KR102130199B1 - Heterocyclic compound and organic electronic device comprising the same - Google Patents

Abstract

The present specification relates to a heterocyclic compound represented by Chemical Formula 1 and an organic electronic device including the same.

Description

A heterocyclic compound and an organic electronic device comprising the same{HETEROCYCLIC COMPOUND AND ORGANIC ELECTRONIC DEVICE COMPRISING THE SAME}

This application claims the benefit of the filing date of Korean Patent Application No. 10-2017-0025487 filed with the Korean Patent Office on February 27, 2017, the entire contents of which are incorporated herein.

The present specification relates to a heterocyclic compound and an organic electronic device including the same.

An organic electronic device means a device that requires charge exchange between an electrode and organic materials using holes and/or electrons. The organic electronic device can be roughly divided into two types according to the operation principle. First, excitons are formed in the organic layer by photons introduced into the device from an external light source, and the excitons are separated into electrons and holes, and the electrons and holes are transferred to different electrodes to be used as a current source (voltage source). It is a form of electric device. The second is an electronic device in which holes and/or electrons are injected into an organic semiconductor that forms an interface with an electrode by applying voltage or current to two or more electrodes, and operated by the injected electrons and holes.

Examples of the organic electronic device include an organic photoelectric device, an organic light emitting device, an organic solar cell, an organic transistor, etc. Hereinafter, mainly an organic photoelectric device will be specifically described, but in the organic electronic devices, holes are injected or transported, An electron injection or transport material, or a light emitting material, works on a similar principle.

The organic photoelectric device is a device that converts light into an electrical signal using a photoelectric effect, and includes a photodiode and a phototransistor, and may be applied to image sensors. The image sensor including the photodiode is getting higher in resolution day by day, and accordingly, the pixel size is getting smaller. In the case of a silicon photodiode mainly used at present, since the size of a pixel decreases and an absorption area decreases, a decrease in sensitivity may occur. Accordingly, organic materials that can replace silicon are being studied.

Since the organic material has a large absorption coefficient and can selectively absorb light in a specific wavelength range according to the molecular structure, it is possible to simultaneously replace a photodiode and a color filter, which is very advantageous for sensitivity improvement and high integration.

Efficiencies via Network of Internal Donor-Acceptor Heterojunctions (G. Yu, J. Gao, J. C. Hummelen, F. Wudl, A. J. Heeger, Science, 270, 1789. (1995))

The present specification provides a heterocyclic compound and an organic electronic device including the same.

According to an exemplary embodiment of the present specification, to provide a heterocyclic compound represented by the formula (1).

[Formula 1]

In Chemical Formula 1,

R1 to R6 and R11 to R16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted thioalkoxy group; A substituted or unsubstituted alkyl thioxy group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or adjacent groups may combine with each other to form a substituted or unsubstituted ring,

Ar1, Ar2, Ar11 and Ar12 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

L1 and L11 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

m1 and m11 are each an integer from 0 to 9,

When m1 and m11 are each integers of 2 or more, structures in the parentheses of 2 or more are the same or different from each other,

G1 is a structure represented by the following formula (A),

[Formula A]

In Chemical Formula A,

X1 to X4 are the same as or different from each other, and each independently -O-, -S-, -C(=O)-, -C(=S)-, -C(=CRR')-, -C(= NR")-, -C(RR')-, or -N(R")-,

R, R'and R" are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group,

Q1 is a substituted or unsubstituted monocyclic or polycyclic aromatic ring,

n1 is 0 or 1,

은 상기 화학식 1의 L1 및 L11에 결합되는 부위를 의미한다.

Means a site that is bound to L1 and L11 in Formula 1 above.

In addition, according to an exemplary embodiment of the present specification, the first electrode; A second electrode provided to face the first electrode; And an organic electronic device including one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the above-described heterocyclic compound.

The heterocyclic compound represented by Formula 1 according to an exemplary embodiment of the present specification includes two indole structures or two indole structures in which an aromatic ring is condensed as an electron donor, thereby effective conjugation. The length of the length) is increased, the unilaterality of the molecule is easily controlled, and the intermolecular stacking is effectively achieved, so the wavelength width of the absorbing light is wide. In addition, N in position 1 and C in position 3 in the structure of two indoles containing N acting as an electron donor or two indole structures in which an aromatic ring is condensed are connected by resonance rather than a single bond. , It is easier to control the interaction between molecules or effective conjugation length than single bond. In addition, in the heterocyclic compound represented by Formula 1, two indole (indole) cores are bonded to the third position of each indole through Formula A, which is a linking group acting as an electron acceptor, and three times of the indole. Since the position has the largest HOMO electron density, when the position 3 of the two indole cores is connected through the formula (A), it is possible to effectively draw the exchange of electrons in the molecule.

In addition, Chemical Formula A, which acts as an electron acceptor, is the third position of the two indole cores, and is located close to the electron donor, without passing through other functional groups such as a phenylene group, and effectively transferring a non-shared electron pair of two indoles to effectively push-pull The system can be achieved.

Therefore, the compound represented by Chemical Formula 1 according to an exemplary embodiment of the specification has the above-described effect, and the organic electronic device including the same has excellent efficiency.

1 is a cross-sectional view showing an organic photoelectric device according to an exemplary embodiment of the present specification.
2 is a diagram showing a FT-NMR graph of Compound 1 according to Preparation Example 1 of the present specification.
3 is a diagram showing a FT-NMR graph of Compound 2 according to Preparation Example 2 of the present specification.
4 is a diagram showing a FT-NMR graph of Compound 3 according to Preparation Example 3 of the present specification.
5 is a diagram showing a FT-NMR graph of Compound 4 according to Preparation Example 4 of the present specification.
6 is a diagram showing a FT-NMR graph of Compound 5 according to Preparation Example 5 of the present specification.
7 is a diagram showing a FT-NMR graph of Compound 6 according to Preparation Example 6 of the present specification.
8 is a diagram showing a FT-NMR graph of Compound 7 according to Preparation Example 7 of the present specification.
9 is a diagram showing a FT-NMR graph of Compound 8 according to Preparation Example 8 of the present specification.
10 is a current density graph according to the voltage in the photocurrent and dark current of the organic photoelectric devices manufactured in Examples 1 and 2 of the present specification.
11 is a graph of current density according to the voltage at the photocurrent of the organic photoelectric devices manufactured in Examples 1 and 2 of the present specification.
12 is a graph showing external quantum efficiency (EQE) according to the wavelength and voltage of the organic photoelectric device manufactured in Example 1 of the present specification.

Hereinafter, the present specification will be described in detail.

The present specification provides a heterocyclic compound represented by Chemical Formula 1 above.

The heterocyclic compound represented by Chemical Formula 1 according to an exemplary embodiment of the present specification includes two indole structures or two indole structures in which an aromatic ring is condensed as an electron donor, and the third position of the indole is Since the HOMO electron density is the largest, the formula A, which acts as an electron acceptor, binds to position 3 of the two indole cores and is located close to the electron donor, so that it does not pass through other functional groups such as a phenylene group, and directly transfers the unshared electron pair of indole. And deliver an effective push-pull system.

In the present specification, when a part “includes” a certain component, it means that the component may further include other components, not to exclude other components, unless otherwise stated.

In this specification, when a member is said to be "on" another member, this includes not only the case where one member is in contact with the other member but also another member between the two members.

Examples of the substituent are described below, but are not limited thereto.

The term "substitution" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where the substituent is substitutable, and when two or more are substituted , 2 or more substituents may be the same or different from each other.

The term "substituted or unsubstituted" in this specification is deuterium; Halogen group; Alkyl groups; Alkenyl group; Alkoxy groups; Ester group; Carbonyl group; Carboxyl group; Hydroxy group; Cycloalkyl group; Silyl group; Aryl alkenyl group; Aryloxy group; Alkyl thioxy group; Alkyl sulfoxy group; Aryl sulfoxyl group; Boron group; Alkylamine groups; Aralkylamine group; Arylamine group; Heterocyclic group; Arylamine group; Aryl group; Nitrile group; Nitro group; Hydroxy group; And one or more substituents selected from the group consisting of heterocyclic groups including at least one of N, O, and S atoms, or having no substituents.

The above substituents may be substituted or unsubstituted with additional substituents.

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

In this 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 nitrogen of the amide group may be 1 or 2 substituted with hydrogen, a straight chain, branched 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 alkyl group may be straight chain or branched chain, and carbon number is not particularly limited, but is preferably 1 to 50. Specific examples are methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl and 5-methylhexyl, and the like, but is not limited to these.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, specifically cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl and cyclooctyl, and the like. Does not.

In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n -Hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy and p-methylbenzyloxy, etc. It is not limited.

In the present specification, the thioalkoxy group means to include S instead of O in the alkoxy group.

In the present specification, the alkenyl group may be straight chain or branched chain, and carbon number is not particularly limited, but is preferably 2 to 40. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, styrenyl group and styrenyl group, and the like, but are not limited thereto.

In the present specification, the silyl group is specifically a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, and a phenylsilyl group. However, it is not limited thereto.

In the present specification, the boron group may be -BR ₁₀₀ R ₁₀₁ , wherein R ₁₀₀ and R ₁₀₁ are the same or different, and each independently hydrogen; heavy hydrogen; halogen; Nitrile group; A substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; A substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; And it may be selected from the group consisting of substituted or unsubstituted monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms.

In the present specification, the phosphine oxide group specifically includes a diphenylphosphine oxide group, a dinaphthylphosphine oxide group, but is not limited thereto.

In the present specification, the aryl group may be a monocyclic aryl group or a polycyclic aryl group, and includes a case in which an alkyl group having 1 to 25 carbon atoms or an alkoxy group having 1 to 25 carbon atoms is substituted. Also, an aryl group in the present specification may mean an aromatic ring.

When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 25 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group and a terphenyl group, but is not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it has 10 to 24 carbon atoms. Specifically, the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group and fluorenyl group, but is not limited thereto.

In the present specification, the fluorenyl group is a structure in which two ring organic compounds are connected through one atom.

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

,

,

및

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

,

,

And

It can be back. However, it is not limited thereto.

In the present specification, the heteroaryl group is a heteroaryl group containing one or more of O, N, and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heteroaryl group include thiophene group, furan group, pyrrol group, imidazole group, thiazole group, oxazole group, oxadiazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, acridil group , Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , Carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isooxazolyl group, thiadiia A zolyl group, a benzothiadiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto.

In the present specification, the heterocyclic group may be monocyclic or polycyclic, aromatic, aliphatic or aromatic and aliphatic condensed ring, and may be selected from examples of the heteroaryl group.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, or a substituted or unsubstituted diarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group containing two or more aryl groups may include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time.

Specific examples of the aryl amine group include phenylamine, naphthylamine, biphenylamine, anthracenylamine, 3-methyl-phenylamine, 4-methyl-naphthylamine, 2-methyl-biphenylamine, and 9-methyl-anthra Senilamine, diphenyl amine group, phenyl naphthyl amine group, ditolyl amine group, phenyl tolyl amine group, carbazole and triphenyl amine group, but are not limited thereto.

In the present specification, the heteroaryl group in the heteroarylamine group may be selected from examples of the heterocyclic group described above.

In the present specification, the aryl group in the aryloxy group, the arylthioxy group, the aryl sulfoxy group, and the aralkylamine group are the same as those of the aryl group described above. Specifically, aryloxy groups include phenoxy, p-toryloxy, m-toryloxy, 3,5-dimethyl-phenoxy, 2,4,6-trimethylphenoxy, p-tert-butylphenoxy, and 3-biphenyl Oxy, 4-biphenyloxy, 1-naphthyloxy, 2-naphthyloxy, 4-methyl-1-naphthyloxy, 5-methyl-2-naphthyloxy, 1-anthryloxy, 2-anthryl Oxy, 9-anthryloxy, 1-phenanthryloxy, 3-phenanthryloxy, 9-phenanthryloxy, and the like, and arylthio groups include phenylthioxy group, 2-methylphenylthioxy group, and 4-tert-butylphenyl Thioxy groups, and aryl sulfoxy groups include benzene sulfoxy group and p-toluene sulfoxyl group, but are not limited thereto.

In the present specification, the alkyl group in the alkyl thioxy group and the alkyl sulfoxy group is the same as the above-described alkyl group. Specifically, the alkyl thioxy group includes a methyl thioxy group, an ethyl thioxy group, a tert-butyl thioxy group, a hexyl thioxy group, an octyl thioxy group, etc., and an alkyl sulfoxy group is methyl sulfoxy group, ethyl sulfoxyl group, propyl sulfoxyl group, and butyl There is a drinking time, but is not limited thereto.

In the present specification, in a substituted or unsubstituted ring formed by bonding adjacent groups to each other, "ring" is a substituted or unsubstituted hydrocarbon ring; Or substituted or unsubstituted heterocyclic ring.

In the present specification, the hydrocarbon ring may be an aromatic, aliphatic or aromatic and aliphatic condensed ring, and may be selected from examples of the cycloalkyl group or aryl group except for the non-monovalent.

In the present specification, the aromatic ring may be monocyclic or polycyclic, and may be selected from examples of the aryl group, except that it is not monovalent.

In the present specification, the heterocycle is a non-carbon atom, and contains one or more heteroatoms. Specifically, the hetero atom may include one or more atoms selected from the group consisting of O, N, Se, and S. The heterocyclic ring may be monocyclic or polycyclic, and may be an aromatic, aliphatic or aromatic and aliphatic condensed ring, and may be selected from examples of the heteroaryl group or heterocyclic group except for non-monovalent.

According to an exemplary embodiment of the present specification, in the general formula 1, Ar1, Ar2, Ar11 and Ar12 are the same as or different from each other, and each independently an alkyl group; An aryl group unsubstituted or substituted with an alkyl group; Or a heteroaryl group unsubstituted or substituted with an alkyl group.

According to an exemplary embodiment of the present specification, in the formula 1, Ar1, Ar2, Ar11 and Ar12 are the same as or different from each other, each independently a methyl group; A phenyl group unsubstituted or substituted with a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or a t-butyl group; Biphenyl group; Or a naphthyl group.

According to one embodiment of the present specification, in Chemical Formula 1, L1 and L11 are the same as or different from each other, and each independently a direct bond; Arylene group; Or a heteroarylene group.

According to one embodiment of the present specification, in Chemical Formula 1, L1 and L11 are the same as or different from each other, and each independently a direct bond; Phenylene group; Or a divalent thiophene group.

According to an exemplary embodiment of the present specification, in the formula A, Q1 is a substituted or unsubstituted benzene ring; A substituted or unsubstituted naphthalene ring; Or a substituted or unsubstituted anthracene ring.

According to an exemplary embodiment of the present specification, in the formula A, Q1 is a benzene ring; Naphthalene ring; Or anthracene ring.

According to an exemplary embodiment of the present specification, the formula A is any one selected from the following structures.

In the above structure,

The definition of X1 to X4 is the same as the formula A,

Y1 to Y22 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted hetero aryl group,

은 상기 화학식 1의 L1 및 L11에 결합되는 부위를 의미한다.

Means a site that is bound to L1 and L11 in Formula 1 above.

According to an exemplary embodiment of the present specification, Y1 to Y22 is hydrogen.

According to the exemplary embodiment of the present specification, in the general formula A, X1 to X4 are the same as or different from each other, and each independently -O- or -C(=O)-.

According to an exemplary embodiment of the present specification, the formula A is represented by the following structure.

According to an exemplary embodiment of the present specification, the compound represented by the formula (1) is any one selected from the following compounds.

According to one embodiment of the present specification, the heterocyclic compound has an absorption edge at 500 nm to 2000 nm, and preferably has an absorption end at 700 nm to 1000 nm.

Since the heterocyclic compound according to the exemplary embodiment of the present specification has an absorption end in the above range, a band gap is reduced, and there is an effect of absorbing light in all regions of visible light.

According to one embodiment of the present specification, the heterocyclic compound exhibits an extinction curve having a half-value width of 50 nm to 500 nm in a film state, preferably an extinction curve having a half-value width of 100 nm to 200 nm.

Since the heterocyclic compound according to the exemplary embodiment of the present specification has a half-value width in the above range, it has an effect of absorbing light in all regions of visible light.

In the present specification, "film state" refers to a state prepared in a film form, not in a solution state, or by mixing the compound represented by Chemical Formula 1 alone or with other components that do not affect half-width, quantum efficiency measurement. do.

In the present specification, the half-value width means the width of the emission peak when half of the maximum height from the maximum emission peak of light emitted from the heterocyclic compound represented by Chemical Formula 1.

According to one embodiment of the present specification, the heterocyclic compound may have a HOMO energy level of -4.0 eV to -6.0 eV, and a band gap of 1.0 eV to 3 eV. By having a HOMO level and an energy band gap in the above range, it can be applied as a p-type organic material layer that effectively absorbs light in the entire wavelength range, and thus can have a high external quantum efficiency (EQE), resulting in photoelectric conversion of organic electronic devices. Efficiency can be improved.

Further, according to an exemplary embodiment of the present specification, the heterocyclic compound may have a HOMO energy level of -5.0 eV to -6.0 eV, and a band gap of 1.2 eV to 2 eV.

According to an exemplary embodiment of the present specification, the first electrode; A second electrode provided to face the first electrode; And an organic electronic device including at least one layer of an organic material provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the heterocyclic compound.

According to an exemplary embodiment of the present specification, the organic electronic device may be an organic transistor.

According to one embodiment of the present specification, an organic transistor including a source, a drain, a gate, and one or more organic material layers, wherein one or more of the organic material layers provides an organic electronic device including the heterocyclic compound.

According to the exemplary embodiment of the present specification, the organic material layer includes a p-type semiconductor layer and an n-type semiconductor layer, and the p-type semiconductor layer includes the heterocyclic compound.

According to an exemplary embodiment of the present specification, the organic electronic device is selected from the group consisting of an organic photoelectric device, an organic transistor, an organic solar cell, and an organic light emitting device.

According to an exemplary embodiment of the present specification, the organic electronic device may be an organic photoelectric device.

According to an exemplary embodiment of the present specification, the first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the heterocyclic compound.

The organic photoelectric device according to the exemplary embodiment of the present specification includes a first electrode, a photoactive layer, and a second electrode. The organic photoelectric device may further include a substrate, a hole transport layer and/or an electron transport layer.

According to the exemplary embodiment of the present specification, the organic photoelectric device may further include an additional organic material layer. The organic photoelectric device may reduce the number of organic material layers by using an organic material having multiple functions simultaneously.

According to an exemplary embodiment of the present specification, the first electrode is an anode, and the second electrode is a cathode. According to another exemplary embodiment, the first electrode is a cathode, and the second electrode is an anode.

According to the exemplary embodiment of the present specification, the organic photoelectric device may be arranged in the order of cathode, photoactive layer and anode, or may be arranged in order of anode, photoactive layer and cathode, but is not limited thereto.

According to another exemplary embodiment, the organic photoelectric device may be arranged in the order of an anode, a hole transport layer, a photoactive layer, an electron transport layer, and a cathode, or may be arranged in the order of a cathode, an electron transport layer, a photoactive layer, a hole transport layer, and an anode. , But is not limited to this.

According to the exemplary embodiment of the present specification, the organic photoelectric device has a normal structure. In the normal structure, a substrate, an anode, an organic material layer including a photoactive layer, and a cathode may be stacked in this order.

According to the exemplary embodiment of the present specification, the organic photoelectric device has an inverted structure. In the inverted structure, a substrate, a cathode, an organic material layer including a photoactive layer, and an anode may be stacked in order.

1 is a view showing an organic photoelectric device 100 according to an exemplary embodiment of the present specification, according to FIG. 1, the organic photoelectric device 100 is the first electrode 10 and / or the second electrode 20 side When light is incident from the photoactive layer 30 absorbs light in the entire wavelength range, excitons may be generated therein. Excitons are separated into holes and electrons in the photoactive layer 30, and the separated holes move toward the anode side, which is one of the first electrode 10 and the second electrode 20, and the separated electrons are separated from the first electrode 10 A current flows through the organic photoelectric device by moving to the cathode side, which is another one of the second electrodes 20.

According to one embodiment of the present specification, the organic photoelectric device has a tandem structure.

According to one embodiment of the present specification, the organic material layer includes a photoactive layer, and the photoactive layer is a bilayer structure including an n-type organic material layer and a p-type organic material layer, and the p-type organic material layer comprises the heterocyclic compound Includes.

According to the exemplary embodiment of the present specification, the p-type organic material layer includes an electron donor material, and the electron donor material includes the heterocyclic compound.

According to the exemplary embodiment of the present specification, the n-type organic material layer includes an electron acceptor material.

According to one embodiment of the present specification, the p-type organic material layer and the n-type organic material layer are deposited or co-deposited at a thickness ratio of 1:99 to 99:1, specifically 1:50 to 50:1, to form the photoactive layer do. The photoactive layer has a bilayer structure.

According to an exemplary embodiment of the present specification, the electron donor material and the electron acceptor material are each deposited or co-deposited at a thickness ratio of 1:99 to 99:1, specifically, a thickness ratio of 1:50 to 50:1, to deposit the photoactive layer. Form. The photoactive layer has a bilayer structure.

According to one embodiment of the present specification, the organic material layer includes a photoactive layer, the photoactive layer includes an electron donor material and an electron acceptor material, and the electron donor material includes the heterocyclic compound.

According to the exemplary embodiment of the present specification, the electron acceptor material and the n-type organic material layer may be selected from the group consisting of fullerene, fullerene derivatives, vasocuproin, semiconducting elements, semiconducting compounds, and combinations thereof. Specifically, fullerene, fullerene derivatives (PCBM((6,6)-phenyl-C61-butyric acid-methylester) or PCBCR((6,6)-phenyl-C61-butyric acid-cholesteryl ester), perylene ( perylene) PBI (polybenzimidazole), and PTCBI (3,4,9,10-perylene-tetracarboxylic bis-benzimidazole).

According to one embodiment of the present specification, the electron donor and the electron acceptor constitute a bulk heterojunction (BHJ).

The bulk heterojunction means that the electron donor material and the electron acceptor material are mixed with each other in the photoactive layer.

The organic photoelectric device according to an exemplary embodiment of the present specification can be used without limiting materials and/or methods in the art, except that the heterocyclic compound represented by Chemical Formula 1 is used as the photoactive layer of the organic photoelectric device. have.

In the present specification, the substrate may be a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, handling ease, and waterproofness, but is not limited thereto, and is not limited if it is a substrate commonly used in organic electronic devices. Specifically, there are glass or PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PP (polypropylene), PI (polyimide), TAC (triacetyl cellulose). It is not limited to this.

The anode electrode may be a material that is transparent and has excellent conductivity, but is not limited thereto. Metals such as vanadium, chromium, copper, zinc, gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO:Al or SnO ₂ : combination of metal and oxide such as Sb; And conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole and polyaniline, but is not limited thereto. .

The method for forming the anode electrode is not particularly limited, for example, sputtering, E-beam, thermal evaporation, spin coating, screen printing, inkjet printing, doctor blade or gravure printing using a method applied to one side of the substrate or coated in a film form It can be formed by.

When the anode electrode is formed on a substrate, it may undergo cleaning, moisture removal, and hydrophilic modification processes.

For example, the patterned ITO substrate is sequentially washed with a cleaning agent, acetone, and isopropyl alcohol (IPA), and then dried on a heating plate at 100°C to 150°C for 1 to 30 minutes, preferably 120°C for 10 minutes to remove moisture. When the substrate is completely cleaned, the surface of the substrate is modified with hydrophilicity.

Through the above surface modification, the junction surface potential can be maintained at a level suitable for the surface potential of the photoactive layer. In addition, it is easy to form a polymer thin film on the anode electrode during modification, and the quality of the thin film may be improved.

Pretreatment techniques for the anode electrode include: a) surface oxidation method using parallel plate discharge, b) method of oxidizing the surface through ozone generated using UV ultraviolet rays in vacuum, and c) oxygen radicals generated by plasma. And oxidation.

One of the above methods can be selected according to the state of the anode electrode or the substrate. However, regardless of which method is commonly used, it is desirable to prevent oxygen desorption of the anode electrode or the substrate surface and to suppress moisture and organic matters as much as possible. At this time, the practical effect of pretreatment can be maximized.

As a specific example, a method of oxidizing the surface through ozone generated using UV may be used. At this time, after the ultrasonic cleaning, the patterned ITO substrate is baked on a hot plate to dry it well, and then put into a chamber, and by operating a UV lamp, the oxygen gas reacts with UV light to generate ozone. The patterned ITO substrate can be cleaned.

However, the method of surface modification of the patterned ITO substrate in the present specification is not particularly limited, and any method may be used as long as it is a method of oxidizing the substrate.

The cathode electrode may be a metal having a small work function, but is not limited thereto. Metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Alternatively, a material having a multilayer structure such as LiF/Al, LiO ₂ /Al, LiF/Fe, Al:Li, Al:BaF ₂ or Al:BaF ₂ :Ba may be used, but is not limited thereto.

The cathode electrode is 5x10 ^- may be formed is deposited on the internal heat evaporator showing a degree of vacuum of less than ⁷ torr, not limited to this method.

The hole transport layer and/or electron transport layer material plays a role of efficiently transferring electrons and holes separated from the photoactive layer to the electrode, and does not specifically limit the material.

The hole transport layer material is PEDOT:PSS (Poly(3,4-ethylenediocythiophene) doped with poly(styrenesulfonic acid)), molybdenum oxide (MoO _x ); Vanadium oxide (V ₂ O ₅ ); Nickel oxide (NiO); And tungsten oxide (WO _x ), but is not limited thereto.

The electron transport layer material may be electron-extracting metal oxides, specifically, a metal complex of 8-hydroxyquinoline; Complexes including Alq ₃ ; Metal complexes including Liq; LiF; Ca; Titanium oxide (TiO _x ); Zinc oxide (ZnO); And cesium carbonate (Cs ₂ CO ₃ ), but is not limited thereto.

The photoactive layer is formed by dissolving a photoactive material such as an electron donor material and/or an electron acceptor material in an organic solvent, followed by spin coating, dip coating, screen printing, spray coating, doctor blade, brush painting, deposition, etc. However, it is not limited to these methods.

The organic electronic device according to an exemplary embodiment of the present specification may be applied to an organic solar cell, an image sensor, a photo detector, an optical sensor, and an organic light emitting device, but is not limited thereto.

One embodiment of the present specification provides an organic image sensor including the organic electronic device.

The organic image sensor according to an exemplary embodiment of the present specification may be applied to an electronic device, for example, a mobile phone, a digital camera, but is not limited thereto.

The production method of the heterocyclic compound and the production of an organic electronic device including the same will be described in detail in the following Production Examples and Examples. However, the following examples are intended to illustrate the specification, and the scope of the specification is not limited by them.

Preparation Example 1 Preparation of Compound 1

1) Preparation of compound 1-A

1,4-dibromo-3,5-dimethoxybenzoquinone (1.63g, 5.00mmol), compound 1- in a 2-neck Schlenk flask a(3.61g, 12.5mmol), Pd(PPh ₃ ) ₄ (82 mg, 0.10 mmol) was dissolved in dimethylformamide (DMF) and stirred at 110° C. under nitrogen for 12 hours. The mixture was filtered through celite, and the filtrate was purified by silica gel column chromatography to obtain compound 1-A (2.35 g, 72%).

2) Preparation of compound 1-B

Compound 1-A (2.00g, 3.05mmol) was dissolved in ethanol (100ml) and 1M NaOH (200ml) was added and stirred at 80°C for 4 hours. Then, the temperature was lowered to room temperature, neutralized with 1N HCl solution (200 ml) at 0° C., and the organic layer was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, filtered and concentrated to give compound 1-B.

3) Preparation of compound 1

Compound 1-B was dissolved in acetic anhydride and dimethyl sulfoxide and reacted at 80°C. After lowering the temperature to room temperature, the reaction was filtered and purified by silica gel column. Thereafter, compound 1 (520 mg, 25%) was obtained by recrystallization with acetonitrile.

2 is a diagram showing a FT-NMR graph of Compound 1 above.

Preparation Example 2 Preparation of Compound 2

Compound 2 was prepared in the same manner as in Production Example 1, except that Compound 2-a was used instead of Compound 1-a in 1) Preparation of Compound 1-A.

3 is a diagram showing a FT-NMR graph of Compound 2.

Preparation Example 3 Preparation of Compound 3

Compound 3 was prepared in the same manner as in Production Example 1, except that Compound 3-a was used instead of Compound 1-a in the preparation of 1) Compound 1-A of Preparation Example 1.

4 is a diagram showing a FT-NMR graph of Compound 3 above.

Preparation Example 4. Preparation of compound 4

Compound 4 was prepared in the same manner as in Production Example 1, except that Compound 4-a was used instead of Compound 1-a in the preparation of 1) Compound 1-A of Preparation Example 1.

5 is a diagram showing an FT-NMR graph of Compound 4 above.

Preparation Example 5. Preparation of compound 5

Compound 5-a (3.9g, 10.5mmol), compound 1-a(4.3g, 21mmol), Pd(PPh ₃ ) ₄ under nitrogen in a 2-neck Schlenk flask ₄ (82 mg, 0.10 mmol) was dissolved in dimethylformamide (DMF) and stirred for 15 hours. After returning to room temperature, the filtrate filtered through celite was concentrated and purified through a silica gel column to obtain compound 5 (5 g, 70%).

6 is a diagram showing a FT-NMR graph of Compound 5.

Preparation 6. Preparation of compound 6

Compound 6 was manufactured by the same method as Production Example 5, except that 2-a was used instead of Compound 1-a in Preparation Example 5.

7 is a diagram showing a FT-NMR graph of Compound 6.

Preparation Example 7. Preparation of compound 7

Compound 7 was prepared by the same method as Production Example 5, except that 7-a was used instead of compound 5-a in Preparation Example 5.

8 is a view showing a FT-NMR graph of Compound 7.

Preparation Example 8. Preparation of compound 8

Compound 8 was manufactured by the same method as Production Example 7 except for using 2-a instead of compound 1-a in Preparation Example 7.

9 is a diagram showing an FT-NMR graph of Compound 8.

Example 1

The organic photoelectric device was manufactured with a normal structure of ITO/MoO ₃ /photoactive layer/BCP/Al. ITO forms an anode with an organic substrate (11.5 Ω/□, 1.1t) coated with 0.2 cm × 0.2 cm in a pinwheel pattern, ultrasonically washed with distilled water, acetone, and 2-propanol, and holes thereon. As a transport layer, a molybdenum oxide (MoO ₃ ) thin film was laminated to a thickness of 30 nm at a rate of 1.0 Pa/s. Subsequently, on the molybdenum oxide (MoO ₃ ) thin film, compound 3 (p-type organic compound layer) and C ₆₀ (n-type organic compound layer) prepared in Preparation Example 3 were co-deposited in a 1:1 thickness ratio to form a 100 nm thick photoactive layer. Subsequently, BCP (Basocuproin) was deposited on the photoactive layer as an electron transport layer at a rate of 1.0 Å/s to a thickness of 8 nm, and aluminum (Al) was sputtered thereon to form a cathode having a thickness of 100 nm to form an organic photoelectric. The device was fabricated.

Example 2

The organic photoelectric device was fabricated with an inverted structure of ITO/BCP/photoactive layer/MoO ₃ /Al. ITO forms a cathode with an organic substrate (11.5 Ω/□, 1.1t) coated with 0.2 cm × 0.2 cm in a pinwheel pattern, ultrasonically washed with distilled water, acetone, 2-propanol, and BCP as an electron transport layer on it. (Basocuproin) was laminated to a thickness of 8 nm at a rate of 1.0 Å/s, and thereon, a 1:1 thickness of Compound 3 (p-type organic compound layer) and C ₆₀ (n-type organic compound layer) prepared in Preparation Example 3 above. Co-evaporation was performed to form a photoactive layer having a thickness of 100 nm. On the photoactive layer, a molybdenum oxide (MoO ₃ ) thin film was deposited as a hole transport layer to a thickness of 30 nm at a rate of 1.0 Pa/s. Aluminum (Al) was sputtered on the hole transport layer to form an anode having a thickness of 100 nm, thereby fabricating an organic photoelectric device.

10 is a graph of current density according to voltages in photocurrent and dark current of the organic photoelectric devices manufactured in Examples 1 and 2, and FIG. 11 is a voltage in photocurrent of the organic photoelectric devices manufactured in Examples 1 and 2; It is a graph of current density.

12 is a graph showing the external quantum efficiency (EQE) according to the wavelength and voltage of the organic photoelectric device manufactured in Example 1 above.

According to FIG. 12, it was found that the organic photoelectric device using Chemical Formula 1 of the present specification as the p-type organic material layer of the photoactive layer has excellent external quantum efficiency (EQE).

10: first electrode
20: second electrode
30: photoactive layer
100: organic photoelectric device

Claims (15)

Heterocyclic compound represented by the following formula (1):
[Formula 1]

In Chemical Formula 1,
R1 to R6 and R11 to R16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted thioalkoxy group; A substituted or unsubstituted alkyl thioxy group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
Ar1, Ar2, Ar11 and Ar12 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
L1 and L11 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
m1 and m11 are 0,
G1 is a structure represented by the following formula (A),
[Formula A]

In Chemical Formula A,
X1 and X3 are -C(=O)-,
X2 and X4 are O,

Means a site that is bound to L1 and L11 in Formula 1 above. The method according to claim 1, wherein Ar1, Ar2, Ar11 and Ar12 are the same as or different from each other, and each independently an aryl group substituted or unsubstituted with an alkyl group; Or a heterocyclic compound that is a substituted or unsubstituted heteroaryl group with an alkyl group. The method according to claim 1, wherein L1 and L11 are the same as or different from each other, and each independently a direct bond; Arylene group; Or a heterocyclic compound that is a heteroarylene group. delete The method according to claim 1, wherein the compound represented by Formula 1 is any one selected from the following compounds:

The method according to claim 1, The heterocyclic compound is a heterocyclic compound having an absorption edge (absorption edge) at 500 nm to 2000 nm. The method according to claim 1, The heterocyclic compound is a heterocyclic compound that exhibits an absorption curve having a half-value width of 50 nm to 500 nm in the film state. A first electrode;
A second electrode provided to face the first electrode; And
An organic electronic device including at least one organic layer provided between the first electrode and the second electrode,
At least one layer of the organic material layer is an organic electronic device comprising the heterocyclic compound according to any one of claims 1 to 3 and 5 to 7. The organic electronic device of claim 8, wherein the organic electronic device is selected from the group consisting of an organic photoelectric device, an organic transistor, an organic solar cell, and an organic light emitting device. The method according to claim 8, The organic electronic device is a first electrode;
A second electrode provided to face the first electrode; And
An organic photoelectric device including at least one organic material layer provided between the first electrode and the second electrode,
At least one layer of the organic material layer is an organic electronic device comprising the heterocyclic compound. The method according to claim 10, The organic layer includes a photoactive layer,
The photoactive layer has a bilayer structure including an n-type organic material layer and a p-type organic material layer,
The p-type organic material layer is an organic electronic device comprising the heterocyclic compound. The method according to claim 8, The organic electronic device is an organic transistor including a source, a drain, a gate and one or more organic material layer,
At least one layer of the organic material layer is an organic electronic device comprising the heterocyclic compound. The method according to claim 12, The organic layer includes a p-type semiconductor layer and an n-type semiconductor layer,
The p-type semiconductor layer is an organic electronic device comprising the heterocyclic compound. Organic image sensor comprising an organic electronic device according to claim 8. An electronic device comprising the organic image sensor according to claim 14.

Images