KR100902511B1 - Compositions of conducting polymers, conducting thin film and opto-electronic device employing the same - Google Patents

Abstract

The present invention provides a polymer composition comprising a conductive polymer and an ionomer and an optoelectronic device including the polymer composition.

The conductive polymer composition of the present invention has a low hygroscopicity, a low content of residues decomposed by reaction with electrons, and is prepared by doping an ionomer having a physical crosslinking ability with the conductive polymer to the conductive polymer, thereby preparing the conductive polymer composition. The optoelectronic device included has high efficiency and long life.

Description

Composition of conducting polymers, conducting thin film and opto-electronic device employing the same}

1A to 1D are diagrams illustrating a structure of a general organic electroluminescent device.

2 is a graph showing the efficiency characteristics of the organic EL device manufactured according to Example 1 and Comparative Example 1 of the present invention.

3 is a graph showing the life characteristics of the organic EL device manufactured according to Example 1 and Comparative Example 1 of the present invention.

<Brief description of the major symbols in the drawings>

10 ... first electrode 11 ... hole injection layer

12 ... light emitting layer 13 ... hole suppression layer

14 ... second electrode 15 ... electron transport layer

16. Hole Transport Layer

The present invention relates to a conductive polymer composition and a photovoltaic device including the polymer composition, and more particularly, has a low hygroscopicity, a small content of residues decomposed by reaction with electrons, and a physical crosslinking ability with a conductive polymer. The present invention relates to a photovoltaic device having a high efficiency and a long life using a polymer composition doped with an ionomer in a conductive polymer.

An optoelectronic device is a device that converts light energy into electrical energy in a broad sense, or vice versa, such as an organic electroluminescent device, a solar cell, a transistor, and the like. At present, many studies have been made on the formation of a conductive polymer film for the purpose of increasing the efficiency of the device by smoothly transporting charges, ie holes and electrons, generated in the electrodes of the photoelectric device.

In particular, the organic electroluminescent device is an active light emitting display device using a phenomenon that light is generated while electrons and holes are combined in an organic film when a current flows through a fluorescent or phosphorescent organic compound thin film (hereinafter referred to as an organic film). For the purpose of improving efficiency and lowering the driving voltage, it is common to have a multilayer structure such as a hole injection layer, a light emitting layer, an electron injection layer, etc. using a conductive polymer, instead of using a single light emitting layer as an organic layer.

In particular, PEDOT (poly (3,4-ethylene dioxythiophene))-PSS (poly (4) manufactured by Bayer AG Tiershaft (Bayer AG) and marketed under the trade name Baytron-P Styrenesulfonate)) is widely used in fabricating an organic light emitting device for the purpose of forming a hole injection layer by spin coating on an indium tin oxide (ITO) electrode, and this PEDOT-PSS is a hole injection material. Has the structure of.

As described above, PEDOT / PSS conductive polymer composition obtained by doping a polyacid of poly (4-styrene sulfonate) (PSS) to a conductive polymer of poly (3,4-ethylenedioxythiophene) (PEDOT) In the case of forming a hole injection layer by using, PSS is difficult to use when water is absorbed well and needs water removal, and it is decomposed by reaction with electrons to release substances such as sulfate and the like, and thus, organic organic matter. A film, for example, a light emitting layer, may be diffused. In this way, diffusion of a substance derived from the hole injection layer into the light emitting layer may cause exciton quenching, leading to a decrease in efficiency and lifespan of the organic EL device.

Therefore, in photovoltaic devices such as organic electroluminescent devices, there is a growing need for the development of novel conductive polymer compositions for obtaining satisfactory efficiency and lifetime.

In order to solve the above problems, the first technical problem to be achieved by the present invention is a conductive polymer comprising an ionomer having a low hygroscopicity, a small content of residues decomposed by the reaction with the electron, crosslinking ability with the conductive polymer It is to provide a composition.

It is a second object of the present invention to provide an optoelectronic device comprising a conductive thin film formed from the conductive polymer composition.

The third technical problem to be achieved by the present invention is to provide a photoelectric device having a high efficiency and a long life by including the conductive polymer composition.

In order to achieve the first technical problem,

The present invention is a conductive polymer; And

It provides a conductive polymer composition comprising an ionomer represented by the formula (1).

Where

0 <m ≤ 10,000,000, 0 ≤ n <10,000,000, 0 ≤ a ≤ 20, 0 ≤ b ≤ 20,

A, B, A 'and B' are each independently selected from the group consisting of C, Si, Ge, Sn, and Pb,

R ₁ , R ₂ , R ₃ , R ₄ , R ₁ ', R ₂ ', R ₃ 'and R ₄ ' are each independently hydrogen, halogen, nitro group, substituted or unsubstituted amino group, cyano group, substituted or Unsubstituted C ₁ -C ₃₀ alkyl group, substituted or unsubstituted C ₁ -C ₃₀ heteroalkyl group, substituted or unsubstituted C ₁ -C30 alkoxy group, substituted or unsubstituted C ₁ -C ₃₀ heteroalkoxy group, substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₆ -C ₃₀ arylalkyl group, a substituted or unsubstituted aryloxy group of C ₆ -C _30, a substituted or unsubstituted C ₂ -C ₃₀ heteroaryl groups, substituted or unsubstituted C ₂ -C ₃₀ heteroarylalkyl groups, substituted or unsubstituted C ₂ -C ₃₀ heteroaryloxy groups, substituted or unsubstituted C ₅ -C ₂₀ cycloalkyl groups , substituted or unsubstituted C ₂ -C ₃₀ heterocycloalkyl group, a substituted or unsubstituted C ₁ -C ₃₀ alkyl ester group, a substituted or unsubstituted C ₁ -C ₃₀ heteroalkyl of S. Encircling, is selected from substituted or unsubstituted aryl ester group of the unsubstituted C ₆ -C ₃₀ and, a heteroaryl group consisting of ester group of a substituted or unsubstituted C ₂ -C _30, However, R _1, R _2, R _3, And at least one of R ₄ is an ionic group or includes an ionic group,

X and X 'are each independently a simple bond, O, S, a substituted or unsubstituted C ₁ -C ₃₀ alkylene group, a substituted or unsubstituted C ₁ -C ₃₀ heteroalkylene group, a substituted or unsubstituted C _6- C ₃₀ arylene group, substituted or unsubstituted C ₆ -C ₃₀ arylalkylene group, substituted or unsubstituted C ₂ -C ₃₀ heteroarylene group, substituted or unsubstituted C ₂ -C ₃₀ heteroarylalkylene group A substituted or unsubstituted C ₅ -C ₂₀ cycloalkylene group, a substituted or unsubstituted C ₅ -C ₃₀ heterocycloalkylene group, a substituted or unsubstituted C ₆ -C ₃₀ arylester group, and a substituted or Unsubstituted C ₂ -C ₃₀ heteroaryl ester group.

Provided that when n is 0, at least one of R ₁ , R ₂ , R ₃ , and R ₄ is a hydrophobic functional group containing a halogen element.

In addition, in order to achieve the second technical problem, the present invention provides a conductive thin film formed from the conductive polymer composition.

In addition, in order to achieve the third technical problem, the present invention provides a photovoltaic device comprising a conductive thin film formed from the conductive polymer composition.

Hereinafter, the present invention will be described in detail.

The conductive polymer composition of the present invention has a low hygroscopicity, has a small content of residues decomposed by reaction with electrons, and is prepared by doping an ionomer having a crosslinking ability with a conductive polymer to the conductive polymer, thereby including a photoelectric including the polymer composition. The device is characterized by high efficiency and long life.

In the present invention, the conductive polymer; And

It provides a conductive polymer composition comprising an ionomer represented by the formula (1):

<Formula 1>

Ionomer generally refers to a polymer containing an ionic group, it may be represented by the above formula. Wherein m, n, a, b, R ₁ , R ₂ , R ₃ , R ₄ , R ₁ ', R ₂ ', R ₃ ', R ₄ ' , X and X 'are as defined above.

In the case of PEDOT / PSS, since the ionic group is substituted for all benzene groups substituted in the main chain and does not contain hydrophobic functional groups, it has high affinity for water. In order to reduce such affinity for water, a method of reducing the ratio of ionic groups to the main chain or introducing a hydrophobic functional group having low hygroscopicity into a substituent may be considered. Therefore, when n is 0, since the ionomer of the present invention essentially includes an ionic group in Chemical Formula 1, a hydrophobic functional group including a halogen element is introduced into the ionomer to give lower hygroscopic properties than hydrocarbons and aromatic hydrocarbons. Therefore, in the present invention, at least one or more of the hydrogen of the main chain or side chain of the ionomer is replaced with a hydrophobic functional group containing a halogen element.

Such hydrophobic functional groups include, for example, a C1-C30 halogenated alkyl group containing at least one halogen atom and a halogen element, a halogenated C1-C30 alkoxy group, a halogenated C1-C30 heteroalkyl group, a C1-C30 halogenated alkoxy group, a halogenated C1-30 Heteroalkoxy group, halogenated C6-C30 aryl group, halogenated C6-C30 arylalkyl group, halogenated C6-C30 aryloxy group, halogenated C2-C30 heteroaryl group, halogenated C2-C30 heteroarylalkyl group, halogenated C2-C30 Heteroaryloxy group, halogenated C5-C20 cycloalkyl group, halogenated C2-C30 heterocycloalkyl group, halogenated C1-C30 alkyl ester group, halogenated C1-C30 heteroalkyl ester group, halogenated C6-C30 aryl ester group, and And heteroaryl ester groups of halogenated C 2 -C 30, among which halogen atoms are preferred, and fluorine atoms are most preferred.

 When 0 <n <10,000,000, the ionomer of the present invention has a structure copolymerized with a nonionic monomer having no ionic group, whereby the content of the ionic group in the ionomer is reduced to an appropriate range and consequently decomposed by reaction with electrons. The content of residues can be reduced. In this case, the content of the nonionic comonomer is preferably 1 mol% to 99 mol%, more preferably 1 to 50 mol% with respect to the total monomer content. When the content of the comonomer is less than 1 mol%, the role of the nonionic group may not be sufficiently performed. If the content of the comonomer is greater than 99 mol%, the ionic group may not be small enough to perform the role of doping.

The conductive polymer composition of the present invention preferably contains 100 to 5,000 parts by weight of the ionomer represented by Formula 1 with respect to 100 parts by weight of the conductive polymer, more preferably 200 to 1,700 parts by weight. When the content of the ionomer represented by Chemical Formula 1 is less than 100 parts by weight, doping may not be performed properly and may not be well dispersed in water, and the state of the thin film may be poorly formed. It is not desirable for reasons of great fall.

In addition, the conductive polymer is polyethylene dioxythiophene (PEDOT), polyaniline, polypyrrole, polyacetylene, polyphenylene, polyphenylenevinylene, polythiophene, copolymers or blends formed by selecting two or more thereof In particular, polyethylenedioxythiophene and polyaniline are preferable.

As described above, at least one of R ₁ , R ₂ , R _3, or R ₄ of Formula 1 may be an ionic group, or may include an ionic group. The ionic groups makin composed of pairs of an anion and a cation, an anion group is ^{_{PO 3 2-, SO 3 -,}} COO -, I -, CHOSO 3 -, CH 3 COO - and the like, as the cation is Na ^+, K ⁺ Metal ions such as, Li ⁺ , Mg ⁺² , Zn ⁺² , Al ⁺³ ; Or H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , ^{_{CHO +, C 2 H 5 OH}} +, CH 3 OH +, CH 3 (CH 2) n CHO + -; such as (R is an alkyl group, that is, CH ₃ (CH _{2) n} n is an integer of 0 to 50) There are organic ions.

In addition, in order to further improve the crosslinking ability of the conductive polymer and the ionomer in the present invention, the conductive polymer composition may further include a physical crosslinking agent and / or a chemical crosslinking agent.

The physical crosslinking agent refers to a low molecular or high molecular compound including a hydroxy group (-OH), which physically plays a role of crosslinking between polymer chains without chemical bonding. Specific examples include low molecular compounds of glycerol and butanol, and high molecular compounds such as polyvinyl alcohol and polyethylene glycol. In addition, polyethyleneimine, polyvinylpyrolidone, and the like can also be used.

At this time, the content of the physical crosslinking agent is preferably 0.001 to 50 parts by weight, more preferably 0.1 to 10 parts by weight based on 100 parts by weight of the conductive polymer composition. If the content is less than 0.001 parts by weight, the amount is small and can not play a role of crosslinking, if larger than 50 parts by weight is not preferable for the reason that the thin film morphology of the conductive polymer film is bad.

In addition, the chemical crosslinking agent is a chemical crosslinking agent, and refers to a chemical substance capable of in-situ polymerization and forming an interpenetrating polymer network (IPN). Many silane-based materials are used and specific examples thereof are tetraethyloxysilane (TEOS). In addition, polyaziridine (Polyaziridine), melamine (Melamine), epoxy (Epoxy) based materials may be used.

At this time, the content of the chemical crosslinking agent is preferably 0.001 to 50 parts by weight, more preferably 0.1 to 10 parts by weight based on 100 parts by weight of the conductive polymer composition. If the content is less than 0.001 parts by weight can not play a role of cross-linking properly, if the content is greater than 50 parts by weight significantly reduces the conductivity of the conductive polymer is not preferred.

As a specific example of Chemical Formula 1 in the present invention, a repeating unit represented by the following Chemical Formulas 2 to 8 may be mentioned.

Wherein m is a number from 1 to 10,000,000, x and y are each independently a number from 0 to 10, and M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (where R is an alkyl group, ie CH ₃ (CH ₂ ) _n ⁻ ; n is an integer from 0 to 50).

Wherein m is a number from 1 to 10,000,000.

Wherein m and n are 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000, x and y are each independently a number from 0 to 20, and M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (where R is an alkyl group, ie CH ₃ (CH ₂ ) _n ⁻ ; n is an integer from 0 to 50).

Wherein m and n are 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000, x and y are each independently a number from 0 to 20, and M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (where R is an alkyl group, ie CH ₃ (CH ₂ ) _n ⁻ ; n is an integer from 0 to 50).

Wherein m and n are 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000, z is a number from 0 to 20, and M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (where R is an alkyl group, ie CH ₃ (CH ₂ ) _n ⁻ ; n is an integer from 0 to 50).

Wherein m and n are 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000, x and y are each independently a number from 0 to 20, Y is -COO ^- M ⁺ , -SO ₃ ^- NHSO ₂ CF 3 ⁺ , -PO ₃ ^2- (M ⁺ ) ₂ , M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50) , NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (where R is an alkyl group, ie CH ₃ (CH ₂ ) _n ⁻ ; n is an integer from 0 to 50).

Wherein m and n are 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000, and M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is 0 to Integer of 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (where R is an alkyl group, ie CH ₃ (CH ₂ ) _n ⁻ ; n is an integer from 0 to 50).

Wherein m and n are 0 <m ≦ 10,000,000 and 0 ≦ n <10,000,000.

Wherein m and n are 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000, x is a number from 0 to 20, and M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (where R is an alkyl group, ie CH ₃ (CH ₂ ) _n ⁻ ; n is an integer from 0 to 50).

Wherein m and n are 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000, x and y are each independently a number from 0 to 20, and M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (where R is an alkyl group, ie CH ₃ (CH ₂ ) _n ⁻ ; n is an integer from 0 to 50).

Wherein m and n are 0 ≤ m <10,000,000, 0 <n ≤ 10,000,000, R _f =-(CF ₂ ) _z- (z is an integer from 1 to 50, except 2),-(CF ₂ CF ₂ O) _z CF ₂ CF _2- (z is an integer from 1 to 50),-(CF ₂ CF ₂ CF ₂ O) _z CF ₂ CF _2- (z is an integer from 1 to 50), M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (where R is an alkyl group, ie CH ₃ (CH ₂ ) _n ⁻ ; n is an integer from 0 to 50).

The above formula, m and n are 0 ≤ m <10,000,000, 0 < n ≤ 10,000,000 and, x and y are each independently a number of 0 to 20, Y are, each _{^{independently, -SO 3 - M +, -COO}} - M ⁺ , -SO ₃ ^- NHSO ₂ CF 3 ⁺ , -PO ₃ ^2- (M ⁺ ) ₂ One selected from, M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (where R is an alkyl group, ie CH ₃ (CH ₂ ) _n ⁻ ; n is an integer from 0 to 50).

Specific examples of the alkyl group which is a substituent used in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl and the like as the linear or branched group. One or more hydrogen atoms included in the halogen atom, hydroxy group, nitro group, cyano group, amino group (-NH ₂ , -NH (R), -N (R ') (R''),R' and R " Are independently an alkyl group having 1 to 10 carbon atoms), an amidino group, a hydrazine, or a hydrazone group.

The heteroalkyl group, which is a substituent used in the present invention, means that at least one carbon atom in the main chain of the alkyl group, preferably 1 to 5 carbon atoms are substituted with a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom, a person atom, etc. The aryl group, which is a substituent used in the present invention, means a carbocycle aromatic system including one or more aromatic rings, and the rings may be attached or fused together by a pendant method. Specific examples of the aryl group include aromatic groups such as phenyl, naphthyl, tetrahydronaphthyl and the like, and one or more hydrogen atoms in the aryl group may be substituted with the same substituents as in the alkyl group.

Heteroaryl group which is a substituent used in the present invention means a ring aromatic system having 5 to 30 ring atoms containing 1, 2 or 3 hetero atoms selected from N, O, P or S, and the remaining ring atoms are C, The rings may be attached or fused together in a pendant manner. At least one hydrogen atom in the heteroaryl group may be substituted with the same substituent as in the alkyl group.

The alkoxy group which is a substituent used in the present invention refers to the radical -O-alkyl, wherein alkyl is as defined above. Specific examples thereof include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, and the like. At least one hydrogen atom of the alkoxy group is an alkyl group. Substituents similar to the above can be substituted.

Heteroalkoxy groups, which are substituents used in the present invention, have essentially the alkoxy meaning that one or more heteroatoms, for example oxygen, sulfur or nitrogen, may be present in the alkyl chain, for example CH ₃ CH ₂ OCH ₂ CH ₂ O—, C ₄ H ₉ OCH ₂ CH ₂ OCH ₂ CH ₂ O—, and CH ₃ O (CH ₂ CH ₂ O) _n H and the like.

The arylalkyl group, which is a substituent used in the present invention, means that some of the hydrogen atoms in the aryl group as defined above are substituted with radicals such as lower alkyl, for example methyl, ethyl, propyl and the like. For example benzyl, phenylethyl and the like. At least one hydrogen atom of the arylalkyl group may be substituted with the same substituent as in the alkyl group.

The heteroarylalkyl group used in the present invention means that some of the hydrogen atoms of the heteroaryl group are substituted with lower alkyl groups, and the definition of heteroaryl in the heteroarylalkyl group is as described above. At least one hydrogen atom of the heteroarylalkyl group may be substituted with the same substituent as in the alkyl group.

The aryloxy group used in the present invention refers to the radical -O-aryl, wherein aryl is as defined above. Specific examples include phenoxy, naphthoxy, anthracenyloxy, phenanthrenyloxy, fluorenyloxy, indenyloxy, and the like, and at least one hydrogen atom in the aryloxy group may be substituted with the same substituent as in the alkyl group. Do.

The heteroaryloxy group used in the present invention refers to the radical —O-heteroaryl, wherein heteroaryl is as defined above.

Specific examples of the heteroaryloxy group used in the present invention include benzyloxy, phenylethyloxy and the like, and at least one hydrogen atom in the heteroaryloxy group may be substituted with the same substituent as in the alkyl group.

Cycloalkyl group used in the present invention means a monovalent monocyclic system having 5 to 30 carbon atoms. At least one hydrogen atom in the cycloalkyl group may be substituted with the same substituent as in the alkyl group.

Heterocycloalkyl group used in the present invention means a monovalent monocyclic system having 5 to 30 ring atoms containing 1, 2 or 3 heteroatoms selected from N, O, P or S, and the remaining ring atoms are C. do. At least one hydrogen atom of the cycloalkyl group may be substituted with the same substituent as in the alkyl group.

The alkyl ester group used in the present invention means a functional group to which an alkyl group and an ester group are bonded, wherein the alkyl group is as defined above.

The heteroalkyl ester group used in the present invention means a functional group to which a heteroalkyl group and an ester group are bonded, and the heteroalkyl group is as defined above.

The aryl ester group used in the present invention means a functional group having an aryl group and an ester group bonded thereto, wherein the aryl group is as defined above.

The heteroaryl ester group used in the present invention means a functional group having a heteroaryl group and an ester group bonded thereto, wherein the heteroaryl group is as defined above.

The amino group used in the present invention means -NH ₂ , -NH (R) or -N (R ') (R "), R' and R" are independently an alkyl group having 1 to 10 carbon atoms.

One or more hydrogen atoms included in the substituents described above may be substituted with halogen atoms, in which fluorine is most preferred.

In the present invention, the conductive polymer composition may further include a second ionomer, in addition to the conductive polymer and the first ionomer, wherein the second ionomer preferentially selects at least one ionomer containing Formula 1, but is represented by Formula 1 Other ionomer forms may be included and each of these ionomers has a different structure.

Examples of the second ionomer include at least one selected from the group consisting of hydrocarbon-based, fluorocarbon-based, and silicon-based polymers having 0 <n <10,000,000 in the repeating unit of Formula 1. One or more selected from ionomers of Formulas 4 to 14 described above can be exemplified.

As another example of the second ionomer, at least one selected from a hydrocarbon-based, fluorocarbon-based, or silicon-based polymer having n = 0 and 0 <m <10,000,000 in the repeating unit of Formula 1 may be exemplified. In the case where the second ionomer is hydrocarbon-based, polystyrene sulfonate (PSS) is preferable. In particular, when the second ionomer is a fluorocarbon type, it is preferable that the second ionomer is a perfluorinated ionomer. As such perfluorinated second ionomer, an ionomer having a repeating unit represented by Chemical Formulas 2 to 3 is particularly preferable.

The second ionomer may be included in the conductive polymer composition in a range of 100 to 5,000 parts by weight, preferably 200 to 1,700, based on 100 parts by weight of the conductive polymer, similar to the first ionomer. If the content of the second ionomer is less than 100 parts by weight, the effect of adding the second ionomer may not be sufficiently obtained. If the content of the second ionomer is more than 5,000 parts, the conductivity may be deteriorated, which is not preferable.

The conductive polymer composition of the present invention may be employed in an optoelectronic device, and specific examples of the optoelectronic device include an organic electroluminescent device, an organic solar cell, an organic transistor, and an organic memory device.

In particular, in the organic electroluminescent device, the conductive polymer composition is used in the charge, that is, the hole or electron injection layer, and serves to enhance the light emission intensity and efficiency of the organic electroluminescent device by injecting holes and electrons into the light emitting polymer in a balanced and efficient manner. do.

In the case of an organic solar cell, a conductive polymer is used as an electrode or an electrode buffer layer for the purpose of increasing quantum efficiency, and in the case of an organic transistor, it is used as an electrode material in a gate and a source-drain electrode.

Hereinafter, an organic electroluminescent device employing the conductive polymer composition of the present invention and a manufacturing method thereof will be described.

1A to 1D are schematic diagrams illustrating a laminated structure of an organic EL device according to exemplary embodiments of the present invention.

In the organic EL device of FIG. 1A, a light emitting layer 12 is stacked on the first electrode 10, and a hole injection layer HIL (or “buffer layer”) including the conductive polymer composition of the present invention is disposed between the electrode and the light emitting layer. 11 is stacked, and a hole suppression layer (HBL) 13 is stacked on the light emitting layer 12, and a second electrode 14 is formed thereon.

The organic electroluminescent device of FIG. 1B has the same stacked structure as that of FIG. 1A except that an electron transport layer (ETL) 15 is formed instead of the hole suppression layer (HBL) 13 formed on the light emitting layer 12. Have

The organic electroluminescent device of FIG. 1C uses a two-layer film in which a hole suppression layer (HBL) 13 and an electron transport layer 15 are sequentially stacked instead of the hole suppression layer (HBL) 13 formed on the light emitting layer 12. Except for that, the laminate structure is the same as in the case of Fig. 1A.

The organic electroluminescent device of FIG. 1D has the same structure as the organic electroluminescent device of FIG. 1C, except that a hole transport layer 16 is further formed between the hole injection layer 11 and the light emitting layer 12. In this case, the hole transport layer 16 plays a role of suppressing impurity penetration from the hole injection layer 11 into the light emitting layer 12.

The organic EL device having the laminated structure of FIGS. 1A to 1D described above can be formed by a conventional manufacturing method, and the manufacturing method is not particularly limited.

Hereinafter, the manufacturing method of the organic EL device according to the preferred embodiment of the present invention will be described.

First, a patterned first electrode 10 is formed on a substrate (not shown). Here, the substrate is a substrate used in a conventional organic electroluminescent device, preferably a glass substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling and waterproof. And the thickness of the substrate is preferably 0.3 to 1.1 mm.

The material for forming the first electrode 10 is not particularly limited. If the first electrode is a cathode, the anode is made of a conductive metal or an oxide thereof that facilitates hole injection. As a specific example, indium tin oxide (ITO), indium zinc oxide (IZO), and nickel (Ni) , Platinum (Pt), gold (Au), iridium (Ir) and the like.

After cleaning the substrate on which the first electrode 10 is formed, UV ozone treatment is performed. At this time, an organic solvent such as isopropanol (IPA) or acetone is used as the washing method.

The hole injection layer 11 including the conductive polymer composition of the present invention is formed on the first electrode 10 of the cleaned substrate. When the hole injection layer 11 is formed as described above, the contact resistance between the first electrode 10 and the light emitting layer 12 is reduced, and the hole transport ability of the first electrode 10 with respect to the light emitting layer 12 is improved. The driving voltage and lifetime characteristics of the device can be improved overall.

The hole injection layer 11 is formed by spin coating the hole injection layer forming composition prepared by dissolving the conductive polymer composition of the present invention in a solvent on the first electrode 10 and then drying it. Herein, the composition for forming a hole injection layer is diluted to 0.5 to 10% by weight using water or alcohol as a solvent by mixing a weight ratio of the conductive polymer composition of the present invention in a weight ratio of 1: 1 to 1:30. Use it.

In this case, any solvent can be used as long as it can dissolve the conductive polymer composition. Specific examples thereof include water, alcohol, dimethylformamide (DMF), toluene, xylene, chlorobenzene, and the like.

The hole injection layer 11 may have a thickness of 5 nm to 100 nm, preferably 20 nm to 70 nm. Among these, a thickness of 50 nm can be used. When the thickness of the hole injection layer is less than 5 nm, there is a problem that hole injection is not properly performed because it is too thin. When the thickness of the hole injection layer exceeds 100 nm, light transmittance may be reduced.

The emission layer 12 is formed on the hole injection layer 11. The material constituting the light emitting layer is not particularly limited. More specifically, oxadiazole dimer dyes (Bis-DAPOXP), spiro compounds (Spiro-DPVBi, Spiro-6P), triarylamine compounds, bis (styryl) Amine (bis (styryl) amine) (DPVBi, DSA), Flrpic, CzTT, Anthracene, TPB, PPCP, DST, TPA, OXD-4, BBOT, AZM-Zn, etc. (above blue), Coumarin 6, C545T, Quinacridone, Ir (ppy) _3, etc. (above green), DCM1, DCM2, Eu (thenoyltrifluoroacetone) 3 (Eu (TTA) 3, Butyl-6- (1,1,7,7-tetra) Methyl joloridyl-9-enyl) -4H-pyran) {butyl-6- (1,1,7,7, -tetramethyljulolidyl-9-enyl) -4H-pyran: DCJTB} You can use a light (above red). In addition, the polymer light emitting material, such as phenylene-based, phenylene vinylene-based, thiophene-based, fluorene-based and spiro-fluorene-based polymers It may include an aromatic compound including a polymer and nitrogen, but is not limited thereto.

The light emitting layer 12 has a thickness of 10 nm to 500 nm, preferably 50 nm to 120 nm. Among these, in particular, the thickness of the blue light emitting layer may be 70 nm. If the thickness of the light emitting layer is less than 10nm, the leakage current increases, the efficiency decreases and the lifetime decreases. If the thickness of the light emitting layer exceeds 500nm, the driving voltage rise is high, which is not preferable.

In some cases, a dopant may be further added to the light emitting layer forming composition. At this time, the content of the dopant is variable depending on the light emitting layer forming material, but is generally 30 to 80 parts by weight based on 100 parts by weight of the light emitting layer forming material (total weight of the host and the dopant). If the content of the dopant is out of the above range, the luminescence property of the EL element is lowered, which is not preferable. Specific examples of the dopant include an arylamine, a peryl compound, a pyrrole compound, a hydrazone compound, a carbazole compound, a stilbene compound, a starburst compound, an oxadiazole compound, and the like.

A hole transport layer 16 may be selectively formed between the hole injection layer 11 and the light emitting layer 12.

The material constituting the hole transport layer is not particularly limited, and for example, a material including at least one selected from the group consisting of a compound having a carbazole group and / or an arylamine group, a phthalocyanine compound, and a triphenylene derivative serving as a hole transporting role. It may be made of. More specifically, the hole transport layer is 1,3,5-tricarbazolylbenzene, 4,4'-biscarbazolylbiphenyl, polyvinylcarbazole, m-biscarbazolylphenyl, 4,4'-biscarbazolyl -2,2'-dimethylbiphenyl, 4,4 ', 4 "-tri (N-carbazolyl) triphenylamine, 1,3,5-tri (2-carbazolylphenyl) benzene, 1,3,5 -Tris (2-carbazolyl-5-methoxyphenyl) benzene, bis (4-carbazolylphenyl) silane, N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1 -Biphenyl] -4,4'diamine (TPD), N, N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine (α-NPD), N, N'-diphenyl- N, N'-bis (1-naphthyl)-(1,1'-biphenyl) -4,4'-diamine (NPB), IDE320 (Idemitsu), poly (9,9-dioctylfluorene -co-N- (4-butylphenyl) diphenylamine) (poly (9,9-dioctylfluorene-co-N- (4-butylphenyl) diphenylamine) (TFB) and poly (9,9-dioctylfluorene- co-bis-N, N-phenyl-1,4-phenylenediamine (poly (9,9-dioctylfluorene-co-bis- (4-butylphenyl-bis-N, N-phenyl-1,4-phenylenediamin) ( PFB) at least one of the compounds It may be made of, but is not limited thereto.

The hole transport layer may have a thickness of 1 nm to 100 nm, preferably 5 nm to 50 nm. Among these, those having a thickness of 30 nm or less are preferable. This is because when the thickness of the hole transport layer is less than 1 nm, the thickness of the hole transport layer may be too low, and the driving voltage may increase when the thickness of the hole transport layer exceeds 100 nm.

The hole suppression layer 13 and / or the electron transport layer 15 are formed on the emission layer 12 by using a deposition or spin coating method. Here, the hole suppression layer 13 prevents excitons formed from the light emitting material from moving to the electron transport layer 15 or prevents holes from moving to the electron transport layer 15.

As the material for forming the hole suppression layer 13, a phenanthrolines-based compound (e.g., UDC, BCP), an imidazole-based compound, a triazoles-based compound, an oxadiazoles-based compound (Eg PBD), aluminum complex (UDC) BAlq having the following structural formula is used.

Phenanthroline-containing organic compounds Imidazole-containing organic compounds

Triazole-containing organic compound Oxadiazole-containing compound

BAlq

Examples of the material for forming the electron transport layer 15 include an oxazole compound, an isoxazole compound, a triazole compound, an isothiazole compound, an oxadiazole compound, a thiadiazole compound, and perylene ( perylene) compounds, aluminum complexes such as Alq3 (tris (8-quinolinolato) -aluminum) BAlq, SAlq, Almq3, gallium complexes such as Gaq'2OPiv, Gaq ' 2OAc, 2 (Gaq'2)).

 Perylene-Based Compound

     Alq3 BAlq

    SAlq Almq3

Gaq'2OPiv Gaq'2Oac

2 (Gaq'2)

The thickness of the hole suppression layer is 5 nm to 100 nm, the thickness of the electron transport layer is preferably 5 nm to 100 nm. If the thickness of the hole suppression layer and the thickness of the electron transport layer are outside the above ranges, it is not preferable in terms of electron transport ability or hole suppression ability.

Subsequently, a second electrode 14 is formed on the resultant, and the resultant is encapsulated to complete an organic EL device.

The material for forming the second electrode 14 is not particularly limited, and a metal having a small work function, that is, Li, Cs, Ba, Ca, Ca / Al, LiF / Ca, LiF / Al, BaF ₂ / Ca, It forms using Mg, Ag, Al, these alloys, or these multilayers. The thickness of the second electrode 14 is preferably 50 to 3000 mm 3.

Fabrication of the organic electroluminescent device of the present invention does not require a special device or method, it can be produced according to the manufacturing method of the organic electroluminescent device using a conventional conductive polymer composition.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the following examples are for illustrative purposes only and are not intended to limit the present invention.

Example 1: Composition of PEDOT Conductive Polymer Ionomer

The ionomer of Chemical Formula 14 was purchased from Dow Chemical Co., Ltd., and dissolved in 1.0 wt% in a mixed solvent (water: ethanol = 4: 6). Thereafter, PEDOT was synthesized using a known synthetic method [Greonendaal et al. Advanced Materials, Vol. 12, p481, 2000]. More specifically, H.C., which sells 3,4-ethylenedioxythiophene (EDOT) commercially. Bayck M was purchased from Starck Corporation, and the conductive polymer composition was completed by polymerizing EDOT in a weight ratio of 10% to the solute of Formula 18 in the solution by chemical chemical polymerization (Oxidative Chemical Polymerization).

M = 2 and n = 5-11 with respect to the said formula.

Example 2: Composition of PANI Conductive Polymer Ionomer

The ionomer of Formula 15 was purchased from DuPont Co., Ltd., and dissolved in 1.0 wt% in a mixed solvent (water: ethanol = 4: 6). Then, polyaniline (PANI) purchased from Sigma Aldrich Co., Ltd. was doped with camphor sulfonic acid to obtain a conductive polymer. Subsequently, PANI polymerized with respect to the ionomer of the formula (19) dissolved at 1.0 wt% was mixed in a weight ratio of 10: 2 to complete the desired conductive polymer composition.

M is 1 and n is 5-11.

Example 3: Composition of PEDOT Conductive Polymer Ionomer

1) Ionomer Synthesis

To the compound of formula 16 was synthesized as follows. Polystyrene having a weight average molecular weight of 230,000 (number average molecular weight of 140,000) was purchased from Sigma Aldrich Co., Ltd. Sulfonation of the polystyrene was performed at a temperature of 50 ° C. in 1,2-dichloroethane solvent using acetyl sulfate as a sulfonation agent. The sulfonate polymer was obtained by steam stripping and dried in a vacuum oven at 60 ° C. for 2 days to remove the remaining solvent. The content of sulfonate of the obtained polymer corresponds to 50 mol% of the polystyrene main chain.

Wherein m = 66 and n = 66 and M ⁺ is H ⁺ .

2) Composition Preparation

The ionomer synthesized above was dissolved in water at 1.5 wt%. Thereafter, EDOT was polymerized in the same manner as in Example 1 with respect to the weight of the solute of the ionomer dissolved at 1.5wt%, and mixed in a weight ratio of 15: 2 to complete the desired conductive polymer composition.

Example 4 Fabrication of Organic Electroluminescent Device

Corning 15Ω / cm ² (1200Å) ITO glass substrates are cut into 50mm x 50mm x0.7mm and ultrasonically cleaned for 5 minutes in isopropyl alcohol and pure water, followed by UV and ozone cleaning for 30 minutes. It was.

Spin-coating 2 wt% of the aqueous conductive polymer solution prepared in Example 1 on the substrate to form a hole injection layer having a thickness of 50 nm. A 10 nm thick hole transport layer was formed by spin coating PFB (hole transport material manufactured by Dow Chemical) on the hole injection layer.

A light emitting layer having a thickness of 70 nm was formed of a spirofluorene-based light emitting polymer which is a blue light emitting material on the hole transport layer, and then a BaF ₂ was deposited on the light emitting layer to form an electron injection layer having a thickness of 4 nm. Ca 2.7 nm and Al 250 nm were formed as a second electrode on the electron injection layer to manufacture an organic EL device. At this time, the organic EL device manufactured in Example 4 is referred to as Sample A.

Comparative Example 1

An organic electroluminescent device was manufactured in the same manner as in Example 4, except that Bayer Batron P 4083, an aqueous solution of PEDOT / PSS, was used as the hole injection layer forming material. At this time, the organic EL device manufactured from Comparative Example 1 is referred to as Sample B.

Evaluation Example 1-Efficiency Characteristic Evaluation

The efficiency of Sample A and Sample B was measured using a SpectraScan PR650 spectroradiometer.

Sample A showed an efficiency of 15 cd / A and Sample B showed an efficiency of 10 cd / A. Therefore, the efficiency improvement of 50% is shown.

As a result, it can be seen that the organic electroluminescent device including the hole injection layer formed of the conductive polymer composition of the present invention has excellent luminous efficiency.

Evaluation Example 2-Life Characteristics Evaluation

Lifespan characteristics were evaluated for Sample A and Sample B. The life characteristic evaluation is evaluated by measuring luminance over time using a photodiode, which can be expressed as a time when the initial luminance is reduced by 50%.

Sample A has a lifespan characteristic of about 1000 hours when the luminance of 800 cd / m ² is driven at an initial luminance, and sample B has a lifespan characteristic of about 400 hours. It can be seen that it has about 150% improved life compared to the conventional organic electroluminescent device.

Example 5: Composition of PEDOT Conductive Polymer Ionomer

Ionomers having the structure of Formula 17 (so-called NAFION) and dissolved in a 4.5: 5.5 mixed solvent of water and alcohol (2-propanol) at 5wt% are manufactured by Sigma-Aldrich Co., Ltd. ). Subsequently, the product name Baytron PH (PEDOT and PSS 1: 2.5 weight ratio composition) purchased from HC Starck was purchased and the mixture was mixed so that the total solid content was 1.5wt% in a mixed solvent of water and ethanol. Prepared. By adjusting the ratio of Nafion and Baytron P H dissolved at 5wt% in a ratio of 4: 1, 2: 1, 1: 1, the desired conductive polymer compositions were prepared, respectively.

In said formula, x = 1, y = 5-11, z = 1 is shown.

Example 6 Fabrication of Organic Electroluminescent Device

Corning 15Ω / cm ² (1200Å) ITO glass substrates are cut into 50mm x 50mm x0.7mm and ultrasonically cleaned for 5 minutes in isopropyl alcohol and pure water, followed by UV and ozone cleaning for 30 minutes. It was.

The hole injection layer having a thickness of 50 nm was formed by spin coating 1.5 wt% of an aqueous solution of the three types of conductive polymer compositions prepared in Example 5 on the substrate. A light emitting layer having a thickness of 70 nm was formed of a spirofluorene-based light emitting polymer which is a blue light emitting material on the hole injection layer, and then a BaF ₂ was deposited on the light emitting layer to form an electron injection layer having a thickness of 4 nm. Ca 2.7 nm and Al 250 nm were formed as a second electrode on the electron injection layer to manufacture an organic EL device. At this time, the organic electroluminescent device prepared in Example 6, the weight ratio of Baytron PH and Nafion in the sample of 4: 1 is C, 2: 1 sample is D, 1: 1 sample is called E.

Comparative Example 2

An organic light emitting diode was manufactured according to the same method as Example 6 except for using an aqueous solution of PEDOT / PSS (weight ratio of 1/16) of Batron P 4083, a hole injection layer forming material. At this time, the organic EL device manufactured from Comparative Example 2 is referred to as Sample F.

Comparative Example 3

An organic electroluminescent device was manufactured in the same manner as in Example 6, except that Bayer Batron P H, an aqueous solution of PEDOT / PSS (weight ratio of 1 / 2.5), was used as a hole injection material. At this time, the organic EL device manufactured from Comparative Example 3 is referred to as sample G.

Evaluation Example 3-Efficiency Characteristic Evaluation

The efficiency of the samples C to G was evaluated and shown in FIG. 2, respectively. The efficiency evaluation was measured using a SpectraScan PR650 spectroradiometer.

Sample E showed efficiencies of 8 lm / W and 10.7 cd / A, showing Sample G 3.8 lm / W 7.78 cd / A and Sample F showed 6.8 lm / W and 9.2 cd / A. Therefore, the efficiency improvement of at least 12% over the samples F and G which are commercial hole injection materials.

As a result, it can be seen that the organic electroluminescent device including the hole injection layer formed of the conductive polymer composition of the present invention has excellent luminous efficiency.

Evaluation Example 4-Life Characteristics Evaluation

The life characteristics of the samples C to G were evaluated and shown in FIG. 3, respectively. The life characteristic evaluation is evaluated by measuring luminance over time using a photodiode, which can be expressed as a time when the initial luminance is reduced by 50%.

Sample C has a lifespan characteristic of about 365 hours when the luminance of 800 cd / m ² is driven to the initial luminance, and samples F and G have a lifespan characteristic of about 250 hours, the organic electroluminescence according to the present invention It can be seen that the device has a lifespan of about 46% compared to the conventional organic electroluminescent device.

As described above, the conductive polymer composition of the present invention has a low hygroscopicity, has a small content of residues decomposed by reaction with electrons, and is prepared by doping an ionomer having a crosslinking ability with a conductive polymer to the conductive polymer, The photovoltaic device including the polymer composition has high efficiency and long lifespan.

Claims (19)

Conductive polymers; And A conductive polymer composition comprising a first ionomer represented by Formula 1 below: <Formula 1>

Where 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000, 0 ≤ a ≤ 20, 0 ≤ b ≤ 20, A, B, A 'and B' are each independently selected from the group consisting of C, Si, Ge, Sn, and Pb, R ₁ , R ₂ , R ₃ , R ₄ , R ₁ ', R ₂ ', R ₃ 'and R ₄ ' are each independently hydrogen, halogen, nitro group, substituted or unsubstituted amino group, cyano group, substituted or Unsubstituted C ₁ -C ₃₀ alkyl group, substituted or unsubstituted C ₁ -C ₃₀ heteroalkyl group, substituted or unsubstituted C ₁ -C ₃₀ alkoxy group, substituted or unsubstituted C ₁ -C ₃₀ heteroalkoxy group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₆ -C aryl group, a substituted or unsubstituted aryloxy-substituted C ₆ -C _30, substituted or unsubstituted C _{2 30} - C ₃₀ heteroaryl group, substituted or unsubstituted C ₂ -C ₃₀ heteroarylalkyl group, substituted or unsubstituted C ₂ -C ₃₀ heteroaryloxy group, substituted or unsubstituted C ₅ -C ₂₀ cyclo alkyl group, a substituted or unsubstituted C ₂ -C ₃₀ heterocycloalkyl group, a substituted or unsubstituted C ₁ -C ₃₀ alkyl ester group, a substituted or unsubstituted C ₁ -C ₃₀ heteroalkyl of S. Encircling, is selected from substituted or unsubstituted aryl ester group of the unsubstituted C ₆ -C ₃₀ and, a heteroaryl group consisting of ester group of a substituted or unsubstituted C ₂ -C _30, However, R _1, R _2, R _3, And at least one of R ₄ is an ionic group or includes an ionic group, X and X 'are each independently a simple bond, O, S, a substituted or unsubstituted C ₁ -C ₃₀ alkylene group, a substituted or unsubstituted C ₁ -C ₃₀ heteroalkylene group, a substituted or unsubstituted C _6- C ₃₀ arylene group, substituted or unsubstituted C ₆ -C ₃₀ arylalkylene group, substituted or unsubstituted C ₂ -C ₃₀ heteroarylene group, substituted or unsubstituted C ₂ -C ₃₀ heteroarylalkylene group A substituted or unsubstituted C ₅ -C ₂₀ cycloalkylene group, a substituted or unsubstituted C ₅ -C ₃₀ heterocycloalkylene group, a substituted or unsubstituted C ₆ -C ₃₀ arylester group, and a substituted or Unsubstituted C ₂ -C ₃₀ heteroaryl ester group. Provided that when n is 0, at least one of R ₁ , R ₂ , R ₃ , and R ₄ is a hydrophobic functional group containing a halogen element or includes a hydrophobic functional group. The conductive polymer composition according to claim 1, wherein the first ionomer is 100 to 5,000 parts by weight based on 100 parts by weight of the conductive polymer. The conductive polymer composition of claim 1, wherein the first ionomer comprises a repeating unit selected from the group consisting of Formulas 2 to 13. <Formula 2>

Wherein m is a number from 1 to 10,000,000, x and y are each independently a number from 0 to 10, and M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n- ; n is an integer from 0 to 50); <Formula 3>

Wherein m is a number from 1 to 10,000,000; <Formula 4>

Wherein m and n are 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000, x and y are each independently a number from 0 to 20, and M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n- ; n is an integer from 0 to 50); <Formula 5>

Wherein m and n are 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000, x and y are each independently a number from 0 to 20, and M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n- ; n is an integer from 0 to 50); <Formula 6>

Wherein m and n are 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000, z is a number from 0 to 20, and M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n- ; n is an integer from 0 to 50); <Formula 7>

Wherein m and n are 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000, x and y are each independently a number from 0 to 20, Y is -COO ^- M ⁺ , -SO ₃ ^- NHSO ₂ CF 3 ⁺ , -PO ₃ ^2- (M ⁺ ) ₂ , M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50) , NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n- ; n is an integer from 0 to 50); <Formula 8>

Wherein m and n are 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000, and M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is 0 to Integer of 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n- ; n is an integer from 0 to 50); <Formula 9>

Wherein m and n are 0 <m ≦ 10,000,000, 0 ≦ n <10,000,000; <Formula 10>

Wherein m and n are 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000, x is a number from 0 to 20, and M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n- ; n is an integer from 0 to 50); <Formula 11>

Wherein m and n are 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000, x and y are each independently a number from 0 to 20, and M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n- ; n is an integer from 0 to 50); <Formula 12>

Wherein m and n are 0 ≤ m <10,000,000, 0 <n ≤ 10,000,000, R _f =-(CF ₂ ) _z- (z is an integer from 1 to 50, except 2),-(CF ₂ CF ₂ O) _z CF ₂ CF _2- (z is an integer from 1 to 50),-(CF ₂ CF ₂ CF ₂ O) _z CF ₂ CF _2- (z is an integer from 1 to 50), M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n- ; n is an integer from 0 to 50); <Formula 13>

The above formula, m and n are 0 ≤ m <10,000,000, 0 < n ≤ 10,000,000 and, x and y are each independently a number of 0 to 20, Y are, each _{^{independently, -SO 3 - M +, -COO}} - M ⁺ , -SO ₃ ^- NHSO ₂ CF 3 ⁺ , -PO ₃ ^2- (M ⁺ ) ₂ One selected from, M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n- ; n is an integer from 0 to 50). The conductive polymer composition of claim 1, further comprising at least one second ionomer represented by Formula 1 based on 100 parts by weight of the conductive polymer, wherein each of these ionomers is different from each other. The conductive polymer composition according to claim 4, wherein the second ionomer is a hydrocarbon-based, fluorocarbon-based, or silicon-based polymer having n = 0 and 0 <m <10,000,000 in Chemical Formula 1. The conductive polymer composition according to claim 5, wherein the fluorocarbon-based second ionomer is a perfluorinated fluorocarbon-based ionomer. The conductive polymer composition of claim 5, wherein the fluorocarbon-based second ionomer comprises ionomers represented by the following Chemical Formulas 2 to 13. <Formula 2>

Wherein m is a number from 1 to 10,000,000, x and y are each independently a number from 0 to 10, and M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n- ; n is an integer from 0 to 50); <Formula 3>

Wherein m is a number from 1 to 10,000,000; <Formula 4>

Wherein m and n are 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000, x and y are each independently a number from 0 to 20, and M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n- ; n is an integer from 0 to 50); <Formula 5>

Wherein m and n are 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000, x and y are each independently a number from 0 to 20, and M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n- ; n is an integer from 0 to 50); <Formula 6>

Wherein m and n are 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000, z is a number from 0 to 20, and M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n- ; n is an integer from 0 to 50); <Formula 7>

Wherein m and n are 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000, x and y are each independently a number from 0 to 20, Y is -COO ^- M ⁺ , -SO ₃ ^- NHSO ₂ CF 3 ⁺ , -PO ₃ ^2- (M ⁺ ) ₂ , M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50) , NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n- ; n is an integer from 0 to 50); <Formula 10>

Wherein m and n are 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000, x is a number from 0 to 20, and M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n- ; n is an integer from 0 to 50); <Formula 11>

Wherein m and n are 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000, x and y are each independently a number from 0 to 20, and M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n- ; n is an integer from 0 to 50); <Formula 12>

Wherein m and n are 0 ≤ m <10,000,000, 0 <n ≤ 10,000,000, R _f =-(CF ₂ ) _z- (z is an integer from 1 to 50, except 2),-(CF ₂ CF ₂ O) _z CF ₂ CF _2- (z is an integer from 1 to 50),-(CF ₂ CF ₂ CF ₂ O) _z CF ₂ CF _2- (z is an integer from 1 to 50), M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n- ; n is an integer from 0 to 50); <Formula 13>

The above formula, m and n are 0 ≤ m <10,000,000, 0 < n ≤ 10,000,000 and, x and y are each independently a number of 0 to 20, Y are, each _{^{independently, -SO 3 - M +, -COO}} - M ⁺ , -SO ₃ ^- NHSO ₂ CF 3 ⁺ , -PO ₃ ^2- (M ⁺ ) ₂ One selected from, M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n- ; n is an integer from 0 to 50). The conductive polymer composition according to claim 5, wherein the hydrocarbon-based second ionomer comprises an ionomer of Formula 8 or 9. <Formula 8>

Wherein m and n are 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000, and M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is 0 to Integer of 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n- ; n is an integer from 0 to 50); <Formula 9>

Wherein m and n are 0 <m ≦ 10,000,000, 0 ≦ n <10,000,000; The method of claim 1, wherein the conductive polymer is at least one polymer selected from the group consisting of polyethylene dioxythiophene (PEDOT), polyaniline, polypyrrole, polyacetylene, polyphenylene, polyphenylenevinylene and polythiophene or copolymerization thereof Conductive polymer composition, characterized in that the chain. The method of claim 1, wherein the ionic group is _{^{PO 3 2-, SO 3 -,}} COO -, I -, CH 3 COO - anion selected from the group consisting of a group, and a ^{Na +, K +, Li +} , Mg +2, Zn ^{+ 2} , metal ions such as Al ⁺ ₃ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n- ; n is an integer of 0 to 50) selected from the group consisting of organic ions A conductive polymer composition comprising a paired cationic group. The conductive polymer composition of claim 1, wherein the hydrophobic functional group is a halogen element. The conductive polymer composition of claim 1, wherein the hydrophobic functional group is fluorine. The method of claim 1, further comprising: a physical crosslinker; Chemical crosslinkers; Or a mixture of a physical crosslinking agent and a chemical crosslinking agent. The conductive polymer composition of claim 13, wherein the physical crosslinking agent is a low molecular or high molecular compound containing a hydroxyl group (-OH). The method of claim 13, wherein the physical crosslinking agent is selected from glycerol, butanol, polyvinylalcohol, polyethyleneglycol, polyethyleneimine, polyvinylpyrolidone A conductive polymer composition, characterized in that the compound. The conductive polymer composition of claim 13, wherein the chemical crosslinking agent is a compound selected from tetraethyloxysilane (TEOS), polyaziridine, melamine, and epoxy. A conductive thin film formed by coating from the conductive polymer composition of any one of claims 1 to 16. The photoelectric device comprising the conductive thin film of claim 17. 19. The photoelectric device according to claim 18, wherein the photoelectric device is an organic electroluminescent device, an organic solar cell, an organic transistor, and an organic memory device.

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