KR102106668B1 - Heterocyclic compound and organic electronic device comprising the same - Google Patents

Abstract

The present specification relates to a heterocyclic compound and an organic solar cell including the same.

Description

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

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

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

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

It is important to increase efficiency so that the organic solar cell can output as much electrical energy as possible from solar energy. In order to increase the efficiency of such an organic solar cell, it is important to generate as many excitons as possible inside the semiconductor, but it is also important to draw the generated charge to the outside without loss. One of the causes of the loss of charge is that the generated electrons and holes are destroyed by recombination. Various methods have been proposed as a method for transferring the generated electrons or holes without being lost to the electrode, but most of them require an additional process and accordingly the manufacturing cost may increase.

US 5331183 US 5454880

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

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

[Formula 1]

In Chemical Formula 1,

X1 and X2 are the same as or different from each other, and each independently CRR ', NR, O, SiRR', PR, S, GeRR ', Se or Te,

Y1 to Y4 are the same as or different from each other, and each independently CR ", N, SiR", P or GeR ",

R1 to R4, R, R 'and R "are the same as or different from each other, and each independently hydrogen; deuterium; halogen group; hydroxy group; substituted or unsubstituted alkyl group; or substituted or unsubstituted alkoxy group,

Ar1 and Ar2 are the same as or different from each other, and each independently a group represented by the following structure,

In the above structure,

R200 to R202 are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group,

a and b are each an integer from 1 to 4,

When a and b are each 2 or more, structures in parentheses of 2 or more are the same or different from each other,

In Chemical Formula 1, Q is a structure represented by the following Chemical Formula A or B,

[Formula A]

[Formula B]

In the above formula A and B,

X, X ', X "and X"' are the same as or different from each other, and each independently S or Se,

G1 to G4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Q1 and Q2 are the same as or different from each other, and each independently a substituted or unsubstituted ring,

n1 and n2 are each an integer from 1 to 5,

When n1 and n2 are each 2 or more, the structures in parentheses are the same or different from each other,

는 상기 화학식 1에 결합되는 부위이다.

Is a site bound to the formula (1).

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

The heterocyclic compound represented by Chemical Formula 1 according to an exemplary embodiment of the present specification freely adjusts the energy absorption region and the energy level through various structures of the terminal groups Ar1 and Ar2 and the core Q, and an organic sun including the same The battery has excellent device performance.

In addition, the organic solar cell using the heterocyclic compound represented by Formula 1 as an n-type organic material layer of the photoactive layer exhibits excellent photo-electric conversion efficiency.

The heterocyclic compound represented by Chemical Formula 1 according to an exemplary embodiment of the present specification has a LUMO energy level similar to that of the existing fullerene-based acceptor PCBM, but is a heterocyclic compound represented by Chemical Formula 1 due to low open voltage loss. An organic solar cell using as an n-type organic material layer of a photoactive layer exhibits a high open voltage (V _oc ).

1 is a view showing an organic solar cell according to an exemplary embodiment of the present specification.
2 is a diagram showing FT-NMR data of Compound 1-A.
3 is a diagram showing FT-NMR data of Compound 2-A.
4 is a diagram showing FT-NMR data of Compound 1 above.
5 is a diagram showing FT-NMR data of Compound 2.
6 is a diagram showing FT-NMR data of Compound 3.
7 is a diagram showing FT-NMR data of Compound 4.
8 is a diagram showing FT-NMR data of Compound 5.
9 is a diagram showing FT-NMR data of Compound 6.
10 is a view showing the current density according to the voltage of the organic solar cells according to Experimental Examples 1-1 to 1-4.
11 is a view showing the current density according to the voltage of the organic solar cells according to Experimental Examples 2-1 to 2-4.
12 is a view showing the current density according to the voltage of the organic solar cells according to Experimental Examples 3-1 to 3-4.
13 is a view showing the current density according to the voltage of the organic solar cells according to Experimental Examples 4-1 to 4-4.

Hereinafter, the present specification will be described in detail.

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

The heterocyclic compound represented by Chemical Formula 1 according to an exemplary embodiment of the present specification freely adjusts the energy absorption region and the energy level through various structures of the terminal groups Ar1 and Ar2 and the core Q, and an organic sun including the same The battery has excellent device performance.

In addition, the organic solar cell using the heterocyclic compound represented by Formula 1 as an n-type organic material layer of the photoactive layer exhibits excellent photo-electric conversion efficiency.

The heterocyclic compound represented by Chemical Formula 1 according to an exemplary embodiment of the present specification has a LUMO energy level similar to that of the existing fullerene-based acceptor PCBM, but is a heterocyclic compound represented by Chemical Formula 1 due to a loss of low open voltage. An organic solar cell using as an n-type organic material layer (electron acceptor material) of a photoactive layer exhibits a high open voltage (V _oc ).

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

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

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

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

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

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

In the present specification, the nitrogen of the amide group may be 1 or 2 substituted with hydrogen, a straight chain, branched or cyclic alkyl group having 1 to 25 carbon atoms, or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

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

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, 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 and cyclooctyl, and the like, but is not limited thereto. Does not.

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

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

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

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

In the present specification, the phosphine oxide group is specifically a diphenylphosphine oxide group, a dinaphthyl phosphine 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 in which an alkyl group having 1 to 25 carbon atoms or an alkoxy group having 1 to 25 carbon atoms is substituted. In addition, an aryl group in the present specification may mean an aromatic ring.

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

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

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

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

,

,

및

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

,

,

And

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

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

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

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

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

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

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

In the present specification, the alkyl thioxy group and the alkyl group in the alkyl sulfoxy group are the same as those of the aforementioned alkyl group. Specifically, the alkyl thioxy group includes a methyl thioxy group, an ethyl thioxy group, a tert-butyl thioxy group, a hexyl thioxy group, and an octyl thioxy group. Examples of the alkyl sulfoxy group include mesyl, ethyl sulfoxy group, propyl sulfoxyl group, and butyl sulfoxyl group. And the like, but is not limited thereto.

In the present specification, in the substituted or unsubstituted ring formed by bonding adjacent groups to each other, "ring" is 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 aromatic and aliphatic condensed ring, and may be selected from examples of the cycloalkyl group or aryl group except for the non-monovalent.

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

In the present specification, the heterocycle includes one or more non-carbon atoms and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S. 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, in the formulas A and B, Q1 and Q2 are the same as or different from each other, and each independently substituted or unsubstituted aromatic ring; Or a substituted or unsubstituted heterocycle.

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

[Formula 1-1]

[Formula 1-2]

In Chemical Formulas 1-1 and 1-2,

The definitions of X1, X2, Y1 to Y4, R1 to R4, Ar1 and Ar2 are the same as defined in Formula 1,

The definitions of X, X ', X ", X"', G1 to G4, Q1, Q2, n1 and n2 are the same as defined in Formulas A and B above.

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

In the above structure,

The definitions of X, X ', G1 and G2 are the same as defined in Formula A above,

X11 and X12 are the same as or different from each other, and each independently S or Se,

G101 to G111 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

g105, g110 and g111 are each 1 or 2,

When g105, g110 and g111 are each 2, structures in two parentheses are the same or different from each other.

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

In the above structure,

The definitions of X ", X" ', G3 and G4 are the same as defined in Formula B above,

G112 and G113 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Y is O or S.

According to an exemplary embodiment of the present specification, the formula 1 is represented by any one of the following formulas 1-3 to 1-6.

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

In Chemical Formulas 1-3 to 1-6,

The definitions of X1, X2, Y1 to Y4, R1 to R4, Ar1 and Ar2 are the same as defined in Chemical Formula 1,

The definitions of X, X ', X ", X"' and G1 to G4 are the same as defined in Formulas A and B above,

X11 and X12 are the same as or different from each other, and each independently S or Se,

G101 to G113 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

g105, g110 and g111 are each 1 or 2,

When g105, g110, and g111 are each 2, structures in two parentheses are the same or different from each other,

Y is O or S.

According to an exemplary embodiment of the present specification, the formula 1 is the following formula 1-3-1 to 1-3-3, 1-4-1 to 1-4-3, 1-5-1 to 1-5-3 And 1-6-1 to 1-6-3.

[Formula 1-3-1]

[Formula 1-3-2]

[Formula 1-3-3]

[Formula 1-4-1]

[Formula 1-4-2]

[Formula 1-4-3]

[Formula 1-5-1]

[Formula 1-5-2]

[Formula 1-5-3]

[Formula 1-6-1]

[Formula 1-6-2]

[Formula 1-6-3]

To the above formulas 1-3-1 to 1-3-3, 1-4-1 to 1-4-3, 1-5-1 to 1-5-3 and 1-6-1 to 1-6-3 In,

The definitions of X1, X2, Y1 to Y4 and R1 to R4 are the same as defined in Chemical Formula 1,

The definitions of X, X ', X ", X"' and G1 to G4 are the same as defined in Formulas A and B above,

X11 and X12 are the same as or different from each other, and each independently S or Se,

G101 to G113 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

g105, g110 and g111 are each 1 or 2,

When g105, g110, and g111 are each 2, structures in two parentheses are the same or different from each other,

Y is O or S,

R200 to R202 and R210 to R212 are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group,

a, b, a1 and b1 are each an integer from 1 to 4,

When a, b, a1, and b1 are each 2 or more, structures in two or more parentheses are the same or different from each other.

According to an exemplary embodiment of the present specification, in the formula A and B, Q1 and Q2 are the same as or different from each other, and each independently substituted or unsubstituted benzene ring; Substituted or unsubstituted thiophene ring; A substituted or unsubstituted cyclopentadiene ring; A substituted or unsubstituted indene ring; Or a substituted or unsubstituted pyran ring.

According to an exemplary embodiment of the present specification, in the formula A and B, Q1 and Q2 are the same as or different from each other, and each independently a benzene ring; Thiophene ring; A cyclopentadiene ring substituted with an aryl group substituted with an alkyl group; A substituted or unsubstituted indene ring substituted with an aryl group substituted with an alkyl group; Or a pyran ring substituted with an alkyl group.

According to an exemplary embodiment of the present specification, in the formula A and B, Q1 and Q2 are the same as or different from each other, and each independently a benzene ring; Thiophene ring; a cyclopentadiene ring substituted with a phenyl group substituted with an n-hexyl group; a substituted or unsubstituted indene ring substituted with a phenyl group substituted with an n-hexyl group; Or a pyran ring substituted with a 3,7-dimethyloctyl group.

According to one embodiment of the present specification, Y1 to Y4 are N.

According to an exemplary embodiment of the present specification, X1, X2, X, X ', X ", X"', X11 and X12 are S.

According to one embodiment of the present specification, R1 to R4, G1 and G2 are hydrogen.

According to an exemplary embodiment of the present specification, the G105, G110 and G111 is hydrogen.

According to one embodiment of the present specification, G101 to G104 and G106 to G109 are phenyl groups substituted with n-hexyl groups.

According to the exemplary embodiment of the present specification, G112 and G113 are 3,7-dimethyloctyl groups.

According to an exemplary embodiment of the present specification, the R200 and R210 are the same as or different from each other, and each independently an substituted or unsubstituted alkyl group.

According to an exemplary embodiment of the present specification, the R200 and R210 are the same as or different from each other, and each independently an ethyl group; Or n-octyl group.

According to one embodiment of the present specification, R200 and R210 are ethyl groups.

According to the exemplary embodiment of the present specification, R200 and R210 are n-octyl groups.

According to an exemplary embodiment of the present specification, the R201, R202, R211 and R212 is hydrogen.

According to an exemplary embodiment of the present specification, the formula 1 is a heterocyclic compound selected from the following compounds:

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

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

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

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

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

1 is a view showing an organic solar cell according to an exemplary embodiment of the present specification.

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

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

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

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

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

According to one embodiment of the present specification, the organic solar cell has a tandem structure.

In the organic solar cell according to the exemplary embodiment of the present specification, the photoactive layer may have one or more layers. In the tandem structure, two or more photoactive layers may be included.

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

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

In addition, an organic solar cell using the heterocyclic compound represented by Formula 1 as an n-type organic material layer (electron acceptor material) of the photoactive layer has most of the p-type organic material (electron donor material) having the maximum absorption wavelength in the visible region. For, it is possible to apply, but is not limited thereto.

According to an exemplary embodiment of the present specification, the electron donor material may be a material applied in the art, for example, poly 3-hexyl thiophene (P3HT), PCDTBT (poly [N- 9'-heptadecanyl-2,7-carbazole-alt-5,5- (4'-7'-di-2-thienyl-2 ', 1', 3'-benzothiadiazole)]), PCPDTBT (poly [2, 6- (4,4-bis- (2-ethylhexyl) -4H-cyclopenta [2,1-b; 3,4-b '] dithiophene) -alt-4,7- (2,1,3-benzothiadiazole) ]), PFO-DBT (poly [2,7- (9,9-dioctyl-fluorene) -alt-5,5- (4,7-di 2-thienyl-2,1,3-benzothiadiazole)]), PTB7 (or PTB7-Th) (Poly [[4,8-bis [(2-ethylhexyl) oxy] benzo [1,2-b: 4,5-b '] dithiophene-2,6-diyl] [3- fluoro-2-[(2-ethylhexyl) carbonyl] thieno [3,4-b] thiophenediyl]]), PSiF-DBT (Poly [2,7- (9,9-dioctyl-dibenzosilole) -alt-4,7 -bis (thiophen-2-yl) benzo-2,1,3-thiadiazole]).

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

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

In one embodiment of the present specification, the photoactive layer further includes an additive.

In one embodiment of the present specification, the molecular weight of the additive is 50 g / mol to 1000 g / mol.

In another exemplary embodiment, the additive has a boiling point of 30 to 300 organics.

In the present specification, the organic material means a material containing at least one carbon atom.

In one embodiment, the additive is 1,8-diiodooctane (DIO: 1,8-diiodooctane), 1-chloronaphthalene (1-CN: 1-chloronaphthalene), diphenyl ether (DPE: diphenylether), Octane dithiol (octane dithiol) and tetrabromothiophene (tetrabromothiophene) may further include one or two kinds of additives selected from the group consisting of.

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

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 is not limited if 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). It is not limited to this.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The photoactive layer may be formed by dissolving a photoactive material such as an electron donor and / or an electron acceptor in an organic solvent, and then spin-coating the solution, dip coating, screen printing, spray coating, doctor blade, brush painting, or the like. It is not limited to the method.

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

Synthesis Example 1. Synthesis of Compound 1-A

The mixture of compound 1-a, compound 1-b, Pd (PPh ₃ ) ₄ and toluene was heated to 100 ° C. for 12 hours under an argon atmosphere. After cooling to room temperature, the reaction mixture was poured into 100 mL of sodium chloride aqueous solution, and extracted three times with chloroform. The organic layer was dried over anhydrous MgSO ₄ and concentrated in vacuo. The residue was purified by silica gel column chromatography to give compound 1-A (blue solid). (Yield 70%)

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

Synthesis Example 2. Synthesis of Compound 2-A

It was prepared in the same manner as in Synthesis Example 1, except that Compound 2-a was used instead of Compound 1-a, to obtain Compound 2-A. (Yield 70%)

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

Preparation Example 1 Preparation of Compound 1

Compound 1-A and compound 1-B were dissolved in tert-butyl alcohol. 3 drops of piperidine were added and the solution was stirred at 85 ° C overnight. The product was extracted with chloroform and dried over MgSO ₄ . The crude product was purified by flash column chromatography on silica with methylene chloride and precipitated from methanol. The precipitate was collected and dried by vacuum filtration to give compound 1. (Yield: 65%)

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

Preparation Example 2 Preparation of Compound 2

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

5 is a diagram showing FT-NMR data of Compound 2.

Preparation Example 3 Preparation of Compound 3

It was prepared in the same manner as in Preparation Example 1, except that Compound 1-D was used instead of Compound 1-B to obtain Compound 3.

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

Preparation Example 4. Preparation of compound 4

It was prepared in the same manner as in Preparation Example 1, except that Compound 1-E was used instead of Compound 1-B to obtain Compound 4.

7 is a diagram showing FT-NMR data of Compound 4.

Preparation Example 5. Preparation of compound 5

It was prepared in the same manner as in Preparation Example 1, except that Compound 2-A was used instead of Compound 1-A to obtain Compound 5.

8 is a diagram showing FT-NMR data of Compound 5.

Preparation Example 6 Preparation of Compound 6

It was prepared in the same manner as in Preparation Example 1, except that Compound 2-A was used instead of Compound 1-A, and Compound 1-C was used instead of Compound 1-B, to obtain Compound 6.

9 is a diagram showing FT-NMR data of Compound 6.

Preparation Example 7. Preparation of compound 7

It was prepared in the same manner as in Preparation Example 1, except that Compound 2-A was used instead of Compound 1-A, and Compound 1-D was used instead of Compound 1-B to obtain Compound 7.

Preparation Example 8. Preparation of compound 8

In Preparation Example 1, Compound 2-A was used instead of Compound 1-A, and Compound 8 was obtained in the same manner except that Compound 1-E was used instead of Compound 1-B.

Experimental Example 1-1. Preparation of organic solar cells

PTB7-Th and Compound 6 were dissolved 1: 1 in chlorobenzene (CB) to prepare a composite solution. At this time, the concentration was adjusted to 4 wt%, and the organic solar cell had an inverted structure of ITO / ZnO NP / photoactive layer / MoO ₃ / Ag.

ITO is a bar type, and a 1.5 cm × 1.5 cm coated glass substrate (11.5 Ω / □) is ultrasonically cleaned using distilled water, acetone, and 2-propanol, and the ITO surface is ozone treated for 10 minutes. ZnO NP (ZnO nanograde N-10 2.5 wt% in 1-butanol, filtered to 0.45 μm PTFE) was made, and this ZnO NP solution was spin-coated at 4000 rpm for 40 seconds, and then at 80 ° C. for 10 minutes. Heat treatment was performed to remove the remaining solvent to complete the electron transport layer. For the coating of the photoactive layer, a composite solution of PTB7-Th and the compound 6 was spin-coated at 70 ° C at 700 rpm for 25 seconds. In the thermal evaporator, MoO ₃ was thermally evaporated to a thickness of 10 nm at 10 ⁻⁷ Torr at a rate of 0.2 Å / s to prepare a hole transport layer. After manufacturing in this order, Ag was deposited inside a thermal evaporator at a rate of 1 Å / s at 100 nm to prepare an organic solar cell having a reverse structure.

Experimental Example 1-2. Preparation of organic solar cells

An organic solar cell was prepared in the same manner as in Experimental Example 1-1, except that the composite solution of PTB7-Th and Compound 6 was spin coated at 900 rpm instead of 700 rpm for coating the photoactive layer in Experimental Example 1-1. .

Experimental Example 1-3. Preparation of organic solar cells

An organic solar cell was prepared in the same manner as in Experimental Example 1-1, except that the composite solution of PTB7-Th and Compound 6 was spin coated at 1100 rpm instead of 700 rpm for coating the photoactive layer in Experimental Example 1-1. .

Experimental Example 1-4. Preparation of organic solar cells

An organic solar cell was prepared in the same manner as in Experimental Example 1-1, except that the composite solution of PTB7-Th and the compound 6 was spin coated at 1300 rpm instead of 700 rpm for coating the photoactive layer in Experimental Example 1-1. .

The photoelectric conversion characteristics of the organic solar cells prepared in Experimental Examples 1-1 to 1-4 were measured under 100 mW / cm ² (AM 1.5) conditions, and the results are shown in Table 1 below.

rpm V _oc
(V) J _sc
(mA / cm ² ) FF η
(%) Experimental Example 1-1 700 0.758 16.443 0.593 7.40 0.746 16.425 0.546 6.69 Experimental Example 1-2 900 0.771 17.200 0.629 8.34 0.765 16.939 0.607 7.86 Experimental Example 1-3 1100 0.774 16.646 0.649 8.37 0.772 16.826 0.638 8.28 Experimental Example 1-4 1300 0.775 15.049 0.652 7.60 0.770 15.383 0.621 7.35

10 is a view showing the current density according to the voltage of the organic solar cells according to Experimental Examples 1-1 to 1-4.

Experimental Example 2-1. Preparation of organic solar cells

An organic solar cell was manufactured in the same manner as in Experimental Example 1-1, except that 3 vol% of 1,8-diiodooctane was added to the composite solution of PTB7-Th and Compound 6 in Experimental Example 1-1.

Experimental Example 2-2. Preparation of organic solar cells

An organic solar cell was manufactured in the same manner as in Experimental Example 1-2, except that 3 vol% of 1,8-diiodooctane was added to the composite solution of PTB7-Th and Compound 6 in Experimental Example 1-2.

Experimental Example 2-3. Preparation of organic solar cells

An organic solar cell was manufactured in the same manner as in Experimental Example 1-3, except that 3 vol% of 1,8-diiodooctane was added to the composite solution of PTB7-Th and Compound 6 in Experimental Example 1-3.

Experimental Example 2-4. Preparation of organic solar cells

An organic solar cell was manufactured in the same manner as in Experimental Example 1-4, except that 3 vol% of 1,8-diiodooctane was added to the composite solution of PTB7-Th and Compound 6 in Experimental Example 1-4.

The photoelectric conversion characteristics of the organic solar cells prepared in Experimental Examples 2-1 to 2-4 were measured under 100 mW / cm ² (AM 1.5) conditions, and the results are shown in Table 2 below.

rpm V _oc
(V) J _sc
(mA / cm ² ) FF η
(%) Experimental Example 2-1 700 0.756 17.376 0.608 7.98 0.751 17.524 0.627 8.24 Experimental Example 2-2 900 0.753 17.700 0.646 8.60 0.749 17.351 0.636 8.27 Experimental Example 2-3 1100 0.755 17.173 0.659 8.54 0.754 17.344 0.662 8.65 Experimental Example 2-4 1300 0.763 16.502 0.664 8.36 0.756 16.400 0.676 8.39

11 is a view showing the current density according to the voltage of the organic solar cells according to Experimental Examples 2-1 to 2-4.

Experimental Example 3-1. Preparation of organic solar cells

In Experimental Example 1-1, except that PTB7-Th and Compound 6 were dissolved 1: 1 in o- xylene instead of chlorobenzene (CB) to prepare a composite solution, Experimental Example 1-1 An organic solar cell was manufactured in the same manner as.

Experimental Example 3-2. Preparation of organic solar cells

In Experimental Example 1-2, except that PTB7-Th and Compound 6 were dissolved in o -xylene in 1: 1 instead of chlorobenzene (CB) to prepare a composite solution, Experimental Example 1-2 An organic solar cell was manufactured in the same manner as.

Experimental Example 3-3. Preparation of organic solar cells

In Experimental Example 1-3, except that a composite solution was prepared by dissolving PTB7-Th and the compound 6 in o -xylene in 1: 1 instead of chlorobenzene (CB), Experimental Example 1-3 An organic solar cell was manufactured in the same manner as.

Experimental Example 3-4. Preparation of organic solar cells

In Experimental Example 1-4, except that PTB7-Th and Compound 6 were dissolved in o -xylene in 1: 1 instead of chlorobenzene (CB) to prepare a composite solution, Experimental Example 1-4 An organic solar cell was manufactured in the same manner as.

The photoelectric conversion characteristics of the organic solar cells prepared in Experimental Examples 3-1 to 3-4 were measured under 100 mW / cm ² (AM 1.5) conditions, and the results are shown in Table 3 below.

rpm V _oc
(V) J _sc
(mA / cm ² ) FF η
(%) Experimental Example 3-1 700 0.784 12.178 0.498 4.76 0.790 12.110 0.501 4.80 Experimental Example 3-2 900 0.801 11.705 0.521 4.88 0.793 11.432 0.511 4.63 Experimental Example 3-3 1100 0.748 10.175 0.380 2.89 0.770 10.407 0.430 3.45 Experimental Example 3-4 1300 0.789 9.981 0.528 4.16 0.788 10.018 0.524 4.13

12 is a view showing the current density according to the voltage of the organic solar cells according to Experimental Examples 3-1 to 3-4.

Experimental Example 4-1. Preparation of organic solar cells

An organic solar cell was manufactured in the same manner as in Experimental Example 3-1, except that 3 vol% of 1,8-diiodooctane was added to the composite solution of PTB7-Th and Compound 6 in Experimental Example 3-1.

Experimental Example 4-2. Preparation of organic solar cells

An organic solar cell was manufactured in the same manner as in Experimental Example 3-2, except that 3 vol% of 1,8-diiodooctane was added to the composite solution of PTB7-Th and Compound 6 in Experimental Example 3-2.

Experimental Example 4-3. Preparation of organic solar cells

An organic solar cell was manufactured in the same manner as in Experimental Example 3-3, except that 3 vol% of 1,8-diiodooctane was added to the composite solution of PTB7-Th and Compound 6 in Experimental Example 3-3.

Experimental Example 4-4. Preparation of organic solar cells

An organic solar cell was manufactured in the same manner as in Experimental Example 3-4, except that 3 vol% of 1,8-diiodooctane was added to the composite solution of PTB7-Th and Compound 6 in Experimental Example 3-4.

The photoelectric conversion characteristics of the organic solar cells prepared in Experimental Examples 4-1 to 4-4 were measured under 100 mW / cm ² (AM 1.5) conditions, and the results are shown in Table 4 below.

rpm V _oc
(V) J _sc
(mA / cm ² ) FF η
(%) Experimental Example 4-1 700 0.758 17.460 0.650 8.61 0.752 17.415 0.665 8.70 Experimental Example 4-2 900 0.760 16.635 0.670 8.47 0.749 16.841 0.672 8.48 Experimental Example 4-3 1100 0.763 15.534 0.682 8.08 0.754 15.111 0.687 7.82 Experimental Example 4-4 1300 0.763 14.181 0.680 7.36 0.753 14.084 0.666 7.06

13 is a view showing the current density according to the voltage of the organic solar cells according to Experimental Examples 4-1 to 4-4.

The V _oc is an open voltage, J _sc is a short-circuit current, FF is a fill factor, and PCE (η) is energy conversion efficiency. The open voltage and short-circuit current are the X-axis and Y-axis intercepts in the quadrant of the voltage-current density curve, respectively, and the higher these two values, the higher the efficiency of the solar cell is. In addition, the fill factor is a value obtained by dividing the area of the rectangle that can be drawn inside the curve by the product of the short-circuit current and the open voltage. The energy conversion efficiency can be obtained by dividing these three values by the intensity of the irradiated light, and the higher the value, the better. As a result of Tables 1 to 4 and FIGS. 10 to 13, it can be confirmed that the heterocyclic compound according to the exemplary embodiment of the present specification exhibits high photo-electric conversion efficiency.

10: first electrode
20: second electrode
30: photoactive layer
100: organic solar cell

Claims (12)

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

In Chemical Formula 1,
X1 and X2 are the same as or different from each other, and each independently CRR ', NR, O, SiRR', PR, S, GeRR ', Se or Te,
Y1 to Y4 are the same as or different from each other, and each independently CR ", N, SiR", P or GeR ",
R1 to R4, R, R 'and R "are the same as or different from each other, and each independently hydrogen; deuterium; halogen group; hydroxy group; substituted or unsubstituted alkyl group; or substituted or unsubstituted alkoxy group,
Ar1 and Ar2 are the same as or different from each other, and each independently a group represented by the following structure,

In the above structure,
R200 to R202 are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group,
a and b are each an integer from 1 to 4,
When a and b are each 2 or more, structures in parentheses of 2 or more are the same or different from each other,
X "and X"'are the same as or different from each other, and each independently S or Se,
G3 and G4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
G112 and G113 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
Y is O or S. delete delete delete The method according to claim 1, wherein Formula 1 is a heterocyclic compound represented by any one of the following Formulas 1-6-1 to 1-6-3:
[Formula 1-6-1]

[Formula 1-6-2]

[Formula 1-6-3]

In Chemical Formulas 1-6-1 to 1-6-3,
The definitions of X1, X2, Y1 to Y4, R1 to R4, X ", X"', G3 and G4 are the same as defined in Formula 1 above,
G112 and G113 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
Y is O or S,
R200 to R202 and R210 to R212 are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group,
a, b, a1 and b1 are each an integer from 1 to 4,
When a, b, a1, and b1 are each 2 or more, structures in two or more parentheses are the same or different from each other. The method according to claim 1, wherein Formula 1 is a heterocyclic compound selected from the following compounds:

A first electrode;
A second electrode provided to face the first electrode; And
An organic electronic device including at least one organic layer provided between the first electrode and the second electrode,
At least one layer of the organic material layer is an organic electronic device comprising the heterocyclic compound according to any one of claims 1, 5 and 6. The organic electronic device according to claim 7, wherein the organic electronic device is selected from the group consisting of an organic photoelectric device, an organic transistor, an organic solar cell, and an organic light emitting device. The method according to claim 7, The organic electronic device is a first electrode;
A second electrode provided to face the first electrode; And
An organic solar cell including at least one organic layer provided between the first electrode and the second electrode,
At least one layer of the organic material layer is an organic electronic device comprising the heterocyclic compound. The method according to claim 9, 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,
The n-type organic material layer is an organic electronic device comprising the heterocyclic compound. The method according to claim 9, The organic layer includes a photoactive layer,
The photoactive layer includes an electron donor material and an electron acceptor material,
The electron acceptor material is an organic electronic device comprising the heterocyclic compound. The method according to claim 11, wherein the electron donor and electron acceptor constitute a bulk heterojunction (BHJ).

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