KR20140111946A - Copolymer and organic electronic device using the same - Google Patents

Abstract

The present application provides a copolymer and an organic electronic device including the same in an organic material layer. The copolymer includes at least one monomer block. The copolymer includes a group having ionic properties. At least one of the monomer blocks includes a conjugated monomer on a main chain thereof. Moreover, the organic electric device includes at least one organic material layer. One or more organic material layers include the copolymer.

Description

TECHNICAL FIELD [0001] The present invention relates to a copolymer and an organic electronic device using the copolymer.

The present disclosure relates to copolymers and organic electronic devices comprising them.

This specification claims the benefit of Korean Patent Application No. 10-2013-0026051, filed on March 12, 2013, to the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.

An organic electronic device means an element requiring charge exchange between an electrode and an organic material using holes and / or electrons. The organic electronic device can be roughly classified into two types according to the operating principle as described below. First, an exciton is formed in an organic material layer by a photon introduced into an element from an external light source. The exciton is separated into an electron and a hole, and the electrons and holes are transferred to different electrodes to be used as a current source Type electric device. The second type is an electronic device that injects holes and / or electrons into an organic semiconductor that interfaces with an electrode by applying a voltage or current to two or more electrodes, and operates by injected electrons and holes.

Examples of the organic electronic device include an organic light emitting device, an organic solar cell, an organic photoconductor (OPC), an organic transistor, and the like. These devices may be used as a hole injecting or transporting material, an electron injecting or transporting material, need. Hereinafter, the organic solar cell will be mainly described.

Organic solar cells are devices that can convert solar energy directly into electric energy by applying photovoltaic effect. Solar cells can be divided into inorganic solar cells and organic solar cells depending on the material constituting the thin film. A typical solar cell is made of p-n junction by doping crystalline silicon (Si), which is an inorganic semiconductor. Electrons and holes generated by absorption of light are diffused to the p-n junction, accelerated by the electric field, and moved to the electrode. The power conversion efficiency of this process is defined as the ratio of the power given to the external circuit to the solar power entering the solar cell, and is achieved up to 24% when measured under the current standardized virtual solar irradiation conditions. However, since conventional inorganic solar cells have already been limited in economic efficiency and supply / demand of materials, organic semiconductor solar cells, which are easy to process, have various functions and are inexpensive, are seen as long-term alternative energy sources.

Solar cells are important to increase efficiency so that they can output as much electrical energy as possible from solar energy. In order to increase the efficiency of such a solar cell, it is also important to generate as much excitons as possible in the semiconductor, but it is also important to draw out generated charges without loss. One of the causes of loss of charge is that the generated electrons and holes are destroyed by recombination. Various methods have been proposed as methods for transferring generated electrons and holes to electrodes without loss, but most of them require additional processing, which may increase the manufacturing cost.

Korean Unexamined Patent Publication No. 2002-0029142

Adv. Mater. 2007, 19, 1835-1838 Adv. Funct. Mater. 2010, 20, 1977-1983 Adv. Mater. 2011, 23, 2759-2763

It is an object of the present invention to provide a copolymer capable of performing various functions required in an organic electronic device and an organic electronic device including the same.

The present disclosure relates to copolymers comprising at least one monomer block,

Wherein the copolymer comprises a group having ionic properties,

Wherein at least one of the monomer blocks comprises a conjugated monomer in the main chain.

The present invention also relates to an organic electronic device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers comprises the copolymer Wherein the organic electronic device is an organic electronic device.

The copolymer according to one embodiment of the present invention can be used as a material for an organic material layer of an organic electronic device, and an organic electronic device using the same exhibits excellent characteristics in terms of an increase in open circuit voltage and an increase in efficiency.

In particular, the copolymer according to one embodiment of the present invention has a charge, so that a vacuum level shift occurs due to a dipole moment, thereby increasing the open-circuit voltage. In addition, it has high solubility in polar solvents such as water and alcohol due to its charge, and is excellent in coating property.

The copolymer according to one embodiment of the present specification includes a monomer block containing a conjugated monomer, and has high charge mobility, and can exhibit excellent properties in an organic electronic device. In addition, copolymers comprising monomer blocks according to one embodiment of the present disclosure can effectively induce polarization.

1 is a cross-sectional view illustrating the structure of an organic solar cell according to an embodiment of the present invention.
2 is an NMR spectrum of the compound prepared in Experimental Example 1. FIG.
3 is an NMR spectrum of the compound prepared in Experimental Example 2. FIG.
4 is a graph showing Gel Permeation Chromatography (GPC) during and after the reaction of the precursor of Copolymer 1. Fig.

Hereinafter, the present invention will be described in detail.

As used herein, a copolymer comprising at least one monomer block, wherein the copolymer comprises a group having ionic character, and at least one of the monomer blocks comprises a conjugated monomer in the main chain.

The copolymer according to one embodiment of the present disclosure includes a monomer block to effectively induce polarization.

It also contains a group having ionic properties in the block, giving synergy to inducing polarization.

In one embodiment of the present specification, the ionic group is included in the copolymer.

In one embodiment of the present specification, the ionic group is contained in a block including a conjugated monomer.

In one embodiment of the present specification, the ionic group is contained in a monomer block other than the block including the conjugated monomer.

In one embodiment of the present invention, the ionic group is an anionic or cationic group.

In one embodiment of the present specification, the ionic group is derived from the side chain of at least one monomer constituting the copolymer.

In one embodiment of the present disclosure, the ionic properties are derived from the side chains of the conjugated monomers.

In one embodiment of the present invention, the ionic group is included at the end of the side chain of the conjugated monomer.

In another embodiment, the ionic group comprises a Sulfite ion (SO ₃ ^- ) or an ammonium ion.

The copolymer having ionic properties according to one embodiment of the present invention has a vacuum level shift due to a dipole moment, thereby increasing the open-circuit voltage.

In addition, the ionic copolymer has a high solubility in a polar solvent, which is advantageous in that it can be easily coated in the production of an organic electronic device.

In the present specification, the main chain of the conjugated monomer includes any one of the monomers represented by the following formulas.

In the above formula,

a is an integer of 0 to 4,

b is an integer of 0 to 6,

c is an integer of 0 to 8,

d and e are each an integer of 0 to 3,

R ₂ to R ₅ are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted ether group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms, or two adjacent substituents may form a condensed ring,

X ₁ to X ₃ are the same or different and each independently selected from the group consisting of CRR ', NR, O, SiRR', PR, S, GeRR '

Y ₁ to Y ₄ are the same or different from each other and each independently selected from the group consisting of CR, N, SiR, P and GeR,

R and R 'are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or non-substituted ether group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms.

In one embodiment of the present disclosure, the main chain of the conjugated monomer includes substituted or unsubstituted thiophene, substituted or unsubstituted fluorenyl, or substituted or unsubstituted carbazole.

The thiophene, fluorenyl, or carbazole-containing monomers are each a substituted or unsubstituted alkyl group; A substituted or unsubstituted ether group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present invention, the monomer block containing the conjugated monomer in the main chain further comprises a monomer other than the conjugated monomer.

In one embodiment of the present invention, the content of the conjugated monomer in the monomer block including the conjugated monomer in the main chain is from 10 mol% to 100 mol%.

The monomer block comprising 10 mole% to 100 mole% of the conjugated monomer has a higher charge mobility than the copolymer having less than 10 mole% of the conjugated monomer.

In this case, the main chain of the copolymer contains a conjugated monomer, and charge transfer is advantageous, so that the open-circuit voltage of the organic electronic device increases and the efficiency of the organic electronic device increases.

In another embodiment, the monomer block containing the conjugated monomer includes 2 to 1,000 conjugated monomers.

When the number of the conjugated monomers is 1,000 or less, the solubility is appropriate, which is advantageous to the solution process.

In one embodiment of the present disclosure, the conjugated monomer includes a side chain selected from the group consisting of an alkyl group, an ether group, an aryl group, and a heterocyclic group.

In one embodiment of the present disclosure, the conjugated monomer comprises a side chain comprising an alkyl group.

In one embodiment of the present disclosure, the conjugated monomer comprises a side chain comprising an ether group.

In one embodiment of the present invention, the alkyl group, the ether group, the aryl group and the heterocyclic group are each a substituted or unsubstituted alkyl group; A substituted or unsubstituted ether group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In the present specification, when the side chain of the conjugated monomer is an alkyl group, solubility of the conjugated polymer in a solvent is increased, which is advantageous in manufacturing an organic electronic device.

As used herein, the term "main chain of the conjugated monomer" means a specific structure in which the conjugated monomer is linked to the copolymer, i.e., a conjugated monomer contained in the main chain of the copolymer.

In the present specification, the term "side chain of the conjugated monomer" means a substituent that is substituted for the conjugated monomer, i.e., a side chain of the copolymer.

The copolymer according to one embodiment of the present disclosure comprises a block comprising at least one conjugated monomer. At least one of the side chains of the conjugated monomers includes a group having ionic properties. Specifically, it includes a group having an ionic property at the terminal of at least one of the side chains of the conjugated monomer.

In the present specification, the portion of the side chain excluding the ionic end portion serves to electrically and spatially separate the main chain of the conjugated monomer from the ionic end portion. In this case, charge transfer of the main chain of the conjugated monomer is advantageous, and the electrooptic characteristics are not affected.

In one embodiment of the present invention, the conjugated monomer includes a side chain having 2 to 30 carbon atoms.

When the number of carbon atoms in the side chain of the conjugated monomer is 2 to 30, it can be effectively and spatially separated from the side chain terminal having ionic activity to the main chain of the conjugated monomer.

The side chain of the conjugated monomer functions to electrically separate from the side chain terminal having an ionic property with the main chain of the conjugated monomer. When the number of carbon atoms in the side chain of the conjugated monomer is 2 or more, it can be prevented that the electrical and / or optical properties of the main chain are affected by hyperconjugation or conjugation.

In one embodiment of the present invention, the copolymer includes two or more kinds of monomer blocks, and at least one species includes a monomer block including a conjugated monomer.

In one embodiment of the present specification, the copolymer includes two or more kinds of monomer blocks, and further includes a monomer other than the monomer blocks containing the conjugated monomers.

In one embodiment of the present invention, the copolymer comprises two or more kinds of monomer blocks, and all of the monomer blocks are monomer blocks containing conjugated monomers.

In one embodiment of the present invention, the copolymer includes two or more kinds of monomer blocks having ionic properties, and each monomer block has a different ionic property from each other.

In one embodiment of the present invention, the copolymer includes two types of monomer blocks having ionic properties, and each of the monomer blocks has a different ionic property from each other.

In one embodiment of the present invention, the copolymer includes two kinds of ionic monomer blocks, all monomer blocks are monomer blocks containing conjugated monomers, and have ionic properties different from each other.

As described above, if opposite charges are made to be different from each other in the two different blocks, the maximum polarization can be effectively induced.

In one embodiment of the present disclosure, the copolymer comprises styrene in which the main chain is substituted or unsubstituted; Or a substituted or unsubstituted alkylene oxide.

In one embodiment of the present disclosure, the copolymer further comprises a monomer block wherein the main chain is substituted or unsubstituted styrene or a substituted or unsubstituted ethylene oxide.

The styrene or ethylene oxide is a substituted or unsubstituted alkyl group; A substituted or unsubstituted ether group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

Illustrative examples of such substituents are set forth below, but are not limited thereto.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 20. Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl and heptyl.

In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. Specific examples thereof include, but are not limited to, an alkenyl group substituted with an aryl group such as a stilbenyl group or a styrenyl group.

In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specific examples include, but are not limited to, a methoxy group, an ethoxy group, a n-propyloxy group, an iso-propyloxy group, a n-butyloxy group, and a cyclopentyloxy group.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and particularly preferably a cyclopentyl group and a cyclohexyl group.

In the present specification, the halogen group may be fluorine, chlorine, bromine or iodine.

In the present specification, the aryl group may be monocyclic or polycyclic. The number of carbon atoms of the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms. Specific examples of the aryl group include monocyclic aromatic and naphthyl groups such as phenyl group, biphenyl group, triphenyl group, terphenyl group and stilbene group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, tetracenyl group, A cyclic aromatic group such as a fluorenyl group, an acenaphthacenyl group, a triphenylene group, and a fluoranthene group, but is not limited thereto.

In the present specification, a fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.

,

,

,

등이 있다. 다만, 이에 한정되는 것은 아니다. When the fluorenyl group is substituted,

,

,

,

. However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a hetero ring group containing at least one of O, N and S atoms as hetero atoms, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrolyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a triazine group, , A quinolinyl group, an isoquinoline group, an indole group, a carbazole group, a benzoxazole group, a benzimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, (phenanthroline), dibenzofuranyl group, and the like, but are not limited thereto.

In the present specification, the heteroaryl group can be selected from the examples of the above-mentioned heterocyclic group.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the amide group may be mono- or di-substituted by nitrogen of the amide group with hydrogen, a straight-chain, branched-chain or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the ester group may be substituted with a straight-chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms in the ester group. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the amine group is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, a 9- , A diphenylamine group, a phenylnaphthylamine group, a ditolylamine group, a phenyltolylamine group, a triphenylamine group, and the like, but are not limited thereto.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monocyclic diarylamine group, a substituted or unsubstituted polycyclic diarylamine group, or a substituted or unsubstituted monocyclic and polycyclic diaryl Amine group.

In the present specification, the aryl group in the aryloxy group, arylthioxy group, arylsulfoxy group and aralkylamine group is the same as the aforementioned aryl group.

In the present specification, the alkyl group in the alkylthio group, alkylsulfoxy group, alkylamine group, and aralkylamine group is the same as the alkyl group described above.

In the present specification, the heteroaryl group in the heteroarylamine group can be selected from the examples of the above-mentioned heterocyclic group.

In the present specification, the arylene group, the alkenylene group, and the heteroarylene group are each a divalent group of an aryl group, an alkenyl group, and a heteroaryl group. The description of the above-mentioned aryl group and alkenyl group heteroaryl group can be applied, except that these are two groups each.

As used herein, "substituted or unsubstituted" A halogen group; An alkyl group; An alkenyl group; An alkoxy group; A cycloalkyl group; Silyl group; An arylalkenyl group; An aryloxy group; An alkyloxy group; An alkylsulfoxy group; Arylsulfoxy group; Boron group; An alkylamine group; An aralkylamine group; An arylamine group; A heteroaryl group; Carbazole group; An arylamine group; An aryl group; A nitrile group; A nitro group; A heterocyclic group containing at least one of a hydroxyl group and at least one of N, O and S atoms, or has no substituent group.

In one embodiment of the present invention, the copolymer is any one of the following formulas (1-1) to (1-6).

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

Each of a to l is a repetition number and is an integer of 2 to 1,000.

In one embodiment of the present invention, the copolymer represented by the formula (1-1) includes a copolymer represented by the following formula (1-11).

 [Formula 1-11]

In one embodiment of the present invention, the copolymer represented by Formula 1-2 includes a copolymer represented by Formula 1-21.

 [Formula 1-21]

 In one embodiment of the present invention, the copolymer represented by Formula 1-3 includes a copolymer represented by the following Formula 1-31.

[Chemical Formula 1-31]

In one embodiment of the present invention, the copolymer represented by Formula 1-4 includes a copolymer represented by the following Formula 1-41.

[Chemical Formula 1-41]

In one embodiment of the present invention, the copolymer represented by Formula 1-5 includes a copolymer represented by the following Formula 1-51.

[Formula 1-51]

In one embodiment of the present invention, the copolymer represented by Formula 1-6 includes a copolymer represented by the following Formula 1-61.

[Chemical Formula 1-61]

In one embodiment of the present disclosure, the terminal group of the copolymer is selected from the group consisting of hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms.

In one embodiment of the present invention, the terminal group of the copolymer is a heterocyclic group.

In one embodiment of the present invention, the terminal group of the copolymer is an aryl group.

According to one embodiment of the present invention, the number average molecular weight of the copolymer is preferably 500 to 1,000,000 g / mol. Preferably, the number average molecular weight of the copolymer is 10,000 to 100,000.

According to one embodiment of the present disclosure, the copolymer may have a molecular weight distribution of from 1 to 100. Preferably, the copolymer has a molecular weight distribution of from 1 to 3.

The lower the molecular weight distribution and the higher the number average molecular weight, the better the electrical and mechanical properties.

In addition, it is preferable that the number average molecular weight is 1,000,000 or less in order to have a solubility of more than a certain level so that application of the solution coating method is advantageous.

The copolymer can be produced on the basis of the following production example.

The copolymers according to the present disclosure can be prepared by a multistage chemical reaction. The monomers may be prepared through alkylation, Grignard reaction, Suzuki coupling reaction, and Stille coupling reaction, followed by carbon-carbon coupling reaction such as a steel coupling reaction, Lt; / RTI > When the substituent to be introduced is a boronic acid or a boronic ester compound, it can be prepared through a Suzuki coupling reaction. When the substituent to be introduced is a tributyltin compound, But it is not limited thereto.

According to an embodiment of the present invention, an organic electronic device includes a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, And a copolymer of ethylene and propylene.

In one embodiment of the present invention, the organic electronic device is selected from the group consisting of an organic light emitting device, an organic solar cell, and an organic transistor.

In one embodiment of the present invention, the organic electronic device may be an organic light emitting device.

In one embodiment of the present disclosure, an organic light-emitting device includes a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers includes And an organic light emitting device comprising the copolymer.

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

Accordingly, in the embodiment of the present invention, the organic material layer includes a hole injection layer or a hole transport layer containing the copolymer.

In another embodiment, the organic layer includes a light-emitting layer comprising the copolymer.

 In another embodiment, the organic layer includes one electron transporting layer containing the copolymer.

In another embodiment, the organic material layer of the organic light-emitting device includes a hole injection layer or a hole transport layer containing a compound including an arylamino group, a carbazole group, or a benzoxazole group in addition to the organic material layer containing the copolymer .

In one embodiment of the present invention, the organic electronic device may be an organic solar cell.

In one embodiment of the present disclosure, the organic electronic device includes a first electrode, a second electrode, and an organic solar cell including at least one organic compound layer provided between the first electrode and the second electrode and including a photoactive layer. A battery, wherein at least one layer of the organic material layer comprises the copolymer.

In one embodiment of the present disclosure, the organic layer includes a charge generating layer containing the copolymer.

In another embodiment, the organic layer includes a buffer layer comprising the copolymer.

In another embodiment, the buffer layer is provided between the photoactive layer and the first electrode.

In another embodiment, the buffer layer is provided between the photoactive layer and the second electrode.

In another embodiment, the buffer layer is in contact with the photoactive layer.

When the buffer layer including the copolymer is provided between the first electrode or the second electrode and the photoactive layer, the roughness of the first electrode or the second electrode is reduced to help increase the efficiency.

In addition, the organic electronic device including the organic compound layer including the copolymer has a vacuum level shift due to a dipole moment, thereby increasing the open-circuit voltage.

In another embodiment, the organic layer comprises a photoactive layer comprising the copolymer.

The organic solar cell may include a photoactive layer, an electron donor and an electron acceptor, and the photoactive layer and the electron donor may include the copolymer.

In one embodiment of the present invention, when the organic solar cell receives photons from an external light source, electrons and holes are generated between the electron beams and the electron acceptors. The generated holes are transported to the anode through the electron donor layer.

In one embodiment of the present disclosure, the organic solar cell may further include an additional organic layer. The organic solar cell can reduce the number of organic layers by using organic materials having various functions at the same time.

In one embodiment of the present invention, the organic solar cell may be arranged in the order of the anode, the photoactive layer, and the cathode, and may be arranged in the order of the cathode, the photoactive layer, and the anode.

In another embodiment, the organic solar cell may be arranged in the order of an anode, a hole transporting layer, a photoactive layer, an electron transporting layer and a cathode, and may be arranged in the order of a cathode, an electron transporting layer, a photoactive layer, a hole transporting layer, , But is not limited thereto.

In another embodiment, a buffer layer may be provided between the photoactive layer and the hole transporting layer or between the photoactive layer and the electron transporting layer. At this time, a hole injection layer may be further provided between the anode and the hole transport layer. Further, an electron injecting layer may be further provided between the anode and the electron transporting layer.

FIG. 1 illustrates a side view of an organic solar cell according to an embodiment of the present invention. In one embodiment, the organic solar cell includes a substrate 101, a first electrode 102, a buffer layer 103, a photoactive layer 104, and a second electrode 105.

In one embodiment of the present disclosure, the organic electronic device may be an organic transistor.

In one embodiment of the present disclosure, an organic transistor comprising a source, a drain, a gate, and at least one organic layer, wherein at least one of the organic layers comprises the copolymer.

In one embodiment of the present disclosure, the organic layer includes a charge generating layer containing the copolymer.

In another embodiment, the organic transistor may comprise an insulating layer, and the insulating layer may be located on the substrate and the gate.

When the organic electronic device includes a plurality of organic layers, the organic layers may be formed of the same material or another material.

In one embodiment of the present disclosure, the first electrode may be an anode and the second electrode may be a cathode.

In one embodiment of the present disclosure, the second electrode may be an anode and the first electrode may be a cathode.

The substrate may be a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness, but is not limited thereto and is not limited as long as it is a substrate commonly used in organic solar cells. Specifically, glass or polyethylene terphthalate (PEN), polyethylene naphthalate (PEN), polypropylene (PP), polyimide (PI), and triacetyl cellulose (TAC) But is not limited thereto.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer. In addition, the material may be transparent and excellent in conductivity, but is not limited thereto. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), tin oxide (SnO ₂ ), zinc oxide (ZnO) and indium zinc oxide (IZO); ZnO: Al or SNO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.

The negative electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure materials such as Al / Li, Al / BaF ₂ , Al / BaF ₂ / Ba, LiF / Al or LiO ₂ / Al.

The hole transporting layer and / or the electron transporting layer material may be a material for efficiently transferring electrons and holes to the photoactive layer, thereby increasing the probability that the generated charge moves to the electrode. However, the hole transporting layer and / or the electron transporting layer material are not particularly limited. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but the present invention is not limited thereto. The hole transport layer material may be selected from the group consisting of poly (3,4-ethylenediocythiophene) doped with poly (styrenesulfonic acid), N, N'-bis (3-methylphenyl) -N, N'- '-Biphenyl] -4,4'-diamine (TPD).

The electron transporting layer material is an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, aluminum tri-hydroxy-quinolinyl (Alq _3), a 1,3,4-oxadiazole derivative PBD (2- (4-bipheyl) -5-phenyl-1,3,4-oxadiazole ), Quinoxaline derivatives such as TPQ (1,3,4-tris [(3-phenyl-6-trifluoromethyl) qunoxaline-2-yl] benzene) and triazole derivatives.

As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene- , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

The photoactive layer may comprise an electron donor material and an electron acceptor material.

In one embodiment, the electron acceptor material may be a fullerene, a fullerene derivative, a heterocyclic compound, a semiconducting element, a semiconducting compound, or a combination thereof. Specifically, PC ₆₁ BM (phenyl C ₆₁ - butyric acid methyl ester) or PC ₇₁ BM (phenyl C ₇₁ -butyric acid methyl ester).

An organic electronic device according to one embodiment of the present disclosure can be manufactured by materials and methods known in the art, except that the organic layer includes the copolymer.

The organic solar cell of the present invention can be manufactured by sequentially laminating, for example, a first electrode, an organic material layer and a second electrode on a substrate. At this time, they may be coated by a wet method such as gravure printing, offset printing, screen printing, ink jet, spin coating, spray coating and the like, but not limited thereto.

[ Experimental Example  1] 2- Bromo -3- (3,6,9,12- Tetraoxatridecanyl ) Thiophene  (2- bromo -3- (3,6,9,12-tetraoxatridecanyl) thiophene)

3- (3,6,9,12-tetraoxatridecanyl) thiophene (10.0 g, 36.4 mmol) was dissolved in 200 ml of anhydrous THF, The temperature was lowered to 0 占 폚. N-bromosuccinimide (NBS) (6.49 g, 36.4 mmol) dissolved in 50 ml of anhydrous tetrahydrofuran (THF) was slowly added to this solution and stirred at 0 ° C for 12 hours.

The THF was removed under reduced pressure, poured into water and extracted three times with ethyl acetate. The organic layer was washed with a 10% aqueous solution of sodium hydrogencarbonate (NaHCO ₃ aq.) And magnesium sulfate (MgSO ₄ ) was added to remove water, and the solvent was removed under reduced pressure. The remaining yellow liquid was purified using silica gel column chromatography.

2 is an NMR spectrum of the compound prepared in Experimental Example 1. FIG.

[ Experimental Example  2] 2- Bromo -5- Iodo -3- (3,6,9,12- Tetraoxatridecanyl ) Thiophene  (2- bromo -5- iodo -3- (3,6,9,12- tetraoxatridecanyl ) thiophene ) Synthesis of

2-bromo-3- (3,6,9,12-tetraoxatridecanyl) thiophene (7.21 g, 20.4 mmol) was added to a solution of 2-bromo-3- (3,6,9,12-tetraoxatridecanyl) thiophene ) Was dissolved in 200 ml of dichloromethane and the temperature was lowered to 0 < 0 > C. To this solution was added iodine (2.69 g, 10.6 mmol) and iodobenzene diacetate (3.69 g, 10.6 mmol) in this order, and the mixed solution was stirred for 12 hours. To this solution was added an aqueous solution of sodium thiosulfate (Na ₂ S ₂ O ₃ aq.) To terminate the reaction. Dichloromethane was added to the solution for extraction, followed by washing with water. Magnesium sulfate (MgSO ₄ ) was added to remove water, and the solvent was removed under reduced pressure. The remaining yellow liquid was purified using silica gel column chromatography.

FIG. 3 is an NMR spectrum of the compound prepared in Experimental Example 2. FIG.

[ Experimental Example  3] Synthesis of Precursor Copolymer 1

2,5-dibromo-3- (6-bromohexyl) thiophene was prepared by referring to the prior literature. (Sebastien Clement, Akim Tizit, Simon Desbief, Ahmad Mehdi, Julien De Winter, Pascal Gerbaux, J.Mater.Chem. 21, 2011, 2733-2739)

2,5-dibromo-3- (6-bromohexyl) thiophene (0.201 g, 0.50 mmol) was added to a 50-ml one neck flask, , Lithium chloride (21.2 mg, 0.5 mmol) and anhydrous tetrahydrofuran (THF) were placed and stirred for 10 minutes. Then, 2M isopropyl magnesium chloride in THF, 0.250 mL , 0.500 mmol) was added to the solution at room temperature and stirred for 1 hour. (Solution A) To another flask was added 2-bromo-5-iodo-3- (3,6,9,12-tetraoxatridecanyl ) 2-bromo-5-iodo-3- (3,6,9,12-tetraoxatridecanyl) thiophene was dissolved in 2M isopropyl magnesium chloride in THF, 0.750 mL, 1.500 mmol ) And Solution A. (Solution B) Ni (dppp) Cl2 catalyst (10.8 mg, 0.02 mmol) was dispersed in THF (20 ml) and added to Solution A and stirred at room temperature for 1 hour It was. All these processes of the combined solution with a syringe into a previously prepared solution B in solution A was reacted at 50 ℃ for 12 hours, was conducted in a glove box filled with nitrogen.

The reaction was terminated by adding a 5 M aqueous hydrochloric acid solution (HCl aq.) To the reacted solution and extracted three times with chloroform. The organic layer was made of magnesium sulfate (MgSO ₄ ) to remove water, and the solvent was removed under reduced pressure. The solid was filtered out by adding cold hexane to synthesize a brown precursor copolymer 1. (182 mg, 36.4%).

4 is a graph showing the gel permeation chromatography of a homopolymer and a diblock copolymer after the reaction.

[ Experimental Example  4] Synthesis of Copolymer 1

Dissolve the precursor copolymer 1 (100 mg) in 50 ml of THF, lower the temperature to -78 ° C, and add 5 ml of concentrated trimethylamine (5 ml) slowly to the solution. The mixture was warmed to room temperature, stirred for 12 hours, and then 50 ml of methanol was added. After addition of trimethylamine (2 ml), the mixture was stirred at room temperature for 24 hours. After the solvent and the remaining trimethylamine were removed under reduced pressure, acetone was added to precipitate, and the precipitated polymer was dried with a filter.

[ Manufacturing example  One]. Manufacture of organic solar cell -1

P3HT and PC61BM were dissolved in chlorobenzene (CB) at a ratio of 1: 0.7 to prepare a composite solution. At this time, the concentration was adjusted to 4.0 wt%, and the organic solar cell had the structure of ITO / PEDOT: PSS / photoactive layer / Al. The ITO coated glass substrate was ultrasonically cleaned using distilled water, acetone, and 2-propanol, and the ITO surface was ozone-treated for 15 minutes and then spin-coated with PEDOT: PSS (AI4083) Lt; / RTI > On top of this, the P3HT-PC61BM complex solution was filtered with a 0.45 μm PP syringe filter and then spin-coated to form a photoactive layer. Then using a thermal evaporator (evaporator thermal) under a was applied by spin coating to a thickness of 5nm on the photoactive layer is dissolved to 0.1wt% of the copolymer 1 prepared in Experimental Example 4 in methanol, 3x10 ^-8 torr vacuum 100 nm And Al was deposited to a thickness of 10 nm to produce an organic solar cell.

[ Comparative Example  One]. Manufacture of organic solar cell -2

P3HT and PC61BM were dissolved in chlorobenzene (CB) at a ratio of 1: 0.7 to prepare a composite solution. At this time, the concentration was adjusted to 4.0 wt%, and the organic solar cell had the structure of ITO / PEDOT: PSS / photoactive layer / Al. The ITO coated glass substrate was ultrasonically cleaned using distilled water, acetone, and 2-propanol, and the ITO surface was ozone-treated for 15 minutes and then spin-coated with PEDOT: PSS (AI4083) Lt; / RTI > The P3HT-PC61BM composite solution was filtered with a 0.45 μm PP syringe filter and then spin-coated to form a photoactive layer. Using a thermal evaporator under a vacuum of 3 × 10 ^-8 torr, a 100 nm thick To form an organic solar cell.

≪ Test Example 1 >

The photoelectric conversion characteristics of the organic solar cells prepared in Production Examples 1 to 1 were measured under the conditions of 100 mW / cm ² (AM 1.5), and the results are shown in Table 1 below.

The presence or absence of coating of copolymer 1 VOC (V) JSC (mA / cm ² ) FF PCE (%) Production Example 1 O 0.64 10.12 62.3 4.04 Comparative Example 1 X 0.61 9.06 57.7 3.19

In Table 1, the total thickness means the thickness of the active layer in the organic solar cell, Voc means open voltage, Jsc means short-circuit current, FF means fill factor, and PCE means energy conversion efficiency. The open-circuit voltage and the short-circuit current are the X-axis and Y-axis intercepts in the fourth quadrant of the voltage-current density curve, respectively. The higher the two values, the higher the efficiency of the solar cell. The fill factor is the width of the rectangle that can be drawn inside the curve divided by the product of the short-circuit current and the open-circuit voltage. The energy conversion efficiency can be obtained by dividing these three values by the intensity of the irradiated light, and a higher value is preferable.

101 substrate
102 first electrode
103 buffer layer
104 photoactive layer
105 second electrode

Claims (30)

A copolymer comprising at least one monomer block,
Wherein the copolymer comprises a group having ionic properties,
Wherein at least one of the monomer blocks comprises a conjugated monomer in the main chain. The method according to claim 1,
Wherein the ionic group is an anionic or cationic group. The method according to claim 1,
Wherein the ionic group is derived from a side chain of at least one monomer constituting the copolymer. The method according to claim 1,
And the ionic group is derived from the side chain of the conjugated monomer. The method according to claim 1,
And the ionic group is contained in the terminal of the side chain of the conjugated monomer. The method according to claim 1,
Wherein the ionic group comprises a sulfite ion (SO < ₃ > ^- ) or an ammonium ion. The method according to claim 1,
Wherein the main chain of the conjugated monomer comprises any one of monomers represented by the following formula:

In the above formula,
a is an integer of 0 to 4,
b is an integer of 0 to 6,
c is an integer of 0 to 8,
d and e are each an integer of 0 to 3,
R ₂ to R ₅ are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted ether group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms, or two adjacent substituents may form a condensed ring,
X ₁ to X ₃ are the same or different and each independently selected from the group consisting of CRR ', NR, O, SiRR', PR, S, GeRR '
Y ₁ to Y ₄ are the same or different from each other and each independently selected from the group consisting of CR, N, SiR, P and GeR,
R and R 'are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or non-substituted ether group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms. The method according to claim 1,
The main chain of the conjugated monomer may be substituted or unsubstituted thiophene; Substituted or unsubstituted fluorenyl; Or a substituted or unsubstituted carbazole. The method according to claim 1,
Wherein the conjugated monomer comprises a side chain selected from the group consisting of an alkyl group, an ether group, an aryl group and a heterocyclic group. The method according to claim 1,
Wherein the conjugated monomer comprises a side chain comprising an alkyl group. The method according to claim 1,
Wherein the conjugated monomer comprises a side chain having 2 to 30 carbon atoms. The method according to claim 1,
Wherein the content of the conjugated monomers in the monomer block including the conjugated monomers in the main chain is from 10 mol% to 100 mol%. The method according to claim 1,
Wherein the monomer block comprising the conjugated monomer comprises 2 to 1,000 conjugated monomers. The method according to claim 1,
The copolymer includes two types of monomer blocks having ionic properties,
Each of the monomer blocks has a different ionic property from each other. The method according to claim 1,
Wherein the copolymer further comprises a monomer block that is substituted or unsubstituted styrene or a substituted or unsubstituted alkylene oxide group. The method according to claim 1,
Wherein the copolymer comprises any one of the following formulas (1-1) to (1-6):
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

In Formulas 1-1 to 1-6,
a to l are the number of repeating units and are an integer of 2 to 1,000, respectively. The method according to any one of claims 1 to 16,
Wherein the end of the copolymer is an aryl group or a heterocyclic group. The method according to any one of claims 1 to 16,
Wherein the number average molecular weight of the copolymer is 500 to 1,000,000 g / mol. The method according to any one of claims 1 to 16,
Wherein the copolymer has a molecular weight distribution of 1 to 100. An organic electronic device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode, wherein at least one of the organic material layers is provided in any one of claims 1 to 16 ≪ / RTI > wherein the copolymer comprises: < RTI ID = 0.0 > The method of claim 20,
Wherein the organic electronic device is selected from the group consisting of an organic light emitting device, an organic solar cell, and an organic transistor. The method of claim 20,
Wherein the organic electronic device comprises at least one organic layer disposed between a first electrode, a second electrode, and the second electrode, wherein at least one of the organic layers comprises the copolymer And an organic material layer containing an organic material layer. The method of claim 20,
Wherein the organic electronic device includes a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode and including a photoactive layer,
Wherein at least one of the organic material layers comprises the copolymer. 24. The method of claim 23,
Wherein the organic material layer comprises a charge generation layer containing the copolymer. 24. The method of claim 23,
Wherein the organic layer comprises a buffer layer comprising the copolymer. 26. The method of claim 25,
Wherein the buffer layer is provided between the photoactive layer and the first electrode. 26. The method of claim 25,
Wherein the buffer layer is provided between the photoactive layer and the second electrode. 26. The method of claim 25,
Wherein the buffer layer is in contact with the photoactive layer. 26. The method of claim 25,
Wherein the organic layer comprises a photoactive layer comprising the copolymer. The method of claim 20,
The organic electronic device is an organic transistor including a source, a drain, a gate, and one or more organic layers,
Wherein at least one of the organic material layers comprises the copolymer.

Images