KR102083711B1 - Heterocyclic compound and organic electronic device comprising the same - Google Patents

Abstract

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

Description

Heterocyclic compound and organic electronic device including the same TECHNICAL FIELD

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

The organic electronic device refers to a device requiring charge exchange between an electrode and an organic material using holes and / or electrons. The organic electronic device can be classified into two types according to the operation principle. First, an exciton is formed in the organic layer by photons introduced into the device from an external light source, and the exciton is separated into electrons and holes, and these electrons and holes are transferred to different electrodes to be used as current sources (voltage sources). It is a form of electric element. The second is an electronic device in which holes and / or electrons are injected into an organic semiconductor forming an interface with the electrodes 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, and an organic transistor. Hereinafter, the organic photoelectric device will be described in detail. However, in the organic electronic device, a hole injection or transport material, The injection or transport material of electrons, or the luminescent material, acts on a similar principle.

The organic photoelectric device is a device that converts light into an electrical signal using a photoelectric effect. The organic photoelectric device includes a photodiode and a phototransistor, and may be applied to an image sensor. The image sensor including the photodiode is increasing in resolution with increasing day by day, and thus the pixel size is getting smaller. In the case of silicon photodiodes, which are commonly used at present, sensitivity decreases because the absorption area is reduced as the size of the pixel becomes smaller. Accordingly, organic materials that can replace silicon are being researched.

Since the organic material has a large absorption coefficient and selectively absorbs light in a specific wavelength region according to its molecular structure, the organic material can be substituted for the photodiode and the color filter at the same time, which is very advantageous for improving sensitivity 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, a heterocyclic compound represented by Formula 1 is provided.

[Formula 1]

In Chemical Formula 1,

또는

이며,Q and G are different from each other, respectively

or

Is,

X1 to X4 are the same as or different from each other, and each independently O, S, NR, or CRR ',

Y1 and Y2 are the same as or different from each other, and each independently, N or CR,

R, R 'and R1 to R9 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted alkyl thioxy group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

m and n are each an integer of 0 to 5,

1 ≤ n + m ≤ 10,

If n and m are plural, the structures in parentheses are the same or different from each other,

Ar1 is a structure that acts as an electron acceptor,

은 화학식 1에 연결되는 부위이다.

Is a site linked to the formula (1).

Further, according to one embodiment of the present specification, the first electrode; A second electrode provided to face the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the aforementioned heterocyclic compound.

The heterocyclic compound represented by Chemical Formula 1 according to an exemplary embodiment of the present specification acts as a benzodithiophene structure as an electron donor, thereby increasing the dipole moment between molecules, thereby reducing a band gap, Increasing the interaction between the two can absorb light of long wavelengths. In addition, the heterocyclic compound represented by the formula (1) has a different functional group at the position 2 of the benzodithiophene structure to form an asymmetric molecule, by inserting a thiophene group or benzothiadiazole group as a linking plane of the molecule Since the intermolecular stacking (stacking) is effectively achieved, the wavelength width of the absorbing light is wide.

In addition, the heterocyclic compound may be used in a deposition process, and the organic electronic device including the compound represented by Formula 1 according to one embodiment of the present specification may absorb light of all wavelengths, thereby improving efficiency of the device.

1 is a cross-sectional view illustrating an organic photoelectric device according to an exemplary embodiment of the present specification.
2 is a diagram showing an FT-NMR graph of the compound 1 according to Preparation Example 1 of the present specification.
3 is a diagram showing an FT-NMR graph of the compound 2 according to Preparation Example 2 of the present specification.

Hereinafter, this specification is demonstrated in detail.

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

In addition, the heterocyclic compound represented by Formula 1 according to an exemplary embodiment of the present specification is a heterocyclic compound represented by Formula 1 is a tee connecting the electron donor portion of the benzodithiophene structure and the electron acceptor portion represented by Ar1 By including an opene group or a benzothiadiazole group, the heterocyclic compound is induced to take the quinoid form.

The heterocyclic compound represented by Chemical Formula 1 according to an exemplary embodiment of the present specification acts as a benzodithiophene structure as an electron donor, thereby increasing the dipole moment between molecules, thereby reducing a band gap, Increasing the interaction between the two can absorb light of long wavelengths. In addition, the heterocyclic compound represented by the formula (1) has a different functional group at the position 2 of the benzodithiophene structure to form an asymmetric molecule, by inserting a thiophene group or benzothiadiazole group as a linking plane of the molecule Since the intermolecular stacking (stacking) is effectively achieved, the wavelength width of the absorbing light is wide.

In the present specification, when a part "includes" a certain component, this means that it may further include other components, without excluding other components, unless specifically stated otherwise.

In this specification, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

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

The term "substituted" means that a hydrogen atom bonded to a 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 a substituent can be substituted, if two or more substituted , Two or more substituents may be the same or different from each other.

As used herein, the term "substituted or unsubstituted" is deuterium; Halogen group; Alkyl groups; Alkenyl groups; An alkoxy group; Ester group; Carbonyl group; Carboxyl groups; Hydroxyl group; Cycloalkyl group; Silyl groups; Aryl alkenyl group; Aryloxy group; Alkyl thioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Boron group; Alkylamine group; Aralkyl amine groups; Arylamine group; Heterocyclic group; Arylamine group; Aryl group; Nitrile group; Nitro group; Hydroxyl group; And one or more substituents selected from the group consisting of a heterocyclic group including one or more of N, O, and S atoms, or means having no substituent.

The 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, although carbon number of an imide group is not specifically limited, It is preferable that it is C1-C25. Specifically, it may be a compound having a structure as follows, but is not limited thereto.

In the present specification, the amide group may be substituted with one or two of the nitrogen of the amide group is hydrogen, a linear, 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 linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 50. Specific examples include 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.

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, but are not limited thereto. Do not.

In the present specification, the alkoxy group may be linear, branched or cyclic. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C20. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, 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, p-methylbenzyloxy and the like It may be, but is not limited to such.

In the present specification, the alkenyl group may be linear or branched chain, 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, stilbenyl group and styrenyl group, but are not limited thereto.

In the present specification, specifically, the silyl group includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like. However, the present invention 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 as or different from each other, 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; Substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; And it may be selected from the group consisting of a 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, dinaphthylphosphine oxide, and the like, 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 where an alkyl group having 1 to 25 carbon atoms or an alkoxy group having 1 to 25 carbon atoms is substituted. In addition, the aryl group in the present specification may mean an aromatic ring.

When the aryl group is a monocyclic aryl group, carbon number is not particularly limited, but 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.

Carbon number is not particularly limited when the aryl group is a polycyclic aryl group. It is preferable that it is C10-24. Specifically, the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, peryllenyl group, chrysenyl group and fluorenyl group, but is not limited thereto.

In the present specification, the fluorenyl group has 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

And so on. However, the present invention 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 a dissimilar element, and the carbon number is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heteroaryl groups include thiophene groups, furan groups, pyrrole groups, imidazole groups, thiazole groups, oxazole groups, oxadiazole groups, pyridyl groups, bipyridyl groups, pyrimidyl groups, triazine groups, triazole groups, and acridil groups , Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl 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, thiazolyl group, isoxazolyl Groups, oxadiazolyl groups, thiadiazolyl groups, benzothiadiazolyl groups, benzothiazolyl groups, phenothiazinyl groups, dibenzofuranyl groups, and the like, but are not limited thereto.

In the present specification, the heterocyclic group may be monocyclic or polycyclic, may be aromatic, aliphatic or a condensed ring of aromatic and aliphatic, 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, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group, may be a polycyclic aryl group. The arylamine group including two or more aryl groups may simultaneously include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group.

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

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

In the present specification, the aryl group in the aryloxy group, arylthioxy group, aryl sulfoxy group and aralkyl amine group is the same as the examples of the aryl group described above. Specifically, as the aryloxy group, phenoxy, p-tolyloxy, m-tolyloxy, 3,5-dimethyl-phenoxy, 2,4,6-trimethylphenoxy, p-tert-butylphenoxy, 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. Examples of the arylthioxy group include a phenylthioxy group, 2-methylphenylthioxy group, and 4-tert-butylphenyl. Thioxy groups and the like, and aryl sulfoxy groups include, but are not limited to, benzene sulfoxy groups and p-toluene sulfoxy groups.

In this specification, the alkyl group in the alkyl thioxy group and the alkyl sulfoxy group is the same as the example of the alkyl group mentioned above. Specifically, alkyl thioxy groups include methyl thioxy group, ethyl thioxy group, tert-butyl thioxy group, hexyl thioxy group and octyl thioxy group, and the alkyl sulfoxy group includes mesyl, ethyl sulfoxy group, propyl sulfoxy group and butyl sulfoxy group. Etc., but is not limited thereto.

In the present specification, in a substituted or unsubstituted ring in which adjacent groups are bonded to each other, a “ring” means a substituted or unsubstituted hydrocarbon ring; Or a substituted or unsubstituted hetero ring.

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

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 includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S, and the like. The heterocycle may be monocyclic or polycyclic, and may be aromatic, aliphatic or a condensed ring of aromatic and aliphatic, and may be selected from examples of the heteroaryl group or heterocyclic group except that it is not monovalent.

According to an exemplary embodiment of the present specification, X1 to X4 is S.

According to an exemplary embodiment of the present specification, Y1 and Y2 is N.

According to an exemplary embodiment of the present specification, Formula 1 is represented by the following formula 1-1 or formula 1-2.

 [Formula 1-1]

[Formula 1-2]

In Chemical Formulas 1-1 and 1-2,

The definitions of R1 to R9, X1 to X4, Y1, Y2, Ar1, m, and n are the same as in Chemical Formula 1.

According to an exemplary embodiment of the present specification, Formula 1 is represented by the following formula 1-3 or 1-4.

[Formula 1-3]

[Formula 1-4]

In Chemical Formulas 1-3 and 1-4,

Definitions of R1 to R9, Ar1, m and n are the same as in the general formula (1).

According to an exemplary embodiment of the present specification, Ar1 is any one selected from the following structures.

In the above structure,

a is an integer from 1 to 7,

b and c are each an integer of 1 to 4,

when a is 2 or more, two or more R102 are the same or different from each other,

when b is 2 or more, two or more R103 are the same as or different from each other,

when c is 2 or more, two or more R1104 are the same as or different from each other,

R101 to R111 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkoxy group; 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.

이다. According to an exemplary embodiment of the present specification, Ar1 is

to be.

In the above structure, the definitions of R104 and c are as described above.

In the above structure, adjacent R104s combine with each other to form a substituted or unsubstituted hydrocarbon ring.

In the above structure, adjacent R104s combine with each other to form a substituted or unsubstituted aromatic ring.

In the above structure, adjacent R104s combine with each other to form a substituted or unsubstituted benzene ring.

In the above structure, adjacent R104s combine with each other to form a benzene ring.

또는

이다.According to yet an embodiment of the present disclosure, Ar1 is

or

to be.

이다.According to an exemplary embodiment of the present specification, Ar1 is

to be.

이다.According to an exemplary embodiment of the present specification, Ar1 is

to be.

In the above structure, the definitions of R108 and R109 are as described above.

In the above structure, R108 and R109 are the same as or different from each other, and are each independently a substituted or unsubstituted alkyl group.

In the above structure, R108 and R109 are the same as or different from each other, and are each independently a substituted or unsubstituted ethyl group.

In the above structure, R108 and R109 are the same as or different from each other, and each independently an ethyl group.

이다.According to an exemplary embodiment of the present specification, Ar1 is

to be.

In the above structure, the definitions of R110 and R1111 are as described above.

In the above structure, R110 and R1111 are the same as or different from each other, and are each independently a substituted or unsubstituted alkyl group.

In the above structure, R110 and R1111 are the same as or different from each other, and are each independently a substituted or unsubstituted ethyl group.

In the above structure, R110 and R1111 are the same as or different from each other, and each independently an ethyl group.

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

R41 and R51 in the compound are the same as or different from each other, and are each independently a linear or branched alkyl group having 1 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, R41 and R51 are the same as or different from each other, and each independently a linear or branched alkyl group having 1 to 15 carbon atoms.

According to an exemplary embodiment of the present specification, the R41 and R51 are the same as or different from each other, and each independently a linear or branched alkyl group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, the R41 and R51 are the same as or different from each other, and each independently a methyl group; Or an ethyl group.

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

According to an exemplary embodiment of the present specification, the heterocyclic compound has a maximum absorption wavelength in 300nm to 900nm, when having the maximum absorption wavelength range, the heterocyclic compound has the effect of absorbing the visible light region.

According to an exemplary embodiment of the present specification, the heterocyclic compound has an absorption curve having a half width of 100 nm to 1000 nm or more in a film state.

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

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

According to an exemplary embodiment of the present specification, the heterocyclic compound may have a HOMO energy level of 4 eV to 7 eV, and a band gap of 1 eV to 3 eV. By having the HOMO level and the energy bandgap 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), thereby providing a photoelectricity of the organic electronic device. The conversion efficiency can be improved.

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 one or more layers of the organic material layers include the heterocyclic compound.

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

According to an exemplary embodiment of the present specification, an organic transistor including a source, a drain, a gate, and at least one organic material layer, and at least one 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.

In one 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 at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers 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 an 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 several functions at the same time.

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

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

In another exemplary embodiment, the organic photoelectric device may be arranged in 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. It is not limited to this.

According to an exemplary embodiment of the present specification, the organic photoelectric device has a normal structure. In the normal structure, a substrate, an anode, and 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 this order.

FIG. 1 is a diagram illustrating an organic photoelectric device 100 according to an exemplary embodiment of the present specification, and according to FIG. 1, the organic photoelectric device 100 has a side of a first electrode 10 and / or a second electrode 20. When light is incident from the active layer 30 to absorb light in the full wavelength region, excitons may be generated inside. The exciton is separated into holes and electrons in the active layer 30, and the separated holes move to 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 and the first electrode. The current flows to the organic photoelectric device by moving to the cathode side, the other of the two electrodes 20.

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

According to the exemplary embodiment of the present specification, the organic material layer includes a photoactive layer, the photoactive layer has a bilayer structure including a n-type organic material layer and a p-type organic material layer, and the p-type organic material layer includes the heterocyclic compound. Include.

According to the exemplary 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 one embodiment of the present specification, the electron acceptor material and the n-type organic compound layer may be selected from the group consisting of fullerenes, fullerene derivatives, vasocuproin, semiconducting elements, semiconducting compounds, and combinations thereof. Specifically, fullerene, fullerene derivative (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) is one or more compounds selected from the group consisting of.

According to an exemplary embodiment of the present specification, the electron donor and the electron acceptor constitute a bulk hetero junction (BHJ).

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 the exemplary embodiment of the present specification may be used without limiting the materials and / or methods in the art, except for using the compound represented by Chemical Formula 1 as the photoactive layer of the organic photoelectric device.

In the present specification, 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 the substrate may be any substrate that is commonly used in organic solar cells. Specifically, there are glass or polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene (PP), polyimide (PI), and triacetyl cellulose (TAC). It is not limited to this.

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

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

When the anode electrode is formed on a substrate, it may be subjected to cleaning, water removal, and hydrophilic modification.

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

Through such surface modification, the bonding 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, the quality of the thin film may be improved.

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

One of the above methods may be selected depending on the state of the anode electrode or the substrate. In any case, however, it is desirable to prevent oxygen escape from the surface of the anode electrode or the substrate and to minimize the residual of moisture and organic matter in common. At this time, the substantial effect of the pretreatment can be maximized.

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

However, the surface modification method of the patterned ITO substrate in this specification does not need to be specifically limited, Any method may be used as long as it is a method of oxidizing a substrate.

The cathode electrode may be a metal having a small work function, but is not limited thereto. Specifically, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Or a material having a multilayer structure such as LiF / Al, LiO ₂ / Al, LiF / Fe, Al: Li, Al: BaF ₂ , Al: BaF ₂ : Ba, 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 the electron transport layer material plays a role of efficiently transferring electrons and holes separated in the photoactive layer to the electrode, and the material is not particularly limited.

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

The photoactive layer may be 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, or the like. However, it is not limited only to these methods.

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

The preparation method of the heterocyclic compound and the preparation of the organic electronic device including the same will be described in detail in the following Preparation Examples and Examples. However, the following examples are intended to illustrate the present specification, and the scope of the present specification is not limited thereto.

Preparation Example 1 Preparation of Compound 1

1) Preparation of Compound B

7.5 g of benzo [1,2-b: 4,5-b '] dithiophene-4,8-dione (Benzo [1,2-b: 4,5-b'] dithiophene-4,8-dione ( Compound A)) After dilution into a 250 mL 2-neck round bottom flask, 45 mL of ethanol and water were injected. A small amount of 3.89 g of NaBH ₄ was added to the mixture, followed by stirring for 1 hour. After the heating was stopped and slowly added 4.39g of KOH and stirred for 30 minutes. Thereafter, 16 mL of dimethyl sulfate was injected, followed by heating and stirring for 64 hours. After the reaction mixture was cooled to room temperature and extracted with water and diethyl ether, the organic layer obtained was washed with brine and then water was removed using magnesium sulfate. The oil obtained after removal of the solvent was column purified to obtain Compound B (5.3 g).

2) Preparation of Compound C

100 mL of 2.5 g of Compound B was dissolved in anhydrous tetrahydrofuran (THF) and then cooled to -78 ° C. 2.5 mL of 1.0M butyllithium (BuLi) was added to the solution, followed by stirring for 2 hours. 2.5 mL of 1.0M trimethyltin chloride was added to the reaction, followed by stirring at room temperature for 12 hours. The reaction product thus obtained was extracted with water and chloroform, the organic layer was treated with MgSO ₄ to remove moisture, and then the solvent was removed to obtain Compound C.

3) Preparation of Compound E

Compound C was dissolved in 100 mL of toluene, Pd ₂ (dba) ₃ and P (o-tol) ₃ were added, and then Compound D was injected and stirred at 90 ° C. for 12 hours. The reaction mixture obtained through this was extracted using water and ethyl acetate, and then the organic layer was treated with MgSO ₄ to remove moisture and then the solvent was removed. Compound E was obtained by column purification of the brown oil obtained through this.

4) Preparation of Compound F

After dissolving 4.0 g of Compound E in a mixed solvent of tetrahydrofuran (THF) and water, 100 mg of PTSA was injected and stirred at room temperature for 12 hours. The reaction mixture was extracted by injecting ethyl acetate and Na ₂ CO ₃ solution. The organic layer was treated with MgSO ₄ to remove moisture, and then the solvent was removed. The brown oil obtained through this was purified by column to obtain compound F (3.0 g).

5) Preparation of Compound 1

3.6 g of Compound F was dissolved in tetrahydrofuran (THF), 1,3-indanedione of 10 eq. Was injected, and then a small amount of piperidine was injected, and the mixture was stirred at 50 ° C. for 12 hours. After removing the solvent of the reaction mixture obtained through this, the obtained solid was washed with methanol to obtain Compound G.

2 is a diagram showing a FT-NMR graph of the compound 1 according to Preparation Example 1.

Preparation Example 2 Preparation of Compound 2

Compound 2

Except for using diethyl sulfate instead of dimethyl sulfate in the preparation of 1) Compound B of Preparation Example 1, Compound 2 was obtained in the same manner as in Preparation Example 1.

3 is a diagram showing an FT-NMR graph of the compound 2 according to Preparation Example 2.

Fabrication of Organic Optoelectronic Devices

Example 1

ITO is deposited on the glass substrate by sputtering to form an anode having a thickness of about 100 nm, and a molybdenum oxide (MoOx, 0 <x≤3) thin film is deposited on the charge auxiliary layer to a thickness of 10 nm. Subsequently, compound 1 (p-type organic compound layer) and C60 (n-type organic compound layer) according to Preparation Example 1 were co-deposited on a molybdenum oxide (MoOx, 0 <x≤3) thin film in a 1: 1 thickness ratio to form an active layer having a thickness of 85 nm. . Subsequently, aluminum (Al) was deposited on the active layer by sputtering to form a cathode having a thickness of 80 nm, thereby manufacturing an organic photoelectric device.

Example 2

An organic photoelectric device was manufactured in the same manner as in Example 1, except that Compound 2 was used instead of Compound 1.

External Quantum Efficiency and Short Current

External quantum efficiency (EQE) according to the wavelength and voltage of the organic photoelectric device according to Examples 1 and 2 was evaluated.

External quantum efficiency is measured using an IPCE measurement system (McScience, South Korea). First, a facility is calibrated using a Si photodiode (Hamamatsu, Japan), and then the organic photoelectric device according to Examples 1 and 2 is mounted in the facility, and the voltage is -3 V and 0 V, the wavelength range is 300 to External quantum efficiency was measured in the 600 nm region, and the results are shown in Table 1 below.

In addition, the short-circuit current of the organic photoelectric device was measured under the conditions of 0 mW / cm ² and 100 mW / cm ² (-3 V), and the results are shown in Table 1 below.

Photoactive layer Maximum External Quantum Efficiency (%) Short circuit current (A / cm ² )
at -3V at 0V λ (nm) at -3V λ (nm) 0 mW / cm ² 100 mW / cm ² Example 1 74.3 490 85.0 490 3.28 × 10 ^-7 1.92 × 10 ^-2 72.1 500 83.9 490 1.31 × 10 ^-5 1.95 × 10 ^-2 75.8 500 84.0 500 4.45 × 10 ^-7 1.92 × 10 ^-2 Example 2 72.9 460 85.1 470 5.44 × 10 ^-7 1.84 × 10 ^-2 69.7 490 84.6 490 7.72 × 10 ^-7 1.86 × 10 ^-2 68.8 520 83.7 510 4.40 × 10 ^-7 1.83 × 10 ^-2

As shown in Table 1, the devices of Examples 1 and 2 including the compound of Formula 1 according to the exemplary embodiment of the present specification in the photoactive layer of the organic photoelectric device have different functional groups at position 2 of the benzodithiophene structure. It forms an asymmetric molecule, and by inserting a thiophene group or benzothiadiazole group as a linker to adjust the planarity of the molecule to effectively stack between the molecules (stacking), the wavelength width of the absorbing light is wide. Therefore, it can be seen that the devices of Examples 1 and 2 have high external quantum efficiency according to the wavelength and voltage, and excellent efficiency of the organic photoelectric device.

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

Claims (18)

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

In Chemical Formula 1,
Q and G

Is,
X1, X2 and X4 are S,
R1 to R3, R8 and R9 are hydrogen,
R4 and R5 are the same as or different from each other, and each independently an alkoxy group,
m and n are each 0 or 1,
1 ≤ n + m ≤ 2,
If n and m are plural, the structures in parentheses are the same or different from each other,
Ar1 is

or

ego,

Is a site linked to the formula (1). delete delete delete delete The heterocyclic compound according to claim 1, wherein the compound represented by Chemical Formula 1 is any one selected from the following compounds:

R41 and R51 in the compound are the same as or different from each other, and are each independently a linear or branched alkyl group having 1 to 20 carbon atoms. The heterocyclic compound of claim 1, wherein the heterocyclic compound has a maximum absorption wavelength at 300 nm to 900 nm. The heterocyclic compound according to claim 1, wherein the heterocyclic compound exhibits an absorption curve having a half width of 100 nm to 1000 nm in a film state. A first electrode;
A second electrode provided to face the first electrode; And
An organic electronic device comprising 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 a heterocyclic compound according to any one of claims 1 and 6 to 8. The organic electronic device of claim 9, 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 of claim 9, wherein the organic electronic device comprises: 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 containing the heterocyclic compound. The method according to claim 11, wherein the organic layer comprises a photoactive layer,
The photoactive layer has a bilayer structure including an n-type organic compound layer and a p-type organic compound layer,
The p-type organic compound layer is an organic electronic device containing the heterocyclic compound. The method according to claim 11, wherein the organic layer comprises a photoactive layer,
The photoactive layer includes an electron donor material and an electron acceptor material,
The electron donor material is an organic electronic device comprising the heterocyclic compound. The organic electronic device of claim 13, wherein the electron donor and the electron acceptor constitute a bulk hetero junction (BHJ). The organic transistor of claim 9, wherein the organic electronic device is an organic transistor including a source, a drain, a gate, and one or more organic material layers.
At least one layer of the organic material layer is an organic electronic device containing the heterocyclic compound. The method of claim 15, wherein the organic material layer comprises a p-type semiconductor layer and an n-type semiconductor layer,
The p-type semiconductor layer is an organic electronic device containing the heterocyclic compound. An organic image sensor comprising the organic electronic device according to claim 9. An electronic device comprising the organic image sensor according to claim 17.

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