns, sprayers, hoses and pipes. In one embodiment, a perforated end, such as a frit glass plate or small diameter tube attached to the apparatus described above, is used to provide a monomer meniscus in the reaction mixture.

  The rate of addition depends on the size of the reaction, the rate at which the solution is stirred and the shape and number of dispensing ends of the dispensing mechanism orifice. In one embodiment, the dispensing end of the dispensing mechanism is submerged in a reaction mixture containing an aqueous colloid-forming polymeric acid. For example, a thiophene monomer addition rate of about 1-1000 microliters / hour can be used for a reaction mixture size of about 100-500 grams of an aqueous colloid-forming polymeric acid composition. In one embodiment, the addition rate is between about 5-100 microliters / hour for about 500 grams of the aqueous colloid-forming polymeric acid composition. For other size (larger or smaller) reaction mixtures, the rate of addition can be increased or decreased linearly in the appropriate direction.

  In one embodiment, at least one co-dispersing liquid is added to the reaction mixture prior to completion of polymerization of the thiophene monomer. In another embodiment, at least one co-dispersing liquid is added to the reaction mixture after completion of thiophene polymerization. In another embodiment, a portion of the at least one co-dispersing liquid is added before the end of the polymerization of thiophene and an additional amount of the at least one co-dispersing liquid is added after the end of the polymerization of thiophene. Is done.

  Polymerization catalysts include, but are not limited to, ferric sulfate, ferric chloride, other materials that have higher oxidation capabilities than oxidants, and mixtures thereof.

  Oxidizing agents include, but are not limited to, sodium persulfate, potassium persulfate, and ammonium persulfate, including combinations thereof. In one embodiment, oxidative polymerization is charged by negatively charged side chains of polymeric acids contained within the colloid, such as sulfonate anion, carboxylate anion, acetylate anion, phosphonate anion, phosphonate anion, and combinations thereof. The result is a stable aqueous dispersion containing a balanced positively charged conducting polymer thiophene.

  In one embodiment, a method of making a novel composition comprising at least one polythiophene having formula I (a) or formula I (b) and at least one colloid-forming polymeric acid comprises: (a) a polymeric acid (B) a step of adding an oxidizing agent to the dispersion of step (a), (c) a step of adding a catalyst to the dispersion of step (b), and (d) step (c) A step of adding a thiophene monomer to the dispersion. One embodiment of the alternative to the method described above involves adding a thiophene monomer to the aqueous dispersion of polymeric acid prior to adding the oxidizing agent. Another embodiment is a thiophene having Formula II (a) or Formula II (b) with a concentration typically in the range of about 0.5 wt% to about 2.0 wt% thiophene and water And adding this thiophene mixture to the aqueous dispersion of polymeric acid prior to adding the oxidant and catalyst.

  The polymerization can be carried out in the presence of a co-dispersing liquid that is miscible with water. Examples of suitable co-dispersing liquids include, but are not limited to ethers, alcohols, alcohol ethers, cyclic ethers, ketones, nitriles, sulfoxides and combinations thereof. In one embodiment, the amount of co-dispersing liquid may be less than about 30% by volume. In one embodiment, the amount of co-dispersing liquid is less than about 60% by volume. In one embodiment, the amount of co-dispersing liquid is between about 5-50% by volume. In one embodiment, the co-dispersing liquid includes alcohol. In one embodiment, the co-dispersing liquid comprises at least one from n-propanol, isopropanol, t-butanol, methanol dimethylacetamide, dimethylformamide, N-methylpyrrolidone.

  The polymerization can be carried out in the presence of a coacid. The acid can be an inorganic acid such as HCl and sulfuric acid or an organic acid such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid and acetic acid. Alternatively, the co-acid is a water-soluble polymer acid such as poly (styrene sulfonic acid) or poly (2-acrylamido-2-methyl-1-propane sulfonic acid, or a second colloid-forming acid, as described above. It is possible to use a combination of co-acids.

  The co-acid can be added to the reaction mixture at any point in the process prior to the last addition of the oxidant or thiophene monomer. In one embodiment, the co-acid is added before both the thiophene monomer and the colloid-forming polymeric acid, and the oxidizing agent is added last. In one embodiment, the co-acid is added prior to the addition of the thiophene monomer, followed by the colloid-forming polymeric acid and the oxidant added last.

  The co-dispersing liquid can be added to the reaction mixture either before, during or after polymerization of the thiophene.

  In one embodiment, a composition comprising an aqueous dispersion of polydioxythiophene, a colloid-forming polymeric acid and at least one co-dispersing liquid is provided. Addition of at least one co-dispersing liquid to an aqueous dispersion of poly (dioxythiophene) and colloid-forming polymeric acid after polymerization results in better wettability, processability, processable viscosity, substantial Can result in polymer dispersions having a small number of large particles, improved stability of the dispersion, improved ink jetting properties, enhanced conductivity, or combinations thereof. Surprisingly, it has been discovered that OLED devices with buffer layers made from such dispersions also have higher efficiency and longer lifetime.

  Co-dispersing liquids contemplated for use in the new compositions are generally polar, water-miscible organic liquids. Examples of suitable types of co-dispersing liquids include ethers, cyclic ethers, alcohols, alcohol ethers, ketones, nitriles, sulfides, sulfoxides, amides, amines and carboxylic acids, and combinations of any two or more thereof. But not limited to.

  Exemplary ether co-dispersing liquids contemplated for use in the new compositions include diethyl ether, ethyl propyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, methyl t-butyl ether, glyme, diglyme, benzyl methyl. Ether, isochroman, 2-phenylethyl methyl ether, n-butyl ethyl ether, 1,2-diethoxyethane, s-butyl ether, diisobutyl ether, ether n-propyl ether, ether isopropyl ether, n-hexyl methyl ether, n- Examples include, but are not limited to, butyl methyl ether and methyl n-propyl ether, and combinations of any two or more thereof.

  Exemplary cyclic ether co-dispersing liquids contemplated for use in the new compositions include 1,4-dioxane, tetrahydrofuran, tetrahydropyran, 4-methyl-1,3-dioxane, 4-phenyl-1 , 3-dioxane, 1,3-dioxolane, 2-methyl-1,3-dioxolane, 1,3-dioxane, 2,5-dimethoxytetrahydrofuran and 2,5-dimethoxy-2,5-dihydrofuran, and the like Although any 2 or more types of combination of these is mentioned, it is not limited to them. In one embodiment, the cyclic ether co-dispersing liquid is tetrahydrofuran, tetrahydropyran or 1,4-dioxane.

  Exemplary alcohol co-dispersing liquids contemplated for use in the novel compositions include methanol, ethanol, 1-propanol, 2-propanol (ie, isopropanol), 1-butanol, 2-butanol, 2-methyl- 1-propanol (ie isobutanol), 2-methyl-2-propanol (ie t-butanol), 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 1-pentanol Hexanol, cyclopentanol, 3-methyl-1-butanol, 3-methyl-2-butanol, 2-methyl-1-butanol, 2,2-dimethyl-1-propanol, 3-hexanol, 2-hexanol, 4- Methyl-2-pentanol, 2-methyl-1-pentanol, 2-ethylbutanol 2,4-dimethyl-3-pentanol, 3-heptanol, 4-heptanol, 2-heptanol, 1-heptanol, 2-ethyl-1-hexanol, 2,6-dimethyl-4-heptanol, 2-methyl Examples thereof include, but are not limited to, cyclohexanol, 3-methylcyclohexanol, 4-methylocthexanol, and combinations of any two or more thereof. In one embodiment, the alcohol co-dispersing liquid is methanol, ethanol or isopropanol.

  Illustrative alcohol ether co-dispersing liquids contemplated for use in the new compositions include 2-butoxyethanol, 1-methoxy-2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy- 2-butanol, ethylene glycol monoisopropyl ether, 1-ethoxy-2-propanol, 3-methoxy-1-butanol, ethylene glycol monoisobutyl ether, ethylene glycol mono-n-butyl ether, 3-methoxy-3-methylbutanol and ethylene Examples include glycol mono-t-butyl ether, and combinations of any two or more thereof, but are not limited thereto. In one embodiment, the alcohol ether co-dispersing liquid is 1-methoxy-2-propanol, 2-methoxyethanol or 2-butoxyethanol.

  Exemplary ketone co-dispersing liquids contemplated for use in the novel compositions include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isopropyl methyl ketone, 2-pentanone, 3-pentanone, 3-hexanone, diisopropyl ketone. 2-hexanone, cyclopentanone, 4-heptanone, isoamyl methyl ketone, 3-heptanone, 2-heptanone, 4-methoxy-4-methyl-2-pentanone, 5-methyl-3-heptanone, 2-methyl Cyclohexanone, diisobutyl ketone, 5-methyl-2-octanone, 3-methylcyclohexanone, 2-cyclohexane-1-one, 4-methylcyclohexanone, cycloheptanone, 4-t-butylcyclohexanone and isophorone, benzylacetone, etc. A combination of two or more any of them include, but are not limited to.

  Exemplary nitrile co-dispersing liquids contemplated for use in the new compositions include acetonitrile, acrylonitrile, trichloroacetonitrile, propionitrile, pivalonitrile, isobutyronitrile, n-butyronitrile, methoxyacetonitrile, 2-methyl. Butyronitrile, isovaleronitrile, n-valeronitrile, n-capronitrile, 3-methoxypropionitrile, 3-ethoxypropionitrile, 3,3′-oxydipropionitrile, n-heptanenitrile, glycolonitrile, Examples include, but are not limited to, benzonitrile, ethylene cyanohydrin, succinonitrile, acetone cyanohydrin and 3-n-butoxypropionitrile, and combinations of any two or more thereof.

  Exemplary sulfoxide co-dispersing liquids contemplated for use in the novel compositions include dimethyl sulfoxide (DMSO), di-n-butyl sulfoxide and tetramethylene sulfoxide, methylphenyl sulfoxide, and the like, and any two of them. Examples include combinations of more than one species, but are not limited thereto.

  Exemplary amide co-dispersing liquids contemplated for use in the novel compositions include dimethylformamide (DMF), dimethylacetamide, acrylamide, 2-acetamidoethanol, N, N-dimethyl-m-toluamide, trifluoro Acetamide, N, N-dimethylacetamide, N, N-diethyldodecanamide, ε-caprolactam, N, N-diethylacetamide, Nt-butylformamide, formamide, pivalamide, N-butylamide, N, N-dimethylacetoacetamide N-methylformamide, N, N-diethylformamide, N-formylethylamine, acetamide, N, N-diisopropylformamide, 1-formylpiperidine and N-methylformanilide, and any two or more of them It includes a combination of, but not limited thereto.

  Illustrative amine co-dispersing liquids contemplated for use in the new compositions include mono-, di- and tri-alkyl amines, cyclic amines such as pyrrolidine, and aromatic amines such as pyridine. And combinations of any two or more thereof, but are not limited thereto. In one embodiment, the amine co-dispersing liquid is pyridine.

Exemplary carboxylic acid co-dispersing liquids contemplated for use in the novel compositions include C ₁ to about C ₆ linear or branched carboxylic acids, and combinations of any two or more thereof But are not limited thereto. In one embodiment, the carboxylic acid co-dispersing liquid is formic acid.

  In one embodiment, the co-dispersing liquid is n-propanol, isopropanol, methanol, butanol, 1-methoxy-2-propanol, dimethylacetamide, n-methylpyrazole, 1,4-dioxane, tetrahydrofuran, tetrahydropyran. 4-methyl-1,3-dioxane, 4-phenyl-1,3-dioxane, 1,3-dioxolane, 2-methyl-1,3-dioxolane, 1,3-dioxane, 2,5-dimethoxytetrahydrofuran, A liquid selected from 2,5-dimethoxy-2,5-dihydrofuran, 1-methylpyrrolidine, 1-methyl-2-pyrrolidinone, dimethyl sulfoxide, and combinations of any two or more thereof.

  In one embodiment, after completion of any of the methods described above and completion of the polymerization reaction, the as-synthesized aqueous dispersion removes decomposed species, side reaction products, unreacted monomers and ionic impurities. And at least one ion exchange resin under conditions suitable for adjusting the pH. The as-synthesized aqueous dispersion can be contacted with at least one ion exchange resin before or after the addition of the co-dispersing liquid. In one embodiment, the as-synthesized aqueous dispersion is contacted with the first ion exchange resin and the second ion exchange resin.

  In another embodiment, the first ion exchange resin is an acidic cation exchange resin such as the sulfonic acid cation exchange resin described above, and the second ion exchange resin is a base such as a tertiary amine or quaternary exchange resin. Anionic anion exchange resin.

  Ion exchange is a reversible chemical reaction in which ions in a fluid medium (such as an aqueous dispersion) are exchanged for similarly charged ions bound to immobile 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 is rendered insoluble due to the crosslinked nature of the polymeric support to which the ion exchange groups are bound. Ion exchange resins are classified as acidic cation exchangers with positively charged mobile ions available for exchange and basic anion exchangers whose exchangeable ions are negatively charged.

  Both acidic cation exchange resins and basic anion exchange resins are considered for use in the novel process. In one embodiment, the acidic cation exchange resin is an organic acid cation exchange resin such as a sulfonic acid cation exchange resin. Sulfonic acid cation exchange resins contemplated for use in the novel compositions include, 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 acid or phosphate cation exchange resin. Furthermore, it is possible to use a mixture of different cation exchange resins. In many cases, basic ion exchange resins can be used to adjust the pH to a desired level. In some cases, the pH can be further adjusted with an aqueous basic solution, such as a solution of sodium hydroxide or ammonium hydroxide.

  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 novel compositions include, for example, tertiary aminated styrene-divinylbenzene copolymers, tertiary aminated crosslinked styrene polymers, tertiary aminated phenol-formaldehyde resins, Mention may be made of triaminated benzene-formaldehyde resins and mixtures thereof. In a further embodiment, the basic anion exchange resin is a quaternary amine anion exchange resin or a mixture of these exchange resins and other exchange resins.

  The first ion exchange resin and the second ion exchange resin may contact the as-synthesized aqueous dispersion simultaneously or sequentially. For example, in one embodiment, both resins are added simultaneously to the as-synthesized aqueous dispersion of conductive polymer and left in contact with the dispersion for at least about 1 hour, such as from about 2 hours to about 20 hours. It remains. Thereafter, the ion exchange resin can be removed from the dispersion by filtration. The size of the filter is selected such that relatively large ion exchange resin particles are removed while smaller dispersed particles pass through. While not wishing to be bound by theory, the ion exchange resin inhibits polymerization and effectively removes most of the ionic and non-ionic impurities and unreacted monomers from the as-synthesized aqueous dispersion. Can be considered. Furthermore, basic anion exchange resins and / or acidic cation exchange resins make acidic sites more basic, thus resulting in a high pH of the dispersion. Generally, at least 1 gram of ion exchange is used per gram of colloid-forming polymeric acid. In other embodiments, the use of ion exchange resins is used in a ratio of up to about 5 grams of ion exchange resin to polythiophene / polymeric acid colloid and depends on the pH to be achieved. In one embodiment, at least 1 gram of “Lewatit” ® MP62WS which is a weakly basic anion exchange resin from Bayer GmbH and a strongly acidic sodium cation exchange resin from Bayer GmbH. About 1 gram of “Lewatit” ® MonoPlus S100 is a gram of a composition of polythiophene having the formula I (a) or formula I (b) and at least one colloid-forming polymeric acid Used per hit.

  In one embodiment, the aqueous dispersion resulting from the polymerization of thiophene having formula II (a) or formula II (b) and a fluorinated polymeric sulfonic acid colloid is first charged to the reaction vessel with the aqueous dispersion of fluorinated polymer. Then, in this order, oxidant, catalyst and thiophene monomer are added to the aqueous dispersion of colloid-forming polymer acid, or in this order, thiophene monomer, oxidant and catalyst are added to the colloid-forming polymer. It is to be added to the aqueous dispersion of acid. The mixture is stirred and then the reaction proceeds at a controlled temperature. When the polymerization is complete, the reaction is quenched with a strong acid cation resin and a basic anion exchange resin, stirred and filtered. Alternatively, thiophene having formula II (a) or formula II (b) can be added to water prior to the addition of “Nafion” ® dispersion, followed by oxidant and catalyst. And can be stirred to homogenize the mixture. The oxidizer: monomer ratio is generally in the range of 0.5 to 2.0. The ratio of fluorinated polymer: thiophene monomer is generally in the range of 1-4. The overall solids content is generally in the range of 1.5% to 6%, and in one embodiment in the range of 2% to 4.5%. The reaction temperature is generally in the range of 5 ° C to 50 ° C, and in one embodiment in the range of 20 ° C to 35 ° C. The reaction time is generally in the range of 1 to 30 hours.

  Aqueous dispersions of the polythiophene and polymeric acid colloids of Formula I (a) or Formula I (b) can have a wide range of pH and are typically adjusted between about 1 and about 8. Possible, generally having a pH of about 3-4. Since acids can be corrosive, it is often desirable to have a higher pH. It has been found that the pH can be adjusted using known techniques such as ion exchange or by titration with aqueous basic solutions.

  In another embodiment, the more conductive dispersion adds a highly conductive additive to an aqueous dispersion of polythiophene and colloid-forming polymeric acid having formula I (a) or formula I (b) It is formed by doing. In one embodiment, the composition further comprises a conductive additive, particularly a metal additive, that is capable of forming a new composition having a relatively high pH and is not eroded by acid in the dispersion. Furthermore, since the polymeric acid is colloidal in nature, the conductive polythiophene having a surface mainly containing acid groups is formed on the colloidal surface.

  In one embodiment, the new composition further comprises at least one conductive additive in a weight percent amount to reach the penetration limit. Examples of suitable conductive additives include, but are not limited to, conductive polymers, metal particles, metal nanoparticles, metal nanowires, carbon nanotubes, carbon nanoparticles, graphite fibers or particles, carbon particles and combinations thereof. Not. A dispersing agent may be included to promote the dispersion of the conductive additive.

  In one embodiment, the novel composition is used to form a conductive or semiconductive layer that is used alone or in combination with other electroactive materials as an electrode, electroactive element, photoactive element or bioactive element. Deposit. As used herein, the terms “electroactive element”, “photoactive element” and “bioactive element” refer to specified activities in response to stimuli such as electromagnetic fields, potentials, solar energy radiation and biostimulation fields. Means the element shown.

  In one embodiment, the new composition is deposited to form a buffer layer in an electronic device. As used herein, the term “buffer layer” is a stack that means a conductive or semiconductive layer that can be used between the anode and the active organic material. The buffer layer, among other aspects, facilitates or improves the performance of the organic electronic device, such as planarization of the underlying layer, hole transport, hole injection; trapping of impurities such as oxygen and metal ions Although not limited to, it is contemplated to perform one or more functions in organic electronic devices including them.

  In one embodiment, a buffer layer deposited from an aqueous dispersion containing polythiophene having Formula I (a) or Formula I (b) and a fluorinated polymeric acid colloid is provided. In another embodiment, the fluorinated polymeric acid colloid is a fluorinated polymeric sulfonic acid colloid. In yet another embodiment, the buffer layer is deposited from an aqueous dispersion containing polythiophene having the formula I (a) or formula I (b) and perfluoroethylene sulfonic acid colloid.

  In another embodiment, an aqueous dispersion comprising at least one polythiophene having formula I (a) or formula I (b), at least one colloid-forming polymeric acid and at least one co-dispersing liquid A buffer layer deposited from is provided. In one embodiment, the co-dispersing liquid is selected from n-propanol, isopropanol, t-butanol, methanol dimethylacetamide, dimethylformamide, N-methylpyrrolidone, ethylene glycol and mixtures thereof.

  In one embodiment, dried layers of polymeric acid colloids such as polythiophene having formula I (a) or formula I (b) and fluorinated polymeric sulfonic acid colloids are not redispersible in water. In one embodiment, the organic device comprising at least one layer comprising the novel composition is fabricated from thin multilayers. In one embodiment, such a layer can be further overcoated with a layer of a different water soluble or water dispersible material without substantially damaging the function or performance of the layer in the organic electronic device.

  In another embodiment, at least one polythiophene and at least one colloid-forming polymer having formula I (a) or formula I (b) blended with other water soluble or water dispersible materials A buffer layer deposited from an aqueous dispersion containing an acid is provided. Examples of types of additional water soluble or water dispersible materials that can be added, depending on the end use of the material, include polymers, dyes, coating aids, carbon nanotubes, metal nanowires, metal nanoparticles, organic and Inorganic conductive inks and pastes, charge transport materials, piezoelectric, pyroelectric or ferroelectric oxide nanoparticles or polymers, photoconductive oxide nanoparticles or polymers, dispersants, crosslinkers and combinations thereof However, it is not limited to them. Such materials can be simple molecules or polymers. Examples of other suitable water-soluble or water-dispersible polymers include polyacrylamide, polyvinyl alcohol, poly (2-vinyl pyridine), poly (vinyl acetate), poly (vinyl methyl ether), poly (vinyl pyrrolidone), poly (Vinyl butyral), poly (styrene sulfonic acid); and conductive polymers such as polythiophene, polyaniline, polyamine, polypyrrole, polyacetylene, colloid-forming polymeric acids, and combinations thereof, but are not limited thereto.

  In another embodiment, an electronic device is provided that includes at least one conductive or semiconductive layer made from the novel composition. Organic electronic devices that can benefit from having one or more layers comprising a composition of at least one polythiophene having formula I (a) or formula I (b) and at least one colloid-forming polymeric acid (1) devices that convert electrical energy into radiation (eg light emitting diodes, light emitting diode displays or diode lasers), (2) devices that detect signals through electronic processes (eg photodetectors (eg photoconductive cells) , Photoresistors, optical switches, phototransistors, light tubes), IR detectors), (3) devices that convert radiation into electrical energy (eg, photovoltaic devices or solar cells) and (4) one or more layers Devices comprising one or more electronic components comprising a plurality of organic conductor layers (eg, transistors Data or diode) include, but are not limited to. Other uses for the new composition include memory storage devices, antistatic films, biosensors, electrochromic devices, solid electrolytic capacitors; energy storage devices such as storage batteries, and coating materials for electromagnetic shielding applications. It is done.

  In one embodiment, the organic electronic device includes an electroactive layer disposed between two electrical contact layers, wherein at least one of the device layers includes a novel buffer layer. One embodiment is illustrated with one type of OLED as shown in FIG. 1, which is a device having an anode layer 110, a buffer layer 120, an electroluminescent layer 130, and a cathode layer 150. Optional electron injection / transport layer 140 is adjacent to cathode layer 150. The electroluminescent layer 130 is between the buffer layer 120 and the cathode layer 150 (or any electron injection / transport layer 140).

  The device may include a support or substrate (not shown) that can be adjacent to the anode layer 110 or the cathode layer 150. Very often, the support is adjacent to the anode layer 110. The support can be flexible or rigid, organic or inorganic. In general, glass or a soft organic film is used as the support. The anode layer 110 is an electrode that is more efficient for hole injection than the cathode layer 150. The anode can include materials containing metals, mixed metals, alloys, metal oxides or mixed oxides. Suitable materials include Group 2 elements (ie, Be, Mg, Ca, Sr, Ba, Ra), Group 11 elements, elements within Groups 4, 5, and 6 and Group 8-10 transition elements. These mixed oxides may be mentioned. If the anode layer 110 should be light transmissive, a mixed oxide of Group 12, Group 13 and Group 14 elements such as indium tin oxide may be used. As used herein, the term “mixed oxide” means an oxide having two or more different cations selected from Group 2 elements or Group 12, 13 or 14 elements. Some non-limiting specific examples of materials for anode layer 110 include indium tin oxide ("ITO"), aluminum tin oxide, gold, silver, copper and nickel, It is not limited. The anode may also include organic materials such as polyaniline, polythiophene or polypyrrole. The IUPAC number system (CRC Handbook of Chemistry and Physics 81st edition, 2000) is used throughout, where families from the periodic table are numbered from left to right as 1-18.

  The anode layer 110 may be formed by chemical vapor deposition, physical vapor deposition, or spin coating. Chemical vapor deposition may be performed as plasma enhanced chemical vapor deposition (“PECVD”) or metal organic chemical vapor deposition (“MOCVD”). Physical vapor deposition methods can include all forms of sputtering, including ion beam sputtering, as well as electron beam evaporation and resistance evaporation. Particular forms of physical vapor deposition include rf magnetron sputtering and inductively coupled plasma physical vapor deposition (“IMP-PVD”). These deposition techniques are well known within semiconductor secondary processing techniques.

  The anode layer 110 may be patterned during a lithographic printing operation. The pattern may be changed as necessary. The layer can be formed in the pattern, for example, by placing a patterning mask or resist on the first soft composite barrier structure prior to depositing the first electrical contact layer material. Alternatively, the layer can be deposited as a generic layer (also referred to as a blanket deposit) and then patterned using, for example, a patterned resist layer and wet chemical etching techniques or dry chemical etching. . Other processes for printing known in the art can also be used. When the electronic device is placed in an array, the anode layer 110 is formed into substantially parallel strips having lengths that typically extend in substantially the same direction.

  The buffer layer 120 can be deposited on the substrate by any technique known to those skilled in the art.

The electroluminescent (EL) layer 130 is typically not limited to fluorescent dyes, fluorescent and phosphorescent metal complexes, conjugated polymers and mixtures thereof, but may be any organic EL material including them. Examples of fluorescent dyes include, but are not limited to, pyrene, perylene, rubrene, derivatives thereof and mixtures thereof. Examples of metal complexes include metal chelated oxinoid compounds such as tris (8-hydroxyquinolate) aluminum (Alq ₃ ), iridium as disclosed in Petrov et al. Cyclometalated iridium and platinum electroluminescent compounds such as complexes of pyridine with phenylpyridine, phenylquinoline or phenylpyrimidine ligands, for example, US Pat. And organometallic complexes disclosed in (Patent Document 13) and mixtures thereof. An electroluminescent light-emitting layer comprising a charge transport host material and a metal complex is described by Thompson et al. In US Pat. No. 4,099,088 and Burrows in US Pat. As described by Thompson. Examples of conjugated polymers include poly (phenylene vinylene), polyfluorene, poly (spirobifluorene), polythiophene, poly (p-phenylene), copolymers thereof and mixtures thereof.

  The particular material selected may vary depending on the particular application, the potential used during operation, or other factors. The EL layer 130 containing the electroluminescent organic material can be deposited using any number of techniques including vapor deposition, solution processing techniques or heat transfer. In another embodiment, an EL polymer precursor can be deposited, after which the EL polymer precursor is typically applied to the polymer by a source of heat or other external energy (eg, visible light or UV radiation). It is possible to convert.

Optional layer 140 can function to facilitate both electron injection / transport, and can also function as a confinement layer to prevent suppression reactions at the layer interface. More particularly, layer 140 can facilitate electron transfer, and if layers 130 and 150 are otherwise in direct contact, the likelihood of an inhibition reaction can be reduced. Examples of materials for the optional layer 140 include metal chelated quinoid compounds (eg, Alq ₃ ), phenanthroline-based compounds (eg, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (“ DDPA ") or 4,7-diphenyl-1,10-phenanthroline (such as" DPA "), azole compounds (eg, 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3 , 4-oxadiazole (such as “PBD”), 3- (4-biphenyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2,4-triazole (such as “TAZ”), Other similar compounds, including but not limited to any one or more combinations thereof, or optional layer 140 may be inorganic and B aO, LiF, Li ₂ O, or the like may be included.

  The cathode layer 150 is an electrode that is particularly effective for the injection of electrons or negative charge carriers. The cathode layer 150 can be any metal or non-metal having a lower work function than the first electrical contact layer (in this case, the anode layer 110). As used herein, the term “lower work function” is a pile meaning a material having a work function of about 4.4 eV or less. As used herein, “higher work function” is an accumulation that refers to a material having a work function of at least about 4.4 eV.

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

  The cathode layer 150 is usually formed by chemical vapor deposition or physical vapor deposition. In general, the cathode layer is patterned as discussed above with respect to the anode layer 110. When the device is present in an array, the cathode layer 150 is formed into substantially parallel strips that extend in substantially the same direction and substantially perpendicular to the length of the anode layer strip. It may be patterned. Electronic elements called pixels are formed at the intersections (the anode layer strip intersects the cathode layer strip when viewing the array from a plan or top view).

  In other embodiments, additional layers may be present in the organic electronic device. For example, a layer (not shown) between the buffer layer 120 and the EL layer 130 can facilitate positive charge transport, the layer matching can be bandgapped, or It can function as a protective layer. Similarly, an additional layer (not shown) between the EL layer 130 and the cathode layer 150 can facilitate negative charge transport or the matching between layers can be bandgapped. Or can function as a protective layer. Layers known in the art can be used. Furthermore, any of the layers described above can be made from more than one layer. Alternatively, some or all of the inorganic anode layer 110, the buffer layer 120, the EL layer 130, and the cathode layer 150 may be surface-treated in order to increase the charge carrier transport efficiency. The selection of materials for each of the component layers may be determined by balancing the goal of providing a device with high device efficiency with manufacturing costs, manufacturing complexity, or potentially other factors.

  The different layers may have any suitable thickness. In one embodiment, the inorganic anode layer 110 is typically about 500 nm or less, such as about 10-200 nm. The buffer layer 120 is usually about 250 nm or less, for example, about 50 to 200 nm. The EL layer 130 is usually about 100 nm or less, for example, about 50 to 80 nm. Optional layer 140 is typically about 100 nm or less, such as about 20-80 nm. The cathode layer 150 is typically about 100 nm or less, for example about 1-50 nm. If the anode layer 110 or the cathode layer 150 needs to transmit at least some light, the thickness of such layer should not exceed about 100 nm.

  In an organic light emitting diode (OLED), electrons and holes injected from the cathode layer 150 and anode layer 110 into the EL layer 130, respectively, form polar ions that are negatively and positively charged in the polymer. These polar ions move under the influence of an applied electric field, form polar ion excitations by oppositely charged species, and subsequently undergo radiative recombination. A sufficient potential difference between the anode and cathode, typically less than about 12 volts, and often about 5 volts or less, may be applied to the device. The actual potential difference may vary depending on the use of the device in larger electronic components. In many embodiments, the anode layer 110 is biased to a positive voltage and the cathode layer 150 is substantially at ground potential or zero volts during operation of the electronic device. A battery or other power source may be electrically connected to the electronic device as part of the circuit, but is not illustrated in FIG.

  In one embodiment, an OLED comprising at least one buffer layer deposited from an aqueous dispersion comprising a polythiophene having formula I (a) or formula I (b) and at least one colloid-forming polymeric acid, It has been found to have an improved lifetime. The buffer layer may be deposited from an aqueous dispersion of polythiophene having formula I (a) or formula I (b) and a fluorinated polymeric sulfonic acid colloid. In one embodiment, the buffer layer is an aqueous dispersion deposited using any solution processing technique and adjusted to have a pH above about 3.5.

  In one embodiment, a pH neutral composition is used in at least one layer of the electronic device. In one OLED embodiment, the pH is adjusted to reduce etching of the ITO layer during device sub-fabrication, so that significantly lower concentrations of In and Sn ions diffuse into the polymer layer of the OLED. This is a significant benefit since it is speculated that In and Sn ions contribute to a short operating lifetime. Lower acidity also reduces corrosion of the metal components of the display (eg, electrical contact pads) during secondary processing and over extended storage. The PEDT / PSSA residue interacts with residual moisture, releasing acid into the display and thus causing slow corrosion.

  The equipment used to dispense acidic PEDT / PSSA needs to be specially designed to handle the strong acidity of PEDT / PSSA. For example, a chrome plated slot die coating head used to coat PEDT / PSSA on an ITO substrate has been found to corrode due to the acidity of PEDT / PSSA. This made the head unusable because the coated film would become contaminated with chromium particles. Certain inkjet printheads are also interesting for secondary processing of OLED displays. Such a head is used to distribute both the buffer layer and the light emitting polymer layer to precise locations on the display. These printheads include a nickel mesh filter as an internal trap for particles in the ink. These nickel filters are degraded by acid PEDT / PSSA and rendered unusable. None of these corrosion problems occur with aqueous polythiophene dispersions of new compositions with reduced acidity.

  Furthermore, certain light-emitting polymers have been found to be sensitive to acidic conditions, and when such polymers are in contact with the acidic buffer layer, the light-emitting ability of the polymer is degraded. It is advantageous to use an aqueous dispersion of the new composition to form a buffer layer because of its ability to adjust pH to lower acidity or neutrality.

  In one embodiment, secondary processing of a full color display or area color display using two or more different luminescent materials is complicated when each luminescent material requires a different cathode material to optimize its performance. . A display device is composed of a number of pixels that emit light. In multicolor devices, there are at least two different types of pixels (sometimes called subpixels) that emit light of different colors. Subpixels are made of different luminescent materials. It is highly desirable to have a single cathode material that provides good device performance for all of the light emitters. This minimizes the complexity of device secondary processing. When the buffer layer is made from an aqueous polythiophene dispersion of the new composition, it may be possible to use a common cathode in a multicolor device while maintaining good device performance for each of the colors. The cathode can be made from any of the materials discussed above and can be barium overcoated with a more inert metal such as aluminum.

  The layer in the organic electronic device containing the novel composition may further comprise a layer of conductive polymer deposited from an aqueous solution or solvent. Conductive polymers can facilitate charge transport and also improve coverage. Examples of suitable conductive polymers include polyaniline / polythiophene, polydioxythiophene / polystyrene sulfonic acid, polyaniline / polymeric acid colloids such as those disclosed in US Pat. Polythiophene / polymeric acid colloids such as those disclosed, polypyrrole, polyacetylene and combinations thereof include, but are not limited to. The composition comprising such a layer may further comprise a conductive polymer, such as a dye, carbon nanotube, carbon nanoparticle, metal nanowire, metal nanoparticle, carbon fiber and carbon particle, graphite fiber and graphite particle, coating aid, organic and Inorganic conductive inks and pastes, charge transport materials, semiconductive or insulating inorganic oxide particles, piezoelectric, pyroelectric or ferroelectric oxide nanoparticles or polymers, photoconductive oxide nanoparticles or polymers , Dispersants, crosslinkers and combinations thereof may also be included. These materials can be added to the novel composition either before or after polymerization of the monomers and / or before or after treatment with at least one ion exchange resin.

In one embodiment, a thin film field effect transistor comprising an electrode comprising a polythiophene comprising at least one of Formula I (a) or Formula I (b) and at least one colloid-forming polymeric sulfonic acid is provided. For use as an electrode in a thin film field effect transistor, the conductive polymer and the liquid for dispersing or dissolving the conductive polymer are semiconductive to avoid re-dissolution of either the conductive polymer or the semiconductive polymer. Must be compatible with the solvent for the polymer and semiconductive polymer. The electrode of the thin film field effect transistor secondary processed from the conductive polymer should have a conductivity greater than 10 S / cm. However, conductive polymers made only with water-soluble polymeric acids provide conductivity in the range of about 10 ⁻³ S / cm or less. Thus, in one embodiment, the electrode comprises polythiophene and fluorinated colloid formation comprising at least one of Formula I (a) or Formula I (b) in combination with a conductivity enhancer such as metal nanowires, metal nanoparticles or carbon nanotubes. Containing high molecular weight sulfonic acid. The novel composition may be used in a thin film field effect transistor as a gate electrode, drain electrode or source electrode.

  Another example of an application for the new composition is a thin film field effect transistor, shown in FIG. In this example, a dielectric polymer or dielectric oxide thin film 210 has a gate electrode 220 on one side and a drain electrode 230 and a source electrode 240 on the other side, respectively. An organic semiconductive film 250 is deposited between the drain electrode and the source electrode. New aqueous dispersions containing nanowires or carbon nanotubes are ideal for gate, drain and source electrode applications due to the compatibility of the new aqueous dispersions with organic dielectric and semiconductive polymers in solution thin film deposition Is. Because of the novel composition as a colloidal dispersion, less weight percent (based on the composition containing the water-soluble polymeric sulfonic acid) to reach the penetration limit for the desired or high conductivity Only conductive filler is required.

  In another embodiment, a field effect resistance device is provided that includes one layer comprising at least one polythiophene having formula I (a) or formula I (b) and at least one colloid-forming polymeric sulfonic acid. Is done. The field effect resistance device undergoes a reversible change in the resistance of the conductive polymer film when exposed to a pulse of gate voltage, as exemplified in (Non-Patent Document 1).

  In another embodiment, an electrochromic display comprising at least one layer comprising at least one polythiophene having formula I (a) or formula I (b) and at least one colloid-forming polymeric sulfonic acid. Provided. Electrochromic displays take advantage of the change in color when a thin film of material is subjected to an electrical potential. In one embodiment, the conductive polythiophene / polymeric acid colloid of the new composition is suitable for this application because of the high pH and low water absorption of the dispersion and the water non-dispersibility of the dry solid film made from the dispersion. It is an excellent material.

  In yet another embodiment, a silicon chip topcoated with a composition comprising at least one polythiophene having formula I (a) or formula I (b) and at least one colloid-forming polymeric sulfonic acid is provided. A memory storage device is provided. For example, a write once read many time (WORM) memory is known in the art (Non-Patent Document 2). When information is recorded, higher voltages at certain points on the circuit grid of the silicon chip will destroy the polythiophene at those points, resulting in “zero” bit data. The polythiophene at the non-contact point remains conductive and becomes “1” bit data.

  In another embodiment, the novel aqueous dispersion comprising at least one polythiophene having formula I (a) or formula I (b) and at least one colloid-forming polymeric acid is a biosensor, electrochromic, Used to form coatings for antistatic, anticorrosion, solid state capacitor or electromagnetic shielding applications.

  In another embodiment, the novel composition comprises an antistatic coating for plastic tubes and cathode-ray tubes, an electrode material for a solid field capacitor, a metal corrosion protection coating, a printed circuit board, a photodiode, a biosensor, a photodetector. It can be used for through-hole plating of storage batteries, photovoltaic devices and photodiodes. Furthermore, examples of other uses of the novel composition can be found, for example, in (Non-Patent Document 3).

  In another embodiment, a method of making an aqueous dispersion of a polythiophene having formula I (a) or formula I (b) and at least one colloid-forming polymeric acid, comprising: A method is provided for polymerizing a thiophene monomer having Formula II (a) or Formula II (b) in the presence. The polymerization is performed in the presence of water. The resulting reaction mixture can be treated with an ion exchange resin to remove reaction byproducts and adjust the pH of the dispersion. The novel compositions and their uses will now be described in more detail by reference to the following non-limiting examples.

Example 1
This example illustrates the polymerization of (sulfonic acid-propylene-ether-methylene-3,4-dioxyethylene) thiophene in the presence of “Nafion” ®. 25% (w / w) of perfluoroethylene sulfonic acid having an EW of 990 using a procedure similar to that of Example 1 Part 2 of US Pat. w) Producing an aqueous colloidal dispersion. The dispersion was diluted with water to form a 12.5% (w / w) dispersion for polymerization.

  63.87 g (8.06 mmol of “Nafion” ® monomer units) of “Nafion” ® aqueous colloidal dispersion and 234.47 g of deionized water in a 500 mL jacket. Place in a three-necked round bottom flask. The mixture is stirred for 45 minutes before the addition of ferric sulfate and sodium persulfate. Stock solution of ferric sulfate by dissolving 0.0141 g ferric sulfate hydrate (97%, Aldrich catalog number # 30, 771-8) with deionized water to a total weight of 3.6363 g. The first manufacture. Thereafter, 0.96 g (0.0072 mmol) of ferric sulfate solution and 0.85 g (3.57 mmol) of sodium persulfate (Fluka catalog number # 71899) were added to the reaction flask while the mixture was stirred. Put in. The mixture is then stirred for 3 minutes before addition of 0.8618 g (2.928 g mmol) of (sulfonic acid-propylene-ether-methylene-3,4-dioxyethylene) thiophene monomer. The monomer is added to the reaction mixture with stirring. The polymerization proceeds with stirring at about 20 ° C. controlled by the circulating fluid. 8.91 g “Lewatit” ® S100, trade name from Bayer (Pittsburgh, Pa.) For sodium sulfonate of cross-linked polystyrene and tertiary amine / second of cross-linked polystyrene Polymerization by adding 7.70 g of “Lewatit” ® MP62WS, trade name from Bayer (Pittsburgh, Pa.) For tetraamine free base / chloride. Finish in 16 hours. The two resins are first washed separately with deionized water before use until no color is present in the water. Resin treatment proceeds for 5 hours. The resulting slurry is then filtered with suction through Whatman # 54 filter paper.

(Example 2)
This example illustrates the polymerization of (propyl-ether-ethylene-3,4-dioxyethylene) thiophene in the presence of “Nafion” ®. “Nafion” (registered trademark) is the same as in Example 1.

  63.87 g (8.06 mmol of “Nafion” ® monomer units) of “Nafion” ® aqueous colloidal dispersion and 234.47 g of deionized water in a 500 mL jacket. Place in a three-necked round bottom flask. The mixture is stirred for 45 minutes before the addition of ferric sulfate and sodium persulfate. Stock solution of ferric sulfate by dissolving 0.0141 g ferric sulfate hydrate (97%, Aldrich catalog number # 30, 771-8) with deionized water to a total weight of 3.6363 g. The first manufacture. Thereafter, 0.96 g (0.0072 mmol) of ferric sulfate solution and 0.85 g (3.57 mmol) of sodium persulfate (Fluka catalog number # 71899) were added to the reaction flask while the mixture was stirred. Put in. The mixture is then stirred for 3 minutes before addition of 0.6685 g (2.928 g mmol) of (propyl-ether-ethylene-3,4-dioxyethylene) thiophene monomer. The monomer is added to the reaction mixture with stirring. The polymerization proceeds with stirring at about 20 ° C. controlled by the circulating fluid. 8.91 g “Lewatit” ® S100, trade name from Bayer (Pittsburgh, Pa.) For sodium sulfonate of cross-linked polystyrene and tertiary amine / second of cross-linked polystyrene Polymerization by adding 7.70 g of “Lewatit” ® MP62WS, trade name from Bayer (Pittsburgh, Pa.) For tetraamine free base / chloride. Finish in 16 hours. The two resins are first washed separately with deionized water before use until no color is present in the water. Resin treatment proceeds for 5 hours. The resulting slurry is then filtered with suction through Whatman # 54 filter paper.

Example 3
This example shows the ethylene dioxythiophene (“EDT”) monomer and oxidant solution in a reaction mixture containing iron (III) sulfate catalyst, water, “Nafion” ® and HCl co-acid. Both slow infusions are illustrated. The “Nafion” (registered trademark) used is the same as in Example 1.

715 g of 12% solids content aqueous “Nafion” ® dispersion (82 mmol SO ₃ H groups), 1470 g water, 0.5 g (0.98 mmol) in a 2000 mL reaction kettle. Charge iron (III) sulfate (Fe ₂ (SO ₄ ) ₃ ) and 1406 μL of 37% HCl (18.1 mmol). The reaction mixture was stirred at 200 RPM for 15 minutes using an overhead stirrer fitted with a double stage propeller blade and then 7.78 g (32.8) in 60 mL water and 3.17 mL ethylenedioxythiophene (EDT). Mmol) of sodium persulfate (Na ₂ S ₂ O ₈ ) is added. The addition is started from a separate syringe with an addition rate of 0.9 mL / h for Na ₂ S ₂ O ₈ / water and 50 μL / h for EDT with continuous stirring at ₂₀₀ RPM. The addition of EDT is performed by placing the monomer in a syringe connected to a “Teflon” ® tube that is sent directly to the reaction mixture. Place the end of the “Teflon” tube connecting the Na ₂ S ₂ O ₈ / water solution on top of the reaction mixture so that the injection is accompanied by individual drops falling from the end of the tube, the injection gradually To be. Add 170 g of each “Lewatit” ® MP62WS and “Lewatit” Monoplus S100 ion exchange resin and 225 g n-propanol to the reaction mixture and stir it further at 150 RPM for 4 hours. The reaction is stopped 2 hours after the end of the monomer addition. Whatman No. The ion exchange resin is finally filtered from the solution using 54 filter paper. The pH of the dispersion is 4, and the dry film derived from the dispersion has a conductivity of 1.4 × 10 ⁻⁴ S / cm at room temperature.

  Analysis by atomic force microscopy (AFM) of the film resulting from spin-coating the dispersion on the ITO substrate showed that all the fine particles in the film were smaller than 60 nm in height (multiple 50 × 50 μm). scan). By comparison, films spin-coated from dispersions made using a procedure that rapidly adds all of the monomers at once have a large number of particles up to 200 nm in height and up to 500 nm in width.

An organic light emitting diode (OLED) was secondary processed to the following specifications. A 6 × 6 ″ substrate containing a patterned indium tin oxide anode was cleaned in an oxygen plasma (300 W) for 10 minutes. Thereafter, a buffer film about 75 nm thick was spin coated and then on a hot plate. Baked for 10 minutes at 130 ° C. After cooling to room temperature, the plate was placed in air with a film of about 75 nm thick “Lumination Green” 1303 electroluminescent polymer from Dow Chemicals. Spin coated. After the electroluminescent film was baked at 130 ° C. for 40 minutes in a vacuum furnace, the cathode consisting of 4 nm Ba and 500 nm Al was evaporated by heat at a pressure of less than 10 ⁻⁶ torr. Encapsulation of the device was achieved by adhering a glass slide on the back of the device using a UV curable epoxy resin.

The resulting devices (a total of 16 devices with an active surface area of 300 mm ² ) have an efficiency of 19.2 ± 0.5 cd / A at 1000 cd / m ² at room temperature and a rectification ratio of 1000 at ± 5 V. It was. Five devices were stressed at 80 ° C. with a constant current of 16.2 mA (about 900 cd / m ² ). After 1000 hours, the light output decreased on average by 32% or about 600 cd / m ² .

(Example 4)
This example is a slow injection of both EDT monomer and oxidant solution into a reaction mixture containing iron (III) sulfate catalyst, water, “Nafion” ® and H ₂ SO ₄ co-acid. Is illustrated. “Nafion” (registered trademark) is the same as in Example 1.

715 g of 12% solid content aqueous “Nafion” ® (82 mmol SO ₃ H group) dispersion in 2000 mL reaction kettle, 1530 g water, 0.5 g (0.98 mmol) Charge iron (III) sulfate (Fe ₂ (SO ₄ ) ₃ ) and 1011 μL of concentrated H ₂ SO ₄ (18.1 mmol). The reaction mixture was stirred at 276 RPM for 15 minutes using an overhead stirrer fitted with a double stage propeller blade, then 4.2 mL / h and EDT for Na ₂ S ₂ O ₈ / water with continuous stirring at 276 RPM Of 8.84 g (37.1 mmol) of sodium persulfate (Na ₂ S ₂ O ₈ ) in 60 mL of water and 3.17 mL of ethylenedioxythiophene (EDT) using an addition rate of 224 μL / h with respect to Start with a separate syringe. The addition of EDT is performed by placing the monomer in a syringe connected to a “Teflon” ® tube that is sent directly to the reaction mixture. The end of the “Teflon” ® tube connecting the Na ₂ S ₂ O ₈ / water solution was placed over the reaction mixture so that the injection was accompanied by individual drops falling from the end of the tube. 170 g of each “Lewatit” MP62WS and “Lewatit” Monoplus S100 ion exchange resin and 225 g of n-propanol were added to the reaction mixture and the reaction was further stirred by stirring at 130 RPM for 7 hours. Stop 7 hours after the addition of. Whatman No. The ion exchange resin is finally filtered from the dispersion using 54 filter paper. The pH of the dispersion is about 4, and the dry film derived from the dispersion has a conductivity of 2.6 × 10 ⁻⁵ S / cm at room temperature.

An organic light emitting diode (OLED) was secondary processed to the following specifications. A 6 × 6 ″ substrate containing a patterned indium tin oxide anode partially covered with 600 nm thick photoresist for device region definition was cleaned in a UV-ozone furnace for 10 minutes. A film of about 75 nm thickness of the buffer layer from PEDOT / "Nafion" (R) made above is spin coated and then baked on a hot plate for 10 minutes at 130 <0> C. After cooling to room temperature (from a 1% w / v solution in p-xylene) with a film about 75 nm thick of “Lumination Green” 1303 electroluminescent polymer from Dow Chemicals Spin coat the plate in air. After baking the electroluminescent film at 130 ° C. for 40 minutes in a vacuum oven, the cathode consisting of 4 nm Ba and 500 nm Al is evaporated by heat at a pressure of less than 10 ⁻⁶ torr. Encapsulation of the device is achieved by adhering a glass slide on the back side of the device using a UV curable epoxy resin.

The resulting device (active surface area 25 mm ² ) has an efficiency of 20 ± 1 cd / A at 1000 cd / m ² and a rectification ratio of 13000 at ± 5V. Six devices are stressed at 25 ° C. with a constant current of 50 mA (about 8,000 cd / m ² ). In 220 hours, the luminance decreases to half of the initial value.

(Example 5)
This example illustrates the effect of the addition of ethylene glycol on the conductivity of as-synthesized PEDOT / "Nafion" (R).

The aqueous PEDT / “Nafion” ® used for this example was prepared as follows.
H. C. 0.309 ml (2.902 mmol) of “Baytron” -M (3,4-ethylenedioxythiophene) from HC Stark GmbH (Leverkusen, Germany) Was dissolved in 229.12 g of deionized water at 20 ° C. for 1 hour at a rate of 175 RPM in a 500 ml jacketed three neck round bottom flask equipped with a stirrer. Thereafter, 69.52 g (8.0 mmol of “Nafion” (registered trademark) monomer unit) DE1021 (patent applicant; EW: 999 g / acid mole) “Nafion” (registered trademark) was added. Placed in the mixture. As soon as “Nafion” ® was added, 0.84 g (3.538 mmol) of sodium persulfate previously dissolved in 10 g of deionized water was added to the reaction vessel. Thereafter, 0.95 g (7.1 mmol) stock solution of ferric sulfate was added. Stock solution of ferric sulfate by dissolving 0.0141 g ferric sulfate hydrate (97%, Aldrich catalog number # 30, 771-8) with deionized water to a total weight of 3.6363 g. The first manufacture. The polymerization proceeded with stirring at about 20 ° C. controlled by the circulating fluid. The polymerization solution started to turn blue in 13 minutes. 11.03 g “Lewatit” ® S100, trade name from Bayer (Pittsburgh, Pa.) For sodium sulfonate of crosslinked polystyrene and tertiary amine / secondary of crosslinked polystyrene. Polymerization by adding 11.03 g of “Lewatit” ® MP62WS, trade name from Bayer (Pittsburgh, Pa.) For tetraamine free base / chloride. It ended in 14 hours. The two resins were first washed separately with deionized water before use until no color was found in the water. Resin treatment proceeded for about 6 hours. The resulting slurry was then suction filtered through Whatman # 54 filter paper. The slurry passed through the filter paper very quickly. The yield was 268g. The percent solids was about 2.8% (w / w) based on the added polymerization raw material. The pH of the aqueous PEDT / "Nafion" (R) is 4.64 on a 315 pH / lon meter from Corning Company (Corning (New York, USA)). It was determined that

Two drops of the dispersion prepared above were spread on a microscope slide and allowed to dry for 30 minutes at ambient conditions before being placed in a vacuum oven set at 90 ° C. A small amount of flowing nitrogen was constantly fed into the furnace. Once baked, the dried film about 2 μm thick was coated with about 0.4 cm parallel vertical lines with a distance of about 0.15 cm between each of the two parallel lines. The thickness was measured using a "Surface Profiler (Model #" Alpha-Step "500 from Tencor Instrument, San Jose, CA, USA)". The resistance was then measured at ambient temperature by applying a voltage between 1 and -1 volts using a "Keithley" 2420 source meter (Source Meter). The average conductivity of the five samples was 1.1 × 10 ⁻⁵ S / cm. It should be pointed out that the membrane used for the resistance measurement does not redisperse in water.

9.5021 g of an aqueous dispersion containing 0.266 g of solids and 9.2361 g of water are mixed with 0.499 g of ethylene glycol (Across Organics, catalog number 295530010) over 3 hours. Stir. Mixing formed a well-mixed dispersion containing 2.7% (w / w) PEDOT / “Nafion” ® and 5.0% (w / w) ethylene glycol. Two drops of the dispersion prepared above were spread on a microscope slide. The membrane was dried for 50 minutes on a hot plate set at about 50 ° C. at ambient conditions before being placed in a vacuum oven set at 90 ° C. A small amount of flowing nitrogen was constantly fed into the furnace. Once baked, the dried film of about 6 μm thickness was painted with about 0.4 cm parallel vertical lines with a distance of about 0.15 cm between each two parallel lines. The resistance was then measured at ambient temperature by applying a voltage between 1 and -1 volts. The average conductivity of the four samples was 2.9 × 10 ⁻⁴ S / cm. The conductivity is approximately 30 times that of a membrane made from as-synthesized PEDOT / "Nafion" (R).

7.9981 g of an aqueous dispersion containing 0.2239 g of solids and 7.7742 g of water was mixed with 2.0154 g of ethylene glycol (Across Organics, catalog number 295530010) over 3 hours. Stir. Mixing formed a well-mixed dispersion containing 2.2% (w / w) PEDOT / “Nafion” ® and 20.1% (w / w) ethylene glycol. Membrane preparation and resistance are as described for 5% ethylene glycol. Once baked, the dried film about 3 μm thick was coated with about 0.4 cm parallel vertical lines with a distance of about 0.152 cm between each of the two parallel lines. The resistance was then measured at ambient temperature by applying a voltage between 1 and -1 volts. The average conductivity of the four samples was 4.6 × 10 ⁻⁴ S / cm. The conductivity is approximately 46 times that of a membrane made from as-synthesized PEDOT / “Nafion” ®.

(Example 6)
This example illustrates one inkjet application of PEDOT / “Nafion” ® with the addition of ethylene glycol.
One preparation of four large batches (1,700 g) of aqueous PEDOT / "Nafion" (R) dispersion combined for microfluidization for particle size reduction is described below To do. The “Nafion” ® used for the polymerization is the same as Example 1 with an EW of 1050.

  366.1 g (46.13 mmol of “Nafion” ® monomer units) of “Nafion” ® aqueous colloidal dispersion and 1693.7 g of deionized water with 2000 mL jacket Placed in a three-necked round bottom flask. Prior to the addition of ferric sulfate and sodium persulfate, the mixture was stirred for 2 hours at a stirring speed of 425 RPM. 19. Stock solution of ferric sulfate by dissolving 0.1017 g of ferric sulfate hydrate (97%, Aldrich catalog number # 30,771-8) with deionized water to a total weight of 19.4005 g. The first manufactured. The reaction flask was then charged with 4.07 g (0.0413 mmol) of ferric sulfate solution and 4.88 g (40.99 mmol) of sodium persulfate (Fluka catalog number # 71899) while stirring the mixture. I put it in. The mixture was then stirred for 4 minutes, after which 1.790 ml (16.796 mmol) of “Baytron” -M (trade name for 3,4-ethylenedioxythiophene, H. of Leverkusen, Germany). C. Stark (Leverkusen, Germany)) was added to the reaction mixture with stirring. The polymerization proceeded with stirring at about 20 ° C. controlled by the circulating fluid. The polymerization solution started to turn blue in 13 minutes. 44.17 g “Lewatit” ® S100, trade name from Bayer (Pittsburgh, Pa.) For sodium sulfonate of cross-linked polystyrene and tertiary amine / second of cross-linked polystyrene Polymerization by adding 48.80 g of “Lewatit” ® MP62WS, trade name from Bayer (Pittsburgh, Pa.) For tetraamine free base / chloride. It was completed in 7 hours. The two resins were first washed separately with deionized water before use until no color was found in the water. Resin treatment proceeded for 5 hours. The resulting slurry was then suction filtered through Whatman # 54 filter paper. The slurry passed through the filter paper very quickly. The percent solids was about 3.0% (w / w). Combining four batches manufactured in the same manner as described above, "Microfluidizer Processor" M-110Y (Massachusetts, USA) using pressures of 5,000-7,000 psi for 5 passes Microfluidics (Microfluidics (MA, USA)). The diameter of the first pressure chamber and the second pressure chamber is 200 μm (H30Z model).

  Viscosity and surface tension are the two most important physical properties for inkjet printing. Viscosity and surface tension affect drop formation, jet stability, substrate wetting, spreading and smoothing, and drying phenomena. The viscosity of 3% PEDOT / “Nafion” ® is about 1.9 cp at 60 rpm, and the viscosity of 1% is about 0.9 cp at 60 rpm. The resulting printed surface is not very smooth. The viscosity is too low and the surface tension is too high for efficient ink jet printing. Accordingly, ethylene glycol was added as described below. It should improve conductivity as demonstrated in Example 5, increase the viscosity of PEDOT / "Nafion" (R) and reduce surface tension.

  8 ml (density about 1.008 g / ml) of microfluidized aqueous dispersion with 14 ml deionized water and 4.0 ml ethylene glycol (density about 1.113 g / ml, Acros Organics, catalog number 295530010). The composition contains 0.91% (w / w) PEDOT / “Nafion” ®, 16.9% ethylene glycol. After mixing well, the ink was filtered through an HV filter. The viscosity of the ink was measured to be 2.45 cps at 60 rpm.

A “Microfab” (single nozzle system) was used for inkjet printing. A 30 μm chip was back flushed with DI water and sprayed dry with N ₂ . The inkjet head was assembled and stable and clean drops were obtained using 15 volts with a 45 μs dwell time. A full-drilled 1 μm undercut plate (5206) was treated with UV-ozone for 15 minutes, followed by treatment with CF ₄ plasma for 3 minutes. The plate was placed on the printing stage at room temperature. Displays 1, 2, 3, 4 were printed. For display 1, Row 1 to Row 5 are printed at 7 drops / pixel, R 6 to R 10 are printed at 8 drops / pixel, R 16 to R 20 are printed at 9 drops / pixel, and R 21 to R 25 are printed at 10 drops / pixel. did. For display 4, R11-R15 are printed at 11 drops / pixel, R21-R25 are printed at 12 drops / pixel, R26-R30 are printed at 13 drops / pixel, and R31-R35 are printed at 14 drops / pixel. did. The plate was then heated to 40 ° C. and displays 5, 6 and 7 were printed at 8 drops, 10 drops and 12 drops / pixel, respectively. The printed plate was baked at 130 ° C. for 30 minutes under vacuum.

  0.91% PEOT / “Nafion” ® with 16.9% ethylene glycol added is 1% PEDOT / “Nafion” ® aqueous ink (0.9 cps at 60 rpm). ) Higher than that of 2.) (2.45 cps at 60 rpm). 0.91% PEDOT / "Nafion" (R) / EG ink gave better printability than the 1% aqueous "Nafion" (R) aqueous system. Stable and clean drops without incidents were easily obtained at low voltage (15v). The addition of 16.9% ethylene glycol also improved the nozzle stability. A smooth surface was obtained with PEDOT / "Nafion" (R) / EG ink.

(Example 7)
This example illustrates the preparation of an aqueous dispersion of PEDT / “Nafion” ® and the effect of methanol addition on conductivity and particle size.

73.46 g (8.81 mmol) of “Nafion” ® aqueous colloidal dispersion and 224.8 g of deionized water were placed in a 500 mL jacketed three neck round bottom flask. “Nafion” ® DE 1020 (commercially available perfluoroethylene sulfonic acid) was a 11.4 (w / w) aqueous colloidal dispersion with an EW of 951 g / acid equivalent. . The mixture was stirred at 20 ° C. for 30 minutes. 0.496 ml (4.40 mmol) "Baytron" -M (HC Starck, Massachusetts, USA) 3,4-ethylenedioxythiophene Was added to the “Nafion” ® / water mixture and stirred for 15 minutes before the addition of ferric sulfate and sodium persulfate. 1.10 g (4.62 mmol) of sodium persulfate (Fluka catalog number # 71899) is first dissolved in 5 g of deionized water in a glass vial, after which the reaction mixture is stirred into the reaction mixture. Transferred. Stock solution of ferric sulfate by dissolving 0.0141 g ferric sulfate hydrate (97%, Aldrich catalog number # 30, 771-8) with deionized water to a total weight of 3.6363 g. The first manufactured. 1.44 g (0.0108 mmol) of ferric sulfate stock solution was added to the reaction flask immediately after the addition of the ferric sulfate solution. The polymerization proceeded with stirring at about 20 ° C. controlled by the circulating fluid. The polymerization solution started to turn blue in 13 minutes. 9.61 g “Lewatit” ® S100, trade name from Bayer (Pittsburgh, Pa.) For sodium sulfonate of cross-linked polystyrene and tertiary amine / second of cross-linked polystyrene The reaction was performed by adding 9.61 g of “Lewatit” ® MP62WS, trade name from Bayer (Pittsburgh, Pa.) For the free base / chloride of the tetraamine. It ended in 12 hours. The two resins were first washed separately with deionized water before use until no color was found in the water. Resin treatment proceeded for 10 hours. The resulting slurry was then filtered with suction through a Buchner funnel containing two Whatman # 4 filter papers. The slurry passed through the filter paper very quickly. The% solids was about 3.0% (w / w) based on the added polymerization raw material. The pH of the aqueous PEDT / "Nafion" (registered trademark) is 4.95 with a 315 pH / lon meter from Corning Company (Corning, New York, USA). Was determined to be. The conductivity of the as-manufactured dispersion was determined to be 2.6 × 10 ⁻⁶ S / cm using a two probe resistance measurement technique. A small portion of the dispersion was added to 10% (w / w) methanol. The conductivity was determined to be 3.8 × 10 ⁻⁶ S / cm, indicating that the conductivity remains similar with the addition of methanol. However, the effect on particle size counts measured with “Accusizer” (Model 780A, Particle Sizing Systems (Santa Barbara, Calif.), Santa Barbara, Calif.) Is illustrated in Table 1. As remarkable as it is. Table 1 shows the number of particles per ml of dispersion having particle sizes greater than 0.75 μm, 1.51 μm and 2.46 μm, respectively. The data clearly shows that methanol not only stabilizes PEDT / “Nafion” ® particles, but also substantially reduces the number of large particles.

(Example 8)
This example illustrates the effect of the addition of n-propanol on the preparation of PEDT / "Nafion" (R) aqueous dispersion and particle size. The “Nafion” (registered trademark) used is the same as in Example 1.

85.9 g of 12% solids content aqueous “Nafion” ® dispersion (9.8 mmol SO ₃ H groups) in 500 mL reaction kettle, 313 g water, 1.86 g (7. 8 mmol) sodium persulfate (Na ₂ S ₂ O ₈ ) and 0.84 g (0.125 mmol) iron (III) sulfate (Fe ₂ (SO ₄ ) ₃ ). The reaction mixture was stirred for 15 minutes at 180 RPM using a propeller blade and then 0.695 mL (6.5 mmol) of ethylenedioxythiophene (6.5 mmol) using an addition rate of 20 μL / h with continuous stirring at 180 RPM. Add EDT). The addition of EDT is performed by placing the monomer in a syringe connected to a “Teflon” ® tube that is sent directly to the reaction mixture. 25 g of each “Lewatit” MP62WS and “Lewatit” Monoplus S100 ion exchange resin was added to the reaction mixture and stirred for 36 hours at 180 RPM for 36 hours after the monomer addition was complete. Stop. Whatman No. The ion exchange resin is finally filtered from the solution using 54 filter paper. Dilute a portion of the dispersion with n-propanol by 10% w / w. 60 hours later, PEDT / “Nafion” ® particle “Accusizer” (Model 780A, Particle Sizing Systems, Santa Barbara, Calif.) Of the dispersion before and after the addition of n-propanol. The number of particles measured by Sizing Systems (Santa Barbara, CA)) is shown in Table 2 and FIG. The data clearly shows that n-propanol, a low boiling liquid, substantially reduced the number of large PEDT / “Nafion” ® particles.

Example 9
This example illustrates the preparation of an aqueous dispersion of PEDT / “Nafion” ®. The “Nafion” (registered trademark) used is the same as in Example 1.

  63.89 g (8.07 mmol of “Nafion” ® monomer units) of “Nafion” ® (990 EW) aqueous colloidal dispersion (12.5%, w / w) And 234.79 g of deionized water were placed in a 500 mL jacketed three-necked round bottom flask. The mixture was stirred for 45 minutes before the addition of ferric sulfate and sodium persulfate. 3. Ferric sulfate stock solution by dissolving 0.0135 g ferric sulfate hydrate (97%, Aldrich catalog number # 30, 771-8) with deionized water to a total weight of 5095 g. The first manufactured. Then, while stirring the mixture, 0.97 g (0.0072 mmol) of ferric sulfate solution and 0.85 g (3.57 mmol) of sodium persulfate (Fluka catalog number # 71899) were added to the reaction flask. I put it in. Then 0.312 ml (2.928 mmol) “Baytron” -M (trade name for 3,4-ethylenedioxythiophene from Bayer (Pittsburgh, Pa.)) The mixture was stirred for 3 minutes before being added to the reaction mixture with stirring. The polymerization proceeded with stirring at about 20 ° C. controlled by the circulating fluid. The polymerization solution turned a medium dark blue color in 30 minutes. 8.97 g of “Lewatit” ® S100 (trade name from Bayer, Pittsburgh, Pa.) For sodium sulfonate of cross-linked polystyrene and 7.70 g of “Lewatit” ) "(Registered trademark) MP62WS (trade name from Bayer (Pittsburgh, PA) for tertiary amine / quaternary amine free base of cross-linked polystyrene / chloride free base / chloride). It was terminated after 19.6 hours. The two resins were first washed separately with deionized water before use until no color was found in the water. Resin treatment proceeded for 5 hours. The resulting slurry was then suction filtered through Whatman # 54 filter paper. The slurry passed through the filter paper very quickly. The yield was 273.7g. The% solids was about 3.1% (w / w) based on the added polymerization raw material.

(Example 10)
This example illustrates the effect of added co-dispersing liquid on the surface tension of PEDT / "Nafion" (R) dispersion.

  The surface tension of the aqueous PEDT / “Nafion” ® from Example 9 without any co-dispersing liquid was measured by FTA T10 “Tensiometer Model 1000 IUD (KSV Instruments, Finland) Measured and determined to be 73 milliN / meter at 19.5 ° C.

  To determine the effect of the co-dispersing liquid on the surface tension, 25.436 ml of PEDT / “Nafion” ® from Example 1 was replaced with 1.4781 ml of n-propanol (n-PA) and Mixed with 2.051 ml of 1-methoxy-2-propanol (1M2P). It constitutes 87.8 V% PEDT / “Nafion” ®, 5.1 V% n-PA and 7.1 V% 1M2P. The mixture of dispersion and co-dispersing liquid was very mixed with no signs of precipitation. The surface tension of the dispersion with the co-dispersing liquid was determined to be 42.24 mN / m. The lower surface tension of the new dispersion indicates the high wettability and ease of coating of the new dispersion.

(Example 11)
This example illustrates the effect of a co-dispersing liquid on the performance of a light emitting diode.

The light emitting diode characteristics of the aqueous PEDT / “Nafion” ® dispersion prepared in Example 9 and the co-dispersing liquid mix described in Example 10 were tested. A glass / ITO substrate (30 mm × 30 mm) with 100-150 nm thick ITO and 15 mm × 20 mm ITO surface for light emission was cleaned and then treated with oxygen plasma. Aqueous PEDT with co-dispersing liquid / "Nafion" (R) dispersion and aqueous PEDT / "Nafion" (R) dispersion without co-dispersing liquid on ITO / glass substrate Spin coated. The thickness was 75 nm for both with and without dispersible liquid. The PEDT / “Nafion” ® coated ITO / glass substrate was dried in vacuo at 90 ° C. for 30 minutes. The PEDT / "Nafion" (R) layer was then topcoated with an HS670 blue light emitting polymer from Covion Organic Semiconductors GmbH (Frankfurt, Germany). The thickness of the EL layer was about 75 nm. The film thickness was measured with a “TENCOR” 500 surface profiler. The HS670 topcoat structure was then baked in vacuum at 100 ° C. for 10 minutes. Ba and Al layers were deposited on the EL layer under a vacuum of 1 × 10 ⁻⁶ Torr. The final thickness of the Ba layer was 30 mm and the thickness of the Al layer was 4000 mm. Devices made from PEDT / "Nafion" (R) with co-dispersing liquids are based on aqueous PEDT / "Nafion, although both devices have similar voltages (about 4.2 volts). ) "(R) has a higher efficiency (6.0 Cd / A) than a device (4.5 Cd / A) produced without a co-dispersing liquid. The device brightness and voltage as a function of time are shown in FIG. Devices made with new dispersions containing co-dispersing liquids have a longer lifetime at 80 ° C. than devices made from aqueous PEDT / “Nafion” ® alone dispersions (50 hours) ( 100 hours).

  While the invention has been described in detail with reference to certain preferred embodiments, it will be understood that modifications and variations are within the spirit and scope described and claimed.

FIG. 3 illustrates a cross-sectional view of an electronic device including a buffer layer that includes one embodiment of a novel composition. 1 illustrates a cross-sectional view of a thin film field effect transistor including an electrode including a novel composition. 6 illustrates the change in conductivity of a polythiophene / FSA aqueous colloidal dispersion (registered trademark) film due to the ratio of oxidant to monomer in the polymerization reaction. 6 illustrates the change in conductivity of a polythiophene / FSA aqueous colloidal dispersion film with the ratio of FSA to monomer in the polymerization reaction. 2 illustrates the operational lifetime of an OLED device with a green light emitting polymer. Fig. 3 illustrates the operational lifetime of an OLED device with a red light emitting polymer. 2 illustrates the operational lifetime of an OLED device with a blue light emitting polymer. Figure 6 illustrates the effect of pH of the PEDT / PSSA buffer layer on the performance of OLED devices. Figure 6 illustrates the effect of pH of the PEDT / PSSA buffer layer on the performance of OLED devices. Figure 6 illustrates the effect of pH of the PEDT / PSSA buffer layer on the performance of OLED devices. Figure 6 illustrates the effect of pH of the PEDT / PSSA buffer layer on the performance of OLED devices. Figure 3 illustrates the effect of pH of polythiophene / FSA aqueous colloidal dispersion buffer layer on the performance of OLED devices. Figure 3 illustrates the effect of pH of polythiophene / FSA aqueous colloidal dispersion buffer layer on the performance of OLED devices. Figure 3 illustrates the effect of pH of polythiophene / FSA aqueous colloidal dispersion buffer layer on the performance of OLED devices. 6 illustrates the change in ITO thickness when immersed in a polythiophene / FSA aqueous colloidal dispersion or PEDT / PSSA dispersion. 2 illustrates device brightness and voltage as a function of time.

Claims (28)

A composition comprising an aqueous dispersion of at least one polythiophene and at least one colloid-forming polymeric acid, wherein the polythiophene comprises formula I (a) or formula I (b) object.

Wherein R ″ is the same or different at each occurrence, and R ″ is hydrogen, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alcohol, amide sulfonate, provided that at least one R ″ is not hydrogen. Selected from benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, sulfonate and urethane;
m is 2 or 3,
n is at least about 4)

Wherein R ′ ₁ and R ₁ are independently selected from hydrogen and alkyl, or
R ′ ₁ and R ₁ are combined to form an alkylene chain having 1 to 4 carbon atoms optionally substituted with an alkyl group or aromatic group having 1 to 12 carbon atoms, Or form a 1,2-cyclohexylene group,
n is at least about 4)   The composition of claim 1, wherein the colloid-forming polymeric acid comprises polymeric sulfonic acid, polymeric phosphoric acid, polymeric phosphonic acid, polymeric carboxylic acid, polymeric acrylic acid and mixtures thereof. object.   The composition of claim 2, wherein the colloid-forming polymeric acid comprises a fluorinated polymeric sulfonic acid.   The composition according to claim 3, wherein the polymer sulfonic acid is perfluorinated.   Polymer, colloid-forming polymer acid, dye, carbon nanotube, metal nanowire, metal nanoparticle, carbon nanoparticle, carbon fiber, carbon particle, graphite fiber, graphite particle, coating aid, organic conductive ink, organic conductive paste , Inorganic conductive ink, inorganic conductive paste, charge transport material, semiconductive inorganic oxide nanoparticles, insulating inorganic oxide nanoparticles, piezoelectric nanoparticles, pyroelectric nanoparticles, ferroelectric oxide nanoparticles An addition wherein at least one is selected from: a piezoelectric polymer, a pyroelectric polymer, a ferroelectric oxide polymer, a photoconductive oxide nanoparticle, a photoconductive oxide polymer, a dispersant, a crosslinker, and combinations thereof The composition of claim 1 further comprising:   The composition of claim 1 further comprising at least one co-dispersing liquid.   The co-dispersed liquid is selected from ethers, cyclic ethers, alcohols, alcohol ethers, ketones, nitriles, sulfides, sulfoxides, amides, amines, carboxylic acids and combinations thereof. Composition.   The co-dispersing liquid is n-propanol, isopropanol, methanol, butanol, 1-methoxy-2-propanol, dimethylacetamide, n-methylpyrazole, 1,4-dioxane, tetrahydrofuran, tetrahydropyran, 4-methyl-1, 3-dioxane, 4-phenyl-1,3-dioxane, 1,3-dioxolane, 2-methyl-1,3-dioxolane, 1,3-dioxane, 2,5-dimethoxytetrahydrofuran, 2,5-dimethoxy-2 , 5-dihydrofuran, 1-methylpyrrolidine, 1-methyl-2-pyrrolidinone, dimethyl sulfoxide, and combinations thereof, at least one selected from the above-mentioned compositions. A conductive or semiconductive layer deposited from a composition comprising an aqueous dispersion of at least one polythiophene and at least one colloid-forming polymeric acid, wherein the polythiophene is of formula I (a) or formula A conductive layer or a semiconductive layer characterized by having I (b).

Wherein R ″ is the same or different at each occurrence, and R ″ is hydrogen, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alcohol, amide sulfonate, provided that at least one R ″ is not hydrogen. Selected from benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, sulfonate and urethane;
m is 2 or 3,
n is at least about 4)

Wherein R ′ ₁ and R ₁ are independently selected from hydrogen and alkyl, or
R ′ ₁ and R ₁ are combined to form an alkylene chain having 1 to 4 carbon atoms optionally substituted with an alkyl group or aromatic group having 1 to 12 carbon atoms, Or form a 1,2-cyclohexylene group,
n is at least about 4) A buffer layer deposited from a composition comprising an aqueous dispersion of at least one polythiophene and at least one colloid-forming polymeric acid, wherein the polythiophene has formula I (a) or formula I (b) A buffer layer characterized by that.

Wherein R ″ is the same or different at each occurrence, provided that R ″ is hydrogen, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alcohol, benzyl, provided that at least one R ″ is not hydrogen. Selected from carboxylates, ethers, ether carboxylates, ether sulfonates, sulfonates and urethanes;
m is 2 or 3,
n is at least about 4)

Wherein R ′ ₁ and R ₁ are independently selected from hydrogen and alkyl, or
R ′ ₁ and R ₁ are combined to form an alkylene chain having 1 to 4 carbon atoms optionally substituted with an alkyl group or aromatic group having 1 to 12 carbon atoms, Or form a 1,2-cyclohexylene group,
n is at least about 4)   The buffer layer according to claim 10, wherein the aqueous dispersion further comprises a co-dispersing liquid.   The buffer layer according to claim 10, wherein the aqueous dispersion has a pH greater than 3.5. An electronic device comprising at least one layer comprising a composition of at least one polythiophene and at least one colloid-forming polymeric acid, said polythiophene having formula I (a) or formula I (b) An electronic device characterized by

Wherein R ″ is the same or different at each occurrence, and R ″ is hydrogen, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alcohol, amide sulfonate, provided that at least one R ″ is not hydrogen. Selected from benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, sulfonate and urethane;
m is 2 or 3,
n is at least about 4)

Wherein R ′ ₁ and R ₁ are independently selected from hydrogen and alkyl, or
R ′ ₁ and R ₁ are combined to form an alkylene chain having 1 to 4 carbon atoms optionally substituted with an alkyl group or aromatic group having 1 to 12 carbon atoms, Or form a 1,2-cyclohexylene group,
n is at least about 4)   The colloid-forming polymeric acid is selected from polymeric sulfonic acid, polymeric phosphoric acid, polymeric phosphonic acid, polymeric acrylic acid, polymeric carboxylic acid and mixtures thereof. Devices.   The polythiophene comprises poly [(sulfonic acid-propylene-ether-methylene-3,4-dioxyethylene) thiophene] and poly [(propyl-ether-ethylene-3,4-dioxyethylene) thiophene], the colloid 9. The device of claim 8, wherein the forming acid comprises a fluorinated polymeric sulfonic acid.   A thin film field effect transistor comprising at least one electrode comprising the composition of claim 1.   The thin film field effect transistor according to claim 16, wherein the composition further comprises metal nanowires, metal nanoparticles or carbon nanotubes, carbon nanoparticles or a mixture thereof.   The device is a light sensor, light switch, light emitting diode, light emitting diode display, photodetector, phototransistor, photoconductor, light tube, infrared detector, diode laser, electrochromic device, electromagnetic shielding device, solid electrolytic capacitor, energy 14. Device according to claim 13, characterized in that it is selected from storage devices, field effect resistance devices, memory storage devices, biosensors, photoconductive cells, photovoltaic devices, solar cells and diodes. A method for producing an aqueous dispersion of at least one polythiophene, said method comprising at least one thiophene in the presence of at least one colloid-forming polymeric acid, one oxidant and one catalyst. Polymerizing the monomer, wherein the thiophene monomer has formula II (a) or formula II (b).

Wherein R ″ is the same or different at each occurrence, and R ″ is hydrogen, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alcohol, amide sulfonate, provided that at least one R ″ is not hydrogen. Selected from benzyl, carboxylate, ether, ether carboxylate, ether sulfonate and urethane;
m is 2 or 3,
R ′ ₁ and R ₁ are independently selected from hydrogen and alkyl, or
R ′ ₁ and R ₁ are combined to form an alkylene chain having 1 to 4 carbon atoms optionally substituted with an alkyl group or aromatic group having 1 to 12 carbon atoms, Or a 1,2-cyclohexylene group)   The method of claim 19, wherein the colloid-forming polymeric acid comprises perfluoroethylene sulfonic acid.   20. The method of claim 19, further comprising the step of adding at least one material selected from co-dispersing liquids, co-acids or mixtures thereof.   20. At least one thiophene monomer is added to a reaction mixture comprising at least one colloid-forming polymeric acid, at least one catalyst and water using a controlled rate of addition. The method described.   23. The method of claim 22, wherein the controlled addition rate is about 1-1000 [mu] L monomer / hour for every about 100-500 grams of the reaction mixture.   20. The method of claim 19, wherein the monomer added to the reaction mixture is added separately and simultaneously with an oxidizing agent.   20. The method of claim 19, wherein after polymerization, the polythiophene dispersion is further contacted with at least one ion exchange resin.   The method according to claim 19, wherein a co-dispersing liquid is added after the polymerization.   27. The co-dispersed liquid is selected from ethers, cyclic ethers, alcohols, alcohol ethers, ketones, nitriles, sulfides, sulfoxides, amides, amines, carboxylic acids and combinations thereof. Method. The co-dispersing liquid is n-propanol, isopropanol, methanol, butanol, 1-methoxy-2-propanol, dimethylacetamide, n-methylpyrazole, 1,4-dioxane, tetrahydrofuran, tetrahydropyran, 4-methyl-1, 3-dioxane, 4-phenyl-1,3-dioxane, 1,3-dioxolane, 2-methyl-1,3-dioxolane, 1,3-dioxane, 2,5-dimethoxytetrahydrofuran, 2,5-dimethoxy-2 27. The method of claim 26, selected from 1,5-dihydrofuran, 1-methylpyrrolidine, 1-methyl-2-pyrrolidinone, dimethyl sulfoxide and combinations thereof.

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