KR102441825B1 - Heterocyclic compound and organic photovoltaic device comprising the same - Google Patents

Abstract

The present specification relates to the heterocyclic compound of Formula 1 and an organic photoelectric device including the same.

Description

Heterocyclic compound and organic photoelectric device comprising the same

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

An organic photoelectric device is a device that converts light into an electrical signal using the photoelectric effect, and includes a photodiode and a phototransistor, and may be applied to an image sensor or the like. An image sensor including a photodiode has an increasing resolution day by day, and accordingly, a pixel size is decreasing. In the case of a silicon photodiode, which is currently mainly used, a decrease in sensitivity may occur because an absorption area decreases as the size of a pixel decreases. Accordingly, organic materials that can replace silicon are being studied.

Since organic materials have a large extinction coefficient and can selectively absorb light in a specific wavelength region according to molecular structure, they can replace photodiodes and color filters at the same time, 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 photoelectric device including the same.

An exemplary embodiment of the present specification provides a heterocyclic compound represented by the following formula (1).

[Formula 1]

In Formula 1,

L1 and L3 are the same as or different from each other, and are each independently a substituted or unsubstituted monocyclic heteroarylene group,

L2 and L4 are the same as or different from each other, and each independently a direct bond; a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

Ar1 and Ar2 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, wherein Ar1 or Ar2 is combined with L2 to form a substituted or unsubstituted ring,

Ar3 and Ar4 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, wherein Ar3 or Ar4 is combined with L4 to form a substituted or unsubstituted ring,

R1 and R2 are the same as or different from each other, and each independently a nitrile group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted hydrocarbon ring bonded to each other; or to form a substituted or unsubstituted heterocycle,

R3 is hydrogen, or combines with L1 to form a substituted or unsubstituted ring,

R4 is hydrogen or combines with L3 to form a substituted or unsubstituted ring,

However, R1 and R2 are the same as or different from each other, and each independently a nitrile group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; or in the case of a substituted or unsubstituted heteroaryl group, 1) R3 and R4 are hydrogen, and L2 and L4 are a direct bond;

2) R3 and L1 combine to form a substituted or unsubstituted ring, R4 and L3 combine to form a substituted or unsubstituted ring, wherein L2 and L4 are the same as or different from each other, and each independently a heteroaryl it's rengi

In addition, an exemplary embodiment of the present specification includes a 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 above-described heterocyclic compound.

The heterocyclic compound according to an exemplary embodiment of the present specification has a wide wavelength width of light absorbed by acting as an electron donor. Accordingly, an organic photoelectric device including the same has excellent photo-electric conversion efficiency.

1 is a cross-sectional view illustrating an organic photoelectric device according to an exemplary embodiment of the present specification.
Figure 2 is a view showing the UV-Vis absorption spectrum in the solution state and film state of Compound 1 of the present specification.
3 is a diagram showing FT-NMR data of Compound 1 of the present specification.
4 is a diagram showing FT-NMR data of Compound 2 of the present specification.
5 is a graph of current density according to voltage at dark current and photocurrent of the organic photoelectric device prepared in Comparative Examples 1-1 and 1-2 of the present specification.
6 is a graph of current density according to voltage in photocurrent of organic photoelectric devices prepared in Comparative Examples 1-1 and 1-2 of the present specification.
7 is a graph showing the external quantum efficiency (EQE) according to the wavelength and voltage of the organic photoelectric device prepared in Comparative Examples 1-1 and 1-2 of the present specification.
8 is a graph of current density according to voltage in dark current and photocurrent of the organic photoelectric device manufactured in Examples 1-1 and 1-2 of the present specification.
9 is a graph of current density according to voltage in photocurrent of organic photoelectric devices manufactured in Examples 1-1 and 1-2 of the present specification.
10 is a graph showing the external quantum efficiency (EQE) according to the wavelength and voltage of the organic photoelectric device manufactured in Examples 1-1 and 1-2 of the present specification.

Hereinafter, the present specification will be described in detail.

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

The heterocyclic compound represented by Formula 1 according to an exemplary embodiment of the present specification includes quinoxaline or a condensed ring thereof as an electron withdrawing group as a core, and the structure is D-A-D (Donor-Acceptor-Donor). Due to this, the wavelength of the absorbed light is widened, and thus it is suitable for use as an electron donor material of the photoactive layer of an organic photoelectric device.

In the present specification, when a part "includes" a certain component, this means that other components may be further included rather than excluding other components unless otherwise stated.

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

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

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

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; nitrile group; nitro group; imid; amide group; carbonyl group; ester group; hydroxyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkylsulfoxy group; a substituted or unsubstituted arylsulfoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylphosphine group; a substituted or unsubstituted phosphine oxide group; a substituted or unsubstituted aryl group; And it means that it is substituted with one or two or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group, is substituted with a substituent to which two or more of the above-exemplified substituents are connected, or does not have any substituents. For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

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

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably from 1 to 30 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the amide group may be substituted with a nitrogen of the amide group with hydrogen, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, in the ester group, the oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 30 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, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. 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, 5-methylhexyl, and the like.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and 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, cyclooctyl, etc., but are limited thereto it is not

In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C30. 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, p-methylbenzyloxy, etc. may be It is not limited.

In the present specification, the amine group is -NH ₂ ; an alkylamine group; N-alkylarylamine group; arylamine group; N-aryl heteroarylamine group; It may be selected from the group consisting of an N-alkylheteroarylamine group and a heteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, and a 9-methyl-anthracenylamine group. , diphenylamine group, N-phenylnaphthylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group; N-phenylnaphthylamine group; N-biphenylnaphthylamine group; N-naphthylfluorenylamine group; N-phenylphenanthrenylamine group; N-biphenylphenanthrenylamine group; N-phenylfluorenylamine group; N-phenylterphenylamine group; N-phenanthrenylfluorenylamine group; There is an N-biphenylfluorenylamine group, and the like, but is not limited thereto.

In the present specification, the N-alkylarylamine group refers to an amine group in which an alkyl group and an aryl group are substituted with N of the amine group.

In the present specification, the N-arylheteroarylamine group refers to an amine group in which an aryl group and a heteroaryl group are substituted with N of the amine group.

In the present specification, the N-alkylheteroarylamine group refers to an amine group in which an alkyl group and a heteroaryl group are substituted with N of the amine group.

In the present specification, the alkyl group in the alkylamine group, N-arylalkylamine group, alkylthioxy group, alkylsulfoxy group, and N-alkylheteroarylamine group is the same as the above-described alkyl group. Specifically, the alkyl thiooxy group includes methyl thiooxy group, ethyl thiooxy group, tert-butyl thioxy group, hexyl thioxy group, octyl thiooxy group, etc., and the alkyl sulfoxy group includes methyl sulfoxy group, ethyl sulfoxy group, propyl sulfoxy group, There is a sulfoxy group, but is not limited thereto.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. 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, styrenyl group, and the like, but is not limited thereto.

In the present specification, the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a 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 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 C1-C30 linear or branched alkyl group; 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 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, a dinaphthyl phosphine oxide group, and the like, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.

When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, and the like, 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 is C10-30. Specifically, the polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a triphenyl group, a pyrenyl group, a phenalenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, a fluoranthenyl group, etc. , but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and adjacent groups 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

etc. can be However, the present invention is not limited thereto.

As used herein, the "adjacent" group means a substituent substituted on an atom directly connected to the atom in which the substituent is substituted, a substituent sterically closest to the substituent, or another substituent substituted on the atom in which the substituent is substituted. can For example, two substituents substituted at an ortho position in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring may be interpreted as "adjacent" groups.

In the present specification, the aryl group in the aryloxy group, the arylthioxy group, the arylsulfoxy group, the N-arylalkylamine group, the N-arylheteroarylamine group and the arylphosphine group is the same as the above-described aryl group. Specifically, the aryloxy group includes a phenoxy group, p-tolyloxy group, m-tolyloxy group, 3,5-dimethyl-phenoxy group, 2,4,6-trimethylphenoxy group, p-tert-butylphenoxy group, 3- Biphenyloxy group, 4-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthryloxy group , 2-anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenanthryloxy group, 9-phenanthryloxy group, etc., and the arylthioxy group includes phenylthioxy group, 2- There is a methylphenylthioxy group, a 4-tert-butylphenylthioxy group, and the like, and the arylsulfoxy group includes a benzenesulfoxy group, a p-toluenesulfoxy group, and the like, but is not limited thereto.

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 including 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. For example, the aryl group in the arylamine group may be selected from the examples of the aryl group described above.

In the present specification, the heteroaryl group 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 number of carbon atoms is not particularly limited, but preferably has 2 to 30 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include a thiophene group, a furanyl group, a pyrrole group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazinyl group, a triazinyl group Jolyl group, acridyl group, pyridazinyl group, pyrazinyl group, quinolyl group, quinazolyl group, quinoxalyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group , isoquinolyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, pe Nonthrolinyl group (phenanthroline), isoxazolyl group, thiadiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, but is not limited thereto.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, or a substituted or unsubstituted diheteroarylamine group. The heteroarylamine group including two or more heteroaryl groups may include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group at the same time. For example, the heteroaryl group in the heteroarylamine group may be selected from the examples of the heteroaryl group described above.

In the present specification, examples of the heteroaryl group in the N-arylheteroarylamine group and the N-alkylheteroarylamine group are the same as the examples of the heteroaryl group described above.

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 it means a substituted or unsubstituted heterocyclic ring.

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

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

In the present specification, the heterocycle includes atoms other than carbon and one or more heteroatoms, and specifically, the heterocyclic atoms 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 for non-monovalent ones.

In the present specification, the arylene group means that the aryl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the aryl group described above may be applied.

In the present specification, the heteroarylene group means that the heteroaryl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the heteroaryl group described above may be applied.

According to an exemplary embodiment of the present specification, in Formula 1, R1 and R2 are combined with each other to form a substituted or unsubstituted monocyclic heterocycle.

According to an exemplary embodiment of the present specification, in Formula 1, R1 and R2 are bonded to each other to form a monocyclic heterocycle.

According to an exemplary embodiment of the present specification, in Formula 1, R1 and R2 are bonded to each other to form a substituted or unsubstituted monocyclic hydrocarbon ring.

According to an exemplary embodiment of the present specification, in Formula 1, R1 and R2 are combined with each other to form a substituted or unsubstituted monocyclic aromatic ring.

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

[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,

X1 to X3 are the same as or different from each other, and are each independently NR, O, S or Se,

Y1 to Y4 are the same as or different from each other, and are each independently N or CR';

L2 and L4 are the same as or different from each other, and each independently a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

Ar1 and Ar2 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, wherein Ar1 or Ar2 is combined with L2 to form a substituted or unsubstituted ring,

Ar3 and Ar4 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, wherein Ar3 or Ar4 is combined with L4 to form a substituted or unsubstituted ring,

R, R' and R11 to R18 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; nitrile group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted thioalkoxy group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

r11 and r12 are each an integer of 1 or 2,

When r11 is 2, the plurality of R11 are the same as or different from each other,

When r12 is 2, the plurality of R12 are the same as or different from each other.

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

[Formula 1-3]

[Formula 1-4]

In Formulas 1-3 and 1-4,

X1 to X3 are the same as or different from each other, and are each independently NR, O, S or Se,

Y1 to Y4 are the same as or different from each other, and are each independently N or CR';

L2 and L4 are the same as or different from each other, and each independently a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

Ar1 and Ar2 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, wherein Ar1 or Ar2 is combined with L2 to form a substituted or unsubstituted ring,

Ar3 and Ar4 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, wherein Ar3 or Ar4 is combined with L4 to form a substituted or unsubstituted ring,

R, R' and R11 to R18 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; nitrile group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted thioalkoxy group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

r11 and r12 are each an integer of 1 or 2,

When r11 is 2, the plurality of R11 are the same as or different from each other,

When r12 is 2, the plurality of R12 are the same as or different from each other.

According to an exemplary embodiment of the present specification, in Formulas 1-1 and 1-3, X1 is S.

According to an exemplary embodiment of the present specification, in Formulas 1-1 and 1-3, Y1 and Y2 are CH.

According to an exemplary embodiment of the present specification, in Formulas 1-1 and 1-3, Y3 and Y4 are N.

According to an exemplary embodiment of the present specification, in Formulas 1-1 and 1-3, Y3 and Y4 are CH.

According to an exemplary embodiment of the present specification, in Formulas 1-2 and 1-4, X2 and X3 are S.

According to an exemplary embodiment of the present specification, in Formula 1, R1 and R2 are nitrile groups; an alkyl group; or an aryl group.

According to an exemplary embodiment of the present specification, in Formula 1, R1 and R2 are nitrile groups; a straight-chain or branched alkyl group; or a monocyclic or polycyclic aryl group.

According to an exemplary embodiment of the present specification, in Formula 1, R1 and R2 are nitrile groups; a straight-chain alkyl group; or a monocyclic aryl group.

According to an exemplary embodiment of the present specification, in Formula 1, R1 and R2 are nitrile groups; methyl group; or a phenyl group.

According to an exemplary embodiment of the present specification, in Formula 1, R1 and R2 are bonded to each other to form a thiophene ring.

According to an exemplary embodiment of the present specification, in Formula 1, R1 and R2 are bonded to each other to form a benzene ring.

According to an exemplary embodiment of the present specification, in Formula 1, L1 and L3 are the same as or different from each other, and each independently represent a monocyclic heteroarylene group.

According to an exemplary embodiment of the present specification, in Formula 1, L1 and L3 are divalent thiophene groups.

According to an exemplary embodiment of the present specification, in Formula 1, L2 and L4 are the same as or different from each other, and each independently a direct bond; monocyclic arylene group; or a monocyclic heteroarylene group.

According to an exemplary embodiment of the present specification, in Formula 1, L2 and L4 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 Formula 1, Ar1 and Ar2 are the same as or different from each other, and are each independently a monocyclic aryl group unsubstituted or substituted with an alkyl group, or Ar1 or Ar2 is bonded to L2 to form a heterocycle substituted or unsubstituted with an alkyl group.

According to an exemplary embodiment of the present specification, in Formula 1, Ar1 and Ar2 are the same as or different from each other, and are each independently a phenyl group substituted or unsubstituted with an alkyl group, or Ar1 or Ar2 is an alkyl group combined with L2 A substituted or unsubstituted acridine ring is formed.

According to an exemplary embodiment of the present specification, in Formula 1, Ar1 and Ar2 are the same as or different from each other, and are each independently a phenyl group unsubstituted or substituted with a methyl group, or Ar1 or Ar2 is a methyl group combined with L2 A substituted or unsubstituted acridine ring is formed.

According to an exemplary embodiment of the present specification, in Formula 1, Ar1 and Ar2 are the same as or different from each other, and each independently represents a phenyl group unsubstituted or substituted with a methyl group.

According to an exemplary embodiment of the present specification, in Formula 1, Ar1 is combined with L2 to form an acridine ring unsubstituted or substituted with a methyl group.

According to an exemplary embodiment of the present specification, in Formula 1, Ar2 is combined with L2 to form an acridine ring unsubstituted or substituted with a methyl group.

According to an exemplary embodiment of the present specification, in Formula 1, Ar3 and Ar4 are the same as or different from each other, and are each independently a monocyclic aryl group unsubstituted or substituted with an alkyl group, or Ar3 or Ar4 is bonded to L4 to form a heterocycle substituted or unsubstituted with an alkyl group.

According to an exemplary embodiment of the present specification, in Formula 1, Ar3 and Ar4 are the same as or different from each other, and are each independently a phenyl group substituted or unsubstituted with an alkyl group, or Ar3 or Ar4 is an alkyl group combined with L4 A substituted or unsubstituted acridine ring is formed.

According to an exemplary embodiment of the present specification, in Formula 1, Ar3 and Ar4 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with a methyl group, or Ar3 or Ar4 is a methyl group combined with L4 A substituted or unsubstituted acridine ring is formed.

According to an exemplary embodiment of the present specification, in Formula 1, Ar3 and Ar4 are the same as or different from each other, and each independently represent a phenyl group unsubstituted or substituted with a methyl group.

According to an exemplary embodiment of the present specification, in Formula 1, Ar3 is combined with L4 to form an acridine ring unsubstituted or substituted with a methyl group.

According to an exemplary embodiment of the present specification, in Formula 1, Ar4 is combined with L4 to form an acridine ring unsubstituted or substituted with a methyl group.

According to an exemplary embodiment of the present specification, in Formula 1, R3 and L1 are bonded to each other to form an aromatic ring; or to form a heterocycle.

According to an exemplary embodiment of the present specification, in Formula 1, R3 and L1 are bonded to each other to form a benzene ring; pyridine ring; or to form a thiophene ring.

According to an exemplary embodiment of the present specification, in Formula 1, R4 and L3 are bonded to each other to form an aromatic ring; or to form a heterocycle.

According to an exemplary embodiment of the present specification, in Formula 1, R4 and L3 are bonded to each other to form a benzene ring; pyridine ring; or to form a thiophene ring.

According to an exemplary embodiment of the present specification, Formula 1 is selected from the following compounds.

An exemplary embodiment of the present specification includes a 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.

An organic photoelectric device according to an 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 multiple 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 the cathode, the photoactive layer and the anode, and may be arranged in the order of the anode, the photoactive layer and the cathode, but is not limited thereto.

In another exemplary embodiment, the organic photoelectric device may be arranged in the order of the anode, the hole transport layer, the photoactive layer, the electron transport layer and the cathode, and the cathode, the electron transport layer, the photoactive layer, the hole transport layer and the anode may be arranged in the order , but not limited thereto.

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, an organic material layer including a photoactive layer, and a cathode may be stacked in this order.

According to an 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.

1 is a view showing an organic photoelectric device 100 according to an exemplary embodiment of the present specification, and according to FIG. 1 , the organic photoelectric device 100 is a first electrode 10 and/or a second electrode 20 side When light is incident from the photoactive layer 30 and absorbs light in the entire wavelength region, excitons may be generated therein. The excitons are separated into holes and electrons in the photoactive layer 30 , the separated holes move toward the anode, 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 second electrode 20 moves toward the cathode, which is the other, so that current can flow through the organic photoelectric device.

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

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

According to an 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.

In the present specification, an electron donor is also referred to as an electron donor and generally has a negative charge or an unshared electron pair, and means donating an electron to a portion lacking a positive charge or an electron pair. In addition, the electron donor in the present specification is an electron acceptor with high electronegativity due to the abundant electron retention properties of the molecule itself when light is received in a mixed state with the electron acceptor even if it does not have a negative charge or a lone pair of electrons (excited electron) include those that can transmit

In the present specification, an electron acceptor means accepting an electron from an electron donor.

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

According to an exemplary embodiment of the present specification, the electron donor and the electron acceptor are respectively deposited or co-deposited to constitute a photoactive layer.

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

The bulk heterojunction means that an electron donor material and an 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 may be used without limiting materials and/or methods in the art, except that the heterocyclic compound represented by 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 and waterproofing properties, but is not limited thereto, and is not limited as long as it is a substrate commonly used in organic solar cells. Specifically, there are glass or PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PP (polypropylene), PI (polyimide), TAC (triacetyl cellulose), etc. However, the present invention is not limited thereto.

The anode electrode may be made of a transparent and highly conductive material, 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 : a combination of a metal such as Sb and an oxide; 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 of forming the anode electrode is not particularly limited, but for example, sputtering, E-beam, thermal evaporation, spin coating, screen printing, inkjet printing, doctor blade or gravure printing is applied to one surface of the substrate or coated in a film form. can be formed by

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

For example, the patterned ITO substrate is sequentially cleaned 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 at 120°C for 10 minutes to remove moisture. And, when the substrate is completely cleaned, the surface of the substrate is modified to be hydrophilic.

Through the surface modification as described above, the bonding surface potential can be maintained at a level suitable for the surface potential of the photoactive layer. In addition, the formation of the polymer thin film on the anode electrode may be facilitated during the modification, and the quality of the thin film may be improved.

As a pretreatment technique for the anode electrode, a) a surface oxidation method using a parallel plate discharge, b) a method of oxidizing the surface through ozone generated using UV ultraviolet rays in a vacuum, and c) oxygen radicals generated by plasma There is a method for oxidation using

One of the above methods may be selected according to the state of the anode electrode or the substrate. However, whichever method is used, it is preferable to prevent oxygen desorption from the surface of the anode electrode or the substrate and to suppress the residual moisture and organic matter as much as possible. In this case, the practical effect of the 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 ultrasonic cleaning, the patterned ITO substrate is baked on a hot plate, dried well, put into the chamber, and the UV lamp is activated to generate oxygen gas reacting with UV light. The patterned ITO substrate can be cleaned.

However, the method for modifying the surface of the patterned ITO substrate in the present specification does not need to be 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. Specifically, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; Alternatively, it may be a material having a multilayer structure such as LiF/Al, LiO ₂ /Al, LiF/Fe, Al:Li, Al:BaF ₂ , and Al:BaF ₂ :Ba, but is not limited thereto.

The cathode electrode may be formed by being deposited in a thermal evaporator showing a vacuum degree of 5x10 ^{- 7} torr or less, but is not limited to this method.

The hole transport layer and/or the electron transport layer material serves to efficiently transfer electrons and holes separated from the photoactive layer to the electrode, and the material is not particularly limited.

The hole transport layer material is PEDOT: PSS (Poly (3,4-ethylenediocythiophene) doped with poly (styrenesulfonic acid)), molybdenum oxide (MoO _x , 0<x≤3); vanadium oxide (V ₂ O ₅ ); nickel oxide (NiO); and tungsten oxide (WO _x , 0<x≤3), but is not limited thereto.

The electron transport layer material is 1,4,5,8-naphthalene-tetracarboxylic dianhydride (1,4,5,8-naphthalene-tetracarboxylic dianhydride, NTCDA), bathocuproine (BCP), LiF , Alq ₃ , Gaq ₃ , Inq ₃ , Znq ₂ , Zn(BTZ) ₂ , BeBq ₂ and may include one selected from combinations thereof, 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 and then spin coating, dip coating, screen printing, spray coating, doctor blade, brush painting, etc. , but not limited to these methods.

The organic photoelectric device according to the exemplary embodiment of the present specification may be applied to a solar cell, an image sensor, a photodetector, a light sensor, a phototransistor, and the like, but is not limited thereto.

An exemplary embodiment of the present specification provides an organic image sensor including the organic photoelectric 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, or the like, but is not limited thereto.

The manufacturing method of the heterocyclic compound and the preparation of an organic photoelectric device including the same will be described in detail in Preparation Examples and Examples below. 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 1-A

3,6-dibromobenzene-1,2-diamine (10g, 37mmol) and 2,3-butanedione (3.3ml, 37mmol) were dissolved in ethanol in a two-neck round bottom flask, and refluxed at 100°C under nitrogen for one day. The temperature was lowered to room temperature and filtered to obtain compound 1-A (light brown solid). (yield 8.8 g, yield 74%)

2) Preparation of compound 1

Compound 1-A (1g, 3.2mmol) , Pd(PPh ₃ ) ₄ (0.4g, 0.32mmol), N,N-di- p -tolyl-5-(trimethylstannyl) in a 2-neck Schlenk flask Thiophene-2-amine (2.9 g, 6.6 mmol) was dissolved in toluene and stirred at 120° C. under nitrogen for 7 hours. Filtered with hexane and recrystallized from ethyl acetate to obtain a dark red solid. (Yield: 1.2 g, Yield: 52%)

2 is data obtained by measuring UV-vis absorption spectra in a solution state and a film state of Compound 1;

Specifically, the UV-vis absorption spectrum in FIG. 2 was measured by Mecasys' Optizen Pop spectrophotometer, and the solution state is a solution sample obtained by dissolving the compound 1 in toluene, and the film state is the compound 1 spin-coated on ITO glass. Measured using a film.

3 is a diagram showing FT-NMR data of Compound 1.

Preparation Example 2. Preparation of compound 2

1) Preparation of compound 2-A

Dissolve 3,6-dibromobenzene-1,2-diamine (10g, 37mmol) and 1,2-diphenyl-1,2-ethanedione (7.9g, 37mmol) in ethanol (250ml, 0.15M) in a 2-neck round bottom flask and refluxed at 100°C under nitrogen for one day. After lowering the temperature to room temperature and filtration, compound 2-A (a pale yellow solid) was obtained. (Yield 16 g, Yield 96%)

2) Preparation of compound 2

Compound (3 g, 6.8 mmol), Pd (tBu ₃ P) ₂ in a 2-neck schlenk flask (0.68mmol), N,N-di- p -tolyl-5-(trimethylstannyl)thiophene-2-amine (6.3g, 14.3mmol) was dissolved in toluene (17ml, 0.4M) at 120℃ and 80℃ Stirred under nitrogen for one day. Filtered with hexane and recrystallized from chloroform to obtain a dark purple solid. (Yield: 1.8 g, Yield: 32%)

4 is a diagram showing FT-NMR data of compound 2;

Fabrication of organic optoelectronic devices

Comparative Example 1-1

The organic photoelectric device was fabricated in 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 using distilled water, acetone, and 2-propanol, and molybdenum as a hole transport layer thereon An oxide (MoO ₃ ) thin film was deposited to a thickness of 30 nm at a rate of 1.0 Å/s. Then, on the molybdenum oxide (MoO ₃ ) thin film, the following Comparative Example Compound 1 (p-type organic material layer) and C ₆₀ (n-type organic material layer) were co-deposited at a thickness ratio of 1:1 to form a 100 nm thick photoactive layer. Then, on the photoactive layer, BCP (vasocuproin) was laminated to a thickness of 8 nm at a rate of 1.0 Å/s as an electron transport layer, and aluminum (Al) was laminated thereon by sputtering to form a cathode having a thickness of 100 nm. The device was fabricated.

[Comparative Example Compound 1]

Comparative Example 1-2

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 using distilled water, acetone, and 2-propanol, and BCP as an electron transport layer thereon (vasocuproin) was laminated to a thickness of 8 nm at a rate of 1.0 Å/s, and on it, the Comparative Example Compound 1 (p-type organic material layer) and C ₆₀ (n-type organic material layer) were co-deposited at a 1:1 thickness ratio. A photoactive layer having a thickness of 100 nm was formed. A molybdenum oxide (MoO ₃ ) thin film was deposited as a hole transport layer on the photoactive layer to a thickness of 30 nm at a rate of 1.0 Å/s. An organic photoelectric device was manufactured by laminating aluminum (Al) on the hole transport layer by sputtering to form an anode having a thickness of 100 nm.

5 is a graph of current density according to voltage in dark current and photocurrent of the organic photoelectric devices prepared in Comparative Examples 1-1 and 1-2.

6 is a graph of current density according to voltage in the photocurrent of the organic photoelectric devices prepared in Comparative Examples 1-1 and 1-2.

7 is a graph showing the external quantum efficiency (EQE) according to the wavelength and voltage of the organic photoelectric devices prepared in Comparative Examples 1-1 and 1-2.

Example 1-1

It was prepared in the same manner as in Comparative Example 1-1, except that Compound 2 prepared in Preparation Example 2 was used instead of Comparative Example Compound 1.

Example 1-2

It was prepared in the same manner as in Comparative Example 1-2, except that Compound 2 prepared in Preparation Example 2 was used instead of Compound 1 of Comparative Example.

8 is a graph of current density according to voltage at dark current and photocurrent of the organic photoelectric devices manufactured in Examples 1-1 and 1-2.

9 is a graph of current density according to voltage in the photocurrent of the organic photoelectric devices manufactured in Examples 1-1 and 1-2.

10 is a graph showing the external quantum efficiency (EQE) according to the wavelength and voltage of the organic photoelectric devices prepared in Examples 1-1 and 1-2.

When comparing FIGS. 7 of Comparative Examples 1-1 and 1-2 with FIGS. 10 of Examples 1-1 and 1-2, L1 and L3 of Formula 1 are heteroarylene groups, and L2 and L4 are a direct bond It was found that when a phosphorus compound is used as a photoactive layer of an organic photoelectric device, external quantum efficiency (EQE) is superior to that of a compound in which L1 to L4 are direct bonds.

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

Claims (12)

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

In Formula 1,
L1 and L3 are the same as or different from each other, and are each independently a substituted or unsubstituted monocyclic heteroarylene group,
L2 and L4 are the same as or different from each other, and each independently a direct bond; a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
Ar1 and Ar2 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,
Ar3 and Ar4 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,
R1 and R2 are the same as or different from each other, and each independently a nitrile group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
R3 is hydrogen,
R4 is hydrogen,
However, R1 and R2 are the same as or different from each other, and each independently a nitrile group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or in the case of a substituted or unsubstituted heteroaryl group, R3 and R4 are hydrogen, and L2 and L4 are a direct bond. delete The heterocyclic compound of claim 1, wherein L1 and L3 are the same as or different from each other, and each independently a monocyclic heteroarylene group. The method according to claim 1, wherein L2 and L4 are the same as or different from each other, and each independently a direct bond; monocyclic arylene group; Or a heterocyclic compound that is a monocyclic heteroarylene group. The method according to claim 1, wherein Ar1 and Ar2 are the same as or different from each other, and each independently represent a monocyclic aryl group unsubstituted or substituted with an alkyl group, and Ar3 and Ar4 are the same as or different from each other, and are each independently substituted with an alkyl group or A heterocyclic compound that is an unsubstituted monocyclic aryl group. delete The heterocyclic compound according to claim 1, wherein Chemical Formula 1 is selected from the following compounds:

a first electrode;
a second electrode provided to face the first electrode; and
An organic photoelectric device comprising one or more organic material layers provided between the first electrode and the second electrode,
At least one layer of the organic material layer is an organic photoelectric device comprising the heterocyclic compound according to any one of claims 1, 3 to 5 and 7. The method according to claim 8, wherein the organic material layer comprises 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 photoelectric device comprising the heterocyclic compound. The method according to claim 8, wherein the organic material 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 photoelectric device comprising the heterocyclic compound. An organic image sensor comprising the organic photoelectric device according to claim 8 . An electronic device comprising the organic image sensor according to claim 11 .

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